Total intracorporeal robot-assisted laparoscopic ileal conduit (Bricker) urinary diversion: technique and outcomes.

PubMed

Rehman, Jamil; Sangalli, Mattia N; Guru, Khurshid; de Naeyer, Geert; Schatteman, Peter; Carpentier, Paul; Mottrie, Alexander

2011-02-01

Several recent preliminary reports have demonstrated that Robot-Assisted Cystectomy with total intracorporeal Ileal Conduit (RACIC) is a feasible option over the open technique. We report our stepwise surgical procedure of robotic total intracorporeal ileal conduit urinary diversion, technical consideration, development, refinements and initial experience. Only the ileal conduit urinary diversion is described with no emphasis on the cystectomy's steps. Between February 2008 and September 2009, nine patients underwent RACIC for muscle invasive transitional cell carcinoma (TCC). The entire procedure, including radical cystoprostatectomy, extended pelvic node dissection (ePLND), ileal conduit urinary diversion (Bricker) including isolation of the ileal loop (20 cm ileal segment) 15 cm away from the ileocecal junction, restoration of bowel continuity with stapled side-to-side ileo-ileal anastomosis, retroperitoneal transfer of the left ureter to the right side, and bilateral stented (8 F feeding tube) ileo-ureteral anastomoses in a Wallace faction were all performed exclusively intracorporeally using the da Vinci Si surgical robot and finally the conduit stoma was fashioned. The RACIC was technically successful in all nine patients (three females and six males. Mean age 74.1; 57 to 87) without open conversion. The mean operative time including extended pelvic lymphadenectomy and urinary diversion was 346.2 minutes (210 to 480). Mean operative time of diversion is 72 minutes (52-113) mean estimated blood loss 258 mL (200 to 500) and the median hospital stay were 14 days (10 to 27). In all three female patients, the specimen was extracted through the vagina. There were no intraoperative complications and only one major postoperative complication: one postoperative iatrogenous necrosis of the ileal conduit caused by uncareful retraction of the organ bag and thereby probably injuring the conduit pedicle, as the ileal conduit was well vascularised at the end of the operation, requiring an open revision (in male patient extracted through the suprapubic incision). A clear liquid diet was started on the third postoperative day. All patients returned to normal activity within 2 weeks (from date of surgery). Postoperative renal function was normal with mean postoperative creatine 0.99 mg/dL) and excretory urography revealed unobstructed upper tracts in all cases. Robot-assisted radical cystoprostatectomy with intracorporeal ileal conduit urinary diversion for the treatment of high risk or invasive bladder cancer with urinary diversion is technically feasible. The robotic system aids in performing a meticulous dissection and all operative steps of the open procedure are replicated precisely while adhering to the sound oncologic principles of traditional radical cystectomy. Robotics brings an unprecedented control of surgical instruments, shorten the learning curve, and allow open surgeons to apply more easily their technical skill in a minimal invasive fashion. Robotic cystectomy with total intracorporeal ileal conduit urinary diversion offers operative and perioperative benefits and functional outcome. In our hands results comparable to open experience with further reduced perioperative morbidity, early recovery, resumption of normal activities, excellent cosmesis and increased quality of life (QOL). In addition, minimal blood loss, fluid shifts, and electrolyte loss considerably reduce systemic and cardiovascular stress in these older groups of patients.

Quantification of phase I / II metabolizing enzyme gene expression and polycyclic aromatic hydrocarbon-DNA adduct levels in human prostate

PubMed Central

John, Kaarthik; Ragavan, Narasimhan; Pratt, M. Margaret; Singh, Paras B.; Al-Buheissi, Salah; Matanhelia, Shyam S.; Phillips, David H.; Poirier, Miriam C.; Martin, Francis L.

2008-01-01

BACKGROUND Studies of migrant populations suggest that dietary and/or environmental factors play a crucial role in the aetiology of prostatic adenocarcinoma (CaP). The human prostate consists of the peripheral zone (PZ), transition zone (TZ) and central zone (CZ); CaP occurs most often in the PZ. METHODS To investigate the notion that an underlying differential expression of phase I/II genes, and/or the presence of polycyclic aromatic hydrocarbon (PAH)-DNA adducts might explain the elevated PZ susceptibility, we examined prostate tissues (matched tissue sets consisting of PZ and TZ) from men undergoing radical retropubic prostatectomy for CaP (n=26) or cystoprostatectomy (n=1). Quantitative gene expression analysis was employed for cytochrome P450 (CYP) isoforms CYP1A1, CYP1B1 and CYP1A2, as well as N-acetyltransferase 1 and 2 (NAT1 and NAT2) and catechol-O-methyl transferase (COMT). RESULTS CYP1B1, NAT1 and COMT were expressed in all tissue sets; levels of CYP1B1 and NAT1 were consistently higher in the PZ compared to TZ. Immunohistochemistry confirmed the presence of CYP1B1 (nuclear-associated and primarily in basal epithelial cells) and NAT1. Tissue sections from 23 of these aforementioned 27 matched tissue sets were analyzed for PAH-DNA adduct levels using antiserum elicited against DNA modified with r7, t8-dihydroxy-t-9,10-oxy-7,8,9,10-tetrahydro-benzo[a]pyrene (BPDE). PAH-DNA adduct levels were highest in glandular epithelial cells, but a comparison of PZ and TZ showed no significant differences. CONCLUSION Although expression of activating and/or detoxifying enzymes may be higher in the PZ, PAH-DNA adduct levels appear to be similar in both zones. Therefore, factors other than PAH-DNA adducts may be responsible for promotion of tumour formation in the human prostate. PMID:19143007

OH radical induced depolymerization of poly(methacrylic acid)

NASA Astrophysics Data System (ADS)

Ulanski, Piotr; Bothe, Eberhard; von Sonntag, Clemens

1999-05-01

Hydroxyl radicals (generated pulse radiolytically in dilute N 2O-saturated aqueous solutions) react with poly(methacrylic acid) producing two kinds of radicals. The primary radical is converted into a secondary one by H-abstraction ( k=3.5 × 10 2 s -1) as monitored by changes in the UV spectrum. Subsequently, the secondary radicals undergo chain scission ( k=1.8 s -1 at pH 7-9). This process has been followed both by spectrophotometry as well as by conductometry. In competition with the bimolecular decay of the radicals the ensuing end-chain radicals undergo efficient depolymerization resulting in the release of monomer. Since the lifetime of the radicals is much longer at high pH, where the polymer attains a rod-like conformation, depolymerization is most efficient in basic solution.

Impact of the Level of Urothelial Carcinoma Involvement of the Prostate on Survival after Radical Cystectomy.

PubMed

Moschini, Marco; Soria, Francesco; Susani, Martin; Korn, Stephan; Briganti, Alberto; Roupret, Morgan; Seitz, Christian; Gust, Killian; Haitel, Andrea; Montorsi, Francesco; Wirth, Gregory; Robinson, Brian D; Karakiewicz, Pierre I; Özsoy, Mehmet; Rink, Michael; Shariat, Shahrokh F

2017-07-27

Urothelial prostatic involvement (UPI) at the time of radical cystoprostatectomy (RCP) was found associated with worse survival outcomes by several previous reports. Our aim is to evaluate the impact of different levels of UPI on survival outcomes using a large series of male patients treated with RCP. Whole step section specimens from 995 male BCa patients were assessed for UPI defined as: no involvement vs. prostatic urethral carcinoma in situ (CIS) vs. lamina propria involvement vs. ductal CIS vs. prostate stromal involvement. Primary end point of the study was predictors of prostatic involvement at RCP and its impact on overall survival after surgery. Prostatic involvement was recorded in 307 (30.9%) patients: 28% with prostatic urethral CIS, 12% with lamina propria involvement, 13% with ductal CIS and 47% with stromal involvement. Median follow-up was 70 months. Patients with stromal involvement had a worse 5-year survival (12%) than those with prostatic urethra CIS (40%), lamina propria involvement (36%), and ductal CIS (35%). Considering predictors of prostatic involvement, multifocal tumor (Odds Ratio [OR]: 6.60, p  < 0.001), lymphovascular invasion (OR: 2.61, p  < 0.001), lymph node metastases (OR: 2.02, p  < 0.001) and CIS (OR: 2.02, p  < 0.001) were found associated. Similar predictors were found assessing stromal involvement. Approximately one third of RCP patients harbor prostatic involvement of urothelial carcinoma. While all UPI are associated with worse overall survival, stromal involvement confers the worst outcome supporting its classification as T4 in the TNM staging.

Simulation of lubricating behavior of a thioether liquid lubricant by an electrochemical method

NASA Technical Reports Server (NTRS)

Morales, W.

1984-01-01

An electrochemical cell was constructed to explore the possible radical anion forming behavior of a thioether liquid lubricant. The electrochemical behavior of the thioether was compared with the electrochemical behavior of biphenyl, which is known to form radical anions. Under controlled conditions biphenyl undergoes a reversible reaction to a radical anion, whereas the thioether undergoes an irreversible reduction yielding several products. These results are discussed in relation to boundary lubrication.

Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

PubMed

De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

2005-01-21

Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

Ionizing radiation-induced destruction of benzene and dienes in aqueous media.

PubMed

Al-Sheikhly, Mohamad; Poster, Dianne L; An, Jung-Chul; Neta, Pedatsur; Silverman, Joseph; Huie, Robert E

2006-05-01

Pulse radiolysis with spectrophotometric and conductometric detection was utilized to study the formation and reactions of radicals from benzene and dienes in aqueous solutions. The benzene OH adduct, *C6H6OH, reacts with O2 (k = 3 x 10(8) L mol(-1) s(-1)) in a reversible reaction. The peroxyl radical, HOC6H6O2*, undergoes O2*- elimination, bimolecular decay, and reaction with benzene to initiate a chain reaction, depending on the dose rate, benzene concentration, and pH. The occurrence of the chain reaction is demonstrated in low-dose-rate gamma radiolysis experiments where the consumption of O2 was monitored. 1,4-Cyclohexadiene, 1,4-hexadiene, and 1,4-pentadiene form OH-adducts and undergo H-abstraction by O*- radicals. The OH-adducts react with O2 to form peroxyl radicals. These peroxyl radicals, however, do not undergo unimolecular O2*- elimination but rather decay by second-order processes, which lead to subsequent steps of O2*- elimination.

3D vision improves outcomes in early cervical cancer treated with laparoscopic type B radical hysterectomy and pelvic lymphadenectomy.

PubMed

Raspagliesi, Francesco; Bogani, Giorgio; Martinelli, Fabio; Signorelli, Mauro; Scaffa, Cono; Sabatucci, Ilaria; Lorusso, Domenica; Ditto, Antonino

2017-01-21

To evaluate the alterations on surgical outcomes after of the implementation of 3D laparoscopic technology for the surgical treatment of early-stage cervical carcinoma. Data of patients undergoing type B radical hysterectomy (with or without bilateral salpingo-oophorectomy) and pelvic lymphadenectomy via 3D laparoscopy were compared with a historical cohort of patients undergoing type B radical hysterectomy via conventional laparoscopy. Complications (within 60 days) were graded per the Accordion severity system. Data of 75 patients were studied: 15 (20%) and 60 (80%) patients undergoing surgery via 3D laparoscopy and conventional laparoscopy, respectively. Baseline patient characteristics as well as pathologic findings were similar between groups (p>0.1). Patients undergoing 3D laparoscopy experienced a trend toward shorter operative time than patients undergoing conventional laparoscopy (176.7 ± 74.6 vs 215.9 ± 61.6 minutes; p = 0.09). Similarly, patients undergoing 3D laparoscopic radical hysterectomy experienced shorter length of hospital stay (2 days, range 2-6, vs 4 days, range 3-11; p<0.001) in comparison to patients in the control group, while no difference in estimated blood loss was observed (p = 0.88). No between-group difference in complication rate was observed. 3D technology is a safe and effective way to perform type B radical hysterectomy and pelvic node dissection in early-stage cervical cancer. Further large prospective studies are warranted in order to assess the cost-effectiveness of the introduction of 3D technology in comparison to robotic assisted surgery.

Prospective evaluation of short-term impact and recovery of health related quality of life in men undergoing robotic assisted laparoscopic radical prostatectomy versus open radical prostatectomy.

PubMed

Miller, Javier; Smith, Angela; Kouba, Erik; Wallen, Eric; Pruthi, Raj S

2007-09-01

In the last few years there have been increasing claims that robotic assisted laparoscopic radical prostatectomy decreases short-term morbidity in patients undergoing surgical treatment for prostate cancer. However, there is surprisingly little objective evidence to support this point, which is often used to market the procedure to patients. To address this issue we prospectively evaluated patients undergoing open and robotic assisted laparoscopic radical prostatectomy at baseline and weekly through the postoperative period using a validated questionnaire. A total of 162 men undergoing radical prostatectomy, including open radical prostatectomy in 120 and robotic assisted laparoscopic radical prostatectomy in 42, for clinically localized prostate cancer completed the SF-12, version 2 Physical and Mental Health Survey Acute Form preoperatively and each week postoperatively for 6 weeks. Physical and Mental Component Scores were calculated from the questionnaires at each time point. Comparisons between the 2 surgical approaches were made at each time point. No significant differences were seen between the open and robotic assisted laparoscopic radical prostatectomy groups with regard to patient age, clinical stage or preoperative prostate specific antigen. Mean surgical blood loss was significantly higher in the open group compared to that in the robotic assisted laparoscopic group. Physical Component Scores in the robotic assisted laparoscopic group were significantly higher than those in the open cohort beginning postoperative week 1 and extending through week 6. On statistical extrapolation Physical Component Scores returned to baseline between weeks 5 and 6 postoperatively in the robotic assisted laparoscopic group and between weeks 6 and 7 in the open group. Mental Component Score scores were not statistically different between the groups except preoperatively. This study helps prospectively define short-term health related quality of life in patients undergoing robotic assisted laparoscopic vs open radical prostatectomy. Higher physical scores were seen in the robotic assisted laparoscopic group than the open group beginning postoperative week 1 and continuing weekly throughout the 6-week study period. Physical Component Score scores returned to baseline sooner in the robotic assisted laparoscopic group than in the open group.

Extended Venous Thromboembolism Prophylaxis after Radical Cystectomy: A Call for Adherence to Current Guidelines.

PubMed

Klaassen, Zachary; Arora, Karan; Goldberg, Hanan; Chandrasekar, Thenappan; Wallis, Christopher J D; Sayyid, Rashid K; Fleshner, Neil E; Finelli, Antonio; Kutikov, Alexander; Violette, Philippe D; Kulkarni, Girish S

2018-04-01

Radical cystectomy is inherently associated with morbidity. We assess the timing and incidence of venous thromboembolism, review current guideline recommendations and provide evidence for considering extended venous thromboembolism prophylaxis in all patients undergoing radical cystectomy. We searched PubMed® for available literature on radical cystectomy and venous thromboembolism, focusing on incidence and timing, evidence supporting extended venous thromboembolism prophylaxis in patients undergoing radical cystectomy or abdominal oncologic surgery, current guideline recommendations, safety considerations and direct oral anticoagulants. Search terms included "radical cystectomy," "venous thromboembolism," "prophylaxis," and "extended oral anticoagulants" and "direct oral anticoagulants" alone and in combination. Relevant articles were reviewed, including original research, reviews and clinical guidelines. References from review articles and guidelines were also assessed to develop a narrative review. The incidence of symptomatic venous thromboembolism in short-term followup after radical cystectomy is 3% to 11.6%, of which more than 50% of cases will occur after hospital discharge. Meta-analyses of clinical trials in patients undergoing major abdominal oncologic operations suggest a decreased risk of venous thromboembolisms for patients receiving extended (4 weeks) venous thromboembolism prophylaxis. Extended prophylaxis should be considered in all radical cystectomy cases. Although the relative risk of bleeding also increases, the overall net benefit of extended prophylaxis clearly favors use for at least 28 days postoperatively. Extrarenal eliminated prophylaxis agents are preferred given the risk of renal insufficiency in radical cystectomy cases, with newer oral anticoagulants providing an alternative route of administration. Patients undergoing radical cystectomy are at high risk for venous thromboembolism after hospital discharge. There is strong evidence that extended prophylaxis significantly decreases the risk of venous thromboembolism in oncologic surgery cases. Use of extended prophylaxis after radical cystectomy has been poorly adopted, emphasizing the need for better adherence to current urology procedure specific guidelines as extended prophylaxis for radical cystectomy is the standard of care. Specific and rare circumstances may require case by case assessment. Copyright © 2018 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Competitive Deprotonation and Superoxide [O₂⁻•)] Radical-Anion Adduct Formation Reactions of Carboxamides under Negative-Ion Atmospheric-Pressure Helium-Plasma Ionization (HePI) Conditions.

PubMed

Hassan, Isra; Pinto, Spencer; Weisbecker, Carl; Attygalle, Athula B

2016-03-01

Carboxamides bearing an N-H functionality are known to undergo deprotonation under negative-ion-generating mass spectrometric conditions. Herein, we report that N-H bearing carboxamides with acidities lower than that of the hydroperoxyl radical (HO-O(•)) preferentially form superoxide radical-anion (O2(-•)) adducts, rather than deprotonate, when they are exposed to the glow discharge of a helium-plasma ionization source. For example, the spectra of N-alkylacetamides show peaks for superoxide radical-anion (O2(-•)) adducts. Conversely, more acidic amides, such as N-alkyltrifluoroacetamides, preferentially undergo deprotonation under similar experimental conditions. Upon collisional activation, the O2(-•) adducts of N-alkylacetamides either lose the neutral amide or the hydroperoxyl radical (HO-O(•)) to generate the superoxide radical-anion (m/z 32) or the deprotonated amide [m/z (M - H)(-)], respectively. For somewhat acidic carboxamides, the association between the two entities is weak. Thus, upon mildest collisional activation, the adduct dissociates to eject the superoxide anion. Superoxide-adduct formation results are useful for structure determination purposes because carboxamides devoid of a N-H functionality undergo neither deprotonation nor adduct formation under HePI conditions.

The natural history of renal function after surgical management of renal cell carcinoma: Results from the Canadian Kidney Cancer Information System.

PubMed

Mason, Ross; Kapoor, Anil; Liu, Zhihui; Saarela, Olli; Tanguay, Simon; Jewett, Michael; Finelli, Antonio; Lacombe, Louis; Kawakami, Jun; Moore, Ronald; Morash, Christopher; Black, Peter; Rendon, Ricardo A

2016-11-01

Patients who undergo surgical management of renal cell carcinoma (RCC) are at risk for chronic kidney disease and its sequelae. This study describes the natural history of renal function after radical and partial nephrectomy and explores factors associated with postoperative decline in renal function. This is a multi-institutional cohort study of patients in the Canadian Kidney Cancer Information System who underwent partial or radical nephrectomy for RCC. Estimated glomerular filtration rate (eGFR) and stage of chronic kidney disease were determined preoperatively and at 3, 12, and 24 months postoperatively. Linear regression was used to determine the association between postoperative eGFR and type of surgery (radical vs. partial), duration of ischemia, ischemia type (warm vs. cold), and tumor size. With a median follow-up of 26 months, 1,379 patients were identified from the Canadian Kidney Cancer Information System database including 665 and 714 who underwent partial and radical nephrectomy, respectively. Patients undergoing radical nephrectomy had a lower eGFR (mean = 19ml/min/1.73m 2 lower) at 3, 12, and 24 months postoperatively (P<0.001). Decline in renal function occurred early and remained stable throughout follow-up. A lower preoperative eGFR and increasing age were also associated with a lower postoperative eGFR (P<0.01). Ischemia type and duration were not predictive of postoperative decline in eGFR (P>0.05). Severe renal failure (eGFR<30ml/min/1.73m 2 ) developed postoperatively in 12.5% and 4.1% of radical and partial nephrectomy patients, respectively (P<0.001). After the initial postoperative decline, renal function remains stable in patients undergoing surgery for RCC. Patients undergoing radical nephrectomy have a greater long-term reduction in renal function compared with those undergoing partial nephrectomy. Ischemia duration and type are not predictive of postoperative renal function when adhering to generally short ischemia durations. Copyright © 2016 Elsevier Inc. All rights reserved.

Radical cystectomy with W-shaped orthotopic ileal neobladder constructed with non-absorbable titanium staples-long term follow-up.

PubMed

Kravchick, Sergey; Lobik, Leonid; Paz, Adrian; Stepnov, Eugeny; Ben-Dor, David; Cytron, Shmuel

2013-01-01

We retrospectively assessed our experience with the W-shaped orthotopic ileal pouch, which was constructed with non-absorbable titanium staples. For these purpose, we discuss the results of bladder capacity, urinary continence and early and long-term postoperative complications. We included in the study 17 patients who underwent radical cystoprostatectomy followed by construction of an orthotopic W-shaped ileal pouch between October 2000 and November 2009. A 65-70 cm segment of ileum was isolated and prearranged into a W-configuration, leaving two 10 cm intact segments on both sides of the ileal fragment. In our technique we entirely anatomized all adjacent limbs in order to create a sphere-shaped pouch. The ureters were directly anastomized to both intact segments of the ileal division. All our patients underwent pouchscopy 6 months after operation and annually. Mean operative time for neobladder reconstruction and ureteral anastomoses was 87 ± 7.67 minutes. In one patient a leak from the ileo-ileal anastomosis was confirmed on the 3rd day after operation. In 2 cases unilateral stricture of the ureteral-neobladder anastomosis was documented. Staple lines were mostly covered with ileal mucosa after 6 months. The mean functional bladder capacity was 340 ± 27.6 mL and 375 ± 43.4 mL at 6 and 12 months, respectively. First-year daytime and nighttime continence was good and acceptable in 90% and 78% of patients, while it increased to 95% during the 2nd year. The long term follow-up shows that non-absorbable titanium staples can be safely used for creation of an orthotopic ileal neobladder. However, these data should be further validated in a larger series of patients.

Formation of ions and radicals from icy grains in comets

NASA Technical Reports Server (NTRS)

Jackson, William M.; Gerth, Christopher; Hendricks, Charles

1991-01-01

Ion and radical formation in comets are thought to occur primarily by photodissociation of gas phase molecules. Experimental evidence and theoretical calculations are presented that show that some of the radical and ions can come directly from ice grains. The experimental evidence suggest that if the frozen molecules on the surface of grains undergo direct dissociation then they may be able to release radicals directly in the gas phase. If the molecules undergo predissociation it is unlikely that they will release radicals in the gas phase since they should be quenched. Calculations of this direct photodissociation mechanism further indicate that even if the parent molecule undergoes direct dissociation, the yield will not be high enough to explain the rays structure in comets unless the radicals are stored in the grains and then released when the grain evaporates. Calculations were also performed to determine the maximum number of ions that can be stored in an icy grain's radius. This number is compared with the ratio of the ion to neutral molecular density. The comparison suggests that some of the ions observed near the nucleus of the comet could have originally been present in the cometary nucleus. It is also pointed out that the presence of these ions in icy grains could lead to radical formation via electron recombination. Finally, an avalanche process was evaluated as another means of producing ions in comets.

Contrast-enhanced transrectal ultrasound (CE-TRUS) with cadence-contrast pulse sequence (CPS) technology for the identification of prostate cancer.

PubMed

Seitz, Michael; Gratzke, Christian; Schlenker, Boris; Buchner, Alexander; Karl, Alexander; Roosen, Alexander; Singer, Bernhard B; Bastian, Patrick J; Ergün, Süleyman; Stief, Christian G; Reich, Oliver; Tilki, Derya

2011-01-01

Various imaging modalities, such as magnetic resonance imaging (MRI), have been assessed with regard to their value in the detection of prostate cancer (CaP). However, there is a need for less time-consuming and more cost effective procedures in urology. In order to determine the ability of contrast-enhanced transrectal ultrasound (CE-TRUS) to identify CaP, we investigated patients scheduled for radical prostatectomy for CaP and radical cystoprostatectomy for bladder cancer. Between May and August 2008, 35 consecutive patients with CaP and muscle-invasive bladder carcinoma were prospectively enrolled in this single center study. All patients underwent B-mode TRUS and CE-TRUS (Sequoia 512 unit with an endocavity probe EV8C4, 8 MHz; Siemens, Erlangen, Germany) by one investigator blinded to any clinical data before radical surgery. Contrast-enhanced images were obtained after intravenous infusion of a bolus (2.4 ml) of the contrast agent SonoVue (Bracco, Milan, Italy). Ultrasound findings (CE-TRUS and B-mode TRUS) were correlated with step-section histology. On a per-patient basis, sensitivity, specificity, positive predictive value (PPV), and negative predictive value (NPV) for detecting CaP with CE-TRUS were 71.0%, 50.0%, 91.7%, and 18.2%, respectively. In comparison with B-mode TRUS (sensitivity 45.2%, specificity 75.0%, PPV 93.3%, and NPV 18.0%), CE-TRUS performed significantly better (P=0.004, McNemar test). On a per-prostate-lobe basis sensitivity, specificity, PPV, and NPV were 69.0%, 33.3%, 83.3%, and 18.2%. CE-TRUS detected prostate cancer with a modest sensitivity and a high PPV in a selected patient cohort. Future randomized-controlled multicenter studies are needed to further validate the value of CE-TRUS in the detection of CaP. Based on our results, CE-TRUS may not be recommended as a routine procedure in the diagnosis of CaP at present. Copyright © 2011 Elsevier Inc. All rights reserved.

A multicomponent theory-based intervention improves uptake of pelvic floor muscle training before radical prostatectomy: a 'before and after' cohort study.

PubMed

Hirschhorn, Andrew D; Kolt, Gregory S; Brooks, Andrew J

2014-03-01

To assess the effect of a multicomponent theory-based intervention, incorporating patient information guides, an evidence summary, audit and feedback processes and a provider directory, in the provision/receipt of preoperative pelvic floor muscle training (PFMT) among patients undergoing radical prostatectomy. Over an 18-month period (9 months before and 9 months after the intervention), we measured the provision/receipt of preoperative PFMT using surveys of patients undergoing radical prostatectomy at one public hospital (n = 32) and two private hospitals (n = 107) in Western Sydney, Australia, as well as practice audits of associated public sector (n = 4) and private sector (n = 2) providers of PFMT. Self-report urinary incontinence was assessed 3 months after radical prostatectomy using the International Consultation on Incontinence Questionnaire - Urinary Incontinence Form (ICIQ-UI Short Form). There was a significant increase in the proportion of survey respondents receiving preoperative PFMT post-intervention (post-intervention: 42/58 respondents, 72% vs pre-intervention: 37/81 respondents, 46%, P = 0.002). There was a corresponding significant increase in provision of preoperative PFMT by private sector providers (mean [sd] post-intervention: 16.7 [3.7] patients/month vs pre-intervention: 12.1 [3.6] patients/month, P = 0.018). Respondents receiving preoperative PFMT had significantly better self-report urinary incontinence at 3 months after radical prostatectomy than those who did not receive preoperative PFMT (mean [sd] ICIQ-UI Short Form sum-scores: 6.2 [5.0] vs 9.2 [5.8], P = 0.002). The intervention increased the provision/receipt of preoperative PFMT among patients undergoing radical prostatectomy. Additional component strategies aimed at increasing the use of public sector providers may be necessary to further improve PFMT receipt among patients undergoing radical prostatectomy in the public hospital system. © 2013 The Authors. BJU International published by John Wiley & Sons Ltd on behalf of BJU International.

Can Carbamates Undergo Radical Oxidation in the Soil Environment? A Case Study on Carbaryl and Carbofuran.

PubMed

Ćwieląg-Piasecka, Irmina; Witwicki, Maciej; Jerzykiewicz, Maria; Jezierska, Julia

2017-12-19

Radical oxidation of carbamate insecticides, namely carbaryl and carbofuran, was investigated with spectroscopic (electron paramagnetic resonance [EPR] and UV-vis) and theoretical (density functional theory [DFT] and ab initio orbital-optimized spin-component scaled MP2 [OO-SCS-MP2]) methods. The two carbamates were subjected to reaction with • OH, persistent DPPH • and galvinoxyl radical, as well as indigenous radicals of humic acids. The influence of fulvic acids on carbamate oxidation was also tested. The results obtained with EPR and UV-vis spectroscopy indicate that carbamates can undergo direct reactions with various radical species, oxidizing themselves into radicals in the process. Hence, they are prone to participate in the prolongation step of the radical chain reactions occurring in the soil environment. Theoretical calculations revealed that from the thermodynamic point of view hydrogen atom transfer is the preferred mechanism in the reactions of the two carbamates with the radicals. The activity of carbofuran was determined experimentally (using pseudo-first-order kinetics) and theoretically to be noticeably higher in comparison with carbaryl and comparable with gallic acid. The findings of this study suggest that the radicals present in soil can play an important role in natural remediation mechanisms of carbamates.

Use of hydrogel spacer for improved rectal dose-sparing in patients undergoing radical radiotherapy for localized prostate cancer: First Canadian experience

PubMed Central

Berlin, Alejandro; Di Tomasso, Anne; Ballantyne, Heather; Patterson, Susan; Lam, Tony; Sundaramurthy, Aravind; Helou, Joelle; Bayley, Andrew; Chung, Peter

2017-01-01

We describe the initial experience using a hydrogel spacer (SpaceOAR) to separate the prostate-rectum interspace in patients planned to undergo radical hypofractionated, image-guided, intensity-modulated radiotherapy (IG-IMRT). We depict and discuss the impact of SpaceOAR in the context of hypofractionated IG-IMRT, and the particular considerations for its applications in the Canadian setting. PMID:29257741

Extended lymphadenectomy in bladder cancer.

PubMed

Dorin, Ryan P; Skinner, Eila C

2010-09-01

Radical cystectomy with pelvic lymph node dissection (PLND) is the preferred treatment for invasive bladder cancer. It not only results in the best disease-free term survival rates, but also provides the most accurate disease staging and most effective local symptom control. Recent investigations have demonstrated a clinical benefit to performance of an extended PLND, including all lymphatic tissue to the level of the aortic bifurcation. This review will summarize recent findings regarding the clinical benefits of radical cystectomy with extended lymphadenectomy, and will also examine the latest surgical techniques for optimizing the performance of this technically demanding procedure. Recent studies have demonstrated increased recurrence-free survival and overall survival rates in patients undergoing radical cystectomy with extended PLND, even in cases of pathologically lymph node negative disease. The growing use of minimally invasive techniques has prompted interest in robotic radical cystectomy and extended PLND, and recent reports have demonstrated the feasibility of this technique. The standardization of extended PLND templates has also been a focus of contemporary research. Contemporary research strongly suggests that all patients undergoing radical cystectomy for bladder cancer should undergo concomitant extended PLND. Randomized trials are still needed to confirm the benefits of extended over 'standard' PLND, and to clarify which patients may receive the greatest benefit from this procedure.

Quadruple primary urogenital cancers - A case report.

PubMed

Elec, Florin-Ioan; Zaharie, Andreea; Ene, Bogdan-Mihai; Ghervan, Liviu

2017-01-01

Urogenital cancers are not an uncommon occurrence in daily practice. Prostate cancer is the second most frequent cancer in men, kidney cancer accounts for 2.4% of all cancers and bladder cancers represent 3.1% of cancers in both men and women [1]. However, the cases of a simultaneous development of all three cancers, including one with a neuroendocrine component, are very few and far between. Our case report involves a case of a patient with prostate adenocarcinoma, clear-cell renal carcinoma, papillary renal carcinoma and small-cell bladder cancer. The patient was treated as if he had separate pathologies by a multidisciplinary team: surgical and oncological, performing radical cystoprostatectomy with left perifascial nephroureterectomy, right ureterostomy and adjuvant chemotherapy, with excellent outcome even four years after the initial diagnosis. The distinct features of this case are the occurence of four different malignancies of the urogenital system, the family history of colon cancer, the development of small-cell carcinoma of the bladder, which is extremely rare and the good outcome, despite the quadruple malignancies and the aggresivity of the small-cell carcinoma. Mutiple primary malignancies are a relatively rare pathology, but should be considered as a possibility in patients who already had a second malignancy. Cases of patients with MPMs should be supervised by a multidisciplinary team and should be followed closely. Copyright © 2017 The Author(s). Published by Elsevier Ltd.. All rights reserved.

Kinetic studies of retinol addition radicals.

PubMed

El-Agamey, Ali; Fukuzumi, Shunichi; Naqvi, K Razi; McGarvey, David J

2011-03-07

Retinol neutral radicals (RS-retinol˙), generated from the reaction of retinol with 4-pyridylthiyl and 2-pyridylthiyl radicals in argon-saturated methanol, undergo β-elimination, which can be monitored via the slow secondary absorption rise at 380 nm attributed to the rearrangement of the unstable retinol neutral addition radicals to the more stable addition radicals. Rate constants for the β-elimination reactions (k(β)) of 4-PyrS-retinol˙ were measured at different temperatures and the Arrhenius equation for the reaction is described by log (k(β)/s(-1)) = (12.7 ± 0.2) - (54.3 ± 1.3)/θ, where θ = 2.3RT kJ mol(-1). The reactivities of retinol addition radicals (RS-retinol˙), generated from the reaction of retinol with various thiyl radicals, towards oxygen have also been investigated in methanol. In the presence of oxygen, the decay of RS-retinol˙ fits to biexponential kinetics and both observed rate constants for the RS-retinol˙ decay are oxygen-concentration dependent. This suggests that at least two thiyl addition radicals, formed from the reaction of RS˙ with retinol, undergo oxygen addition reactions. In light of the estimated rate constants for oxygen addition to RS-retinol˙ and RS-CAR˙ (CAR: carotenoid), the antioxidant-prooxidant properties of retinol are discussed.

Radiation-induced changes affecting polyester based polyurethane binder

NASA Astrophysics Data System (ADS)

Pierpoint, Sujita Basi

The application of thermoplastic polyurethane elastomers as binders in the high energy explosives particularly when used in weapons presents a significantly complex and challenging problem due to the impact of the aging of this polymer on the useful service life of the explosive. In this work, the effects of radiation on the aging of the polyester based polyurethane were investigated using both electron beam and gamma irradiation at various dose rates in the presence and absence of oxygen. It was found by means of GPC that, in the presence and absence of oxygen, the poly (ester urethane) primarily undergoes cross-linking, by means of a carbon-centered secondary alkyl radical. It was also concluded that the polymer partially undergoes scission of the backbone of the main chain at C-O, N-C, and C-C bonds. Substantial changes in the conditions of irradiation and in dose levels did not affect the cross-linking and scission yields. Experiments were also performed with EPR spectroscopy for the purpose of identifying the initial carbon-centered free radicals and for studying the decay mechanisms of these radicals. It was found that the carbon-centered radical which is produced via C-C scission (primary alkyl radical) is rapidly converted to a long-lived allylic species at higher temperatures; more than 80% radicals are converted to allyl species in 2.5 hours. In the presence of oxygen, the allyl radical undergoes a fast reaction to produce a peroxyl radical; this radical decays with a 1.7 hour half-life by pseudo first-order kinetics to negligible levels in 13 hours. FTIR measurements were conducted to identify the radiation-induced changes to the functional groups in the polyester polyurethane. These measurements show an increase in carbonyl, amine and carboxylic groups as a result of reaction of H atoms with R-C-O·, ·NH-R and R-COO·. The FTIR results also demonstrate the production of the unsaturation resulting from hydrogen atom transfer during intrachain conversion of the primary alkyl radical to the allyl species, prompt trans-vinylene production in tetramethylene units, and hydrogen atom abstraction by alkyl radicals on neighboring chains. The production of unsaturation is substantiated by the EPR studies. Finally, a free radical mechanism is proposed for the production of cross-linking in polyester polyurethane.

Formal radical cyclization onto benzene rings: a general method and its use in the synthesis of ent-nocardione A.

PubMed

Clive, Derrick L J; Fletcher, Stephen P; Liu, Dazhan

2004-05-14

An indirect method is described for effecting radical cyclization onto a benzene ring. Cross-conjugated dienones 6, which are readily prepared from phenols, undergo radical cyclization (6 --> 7 --> 8), and the products (8) are easily aromatized. The method has been applied to the synthesis of ent-nocardione A (21).

[Recto-vesico-cutaneous fistula following salvage cryotherapy of the prostate due to recurrent localized prostate cancer].

PubMed

Kocot, A; Spahn, M; Loeser, A; Riedmiller, H

2011-11-01

For patients with recurrent prostate cancer after initial external beam radiation salvage cryotherapy is considered as an alternative to salvage prostatectomy. We report a serious complication of salvage cryotherapy in a 72-year-old man suffering from a severe recto-vesico-cutaneous fistula 6 weeks after salvage cryotherapy. To manage this situation salvage cystoprostatectomy and continent urinary diversion with creation of an ileocaecal pouch with cutaneous stoma had to be performed.

[Waist-hip ratio and perioperative bleeding in patients who underwent radical prostatectomy].

PubMed

León-Ramírez, Víctor; Santiago-López, Janaí; Reyes-Rivera, Juan Gabriel; Miguel-Soto, Edgar

2016-01-01

Radical prostatectomy is associated with perioperative bleeding and multiple transfusions. Abdominal obesity is a perioperative risk factor. We suggest that the adipocytes have a protective effect in oncological patients undergoing radical prostatectomy. The aim was to evaluate the effect of waist-hip ratio (WHR) on the amount of bleeding and perioperative transfusion requirements in oncological patients undergoing radical prostatectomy. We performed a cohort study in 156 patients. We had two groups: the control group (WHR<0.95) and the problem group (WHR≥0.95). Blood loss and fractions transfused during surgery and in the postoperative period were recorded. In the analysis of variables, for descriptive statistics we used measures of central tendency and dispersion. Inferential statistics was obtained by chi square, Student's t test, Mann-Whitney U and ANOVA. A p<0.05 was significant. We found significant differences in weight, body mass index, waist, WHR, perioperative bleeding, fractions transfused, permanence of the catheter, and hospital days. Patients who underwent radical prostatectomy with a WHR≥0.95 had a magnitude of perioperative bleeding and transfusion requirements with a WHR<0.95.

Education Reform When Nations Undergo Radical Political and Social Transformation.

ERIC Educational Resources Information Center

La Belle, Thomas J.; Ward, Christopher R.

1990-01-01

Analyzes the relationship between radical social transformation and educational reform in Algeria, China, Cuba, Ethiopia, Iran, Mozambique, and Nicaragua. Examines seven policy areas before and after transformation: centralized control, access to education, tracking, curriculum, personnel, language of instruction, and literacy. (28 references) (SV)

Painful orgasm in an adolescent after seminal-sparing cystoprostatectomy: a puzzling symptom.

PubMed

Angelini, Lorenzo; Castagnetti, Marco; Rigamonti, Waifro

2015-01-01

An 18-year-old boy, followed up after seminal-sparing cystectomy for bladder rhabdomyosarcoma, presented complaining of recurrent episodes of left scrotal/inguinal pain arising after orgasms. Full work-up ruled out disease recurrence, but showed enlarged seminal vesicles. Ligation of the vas deferens was unsuccessful. The patient was started on α-blockers to reduce vas contractions with improvement of symptoms. The possible pathophysiology and treatments of this symptom are discussed. 2014 S. Karger AG, Basel

Incidental prostate cancer at the time of cystectomy: the incidence and clinicopathological features in Chinese patients.

PubMed

Pan, Jiahua; Xue, Wei; Sha, Jianjun; Yang, Hu; Xu, Fan; Xuan, Hanqing; Li, Dong; Huang, Yiran

2014-01-01

To evaluate the incidence and the clinicopathological features of incidental prostate cancer detected in radical cystoprostatectomy (RCP) specimens in Chinese men and to estimate the oncological risk of prostate apex-sparing surgery for such patients. The clinical data and pathological feature of 504 patients who underwent RCP for bladder cancer from January 1999 to March 2013 were retrospectively reviewed. Whole mount serial section of the RCP specimens were cut transversely at 3-4 mm intervals and examined in same pathological institution. Thirty-four out of 504 patients (6.8%) had incidental prostate cancer with a mean age of 70.3 years. 12 cases (35.2%) were diagnosed as significant disease. 4 cases were found to have apex involvement of adenocarcinoma of the prostate while in 5 cases the prostate stroma invasion by urothelial carcinoma were identified (one involved prostate apex). The mean follow-up time was 46.4±33.8 months. Biochemical recurrence occurred in 3 patients but no prostate cancer-related death during the follow-up. There was no statistical significance in cancer specific survival between the clinically significant and insignificant cancer group. The prevalence of incidental prostate cancer in RCP specimens in Chinese patients was remarkably lower than in western people. Most of the incidental prostate cancer was clinically insignificant and patient's prognosis was mainly related to the bladder cancer. Sparing the prostate apex was potentially associated with a 1.0% risk of leaving significant cancer of the prostate or urothelial carcinoma.

Incorporating 3D laparoscopy for the management of locally advanced cervical cancer: a comparison with open surgery.

PubMed

Raspagliesi, Francesco; Bogani, Giorgio; Martinelli, Fabio; Signorelli, Mauro; Chiappa, Valentina; Scaffa, Cono; Sabatucci, Ilaria; Adorni, Marco; Lorusso, Domenica; Ditto, Antonino

2016-08-03

To test the effects of the implementation of 3D laparoscopic technology for the execution of nerve-sparing radical hysterectomy. Thirty patients undergoing nerve-sparing radical hysterectomy via 3D laparoscopic (3D-LNSRH, n = 10) or open surgery (NSRH, n = 20) were studied prospectively. No significant differences were observed in baseline patient characteristics. Operative times were similar between groups. We compared the first 10 patients undergoing 3D-LNSRH with the last 20 patients undergoing NSRH. Baseline characteristics were similar between groups (p>0.2). Patients undergoing 3D-LNSRH had longer operative time (264.4 ± 21.5 vs 217.2 ± 41.0 minutes; p = 0.005), lower blood loss (53.4 ± 26.1 vs 177.7 ± 96.0 mL; p<0.001), and shorter length of hospital stay (4.3 ± 1.2 vs 5.4 ± 0.7 days; p = 0.03) in comparison to patients undergoing open abdominal procedures. No intraoperative complication occurred. One (10%) patient had conversion to open surgery due to technical difficulties and the inability to insert the uterine manipulator. A trend towards higher complication (grade 2 or worse) rate was observed for patients undergoing NSRH in comparison to 3D-LNSRH (p = 0.06). Considering only severe complications (grade 3 or worse), no difference was observed (0/10 vs 2/20; p = 0.54). 3D-laparoscopic nerve-sparing radical hysterectomy is a safe and effective procedure. The implementation of 3D laparoscopic technology allows the execution of challenging operations via minimally invasive surgery, thus reducing open abdominal procedure rates. Further large prospective studies are warranted.

Comparative analysis between clinical outcomes of primary radical resection and second completion radical resection for T2 gallbladder cancer: single-center experience.

PubMed

Cho, Seong Yeon; Park, Sang-Jae; Kim, Seong Hoon; Han, Sung-Sik; Kim, Young-Kyu; Lee, Kwang-Woong

2010-07-01

Gallbladder (GB) cancer may be discovered incidentally by histopathologic examination following simple cholecystectomy. Incidental GB cancer > or =T2 or > or =N1 needs a second radical resection. It is a matter of concern whether the prognosis may be worse in patients with T2GB cancer who undergo a second radical resection than in those who undergo primary radical resection. Between March 2001 and March 2009, 21 patients underwent a one-step operation (OSO group), and 17 patients underwent a two-step operation (TSO group) for T2GB cancer. We compared clinicopathologic factors and survival between patients in the OSO group (n = 9) and those in the TSO group (n = 9) with T2N0M0 GB cancer and between patients in the OSO group (n = 12) and those in the TSO group (n = 8) with T2N1M0 GB cancer. Except for patient age, clinicopathologic factors as well as disease-free survival were not significantly different between the OSO group and the TSO group in the aforementioned cancer stages. Patient age was significantly higher in the OSO group than in the TSO group. Second completion radical resection following initial simple cholecystectomy (TSO) provided a survival benefit similar to that of primary radical surgery (OSO) for patients with both T2N0M0 and T2N1M0 GB cancers in our study.

[Concomitant oncopathological changes in the prostate of urinary bladder cancer patients undergoing radical cystoprostateectomy].

PubMed

Komyakov, B K; Sergeev, A V; Fadeev, V A; Ismailov, K I; Ulyanov, A Yu; Shmelev, A Yu; Onoshko, M V

2017-09-01

To determine the incidence of spreading bladder transitional cell carcinoma and primary adenocarcinoma to the prostate in patients with bladder cancer undergoing radical cystectomy. From 1995 to 2016, 283 men underwent radical cystectomy with removal of the bladder, perivesical tissue, prostate, seminal vesicles and pelvic lymph nodes. Prostate sparing cystectomy was performed in 45 (13.7%) patients. The whole prostate and the apex of the prostate were preserved in 21 (6.4%) and 24 (7.3%) patients, respectively. The spread of transitional cell cancer of the bladder to the prostate occurred in 50 (15.2%) patients. Twelve (3.6%) patients were found to have primary prostate adenocarcinoma. Clinically significant prostate cancer was diagnosed in 4 (33.3%) patients. We believe that the high oncological risk of prostate sparing cystectomy, despite some functional advantages, dictates the need for complete removal of the prostate in the surgical treatment of bladder cancer.

Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues.

PubMed

Ji, Xinjian; Li, Yongzhen; Xie, Liqi; Lu, Haojie; Ding, Wei; Zhang, Qi

2016-09-19

Radical S-adenosyl-l-methionine (SAM) enzymes utilize a [4Fe-4S] cluster to bind SAM and reductively cleave its carbon-sulfur bond to produce a highly reactive 5'-deoxyadenosyl (dAdo) radical. In almost all cases, the dAdo radical abstracts a hydrogen atom from the substrates or from enzymes, thereby initiating a highly diverse array of reactions. Herein, we report a change of the dAdo radical-based chemistry from hydrogen abstraction to radical addition in the reaction of the radical SAM enzyme NosL. This change was achieved by using a substrate analogue containing an olefin moiety. We also showed that two SAM analogues containing different nucleoside functionalities initiate the radical-based reactions with high efficiencies. The radical adduct with the olefin produced in the reaction was found to undergo two divergent reactions, and the mechanistic insights into this process were investigated in detail. Our study demonstrates a promising strategy in expanding radical SAM chemistry, providing an effective way to access nucleoside-containing compounds by using radical SAM-dependent reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Population-based assessment of racial/ethnic differences in utilization of radical cystectomy for patients diagnosed with bladder cancer.

PubMed

Williams, Stephen B; Huo, Jinhai; Kosarek, Christopher D; Chamie, Karim; Rogers, Selwyn O; Williams, Michele A; Giordano, Sharon H; Kim, Simon P; Kamat, Ashish M

2017-07-01

Radical cystectomy is a surgical treatment for recurrent non-muscle-invasive and muscle-invasive bladder cancer; however, many patients may not receive this treatment. A total of 27,578 patients diagnosed with clinical stage I-IV bladder cancer from 1 January 2007 to 31 December 2013 were identified from the Surveillance, Epidemiology, and End Results (SEER) registry database. We used multivariable regression analyses to identify factors predicting the use of radical cystectomy and pelvic lymph node dissection. Cox proportional hazards models were used to analyze survival outcomes. A total of 1,693 (6.1%) patients with bladder cancer underwent radical cystectomy. Most patients (92.4%) who underwent radical cystectomy also underwent pelvic lymph node dissection. When compared with white patients, non-Hispanic blacks were less likely to undergo a radical cystectomy [odds ratio (OR) 0.79, 95% confidence interval (CI) 0.64-0.96, p = 0.019]. Moreover, recent year of surgery 2013 versus 2007 (OR 2.32, 95% CI 1.90-2.83, p < 0.001), greater percentage of college education ≥36.3 versus <21.3% (OR 1.23, 95% CI 1.04-1.44, p = 0.013), Midwest versus West (OR 1.64, 95% CI 1.39-1.94, p < 0.001), and more advanced clinical stage III versus I (OR 29.1, 95% CI 23.9-35.3, p < 0.001) were associated with increased use of radical cystectomy. Overall survival was improved for patients who underwent radical cystectomy compared with those who did not undergo a radical cystectomy (hazard ratio 0.88, 95% CI 0.80-0.97, p = 0.008). There is significant underutilization of radical cystectomy in patients across all age groups diagnosed with bladder cancer, especially among older, non-Hispanic black patients.

Oncologic effectiveness of nerve-sparing radical hysterectomy in cervical cancer.

PubMed

Ditto, Antonino; Bogani, Giorgio; Leone Roberti Maggiore, Umberto; Martinelli, Fabio; Chiappa, Valentina; Lopez, Carlos; Perotto, Stefania; Lorusso, Domenica; Raspagliesi, Francesco

2018-05-01

Nerve-sparing radical hysterectomy (NSRH) was introduced with the aim to reduce pelvic dysfunctions related to conventional radical hysterectomy (RH). Here, we sought to assess the effectiveness and safety of NSRH in a relatively large number of the patients of cervical cancer (CC) patients undergoing either primary surgery or neoadjuvant chemotherapy (NACT) followed by surgery. Outcomes of consecutive patients undergoing NSRH and of a historical cohort of patients undergoing conventional RH were retrospectively reviewed. This study included 325 (49.8%) and 327 (50.2%) undergoing NSRH and RH, respectively. Via a multivariable model, nodal status was the only factor predicting for DFS (hazard ratio [HR]=2.09; 95% confidence interval [CI]=1.17-3.73; p=0.01). A trend towards high risk of recurrence was observed for patients affected by locally advanced cervical cancer (LACC) undergoing NACT followed by surgery (HR=2.57; 95% CI=0.95-6.96; p=0.06). Type of surgical procedures (NSRH vs. RH) did not influence risk of recurrence (p=0.47). Similarly, we observed that the execution of NSRH rather than RH had not a detrimental effect on OS (HR=1.19; 95% CI=0.16-9.01; p=0.87). Via multivariable model, no factor directly correlated with OS. No difference in early complication rates was observed between the study groups. Conversely, a significant higher number of late complications was reported in RH versus NSRH groups (p=0.02). Our data suggested that NSRH upholds effectiveness of conventional RH, without increasing recurrence and complication rates but improving pelvic dysfunction rates. Copyright © 2018. Asian Society of Gynecologic Oncology, Korean Society of Gynecologic Oncology.

Introducing nerve-sparing approach during minimally invasive radical hysterectomy for locally-advanced cervical cancer: A multi-institutional experience.

PubMed

Raspagliesi, Francesco; Bogani, Giorgio; Spinillo, Arsenio; Ditto, Antonino; Bogliolo, Stefano; Casarin, Jvan; Leone Roberti Maggiore, Umberto; Martinelli, Fabio; Signorelli, Mauro; Gardella, Barbara; Chiappa, Valentina; Scaffa, Cono; Ferrero, Simone; Cromi, Antonella; Lorusso, Domenica; Ghezzi, Fabio

2017-11-01

To evaluate the impact of nerve-sparing (NS) approach on outcomes of patients undergoing minimally invasive radical hysterectomy (MRH) for locally advanced stage cervical cancer (LACC). Data of consecutive patients undergoing minimally invasive surgery for LACC were retrospectively retrieved in a multi-institutional setting from 2009 to 2016. All patients included had minimally invasive class III radical hysterectomy (MRH or NS-MRH). Propensity matching algorithm was used to decrease possible allocation bias when comparing outcomes between groups. Overall, 83 patients were included. The prevalence of patients undergoing NS approach increased aver the study period (from 7% in the year 2009-2010 to 97% in the year 2015-2016; p-for-trend < 0.001). NS-MRH and MRH were performed in 47 (57%) and 36 (43%) patients, respectively. After the application the propensity-matching algorithm, we compared 35 patients' pair (total 70 patients). Postoperative complications rate was similar between groups. Patients undergoing NS-LRH experienced shorter hospital stay than patients undergoing LRH (3.6 vs. 5.0 days). 60-day pelvic floor dysfunction rates, including voiding, fecal and sexual alterations, were lower in the NS group in comparison to control group (p = 0.02). Five-year disease-free (p = 0.77) and overall (p = 0.36) survivals were similar comparing NS-MRH with MRH. The implementation of NS approach in the setting of LACC improves patients' outcomes, minimizing pelvic dysfunction rates. NS approach has not detrimental effects on survival outcomes. Copyright © 2017 Elsevier Ltd, BASO ~ The Association for Cancer Surgery, and the European Society of Surgical Oncology. All rights reserved.

Near-Infrared Free-Radical and Free-Radical-Promoted Cationic Photopolymerizations by In-Source Lighting Using Upconverting Glass.

PubMed

Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf

2017-11-13

A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions

NASA Astrophysics Data System (ADS)

Nguyen, John D.; D'Amato, Erica M.; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

2012-10-01

Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

The long-sought seventeen-electron radical [(C6Me6)Cr(CO)3](+): isolation, crystal structure and substitution reaction.

PubMed

Wang, Wenqing; Wang, Xingyong; Zhang, Zaichao; Yuan, Ningning; Wang, Xinping

2015-05-18

A highly air-sensitive seventeen-electron half-sandwich radical, [(C6Me6)Cr(CO)3](+), which has been long sought over 40 years, was isolated and structurally characterized. EPR spectroscopy and theoretical calculations indicate that the spin density mainly resides on the chromium atom. The radical can undergo a substitution reaction with PPh3 to form a more stable cation, [(C6Me6)Cr(CO)2(PPh3)](+). This work provides a direct observation of the radical process for CO-substitution reactions found in (arene)M(CO)3 (M = Cr, Mo, or W) systems, and suggests that other stable radicals of the type [(arene)M(CO)3](+) are accessible.

A modified cutaneous ureterostomy provides satisfactory short and midterm outcomes in select cases.

PubMed

Yadav, Priyank; Mittal, Varun; Gaur, Pankaj; Srivastava, Devarshi; Sureka, Sanjoy Kumar; Mandhani, Anil

2018-03-06

We present the outcomes of modification of cutaneous ureterostomy by extreme lateralization of the stoma and use of skin flap for formation of ureterostomy. Between June 2012 and June 2016, 36 patients had modified cutaneous ureterostomy for ureteral obstruction due to pelvic malignancy or genitourinary tuberculosis. Transureteroureterostomy was made with cutaneous stoma at anterior axillary line between iliac crest and lower rib cage, instead of spinoumbilical line. To prevent stenosis a 'V' shaped skin was fed into the stoma. Double J stents were used in all patients for 6 weeks. Perioperative morbidity and mortality were evaluated. All patients were followed up at 3 month intervals. Of 36 patients, 22 had radical cystoprostatectomy (including nephroureterectomy in 2 patients) and 7 had palliative cystectomy. Others had locally advanced prostate cancer (n=1), locally advanced cervical cancer (n=3), ovarian cancer (n=1) and genitourinary tuberculosis with small capacity bladder along with a large vesicovaginal fistula (n=1). One patient developed ureteral necrosis requiring conversion to ileal conduit. Three patients developed stomal stenosis: two were managed by self-dilatation while one required revision of stoma. Thirteen patients died of the disease at a median follow up of 6 months with functioning stoma. Remaining 19 patients survived without any complications at a median follow-up of 20.5 months (5.5-43.5 months). None of the patients had any problem related to ureterostomy bag application. Modified lateral cutaneous ureterostomy provides relatively straighter and shorter retroperitoneal course of ureter with acceptable morbidity and avoids use of bowel in selected patients.

Tropospheric reactions of the haloalkyl radicals formed from hydroxyl radical reaction with a series of alternative fluorocarbons

NASA Technical Reports Server (NTRS)

Atkinson, Roger

1990-01-01

In the present assessment, the hydrogen containing halocarbons being considered as alternatives to the the presently used chlorofluorocarbons are the hydrochlorofluorocarbons (HCFCs) 123 (CF3CHCl2), 141b (CFCl2CH3), 142b (CF2ClCH3), 22 (CHF2Cl) and 124 (CF3CHFCl) and the hydrofluorocarbons (HFCs) 134a (CF3CH2F), 152a (CHF2CH3) and 125 (CF3CHF2). All of these HCFCs and HFCs will react with the hydroxyl (OH) radical in the troposphere, giving rise to haloalkyl radicals which then undergo a complex series of reactions in the troposphere. These reactions of the haloalkyl radicals formed from the initial OH radical reactions with the HCFCs and HFCs under tropospheric conditions are the focus here.

Photochemical Kinetics of a Phosphine Oxide Free Radical Initiator from Femtosecond UV-Pump/Mid-IR-Probe Spectroscopy.

PubMed

Straub, Steffen; Lindner, Jörg; Vöhringer, Peter

2017-07-06

Femtosecond UV-pump/mid-infrared-probe spectroscopy was used to explore in detail the primary photochemical events of the free radical initiator, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, in liquid dichloromethane solution at room temperature. Following electronic excitation of its lowest excited singlet state, S 1 , the radical initiator undergoes an intersystem crossing to the triplet ground state, T 1 , with a time constant of 135 ps. A subsequent α-cleavage occurs from the triplet state with a time constant of 15 ps and yields a trimethylbenzoyl radical together with a diphenylphosphinoyl radical. Transient absorptions from the S 1 and T 1 states are observed that can be assigned to the P═O stretching mode and the symmetric in-plane deformation mode of the trimethylphenyl moiety of the radical initiator.

A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiator via C-C σ-bond formation.

PubMed

Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K

2017-11-01

The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

Regioselectivity of enzymatic and photochemical single electron transfer promoted carbon-carbon bond fragmentation reactions of tetrameric lignin model compounds.

PubMed

Cho, Dae Won; Latham, John A; Park, Hea Jung; Yoon, Ung Chan; Langan, Paul; Dunaway-Mariano, Debra; Mariano, Patrick S

2011-04-15

New types of tetrameric lignin model compounds, which contain the common β-O-4 and β-1 structural subunits found in natural lignins, have been prepared and carbon-carbon bond fragmentation reactions of their cation radicals, formed by photochemical (9,10-dicyanoanthracene) and enzymatic (lignin peroxidase) SET-promoted methods, have been explored. The results show that cation radical intermediates generated from the tetrameric model compounds undergo highly regioselective C-C bond cleavage in their β-1 subunits. The outcomes of these processes suggest that, independent of positive charge and odd-electron distributions, cation radicals of lignins formed by SET to excited states of sensitizers or heme-iron centers in enzymes degrade selectively through bond cleavage reactions in β-1 vs β-O-4 moieties. In addition, the findings made in the enzymatic studies demonstrate that the sterically large tetrameric lignin model compounds undergo lignin peroxidase-catalyzed cleavage via a mechanism involving preliminary formation of an enzyme-substrate complex.

Fundamental study of hydrogen-attachment-induced peptide fragmentation occurring in the gas phase and during the matrix-assisted laser desorption/ionization process.

PubMed

Asakawa, Daiki; Takahashi, Hidenori; Iwamoto, Shinichi; Tanaka, Koichi

2018-05-09

Mass spectrometry with hydrogen-radical-mediated fragmentation techniques has been used for the sequencing of proteins/peptides. The two methods, matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) and hydrogen attachment/abstraction dissociation (HAD) are known as hydrogen-radical-mediated fragmentation techniques. MALDI-ISD occurs during laser induced desorption processes, whereas HAD utilizes the association of hydrogen with peptide ions in the gas phase. In this study, the general mechanisms of MALDI-ISD and HAD of peptides were investigated. We demonstrated the fragmentation of four model peptides and investigated the fragment formation pathways using density functional theory (DFT) calculations. The current experimental and computational joint study indicated that MALDI-ISD and HAD produce aminoketyl radical intermediates, which immediately undergo radical-induced cleavage at the N-Cα bond located on the C-terminal side of the radical site, leading to the c'/z˙ fragment pair. In the case of MALDI-ISD, the z˙ fragments undergo a subsequent reaction with the matrix to give z' and matrix adducts of the z fragments. In contrast, the c' and z˙ fragments react with hydrogen atoms during the HAD processes, and various fragment species, such as c˙, c', z˙ and z', were observed in the HAD-MS/MS mass spectra.

The Patient Burden of Bladder Outlet Obstruction after Prostate Cancer Treatment.

PubMed

Liberman, Daniel; Jarosek, Stephanie; Virnig, Beth A; Chu, Haitao; Elliott, Sean P

2016-05-01

Bladder outlet obstruction after prostate cancer therapy imposes a significant burden on health and quality of life in men. Our objective was to describe the burden of bladder outlet obstruction after prostate cancer therapy by detailing the type of procedures performed and how often those procedures were repeated in men with recurrent bladder outlet obstruction. Using SEER (Surveillance, Epidemiology and End Results)-Medicare linked data from 1992 to 2007 with followup through 2009 we identified 12,676 men who underwent at least 1 bladder outlet obstruction procedure after prostate cancer therapy, including external beam radiotherapy in 3,994, brachytherapy in 1,485, brachytherapy plus external beam radiotherapy in 1,847, radical prostatectomy in 4,736, radical prostatectomy plus external beam radiotherapy in 369 and cryotherapy in 245. Histogram, incidence rates and Cox proportional hazards models with repeat events analysis were done to describe the burden of repeat bladder outlet obstruction treatments stratified by prostate cancer therapy type. We describe the type of bladder outlet obstruction surgery grouped by level of invasiveness. At a median followup of 8.8 years 44.6% of men underwent 2 or more bladder outlet obstruction procedures. Compared to men who underwent radical prostatectomy those treated with brachytherapy and brachytherapy plus external beam radiotherapy were at increased adjusted risk for repeat bladder outlet obstruction treatment (HR 1.2 and 1.32, respectively, each p <0.05). After stricture incision the men treated with radical prostatectomy or radical prostatectomy plus external beam radiotherapy were most likely to undergo dilation at a rate of 34.7% to 35.0%. Stricture resection/ablation was more common after brachytherapy, external beam radiotherapy or brachytherapy plus external beam radiotherapy at a rate of 28.9% to 41.2%. Almost half of the men with bladder outlet obstruction after prostate cancer therapy undergo more than 1 procedure. Furthermore men with bladder outlet obstruction after radiotherapy undergo more invasive endoscopic therapies and are at higher risk for multiple treatments than men with bladder outlet obstruction after radical prostatectomy. Copyright © 2016 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Evidence of high *OH radical quenching efficiency by vitamin B6.

PubMed

Matxain, Jon M; Padro, Daniel; Ristilä, Mikael; Strid, Ake; Eriksson, Leif A

2009-07-23

Molecules acting as antioxidants capable of scavenging reactive oxygen species (ROS) are of the utmost importance in the living cell. The antioxidative properties of pyridoxine (vitamin B6) have recently been discovered. Previous theoretical calculations have shown a high reactivity of pyridoxine toward hydroxyl radicals, where the latter preferably abstract H from either carbon of the two methanol substituents (C8 or C9). In this study, we have explored the reactivity of pyridoxine toward further hydroxyl radicals, considering as the first step the H abstraction from either C8 or C9, also including addition reactions and cyclization. Many of the reactions display similar DeltaG, and hence, the quenching of hydroxyl radicals by pyridoxine may undergo different pathways leading to a mix of products. In addition, we observe that pyridoxine, under high hydroxyl radical concentrations, may scavenge up to eight radicals, supporting its observed high antioxidant activity.

Effect of preoperative consumption of high carbohydrate drink (Pre-Op) on postoperative metabolic stress reaction in patients undergoing radical prostatectomy.

PubMed

Canbay, Özgür; Adar, Serdar; Karagöz, Ayşe Heves; Çelebi, Nalan; Bilen, Cenk Yücel

2014-07-01

To investigate the effects of oral carbohydrate solution consumed until 2 h before the surgery in the patients that would undergo open radical retropubic prostatectomy on postoperative metabolic stress, patient anxiety, and comfort. A total of 50 adult patients, who were in ASA I-II group and would undergo open radical retropubic prostatectomy, were included in the study. While Group 1 = CH (n = 25) received oral glucose solution, Group 2 = FAM (n = 25) was famished starting from 24:00 h. Blood glucose, insulin, and procalcitonin levels of the patients were recorded, and the patients completed state-trait anxiety inventory (STAI) test, which reflects the anxiety level of the patients, both before surgery and on the postoperative 24th hour. In order to evaluate patient comfort, senses of hunger, thirst, nausea, and cold were assessed in the morning prior to the surgery. No difference was observed between the two groups in terms of demographic data and insulin resistance levels (p > 0.05). Comparing with the preoperative levels, insulin resistance showed statistically significant elevation in both groups (p < 0.05). Procalcitonin levels were similarly increased in both groups in the postoperative period (p < 0.05). Preoperative and postoperative STAI state scores were similar in both groups (p > 0.05). With regard to preoperative patient comfort, sense of hunger was present in lesser number of subjects and at lower level in Group 1 (p < 0.05). Preoperative consumption of high carbohydrate drink (Pre-op) decreases insulin resistance and enhances patient comfort leading to lesser sense of hunger and thirst in the preoperative period in open radical retropubic prostatectomies.

Acute normovolemic haemodilution for management of blood loss during radical prostatectomy.

PubMed

Gal, R

2008-01-01

The reduction of the risks of anemia and allogeneic transfusion is one the basic parts of the anaesthesia management in large urological procedures. We used acute normovolemic haemodilution (ANH) as a technique of autologous blood procurement in patients scheduled for radical prostatectomy. 15 patients undergoing radical prostatectomy were enrolled in our study. After starting general anaesthesia the left radial artery line was placed for invasive blood pressure monitoring and withdrawing blood for ANH. The restoration of circulated volume was instituted by infusion of crystalloids and colloids. Reinfusion of gained blood was started after transfusion trigger was reached (Hct 0.25). The average total blood loss was in amount of 2393 +/- 238 (ml), autologous blood was infused in amount of 1919 +/- 220 (ml). The preoperative haematocrit was 41 +/- 3, after ANH 29 +/-2 and 31 +/- 3 (%) postoperatively. One unit of allogeneic blood was transfused in 2 patients only. All patients were hemodynamically stable during the entire surgery, with minimal systolic blood pressure of 100 mmHg and were extubated in the operation room with no complications. This study demonstrated the effectiveness and safety of ANH as a method for avoiding the allogeneic blood transfusion in patients undergoing radical prostatectomy (Tab. 1, Ref. 10). Full Text (Free, PDF) www.bmj.sk.

Hydroxo radicals, C-H activation, and Pt-C bond formation from 77 K photolysis of a platinum(IV) hydroxo complex.

PubMed

Wickramasinghe, Lasantha A; Sharp, Paul R

2014-11-17

Photolysis (380 nm) of trans,cis-Pt(PEt3)2(Cl)2(OH)(4-tft) (4-tft = 4-trifluoromethylphenyl) at 77 K in 2-methyltetrahydrofuran gives triplet emission, platinum(III), and a hydroxo radical. Benzyl radical emission is observed in toluene from the reaction of a portion of the OH radicals with toluene. Warming the photolyzed solutions gives platinacycle trans-Pt(CH2CH2PEt2)(PEt3)(Cl)2(4-tft) by hydrogen-atom abstraction from a PEt3 ligand and trans-Pt(PEt3)2(Cl)(4-tft) from net HOCl photoelimination. The platinacycle undergoes thermal reductive elimination at 298 K or photolytic reductive elimination, even at 77 K.

Radiolysis of poly(acrylic acid) in aqueous solution

NASA Astrophysics Data System (ADS)

Ulanski, Piotr; Bothe, Eberhard; Hildenbrand, Knut; Rosiak, Janusz M.; von Sonntag, Clemens

1995-02-01

Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CHCH(CO 2H)- (β-radicals) and -CH 2C(CO 2H)- (α-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of α-radicals from model systems. The β-radicals convert slowly into α-radicals ( k = 0.7 s -1 at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10 -2 mol dm -3 chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 × 10 -2s -1 was observed. Oxygen reacts with PAA-radicals with k = 3.1 × 10 8 dm 3 mol -1 s -1 at pH 3.5 and k = 1.0 × 10 8 dm 3 mol -1 s -1 at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones.

Colon pouch (Mainz III) for continent urinary diversion.

PubMed

Stolzenburg, Jens-Uwe; Schwalenberg, Thilo; Liatsikos, Evangelos N; Sakelaropoulos, George; Rödder, Kilian; Hohenfellner, Rudolph; Fisch, Margit

2007-06-01

To evaluate the use of a continent cutaneous pouch made exclusively of colon (Mainz pouch III), as excellent results with the Mainz pouch III in irradiated patients suggested that the indication for this type of urinary diversion could be extended. The outcome of 24 patients with continent cutaneous urinary diversions using colon segments (Mainz pouch III) was investigated retrospectively. Overall, 22 of the patients had a malignant disease and two a benign disease; 16 had a hysterectomy and pelvic exenteration for gynaecological tumours; two men with a rhabdomyosarcoma of the prostate had a radical cystoprostatectomy; one woman had pelvic exenteration for bladder cancer; one man had a simultaneous rectum resection due to infiltrating rectal cancer, and another a left nephrectomy with cystectomy for concomitant kidney and bladder tumour. Benign indications were hyper-reflexive bladder after polytrauma and two cases of neurogenic bladder dysfunction. Eighteen patients had radiotherapy (32-48 Gy) before the urinary diversion. The mean (range) follow-up was 35 (12-65) months. The mean pouch capacity was 293.8 mL. Three patients died during the follow-up (two from disease progression and one suicide); 20 patients were fully continent, four with reduced pouch capacity (<300 mL) had slight incontinence and are wearing a protective pad (band-aid at the umbilicus). All patients use intermittent self-catheterization (mean catheterization frequency 6.8/day, range 6-12). Complications related to the pouch were one outlet stenosis that required revision. Postoperative pouchograms showed asymptomatic reflux in four patients. None of the patients developed metabolic acidosis or diarrhoea. The Mainz pouch III is an alternative to other types of continent urinary diversion.

[Does chewing gum improve postoperative results in patients undergoing radical cystectomy? A systematic review of literature and meta-analysis].

PubMed

Ziouziou, I; Ammani, A; Karmouni, T; El Khader, K; Koutani, A; Iben Attya Andaloussi, A

2017-09-01

Postoperative ileus occurs in different degrees, in the majority of patients undergoing radical cystectomy, which may increase the length of hospital stay. The use of chewing gum has demonstrated its effectiveness in reducing time-to-bowel function and the length of hospital stay in several surgical procedures. To evaluate the benefit of post-operative chewing gum use in patients undergoing radical cystectomy through a systematic review of the literature and meta-analysis. We performed a literature search of MedLine, Scopus, CochraneLibrary and ClinicalTrials.Gov in March 2017 according to the Cochrane Handbook and the Preferred Reporting Items for Systematic Reviews and Meta-Analyzes. The studies were evaluated according to the "Oxford Center for Evidence-Based Medicine" criteria. The outcome measures evaluated were time-to-flatus, time-to-defecation, length of the hospital stay, and the rates of general and gastrointestinal postoperative complications. Continuous and dichotomous variables were compared respectively using weighted means differences and odds ratios with 95 % confidence intervals. The presence of publication bias was examined by funnel plots. Three studies (including 274 patients in total) met the inclusion criteria. The pooled results demonstrated a 11.82hour reduction in time-to-flatus (95 % CI : -15.43, -8.22h, P <0.00001), and 19.57hours in time-to-defecation (95 % CI : -29.33, -9.81h, P <0.0001), and a decreasing trend of 2.85 days in the length of the hospital stay (95 % CI : -6.13, -0.43, P=0.09), by the use of chewing gum. There was no significant difference between the "chewing gum" and "control" groups in terms of general and gastrointestinal complications (Peto Odds ratio 1.04 [0.60, 1.79], 95 % CI, P=0.89 and Peto Odds ratio 0.65 [0.26, 1.61], 95 % CI, P=0.35 respectively). Chewing gum may be recommended postoperatively in patients undergoing radical cystectomy to improve time-to-bowel function. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Enantioselective Cyanation of Benzylic C–H Bonds via Copper-Catalyzed Radical Relay

PubMed Central

Zhang, Wen; Wang, Fei; McCann, Scott D.; Wang, Dinghai; Chen, Pinhong; Stahl, Shannon; Liu, Guosheng

2017-01-01

Direct methods for stereoselective functionalization of C(sp3)–H bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp3)–CN bond upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90-99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C–H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways. PMID:27701109

Radiolysis of berberine or palmatine in aqueous solution

NASA Astrophysics Data System (ADS)

Marszalek, Milena; Wolszczak, Marian

2011-01-01

The reactions of hydrated electron (eaq-), hydrogen atom (H rad ) (reducing species) and Cl2•-, Br2•-, N,O•H radicals (oxidizing species) with berberine or palmatine in aqueous solution have been studied by steady-state and pulse radiolysis. The spectra of transient intermediates, leading to the final products, are presented. The rate constants of the reaction of eaq- and rad OH radical with both alkaloids in the homogenous solution and in the presence of DNA are reported. It is demonstrated that the primary products of the reaction of berberine and palmatine with eaq- and radicals generated during radiolysis are unstable and undergo further reactions.

Ground and Excited-Electronic-State Dissociations of Hydrogen-Rich and Hydrogen-Deficient Tyrosine Peptide Cation Radicals

NASA Astrophysics Data System (ADS)

Viglino, Emilie; Lai, Cheuk Kuen; Mu, Xiaoyan; Chu, Ivan K.; Tureček, František

2016-09-01

We report a comprehensive study of collision-induced dissociation (CID) and near-UV photodissociation (UVPD) of a series of tyrosine-containing peptide cation radicals of the hydrogen-rich and hydrogen-deficient types. Stable, long-lived, hydrogen-rich peptide cation radicals, such as [AAAYR + 2H]+● and several of its sequence and homology variants, were generated by electron transfer dissociation (ETD) of peptide-crown-ether complexes, and their CID-MS3 dissociations were found to be dramatically different from those upon ETD of the respective peptide dications. All of the hydrogen-rich peptide cation radicals contained major (77%-94%) fractions of species having radical chromophores created by ETD that underwent photodissociation at 355 nm. Analysis of the CID and UVPD spectra pointed to arginine guanidinium radicals as the major components of the hydrogen-rich peptide cation radical population. Hydrogen-deficient peptide cation radicals were generated by intramolecular electron transfer in CuII(2,2 ':6 ',2 ″-terpyridine) complexes and shown to contain chromophores absorbing at 355 nm and undergoing photodissociation. The CID and UVPD spectra showed major differences in fragmentation for [AAAYR]+● that diminished as the Tyr residue was moved along the peptide chain. UVPD was found to be superior to CID in localizing Cα-radical positions in peptide cation radical intermediates.

Reaction mechanism and kinetics of the degradation of terbacil initiated by OH radical - A theoretical study

NASA Astrophysics Data System (ADS)

Ponnusamy, S.; Sandhiya, L.; Senthilkumar, K.

2018-02-01

The reaction of terbacil with OH radical is studied by using electronic structure calculations. The reaction of terbacil with OH radical is found to proceed by H-atom abstraction, Cl-atom abstraction and OH addition reactions. The initially formed alkyl radical will undergo atmospheric transformation in the presence of molecular oxygen leading to the formation of peroxy radical. The reaction of peroxy radical with other atmospheric oxidants, such as HO2 and NO radicals is studied. The rate constant is calculated for the H-atom abstraction reactions over the temperature range of 200-1000 K. The results obtained from electronic structure calculations and kinetic study show that the H-atom abstraction reaction is more favorable. The calculated lifetime of terbacil is 24 h in normal atmospheric OH concentration. The rate constant calculated for H-atom abstraction reactions is 6 × 10-12, 4.4 × 10-12 and 3.2 × 10-12 cm3molecule-1s-1, respectively which is in agreement with the previous literature value of 1.9 × 10-12 cm3molecule-1s-1.

Introduction of an enhanced recovery protocol to reduce short-term complications following radical cystectomy and intestinal urinary diversion with vescica ileale Padovana neobladder.

PubMed

Cerruto, Maria Angela; De Marco, Vincenzo; D'Elia, Carolina; Bizzotto, Leonardo; Curti, Pierpaolo; Baldassarre, Roberto; Artibani, Walter

2014-01-01

To reduce short-term complications of radical cystectomy (RC) and intestinal urinary diversion with vescica ileale Padovana (VIP) neobladder, we described and assessed an enhanced recovery protocol (ERP) in a series of consecutive patients. An ERP was introduced focusing on reduced bowel preparation, standardized feeding and analgesic regimens. We analyzed the outcomes with all patients consecutively undergoing RC and VIP neobladder who met the following inclusion criteria: American Society of Anesthesiologists score <3; absence of malnutrition according to the Mini Nutritional Assessment-Short Form criteria; absence of inflammatory bowel diseases. Thirty-one consecutive patients were recruited to undergo our ERP. Mean age of patients was 62.16 years. No patients died due to surgical complications. Nine of 31 patients experienced complications (29.03%), none requiring surgical intervention. According to Clavien grading, all complications were grade <2. The application of our ERP to our patients undergoing RC and VIP neobladder contributed to reduce postoperative morbidity. Copyright © 2013 S. Karger AG, Basel.

Reactions of Free Radicals with Nitro-Compounds and Nitrates

DTIC Science & Technology

1981-03-31

PAGE(I/hmm a•Ia ntatemd the fragment derived from the nitrates but not from the nitro-compounds could undergo exothermic rearrangement. Product analyses...compounds could undergo exothermic rearrangement. Product analyses and computer modelling were undertaken, these provided a clear explanation of why the...Nitrate 14 Reaction of Oxygen Atoms with Nitromethane 16 Reaction of Oxygen Atoms with Nitroethane 17 Products from Nitrocompounds 18 Effect of Carbon

Facile Rearrangement of 3-Oxoalkyl Radicals is Evident in Low-Temperature Gas-Phase Oxidation of Ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheer, Adam M.; Welz, Oliver; Sasaki, Darryl Y.

The pulsed photolytic chlorine-initiated oxidation of methyl-tert-butyl ketone (MTbuK), di-tert-butyl ketone (DTbuK), and a series of partially deuterated diethyl ketones (DEK) is studied in the gas phase at 8 Torr and 550–650 K. Products are monitored as a function of reaction time, mass, and photoionization energy using multiplexed photoionization mass spectrometry with tunable synchrotron ionizing radiation. The results establish that the primary 3-oxoalkyl radicals of those ketones, formed by abstraction of a hydrogen atom from the carbon atom in γ-position relative to the carbonyl oxygen, undergo a rapid rearrangement resulting in an effective 1,2-acyl group migration, similar to that inmore » a Dowd–Beckwith ring expansion. Without this rearrangement, peroxy radicals derived from MTbuK and DTbuK cannot undergo HO2 elimination to yield a closed-shell unsaturated hydrocarbon coproduct. However, not only are these coproducts observed, but they represent the dominant oxidation channels of these ketones under the conditions of this study. For MTbuK and DTbuK, the rearrangement yields a more stable tertiary radical, which provides the thermodynamic driving force for this reaction. Even in the absence of such a driving force in the oxidation of partially deuterated DEK, the 1,2-acyl group migration is observed. Quantum chemical (CBS-QB3) calculations show the barrier for gas-phase rearrangement to be on the order of 10 kcal mol–1. The MTbuK oxidation experiments also show several minor channels, including β-scission of the initial radicals and cyclic ether formation.« less

Repair of the threatened feminine identity: experience of women with cervical cancer undergoing fertility preservation surgery.

PubMed

Komatsu, Hiroko; Yagasaki, Kaori; Shoda, Rie; Chung, Younghui; Iwata, Takashi; Sugiyama, Juri; Fujii, Takuma

2014-01-01

Fertility preservation is important for women of reproductive age with cervical cancer. The underlying reasons behind suboptimal reproductive results after successful fertility-preserving surgery have not yet been fully revealed. The objective of this study was to explore the experience of fertility preservation with radical trachelectomy from the perspective of women with cervical cancer. We conducted interviews with women with cervical cancer who underwent radical trachelectomy using a Grounded Theory methodology with a theoretical framework of symbolic interactionism. Our findings articulate a process in which feminine identity is first threatened by a diagnosis of cancer, then repaired by fertility preservation with radical trachelectomy, and finally reconstructed after the surgery, through interactions with self, others, and external events in women with cervical cancer. Feeling incomplete as a woman because of the loss of the uterus was a critical factor in the women's feeling that their feminine identity was threatened. Thus, fertility preservation was significant for these women. The meaning of fertility preservation varied among the women, and their life perspectives were therefore distinct after the surgery. Women with cervical cancer who undergo radical trachelectomy experience an identity transformation process, and child bearing is not the only expected outcome of fertility preservation. Nurses should coordinate care through the cancer trajectory. Understanding the identity transformation process helps nurses to assess patients' needs and provide appropriate individual care.

The Expanding Role of Oxygen Free Radicals in Clinical Medicine

PubMed Central

Katz, Murray A.

1986-01-01

In 1969 McCord and Fridovich discovered superoxide dismutase, which converts the oxygen free radical O2- to hydrogen peroxide H2O2. In the presence of excess O2-, H2O2 may then undergo further reduction to the highly toxic hydroxyl radical, OH•. Since the description of this enzymatic process, there has been explosive growth in related biochemical research, which has now percolated through to clinical investigation. The hypoxanthine-xanthine oxidase system originally used as a radical production model has a close counterpart in the ischemia-reperfusion phenomenon purported to cause diseases of heart, brain and gastrointestinal tract, and free radicals are now known to have a critical role in postphagocytic bacterial killing. Prototypic deficiency diseases such as chronic granulomatous disease are now recognized. Some evidence indicates that excess states such as perhaps Batten's disease also occur, and environmental influences such as selenium and vitamin E deficiency may augment free radical levels. Many disorders including microvasculopathies, noncardiogenic pulmonary edema, glomerulopathies and radiation damage may owe part of their proximate pathogenesis to free radicals. Control of tissue free radical levels is now pharmacologically feasible and perhaps justified for specific diseases. PMID:3521094

Light-dependent magnetoreception in birds: the crucial step occurs in the dark.

PubMed

Wiltschko, Roswitha; Ahmad, Margaret; Nießner, Christine; Gehring, Dennis; Wiltschko, Wolfgang

2016-05-01

The Radical Pair Model proposes that the avian magnetic compass is based on spin-chemical processes: since the ratio between the two spin states singlet and triplet of radical pairs depends on their alignment in the magnetic field, it can provide information on magnetic directions. Cryptochromes, blue light-absorbing flavoproteins, with flavin adenine dinucleotide as chromophore, are suggested as molecules forming the radical pairs underlying magnetoreception. When activated by light, cryptochromes undergo a redox cycle, in the course of which radical pairs are generated during photo-reduction as well as during light-independent re-oxidation. This raised the question as to which radical pair is crucial for mediating magnetic directions. Here, we present the results from behavioural experiments with intermittent light and magnetic field pulses that clearly show that magnetoreception is possible in the dark interval, pointing to the radical pair formed during flavin re-oxidation. This differs from the mechanism considered for cryptochrome signalling the presence of light and rules out most current models of an avian magnetic compass based on the radical pair generated during photo-reduction. Using the radical pair formed during re-oxidation may represent a specific adaptation of the avian magnetic compass. © 2016 The Authors.

Dynamics of Peroxy and Alkenyl Radicals Undergoing Competing Rearrangements in Biodiesel Combustion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dibble, Theodore S.

Biodiesel fuel is increasingly being used worldwide. Although we have a fair understanding of the molecular details of the chemistry of peroxy radicals derived from alkanes, biodiesel fuels contain ester and olefin groups which significantly impact the thermodynamics and kinetics of biodiesel ignition. The broader goal of this research is to carry out systematic computational studies of the elementary kinetics of the chemistry of ROO•, QOOH and •OOQOOH compounds that are models for biodiesel ignition.

Analytical chemical kinetic investigation of the effects of oxygen, hydrogen, and hydroxyl radicals on hydrogen-air combustion

NASA Technical Reports Server (NTRS)

Carson, G. T., Jr.

1974-01-01

Quantitative values were computed which show the effects of the presence of small amounts of oxygen, hydrogen, and hydroxyl radicals on the finite-rate chemical kinetics of premixed hydrogen-air mixtures undergoing isobaric autoignition and combustion. The free radicals were considered to be initially present in hydrogen-air mixtures at equivalence ratios of 0.2, 0.6, 1.0, and 1.2. Initial mixture temperatures were 1100 K, 1200 K, and 1500 K, and pressures were 0.5, 1.0, 2.0, and 4.0 atm. Of the radicals investigated, atomic oxygen was found to be the most effective for reducing induction time, defined as the time to 5 percent of the total combustion temperature rise. The reaction time, the time between 5 percent and 95 percent of the temperature rise, is not decreased by the presence of free radicals in the initial hydrogen-air mixture. Fuel additives which yield free radicals might be used to effect a compact supersonic combustor design for efficient operation in an otherwise reaction-limited combustion regime.

Nerve-Sparing Approach Improves Outcomes of Patients Undergoing Minimally Invasive Radical Hysterectomy: A Systematic Review and Meta-Analysis.

PubMed

Bogani, Giorgio; Rossetti, Diego Oreste; Ditto, Antonino; Signorelli, Mauro; Martinelli, Fabio; Mosca, Lavinia; Scaffa, Cono; Leone Roberti Maggiore, Umberto; Chiappa, Valentina; Sabatucci, Ilaria; Lorusso, Domenica; Raspagliesi, Francesco

Few studies have investigated the efficacy and safety of the nerve-sparing approach via minimally invasive surgery for the treatment of cervical cancer. We aimed to review the current evidence comparing nerve-sparing minimally invasive radical hysterectomy (NS-MRH) with conventional minimally invasive radical hysterectomy (MRH). This systematic review was registered in the International Prospective Register of Systematic Reviews (CRD#57655). Overall, 675 patients were included: 350 (51.9%) and 325 (48.1%) patients undergoing MRH and NS-MRH, respectively. MRH was associated with a shorter operative time in comparison with NS-MRH (mean difference = 32.57 minutes; 95% CI, 22.87-42.48). The estimated blood loss (mean difference = 97.14 mL, 20.01-214.29) and transfusion rate (odds ratio [OR] = 0.67; 95% confidence interval [CI], 0.15-3.01) did not differ statistically between the 2 groups. The risk of developing intraoperative (OR = 0.43; 95% CI, 0.08-2.23) and severe postoperative (OR = 0.63; 95% CI, 0.17-2.39) complications was similar between NS-MRH and MRH. Patients undergoing NS-MRH experienced lower voiding (OR = 0.39; 95% CI, 0.19-0.81) dysfunction rates than patients undergoing MRH. Moreover, a trend toward lower sexual (OR = 0.25; 95% CI, 0.06-1.07) and rectal (OR = 0.12; 95% CI, 0.01-1.02) issues was observed for patients having NS-MRH compared with patients undergoing MRH. Survival outcomes are not influenced by the type of surgical approach (recurrence [OR = 1.27; 95% CI, 0.49-3.28] and death [OR = 1.01; 95% CI, 0.36-2.83]) rates. The pooled data suggested that NS-MRH is equivalent to MRH for the treatment of cervical cancer and may be superior in reducing pelvic floor dysfunction rates. However, because of the low level of evidence of the included studies, further randomized trials are warranted. Copyright © 2017 American Association of Gynecologic Laparoscopists. Published by Elsevier Inc. All rights reserved.

Manometric characterization of rectal dysfunction following radical hysterectomy.

PubMed

Barnes, W; Waggoner, S; Delgado, G; Maher, K; Potkul, R; Barter, J; Benjamin, S

1991-08-01

Bladder dysfunction thought to be due to partial denervation has been described following radical hysterectomy. Some patients experience acute and chronic rectal dysfunction characterized by difficulty with defecation and loss of defecatory urge. To define this abnormality, anorectal pressure profiles were examined in 15 patients with Stage I carcinoma of the cervix before and after radical hysterectomy. Profiles were done using standard anorectal manometry with a water-infused system. In all patients preoperative manometric profiles were normal; postoperative studies were abnormal in all patients. Features seen include altered relaxation of the internal sphincter, increased distension needed to trigger relaxation, and decreased rectal sensation; external sphincters and resting internal sphincters were unchanged. Postoperatively, 12 patients reported problems with rectal function. A physiologic defect is definable in patients undergoing radical hysterectomy; this suggests disruption of the spinal reflex arcs controlling rectal emptying. These physiologic abnormalities correlate with the clinical symptomatology experienced by some patients. Continuing definition and evaluation of management options in this situation should be useful in developing effective therapy for rectal dysfunction following radical hysterectomy.

Health-related quality of life from a prospective randomised clinical trial of robot-assisted laparoscopic vs open radical cystectomy.

PubMed

Messer, Jamie C; Punnen, Sanoj; Fitzgerald, John; Svatek, Robert; Parekh, Dipen J

2014-12-01

To compare health-related quality-of-life (HRQoL) outcomes for robot-assisted laparoscopic radical cystectomy (RARC) with those of traditional open radical cystectomy (ORC) in a prospective randomised fashion. This was a prospective randomised clinical trial evaluating the HRQoL for ORC vs RARC in consecutive patients from July 2009 to June 2011. We administered the Functional Assessment of Cancer Therapy-Vanderbilt Cystectomy Index questionnaire, validated to assess HRQoL, preoperatively and then at 3, 6, 9 and 12 months postoperatively. Scores for each domain and total scores were compared in terms of deviation from preoperative values for both the RARC and the ORC cohorts. Multivariate linear regression was used to assess the association between the type of radical cystectomy and HRQoL. At the time of the study, 47 patients had met the inclusion criteria, with 40 patients being randomised for analysis. The cohorts consisted of 20 patients undergoing ORC and 20 undergoing RARC, who were balanced with respect to baseline demographic and clinical features. Univariate analysis showed a return to baseline scores at 3 months postoperatively in all measured domains with no statistically significant difference among the various domains between the RARC and the ORC cohorts. Multivariate analysis showed no difference in HRQoL between the two approaches in any of the various domains, with the exception of a slightly higher physical well-being score in the RARC group at 6 months. There were no significant differences in the HRQoL outcomes between ORC and RARC, with a return of quality of life scores to baseline scores 3 months after radical cystectomy in both cohorts. © 2014 The Authors. BJU International © 2014 BJU International.

Free radical scavenging window of infertile patients with polycystic ovary syndrome: correlation with embryo quality.

PubMed

Huang, Bo; Li, Zhou; Ren, Xinling; Ai, Jihui; Zhu, Lixia; Jin, Lei

2017-06-01

The activity of free radicals in follicular fluid was related to ovarian responsiveness, in vitro fertilization (IVF), and embryo transfer success rate. However, studies analyzing the relationship between the free radical scavenging capacity and embryo quality of infertile women with polycystic ovarian syndrome (PCOS) were lacking. The aim of this study was to evaluate the relationship between the free radical scavenging window of women with PCOS and their embryo quality. The free radical scavenging capacity of follicular fluid from women with PCOS was determined by a,a-diphenyl-b-picrylhydrazyl (DPPH), 2,2-azinobis (3-ethylbenzthiazoline-6-sulphonic acid) assay, superoxide radical, and reactive oxygen species (ROS) assay. In the DPPH and ROS assays, the follicular fluid from grades I and II embryos was significantly higher than the follicular fluid from grades III and IVembryos. The lower control limit of DPPH radical scavenging capacity and upper control limit of ROS level were 13.2% and 109.0 cps, respectively. The calculated lower control limit and upper control limit were further confirmed in the follicular fluid of embryos of all grades. These cut-off values of free radical scavenging activity of follicular fluid could assist embryologists in choosing the development of embryos in PCOS patients undergoing IVF.

Outcomes of fertility-sparing surgery among young women with FIGO stage I clear cell carcinoma of the ovary.

PubMed

Park, Jeong-Yeol; Suh, Dae-Shik; Kim, Jong-Hyeok; Kim, Yong-Man; Kim, Young-Tak; Nam, Joo-Hyun

2016-07-01

To evaluate the outcome of fertility-sparing surgery among young women with early-stage clear cell carcinoma of the ovary. In a retrospective study, data were reviewed for patients aged 45years or younger who had FIGO stage I clear cell carcinoma of the ovary and had attended one institution in South Korea between December 1999 and December 2009. Outcomes were compared between women undergoing fertility-sparing surgery, defined as preservation of the uterus and at least one adnexa, and those undergoing radical surgery. Overall, 47 patients were included (22 underwent fertility-sparing surgery, 25 radical surgery). After a median follow-up of 72months (range 8-175), 5 (23%) patients who underwent fertility-sparing surgery and 5 (20%) in the radical surgery group had recurrent disease (P=0.820). The mean time to recurrence was 19months after fertility-sparing surgery versus 20months after radical surgery (P=0.935). The anatomical location of recurrence did not differ. There was no difference in 5-year disease-free survival (77% vs 84%; P=0.849) or 5-year overall survival (91% vs 88%; P=0.480). Fertility-sparing surgery was found to be a safe alternative for young women with FIGO stage I clear cell carcinoma of the ovary who wish to preserve fertility. Copyright © 2016 International Federation of Gynecology and Obstetrics. Published by Elsevier Ireland Ltd. All rights reserved.

National cohort study comparing severe medium-term urinary complications after robot-assisted vs laparoscopic vs retropubic open radical prostatectomy.

PubMed

Sujenthiran, Arunan; Nossiter, Julie; Parry, Matthew; Charman, Susan C; Aggarwal, Ajay; Payne, Heather; Dasgupta, Prokar; Clarke, Noel W; van der Meulen, Jan; Cathcart, Paul

2018-03-01

To evaluate the occurrence of severe urinary complications within 2 years of surgery in men undergoing either robot-assisted radical prostatectomy (RARP), laparoscopic radical prostatectomy (LRP) or retropubic open radical prostatectomy (ORP). We conducted a population-based cohort study in men who underwent RARP (n = 4 947), LRP (n = 5 479) or ORP (n = 6 873) between 2008 and 2012 in the English National Health Service (NHS) using national cancer registry records linked to Hospital Episodes Statistics, an administrative database of admissions to NHS hospitals. We identified the occurrence of any severe urinary or severe stricture-related complication within 2 years of surgery using a validated tool. Multi-level regression modelling was used to determine the association between the type of surgery and occurrence of complications, with adjustment for patient and surgical factors. Men undergoing RARP were least likely to experience any urinary complication (10.5%) or a stricture-related complication (3.3%) compared with those who had LRP (15.8% any or 5.7% stricture-related) or ORP (19.1% any or 6.9% stricture-related). The impact of the type of surgery on the occurrence of any urinary or stricture-related complications remained statistically significant after adjustment for patient and surgical factors (P < 0.01). Men who underwent RARP had the lowest risk of developing severe urinary complications within 2 years of surgery. © 2017 The Authors BJU International published by John Wiley & Sons Ltd on behalf of BJU International.

Hypochlorite and superoxide radicals can act synergistically to induce fragmentation of hyaluronan and chondroitin sulphates

PubMed Central

2004-01-01

Activated phagocytes release the haem enzyme MPO (myeloperoxidase) and also generate superoxide radicals (O2•−), and hence H2O2, via an oxidative burst. Reaction of MPO with H2O2 in the presence of chloride ions generates HOCl (the physiological mixture of hypochlorous acid and its anion present at pH 7.4). Exposure of glycosaminoglycans to a MPO–H2O2–Cl− system or reagent HOCl generates long-lived chloramides [R-NCl-C(O)-R′] derived from the glycosamine N-acetyl functions. Decomposition of these species by transition metal ions gives polymer-derived amidyl (nitrogen-centred) radicals [R-N•-C(O)-R′], polymer-derived carbon-centred radicals and site-specific strand scission. In the present study, we have shown that exposure of glycosaminoglycan chloramides to O2•− also promotes chloramide decomposition and glycosaminoglycan fragmentation. These processes are inhibited by superoxide dismutase, metal ion chelators and the metal ion-binding protein BSA, consistent with chloramide decomposition and polymer fragmentation occurring via O2•−-dependent one-electron reduction, possibly catalysed by trace metal ions. Polymer fragmentation induced by O2•− [generated by the superoxide thermal source 1, di-(4-carboxybenzyl)hyponitrite] was demonstrated to be entirely chloramide dependent as no fragmentation occurred with the native polymers or when the chloramides were quenched by prior treatment with methionine. EPR spin-trapping experiments using 5,5-dimethyl1-pyrroline-N-oxide and 2-methyl-2-nitrosopropane have provided evidence for both O2•− and polymer-derived carbon-centred radicals as intermediates. The results obtained are consistent with a mechanism involving one-electron reduction of the chloramides to yield polymer-derived amidyl radicals, which subsequently undergo intramolecular hydrogen atom abstraction reactions to give carbon-centred radicals. The latter undergo fragmentation reactions in a site-specific manner. This synergistic damage to glycosaminoglycans induced by HOCl and O2•− may be of significance at sites of inflammation where both oxidants are generated concurrently. PMID:15078224

Efficacy and Safety of Stroke Volume Variation-Guided Fluid Therapy for Reducing Blood Loss and Transfusion Requirements During Radical Cystectomy: A Randomized Clinical Trial.

PubMed

Kong, Yu-Gyeong; Kim, Ji Yoon; Yu, Jihion; Lim, Jinwook; Hwang, Jai-Hyun; Kim, Young-Kug

2016-05-01

Radical cystectomy, which is performed to treat muscle-invasive bladder tumors, is among the most difficult urological surgical procedures and puts patients at risk of intraoperative blood loss and transfusion. Fluid management via stroke volume variation (SVV) is associated with reduced intraoperative blood loss. Therefore, we evaluated the efficacy and safety of SVV-guided fluid therapy for reducing blood loss and transfusion requirements in patients undergoing radical cystectomy.This study included 48 patients who underwent radical cystectomy, and these patients were randomly allocated to the control group and maintained at <10% SVV (n = 24) or allocated to the trial group and maintained at 10% to 20% SVV (n = 24). The primary endpoints were comparisons of the amounts of intraoperative blood loss and transfused red blood cells (RBCs) between the control and trial groups during radical cystectomy. Intraoperative blood loss was evaluated through the estimated blood loss and estimated red cell mass loss. The secondary endpoints were comparisons of the postoperative outcomes between groups.A total of 46 patients were included in the final analysis: 23 patients in the control group and 23 patients in the trial group. The SVV values in the trial group were significantly higher than in the control group. Estimated blood loss, estimated red cell mass loss, and RBC transfusion requirements in the trial group were significantly lower than in the control group (734.3 ± 321.5 mL vs 1096.5 ± 623.9 mL, P = 0.019; 274.1 ± 207.8 mL vs 553.1 ± 298.7 mL, P <0.001; 0.5 ± 0.8 units vs 1.9 ± 2.2 units, P = 0.005). There were no significant differences in postoperative outcomes between the two groups.SVV-guided fluid therapy (SVV maintained at 10%-20%) can reduce blood loss and transfusion requirements in patients undergoing radical cystectomy without resulting in adverse outcomes. These findings provide useful information for optimal fluid management during radical cystectomy.

Preliminary results of the comparison of the electrochemical behavior of a thioether and biphenyl

NASA Technical Reports Server (NTRS)

Morales, W.; Jones, W. R.

1983-01-01

An electrochemical cell was constructed to explore the feasibility of using electrochemical techniques to simulate the tribochemistry of various substances. The electrochemical cell was used to study and compare the behavior of a thioether 1,3-bis(phenylthio) benzene and biphenyl. It is found that under controlled conditions biphenyl undergoes a reversible reduction to a radical anion whereas the thioether undergoes an irreversible reduction yielding several products. The results are discussed in relationship to boundary lubrication.

Reduction of protein radicals by GSH and ascorbate: potential biological significance.

PubMed

Gebicki, Janusz M; Nauser, Thomas; Domazou, Anastasia; Steinmann, Daniel; Bounds, Patricia L; Koppenol, Willem H

2010-11-01

The oxidation of proteins and other macromolecules by radical species under conditions of oxidative stress can be modulated by antioxidant compounds. Decreased levels of the antioxidants glutathione and ascorbate have been documented in oxidative stress-related diseases. A radical generated on the surface of a protein can: (1) be immediately and fully repaired by direct reaction with an antioxidant; (2) react with dioxygen to form the corresponding peroxyl radical; or (3) undergo intramolecular long range electron transfer to relocate the free electron to another amino acid residue. In pulse radiolysis studies, in vitro production of the initial radical on a protein is conveniently made at a tryptophan residue, and electron transfer often leads ultimately to residence of the unpaired electron on a tyrosine residue. We review here the kinetics data for reactions of the antioxidants glutathione, selenocysteine, and ascorbate with tryptophanyl and tyrosyl radicals as free amino acids in model compounds and proteins. Glutathione repairs a tryptophanyl radical in lysozyme with a rate constant of (1.05±0.05)×10(5) M(-1) s(-1), while ascorbate repairs tryptophanyl and tyrosyl radicals ca. 3 orders of magnitude faster. The in vitro reaction of glutathione with these radicals is too slow to prevent formation of peroxyl radicals, which become reduced by glutathione to hydroperoxides; the resulting glutathione thiyl radical is capable of further radical generation by hydrogen abstraction. Although physiologically not significant, selenoglutathione reduces tyrosyl radicals as fast as ascorbate. The reaction of protein radicals formed on insulin, β-lactoglobulin, pepsin, chymotrypsin and bovine serum albumin with ascorbate is relatively rapid, competes with the reaction with dioxygen, and the relatively innocuous ascorbyl radical is formed. On the basis of these kinetics data, we suggest that reductive repair of protein radicals may contribute to the well-documented depletion of ascorbate in living organisms subjected to oxidative stress.

The association of lymph node dissection with 30-day perioperative morbidity among men undergoing minimally invasive radical prostatectomy: analysis of the National Surgical Quality Improvement Program (NSQIP).

PubMed

Brito, Joseph; Pereira, Jorge; Moreira, Daniel M; Pareek, Gyan; Tucci, Christopher; Guo, Ruiting; Zhang, Zheng; Amin, Ali; Mega, Anthony; Renzulli, Joseph; Golijanin, Dragan; Gershman, Boris

2018-06-01

The incremental morbidity of lymph node dissection (LND) among men undergoing radical prostatectomy remains uncertain. We therefore evaluated  the association of LND with perioperative morbidity among men undergoing minimally invasive radical prostatectomy (MIRP). We identified 29,012 men aged 35-89 who underwent MIRP from 2010-2015 in the National Surgical Quality Improvement Program (NSQIP) database, of whom 47% underwent concomitant LND. The associations of LND with 30-day perioperative morbidity and mortality were evaluated using logistic regression, adjusted for patient features. Median age at surgery was 63 (IQR 57, 67) years. There were statistically significant, but clinically insignificant, differences in several baseline characteristics stratified by performance of LND, including older age at surgery (p < 0.001), higher American Society of Anesthesiology (ASA) class (p < 0.001), and longer operative time (p < 0.001) for men who underwent LND. Overall, 30-day complications occurred in 4.3% of patients. There were no statistically significant differences in rates of 30-day complications (4.2 vs. 4.4%, p = 0.44), perioperative blood transfusion (1.7 vs. 1.7%, p = 0.99), hospital readmission (3.6 vs. 4.0%, p = 0.09), reoperation (1.1 vs. 1.1%, p = 0.80), or 30-day mortality (0.1 vs. 0.2%, p = 0.56) between patients who underwent MIRP alone or MIRP with LND, respectively. On multivariable analysis, LND was not significantly associated with an increased risk of perioperative morbidity or 30-day mortality. LND at the time of MIRP does not appear to be associated with an increased risk of perioperative morbidity.

Prospective evaluation of a 12-week walking exercise program and its effect on fatigue in prostate cancer patients undergoing radical external beam radiotherapy.

PubMed

Truong, Pauline T; Gaul, Catherine A; McDonald, Rachel E; Petersen, Ross B; Jones, Stuart O; Alexander, Abraham S; Lim, Jan T W; Ludgate, Charles

2011-08-01

To evaluate tolerability and compliance to a walking exercise program and its effect on fatigue during and after radical external beam radiation therapy (EBRT) for prostate cancer. A total of 50 subjects with prostate cancer undergoing EBRT over 6 to 8 weeks were prospectively accrued to an exercise intervention group, matched for age and clinical characteristics to 30 subjects in a historical control group who underwent EBRT with no specific exercise intervention. Starting 1 week before EBRT, exercise participants performed moderate-intensity walking targeting 60% to 70% age-predicted maximum heart rate, at least 20 min/d, 3 d/wk over 12 weeks. The Brief Fatigue Inventory was administered at baseline, mid-EBRT (week 3-4), end-EBRT (week 6-8), and 6 months post-EBRT. Of 50, 42 (84%) of exercise participants completed the walking program. There were no cardiovascular complications, musculoskeletal injuries, or other adverse events. A total of 89% subjects reported "Good-Excellent" satisfaction during and up to 6 months post-EBRT. Fatigue in control subjects escalated from baseline to end-EBRT, remaining high at 6 months post-EBRT (P[r] = 0.03). In contrast, mean total fatigue scores in exercise subjects were stable from baseline up to 6 months post-EBRT (P = 0.52). Trends for higher fatigue interference with quality of life were observed in the control group as compared with the exercise group. Moderate-intensity walking exercise during radical EBRT is safe and feasible. The high convenience and satisfaction ratings, in conjunction with the observed fatigue trends, indicate that this activity has the potential to attenuate fatigue and improve quality of life for patients with localized prostate cancer undergoing curative therapy.

A systematic review of exercise and psychosocial rehabilitation interventions to improve health-related outcomes in patients with bladder cancer undergoing radical cystectomy.

PubMed

Rammant, Elke; Decaestecker, Karel; Bultijnck, Renée; Sundahl, Nora; Ost, Piet; Pauwels, Nele S; Deforche, Benedicte; Pieters, Ronny; Fonteyne, Valérie

2018-05-01

Summarizing the evidence on the effects of pre- and postoperative exercise and psychosocial rehabilitation interventions on patient-reported outcomes (PROs) and physical fitness in bladder cancer patients undergoing radical cystectomy. The Cochrane Central Register of Controlled Trials, MEDLINE, Embase, Web of Science and the Physiotherapy Evidence Database were searched independently by two authors from inception until 10 November 2017. Cited references of the studies and citing references retrieved via Web of Science were also checked. Randomized controlled trials (RCTs) and non-randomized studies assessing effects of exercise and psychosocial interventions in bladder cancer patients undergoing radical cystectomy were eligible. Primary outcome measures were PROs and physical fitness. Risk of bias was assessed using the Cochrane Collaboration tool and the Newcastle-Ottawa Scale. Five RCTs (three exercise and two psychosocial studies) and one non-randomized psychosocial study comprising 317 bladder cancer patients were included. Timing of the intervention was preoperative ( n = 2), postoperative ( n = 2) or both pre- and postoperative ( n = 2). Positive effects of exercise were found for physical fitness ( n = 3), some health-related quality-of-life (HRQoL) domains ( n = 2), personal activities in daily living ( n = 1) and muscle strength ( n = 1). Psychosocial interventions showed positive effects on anxiety ( n = 1), fatigue ( n = 1), depression ( n = 1), HRQoL ( n = 1) and posttraumatic growth ( n = 1). Quality assessment showed most shortcomings with sample sizes and strong heterogeneity was observed between studies. The evidence relating to the effects of exercise in bladder cancer is very limited and is even less for psychosocial interventions.

Comparative analysis of outcomes and costs following open radical cystectomy versus robot-assisted laparoscopic radical cystectomy: results from the US Nationwide Inpatient Sample.

PubMed

Yu, Hua-yin; Hevelone, Nathanael D; Lipsitz, Stuart R; Kowalczyk, Keith J; Nguyen, Paul L; Choueiri, Toni K; Kibel, Adam S; Hu, Jim C

2012-06-01

Although robot-assisted laparoscopic radical cystectomy (RARC) was first reported in 2003 and has gained popularity, comparisons with open radical cystectomy (ORC) are limited to reports from high-volume referral centers. To compare population-based perioperative outcomes and costs of ORC and RARC. A retrospective observational cohort study using the US Nationwide Inpatient Sample to characterize 2009 RARC compared with ORC use and outcomes. Propensity score methods were used to compare inpatient morbidity and mortality, lengths of stay, and costs. We identified 1444 ORCs and 224 RARCs. Women were less likely to undergo RARC than ORC (9.8% compared with 15.5%, p = 0.048), and 95.7% of RARCs and 73.9% of ORCs were performed at teaching hospitals (p<0.001). In adjusted analyses, subjects undergoing RARC compared with ORC experienced fewer inpatient complications (49.1% and 63.8%, p = 0.035) and fewer deaths (0% and 2.5%, p<0.001). RARC compared with ORC was associated with lower parenteral nutrition use (6.4% and 13.3%, p = 0.046); however, there was no difference in length of stay. RARC compared with ORC was $3797 more costly (p = 0.023). Limitations include retrospective design, absence of tumor characteristics, and lack of outcomes beyond hospital discharge. RARC is associated with lower parenteral nutrition use and fewer inpatient complications and deaths. However, lengths of stay are similar, and the robotic approach is significantly more costly. Copyright © 2012 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Combining UV photodissociation action spectroscopy with electron transfer dissociation for structure analysis of gas-phase peptide cation-radicals.

PubMed

Shaffer, Christopher J; Pepin, Robert; Tureček, František

2015-12-01

We report the first example of using ultraviolet (UV) photodissociation action spectroscopy for the investigation of gas-phase peptide cation-radicals produced by electron transfer dissociation. z-Type fragment ions (●) Gly-Gly-Lys(+), coordinated to 18-crown-6-ether (CE), are generated, selected by mass and photodissociated in the 200-400 nm region. The UVPD action spectra indicate the presence of valence-bond isomers differing in the position of the Cα radical defect, (α-Gly)-Gly-Lys(+) (CE), Gly-(α-Gly)-Lys(+) (CE) and Gly-Gly-(α-Lys(+))(CE). The isomers are readily distinguishable by UV absorption spectra obtained by time-dependent density functional theory (TD-DFT) calculations. In contrast, conformational isomers of these radical types are calculated to have similar UV spectra. UV photodissociation action spectroscopy represents a new tool for the investigation of transient intermediates of ion-electron reactions. Specifically, z-type cation radicals are shown to undergo spontaneous hydrogen atom migrations upon electron transfer dissociation. Copyright © 2015 John Wiley & Sons, Ltd.

On the formation of niacin (vitamin B3) and pyridine carboxylic acids in interstellar model ices

NASA Astrophysics Data System (ADS)

McMurtry, Brandon M.; Turner, Andrew M.; Saito, Sean E. J.; Kaiser, Ralf I.

2016-06-01

The formation of pyridine carboxylic acids in interstellar ice grains was simulated by electron exposures of binary pyridine (C5H5N)-carbon dioxide (CO2) ice mixtures at 10 K under contamination-free ultrahigh vacuum conditions. Chemical processing of the pristine ice and subsequent warm-up phase was monitored on line and in situ via Fourier transform infrared spectroscopy to probe for the formation of new radiation induced species. In the infrared spectra of the irradiated ice, bands assigned to nicotinic acid (niacin; vitamin B3; m-C5H4NCOOH) along with 2,3-, 2,5-, 3,4-, and 3,5-pyridine dicarboxylic acid (C5H3N(COOH)2) were unambiguously identified along with the hydroxycarbonyl (HOCO) radical. Our study suggests that the reactive pathway responsible for pyridine carboxylic acids formation involves a HOCO intermediate, which forms through the reaction of suprathermal hydrogen ejected from pyridine with carbon dioxide. The newly formed pyridinyl radical may then undergo radical-radical recombination with a hydroxycarbonyl radical to form a pyridine carboxylic acid.

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling.

PubMed

Dubnikova, Faina; Tamburu, Carmen; Lifshitz, Assa

2016-09-29

The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

Free Radical Metabolism of Methyleugenol and Related Compounds

PubMed Central

2015-01-01

Methyleugenol, the methyl ether of eugenol, both of which are flavorant constituents of spices, has been listed by the National Toxicology Program’s Report on Carcinogens as reasonably anticipated to be a human carcinogen. This finding is based on the observation of increased incidence of malignant tumors at multiple tissue sites in experimental animals of different species. By contrast, eugenol is not listed. In this study, we show that both methyleugenol and eugenol readily undergo peroxidative metabolism in vitro to form free radicals with large hyperfine interactions of the methylene allylic hydrogen atoms. These large hyperfine splittings indicate large electron densities adjacent to those hydrogen atoms. Methyleugenol undergoes autoxidation such that the commercial product contains 10–30 mg/L hydroperoxide and is capable of activating peroxidases without the presence of added hydrogen peroxide. Additionally, the hydroperoxide is not a good substrate for catalase, which demonstrates that these antioxidant defenses will not be effective in protecting against methyleugenol exposure. PMID:24564854

Temporal Trends in Clinical and Pathological Characteristics for Men Undergoing Radical Prostatectomy Between 1995 and 2013 at Rigshospitalet, Copenhagen, Denmark, and Stanford University Hospital, United States.

PubMed

Loft, Mathias Dyrberg; Berg, Kasper Drimer; Kjaer, Andreas; Iversen, Peter; Ferrari, Michelle; Zhang, Chiyuan A; Brasso, Klaus; Brooks, James D; Røder, Martin Andreas

2017-09-06

To analyze how prostate-specific antigen (PSA) screening and practice patterns has affected trends in tumor characteristics in men undergoing radical prostatectomy (RP) in the United States and Denmark. Unlike in the United States, PSA screening has not been recommended in Denmark. We performed an observational register study using pre- and postoperative data on 2168 Danish patients from Rigshospitalet, Copenhagen, Denmark, and 2236 patients from Stanford University Hospital, Stanford, CA, who underwent RP between 1995 and 2013. Patients were stratified according to Cancer of the Prostate Risk Assessment-Postsurgical (CAPRA-S) risk groups and D'Amico risk classification and were clustered into 4 time periods (1995-1999, 2000-2004, 2005-2009, and 2010-2013). Temporal trends in the proportions of patients of a given variable at the 2 institutions were evaluated with Cochran-Armitage test for trends and chi-square testing. A total of 4404 patients were included. Temporal changes in preoperative PSA, age, grade, and stage was found in both cohorts. Median preoperative PSA declined in both cohorts, while median age increased, with the Danish cohort showing the greatest changes in both PSA and age. In both cohorts, there was a trend for higher-risk preoperative features before RP over time. In 2010-2013, 27.7% and 21.8% of the patients were in the D'Amico high-risk group at Copenhagen and Stanford, respectively. Despite recommendation against PSA screening in Denmark, Danish men undergoing RP at Rigshospitalet to a considerable extent now resemble American men undergoing RP at Stanford. At both sites, there is continued trend to reduce the number of men undergoing RP for low-risk prostate cancer. Copyright © 2017 Elsevier Inc. All rights reserved.

Low central venous pressure versus acute normovolemic hemodilution versus conventional fluid management for reducing blood loss in radical retropubic prostatectomy: a randomized controlled trial.

PubMed

Habib, Ashraf S; Moul, Judd W; Polascik, Thomas J; Robertson, Cary N; Roche, Anthony M; White, William D; Hill, Stephen E; Nosnick, Israel; Gan, Tong J

2014-05-01

To compare acute normovolemic hemodilution versus low central venous pressure strategy versus conventional fluid management in reducing intraoperative estimated blood loss, hematocrit drop and need for blood transfusion in patients undergoing radical retropubic prostatectomy under general anesthesia. Patients undergoing radical retropubic prostatectomy under general anesthesia were randomized to conventional fluid management, acute normovolemic hemodilution or low central venous pressure (≤5 mmHg). Treatment effects on estimated blood loss and hematocrit change were tested in multivariable regression models accounting for surgeon, prostate size, and all two-way interactions. Ninety-two patients completed the study. Estimated blood loss (mean ± SD) was significantly lower with low central venous pressure (706 ± 362 ml) compared to acute normovolemic hemodilution (1103 ± 635 ml) and conventional (1051 ± 714 ml) groups (p = 0.0134). There was no difference between the groups in need for blood transfusion, or hematocrit drop from preoperative values. The multivariate model predicting estimated blood loss showed a significant effect of treatment (p = 0.0028) and prostate size (p = 0.0323), accounting for surgeon (p = 0.0013). In the model predicting hematocrit change, accounting for surgeon difference (p = 0.0037), the treatment effect depended on prostate size (p = 0.0007) with the slope of low central venous pressure differing from the other two groups. Hematocrit was predicted to drop more with increased prostate size in acute normovolemic hemodilution and conventional groups but not with low central venous pressure. Limitations include the inability to blind providers to group assignment, possible variability between providers in estimation of blood loss, and the relatively small sample size that was not powered to detect differences between the groups in need for blood transfusion. Maintaining low central venous pressure reduced estimated blood loss compared to conventional fluid management and acute normovolemic hemodilution in patients undergoing radical retropubic prostatectomy but there was no difference in allogeneic blood transfusion between the groups.

Effects of ionizing radiations on a pharmaceutical compound, chloramphenicol

NASA Astrophysics Data System (ADS)

Varshney, L.; Patel, K. M.

1994-05-01

Chloramphenicol, a broad spectrum antibiotic, has been irradiated using Cobalt-60 γ radiation and electron beam at graded radiation doses upto 100 kGy. Several degradation products and free radicals are formed on irradiation. Purity, degradation products, free radicals, discolouration, crystallinity, solubility and entropy of radiation processing have been investigated. Aqueous solutions undergo extensive radiolysis even at low doses. Physico-chemical, microbiological and toxicological tests do not show significant degradation at sterilization dose. High performance liquid chromatography (HPLC), differential scanning calorimetry (DSC), UV-spectrophotometry, diffuse reflectance spectroscopy (DRS) and electron spin resonance spectroscopy (ESR) techniques were employed for the investigations.

Ultrasensitive prostate specific antigen assay following laparoscopic radical prostatectomy--an outcome measure for defining the learning curve.

PubMed

Viney, R; Gommersall, L; Zeif, J; Hayne, D; Shah, Z H; Doherty, A

2009-07-01

Radical retropubic prostatectomy (RRP) performed laparoscopically is a popular treatment with curative intent for organ-confined prostate cancer. After surgery, prostate specific antigen (PSA) levels drop to low levels which can be measured with ultrasensitive assays. This has been described in the literature for open RRP but not for laparoscopic RRP. This paper describes PSA changes in the first 300 consecutive patients undergoing non-robotic laparoscopic RRP by a single surgeon. To use ultrasensitive PSA (uPSA) assays to measure a PSA nadir in patients having laparoscopic radical prostatectomy below levels recorded by standard assays. The aim was to use uPSA nadir at 3 months' post-prostatectomy as an early surrogate end-point of oncological outcome. In so doing, laparoscopic oncological outcomes could then be compared with published results from other open radical prostatectomy series with similar end-points. Furthermore, this end-point could be used in the assessment of the surgeon's learning curve. Prospective, comprehensive, demographic, clinical, biochemical and operative data were collected from all patients undergoing non-robotic laparoscopic RRP. We present data from the first 300 consecutive patients undergoing laparoscopic RRP by a single surgeon. uPSA was measured every 3 months post surgery. Median follow-up was 29 months (minimum 3 months). The likelihood of reaching a uPSA of < or = 0.01 ng/ml at 3 months is 73% for the first 100 patients. This is statistically lower when compared with 83% (P < 0.05) for the second 100 patients and 80% for the third 100 patients (P < 0.05). Overall, 84% of patients with pT2 disease and 66% patients with pT3 disease had a uPSA of < or = 0.01 ng/ml at 3 months. Pre-operative PSA, PSA density and Gleason score were not correlated with outcome as determined by a uPSA of < or = 0.01 ng/ml at 3 months. Positive margins correlate with outcome as determined by a uPSA of < or = 0.01 ng/ml at 3 months but operative time and tumour volume do not (P < 0.05). Attempt at nerve sparing had no adverse effect on achieving a uPSA of < or = 0.01 ng/ml at 3 months. uPSA can be used as an early end-point in the analysis of oncological outcomes after radical prostatectomy. It is one of many measures that can be used in calculating a surgeon's learning curve for laparoscopic radical prostatectomy and in bench-marking performance. With experience, a surgeon can achieve in excess of an 80% chance of obtaining a uPSA nadir of < or = 0.01 ng/ml at 3 months after laparoscopic RRP for a British population. This is equivalent to most published open series.

Pulse radiolysis in model studies toward radiation processing

NASA Astrophysics Data System (ADS)

Von Sonntag, C.; Bothe, E.; Ulanski, P.; Deeble, D. J.

1995-02-01

Using the pulse radiolysis technique, the OH-radical-induced reactions of poly(vinyl alcohol) PVAL, poly(acrylic acid) PAA, poly(methacrylic acid) PMA, and hyaluronic acid have been investigated in dilute aqueous solution. The reactions of the free-radical intermediates were followed by UV-spectroscopy and low-angle laser light-scattering; the scission of the charged polymers was also monitored by conductometry. For more detailed product studies, model systems such as 2,4-dihydroxypentane (for PVAL) and 2,4-dimethyl glutaric acid (for PAA) was also investigated. With PVA, OH-radicals react predominantly by abstraction of an H-atom in α-position to the hydroxyl group (70%). The observed bimolecular decay rate constant of the PVAL-radicals decreases with time. This has been interpreted as being due to an initially fast decay of proximate radicals and a decrease of the probability of such encounters with time. Intramolecular crosslinking (loop formation) predominates at high doses per pulse. In the presence of O 2, peroxyl radicals are formed which in the case of the α-hydroxyperoxyl radicals can eliminate HO 2-radicals in competition with bimolecular decay processes which lead to a fragmentation of the polymer. In PAA, radicals both in α-position (characterized by an absorption near 300 nm) and in β-position to the carboxylate groups are formed in an approximately 1:2 ratio. The lifetime of the radicals increases with increasing electrolytic dissociation of the polymer. The β-radicals undergo a slow (intra- as well as intermolecular) H-abstraction yielding α-radicals, in competition to crosslinking and scission reactions. In PMA only β-radicals are formed. Their fragmentation has been followed by conductometry. In hyaluronic acid, considerable fragmeentation is observed even in the absence of oxygen which, in fact, has some protective effect against this process. Thus free-radical attack on this important biopolymer makes it especially vulnerable with respect to a reduction of its viscosity, and in rheumatic diseases this effect may be the reason for their painfulnes.

Internal to external jugular vein bypass allowing for simultaneous bilateral radical neck dissection.

PubMed

Mourad, Moustafa; Saman, Masoud; Ducic, Yadranko

2015-11-01

The goal of the study was to determine the role of internal jugular vein (IJV) to external jugular vein (EJV) bypass grafting in the setting of bilateral radical neck dissection with IJV sacrifice. The study group consisted of eight patients who underwent bilateral radical neck dissection with IJV sacrifice. Demographic and oncologic parameters were defined for each patient, including age, gender, and pathology. Patients were monitored and evaluated for potential effects of increased intracranial pressure (ICP). Doppler ultrasonic evaluation was performed to assess patency of the site of anastamoses. In all, six patients underwent unilateral bypass grafting, whereas two patients underwent bilateral bypass grafts. Average age at time of surgery was 68.2 (range 56-71). Postoperatively, no sequelae of increased ICP were noted. Follow-up ultrasonic evaluation revealed patent vessels in all patients. We presently report on the use of EJV-to-IJV bypass grafting for all patients undergoing bilateral radical neck dissection for extensive neck disease. 4. © 2015 The American Laryngological, Rhinological and Otological Society, Inc.

Phase transitions and proton ordering in hemimorphite: new insights from single-crystal EPR experiments and DFT calculations

NASA Astrophysics Data System (ADS)

Mao, Mao; Li, Zucheng; Pan, Yuanming

2013-02-01

Single-crystal electron paramagnetic resonance spectra of gamma-ray-irradiated hemimorphite (Mapimi, Durango, Mexico) after storage at room temperature for 3 months, measured from 4 to 275 K, reveal a hydroperoxy radical HO2 derived from the water molecule in the channel. The EPR spectra of the HO2 radical confirm that hemimorphite undergoes two reversible phase transitions at ~98 and ~21 K and allow determinations of its spin Hamiltonian parameters, including superhyperfine coupling constants of two more-distant protons from the neighboring hydroxyl groups, at 110, 85, 40 and 7 K. These EPR results show that the HO2 radical changes in site symmetry from monoclinic to triclinic related to the ordering and rotation of its precursor water molecule in the channel at <98 K. The monoclinic structure of hemimorphite with completely ordered O-H systems at low temperature has been evaluated by both the EPR spectra of the HO2 radical at <21 K and periodic density functional theory calculations.

Reaction between peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

PubMed Central

Sikora, Adam; Zielonka, Jacek; Lopez, Marcos; Dybala-Defratyka, Agnieszka; Joseph, Joy; Marcinek, Andrzej; Kalyanaraman, Balaraman

2013-01-01

Recently we showed that peroxynitrite (ONOO−) reacts directly and rapidly with aromatic and aliphatic boronic acids (k ≈ 106 M−1s−1). Product analyses and substrate consumption data indicated that ONOO− reacts stoichiometrically with boronates, yielding the corresponding phenols as the major product (~85–90%), and the remaining products (10–15%) were proposed to originate from free radical intermediates (phenyl and phenoxyl radicals). Here we investigated in detail the minor, free radical pathway of boronate reaction with ONOO−. The electron paramagnetic resonance (EPR) spin-trapping technique was used to characterize the free radical intermediates formed from the reaction between boronates and ONOO−. Using 2-methyl-2-nitrosopropane (MNP) and 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) spin traps, phenyl radicals were trapped and detected. Although phenoxyl radicals were not detected, the positive effects of molecular oxygen, and inhibitory effects of hydrogen atom donors (acetonitrile, and 2-propanol) and general radical scavengers (GSH, NADH, ascorbic acid and tyrosine) on the formation of phenoxyl radical-derived nitrated product, suggest that phenoxyl radical was formed as the secondary species. We propose that the initial step of the reaction involves the addition of ONOO− to the boron atom in boronates. The anionic intermediate undergoes both heterolytic (major pathway) and homolytic (minor pathway) cleavage of the peroxy (O-O) bond to form phenol and nitrite as a major product (via a non-radical mechanism), or a radical pair PhB(OH)2O•−…•NO2 as a minor product. It is conceivable that phenyl radicals are formed by the fragmentation of PhB(OH)2O•− radical anion. According to the DFT quantum mechanical calculations, the energy barrier for the dissociation of PhB(OH)2O•− radical anion to form phenyl radicals is only a few kcal/mol, suggesting rapid and spontaneous fragmentation of PhB(OH)2O•− radical anion in aqueous media. Biological implications of the minor free radical pathway are discussed in the context of ONOO− detection, using the boronate probes. PMID:21434648

Isoprene Peroxy Radical Dynamics.

PubMed

Teng, Alexander P; Crounse, John D; Wennberg, Paul O

2017-04-19

Approximately 500 Tg of 2-methyl-1,3-butadiene (isoprene) is emitted by deciduous trees each year. Isoprene oxidation in the atmosphere is initiated primarily by addition of hydroxyl radicals (OH) to C 4 or C 1 in a ratio 0.57 ± 0.03 (1σ) to produce two sets of distinct allylic radicals. Oxygen (O 2 ) adds to these allylic radicals either δ (Z or E depending on whether the allylic radical is cis or trans) or β to the OH group forming six distinct peroxy radical isomers. Due to the enhanced stability of the allylic radical, however, these peroxy radicals lose O 2 in competition with bimolecular reactions. In addition, the Z-δ hydroxy peroxy radical isomers undergo unimolecular 1,6 H-shift isomerization. Here, we use isomer-resolved measurements of the reaction products of the peroxy radicals to diagnose this complex chemistry. We find that the ratio of δ to β hydroxy peroxy radicals depends on their bimolecular lifetime (τ bimolecular ). At τ bimolecular ≈ 0.1 s, a transition occurs from a kinetically to a largely thermodynamically controlled distribution at 297 K. Thus, in nature, where τ bimolecular > 10 s, the distribution of isoprene hydroxy peroxy radicals will be controlled primarily by the difference in the relative stability of the peroxy radical isomers. In this regime, β hydroxy peroxy radical isomers comprise ∼95% of the radical pool, a much higher fraction than in the nascent (kinetic) distribution. Intramolecular 1,6 H-shift isomerization of the Z-δ hydroxy peroxy radical isomers produced from OH addition to C 4 is estimated to be ∼4 s -1 at 297 K. While the Z-δ isomer is initially produced in low yield, it is continually reformed via decomposition of the β hydroxy peroxy radicals. As a result, unimolecular chemistry from this isomer contributes about half of the atmospheric fate of the entire pool of peroxy radicals formed via addition of OH at C 4 for typical atmospheric conditions (τ bimolecular = 100 s and T = 25 C). In contrast, unimolecular chemistry following OH addition at C 1 is slower and less important.

Pulse radiolysis studies of 3,5-dimethyl pyrazole derivatives of selenoethers.

PubMed

Barik, Atanu; Singh, Beena G; Sharma, Asmita; Jain, Vimal K; Priyadarsini, K Indira

2014-11-06

One electron redox reaction of two asymmetric 3,5-dimethyl pyrazole derivatives of selenoethers attached to ethanoic acid (DPSeEA) and propionic acid (DPSePA) were studied by pulse radiolysis technique using transient absorption detection. The reaction of the hydroxyl ((•)OH) radical with DPSeEA or DPSePA at pH 7 produced transients absorbing at 500 nm and at 300 nm, respectively. The absorbance at 500 nm increased with increasing parent concentration indicating formation of dimer radical cations. From the absorbance changes, the equilibrium constants for the formation of dimer radical cation of DPSeEA and DPSePA were estimated as 2020 and 1608 M(-1), respectively. The rate constants at pH 7 for the reaction of the (•)OH radical with DPSeEA and DPSePA were determined to be 9.6 × 10(9) and 1.4 × 10(10) M(-1) s(-1), respectively. The dimer radical cation of DPSeEA and DPSePA decayed by first order kinetics with a rate constant of 2.8 × 10(4) and 5.5 × 10(3) s(-1), respectively. The yield of radical cations of DPSeEA and DPSePA were estimated from the secondary electron transfer reaction, which corresponds to 38% and 48% of (•)OH radical yield, respectively. Some fraction of monomer radical cation undergoes decarboxylation reaction, and the yield of decarboxylation was 25% and 20% for DPSeEA and DPSePA, respectively. These results have implication in understanding their antioxidant activity. The reaction of trichloromethyl peroxyl radical, glutathione, and ascorbic acid further support their antioxidant behavior.

Comparative hospital cost-analysis of open and robotic-assisted radical prostatectomy.

PubMed

Tomaszewski, Jeffrey J; Matchett, Jarred C; Davies, Benjamin J; Jackman, Stephen V; Hrebinko, Ronald L; Nelson, Joel B

2012-07-01

To perform a contemporary comparative cost-analysis of robotic-assisted laparoscopic radical prostatectomy (RARP) and open radical retropubic prostatectomy (RRP). All patients undergoing RARP (n = 115) or RRP (n = 358) by 1 of 4 surgeons at a single institution during a 15-month period were retrospectively reviewed. The hospital length of stay (LOS), operative time, hospital charges, reimbursement, and direct and indirect hospital costs were analyzed and compared. The mean LOS between patients undergoing RARP (1.2 ± 0.6 days) and RRP (1.4 ± 0.8 days) was not significantly different. The operating room supply costs per case were almost 7 times greater for RARP ($2852 ± $528) than for RRP ($417 ± $59; P < .05). The ancillary, cardiology, imaging, administrative, laboratory, and pharmacy costs were not significantly different between the 2 approaches. The mean total costs per case for RARP exceeded the total costs for RRP by 62% ($14 006 ± $1641 vs $8686 ± $1989; P < .05). Payment to the hospital from all sources was nearly equivalent: $10 011 for RRP and $9993 for RARP. Therefore, the average profit for each RRP was $1325 and each RARP lost $4013. In the present single-institution analysis, the total actual costs associated with RARP were significantly greater than those for RRP and were attributable to the robotic equipment and supplies. Copyright © 2012 Elsevier Inc. All rights reserved.

Ovarian preservation in locally advanced cervical cancer undergoing neoadjuvant chemotherapy and radical surgery: our experience and analysis of the literature.

PubMed

Signorelli, Mauro; Bogani, Giorgio; Chiappa, Valentina; Ditto, Antonino; Scaffa, Cono; Martinelli, Fabio; Lorusso, Domenica; Raspagliesi, Francesco

2018-03-30

The aim of this study was to estimate the rate of ovarian metastases and recurrences among patients affected by locally advanced stage cancer patients (LACC), undergoing neoadjuvant chemotherapy (NACT) and radical surgery with conservation of ovaries. Retrospective evaluation of consecutive patients affected by LACC (stage IB2- IIB), treated by NACT followed by radical surgery at National Cancer Institute, Milan, Italy, between 1990-2015. Overall, 331 patients were included. Stage at presentation included stage IB2, IIA and IIB in 120 (36.3%), 63 (19%) and 148 (44.7%) patients, respectively. Main histotype was squamous cell carcinoma (n=265, 80.1%) followed by adenocarcinoma/adenosquamous (n=51, 15.4%), and more than half of patients had a grade 3 carcinoma . Overall, 102 (30.8%) women had at least one ovary preserved during surgery, while 229 (69.2%) had bilateral salpingo-oophorectomy. Comparing patients who had ovarian preservation with patients who had not, we observed that the two groups were comparable in terms of baseline characteristics. Survival outcomes were not influenced by ovarian preservation (disease-free (p=0.93) and overall (p=0.65) survivals). One (1%) woman had a localized ovarian recurrence. Our data suggest that ovarian preservation at the time of surgery is a safe option among women with LACC after NACT with no detrimental impact on oncologic outcome. Further prospective studies are warranted.

The Public Good vs. Commercial Interest: Research Scientists in Search of an Accommodation

ERIC Educational Resources Information Center

Wong, Rose H. C.; Westwood, Robert

2010-01-01

The environment for scientific research in public organisations is undergoing radical change, particularly with commercialisation pressures and blurring of the distinction between public and private research. The commercialisation pressures are reflected in government policy frameworks and institutional contexts for scientific work which are…

Managing Strategic Change through TQM: Learning from Failure.

ERIC Educational Resources Information Center

Redman, Tom; Grieves, Jim

1999-01-01

Case study of a manufacturing firm that implemented total quality management (TQM) found that the initiative may have failed because the company was undergoing rapid, radical structural change. Other problems included short-term focus, communication problems, and employee concerns about job security. TQM may be more compatible with continuous…

Counterstatement: Reesponse to Maxine Hairston, "The Winds of Change: Thomas Kuhn and the Revolution in the Teaching of Writing" (with a Reply by Maxine Hairston).

ERIC Educational Resources Information Center

Blom, Thomas E.

1984-01-01

Presents an essay refuting Hairston's proposal that the composition profession is undergoing a radical shift in paradigm to one based more on the writing process. Presents Hairston's defense of her proposal. (HTH)

Transformations in Higher Education: Online Distance Learning

ERIC Educational Resources Information Center

Kobayashi, Victor

2002-01-01

Higher education is undergoing radical shifts that are part of the larger wave of changes taking place in the society. The transformation affects all sectors of higher education, especially distance learning and how it relates to the University's regular offerings. In this article, the author begins with clarifying the terms commonly associated…

Radical covalent organic frameworks: a general strategy to immobilize open-accessible polyradicals for high-performance capacitive energy storage.

PubMed

Xu, Fei; Xu, Hong; Chen, Xiong; Wu, Dingcai; Wu, Yang; Liu, Hao; Gu, Cheng; Fu, Ruowen; Jiang, Donglin

2015-06-01

Ordered π-columns and open nanochannels found in covalent organic frameworks (COFs) could render them able to store electric energy. However, the synthetic difficulty in achieving redox-active skeletons has thus far restricted their potential for energy storage. A general strategy is presented for converting a conventional COF into an outstanding platform for energy storage through post-synthetic functionalization with organic radicals. The radical frameworks with openly accessible polyradicals immobilized on the pore walls undergo rapid and reversible redox reactions, leading to capacitive energy storage with high capacitance, high-rate kinetics, and robust cycle stability. The results suggest that channel-wall functional engineering with redox-active species will be a facile and versatile strategy to explore COFs for energy storage. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

NASA Astrophysics Data System (ADS)

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-09-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions.

Multi-Modal Preemptive Analgesia With Pregabalin, Acetaminophen, Naproxen, and Dextromethorphan in Radical Neck Dissection Surgery: A Randomized Clinical Trial

PubMed Central

Amiri, Hamid Reza; Mirzaei, Mojtaba; Beig Mohammadi, Mohammad Taghi; Tavakoli, Farhad

2016-01-01

Background Preemptive analgesia may be considered as a method not only to alleviate postoperative pain but also to decrease analgesic consumption. Different regimens are suggested, but there is currently no standard. Objectives The aim was to measure the efficacy of preemptive analgesia with pregabalin, acetaminophen, naproxen, and dextromethorphan in radical neck dissection surgery for reducing the intensity of pain and morphine consumption. Patients and Methods This study was conducted as a randomized double-blind clinical trial. Eighty adult patients (18 to 60 years of age) under the American society of anesthesiologists (ASA) physical status I and II undergoing elective radical neck dissection were enrolled. Patients were randomized into two groups of 40 with a simple randomization method. The case group received a combination of 15 mg/kg acetaminophen, 2.5 mg/kg pregabalin, 7 mg/kg naproxen, and 0.3 mg/kg dextromethorphan administered orally one hour prior to surgery. Postoperative pain was assessed with the universal pain assessment tool (UPAT) at 0, 2, 4, 6, 12, and 24 hours after surgery. Subjects received morphine based on postoperative pain control protocol. Total administered morphine doses were noted. Results Postoperative pain rates at 0, 2, 4, 6, 12, and 24 hours after surgery were significantly lower for the case group than the control group (P values = 0.014, 0.003, 0.00, 0.00, and 0.00, respectively). Total morphine doses for the preemptive analgesia group were 45% lower than those of the other group. Side effects were similar for both groups. Conclusions A single preoperative oral dose of pregabalin, acetaminophen, dextromethorphan, and naproxen one hour before surgery is an effective method for reducing postoperative pain and morphine consumption in patients undergoing radical neck dissection. PMID:27843771

Factors influencing the operating time for single-port laparoscopic radical nephrectomy: focus on the anatomy and distribution of the renal artery and vein.

PubMed

Matsumoto, Kazuhiro; Miyajima, Akira; Fukumoto, Keishiro; Komatsuda, Akari; Niwa, Naoya; Hattori, Seiya; Takeda, Toshikazu; Kikuchi, Eiji; Asanuma, Hiroshi; Oya, Mototsugu

2017-10-01

It is considered that laparoscopic single-site surgery should be performed by specially trained surgeons because of the technical difficulty in using special instruments through limited access. We investigated suitable patients for single-port laparoscopic radical nephrectomy, focusing on the anatomy and distribution of the renal artery and vein. This retrospective study was conducted in 52 consecutive patients who underwent single-port radical nephrectomy by the transperitoneal approach. In patients undergoing right nephrectomy, a 2-mm port was added for liver retraction. We retrospectively re-evaluated all of the recorded surgical videos and preoperative computed tomography images. The pneumoperitoneum time (PT) was used as an objective index of surgical difficulty. The PT was significantly shorter for right nephrectomy than left nephrectomy (94 vs. 123 min, P = 0.004). With left nephrectomy, dissection of the spleno-renal ligament to mobilize the spleen medially required additional time. Also, the left renal vein could only be divided after securing the adrenal, gonadal and lumbar veins. In patients whose renal artery was located cranial to the renal vein, PT tended to be longer than in the other patients (131 vs. 108 min, P = 0.070). In patients with a superior renal artery, the inferior renal vein invariably covered the artery and made it difficult to ligate the renal artery via the umbilical approach at the first procedure. These findings indicate that patients undergoing right nephrectomy in whom the renal artery is not located cranial to the renal vein are suitable for single-port laparoscopic radical nephrectomy. © The Author 2017. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com

Why Nature Uses Radical SAM Enzymes so Widely: Electron Nuclear Double Resonance Studies of Lysine 2,3-Aminomutase Show the 5'-dAdo• "Free Radical" Is Never Free.

PubMed

Horitani, Masaki; Byer, Amanda S; Shisler, Krista A; Chandra, Tilak; Broderick, Joan B; Hoffman, Brian M

2015-06-10

Lysine 2,3-aminomutase (LAM) is a radical S-adenosyl-L-methionine (SAM) enzyme and, like other members of this superfamily, LAM utilizes radical-generating machinery comprising SAM anchored to the unique Fe of a [4Fe-4S] cluster via a classical five-membered N,O chelate ring. Catalysis is initiated by reductive cleavage of the SAM S-C5' bond, which creates the highly reactive 5'-deoxyadenosyl radical (5'-dAdo•), the same radical generated by homolytic Co-C bond cleavage in B12 radical enzymes. The SAM surrogate S-3',4'-anhydroadenosyl-L-methionine (anSAM) can replace SAM as a cofactor in the isomerization of L-α-lysine to L-β-lysine by LAM, via the stable allylic anhydroadenosyl radical (anAdo•). Here electron nuclear double resonance (ENDOR) spectroscopy of the anAdo• radical in the presence of (13)C, (2)H, and (15)N-labeled lysine completes the picture of how the active site of LAM from Clostridium subterminale SB4 "tames" the 5'-dAdo• radical, preventing it from carrying out harmful side reactions: this "free radical" in LAM is never free. The low steric demands of the radical-generating [4Fe-4S]/SAM construct allow the substrate target to bind adjacent to the S-C5' bond, thereby enabling the 5'-dAdo• radical created by cleavage of this bond to react with its partners by undergoing small motions, ∼0.6 Å toward the target and ∼1.5 Å overall, that are controlled by tight van der Waals contact with its partners. We suggest that the accessibility to substrate and ready control of the reactive C5' radical, with "van der Waals control" of small motions throughout the catalytic cycle, is common within the radical SAM enzyme superfamily and is a major reason why these enzymes are the preferred means of initiating radical reactions in nature.

Solitary fibrous tumor of the prostate: case report and review of the literature.

PubMed

Moureau-Zabotto, Laurence; Chetaille, Bruno; Bladou, Franck; Dauvergne, Pierre-Yves; Marcy, Myriam; Perrot, Delphine; Guiramand, Jérôme; Sarran, Anthony; Bertucci, François

2012-01-01

Solitary fibrous tumor (SFT), usually described in the pleura, is exceedingly rare in the prostate. We report a 60-year-old man with prostatic SFT revealed by obstructive urinary symptoms, and detected by ultrasonography. Computed tomography (CT) and magnetic resonance imaging suggested a prostatic origin. CT-guided tumor biopsy diagnosed a SFT. A cystoprostatectomy was performed. Pathologic examination showed a 15-cm tumor arising from the prostate and showing histological criteria suggestive of aggressiveness. The surgical resection margins were tumor-free. The patient was then regularly monitored and is still alive in complete remission, 28 months after surgery. In conclusion, we report a new exceptional case of prostatic SFT. We review the literature and discuss the challenging issues of misdiagnosis, prognosis and treatment.

Solitary Fibrous Tumor of the Prostate: Case Report and Review of the Literature

PubMed Central

Moureau-Zabotto, Laurence; Chetaille, Bruno; Bladou, Franck; Dauvergne, Pierre-Yves; Marcy, Myriam; Perrot, Delphine; Guiramand, Jérôme; Sarran, Anthony; Bertucci, François

2012-01-01

Solitary fibrous tumor (SFT), usually described in the pleura, is exceedingly rare in the prostate. We report a 60-year-old man with prostatic SFT revealed by obstructive urinary symptoms, and detected by ultrasonography. Computed tomography (CT) and magnetic resonance imaging suggested a prostatic origin. CT-guided tumor biopsy diagnosed a SFT. A cystoprostatectomy was performed. Pathologic examination showed a 15-cm tumor arising from the prostate and showing histological criteria suggestive of aggressiveness. The surgical resection margins were tumor-free. The patient was then regularly monitored and is still alive in complete remission, 28 months after surgery. In conclusion, we report a new exceptional case of prostatic SFT. We review the literature and discuss the challenging issues of misdiagnosis, prognosis and treatment. PMID:22379473

Geometrical isomerization of carotenoids mediated by cation radical/dication formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, G.; Wei, C.C.; Jeevarajan, A.S.

1996-03-28

Electrochemical oxidation of all-trans-canthaxanthin and {beta}-carotene in dichloromethane leads to significant trans-to-cis isomerization, with cis isomers accounting for about 40% of the products formed. The electrochemically generated isomers were separated by reverse-phase high-performance liquid chromatography and identified as 9-cis, 13-cis, 15-cis, and 9,13-di-cis isomers of the carotenoids by {sup 1}H-NMR spectroscopy and optical spectroscopy (Q ratio). The results of simultaneous bulk electrolysis and optical absorption spectroscopy indicate the following isomerization mechanism: the all-trans cation radicals and/or dications formed by electrochemical oxidation of all-trans-carotenoids can easily undergo geometrical isomerization to form cis cation radicals and/or dications. The latter are converted bymore » the comproportionation equilibrium to cation radicals which are then transformed to neutral cis-carotenoids by exchanging one electron with neutral carotenoids. AM1 molecular orbital calculations, which show that the energy barriers of configurational transformation from trans to cis are much lower in the cation radical and dication species than in the neutral molecule, strongly support the first step of this mechanism. 36 refs., 5 figs., 2 tabs.« less

Utility of an Internal Retractor (EndoGrab) for the Management of the Vesicouterine Ligament during Laparoscopic Radical Hysterectomy.

PubMed

Kobayashi, Eiji; Kakuda, Mamoru; Tanaka, Yusuke; Morimoto, Akiko; Egawa-Takata, Tomomi; Matsuzaki, Shinya; Ueda, Yutaka; Yoshino, Kiyoshi; Kimura, Tadashi

2016-01-01

The study aims to prevent serious urologic injury during a radical hysterectomy; we propose that one of the most important procedural steps is the careful management of the vesicouterine ligament (VUL). Between January 2013 and October 2014, we used a novel internal retractor in 17 patients undergoing a laparoscopic radical hysterectomy (LRH) for early-stage cervical cancer to obtain and secure a better surgical view. For management of the VUL during the laparoscopic procedure, we routinely used an internal retractor (EndoGrab; Virtual Ports, Misgav, Israel) and vessel tape to reposition the ureter in a safe lateral-caudal direction. Using an EndoGrab, we were easily able to reproduce a suitable surgical view that simulated the one obtained by an abdominal route for radical hysterectomy. Using this improved laparoscopic procedure, we completed radical hysterectomies in all 17 cases without a ureteral injury complication. Our modified method using an EndoGrab is effective for the prevention of ureteral injury during a LRH, and its ease of use makes it suitable even for those surgeons early in their laparoscopic learning curve. © 2016 S. Karger AG, Basel.

Quality of Life in Patients with Bladder Cancer Undergoing Ileal Conduit: A Comparison of Women Versus Men

PubMed Central

SIRACUSANO, SALVATORE; D’ELIA, CAROLINA; CERRUTO, MARIA ANGELA; SALEH, OMAR; SERNI, SERGIO; GACCI, MAURO; CICILIATO, STEFANO; SIMONATO, ALCHIEDE; PORCARO, ANTONIO; DE MARCO, VINCENZO; TALAMINI, RENATO; TOFFOLI, LAURA; VISALLI, FRANCESCO; NIERO, MAURO; LONARDI, CRISTINA; IMBIMBO, CIRO; VERZE, PAOLO; MIRONE, VINCENZO; RACIOPPI, MARCO; IAFRATE, MASSIMO; CACCIAMANI, GIOVANNI; DE MARCHI, DAVIDE; BASSI, PIERFRANCESCO; ARTIBANI, WALTER

2018-01-01

Background/Aim: Studies comparing health-related quality of life (HR-QoL) between patients who underwent radical cystectomy (RC) and those who underwent a different form of urinary diversion has not reached yet univocal and reliable conclusions. The aim of our study was to evaluate bladder-specific long-term HR-QoL after radical cystectomy and ileal conduit. Patients and Methods: A multicenter study was carried out on 145 consecutive patients (112 males and 33 females) undergoing RC and ileal conduit (IC). HR-QoL assessment was conducted using Italian versions of European Organisation for Research and Treatment of Cancer QLQ-C30 and EORTC BLM-30 questionnaires. Results: Our data showed that women who underwent IC presented greater problems than men in cognitive functioning (mean score±SD: 77.3±27.9 vs. 87.8±18.6) as well in future perspective (score: 42.4±34.4 vs. 21.9±24.6). Nevertheless, men undergoing IC had more problems in sexual functioning than women (score: 23.3±24.5 vs. 7.0±20.3) (all p<0.05). Conclusion: In our series, female patients presented a greater burden than male patients in cognitive functioning as well in future perspective, but lower concerns with regard to sexual function. PMID:29275311

Quality of Life in Patients with Bladder Cancer Undergoing Ileal Conduit: A Comparison of Women Versus Men.

PubMed

Siracusano, Salvatore; D'Elia, Carolina; Cerruto, Maria Angela; Saleh, Omar; Serni, Sergio; Gacci, Mauro; Ciciliato, Stefano; Simonato, Alchiede; Porcaro, Antonio; DE Marco, Vincenzo; Talamini, Renato; Toffoli, Laura; Visalli, Francesco; Niero, Mauro; Lonardi, Cristina; Imbimbo, Ciro; Verze, Paolo; Mirone, Vincenzo; Racioppi, Marco; Iafrate, Massimo; Cacciamani, Giovanni; DE Marchi, Davide; Bassi, Pierfrancesco; Artibani, Walter

2018-01-01

Studies comparing health-related quality of life (HR-QoL) between patients who underwent radical cystectomy (RC) and those who underwent a different form of urinary diversion has not reached yet univocal and reliable conclusions. The aim of our study was to evaluate bladder-specific long-term HR-QoL after radical cystectomy and ileal conduit. A multicenter study was carried out on 145 consecutive patients (112 males and 33 females) undergoing RC and ileal conduit (IC). HR-QoL assessment was conducted using Italian versions of European Organisation for Research and Treatment of Cancer QLQ-C30 and EORTC BLM-30 questionnaires. Our data showed that women who underwent IC presented greater problems than men in cognitive functioning (mean score±SD: 77.3±27.9 vs. 87.8±18.6) as well in future perspective (score: 42.4±34.4 vs. 21.9±24.6). Nevertheless, men undergoing IC had more problems in sexual functioning than women (score: 23.3±24.5 vs. 7.0±20.3) (all p<0.05). In our series, female patients presented a greater burden than male patients in cognitive functioning as well in future perspective, but lower concerns with regard to sexual function. Copyright© 2018, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

Browns in Anger: The Overlooked Minority.

ERIC Educational Resources Information Center

Lara-Braud, Jorge

This speech advocates that Mexican-Americans must undergo a process of radicalization to attempt to transfer anger from deeds to words. This minority is losing faith in speech as a means of redress, but corrective measures should come through dialogue and not collision. Few Mixican Americans designated themselves "browns" a year ago--but it is now…

Becoming a Learning Organization: A Precondition for Person Centered Services to People with Learning Difficulties.

ERIC Educational Resources Information Center

Iles, Ian K.

2003-01-01

This article suggests that services for people with intellectual disabilities in England will need to undergo radical revision as agencies strive to implement person centered planning as described in the White Paper, "Valuing People." It further suggests that services need to become learning organizations, committed to values of…

Nonequilibrium Theory: Implications for Educational Systems Undergoing Radical Change in Eastern Europe.

ERIC Educational Resources Information Center

Rust, Val D.

The change processes involving schools that are currently experiencing turbulent social reconstruction in eastern Europe are examined in this paper, which calls for the development of a new paradigm for social change. The first section describes recent educational reform activities and their flaws in three eastern European countries--Russia,…

Thermochemical and kinetic analyses on oxidation of isobutenyl radical and 2-hydroperoxymethyl-2-propenyl radical.

PubMed

Zheng, X L; Sun, H Y; Law, C K

2005-10-13

In recognition of the importance of the isobutene oxidation reaction in the preignition chemistry associated with engine knock, the thermochemistry, chemical reaction pathways, and reaction kinetics of the isobutenyl radical oxidation at low to intermediate temperature range were computationally studied, focusing on both the first and the second O2 addition to the isobutenyl radical. The geometries of reactants, important intermediates, transition states, and products in the isobutenyl radical oxidation system were optimized at the B3LYP/6-311G(d,p) and MP2(full)/6-31G(d) levels, and the thermochemical properties were determined on the basis of ab initio, density functional theory, and statistical mechanics. Enthalpies of formation for several important intermediates were calculated using isodesmic reactions at the DFT and the CBS-QB3 levels. The kinetic analysis of the first O2 addition to the isobutenyl radical was performed using enthalpies at the CBS-QB3 and G3(MP2) levels. The reaction forms a chemically activated isobutenyl peroxy adduct which can be stabilized, dissociate back to reactants, cyclize to cyclic peroxide-alkyl radicals, and isomerize to the 2-hydroperoxymethyl-2-propenyl radical that further undergoes another O2 addition. The reaction channels for isomerization and cyclization and further dissociation on this second O2 addition were analyzed using enthalpies at the DFT level with energy corrections based on similar reaction channels for the first O2 addition. The high-pressure limit rate constants for each reaction channel were determined as functions of temperature by the canonical transition state theory for further kinetic model development.

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

PubMed Central

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-01-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions. PMID:27671606

Water-Network Mediated, Electron Induced Proton Transfer in Anionic [C5H5N\\cdot(H2O)n]- Clusters: Size Dependent Formation of the Pyridinium Radical for n ≥ 3

NASA Astrophysics Data System (ADS)

DeBlase, Andrew F.; Weddle, Gary H.; Archer, Kaye A.; Jordan, Kenneth D.; Johnson, Mark

2015-06-01

As an isolated species, the radical anion of pyridine (Py-) exists as an unstable transient negative ion, while in aqueous environments it is known to undergo rapid protonation to form the neutral pyridinium radical [PyH(0)] along with hydroxide. Furthermore, the negative adiabatic electron affinity (AEA) of Py- can become diminished by the solvation energy associated with cluster formation. In this work, we focus on the hydrates [Py\\cdot(H2O)n]- with n = 3-5 and elucidate the structures of these water clusters using a combination of vibrational predissociation and photoelectron spectroscopies. We show that H-trasfer to form PyH(0) occurs in these clusters by the infrared signature of the nascent hydroxide ion and by the sharp bending vibrations of aromatic ring CH bending.

Is simple nephrectomy truly simple? Comparison with the radical alternative.

PubMed

Connolly, S S; O'Brien, M Frank; Kunni, I M; Phelan, E; Conroy, R; Thornhill, J A; Grainger, R

2011-03-01

The Oxford English dictionary defines the term "simple" as "easily done" and "uncomplicated". We tested the validity of this terminology in relation to open nephrectomy surgery. Retrospective review of 215 patients undergoing open, simple (n = 89) or radical (n = 126) nephrectomy in a single university-affiliated institution between 1998 and 2002. Operative time (OT), estimated blood loss (EBL), operative complications (OC) and length of stay in hospital (LOS) were analysed. Statistical analysis employed Fisher's exact test and Stata Release 8.2. Simple nephrectomy was associated with shorter OT (mean 126 vs. 144 min; p = 0.002), reduced EBL (mean 729 vs. 859 cc; p = 0.472), lower OC (9 vs. 17%; 0.087), and more brief LOS (mean 6 vs. 8 days; p < 0.001). All parameters suggest favourable outcome for the simple nephrectomy group, supporting the use of this terminology. This implies "simple" nephrectomies are truly easier to perform with less complication than their radical counterpart.

Chapter 8: Pyrolysis Mechanisms of Lignin Model Compounds Using a Heated Micro-Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robichaud, David J.; Nimlos, Mark R.; Ellison, G. Barney

2015-10-03

Lignin is an important component of biomass, and the decomposition of its thermal deconstruction products is important in pyrolysis and gasification. In this chapter, we investigate the unimolecular pyrolysis chemistry through the use of singly and doubly substituted benzene molecules that are model compounds representative of lignin and its primary pyrolysis products. These model compounds are decomposed in a heated micro-reactor, and the products, including radicals and unstable intermediates, are measured using photoionization mass spectrometry and matrix isolation infrared spectroscopy. We show that the unimolecular chemistry can yield insight into the initial decomposition of these species. At pyrolysis and gasificationmore » severities, singly substituted benzenes typically undergo bond scission and elimination reactions to form radicals. Some require radical-driven chain reactions. For doubly substituted benzenes, proximity effects of the substituents can change the reaction pathways.« less

Why Nature Uses Radical SAM Enzymes so Widely: Electron Nuclear Double Resonance Studies of Lysine 2,3-Aminomutase Show the 5′-dAdo• “Free Radical” Is Never Free

PubMed Central

Horitani, Masaki; Byer, Amanda S.; Shisler, Krista A.; Chandra, Tilak; Broderick, Joan B.; Hoffman, Brian M.

2015-01-01

Lysine 2,3-aminomutase (LAM) is a radical S-adenosyl-L-methionine (SAM) enzyme and, like other members of this superfamily, LAM utilizes radical-generating machinery comprising SAM anchored to the unique Fe of a [4Fe-4S] cluster via a classical five-membered N,O chelate ring. Catalysis is initiated by reductive cleavage of the SAM S–C5′ bond, which creates the highly reactive 5′-deoxyadenosyl radical (5′-dAdo•), the same radical generated by homolytic Co–C bond cleavage in B12 radical enzymes. The SAM surrogate S-3′,4′-anhydroadenosyl-L-methionine (anSAM) can replace SAM as a cofactor in the isomerization of L-α-lysine to L-β-lysine by LAM, via the stable allylic anhydroadenosyl radical (anAdo•). Here electron nuclear double resonance (ENDOR) spectroscopy of the anAdo• radical in the presence of 13C, 2H, and 15N-labeled lysine completes the picture of how the active site of LAM from Clostridium subterminale SB4 “tames” the 5′-dAdo• radical, preventing it from carrying out harmful side reactions: this “free radical” in LAM is never free. The low steric demands of the radical-generating [4Fe-4S]/SAM construct allow the substrate target to bind adjacent to the S–C5′ bond, thereby enabling the 5′-dAdo• radical created by cleavage of this bond to react with its partners by undergoing small motions, ~0.6 Å toward the target and ~1.5 Å overall, that are controlled by tight van der Waals contact with its partners. We suggest that the accessibility to substrate and ready control of the reactive C5′ radical, with “van der Waals control” of small motions throughout the catalytic cycle, is common within the radical SAM enzyme superfamily and is a major reason why these enzymes are the preferred means of initiating radical reactions in nature. PMID:25923449

Effect of preemptive analgesia with parecoxib sodium in patients undergoing radical resection of lung cancer.

PubMed

Lu, Jing; Liu, Zhongkai; Xia, Kunpeng; Shao, Changzhong; Guo, Shengdong; Wang, Shenggang; Li, Kezhong

2015-01-01

To discuss the effect of preemptive analgesia with parecoxib sodium in patients undergoing radical resection of lung cancer. 115 cases of lung cancer patients with American society of anesthesiologists class (ASA) grade I~II who received selective operation were randomly divided into the research group and the control group. The research group patients were given preoperative parecoxib sodium 40 mg plus postoperative normal saline 2 ml, while the control group patients were treated with preoperative normal saline 2 ml plus postoperative parecoxib sodium 40 mg. The pain condition at postoperative 1, 2, 4, 8, 12, 24 and 48 h were evaluated by visual analogue scale (VAS), and emergence agitation was tested by agitation score. Finally there were 56 cases and 57 cases can be used for evaluation in the research group and control group. The VAS scores after 1, 2, 4, 8, 12, 24 and 48 h in the research group and control group were [2.23±0.45, 2.35±0.48, 2.51±0.51, 2.41±0.45, 2.28±0.42, 2.16±0.39, 2.11±0.40] and [3.80±0.62, 4.01±0.64, 4.31±0.67, 4.10±0.64, 3.65±0.70, 3.12±0.66, 2.46±0.53], respectively. The research group were obviously lower than the control group, the difference were statistically significant (P<0.05). The rate of agitation was 24.44% (11/56) in the research group, significantly lower than the control group of 59.65% (34/57) (P<0.05). Preemptive analgesia with parecoxib sodium can obviously relieve acute pain using in patients undergoing radical resection of lung cancer, and is helpful to reduce the incidence of emergence agitation.

Impact of Blood Transfusions on Survival of Locally Advanced Cervical Cancer Patients Undergoing Neoadjuvant Chemotherapy Plus Radical Surgery.

PubMed

Bogani, Giorgio; Ditto, Antonino; Martinelli, Fabio; Signorelli, Mauro; Chiappa, Valentina; Lopez, Carlos; Indini, Alice; Leone Roberti Maggiore, Umberto; Sabatucci, Ilaria; Lorusso, Domenica; Raspagliesi, Francesco

2017-03-01

Transfusions represent one of the main progresses of modern medicine. However, accumulating evidence supports that transfusions correlate with worse survival outcomes in patients affected by solid cancers. In the present study, we aimed to investigate the effects of perioperative blood transfusion in locally advanced cervical cancer. Data of consecutive patients affected by locally advanced cervical cancer scheduled to undergo neoadjuvant chemotherapy plus radical surgery were retrospectively searched to test the impact of perioperative transfusions on survival outcomes. Five-year survival outcomes were evaluated using Kaplan-Meier and Cox models. The study included 275 patients. Overall, 170 (62%) patients had blood transfusion. Via univariate analysis, we observed that transfusion correlated with an increased risk of developing recurrence (hazard ratio [HR], 2.2; 95% confidence interval [CI], 1.09-4.40; P = 0.02). Other factors associated with 5-year disease-free survival were noncomplete clinical response after neoadjuvant chemotherapy (HR, 2.99; 95% CI, 0.92-9.63; P = 0.06) and pathological (P = 0.03) response at neoadjuvant chemotherapy as well as parametrial (P = 0.004), vaginal (P < 0.001), and lymph node (P = 0.002) involvements. However, via multivariate analysis, only vaginal (HR, 3.07; 95% CI, 1.20-7.85; P = 0.01) and lymph node involvements (HR, 2.4; 95% CI, 1.00-6.06; P = 0.05) correlate with worse disease-free survival. No association with worse outcomes was observed for patients undergoing blood transfusion (HR, 2.71; 95% CI, 0.91-8.03; P = 0.07). Looking at factors influencing overall survival, we observed that lymph node status (P = 0.01) and vaginal involvement (P = 0.06) were independently associated with survival. The role of blood transfusions in increasing the risk of developing recurrence in LAAC patients treated by neoadjuvant chemotherapy plus radical surgery remains unclear; further prospective studies are warranted.

How often parametrial involvement leads to post-operative adjuvant treatment in locally advanced cervical cancer after neoadjuvant chemotherapy and type C radical hysterectomy?

PubMed

Martinelli, F; Bogani, G; Ditto, A; Carcangiu, M; Papadia, A; Lecce, F; Chiappa, V; Lorusso, D; Raspagliesi, F

2015-08-01

Parametrial involvement (PMI) is one of the most important factors influencing prognosis in locally advanced stage cervical cancer (LACC) patients. We aimed to evaluate PMI rate among LACC patients undergoing neoadjuvant chemotherapy (NACT), thus evaluating the utility of parametrectomy in tailor adjuvant treatments. Retrospective evaluation of consecutive 275 patients affected by LACC (IB2-IIB), undergoing NACT followed by type C/class III radical hysterectomy. Basic descriptive statistics, univariate and multivariate analyses were applied in order to identify factors predicting PMI. Survival outcomes were assessed using Kaplan-Meier and Cox models. PMI was detected in 37 (13%) patients: it was associated with vaginal involvement, lymph node positivity and both in 10 (4%), 5 (2%) and 12 (4%) patients, respectively; while PMI alone was observed in only 10 (4%) patients. Among this latter group, adjuvant treatment was delivered in 3 (1%) patients on the basis of pure PMI; while the remaining patients had other characteristics driving adjuvant treatment. Considering factors predicting PMI we observed that only suboptimal pathological responses (OR: 1.11; 95% CI: 1.01, 1.22) and vaginal involvement (OR: 1.29 (95%) CI: 1.17, 1.44) were independently associated with PMI. PMI did not correlate with survival (HR: 2.0; 95% CI: 0.82, 4.89); while clinical response to NACT (HR: 3.35; 95% CI: 1.59, 7.04), vaginal involvement (HR: 2.38; 95% CI: 1.12, 5.02) and lymph nodes positivity (HR: 3.47; 95% CI: 1.62, 7.41), independently correlated with worse survival outcomes. Our data suggest that PMI had a limited role on the choice to administer adjuvant treatment, thus supporting the potential embrace of less radical surgery in LACC patients undergoing NACT. Further prospective studies are warranted. Copyright © 2015 Elsevier Ltd. All rights reserved.

Does penile rehabilitation have a role in the treatment of erectile dysfunction following radical prostatectomy?

PubMed Central

Blecher, Gideon; Almekaty, Khaled; Kalejaiye, Odunayo; Minhas, Suks

2017-01-01

In men undergoing radical treatment for prostate cancer, erectile function is one of the most important health-related quality-of-life outcomes influencing patient choice in treatment. Penile rehabilitation has emerged as a therapeutic measure to prevent erectile dysfunction and expedite return of erectile function after radical prostatectomy. Penile rehabilitation involves a program designed to increase the likelihood of return to baseline-level erectile function, as opposed to treatment, which implies the therapeutic treatment of symptoms, a key component of post–radical prostatectomy management. Several pathological theories form the basis for rehabilitation, and a plethora of treatments are currently in widespread use. However, whilst there is some evidence supporting the concept of penile rehabilitation from animal studies, randomised controlled trials are contradictory in outcomes. Similarly, urological guidelines are conflicted in terms of recommendations. Furthermore, it is clear that in spite of the lack of evidence for the role of penile rehabilitation, many urologists continue to employ some form of rehabilitation in their patients after radical prostatectomy. This is a significant burden to health resources in public-funded health economies, and no effective cost-benefit analysis has been undertaken to support this practice. Thus, further research is warranted to provide both scientific and clinical evidence for this contemporary practice and the development of preventative strategies in treating erectile dysfunction after radical prostatectomy. PMID:29152231

Radiolytic degradation of 4-nitrophenol in aqueous solutions: Pulse and steady state radiolysis study

NASA Astrophysics Data System (ADS)

Biswal, Jayashree; Paul, Jhimli; Naik, D. B.; Sarkar, S. K.; Sabharwal, S.

2013-04-01

The radiation induced degradation of 4-nitrophenol (4-NP) has been studied by gamma irradiation, while the reactivity and spectral features of the short lived transients formed by reaction with primary transient radicals at different pHs has been investigated by pulse radiolysis technique. In steady state radiolysis a dose of 4.4 k Gy is able to degrade 98% of 1×10-4 mol dm-3 4-NP. 4-NP has pKa at 7.1, above which it is present in the anionic form. At pH 5.2, •OH and N3• radicals were found to react with 4-NP with rate constants of 4.1×109 dm3 mol-1 s-1 and 2.8×108 dm3 mol-1 s-1, respectively. Differences in the absorption spectra of species formed in the reactions of 4-NP with •OH and N3• radicals suggested that •OH radicals add to the aromatic ring of 4-NP along with electron transfer reaction, whereas N3• radicals undergo only electron transfer reaction. At pH 9.2, rate constants for the reaction of •OH radicals with 4-NP was found to be higher by a factor of 2 compared to that at pH 5.2. This has been assigned to the deprotonation of 4-NP at pH 9.2.

Does penile rehabilitation have a role in the treatment of erectile dysfunction following radical prostatectomy?

PubMed

Blecher, Gideon; Almekaty, Khaled; Kalejaiye, Odunayo; Minhas, Suks

2017-01-01

In men undergoing radical treatment for prostate cancer, erectile function is one of the most important health-related quality-of-life outcomes influencing patient choice in treatment. Penile rehabilitation has emerged as a therapeutic measure to prevent erectile dysfunction and expedite return of erectile function after radical prostatectomy. Penile rehabilitation involves a program designed to increase the likelihood of return to baseline-level erectile function, as opposed to treatment, which implies the therapeutic treatment of symptoms, a key component of post-radical prostatectomy management. Several pathological theories form the basis for rehabilitation, and a plethora of treatments are currently in widespread use. However, whilst there is some evidence supporting the concept of penile rehabilitation from animal studies, randomised controlled trials are contradictory in outcomes. Similarly, urological guidelines are conflicted in terms of recommendations. Furthermore, it is clear that in spite of the lack of evidence for the role of penile rehabilitation, many urologists continue to employ some form of rehabilitation in their patients after radical prostatectomy. This is a significant burden to health resources in public-funded health economies, and no effective cost-benefit analysis has been undertaken to support this practice. Thus, further research is warranted to provide both scientific and clinical evidence for this contemporary practice and the development of preventative strategies in treating erectile dysfunction after radical prostatectomy.

Initial experience with ketamine-based analgesia in patients undergoing robotic radical cystectomy and diversion.

PubMed

Jacobsohn, Kenneth; Davis, Tanya D; El-Arabi, Ahmad M; Tlachac, Jonathan; Langenstroer, Peter; O'Connor, R Corey; Guralnick, Michael L; See, William A; Schlosser, Robert

2015-01-01

We instituted a ketamine-predominant analgesic regimen in the peri- and postoperative periods to limit the effects of narcotic analgesia on bowel function in patients undergoing radical cystectomy. The primary end points of interest were time to return of bowel function, time to discharge, and efficacy of the analgesic regimen. We performed a retrospective chart review of patients undergoing robotic-assisted laparoscopic cystectomy (RARC) with urinary diversion by a single surgeon at our institution from January 1, 2011 to June 30, 2012. Patients receiving the opioid-minimizing ketamine protocol were compared to a cohort of patients undergoing RARC with an opioid-predominant analgesic regimen. In total, 15 patients (Group A) were included in the ketamine-predominant regimen and 25 patients (Group B) in the opioid-predominant control group. Three patients (19%) in Group A discontinued the protocol due to ketamine side effects. The mean time to bowel movement and length of stay in Group A versus Group B was 3 versus 6 days (p < 0.001), and 4 versus 8 days, respectively (p < 0.001). Group A patients received an average of 13.0 mg of morphine versus 97.5 mg in Group B (p < 0.001). Patients who received our ketamine pain control regimen had a shorter time to return of bowel function and length of hospitalization after RARC. Our study has its limitations as a retrospective, single surgeon, single institution study and the non-randomization of patients. Notwithstanding these limitations, this study was not designed to show inferiority of one approach, but instead to show that our protocol is safe and efficacious, warranting further study in a prospective fashion.

Intraoperative Conversion From Partial to Radical Nephrectomy: Incidence, Predictive Factors, and Outcomes.

PubMed

Petros, Firas G; Keskin, Sarp K; Yu, Kai-Jie; Li, Roger; Metcalfe, Michael J; Fellman, Bryan M; Chang, Courtney M; Gu, Cindy; Tamboli, Pheroze; Matin, Surena F; Karam, Jose A; Wood, Christopher G

2018-06-01

To evaluate preoperative and intraoperative predictors of conversion to radical nephrectomy (RN) in a cohort of patients undergoing a planned partial nephrectomy (PN) for renal cell carcinoma (RCC). A single-center, retrospective review was conducted using our PN database that includes patients who were scheduled to undergo PN (regardless of the approach) but were converted to RN between August 1990 and December 2016. Reasons for conversion were collected from the operative report. Patient demographics and perioperative variables were compared with the successful PN group. Univariate and multivariate logistic regression analyses were conducted to assess predictors of conversion. A total of 1857 patients were scheduled to undergo PN. Of these patients, 90 (5%) were converted to RN. The multivariate model showed that larger tumor size (odds ratio [OR] = 1.20, P = .040), higher RENAL nephrometry score (OR = 1.41, P = .001), hilar tumor or renal sinus invasion (OR = 2.80, P = .004), laparoscopic PN (OR = 7.34, P <.001), intraoperative bleeding (OR = 19.62, P <.001), positive surgical margin (OR = 31.85, P <.001), and advanced pathologic tumor-stage (T3 or T4) (OR = 7.29, P <.001) were associated with increased odds of intraoperative conversion to RN. The rate of conversion to RN was low in patients who were scheduled to undergo PN in this series. Larger tumor size with increasing complexity, hilar tumor location or renal sinus invasion, locally advanced tumors, laparoscopic PN but not robotic PN, bleeding complication, and positive surgical margin were associated with intraoperative conversion from scheduled PN to RN. Copyright © 2018 Elsevier Inc. All rights reserved.

Governance and Leadership in Public Schools: Opportunities and Challenges Facing School Leaders in Italy

ERIC Educational Resources Information Center

Paletta, Angelo; Bezzina, Christopher

2016-01-01

This article aims to explore the evolution of school leadership in Italy toward a model of leadership for learning. Italy is undergoing radical changes in the governance structures (school autonomy and accountability) affecting schools in general, and school principals in particular, based on the way they promote, manage, and monitor the…

Mindful Pedagogy in Dance: Honoring the Life of the Child

ERIC Educational Resources Information Center

Sansom, Adrienne

2009-01-01

Recent innovations in the field of early childhood education have prompted a re-thinking of teaching and learning. Traditional notions of child development have been undergoing some radical changes and, as such, have resulted in a reviewing and re-formulation of early years pedagogy. In Aotearoa New Zealand the field of early childhood education…

Antioxidative Activity of Colostrum and Human Milk: Effects of Pasteurization and Storage.

PubMed

Marinković, Vesna; Ranković-Janevski, Milica; Spasić, Snežana; Nikolić-Kokić, Aleksandra; Lugonja, Nikoleta; Djurović, Dijana; Miletić, Srdjan; Vrvić, Miroslav M; Spasojević, Ivan

2016-06-01

Milk banks collect, pasteurize, and freeze/store human milk. The processing may alter redox properties of milk, but the effects have not been fully examined. We collected 10 mature milk and 10 colostrum samples and applied a battery of biochemical assays and electron paramagnetic resonance spectroscopy to inspect changes that milk undergoes with pasteurization and 30 days storage at -20°C. Pasteurization and storage of raw milk did not affect total nonenzymatic antioxidative capacity, but specific components and features were altered. Urate radical and ascorbyl radical emerge as products of exposure of milk to hydroxyl radical-generating system. Processing shifted the load of antioxidative activity from ascorbate to urate and lowered the capacity of milk to diminish hydroxyl radical. Pasteurization caused a significant drop in the activity of 2 major antioxidative enzymes-superoxide dismutase and glutathione peroxidase, whereas freezing/storage of raw milk affected only superoxide dismutase. Colostrum showed drastically higher total nonenzymatic antioxidative capacity, hydroxyl radical scavenging ability, and glutathione reductase activity compared with mature milk. Pasteurization and storage affect nonenzymatic and enzymatic antioxidative agents in human milk. It appears that nonenzymatic antioxidative systems in colostrum and milk are different. The effects of processing may be partially compensated by fortification/spiking with ascorbate before use.

Mechanistic Insights from Reaction of α-Oxiranyl-Aldehydes with Cyanobacterial Aldehyde Deformylating Oxygenase

PubMed Central

Das, Debasis; Ellington, Benjamin; Paul, Bishwajit; Marsh, E. Neil G.

2014-01-01

The biosynthesis of long-chain aliphatic hydrocarbons, which are derived from fatty acids, is widespread in Nature. The last step in this pathway involves the decarbonylation of fatty aldehydes to the corresponding alkanes or alkenes. In cyanobacteria this is catalyzed by an aldehyde deformylating oxygenase. We have investigated the mechanism of this enzyme using substrates bearing an oxirane ring adjacent to the aldehyde carbon. The enzyme catalyzed the deformylation of these substrates to produce the corresponding oxiranes. Performing the reaction in D2O allowed the facial selectivity of proton addition to be examined by 1H-NMR spectroscopy. The proton is delivered with equal probability to either face of the oxirane ring, indicating the formation of an oxiranyl radical intermediate that is free to rotate during the reaction. Unexpectedly, the enzyme also catalyzes a side reaction in which oxiranyl-aldehydes undergo tandem deformylation to furnish alkanes two carbons shorter. We present evidence that this involves the rearrangement of the intermediate oxiranyl radical formed in the first step, resulting an aldehyde that is further deformylated in a second step. These observations provide support for a radical mechanism for deformylation and, furthermore, allow the lifetime of the radical intermediate to be estimated based on prior measurements of rate constants for the rearrangement of oxiranyl radicals. PMID:24313866

Theoretical perspectives on the mechanism and kinetics of the OH radical-initiated gas-phase oxidation of PCB126 in the atmosphere.

PubMed

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

2015-06-01

Polychlorinated biphenyls (PCBs) primarily exist in the gas phase in air and may undergo atmospheric oxidation degradations, particularly the oxidation reaction initiated by OH radicals. In this work, the mechanism of the OH radical-initiated atmospheric oxidation of the most toxic PCB congener 3,3',4,4',5-pentachlorobiphenyl (PCB126) was investigated by using quantum chemistry methods. The rate constants of the crucial elementary reactions were estimated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The oxidation products of the reaction of PCB126 with OH radicals include 3,3',4,4',5-pentachlorobiphenyl-ols, chlorophenols, 2,3,4,7,8-pentachlorodibenzofuran, 2,3,4,6,7-pentachlorodibenzofuran, dialdehydes, 3,3',4,4',5-pentachloro-5'-nitro-biphenyl, and 4,5-dichloro-2-nitrophenol. Particularly, the formation of polychlorinated dibenzofurans (PCDFs) from the atmospheric oxidation of PCBs is revealed for the first time. The overall rate constant of the OH addition reaction is 2.52×10(-13)cm(3)molecule(-1)s(-1) at 298K and 1atm. The atmospheric lifetime of PCB126 determined by OH radicals is about 47.08days which indicates that PCB126 can be transported long distances from local to global scales. Copyright © 2015 Elsevier B.V. All rights reserved.

Robot-assisted versus open radical prostatectomy: an evidence-based comparison.

PubMed

Minniti, D; Chiadò Piat, S; Di Novi, C

2011-01-01

A robotic system has been used in tens of thousands of minimally invasive prostate cancer treatment surgeries worldwide. The aim of the paper is to evaluate the effectiveness of the robotic surgery versus traditional surgery for the treatment of early prostate cancer in Italy. Since this study is an observational study, we have no control over the treatment assignment. However, the treated (patient who undergo robotic assisted laparoscopic prostatectomy (RALP)) and control groups (patient who undergo open radical prostatectomy (ORP)) may differ significantly prior to treatment in ways that may affect the outcomes under study. In order to avoid erroneous conclusions we have dealt with the problem of significant group differences by using a propensity score matching procedure. The average age at radical prostatectomy for the two groups was similar. 97% of patients have bladder neck sparing during the open prostatectomy versus 77% of patients who belong to RALP group. RALP group presents higher urinary continence and lower blood loss rate with respect to ORP group (86.3% versus 65.6% and 9% versus 31.1% respectively). Among patients who underwent ORP 20.4% were spared nerves versus 4.5% of patients who were treated with RALP. The body mass and self-assessed health for the two groups were similar. In the logistic regression model used for the calculation of Propensity Score, bladder neck sparing and the size of the tumor were significant and presented a negative coefficient. Older age, advanced stage of the tumor, and linfonodal involvement negatively affect the likelihood of robotic technology. From our empirical analysis it arises that the robot technique does not significantly affect the hospital stay, blood loss nor the variables about post-intervention quality of life (urinary continence and self-assessed health). The robotic system does not seem to present major efficacy with respect to open radical prostatectomy. In particular our findings do not support any significant differences in quality of life, blood loss, hospital stay, and urinary incontinence in patients operated with robot-assisted surgery versus open retropubic radical prostatectomy.

[Day surgery in breast reconstructive surgery: our experience].

PubMed

Fierro, N; D'Ermo, G; Barbetti, E; Mazza, E; Gallinaro, L S; Amanti, C; De Biasio, G; Galassi, G; Galassi, G

2004-10-01

Breast cancer is the most common tumour in Italy in the female population, counting for about 40000 new cases every year. The psychological aspects of breast mutilation and the social and economic implications are receiving increasing attention. Despite of the diffusion of screening programs to detect pre-clinical breast cancers, 30% of patients still undergo radical interventions. Therefore, many women present serious limitations of their social-life that can lead to severe depression since, in occidental countries, the biological function of the breast is less considered than its primary role of femininity and sexuality. The gold-standard is to conceal oncological radicality and aesthetic preservation. The Authors present their experience analysing the techniques employed.

Bulky mesonephric adenocarcinoma of the uterine cervix treated with neoadjuvant chemotherapy and radical surgery: report of the first case.

PubMed

Ditto, Antonino; Martinelli, Fabio; Bogani, Giorgio; Gasparri, Maria L; Donato, Violante Di; Paolini, Biagio; Carcangiu, Maria L; Lorusso, Domenica; Raspagliesi, Francesco

2016-11-11

Malignant mesonephric adenocarcinoma of the uterine cervix is a rare occurrence with few cases described in the literature. Although surgery seems to be effective in the treatment of early-stage tumor, no cases describing outcomes of locally advanced stage are available. We report the first case of a patient with International Federation of Obstetrics and Gynecologists stage IIB mesonephric adenocarcinoma undergoing neoadjuvant chemotherapy and radical surgery. Despite the inherent limitation of a single description of a case, our experience supports the utilization of neoadjuvant chemotherapy in patients with malignant mesonephric adenocarcinoma of the uterine cervix. Further prospective multi-institutional studies are needed.

High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction

NASA Astrophysics Data System (ADS)

Weidman, Jared D.; Allen, Ryan T.; Moore, Kevin B.; Schaefer, Henry F.

2018-05-01

Numerous processes in atmospheric and combustion chemistry produce the vinoxy radical (•CH2CHO). To understand the fate of this radical and to provide reliable energies needed for kinetic modeling of such processes, we have examined its reaction with O2 using highly reliable theoretical methods. Utilizing the focal point approach, the energetics of this reaction and subsequent reactions were obtained using coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set limit. These extrapolated energies were appended with several corrections including a treatment of full triples and connected quadruple excitations, i.e., CCSDT(Q). In addition, this study models the initial vinoxy radical + O2 reaction for the first time with multireference methods. We predict a barrier for this reaction of approximately 0.4 kcal mol-1. This result agrees with experimental findings but is in disagreement with previous theoretical studies. The vinoxy radical + O2 reaction produces a 2-oxoethylperoxy radical which can undergo a number of unimolecular reactions. Abstraction of a β-hydrogen (a 1,4-hydrogen shift) and dissociation back to reactants are predicted to be competitive to each other due to their similar barriers of 21.2 and 22.3 kcal mol-1, respectively. The minimum-energy β-hydrogen abstraction pathway produces a hydroperoxy radical (QOOH) that eventually decomposes to formaldehyde, CO, and •OH. Two other unimolecular reactions of the peroxy radical are α-hydrogen abstraction (38.7 kcal mol-1 barrier) and HO2• elimination (43.5 kcal mol-1 barrier). These pathways lead to glyoxal + •OH and ketene + HO2• formation, respectively, but they are expected to be uncompetitive due to their high barriers.

Conversion of 3-imidazoline-3-oxide nitroxyl radicals into nitronylnitroxyl radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grigor'ev, I.A.; Shchukin, G.I.; Khramtsov, V.V.

1986-04-20

Continuing the studies of the effect of the pH of the medium on the EPR spectra of nitroxyl radicals (NR) containing acid-base functional groups at a distance of 2-3 sigma-bonds from the radical center, they have examined the EPR spectra of NR, which contain OH groups in the 2-position of the heterocycle. It is assumed that deprotonation of the OH group is accompanied by changes in the hfc constant a/sub N//sup 1/ and the g-factor. At pH values greater than or equal to 12, however, the EPR spectra of aqueous solutions of radicals undergo irreversible changes from a triplet tomore » a more complex multiplet, similar to the spectra of nitronylnitroxyl radicals. The EPR spectra of these solutions remain unchanged over periods of several days. The spectra have a quintet structure, with further splitting into four or three components. When similar experiments are carried out in D/sub 2/O, the additional hfs disappear as a result of deuterium exchange in the CH/sub 2/ and CH/sub 3/ groups of the radicals. A simulation of the EPR spectra was carried out, assuming splitting into two N nuclei (a/sub N//sup 1/ and a/sub N//sup 3/), with three or two equivalent H. This resulted in complete agreement between the calculated and experimental spectra. In order to assign the nitrogen hfc constants, they synthesized radicals containing the N/sup 15/ isotope in the 3-position of the imidazole ring. Comparison of the results of simulations of the EPR spectra enabled unambiguous assignments of the hfc constants a/sub N//sup 1/ and a/sub N//sup 3/ to be made.« less

Tyrosine-lipid peroxide adducts from radical termination: para coupling and intramolecular Diels-Alder cyclization.

PubMed

Shchepin, Roman; Möller, Matias N; Kim, Hye-young H; Hatch, Duane M; Bartesaghi, Silvina; Kalyanaraman, Balaraman; Radi, Rafael; Porter, Ned A

2010-12-15

Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogues of tyrosine gave rise to lipid peroxide-tyrosine (phenol) adducts in both aqueous micellar and organic solutions. The novel adducts were isolated and characterized by 1D and 2D NMR spectroscopy as well as by mass spectrometry (MS). The spectral data suggest that the polyunsaturated lipid peroxyl radicals give stable peroxide coupling products exclusively at the para position of the tyrosyl (phenoxy) radicals. These adducts have characteristic (13)C chemical shifts at 185 ppm due to the cross-conjugated carbonyl of the phenol-derived cyclohexadienone. The primary peroxide adducts subsequently undergo intramolecular Diels-Alder (IMDA) cyclization, affording a number of diastereomeric tricyclic adducts that have characteristic carbonyl (13)C chemical shifts at ~198 ppm. All of the NMR HMBC and HSQC correlations support the structure assignments of the primary and Diels-Alder adducts, as does MS collision-induced dissociation data. Kinetic rate constants and activation parameters for the IMDA reaction were determined, and the primary adducts were reduced with cuprous ion to give a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found in either the primary or cuprous reduction product mixtures. These studies provide a framework for understanding the nature of lipid-protein adducts formed by peroxyl-tyrosyl radical-radical termination processes. Coupling of lipid peroxyl radicals with tyrosyl radicals leads to cyclohexenone and cyclohexadienone adducts, which are of interest in and of themselves since, as electrophiles, they are likely targets for protein nucleophiles. One consequence of lipid peroxyl reactions with tyrosyls may therefore be protein-protein cross-links via interprotein Michael adducts.

Tyrosine-Lipid Peroxide Adducts from Radical Termination: Para-Coupling and Intramolecular Diels-Alder Cyclization

PubMed Central

Shchepin, Roman; Möller, Matias N.; Kim, Hye-young H.; Hatch, Duane M.; Bartesaghi, Silvina; Kalyanaraman, Balaraman; Radi, Rafael

2013-01-01

Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogs of tyrosine gave rise to lipid peroxide-tyrosine (phenol) adducts in both aqueous micellar and organic solutions. The novel adducts were isolated and characterized by 1D and 2D NMR as well as by mass spectrometry. The spectral data suggest that the polyunsaturated lipid peroxyl radicals give stable peroxide coupling products exclusively at the para position of the tyrosyl (phenoxy) radicals. These adducts have characteristic 13C chemical shifts at 185 ppm due to the cross-conjugated carbonyl of the phenol-derived cyclohexadienone. The primary peroxide adducts subsequently undergo intramolecular Diels-Alder (IMDA) cyclization, affording a number of diastereomeric tricyclic adducts that have characteristic carbonyl 13C chemical shifts at ~198 ppm. All NMR HMBC and HSQC correlations support the structure assignment of the primary and Diels-Alder adducts, as does MS collision induced dissociation. Kinetic rate constants and activation parameters for the IMDA reaction were determined and the primary adducts were reduced with cuprous ion giving a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found either in the primary or the cuprous reduction product mixtures. These studies provide a framework for understanding the nature of lipid-protein adducts formed by peroxyl-tyrosyl radical-radical termination processes. Coupling of lipid peroxyl radicals with tyrosyl radicals leads to cyclohexenone and cyclohexadienone adducts which are of interest in and of themselves since, as electrophiles, they are likely targets for protein nucleophiles. One consequence of lipid peroxyl reactions with tyrosyls may therefore be protein-protein crosslinks via interprotein Michael adducts. PMID:21090613

Generation and reactivity of ketyl radicals with lignin related structures. On the importance of the ketyl pathway in the photoyellowing of lignin containing pulps and papers.

PubMed

Fabbri, Claudia; Bietti, Massimo; Lanzalunga, Osvaldo

2005-04-01

[reaction: see text] Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pKa = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k2 = 1.8-2.7 x 10(9) M(-1) s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation of the reduced acceptor (methyl viologen radical cation, MV+*), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2*))(OH)CH2(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled with the low rates of beta-fragmentation of the same species have an important bearing in the context of the photoyellowing of lignin containing pulps and papers.

The dissociation of vibrationally excited CH3OSO radicals and their photolytic precursor, methoxysulfinyl chloride.

PubMed

Alligood, Bridget W; Womack, Caroline C; Straus, Daniel B; Blase, Frances R; Butler, Laurie J

2011-05-21

The dissociation dynamics of methoxysulfinyl radicals generated from the photodissociation of CH(3)OS(O)Cl at 248 nm is investigated using both a crossed laser-molecular beam scattering apparatus and a velocity map imaging apparatus. There is evidence of only a single photodissociation channel of the precursor: S-Cl fission to produce Cl atoms and CH(3)OSO radicals. Some of the vibrationally excited CH(3)OSO radicals undergo subsequent dissociation to CH(3) + SO(2). The velocities of the detected CH(3) and SO(2) products show that the dissociation occurs via a transition state having a substantial barrier beyond the endoergicity; appropriately, the distribution of velocities imparted to these momentum-matched products is fit by a broad recoil kinetic energy distribution extending out to 24 kcal/mol in translational energy. Using 200 eV electron bombardment detection, we also detect the CH(3)OSO radicals that have too little internal energy to dissociate. These radicals are observed both at the parent CH(3)OSO(+) ion as well as at the CH(3)(+) and SO(2)(+) daughter ions; they are distinguished by virtue of the velocity imparted in the original photolytic step. The detected velocities of the stable radicals are roughly consistent with the calculated barriers (both at the CCSD(T) and G3B3 levels of theory) for the dissociation of CH(3)OSO to CH(3) + SO(2) when we account for the partitioning of internal energy between rotation and vibration as the CH(3)OSOCl precursor dissociates. © 2011 American Institute of Physics.

LC/ESR/MS study of pH-dependent radical generation from 15-LOX catalyzed DPA peroxidation

PubMed Central

Purwaha, Preeti; Gu, Yan; Kelavkar, Uddhav; Kang, Jing Xuan; Law, Benedict; Wu, Erxi; Qian, Steven Y.

2011-01-01

Docosapentaenoic acid (DPA) is a unique fatty acid that exists in two isomeric forms (n-3 and n-6) which differ in their physiological behaviors. DPA can undergo free-radical mediated peroxidation via lipoxygenase (LOX). 15-LOX, one of the LOX isomers, has received much attention in cancer research due to its very different expression level in normal tissues compared to tumors and some bioactive fatty acid metabolites modulating the tumorigenic pathways in cancer. However, the mechanism linking 15-LOX, DPA-metabolites, and the bioactivities is still unclear, and the free radicals generated in DPA peroxidation have never been characterized. In this study, we have studied radicals formed from both soybean and human cellular (PC3-15LOS cells) 15-LOX-catalyzed peroxidation of DPAs at different pH’s using a combination of LC/ESR/MS with the spin trapping technique. We observed a total of three carbon-centered radicals formed in 15-LOX/DPA (n-3) stemming from its 7-, 17- and 20-hydroperoxides, while only one formed from 17-hydroperoxide in DPA (n-6). A change in the reaction pH from 8.5 (15-LOX enzyme optimum) to 7.4 (physiological) and to 6.5 (tumor, acidic) not only decreased the total radical formation but also altered the preferred site of oxygenation. This pH-dependent alteration of radical formation and oxygenation pattern may have significant implications and provide a basis for our ongoing investigations of LOXs as well as fatty acids in cancer biology. PMID:21807091

Implementation of the Exeter enhanced recovery programme for patients undergoing radical cystectomy.

PubMed

Dutton, Thomas J; Daugherty, Mark O; Mason, Robert G; McGrath, John S

2014-05-01

To describe our experience with the implementation and refinement of an enhanced recovery programme (ERP) for radical cystectomy (RC) and urinary diversion. To assess the impact on length of stay (LOS), complication and readmission rates. In all, 165 consecutive patients undergoing open RC (ORC) and urinary diversion between January 2008 and April 2013 were entered into an ERP. A retrospective case note review was undertaken. Outcomes recorded included LOS, time to mobilisation, complication rates within the first 30 days (Clavien-Dindo classification) and readmissions. All patients were successfully entered into the ERP. As enhanced recovery principles became embedded in the unit, LOS reduced from a mean of 14 days over the initial year of the ERP to a mean of 9.2 days. The complication rate was 6.6% for Clavien ≥3, and 43.5% for Clavien ≤2. The 30-day mortality rate was 1.2%. The 30-day readmission rate was 13.9%. In the most contemporary subset of 52 patients: the median time after ORC to sit out of bed, mobilise and open bowels was day 1, 2 and 6, respectively. The ERP described for patients undergoing ORC appears to be safe. Benefits include early feeding, mobilisation and hospital discharge. The ERP will continue to develop with the incorporation of advancing evidence and technology, in particular the introduction of robot-assisted RC. © 2013 The Authors. BJU International © 2013 BJU International.

Sarcopenia predicts survival outcomes among patients with urothelial carcinoma of the upper urinary tract undergoing radical nephroureterectomy: a retrospective multi-institution study.

PubMed

Ishihara, Hiroki; Kondo, Tsunenori; Omae, Kenji; Takagi, Toshio; Iizuka, Junpei; Kobayashi, Hirohito; Hashimoto, Yasunobu; Tanabe, Kazunari

2017-02-01

We aimed to evaluate the effect of sarcopenia, a condition of low muscle mass, on the survival among patients who were undergoing radical nephroureterectomy (RNU) for urothelial carcinoma of the upper urinary tract (UCUT). We retrospectively reviewed consecutive patients with UCUT (cT[any]N0M0) who underwent RNU between 2003 and 2013 at our department and its affiliated institutions. Preoperative computed tomography images were used to calculate each patient's skeletal muscle index, an indicator of whole-body muscle mass. Sarcopenia was defined according to the sex-specific consensus definitions, based on the patient's skeletal muscle and body mass indexes. We analyzed the relapse-free survival (RFS), cancer-specific survival (CSS), and overall survival (OS) after RNU to identify factors that predicted patient survival. A total of 137 patients were included, and 90 patients (65.7 %) were diagnosed with sarcopenia. Compared to the non-sarcopenic patients, the sarcopenic patients had a significant inferior 5-year RFS (48.8 vs. 79.6 %, p = 0.0002), CSS (57.1 vs. 92.6 %, p < 0.0001), and OS (48.2 vs. 90.6 %, p < 0.0001). Multivariate analyses revealed that sarcopenia was an independent predictor of shorter RFS, CSS, and OS (all, p < 0.0001). Sarcopenia was an independent predictor of survival among patients with UCUT who were undergoing RNU.

Use of rectus sheath catheters for pain relief in patients undergoing major pelvic urological surgery.

PubMed

Dutton, Thomas J; McGrath, John S; Daugherty, Mark O

2014-02-01

To report on the safety and efficacy of rectus sheath blocks, 'topped-up' using bilateral rectus sheath catheters (RSCs), in patients undergoing major open urological surgery. The RSCs were inserted under ultrasound guidance into 200 patients between April 2008 and August 2011, of whom 106 patients underwent radical retropubic prostatectomy (RRP) and 94 underwent open radical cystectomy (ORC). A retrospective case-note review was undertaken. Outcomes included technical success and complication rates of the insertion and use of RSC, visual analogue pain scores, additional analgesia requirements and length of hospital stay (LOS). All RSCs were successfully placed without complication and used for a mean of 3.6 days for ORC and 2.1 days for RRP. Early removal occurred in 6.49% of patients. Low overall pain scores were reported in both groups. Patients were more likely to require a patient-controlled analgesia system in the ORC group but the overall need for additional analgesia was low in both groups, reducing significantly after the initial 24 h. In combination with an enhanced recovery programme, LOS reduced from 17.0 to 10.8 days in the ORC group and from 6.2 to 2.8 days in the RRP group. The use of RSCs appears to offer an effective and safe method of peri-operative analgesia in patients undergoing major open urological pelvic surgery. © 2013 The Authors. BJU International © 2013 BJU International.

Quality of life and satisfaction with information after radical prostatectomy, radical external beam radiotherapy and postoperative radiotherapy: a long-term follow-up study.

PubMed

Nicolaisen, Marianne; Müller, Stig; Patel, Hitendra R H; Hanssen, Tove Aminda

2014-12-01

To assess patients' symptoms, quality of life and satisfaction with information three to four years after radical prostatectomy, radical external beam radiotherapy and postoperative radiotherapy and to analyse differences between treatment groups and the relationship between disease-specific, health-related and overall quality of life and satisfaction with information. Radical prostate cancer treatments are associated with changes in quality of life. Differences between patients undergoing different treatments in symptoms and quality of life have been reported, but there are limited long-term data comparing radical prostatectomy with radical external beam radiotherapy and postoperative radiotherapy. A cross-sectional survey design was used. The study sample included 143 men treated with radical prostatectomy and/or radical external beam radiotherapy. Quality of life was measured using the 12-item Short Form Health Survey and the 50-item Expanded Prostate Cancer Index Composite Instrument. Questions assessing overall Quality of life and satisfaction with information were included. Descriptive statistics and interference statistical methods were applied to analyse the data. Radical external beam radiotherapy was associated with less urinary incontinence and better urinary function. There were no differences between the groups for disease-specific quality of life sum scores. Sexual quality of life was reported very low in all groups. Disease-specific quality of life and health-related quality of life were associated with overall quality of life. Patients having undergone surgery were more satisfied with information, and there was a positive correlation between quality of life and patient satisfaction. Pretreatment information and patient education lead to better quality of life and satisfaction. This study indicates a need for structured, pretreatment information and follow-up for all men going through radical prostate cancer treatment. Long-term quality of life effects should be considered when planning follow-up and information for men after radical prostate cancer treatment. Structured and organised information/education may increase preparedness for symptoms and bother after the treatment, improve symptom management strategies and result in improved quality of life. © 2014 John Wiley & Sons Ltd.

Multicomponent kinetic analysis and theoretical studies on the phenolic intermediates in the oxidation of eugenol and isoeugenol catalyzed by laccase.

PubMed

Qi, Yan-Bing; Wang, Xiao-Lei; Shi, Ting; Liu, Shuchang; Xu, Zhen-Hao; Li, Xiqing; Shi, Xuling; Xu, Ping; Zhao, Yi-Lei

2015-11-28

Laccase catalyzes the oxidation of natural phenols and thereby is believed to initialize reactions in lignification and delignification. Numerous phenolic mediators have also been applied in laccase-mediator systems. However, reaction details after the primary O-H rupture of phenols remain obscure. In this work two types of isomeric phenols, EUG (eugenol) and ISO (trans-/cis-isoeugenol), were used as chemical probes to explore the enzymatic reaction pathways, with the combined methods of time-resolved UV-Vis absorption spectra, MCR-ALS, HPLC-MS, and quantum mechanical (QM) calculations. It has been found that the EUG-consuming rate is linear to its concentration, while the ISO not. Besides, an o-methoxy quinone methide intermediate, (E/Z)-4-allylidene-2-methoxycyclohexa-2,5-dienone, was evidenced in the case of EUG with the UV-Vis measurement, mass spectra and TD-DFT calculations; in contrast, an ISO-generating phenoxyl radical, a (E/Z)-2-methoxy-4-(prop-1-en-1-yl) phenoxyl radical, was identified in the case of ISO. Furthermore, QM calculations indicated that the EUG-generating phenoxyl radical (an O-centered radical) can easily transform into an allylic radical (a C-centered radical) by hydrogen atom transfer (HAT) with a calculated activation enthalpy of 5.3 kcal mol(-1) and then be fast oxidized to the observed eugenol quinone methide, rather than an O-radical alkene addition with barriers above 12.8 kcal mol(-1). In contrast, the ISO-generating phenoxyl radical directly undergoes a radical coupling (RC) process, with a barrier of 4.8 kcal mol(-1), while the HAT isomerization between O- and C-centered radicals has a higher reaction barrier of 8.0 kcal mol(-1). The electronic conjugation of the benzyl-type radical and the aromatic allylic radical leads to differentiation of the two pathways. These results imply that competitive reaction pathways exist for the nascent reactive intermediates generated in the laccase-catalyzed oxidation of natural phenols, which is important for understanding the lignin polymerization and may shed some light on the development of efficient laccase-mediator systems.

Ionizing Collisions of Electrons with Radical Species OH, H2 O2 and HO2; Theoretical Calculations

NASA Astrophysics Data System (ADS)

Joshipura, K. N.; Pandya, S. H.; Vaishnav, B. G.; Patel, U. R.

2016-05-01

In this paper we present our calculated total ionization cross sections (TICS) of electron impact on radical targets OH, H2 O2 and HO2 at energies from threshold to 2000 eV. Reactive species such as these pose difficulties in measurements of electron scattering cross sections. No measured data have been reported in this regard except an isolated TICS measurement on OH radical, and hence the present work on the title radicals hold significance. These radical species are present in an environment in which water molecules undergo dissociation (neutral or ionic) in interactions with photons or electrons. The embedding environments could be quite diverse, ranging from our atmosphere to membranes of living cells. Ionization of OH, H2 O2 or HO2 can give rise to further chemistry in the relevant bulk medium. Therefore, it is appropriate and meaningful to examine electron impact ionization of these radicals in comparison with that of water molecules, for which accurate da are available. For the OH target single-centre scattering calculations are performed by starting with a 4-term complex potential, that describes simultaneous elastic plus inelastic scattering. TICS are obtained from the total inelastic cross sections in the complex scattering potential - ionization contribution formalism , a well established method. For H2 O2 and HO2 targets, we employ the additivity rule with overlap or screening corrections. Detailed results will be presented in the Conference.

Efficacy of pectoral nerve block versus thoracic paravertebral block for postoperative analgesia after radical mastectomy: a randomized controlled trial.

PubMed

Kulhari, S; Bharti, N; Bala, I; Arora, S; Singh, G

2016-09-01

Pectoral nerve (PecS) block is a recently introduced technique for providing surgical anaesthesia and postoperative analgesia during breast surgery. The present study was planned to compare the efficacy and safety of ultrasound-guided PecS II block with thoracic paravertebral block (TPVB) for postoperative analgesia after modified radical mastectomy. Forty adult female patients undergoing radical mastectomy were randomly allocated into two groups. Group 1 patients received a TPVB with ropivacaine 0.5%, 25 ml, whereas Group 2 patents received a PecS II block using same volume of ropivacaine 0.5% before induction of anaesthesia. Patient-controlled morphine analgesia was used for postoperative pain relief. The duration of analgesia was significantly prolonged in patients receiving the PecS II block compared with TPVB [mean (sd), 294.5 (52.76) vs 197.5 (31.35) min in the PecS II and TPVB group, respectively; P<0.0001]. The 24 h morphine consumption was also less in the PecS II block group [mean (sd), 3.90 (0.79) vs 5.30 (0.98) mg in PecS II and TPVB group, respectively; P<0.0001]. Postoperative pain scores were lower in the PecS II group compared with the TVPB group in the initial 2 h after surgery [median (IQR), 2 (2-2.5) vs 4 (3-4) in the Pecs II and TPVB group, respectively; P<0.0001]. Seventeen patients in the PecS II block group had T2 dermatomal spread compared with four patients in the TPVB group (P<0.001). No block-related complication was recorded. We found that the PecS II block provided superior postoperative analgesia than the TPVB in patients undergoing modified radical mastectomy without causing any adverse effect. CTRI/2014/06/004692. © The Author 2016. Published by Oxford University Press on behalf of the British Journal of Anaesthesia. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

A Prospective Randomized Study of Pfannenstiel Versus Expanded Port Site Incision for Intact Specimen Extraction in Laparoscopic Radical Nephrectomy.

PubMed

Binsaleh, Saleh; Madbouly, Khaled; Matsumoto, Edward D; Kapoor, Anil

2015-08-01

To compare intra- and postoperative outcome of patients undergoing laparoscopic radical nephrectomy with intact specimen extraction through a Pfannenstiel (PFN) transverse suprapubic or expanded port site (EPS) incision in a prospective randomized fashion. Patients undergoing laparoscopic transperitoneal radical nephrectomies for suspected renal tumors were randomized for intact renal specimen extraction via a PFN or EPS incision. Operative, perioperative, 1 week, 6 weeks, and 6 months postoperative parameters were prospectively recorded and analyzed including specimen weight, size in maximum diameter, incision length, total operative time, extraction time, estimated blood loss, length of hospital stay, pain score in the postoperative holding area and on the first post operative day, narcotic consumption, time to fluid intake/full diet intake, unassisted ambulation, cosmesis, and wound-related complications. A postoperative quality-of-life questionnaire was also filled out by all the patients. Our series included 51 patients: 26 in the PFN group and 25 in the EPS group. The two groups were similar in demographic characteristics and intraoperative and postoperative parameters apart from a longer PFN incision (P<0.00). First postoperative day pain score was significantly less in the PFN group than in the EPS group (P=0.023). Complication rate was less in the PFN group, although not statistically significant. Hospital stay was significantly shorter in the PFN than in the EPS group (P=0.01). Mean cosmesis and operative satisfaction scores at week 1, week 6, and 6 month visits were not significantly different between both groups. Compared with the EPS group, PFN group patients significantly will choose the same operation if they would do it again (P=0.004). PFN incision has less morbidity, pain score, and hospital stay compared with EPS incision for intact specimen extraction after transperitoneal laparoscopic radical nephrectomy. Both incisions are associated with high operative satisfaction, good cosmesis, and a low rate of wound complications.

Controlled aqueous polymerization of acrylamides and acrylates and "in situ" depolymerization in the presence of dissolved CO2.

PubMed

Lloyd, Danielle J; Nikolaou, Vasiliki; Collins, Jennifer; Waldron, Christopher; Anastasaki, Athina; Bassett, Simon P; Howdle, Steven M; Blanazs, Adam; Wilson, Paul; Kempe, Kristian; Haddleton, David M

2016-05-05

Aqueous copper-mediated radical polymerization of acrylamides and acrylates in carbonated water resulted in high monomer conversions (t < 10 min) before undergoing depolymerization (60 min > t > 10 min). The regenerated monomer was characterized and repolymerized following deoxygenation of the resulting solutions to reyield polymers in high conversions that exhibit low dispersities.

Photoelectron Spectroscopy Study of Quinonimides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hossain, Ekram; Deng, Shihu M.; Gozem, Samer

Structures and energetics of o-, m- and p-quinonimide anions (OC6H4N) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, andmore » it is shown that accurate predictions for the electronic structure of the para quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.« less

Pyrene-Functionalized PTMA by NRC for Greater π-π Stacking with rGO and Enhanced Electrochemical Properties.

PubMed

Zhang, Kai; Hu, Yuxiang; Wang, Lianzhou; Monteiro, Michael J; Jia, Zhongfan

2017-10-11

Nitroxide radical polymers can undergo both excellent electrochemical redox reactions and a rapid "click" coupling reaction with carbon-centered radicals (i.e., nitroxide radical coupling (NRC) reaction). In this work, we report a strategy to functionalize poly(2,2,6,6,-tetramethylpiperidinyl-1-oxyl methacrylate) (PTMA) with pyrene side groups through a rapid and near quantitative NRC reaction. This resulted in P(TMA-co-PyMA) random copolymers with near quantitative amounts of pyrene along the PTMA chain for greater π-π interaction with rGO, while the nitroxide radicals on the polymer could simultaneously be used for energy storage. These copolymers can bind with reduced graphene oxide (rGO) and form layered composites through noncovalent π-π stacking, attaining molecular-level dispersion. Electrochemical performance of the composites with different polymer contents (24, 35, and 45 wt %), tested in lithium ion batteries, indicated that the layered structures consisting of P(TMA-co-PyMA) maintained greater capacities at high C-rates. This simple and efficient strategy to synthesize pyrene-functionalized polymers will provide new opportunities to fabricate many other polymer composite electrodes for desired electrochemical performance.

A Distonic Radical-Ion for Detection of Traces of Adventitious Molecular Oxygen (O2) in Collision Gases Used in Tandem Mass Spectrometers

NASA Astrophysics Data System (ADS)

Jariwala, Freneil B.; Hibbs, John A.; Weisbecker, Carl S.; Ressler, John; Khade, Rahul L.; Zhang, Yong; Attygalle, Athula B.

2014-09-01

We describe a diagnostic ion that enables rapid semiquantitative evaluation of the degree of oxygen contamination in the collision gases used in tandem mass spectrometers. Upon collision-induced dissociation (CID), the m/z 359 positive ion generated from the analgesic etoricoxib undergoes a facile loss of a methyl sulfone radical [•SO2(CH3); 79-Da] to produce a distonic radical cation of m/z 280. The product-ion spectrum of this m/z 280 ion, recorded under low-energy activation on tandem-in-space QqQ or QqTof mass spectrometers using nitrogen from a generator as the collision gas, or tandem-in-time ion-trap (LCQ, LTQ) mass spectrometers using purified helium as the buffer gas, showed two unexpected peaks at m/z 312 and 295. This enigmatic m/z 312 ion, which bears a mass-to-charge ratio higher than that of the precursor ion, represented an addition of molecular oxygen (O2) to the precursor ion. The exceptional affinity of the m/z 280 radical cation towards oxygen was deployed to develop a method to determine the oxygen content in collision gases.

Comparative Effectiveness of Cancer Control and Survival after Robot-Assisted versus Open Radical Prostatectomy.

PubMed

Hu, Jim C; O'Malley, Padraic; Chughtai, Bilal; Isaacs, Abby; Mao, Jialin; Wright, Jason D; Hershman, Dawn; Sedrakyan, Art

2017-01-01

Robot-assisted surgery has been rapidly adopted in the U.S. for prostate cancer. Its adoption has been driven by market forces and patient preference, and debate continues regarding whether it offers improved outcomes to justify the higher cost relative to open surgery. We examined the comparative effectiveness of robot-assisted vs open radical prostatectomy in cancer control and survival in a nationally representative population. This population based observational cohort study of patients with prostate cancer undergoing robot-assisted radical prostatectomy and open radical prostatectomy during 2003 to 2012 used data captured in the SEER (Surveillance, Epidemiology, and End Results)-Medicare linked database. Propensity score matching and time to event analysis were used to compare all cause mortality, prostate cancer specific mortality and use of additional treatment after surgery. A total of 6,430 robot-assisted radical prostatectomies and 9,161 open radical prostatectomies performed during 2003 to 2012 were identified. The use of robot-assisted radical prostatectomy increased from 13.6% in 2003 to 2004 to 72.6% in 2011 to 2012. After a median followup of 6.5 years (IQR 5.2-7.9) robot-assisted radical prostatectomy was associated with an equivalent risk of all cause mortality (HR 0.85, 0.72-1.01) and similar cancer specific mortality (HR 0.85, 0.50-1.43) vs open radical prostatectomy. Robot-assisted radical prostatectomy was also associated with less use of additional treatment (HR 0.78, 0.70-0.86). Robot-assisted radical prostatectomy has comparable intermediate cancer control as evidenced by less use of additional postoperative cancer therapies and equivalent cancer specific and overall survival. Longer term followup is needed to assess for differences in prostate cancer specific survival, which was similar during intermediate followup. Our findings have significant quality and cost implications, and provide reassurance regarding the adoption of more expensive technology in the absence of randomized controlled trials. Copyright © 2017 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Study on isopropanol degradation by UV/TiO2 nanotube

NASA Astrophysics Data System (ADS)

Cheng, Hsiu-Yueh; Chang, Kai-Chau; Lin, Kae-Long; Ma, Chih-Ming

2018-04-01

When a semiconductor molecule absorbs photons with energy equal to or greater than its band-gap, electrons in the valence band can be excited and jump up into the conduction band and thus charge carriers are generated. When these charge carriers successfully migrate to the solid surface without recombining, the electrons and holes may undergo electron-transfer processes with adsorbates of suitable redox potentials. The photogenerated holes react with the water to produce hydroxyl radicals, while the photogenerated electrons react with molecular oxygen to give superoxide radical anions. These radicals so produced are highly reactive and they work together to completely oxidize the organic species. In this study, TiO2 nanotube has been prepared and was to be used to control acetone. In this work, mesoporous nanotubes by hydrothermal treatment in aqueous sodium hydroxide solution have been synthesized. Direct hydrothermal synthesis method is easy and efficient to synthesize titanate nanotubes. Using sodium hydroxide, the considerable decrease in reaction time and reaction temperature was achieved.

Isolation and reversible dimerization of a selenium-selenium three-electron σ-bond.

PubMed

Zhang, Senwang; Wang, Xingyong; Su, Yuanting; Qiu, Yunfan; Zhang, Zaichao; Wang, Xinping

2014-06-11

Three-electron σ-bonding that was proposed by Linus Pauling in 1931 has been recognized as important in intermediates encountered in many areas. A number of three-electron bonding systems have been spectroscopically investigated in the gas phase, solution and solid matrix. However, X-ray diffraction studies have only been possible on simple noble gas dimer Xe∴Xe and cyclic framework-constrained N∴N radical cations. Here, we show that a diselena species modified with a naphthalene scaffold can undergo one-electron oxidation using a large and weakly coordinating anion, to afford a room-temperature-stable radical cation containing a Se∴Se three-electron σ-bond. When a small anion is used, a reversible dimerization with phase and marked colour changes is observed: radical cation in solution (blue) but diamagnetic dimer in the solid state (brown). These findings suggest that more examples of three-electron σ-bonds may be stabilized and isolated by using naphthalene scaffolds together with large and weakly coordinating anions.

Kinetics and thermochemistry of 2,5-dimethyltetrahydrofuran and related oxolanes: next next-generation biofuels.

PubMed

Simmie, John M

2012-05-10

The enthalpies of formation, entropies, specific heats at constant pressure, enthalpy functions, and all carbon-hydrogen and carbon-methyl bond dissociation energies have been computed using high-level methods for the cyclic ethers (oxolanes) tetrahydrofuran, 2-methyltetrahydrofuran, and 2,5-dimethyltetrahydrofuran. Barrier heights for hydrogen-abstraction reactions by hydrogen atoms and the methyl radical are also computed and shown to correlate with reaction energy change. The results show a pleasing consistency and considerably expands the available data for these important compounds. Abstraction by ȮH is accompanied by formation of both pre- and postreaction weakly bound complexes. The resulting radicals formed after abstraction undergo ring-opening reactions leading to readily recognizable intermediates, while competitive H-elimination reactions result in formation of dihydrofurans. Formation enthalpies of all 2,3- and 2,5-dihydrofurans and associated radicals are also reported. It is probable that the compounds at the center of this study will be relatively clean-burning biofuels, although formation of intermediate aldehydes might be problematic.

Outcomes of Minimally Invasive Inguinal Hernia Repair at the Time of Robotic Radical Prostatectomy.

PubMed

Soto-Palou, Francois G; Sánchez-Ortiz, Ricardo F

2017-06-01

Abdominal straining associated with voiding dysfunction or constipation has traditionally been associated with the development of abdominal wall hernias. Thus, classic general surgery dictum recommends that any coexistent bladder outlet obstruction should be addressed by the urologist before patients undergo surgical repair of a hernia. While organ-confined prostate cancer is usually not associated with the development of lower urinary tract symptoms, a modest proportion of patients treated with radical prostatectomy may have coexisting benign prostatic hyperplasia with elevated symptom scores and hernias may be incidentally detected at the time of surgery. Furthermore, dissection of the space of Retzius during retropubic or minimally invasive prostatectomy may result exposure of abdominal wall defects which may have been present, but asymptomatic if plugged with preperitoneal fat. Herein we examine the literature regarding the incidence of postoperative inguinal hernias after prostatectomy, review potential risk factors which could aid in preoperative patient identification, and discuss the published experience regarding concurrent hernia repair at the time of open or minimally invasive radical prostatectomy.

Estimation of Free Radical Ionization Energies by the Kinetic Method and the Relationship between the Kinetic Method and the Hammett Equation.

PubMed

Chen, G; Wong, P; Cooks, R G

1997-09-01

Substituted 1,2-diphenylethanes undergo competitive dissociations upon electron ionization (EI) to generate substituted benzyl cation and benzyl radical pairs. Application of the kinetic method to the previous reported EI mass spectra of these covalently bound precursor ions (data are taken from McLafferty et al. J. Am. Chem. Soc. 1970, 92, 6867)) is used to estimate the ionization energies of substituted benzyl free radicals. A correlation is observed between the Hammett σ constant of the substituents and the kinetic method parameter, ln(k(x)/k(H)), where k(x) is the rate of fragmentation to give the substituted product ion and k(H) is the rate to give the benzyl ion itself. Systems involving weakly bound cluster ions, including proton-bound dimers of meta- and para-substituted pyridines and meta- and para-substituted anilines, and electron-bound dimers of meta- and para-substituted nitrobenzenes, also show good correlations between the kinetic method parameter and the Hammett σ constant.

Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

NASA Technical Reports Server (NTRS)

Reddy, K. T.; Cernansky, N. P.; Cohen, R. S.

1988-01-01

The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.

(abstract) Effects of Radiation and Oxidative Stress on Development and Morphology of Intestinal Cells

NASA Technical Reports Server (NTRS)

Honda, Shuji; Nelson, Gregory; Schubert, Wayne

1993-01-01

Intestinal cells when subjected to oxidative stress or radiation exhibit abnormal nuclear divisions observed as: 1) supernumerary cell divisions in anterior intestinal cells or 2) incomplete nuclear division and the persistence of anaphase bridges between daughter nuclei. Two oxygen sensitive mutants, mev-1 and rad-8 were observed to exhibit spontaneous supernumerary nuclear divisions at low frequency. N2 can be induced to undergo these divisions by treatment with the superoxide dismutase (SOD) inhibitor diethyl dithicarbamate or with the free radical generator methyl viologen. By contrast, the free radical generator bleomycin produces anaphase bridges in N2 intestinal nuclei at high frequency. Intestinal anaphase bridges can be induced by ionizing radiation and their formation is dependent on dose and radiation type.

[Effect of calcium cations on acid-base properties and free radical oxidation of dopamine and pyrocatechol].

PubMed

Lebedev, A V; Ivanova, M V; Timoshin, A A; Ruuge, E K

2008-01-01

Ca2+-induced increase in the rate of pyrocatechol and dopamine oxidation by dioxygen and Ca2+-dependent acid-base properties of the catechols were studied by potentiometric titration, UV/Vis-spectrophotometry, EPR-spectroscopy, and by measurement of oxygen consumption. The effect of Ca2+ on the chain reactions of oxidation can be explained by additional deprotonation (decrease in pKai) of the catechols that accelerates one electron transport to dioxygen and formation of calcium semiquinonate, undergoing further oxidation. The described Ca2+-dependent redox-conversion of ortho-phenols proposes that an additional function of calcium in the cell can be its involvement in free radical oxidoreductive reactions at pH > pKai.

Cranioplasty by means of molded polymethylmethacrylate prosthetic reconstruction after radical excision of neoplasms of the skull in two dogs.

PubMed

Bryant, Karen J; Steinberg, Howard; McAnulty, Jonathan F

2003-07-01

Two dogs with osteoma or multilobulated tumor of bone of the skull were treated with large en bloc resections. The resections resulted in exposure of the brain above the horizon line of the remaining calvarium; in 1 dog, the removal of the dorsal orbital rims also exposed both orbits dorsally. Protection of the brain and exposed tissues and restoration of the cosmetic appearance of the skull were attempted by use of molded polymethylmethacrylate prosthetic reconstruction of the calvarium. The technique described involves cranioplasty by use of a preformed molded polymethylmethacrylate implant. Such prosthetic cranioplasty may benefit dogs undergoing radical excision of extensive tumors, and the usefulness and potential complications of its application are discussed.

Atmospheric Oxidation Mechanism of Furfural Initiated by Hydroxyl Radicals.

PubMed

Zhao, Xiaocan; Wang, Liming

2017-05-04

Furfural is emitted into the atmosphere because of its potential applications as an intermediate to alkane fuels from biomass, industrial usages, and biomass burning. The kinetic and mechanistic information on the furfural chemistry is necessary to assess the fate of furfural in the atmosphere and its impact on the air quality. Here we studied the atmospheric oxidation mechanisms of furfural initiated by the OH radicals using quantum chemistry and kinetic calculations. The reaction of OH and furfural was initiated mainly by OH additions to C 2 and C 5 positions, forming R2 and R5 adducts, which could undergo rapid ring-breakage to form R2B and R5B, respectively. Our calculations showed that these intermediate radicals reacted rather slowly with O 2 under the atmospheric conditions because the additions of O 2 to these radicals are only slightly exothermic and highly reversible. Alternatively, these radicals would react directly with O 3 , NO 2 , HO 2 /RO 2 , etc. Namely, the atmospheric oxidation of furfural would unlikely result in ozone formation. Under typical atmospheric conditions, the main products in OH-initiated furfural oxidation include 2-oxo-3-pentene-1,5-dialdehyde, 5-hydroxy-2(5H)-furanone, 4-oxo-2- butenoic acid, and 2,5-furandione. These compounds will likely stay in the gas phase and are subject to further photo-oxidation.

Electrochemical models for the radical annihilation reactions in organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Armstrong, Neal R.; Anderson, Jeffrey D.; Lee, Paul A.; McDonald, Erin; Wightman, R. M.; Hall, Hank K.; Hopkins, Tracy; Padias, Anne; Thayumanavan, Sankaran; Barlow, Stephen; Marder, Seth R.

1998-12-01

Bilayer organic light emitting diodes (OLEDs), based upon vacuum deposited molecules, or single layer OLEDs, based upon spin-cast polymeric materials, doped with these same molecules, produce light from emissive states of the lumophores which are created through annihilation reactions of radical species, which can be modeled through solution electrochemistry. Difference seen in solution reduction and oxidation potentials of molecular components of OLEDs are a lower limit estimate to the differences in energy of these same radical species in the condensed phase environmental. The light emitted from an aluminum quinolate (Alq3)/triarylamine (TPD)-based OLED, or an Alq3/PVK single layers OLED, can be reproduce from solution cross reactions of Alq3/TPD+. The efficiency of this process increases as the oxidation potential of the TPD increases, due to added substituents. Radical cations and anions of solubilized version of quinacridone dopants (DIQA) which have been used to enhance efficiencies in these OLEDs, are shown to be electrochemically more stable than Alq3 and Alq3, and DIQA radical annihilation reactions produce the same emissive state as in the quinacridone-doped OLEDs. Electrochemical studies demonstrate the ways in which other dopants might enhance the efficiency and shift the color output of OLEDs, across the entire visible and near-IR spectrum. Chemical degradation pathways of these same molecular components, which they may undergo during OLED operation, are also revealed by these electrochemical studies.

Reaction Paths and Chemical Activation Reactions of 2-Methyl-5-Furanyl Radical with 3O2.

PubMed

Hudzik, Jason M; Bozzelli, Joseph W

2017-10-05

Interest in high-energy substituted furans has been increasing due to their occurrence in biofuel production and their versatility in conversion to other useful products. Methylfurans are the simplest substituted furans and understanding their reaction pathways, thermochemical properties, including intermediate species stability, and chemical kinetics would aid in the study of larger furans. Furan ring C-H bonds have been shown to be extremely strong, approximately 120 kcal mol -1 , due in part to the placement of the oxygen atom and aromatic-like resonance, both within the ring. The thermochemistry and kinetics of the oxidation of 2-methyfuran radical at position 5 of the furan ring, 2-methyl-5-furanyl radical (2MF5j), is analyzed. The resulting chemically activated species, 2MF5OOj radical, has a well depth of 51 kcal mol -1 below the 2MF5j + O 2 reactants; this is 4-5 kcal mol -1 deeper than that of phenyl and vinyl radical plus O 2 , with both of these reactions known to undergo chain branching. Important, low-energy reaction pathways include chain branching dissociations, intramolecular abstractions, group transfers, and radical oxygen additions. Enthalpies of formation, entropies, and heat capacities for the stable molecules, radicals, and transition-state species are analyzed using computational methods. Calculated ΔH ° f 298 values were determined using an isodesmic work reaction from the CBS-QB3 composite method. Elementary rate parameters are from saddle point transition-state structures and compared to variational transition-state analysis for the barrierless reactions. Temperature- and pressure-dependent rate constants which are calculated using QRRK and master equation analysis is used for falloff and stabilization.

Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy

DOE PAGES

Mani, Tomoyasu; Grills, David C.

2017-07-05

Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we showmore » that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1. IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.« less

Correlation between CO2 storage at the last minute of gas insufflation and area of retroperitoneal lacuna during retroperitoneal laparoscopic radical nephrectomy.

PubMed

Hu, Jian-Jun; Liu, Ya-Hua; Yu, Chan-Juan; Jialielihan, Nuerbolati

2016-07-22

Adequate operation interspace is the premise of laparoscopy, and carbon dioxide (CO2) was an ideal gas for forming lacuna. A retroperitoneal space is used to form operation interspace in retroperitoneal laparoscopic radical nephrectomy by making ballooning, and the retroperitoneal space has no relative complete and airtight serous membrane, therefore CO2 absorption may be greater in retroperitoneal than transperitoneal laparoscopic radical nephrectomy. Excess CO2 absorption may induce hypercapnemia and further cause physiopathological change of respiratory and circulatory system. Therefore, exact evaluation of amount of CO2 which is eliminated from body via minute ventilation is important during retroperitoneal laparoscopic radical nephrectomy. The aim of the paper is to study the correlation between CO2 storage at the last minute of gas insufflation and area of retroperitoneal lacuna during retroperitoneal laparoscopic radical nephrectomy. Forty ASA I/II patients undergoing retroperitoneal laparoscopic radical nephrectomy were enrolled. CO2 storage at the last minute of gas insufflation and area of a retroperitoneal lacuna were observed. Linear correlation and regression were performed to determine the correlation between them. There was positive correlation between CO2 storage at the last minute of gas insufflation and area of retroperitoneal lacuna (r = 0.880, P = 0.000), and the equation of linear regression was y = -83.097 + 0.925x (R(2) = 0.780, t = 11.610, P = 0.000). Amount of CO2 which is eliminated from body via mechanical ventilation could be calculated by measuring the area of retroperitoneal lacuna during retroperitoneal laparoscopic radical nephrectomy, and an anesthetist should be aware of the size of lacuna to predict high CO2 storage at the last minute of gas insufflation.

Photodissociable dimer reduction products of 2-thiopyrimidine derivatives.

PubMed Central

Wrona, M; Giziewicz, J; Shugar, D

1975-01-01

Both 4,6-dimethyl-2-thipyrimidine and its 1-methyl derivative undergo polarographic reduction in aqueous medium, via a 1e/1H+ reduction to a free radical which rapidly dimerizes to products isolates and identified as 4,4'-bis-(4,6-dimethyl-3,4-dihydropyrimidin-2-thione) and the corresponding 1-methyl dimer. The dimers may be oxidized electrolytically to regenerate the parent monomers. Both dimers also undergo photodissociation to quantitatively regenerate the parent monomers, in high quantum yield, 0.23 and 0.35 M/Einstein. The correlation between electrochemical and photochemical reductions of 2-thiopyrimidines are discussed, as well as the significance of the dimer photodissociation reactions in relation to nucleic acid photochemistry. PMID:28516

Age-stratified outcomes after robotic-assisted laparoscopic radical prostatectomy.

PubMed

Zorn, Kevin C; Mendiola, Frederick P; Rapp, David E; Mikhail, Albert A; Lin, Shang; Orvieto, Marcelo A; Zagaja, Gregory P; Shalhav, Arieh L

2007-01-01

We sought to evaluate post-operative return of urinary and sexual function in men undergoing robotic-assisted laparoscopic radical prostatectomy (RLRP). Prospective assessment of urinary continence and sexual function was performed in patients undergoing RLRP. Subjective assessment involved the use of the validated RAND-36 Item Health Survey/UCLA Prostate Cancer Index questionnaire. Questionnaires were completed pre-operatively and at 1, 3, 6 and 12 months post-operatively. Subset analyses were performed to assess the effect of age on functional outcomes. A total of 338 consecutive patients underwent RLRP between February 2003 and August 2005. Included patients for evaluation comprised of 21, 129, and 150 patients, aged <50, 50-59, and ≥60 years old, respectively. Kaplan-Meier curve analysis demonstrated that younger men (<60 years) achieved subjective continence significantly earlier than older age group (≥60 years) (P = 0.02). Continence rates, however, equalized among all age groups at 1 year follow-up. Younger men (<50 years) also demonstrated a quicker and greater return of sexual function (P = 0.01), which persisted through assessment at 1 year post-operatively. Our results suggest that younger men may have an earlier return of continence and potency when compared to men > 60 years. Despite this finding, continence outcomes appear to be equal among age groups after 1 year of follow-up. Moreover, men < 60 years continue to report superior potency outcomes compared to men > 60 years at 1 year post-operatively. Such findings are valuable in counseling patients undergoing RLRP.

Impact of penile rehabilitation with low-dose vardenafil on recovery of erectile function in Japanese men following nerve-sparing radical prostatectomy

PubMed Central

Nakano, Yuzo; Miyake, Hideaki; Chiba, Koji; Fujisawa, Masato

2014-01-01

Erectile dysfunction (ED) is a major complication after radical prostatectomy (RP); however, debate continues regarding the efficacy of penile rehabilitation in the recovery of the postoperative erectile function (EF). This study included a total of 103 consecutive sexually active Japanese men with localized prostate cancer undergoing nerve-sparing RP, and analyzed the postoperative EF, focusing on the significance of penile rehabilitation. In this series, 24 and 79 patients underwent bilateral and unilateral nerve-sparing RPs, respectively, and 10 or 20 mg of vardenafil was administered to 35 patients at least once weekly, who agreed to undergo penile rehabilitation. Twelve months after RP, 48 (46.6%) of the 103 patients were judged to have recovered EF sufficient for sexual intercourse without any assistance. The proportion of patients who recovered EF in those undergoing penile rehabilitation (60.0%) was significantly greater than that in those without penile rehabilitation (38.2%). Of several parameters examined, the preoperative International Index of Erectile Function-5 (IIEF-5) score and nerve-sparing procedure were significantly associated with the postoperative EF recovery rates in patients with and without management by penile rehabilitation, respectively. Furthermore, univariate analysis identified the preoperative IIEF-5 score, nerve-sparing procedure and penile rehabilitation as significant predictors of EF recovery, among which the preoperative IIEF-5 score and nerve-sparing procedure appeared to be independently associated with EF recovery. Considering these findings, despite the lack of independent significance, penile rehabilitation with low-dose vardenafil could exert a beneficial effect on EF recovery in Japanese men following nerve-sparing RP. PMID:24994781

Effect of preoperative pelvic floor muscle therapy with biofeedback versus standard care on stress urinary incontinence and quality of life in men undergoing laparoscopic radical prostatectomy: a randomised control trial.

PubMed

Dijkstra-Eshuis, Joke; Van den Bos, Tine W L; Splinter, Rosa; Bevers, Rob F M; Zonneveld, Willemijn C G; Putter, Hein; Pelger, Rob C M; Voorham-van der Zalm, Petra J

2015-02-01

Laparoscopic radical prostatectomy (LARP) may cause stress urinary incontinence (SUI). This study reports the effects of preoperative pelvic floor muscle therapy (PFMT) on SUI and quality of life (QoL) in men undergoing LARP. In this single-center randomized controlled trial, 122 patients undergoing LARP were assigned to an intervention group of PFMT with biofeedback once a week preoperatively, with 4 weeks' follow-up or to a control group receiving standard care. Randomization and allocation to the trial group were carried out by a central computer system. The primary analysis was based on 121 (n = 65; n = 56), comparing SUI rates and QoL in the two groups in a 1-year follow-up. Validated questionnaires, the Pelvic Floor Inventories (PeLFls), the King's Health Questionnaire (KHQ), the International Prostate Symptom Score (IPSS), a bladder diary, a 24-hr pad test and pelvic floor examination were used. Continence was defined as no leakage at all. All analyses were performed according to intention-to-treat. One hundred twenty-two patients were randomized, 19 patients were excluded from analysis because of early drop-out. There were no significant differences between both groups in the incidence of SUI and QoL based on the KHQ, IPSS, and pad tests (P ≥ 0.05). In all patients continence was achieved in 77.2% at 1 year postoperatively. Preoperative PFMT does not appear to be effective in the prevention of SUI and QoL following LARP. © 2014 Wiley Periodicals, Inc.

Comparative study of the radical and standard lymphadenectomy in the surgical treatment of adenocarcinoma of the ampula of Vater.

PubMed

Albagli, Rafael Oliveira; Carvalho, Gustavo Santos Stoduto de; Mali Junior, Jorge; Eulálio, José Marcos Raso; de Melo, Eduardo Linhares Rielo

2010-12-01

To evaluate the morbidity and mortality in patients undergoing surgical pancreatoduodenectomy (PD) in standard and radical lymphadenectomy for adenocarcinoma of papilla, analyzing the prognostic factors related to overall and disease-free survival. Were analyzed retrospectively from 1999 to 2007, in the Department of Abdominal and Pelvic Surgery (INCa-RJ), 50 cases of PD for adenocarcinoma of the duodenal papilla divided into two groups according to lymphadenectomy (group A: standard lymphadenectomy and group B: radical lymphadenectomy). The median age was similar in both groups, as well as the distribution between the sex. In the comparison between the lymphadenectomies, only the number of lymph nodes resected (group A: 12.3 and group B: 26.5) and operative time (group A: 421 and group B: 474) were significantly different. There were no statistically significant differences in the two groups with respect to morbidity and mortality rate and length of hospitalization. The disease-free survival (group A: 35 months and group B: 51 months) and overall survival (group A: 38 months and group B: 53 months) was higher in the group of radical lymphadenectomy, but were not statistically significant. In this study there were no cases of metastatic lymph nodes to other groups without nodal involvement of the pancreatic-duodenal lymph node chains (13, 17), suggesting a pattern of lymph node spread. Despite the radical lymphadenectomy present rates of disease-free survival and overall survival largest such data were not statistically significant. Further studies should be conducted to evaluate the real role of radical lymphadenectomy in adenocarcinoma of the duodenal papilla.

Radical parametrectomy after 'cut-through' hysterectomy in low-risk early-stage cervical cancer: Time to consider this procedure obsolete.

PubMed

Pareja, Rene; Echeverri, Lina; Rendon, Gabriel; Munsell, Mark; Gonzalez-Comadran, Mireia; Sanabria, Daniel; Isla, David; Frumovitz, Michael; Ramirez, Pedro T

2018-03-01

The goal of this study is to identify predictive factors in patients with a diagnosis of early-stage cervical cancer after simple hysterectomy in order to avoid a radical parametrectomy. A retrospective review was performed of all patients who underwent radical parametrectomy and bilateral pelvic lymphadenectomy at MD Anderson Cancer Center and at the Instituto de Cancerologia Las Americas in Medellin, Colombia from December 1999 to September 2017. We sought to determine the outcomes in patients diagnosed with low-risk factors (squamous, adenocarcinoma or adenosquamous lesions<2cm in size, and invading<10mm) undergoing radical parametrectomy and pelvic lymphadenectomy. A total of 30 patients were included in the study. The median age was 40.4years (range; 26-60) and median body mass index (BMI) was 26.4kg/m 2 (range; 17.7-40.0). A total 22 patients had tumors<1cm and 8 had tumors between 1 and 2cm. A total of 6 (33%) of 18 patients had evidence of lymph-vascular invasion (LVSI). No radical parametrectomy specimen had residual tumor, involvement of the parametrium, vaginal margin positivity, or lymph node metastasis. None of the patients received adjuvant therapy. After a median follow-up of 99months (range; 6-160) only one patient recurred. Radical parametrectomy may be avoided in patients with low-risk early-stage cervical cancer detected after a simple hysterectomy. Rates of residual disease (parametrial or vaginal) and the need for adjuvant treatments or recurrences are very low. Copyright © 2018 Elsevier Inc. All rights reserved.

Predicting the effect of angular momentum on the dissociation dynamics of highly rotationally excited radical intermediates.

PubMed

Brynteson, Matthew D; Butler, Laurie J

2015-02-07

We present a model which accurately predicts the net speed distributions of products resulting from the unimolecular decomposition of rotationally excited radicals. The radicals are produced photolytically from a halogenated precursor under collision-free conditions so they are not in a thermal distribution of rotational states. The accuracy relies on the radical dissociating with negligible energetic barrier beyond the endoergicity. We test the model predictions using previous velocity map imaging and crossed laser-molecular beam scattering experiments that photolytically generated rotationally excited CD2CD2OH and C3H6OH radicals from brominated precursors; some of those radicals then undergo further dissociation to CD2CD2 + OH and C3H6 + OH, respectively. We model the rotational trajectories of these radicals, with high vibrational and rotational energy, first near their equilibrium geometry, and then by projecting each point during the rotation to the transition state (continuing the rotational dynamics at that geometry). This allows us to accurately predict the recoil velocity imparted in the subsequent dissociation of the radical by calculating the tangential velocities of the CD2CD2/C3H6 and OH fragments at the transition state. The model also gives a prediction for the distribution of angles between the dissociation fragments' velocity vectors and the initial radical's velocity vector. These results are used to generate fits to the previously measured time-of-flight distributions of the dissociation fragments; the fits are excellent. The results demonstrate the importance of considering the precession of the angular velocity vector for a rotating radical. We also show that if the initial angular momentum of the rotating radical lies nearly parallel to a principal axis, the very narrow range of tangential velocities predicted by this model must be convoluted with a J = 0 recoil velocity distribution to achieve a good result. The model relies on measuring the kinetic energy release when the halogenated precursor is photodissociated via a repulsive excited state but does not include any adjustable parameters. Even when different conformers of the photolytic precursor are populated, weighting the prediction by a thermal conformer population gives an accurate prediction for the relative velocity vectors of the fragments from the highly rotationally excited radical intermediates.

Sentinel node detection in cervical cancer with (99m)Tc-phytate.

PubMed

Silva, Lucas B; Silva-Filho, Agnaldo L; Traiman, Paulo; Triginelli, Sérgio A; de Lima, Carla Flávia; Siqueira, Cristiano Ferrari; Barroso, Adelanir; Rossi, Telma Maria F F; Pedrosa, Moises Salgado; Miranda, Dairton; Melo, José Renan Cunha

2005-05-01

The aim of this study was to investigate the feasibility of sentinel lymph node (SLN) identification using radioisotopic lymphatic mapping with technetium-99 m-labeled phytate in patients undergoing radical hysterectomy with pelvic lymphadenectomy for treatment of early cervical cancer. Between July 2001 and February 2003, 56 patients with cervical cancer FIGO stage I (n = 53) or stage II (n = 3) underwent sentinel lymph node detection with preoperative lymphoscintigraphy ((99m)Tc-labeled phytate injected into the uterine cervix, at 3, 6, 9, and 12 o'clock, at a dose of 55-74 MBq in a volume of 0.8 ml) and intraoperative lymphatic mapping with a handheld gamma probe. Radical hysterectomy was aborted in three cases because parametrial invasion was found intraoperatively and we performed only sentinel node resection. The remaining 53 patients underwent radical hysterectomy with complete pelvic lymphadenectomy. Sentinel nodes were detected using a handheld gamma-probe and removed for pathological assessment during the abdominal radical hysterectomy and pelvic lymphadenectomy. One or more sentinel nodes were detected in 52 out of 56 eligible patients (92.8%). A total of 120 SLNs were detected by lymphoscintigraphy (mean 2.27 nodes per patient) and intraoperatively by gamma probe. Forty-four percent of SLNs were found in the external iliac area, 39% in the obturator region, 8.3% in interiliac region, and 6.7% in the common iliac area. Unilateral sentinel nodes were found in thirty-one patients (59%). The remaining 21 patients (41%) had bilateral sentinel nodes. Microscopic nodal metastases were confirmed in 17 (32%) cases. In 10 of these patients, only SLNs had metastases. The 98 sentinel nodes that were negative on hematoxylin and eosin were submitted to cytokeratin immunohistochemical analysis. Five (5.1%) micrometastases were identified with this technique. The sensitivity of the sentinel node was 82.3% (CI 95% = 56.6-96.2) and the negative predictive value was 92.1% (CI 95% = 78.6-98.3). The accuracy of sentinel node in predicting the lymph node status was 94.2%. Preoperative lymphoscintigraphy and intraoperative lymphatic mapping with (99m)Tc-labeled phytate are effective in identifying sentinel nodes in patients undergoing radical hysterectomy and to select women in whom lymph node dissection can be avoided.

Prevalence of Clostridium Difficile Infection in Patients After Radical Cystectomy and Neoadjuvant Chemotherapy.

PubMed

Cotter, Katherine J; Fan, Yunhua; Sieger, Gretchen K; Weight, Christopher J; Konety, Badrinath R

2017-10-27

Clostridium Difficile is the most common cause of nosocomial infectious diarrhea. This study evaluates the prevalence and predictors of Clostridium Difficile infections in patients undergoing radical cystectomy with or without neoadjuvant chemotherapy. Retrospective chart review was performed of all patients undergoing cystectomy and urinary diversion at a single institution from 2011-2017. Infection was documented in all cases with testing for Clostridium Difficile polymerase chain reaction toxin B. Patient and disease related factors were compared for those who received neoadjuvant chemotherapy vs. those who did not in order to identify potential risk factors associated with C. Difficile infections. Chi squared test and logistic regression analysis were used to determine statistical significance. Of 350 patients who underwent cystectomy, 41 (11.7%) developed Clostridium Difficile in the 30 day post-operative period. The prevalence of C. Difficile infection was higher amongst the patients undergoing cystectomy compared to the non-cystectomy admissions at our hospital (11.7 vs. 2.9%). Incidence was not significantly different among those who underwent cystectomy for bladder cancer versus those who underwent the procedure for other reasons. Median time to diagnosis was 6 days (range 3-28 days). The prevalence of C. Diff infections was not significantly different among those who received neoadjuvant chemotherapy vs. those who did not (11% vs. 10.4% p  = 0.72). A significant association between C. Difficile infection was not seen with proton pump inhibitor use ( p  = 0.48), patient BMI ( p  = 0.67), chemotherapeutic regimen ( p  = 0.94), individual surgeon ( p  = 0.54), type of urinary diversion (0.41), or peri-operative antibiotic redosing ( p  = 0.26). Clostridium Difficile infection has a higher prevalence in patients undergoing cystectomy. No significant association between prevalence and exposure to neoadjuvant chemotherapy was seen.

5-Nitrosalicylic Acid as a Novel Matrix for In-Source Decay in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

PubMed Central

Asakawa, Daiki

2013-01-01

The matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) of peptides and glycans was studied using an oxidizing chemical, 5-nitrosalicylic acid (5-NSA) as the matrix. The use of 5-NSA for the MALDI-ISD of peptides and glycans promoted fragmentation pathways involving “hydrogen-deficient” radical precursors. Hydrogen abstraction from peptides resulted in the production of a “hydrogen-deficient” peptide radical that contained a radical site on the amide nitrogen in the peptide backbone with subsequent radical-induced cleavage at the Cα–C bonds. Cleavage at the Cα–C bond leads to the production of an a•/x fragment pair and the radical a• ions then undergo further hydrogen abstraction to form a ions after Cα–C bond cleavage. Since the Pro residue does not contain a nitrogen-centered radical site, Cα–C bond cleavage does not occur at this site. Alternatively, the specific cleavage of CO−N bonds leads to a b•/y fragment pair at Xxx−Pro which occurs via hydrogen abstraction from the Cα−H in the Pro residue. In contrast, “hydrogen-deficient” glycan radicals were generated by hydrogen abstraction from hydroxyl groups in glycans. Both glycosidic and cross-ring cleavages occurred as the result of the degradation of “hydrogen-deficient” glycan radicals. Cross-ring cleavage ions are potentially useful in linkage analysis, one of the most critical steps in the characterization of glycans. Moreover, isobaric glycans could be distinguished by structure specific ISD ions, and the molar ratio of glycan isomers in a mixture can be estimated from their fragment ions abundance ratios. MALDI-ISD with 5-NSA could be a useful method for the sequencing of peptides including the location of post-translational modifications, identification and semi-quantitative analysis of mixtures of glycan isomers. PMID:24860709

Impact of different variables on the outcome of patients with clinically confined prostate carcinoma: prediction of pathologic stage and biochemical failure using an artificial neural network.

PubMed

Ziada, A M; Lisle, T C; Snow, P B; Levine, R F; Miller, G; Crawford, E D

2001-04-15

The advent of advanced computing techniques has provided the opportunity to analyze clinical data using artificial intelligence techniques. This study was designed to determine whether a neural network could be developed using preoperative prognostic indicators to predict the pathologic stage and time of biochemical failure for patients who undergo radical prostatectomy. The preoperative information included TNM stage, prostate size, prostate specific antigen (PSA) level, biopsy results (Gleason score and percentage of positive biopsy), as well as patient age. All 309 patients underwent radical prostatectomy at the University of Colorado Health Sciences Center. The data from all patients were used to train a multilayer perceptron artificial neural network. The failure rate was defined as a rise in the PSA level > 0.2 ng/mL. The biochemical failure rate in the data base used was 14.2%. Univariate and multivariate analyses were performed to validate the results. The neural network statistics for the validation set showed a sensitivity and specificity of 79% and 81%, respectively, for the prediction of pathologic stage with an overall accuracy of 80% compared with an overall accuracy of 67% using the multivariate regression analysis. The sensitivity and specificity for the prediction of failure were 67% and 85%, respectively, demonstrating a high confidence in predicting failure. The overall accuracy rates for the artificial neural network and the multivariate analysis were similar. Neural networks can offer a convenient vehicle for clinicians to assess the preoperative risk of disease progression for patients who are about to undergo radical prostatectomy. Continued investigation of this approach with larger data sets seems warranted. Copyright 2001 American Cancer Society.

Oncologic outcomes in patients with nonurothelial bladder cancer.

PubMed

Patel, Sanjay G; Weiner, Adam Benjamin; Keegan, Kirk; Morgan, Todd

2018-01-01

We aimed to evaluate the relative prognostic impact of the most common variant histologies on disease-specific survival (DSS) in patients undergoing radical cystectomy. The Surveillance, Epidemiology, and End Result database was used to identify patients who underwent radical cystectomy for bladder cancer from 1990 to 2007. Patients with urothelial cell carcinoma (UCC), squamous cell carcinoma (SCC), adenocarcinoma (AC), sarcoma, small cell carcinoma, signet ring carcinoma, and spindle cell carcinoma were included in the study. Multivariable analysis was performed using Cox proportional hazards model to assess independent predictors of disease-specific survival (DSS). Mortality rates were estimated using Kaplan-Meier analyses. A total of 14,130 patients met inclusion criteria with the following histologies: UCC (90.1%), SCC (4.6%), AC, (2.3%), sarcoma (0.8%), small cell carcinoma (0.8%), signet ring carcinoma (0.5%), and spindle cell carcinoma (0.9%). Three-year DSS was most favorable in patients with UCC (63.7%; 95% confidence interval [62.9%-64.8%]) and AC (65.3% [59.3%-70.6%]), whereas 3-year DSS was the least favorable for small cell carcinoma (41.6% [31.3%-51.6%]) and sarcoma (45.4% [35.1%-55.1%]). In the multivariable analysis, independent predictors of DSS were age, marital status, grade, T-stage, N-stage, and variant histology. With respect to UCC, there was an increased risk of disease-specific death associated with all variants except AC. Sarcoma and spindle cell carcinoma were associated with the highest risk of death. With the exception of AC, the most common variant bladder cancer histologies are all independently associated with worse DSS relative to UCC in patients undergoing radical cystectomy.

Preemptive multimodal pain regimen reduces opioid analgesia for patients undergoing robotic-assisted laparoscopic radical prostatectomy.

PubMed

Trabulsi, Edouard J; Patel, Jitesh; Viscusi, Eugene R; Gomella, Leonard G; Lallas, Costas D

2010-11-01

Minimally invasive surgical techniques have many benefits, including reduced postoperative pain. Despite this, most patients require opioid analgesia, which can have significant side effects and toxicity. We report the first urologic study using multimodal analgesia with pregabalin, a gabapentinoid. The present retrospective study included 60 patients who underwent robotic-assisted laparoscopic radical prostatectomy. Of the 60 patients, 30 received multimodal treatment with pregabalin 150 mg, acetaminophen 975 mg, and celecoxib 400 mg orally 2 hours before the start of the procedure and continued postoperatively. These patients were compared with 30 consecutive previous patients, who had received a standard postoperative analgesic regimen with intravenous ketorolac 15 mg every 6 hours with oxycodone 5 mg and acetaminophen 325 mg, 1 to 2 tablets, every 4 hours as needed for pain. The patients in the multimodal treatment group had a significantly reduced intraoperative opioid requirement, as measured by the mean morphine equivalent dose administered (38.4 ± 2.73 mg vs 49.1 ± 2.65 mg; P < .01). The mean postoperative opioid use was also significantly reduced (10.7 ± 2.82 mg vs 26.2 ± 6.56 mg; P = .034), as was the mean total morphine equivalent dose administered (49.1 ± 2.7 mg vs 75.3 ± 4.6 mg; P < .001). The operative time, estimated operative blood loss, antiemetic use, postoperative creatinine and hemoglobin levels, and length of stay were similar in the 2 groups. No operative or treatment complications occurred in either group. The present retrospective review has indicated that a multimodal analgesic approach with pregabalin and celecoxib administered preoperatively decreases intraoperative and postoperative opioid use in patients undergoing robotic-assisted laparoscopic radical prostatectomy. Copyright © 2010 Elsevier Inc. All rights reserved.

A model to predict the risk of lethal nasopharyngeal necrosis after re-irradiation with intensity-modulated radiotherapy in nasopharyngeal carcinoma patients.

PubMed

Yu, Ya-Hui; Xia, Wei-Xiong; Shi, Jun-Li; Ma, Wen-Juan; Li, Yong; Ye, Yan-Fang; Liang, Hu; Ke, Liang-Ru; Lv, Xing; Yang, Jing; Xiang, Yan-Qun; Guo, Xiang

2016-06-29

For patients with nasopharyngeal carcinoma (NPC) who undergo re-irradiation with intensity-modulated radiotherapy (IMRT), lethal nasopharyngeal necrosis (LNN) is a severe late adverse event. The purpose of this study was to identify risk factors for LNN and develop a model to predict LNN after radical re-irradiation with IMRT in patients with recurrent NPC. Patients who underwent radical re-irradiation with IMRT for locally recurrent NPC between March 2001 and December 2011 and who had no evidence of distant metastasis were included in this study. Clinical characteristics, including recurrent carcinoma conditions and dosimetric features, were evaluated as candidate risk factors for LNN. Logistic regression analysis was used to identify independent risk factors and construct the predictive scoring model. Among 228 patients enrolled in this study, 204 were at risk of developing LNN based on risk analysis. Of the 204 patients treated, 31 (15.2%) developed LNN. Logistic regression analysis showed that female sex (P = 0.008), necrosis before re-irradiation (P = 0.008), accumulated total prescription dose to the gross tumor volume (GTV) ≥145.5 Gy (P = 0.043), and recurrent tumor volume ≥25.38 cm(3) (P = 0.009) were independent risk factors for LNN. A model to predict LNN was then constructed that included these four independent risk factors. A model that includes sex, necrosis before re-irradiation, accumulated total prescription dose to GTV, and recurrent tumor volume can effectively predict the risk of developing LNN in NPC patients who undergo radical re-irradiation with IMRT.

Removal of polycyclic synthetic musks and antineoplastic drugs in ozonated wastewater: Quantitation based on the data of differential spectroscopy.

PubMed

Li, Wei; Nanaboina, Venkateswarlu; Chen, Fang; Korshin, Gregory V

2016-03-05

This study examined the degradation behavior of polycyclic musks (PMs) and antineoplastic drugs (ADs) and the absorbance spectra of effluent organic matter (EfOM) in municipal wastewater by ozone. Specific ozone doses used in the experiments ranged from 0 to 1mg O3/mg dissolved organic matter (DOC). The examined PMs included galaxolide, tonalide, celestolide, traseolide and phantolide. ADs included busulfan, chlorambucil, cyclophosphamide, dacarbazine, flutamide, ifosfamide, tamoxifen and methotrexate. Strong monotonic albeit nonlinear correlations were found to exist between relative changes of EfOM absorbance at 254 nm (i.e. ΔA254/A(0)254) and the degradation of the selected PMs and ADs. This result was interpreted based on the concept of the simultaneous oxidation of EfOM and, on the other hand, PMs and ADs. This interpretation showed that PMs were degraded primarily via OH radical attack, with tonalide and phantolide being less reactive compared with the other PMs. ADs such as cyclophosphamide, ifosfamide and busulfan were also determined to undergo oxidation by OH radicals. Comparison of the behavior of the radical probe para-chlorobenzoic acid and the examined ADs and PMs allowed evaluating corresponding reaction rate constants for reactions between these species and OH radicals. Copyright © 2015 Elsevier B.V. All rights reserved.

Routine pelvic drainage not required after open or robotic radical prostatectomy.

PubMed

Sharma, Satish; Kim, Hyung Lae; Mohler, James L

2007-02-01

To determine whether radical prostatectomy requires urinary drainage. All patients with clinically localized prostate cancer had complete clinical and pathologic information recorded prospectively in a database. The criteria for omission of pelvic drainage were successful bladder neck preservation; urethrovesical anastomosis performed using 6 interrupted sutures in open cases or 12 continuous sutures in robotic cases; and a watertight urethrovesical anastomosis on irrigation. Most patients were discharged on the first or second postoperative day. The catheters were removed routinely on postoperative day 9. A pelvic drain was not placed in 78% of 325 consecutive patients. A drain was omitted in 73% of 225 open cases and 90% of 100 robotic cases. The recovery of continence and the complication rates were similar between the two groups with and without pelvic drainage. Complications occurred in 11% of the group with pelvic drainage and 6% in the group without pelvic drainage. In the past 2 years, 17 of 126 patients required pelvic drainage. The frequency of complications in robotic versus open procedures was similar (chi-square test, P >0.05). Pelvic drainage may be omitted after radical prostatectomy when the urethrovesical anastomosis is performed well. Drainage omission could contribute to shortened hospital stays and reduced costs, without added complications. These benefits can be extended safely to patients undergoing open or robotic radical prostatectomy.

New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes.

PubMed

Ge, Linke; Na, Guangshui; Zhang, Siyu; Li, Kai; Zhang, Peng; Ren, Honglei; Yao, Ziwei

2015-09-15

The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (td,E) and hydroxyl-radical oxidation half-lives (tOH,E) in sunlit surface waters. The td,E values range from 0.56 min to 28.8 min at 45° N latitude, whereas tOH,E ranges from 3.24h to 33.6h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. Copyright © 2015. Published by Elsevier B.V.

Magnetoreception in birds: different physical processes for two types of directional responses

PubMed Central

Wiltschko, Roswitha; Stapput, Katrin; Ritz, Thorsten; Thalau, Peter; Wiltschko, Wolfgang

2007-01-01

Migratory orientation in birds involves an inclination compass based on radical-pair processes. Under certain light regimes, however, “fixed-direction” responses are observed that do not undergo the seasonal change between spring and autumn typical for migratory orientation. To identify the underlying transduction mechanisms, we analyzed a fixed-direction response under a combination of 502 nm turquoise and 590 nm yellow light, with migratory orientation under 565 nm green light serving as the control. High-frequency fields, diagnostic for a radical-pair mechanism, disrupted migratory orientation without affecting fixed-direction responses. Local anaesthesia of the upper beak where magnetite is found in birds, in contrast, disrupted the fixed-direction response without affecting migratory orientation. The two types of responses are thus based on different physical principles, with the compass response based on a radical pair mechanism and the fixed-direction responses probably originating in magnetite-based receptors in the upper beak. Directional input from these receptors seems to affect the behavior only when the regular inclination compass does not work properly. Evolutionary considerations suggest that magnetite-based receptors may represent an ancient mechanism that, in birds, has been replaced by the modern inclination compass based on radical-pair processes now used for directional orientation. PMID:19404459

Theoretical insight into reaction mechanisms of 2,4-dinitroanisole with hydroxyl radicals for advanced oxidation processes.

PubMed

Zhou, Yang; Liu, Xiaoqiang; Jiang, Weidong; Shu, Yuanjie

2018-01-24

The detailed degradation mechanism of an insensitive explosive, 2,4-dinitroanisole (DNAN), in advanced oxidation processes (AOPs) was investigated computationally at the M06-2X/6-311 + G(d,p)/SMD level of theory. Results obtained show that the addition-elimination reaction is the dominant mechanism. The phenol products formed can continue to be oxidized to benzoquinone radicals that are often detected by experiments and may be the initial reactants of ring-opening reactions. The H-abstraction reaction is an unavoidable competing mechanism; the intermediate generated can also undergo the process of addition-elimination reaction. The nitro departure reaction involves not only hydroxyl radical (•OH), but also other active substances (such as •H). More importantly, we found that AOP technology can easily degrade DNAN, similar to TNT and DNT. Thus, this method is worth trying in experiments. The conclusions of this work provide theoretical support for such experimental research. Graphical abstract Possible pathways of degradation by •OH radicals in advanced oxidation processes (AOPs) of the typical insensitive explosive 2,4-dinitroanisole (DNAN) were investigated by density functional theory (DFT) methods. Based on the Gibbs free energy barriers and intermediates, the dominant reaction mechanism was determined. The conclusions will be helpful in utilizing AOP technology to remove DNAN pollution.

Parameters of two-dimensional perineal ultrasonography for evaluation of urinary incontinence after Radical Prostatectomy.

PubMed

Costa Cruz, Danilo Souza Lima da; D'Ancona, Carlos Arturo Levi; Baracat, Jamal; Alves, Marco Antonio Dionisio; Cartapatti, Marcelo; Damião, Ronaldo

2014-01-01

Urinary incontinence remains a major concern for patients undergoing radical prostatectomy. Its prevalence can reach 20% in the late postoperative period. This clinical study investigated the differences of a dynamic evaluation of the urethra and pelvic floor contraction using perineal ultrasound in men without prostate surgery and in men submitted to radical prostatectomy with and without stress urinary incontinence. Ninety two male patients were included, which 70% of them underwent radical prostatectomy (RP) for more than one year. Thirty one men with clinically post prostatectomy incontinence were compared by two-dimensional (2D) perineal ultrasound to 34 patients without post prostatectomy incontinence and to 27 men without surgery in two centers in Brazil. Our results showed that the continent group presented the urethral angle at rest significantly lower than the prostate group (p = 0.0002). We also observed that the incontinent group showed the displacement of the anterior bladder neck during contraction significantly lower than the continent group (p = 0.008). We found that the continent group presented the urethral angle at rest significantly lower than the prostate group. The incontinent group also showed the anterior bladder neck displacement during contraction significantly lower than the continent group. It was more evident when the severe incontinent group and the continent group were compared.

Impact of posterior rhabdosphincter reconstruction during robot-assisted radical prostatectomy: retrospective analysis of time to continence.

PubMed

Woo, Jason R; Shikanov, Sergey; Zorn, Kevin C; Shalhav, Arieh L; Zagaja, Gregory P

2009-12-01

Posterior rhabdosphincter (PR) reconstruction during robot-assisted radical prostatectomy (RARP) was introduced in an attempt to improve postoperative continence. In the present study, we evaluate time to achieve continence in patients who are undergoing RARP with and without PR reconstruction. A prospective RARP database was searched for most recent cases that were accomplished with PR reconstruction (group 1, n = 69) or with standard technique (group 2, n = 63). We performed the analysis applying two definitions of continence: 0 pads per day or 0-1 security pad per day. Patients were evaluated by telephone interview. Statistical analysis was carried out using the Kaplan-Meier method and log-rank test. With PR reconstruction, continence was improved when defined as 0-1 security pad per day (median time of 90 vs 150 days; P = 0.01). This difference did not achieve statistical significance when continence was defined as 0 pads per day (P = 0.12). A statistically significant improvement in continence rate and time to achieve continence is seen in patients who are undergoing PR reconstruction during RARP, with continence defined as 0-1 security/safety pad per day. A larger, prospective and randomized study is needed to better understand the impact of this technique on postoperative continence.

Sentinel lymph node detection in patients with early cervical cancer.

PubMed

Acharya, B C; Jihong, L

2009-01-01

Lymph node status is the most important independent prognostic factor in early stage cervical cancer. Intraoperative lymphatic mapping and sentinel lymph node detection have been increasingly evaluated in the treatment of a variety of solid tumors, particularly breast cancer and cutaneous melanoma. This study evaluated the feasibility of these procedures in patients undergoing radical hysterectomy with pelvic lymphadenectomy for early cervical cancer. A total of 30 patients with histologically diagnosed FIGO stage IA to IIA cervical cancer were enrolled to this study. They were scheduled to undergo radical abdominal hysterectomy and pelvic lymphadenectomy after injecting patent blue dye in cervix. A total of 60 SLNs (mean 2.5) were detected in 24 patients with detection rate of 80%. Bilateral SLNs were detected in 70.1% of cases. SLNs were identified in obturator and external iliac areas in 50% and 31.7%, respectively; no SLNs were discovered in the common iliac region. Seven patients (23.3%) had lymph node metastases; one of these had false negative SLN.The false negative rate and negative predictive value were 14.3% and 94.4%, respectively. SLN detection procedure with blue dye technique is a feasible procedure in cervical cancer. Patent blue dye is cheap, safe and effective tracer to detect sentinel node in carcinoma of cervix.

Bladder Cancer Recovery Pathways: A Systematic Review

PubMed Central

Maloney, Ian; Parker, Daniel C.; Cookson, Michael S.; Patel, Sanjay

2017-01-01

Background: Enhanced recovery pathways, also known as fast-track protocols, have been adopted since the early 2000s by various surgical specialties with the goal of improving patient outcomes and reducing the cost burden of major surgery on the health care system. Objective: To review the scientific literature on the origin of enhanced recovery pathways, track the contemporary utilization of such practices for patients undergoing radical cystectomy, and analyze the available data regarding their effect on morbidity, mortality, and treatment cost. Methods: A literature search of multiple electronic databases was undertaken. Manuscripts including patients undergoing radical cystectomy were chosen based on predefined criteria with an emphasis on randomized controlled trials and cohort studies. Strength of evidence for each study that met inclusion criteria was assessed based on the risk of bias, consistency, directness, and precision. Results: Database searches resulted in 1,236 potentially relevant articles. A total of 485 articles were selected for full-text dual review and 106 studies in 52 publications met the inclusion criteria. Conclusion: The utilization of enhanced recovery pathways with the goal of improving overall patient morbidity and mortality is well supported in the literature, however standardization of implementation and adherence across institutions is lacking, and their direct efficacy on reducing preventable treatment related expenditures is unconfirmed. PMID:29152551

Commentary on "Robot-assisted laparoscopic vs open radical cystectomy: Comparison of complications and perioperative oncological outcomes in 200 patients." Kader AK, Richards KA, Krane LS, Pettus JA, Smith JJ, Hemal AK, Division of Urology, UC San Diego Health System, San Diego, CA.: BJU Int 2013; 112(4):E290-4. doi:10.1111/bju.12167. [Epub 2013 Jul 1].

PubMed

See, William A

2014-11-01

To compare perioperative morbidity and oncological outcomes of robot-assisted laparoscopic radical cystectomy (RARC) to open RC (ORC) at a single institution. A retrospective analysis was performed on a consecutive series of patients undergoing RC (100 RARC and 100 ORC) at Wake Forest University with curative intent from 2006 until 2010. Complication data using the Clavien system were collected for 90 days postoperatively. Complications and other perioperative outcomes were compared between patient groups. Patients in both groups had comparable preoperative characteristics. The overall and major complication (Clavien ≥ 3) rates were lower for RARC patients at 35 vs 57% (P = 0.001) and 10 vs 22% (P = 0.019), respectively. There were no significant differences between groups for pathological outcomes, including stage, number of nodes harvested or positive margin rates. Our data suggest that patients undergoing RARC have perioperative oncological outcomes comparable with ORC, with fewer overall or major complications. Definitive claims about comparative outcomes with RARC require results from larger, randomised controlled trials. Copyright © 2014 Elsevier Inc. All rights reserved.

Outcomes assessment in men undergoing open retropubic radical prostatectomy, laparoscopic radical prostatectomy, and robotic-assisted radical prostatectomy.

PubMed

Kowalczyk, Keith J; Yu, Hua-Yin; Ulmer, William; Williams, Stephen B; Hu, Jim C

2012-02-01

To review the various methods of outcomes assessment used for effectiveness studies comparing retropubic radical prostatectomy (RRP), laparoscopic radical prostatectomy (LRP), and robotic-assisted laparoscopic prostatectomy (RALP). A review of the peer reviewed literature was performed for reported series of RRP, LRP, and RALP using Pubmed and MEDLINE with emphasis on comparing perioperative, functional, and oncologic outcomes. Common methods used for outcomes assessment were categorized and compared, highlighting the pros and cons of each approach. The majority of the literature comparing RRP, LRP, and RALP comes in the form of observational data or administrative data from secondary datasets. While randomized controlled trials are ideal for outcomes assessment, only one such study was identified and was limited. Non-randomized observational studies contribute to the majority of data, however are limited due to retrospective study design, lack of consistent endpoints, and limited application to the general community. Administrative data provide accurate assessment of operative outcomes in both academic and community settings, however has limited ability to convey accurate functional outcomes. Non-randomized observational studies and secondary data are useful resources for assessment of outcomes; however, limitations exist for both. Neither is without flaws, and conclusions drawn from either should be viewed with caution. Until standardized prospective comparative analyses of RRP, LRP, and RALP are established, comparative outcomes data will remain imperfect. Urologic researchers must strive to provide the best available outcomes data through accurate prospective data collection and consistent outcomes reporting.

Synthesis and characterization of biodegradable poly (ethylene glycol) and poly (caprolactone diol) end capped poly (propylene fumarate) cross linked amphiphilic hydrogel as tissue engineering scaffold material.

PubMed

Krishna, Lekshmi; Jayabalan, Muthu

2009-12-01

Biodegradable poly (caprolactone diol-co-propylene fumarate-co-ethylene glycol) amphiphilic polymer with poly (ethylene glycol) and poly (caprolactone diol) chain ends (PCL-PPF-PEG) was prepared. PCL-PPF-PEG undergoes fast setting with acrylamide (aqueous solution) by free radical polymerization and produces a crosslinked hydrogel. The cross linked and freeze-dried amphiphilic material has porous and interconnected network. It undergoes higher degree of swelling and water absorption to form hydrogel with hydrophilic and hydrophobic domains at the surface and appreciable tensile strength. The present hydrogel is compatible with L929 fibroblast cells. PCL-PPF-PEG/acrylamide hydrogel is a candidate scaffold material for tissue engineering applications.

Controlling the orientation of spin-correlated radical pairs by covalent linkage to nanoporous anodic aluminum oxide membranes.

PubMed

Chen, Hsiao-Fan; Gardner, Daniel M; Carmieli, Raanan; Wasielewski, Michael R

2013-10-07

Ordered multi-spin assemblies are required for developing solid-state molecule-based spintronics. A linear donor-chromophore-acceptor (D-C-A) molecule was covalently attached inside the 150 nm diam. nanopores of an anodic aluminum oxide (AAO) membrane. Photoexcitation of D-C-A in a 343 mT magnetic field results in sub-nanosecond, two-step electron transfer to yield the spin-correlated radical ion pair (SCRP) (1)(D(+)˙-C-A(-)˙), which then undergoes radical pair intersystem crossing (RP-ISC) to yield (3)(D(+)˙-C-A(-)˙). RP-ISC results in S-T0 mixing to selectively populate the coherent superposition states |S'> and |T'>. Microwave-induced transitions between these states and the unpopulated |T(+1)> and |T(-1)> states result in spin-polarized time-resolved EPR (TREPR) spectra. The dependence of the electron spin polarization (ESP) phase of the TREPR spectra on the orientation of the AAO membrane pores relative to the externally applied magnetic field is used to determine the overall orientation of the SCRPs within the pores at room temperature.

Electron-transfer reactions in cyanine borate ion pairs: photopolymerization initiators sensitive to visible light

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, S.; Gottschalk, P.; Davis, P.D.

1988-03-30

Photoinitiation of polymerization is a process of immense practical, economic, and theoretical importance. In typical examples the polymerization of an acrylate or styrene-derived monomer is initiated by irradiation of a sensitizer with ultraviolet light. The excited state of the sensitizer may dissociate directly to form active free radicals as in the case of the benzoin ethers, or it may first undergo a bimolecular electron-transfer reaction whose products initiate polymerization as is the case in the benzophenone-dimethylaniline system. Efforts to extend the range of useful photoinitiators of free-radical polymerization to the visible region of the spectrum have heretofore met with onlymore » modest success. These special initiators typically are sensitive only to blue light or suffer from thermal instability and have low quantum efficiencies. The authors report herein the discovery that triphenylalkylborate salts of cyanine dyes (Chart I) are photoinitiators of free-radical polymerization whose sensitivity throughout the entire visible spectral region is the result of a novel intra-ion-pair electron-transfer reaction.« less

2-Aminobenzamide and 2-Aminobenzoic Acid as New MALDI Matrices Inducing Radical Mediated In-Source Decay of Peptides and Proteins

NASA Astrophysics Data System (ADS)

Smargiasso, Nicolas; Quinton, Loic; de Pauw, Edwin

2012-03-01

One of the mechanisms leading to MALDI in-source decay (MALDI ISD) is the transfer of hydrogen radicals to analytes upon laser irradiation. Analytes such as peptides or proteins may undergo ISD and this method can therefore be exploited for top-down sequencing. When performed on peptides, radical-induced ISD results in production of c- and z-ions, as also found in ETD and ECD activation. Here, we describe two new compounds which, when used as MALDI matrices, are able to efficiently induce ISD of peptides and proteins: 2-aminobenzamide and 2-aminobenzoic acid. In-source reduction of the disulfide bridge containing peptide Calcitonin further confirmed the radicalar mechanism of the ISD process. ISD of peptides led, in addition to c- and z-ions, to the generation of a-, x-, and y-ions both in positive and in negative ion modes. Finally, good sequence coverage was obtained for the sequencing of myoglobin (17 kDa protein), confirming the effectiveness of both 2-aminobenzamide and 2-aminobenzoic acid as MALDI ISD matrices.

2-Aminobenzamide and 2-aminobenzoic acid as new MALDI matrices inducing radical mediated in-source decay of peptides and proteins.

PubMed

Smargiasso, Nicolas; Quinton, Loic; De Pauw, Edwin

2012-03-01

One of the mechanisms leading to MALDI in-source decay (MALDI ISD) is the transfer of hydrogen radicals to analytes upon laser irradiation. Analytes such as peptides or proteins may undergo ISD and this method can therefore be exploited for top-down sequencing. When performed on peptides, radical-induced ISD results in production of c- and z-ions, as also found in ETD and ECD activation. Here, we describe two new compounds which, when used as MALDI matrices, are able to efficiently induce ISD of peptides and proteins: 2-aminobenzamide and 2-aminobenzoic acid. In-source reduction of the disulfide bridge containing peptide Calcitonin further confirmed the radicalar mechanism of the ISD process. ISD of peptides led, in addition to c- and z-ions, to the generation of a-, x-, and y-ions both in positive and in negative ion modes. Finally, good sequence coverage was obtained for the sequencing of myoglobin (17 kDa protein), confirming the effectiveness of both 2-aminobenzamide and 2-aminobenzoic acid as MALDI ISD matrices.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mani, Tomoyasu; Grills, David C.

Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we showmore » that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1. IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.« less

The perioperative charge equivalence of interstitial brachytherapy and radical prostatectomy with 1-year followup.

PubMed

Kohan, A D; Armenakas, N A; Fracchia, J A

2000-02-01

We compare the comprehensive 1-year charges in a consecutive group of patients undergoing radical prostatectomy and transperineal interstitial brachytherapy for clinically localized prostate cancer at a single urban institution. A total of 60 consecutive men with clinically localized prostate cancer (T1-T2, N0, M0) were treated during a 15-month period with radical prostatectomy or interstitial brachytherapy. Hospital and outpatient records were analyzed for each patient in regard to preoperative, operative and postoperative charges. Parameters included number of encounters, diagnostic and therapeutic interventions, hospitalization and operative charges, and followup visits, diagnostic tests and interventions for 1 year. All charge calculations were based arbitrarily on the 1996 Medicare fee schedule, factoring in the mandated global charge reimbursement period of 90 days for both procedures. Of the patients 38 underwent radical prostatectomy (prostatectomy group) and 22 underwent interstitial brachytherapy (brachytherapy group). The brachytherapy group was older with higher pretreatment serum prostate specific antigen and clinical stage disease, and more frequently received neoadjuvant hormonal therapy compared to the prostatectomy group. The 2 groups were similar in Gleason score and, when applicable, duration of neoadjuvant hormonal therapy. Preoperative charges were 15.3% lower for prostatectomy than for brachytherapy (not statistically significant). Conversely, operative charges for prostatectomy were 13.5% higher (p = 0.04). The major difference among preoperative, operative and postoperative charges was for those incurred postoperatively by the brachytherapy group, which were 56.0% higher than those for the prostatectomy group ($2,285.20 versus $1,007.20, p = 0.0004). Transperineal interstitial seed implantation is perceived by many as more cost-effective than radical prostatectomy for patients with clinically localized prostate cancer. We demonstrated that when such patients were followed for 1 year, the comprehensive charges for radical prostatectomy and interstitial brachytherapy were equivalent.

ESR study of electron reactions with esters and triglycerides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sevilla, M.D.; Morehouse, K.M.; Swarts, S.

1981-04-02

Reactions which occurred after electron attachment at 77K to a number of small carboxylic acid esters and triglycerides in an aqueous glass are reported. Most ester anions are found to decay on warming to form alkyl radicals by ..beta.. scission: RC(O/sup -/)OR' ..-->.. RCO/sub 2//sup -/ + R'.. The alkyl radical (R'.) produced by annealing is found to abstract hydrogen from the parent ester at an ..cap alpha..-carbon site, R'.+ R''CH/sub 2/CO/sub 2/R' ..-->.. R''CHCO/sub 2/R', or in the case of ethyl formate from the formate hydrogen, CH/sub 3/CH/sub 2/.+ HCO/sub 2/C/sub 2/H/sub 5/ ..-->.. C/sub 2/H/sub 6/ +.CO/sub 2/C/submore » 2/H/sub 5/. Results found for the methyl formate anion suggest hydrogen abstraction by the anion itself may compete with alkyl radical formation. The anion of the triglyceride triacetin is found to undergo an analogous mechanism to the ester anions producing the propane diol diester radical, .CH/sub 2/CH(Ac)CH/sub 2/(Ac), Ac = acetate. This species subsequently abstracts hydrogen from the parent compound to produce the ..cap alpha..-carbon radical, .CH/sub 2/CO/sub 2/R. Results found after annealing the tripropionin radical anion give evidence for abstraction from the ..cap alpha.. carbon in the propionate side groups producing CH/sub 3/CHCO/sub 2/R. Studies of a ..gamma..-irradiated ester (ethyl myristate) and two triglycerides (tripalmitin and tristearin) yield results which suggest that the mechanism of ester anion decay found in aqueous glasses applies to ..gamma..-irradiated neat long-chain esters and triglycerides. Results found in this work are compared to the results of product analysis.« less

Quality of Life After Open Radical Prostatectomy Compared with Robot-assisted Radical Prostatectomy.

PubMed

Wallerstedt, Anna; Nyberg, Tommy; Carlsson, Stefan; Thorsteinsdottir, Thordis; Stranne, Johan; Tyritzis, Stavros I; Stinesen Kollberg, Karin; Hugosson, Jonas; Bjartell, Anders; Wilderäng, Ulrica; Wiklund, Peter; Steineck, Gunnar; Haglind, Eva

2018-01-20

Surgery for prostate cancer has a large impact on quality of life (QoL). To evaluate predictors for the level of self-assessed QoL at 3 mo, 12 mo, and 24 mo after robot-assisted laparoscopic (RALP) and open radical prostatectomy (ORP). The LAParoscopic Prostatectomy Robot Open study, a prospective, controlled, nonrandomised trial of more than 4000 men who underwent radical prostatectomy at 14 centres. Here we report on QoL issues after RALP and ORP. The primary outcome was self-assessed QoL preoperatively and at 3 mo, 12 mo, and 24 mo postoperatively. A direct validated question of self-assessed QoL on a seven-digit visual scale was used. Differences in QoL were analysed using logistic regression, with adjustment for confounders. QoL did not differ between RALP and ORP postoperatively. Men undergoing ORP had a preoperatively significantly lower level of self-assessed QoL in a multivariable analysis compared with men undergoing RALP (odds ratio: 1.21, 95% confidence interval: 1.02-1.43), that disappeared when adjusted for preoperative preparedness for incontinence, erectile dysfunction, and certainty of being cured (odds ratio: 1.18, 95% confidence interval: 0.99-1.40). Incontinence and erectile dysfunction increased the risk for poor QoL at 3 mo, 12 mo, and 24 mo postoperatively. Biochemical recurrence did not affect QoL. A limitation of the study is the nonrandomised design. QoL at 3 mo, 12 mo, and 24 mo after RALP or ORP did not differ significantly between the two techniques. Poor QoL was associated with postoperative incontinence and erectile dysfunction but not with early cancer relapse, which was related to thoughts of death and waking up at night with worry. We did not find any difference in quality of life at 3 mo, 12 mo, and 24 mo when open and robot-assisted surgery for prostate cancer were compared. Postoperative incontinence and erectile dysfunction were associated with poor quality of life. Copyright © 2017 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Long-term outcomes of open radical retropubic prostatectomy for clinically localized prostate cancer in the prostate-specific antigen era.

PubMed

Dorin, Ryan P; Daneshmand, Siamak; Lassoff, Mark A; Cai, Jie; Skinner, Donald G; Lieskovsky, Gary

2012-03-01

To determine long-term oncological outcomes and complication rates for patients with clinically organ confined prostate adenocarcinoma (PCa) treated with open radical retropubic prostatectomy and pelvic lymph node dissection (RRP/PLND) in the prostate-specific antigen (PSA) era. Outcomes data were obtained from a prospectively maintained prostate cancer database. Patients with cT1/cT2 PCa undergoing RRP/PLND without neoadjuvant therapy between July 1988 and June 2008 were included. Kaplan-Meier and Cox proportional regression models were used to evaluate factors influencing biochemical recurrence, clinical recurrence, and overall survival (OS). A total of 2487 patients met inclusion criteria, and median follow-up was 7.2 years (range 1-21 years). Of the patients, 49.7% were low risk, 33.2% intermediate risk, and 16.1% high risk by D'Amico criteria, and 6% were LN+. The 10-year biochemical recurrence-free survival (BCRFS) for low-, intermediate-, and high-risk patients was 92%, 83%, and 76%, respectively (P < .001), and 10 year OS was 91%, 83%, and 74%, respectively (P < .001). BCRFS at 10 years was 76% and 88% for patients with positive and negative margins, respectively (P < .001). Of the 2487 patients, 11% developed BCR, and 3.7% experienced CR, with 9 local recurrences. The overall complication rate was 2.3%, and the cancer specific mortality rate was 2%. D'Amico risk group, margin status, and LN status are significantly correlated with outcomes in patients undergoing RRP/PLND for clinically localized PCa. Local recurrence and death from prostate cancer are rare in patients undergoing open RRP/PLND for clinically organ confined disease in the PSA era. Copyright © 2012 Elsevier Inc. All rights reserved.

The impact of primary tumour location in patients undergoing hepatic resection for colorectal liver metastasis.

PubMed

Wang, Kun; Xu, Da; Yan, Xiao-Luan; Poston, Graeme; Xing, Bao-Cai

2018-06-01

Primary tumour location has long been debated as a prognostic factor in colorectal cancer patients with liver metastases (CRLM) undergoing liver resection. This retrospective study was conducted to clarify the prognostic value of tumour location after radical hepatectomy for CRLM and its underlying causes. We retrospectively analysed clinical data from 420 patients with CRLM whom underwent liver resection between January 2002 and December 2015. Right-sided (RS) tumours include tumours located in the cecum, ascending colon, and transverse colon, and left-sided (LS) tumours include those located in the splenic flexure, descending colon, sigmoid colon, and rectum. Both overall survival (OS) and disease-free survival (DFS) were similar between patients with RS and LS primary tumours (5-year OS: 46.5% vs 38.3%, P = 0.699; 5-year DFS: 29.1% vs 22.4%, P = 0.536). Specifically, RAS mutation rate was significantly higher in patients with RS tumours (P = 0.007). Subgroup analysis showed that the RAS mutation on the LS and RS tumours have different prognostic impact for CRLM patients on long-term survival after hepatic resection (RS, OS: P = 0.437, DFS: P = 0.471; LS, OS: P < 0.001, DFS: P = 0.002). The multivariable analysis showed that RAS mutant is an independent factor influencing OS in patients with LS primary tumour only. The site of the primary tumour has no significant impact on the long-term survival in patients with CRLM undergoing radical surgery. However, prognostic value of RAS status differs depending on the site of the primary tumour. Copyright © 2018. Published by Elsevier Ltd.

Internal versus external ureteric stents for uretero-ileal anastomosis after laparoscopic radical cystectomy with orthotopic neobladder: A prospective comparative study.

PubMed

Abdel Hakim, Mahmoud A; Abdalla, Ahmed A; Saad, Ismail R; ElSheemy, Mohammed S; El Feel, Ahmed S; Salem, Hosni K; Abdel Hakim, Amr M

2016-06-01

To prospectively compare the use of external ureteric stents with internal JJ stenting of the uretero-ileal anastomosis in patients undergoing laparoscopic radical cystectomy (LRC) with a Y-shaped ileal orthotopic neobladder (ON). The study included 69 patients undergoing LRC with ON. Patients were grouped according to the type of uretero-ileal stents used. An external ureteric stent was used in Group A (33 patients) and a JJ stent was used in Group B (36). We prospectively compared the duration of hospital stay, the incidence of short- and intermediate-term complications in the two study groups. The mean (SD) follow-up periods were 29.18 (3.94) and 28.19 (3.37) months for patients in Groups A and B, respectively. Perioperative patient characteristics were comparable in the two study groups. The use of JJ stenting was associated with a shorter hospital stay compared with external stenting, at a mean (SD) of 14.63 (3.74) and 6.8 (3.03) days in Groups A and B, respectively (P < 0.001). The incidence of urinary leakage was comparable in the two study groups, at 6.1% in Group A vs 8.3% in Group B (P = 1.0). Strictures of the uretero-ileal anastomosis occurred in two patients (6%) in Group A and confirmed by intravenous urography. All strictures were treated with antegrade JJ fixation. JJ stents could be used as an effective alternative to external ureteric stents to support the uretero-ileal anastomosis. JJ stenting is associated with a shorter hospital stay and similar complication rates compared with external stenting in patients undergoing LRC with ON.

Clindamycin-induced anaphylactic shock during general anesthesia.

PubMed

Chiou, Chiuan-Shiou; Lin, Su-Man; Lin, Shih-Pin; Chang, Wen-Guei; Chan, Kwok-Hon; Ting, Chien-Kun

2006-11-01

Clindamycin-related anaphylactic reaction is rarely reported. We report a male patient with buccal cancer who was undergoing radical neck dissection when life-threatening anaphylactic shock developed soon after intravenous infusion of clindamycin. Immediate cardiopulmonary resuscitation was performed, and the patient recovered uneventfully. Perioperative anaphylactic shock is a serious problem due to the difficulty of judgment and potentially disastrous outcome. Immediate diagnosis and halting of drug infusion should be the first actions taken.

Epithelial Plasticity in Castration-Resistant Prostate Cancer: Biology of the Lethal Phenotype

DTIC Science & Technology

2012-07-01

mCRPC, with metastatic progres- sion by prostate - specific antigen (PSA; 2 consecutive rises over nadir separated by more than 1 week) or radiologic...Abbreviations: CRPC, castration-resistant prostate cancer; PSA, prostate specific antigen . Armstrong et al. Mol Cancer Res; 9(8) August 2011 Molecular... antigen , which we found did correlate with PSA outcomes and high risk disease among men with localized prostate cancer who were undergoing radical

Harmonic Scalpel versus Electrocautery Dissection in Modified Radical Mastectomy for Breast Cancer: A Meta-Analysis.

PubMed

Huang, Jinbo; Yu, Yinghua; Wei, Changyuan; Qin, Qinghong; Mo, Qinguo; Yang, Weiping

2015-01-01

Despite the common use of conventional electrocautery in modified radical mastectomy for breast cancer, the harmonic scalpel is recently emerging as a dominant surgical instrument for dissection and haemostasis, which is thought to reduce the morbidity, such as seroma and blood loss. But the results of published trials are inconsistent. So we made the meta-analysis to assess the intraoperative and postoperative endpoints among women undergoing modified radical mastectomy with harmonic scalpel or electrocautery. A comprehensive literature search of case-control studies from PubMed, MEDLINE, EMBASE and Cochrane Library databases involving modified radical mastectomy with harmonic scalpel or electrocautery was performed. We carried out a meta-analysis of primary endpoints including postoperative drainage, seroma development, intraoperative blood loss and secondly endpoints including operative time and wound complications. We used odds ratios (ORs) with 95% confidence intervals (CIs) to evaluate the effect size for categorical outcomes and standardised mean differences (SMDs) for continuous outcomes. A total of 11 studies with 702 patients were included for this meta-analysis. There was significant difference in total postoperative drainage (SMD: -0.74 [95%CI: -1.31, -0.16]; P< 0.01), seroma development[OR: 0.49 (0.34, 0.70); P < 0.01], intraoperative blood loss(SMD: -1.14 [95%CI: -1.81,-0.47]; P < 0.01) and wound complications [OR: 0.38 (0.24, 0.59); P < 0.01] between harmonic scalpel dissection and standard electrocautery in modified radical mastectomy for breast cancer. No difference was found as for operative time between harmonic scalpel dissection and standard electrocautery (SMD: 0.04 [95%CI: -0.41, 0.50]; P = 0.85). Compared to standard electrocautery, harmonic scalpel dissection presents significant advantages in decreasing postoperative drainage, seroma development, intraoperative blood loss and wound complications in modified radical mastectomy for breast cancer, without increasing operative time. Harmonic scalpel can be recommended as a preferential surgical instrument in modified radical mastectomy.

Harmonic Scalpel versus Electrocautery Dissection in Modified Radical Mastectomy for Breast Cancer: A Meta-Analysis

PubMed Central

Huang, Jinbo; Yu, Yinghua; Wei, Changyuan; Qin, Qinghong; Mo, Qinguo; Yang, Weiping

2015-01-01

Background Despite the common use of conventional electrocautery in modified radical mastectomy for breast cancer, the harmonic scalpel is recently emerging as a dominant surgical instrument for dissection and haemostasis, which is thought to reduce the morbidity, such as seroma and blood loss. But the results of published trials are inconsistent. So we made the meta-analysis to assess the intraoperative and postoperative endpoints among women undergoing modified radical mastectomy with harmonic scalpel or electrocautery. Methods A comprehensive literature search of case-control studies from PubMed, MEDLINE, EMBASE and Cochrane Library databases involving modified radical mastectomy with harmonic scalpel or electrocautery was performed. We carried out a meta-analysis of primary endpoints including postoperative drainage, seroma development, intraoperative blood loss and secondly endpoints including operative time and wound complications. We used odds ratios (ORs) with 95% confidence intervals (CIs) to evaluate the effect size for categorical outcomes and standardised mean differences (SMDs) for continuous outcomes. Results A total of 11 studies with 702 patients were included for this meta-analysis. There was significant difference in total postoperative drainage (SMD: -0.74 [95%CI: -1.31, -0.16]; P< 0.01), seroma development[OR: 0.49 (0.34, 0.70); P < 0.01], intraoperative blood loss(SMD: -1.14 [95%CI: -1.81,-0.47]; P < 0.01) and wound complications [OR: 0.38 (0.24, 0.59); P < 0.01] between harmonic scalpel dissection and standard electrocautery in modified radical mastectomy for breast cancer. No difference was found as for operative time between harmonic scalpel dissection and standard electrocautery (SMD: 0.04 [95%CI: -0.41, 0.50]; P = 0.85). Conclusion Compared to standard electrocautery, harmonic scalpel dissection presents significant advantages in decreasing postoperative drainage, seroma development, intraoperative blood loss and wound complications in modified radical mastectomy for breast cancer, without increasing operative time. Harmonic scalpel can be recommended as a preferential surgical instrument in modified radical mastectomy. PMID:26544716

Characterization of a Cross-Linked Protein–Nucleic Acid Substrate Radical in the Reaction Catalyzed by RlmN

PubMed Central

2015-01-01

RlmN and Cfr are methyltransferases/methylsynthases that belong to the radical S-adenosylmethionine superfamily of enzymes. RlmN catalyzes C2 methylation of adenosine 2503 (A2503) of 23S rRNA, while Cfr catalyzes C8 methylation of the exact same nucleotide, and will subsequently catalyze C2 methylation if the site is unmethylated. A key feature of the unusual mechanisms of catalysis proposed for these enzymes is the attack of a methylene radical, derived from a methylcysteine residue, onto the carbon center undergoing methylation to generate a paramagnetic protein–nucleic acid cross-linked species. This species has been thoroughly characterized during Cfr-dependent C8 methylation, but does not accumulate to detectible levels in RlmN-dependent C2 methylation. Herein, we show that inactive C118S/A variants of RlmN accumulate a substrate-derived paramagnetic species. Characterization of this species by electron paramagnetic resonance spectroscopy in concert with strategic isotopic labeling shows that the radical is delocalized throughout the adenine ring of A2503, although predominant spin density is on N1 and N3. Moreover, 13C hyperfine interactions between the radical and the methylene carbon of the formerly [methyl-13C]Cys355 residue show that the radical species exists in a covalent cross-link between the protein and the nucleic acid substrate. X-ray structures of RlmN C118A show that, in the presence of SAM, the substitution does not alter the active site structure compared to that of the wild-type enzyme. Together, these findings have new mechanistic implications for the role(s) of C118 and its counterpart in Cfr (C105) in catalysis, and suggest involvement of the residue in resolution of the cross-linked species via a radical mediated process. PMID:24806349

Health Related Quality of Life Following Radical Cystectomy: Comparative Analysis from the Medicare Health Outcomes Survey.

PubMed

Winters, Brian R; Wright, Jonathan L; Holt, Sarah K; Dash, Atreya; Gore, John L; Schade, George R

2017-09-05

Health related quality of life after radical cystectomy and ileal conduit is not well quantified at the population level. We evaluated health related quality of life in patients with bladder cancer compared with noncancer controls and patients with colorectal cancer using data from SEER (Surveillance, Epidemiology and End Results)-MHOS (Medicare Health Outcomes Survey). SEER-MHOS data from 1998 to 2013 were used to identify patients with bladder cancer and those with colorectal cancer who underwent extirpative surgery with ileal conduit or colostomy creation, respectively. A total of 166 patients with bladder cancer treated with radical cystectomy were propensity matched 1:5 to 830 noncancer controls and compared with 154 patients with colorectal cancer. Differences in Mental and Physical Component Summary scores as well as component subscores were determined between patients with bladder cancer, patients with colorectal cancer and noncancer controls. SEER-MHOS patients were more commonly male and white with a mean ± SD age of 77 ± 6 years. Patients treated with radical cystectomy had significantly lower Physical Component Summary scores, select physical subscale scores and all mental subscale scores compared with noncancer controls. These findings were similar in the subset of 40 patients treated with radical cystectomy who had available preoperative and postoperative survey data. Global Mental Component Summary scores did not differ significantly between the groups. No significant differences were observed in global Mental Component Summary, Physical Component Summary or subscale scores between patients with bladder cancer and patients with colorectal cancer. Patients with bladder cancer who undergo radical cystectomy have significant declines in multiple components of physical and mental health related quality of life vs noncancer controls, which mirror those of patients with colorectal cancer. Further longitudinal study is required to better codify the effectors of poor health related quality of life after radical cystectomy to improve patient expectations and outcomes. Copyright © 2018 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Characterization of a Cross-Linked Protein-Nucleic Acid Substrate Radical in the Reaction Catalyzed by RlmN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silakov, Alexey; Grove, Tyler L.; Radle, Matthew I.

2014-08-14

RlmN and Cfr are methyltransferases/methylsynthases that belong to the radical S-adenosylmethionine superfamily of enzymes. RlmN catalyzes C2 methylation of adenosine 2503 (A2503) of 23S rRNA, while Cfr catalyzes C8 methylation of the exact same nucleotide, and will subsequently catalyze C2 methylation if the site is unmethylated. A key feature of the unusual mechanisms of catalysis proposed for these enzymes is the attack of a methylene radical, derived from a methylcysteine residue, onto the carbon center undergoing methylation to generate a paramagnetic protein–nucleic acid cross-linked species. This species has been thoroughly characterized during Cfr-dependent C8 methylation, but does not accumulate tomore » detectible levels in RlmN-dependent C2 methylation. Herein, we show that inactive C118S/A variants of RlmN accumulate a substrate-derived paramagnetic species. Characterization of this species by electron paramagnetic resonance spectroscopy in concert with strategic isotopic labeling shows that the radical is delocalized throughout the adenine ring of A2503, although predominant spin density is on N1 and N3. Moreover, 13C hyperfine interactions between the radical and the methylene carbon of the formerly [methyl- 13C]Cys355 residue show that the radical species exists in a covalent cross-link between the protein and the nucleic acid substrate. X-ray structures of RlmN C118A show that, in the presence of SAM, the substitution does not alter the active site structure compared to that of the wild-type enzyme. Together, these findings have new mechanistic implications for the role(s) of C118 and its counterpart in Cfr (C105) in catalysis, and suggest involvement of the residue in resolution of the cross-linked species via a radical mediated process« less

Detection of patent ductus arteriosus with intraoperative transesophageal echocardiography in a patient undergoing closure of coronary artery to pulmonary artery fistula.

PubMed

Miyata, Yuka; Hayashi, Yukio

2017-01-01

Coronary artery to pulmonary artery fistula is an unusual vascular anomaly, and the shunt ratio of this fistula is usually small. We report anesthetic management of a 55-year-old female with annuloaortic ectasia, aortic valve regurgitation, and coronary artery to pulmonary artery fistula undergoing radical repair. We calculated the left-to-right shunt ratio after placement of a pulmonary artery catheter and found that the ratio was unexpectedly high. Thus, we explored the presence of another shunt by intraoperative transesophageal echocardiography and found patent ductus arteriosus undiagnosed before operation. A combination of a pulmonary artery catheter and transesophageal echocardiography is useful to explore the presence of another shunt, such as patent ductus arteriosus during anesthesia.

Radical production inside an acoustically driven microbubble.

PubMed

Stricker, Laura; Lohse, Detlef

2014-01-01

The chemical production of radicals inside acoustically driven bubbles is determined by the local temperature inside the bubbles and by their composition at collapse. By means of a previously validated ordinary differential equations (ODE) model [L. Stricker, A. Prosperetti, D. Lohse, Validation of an approximate model for the thermal behavior in acoustically driven bubbles, J. Acoust. Soc. Am. 130 (5) (2011) 3243-3251], based on boundary layer assumption for mass and heat transport, we study the influence of different parameters on the radical production. We perform different simulations by changing the driving frequency and pressure, the temperature of the surrounding liquid and the composition of the gas inside the bubbles. In agreement with the experimental conditions of new generation sonochemical reactors, where the bubbles undergo transient cavitation oscillations [D. F. Rivas, L. Stricker, A. Zijlstra, H. Gardeniers, D. Lohse, A. Prosperetti, Ultrasound artificially nucleated bubbles and their sonochemical radical production, Ultrason. Sonochem. 20 (1) (2013) 510-524], we mainly concentrate on the initial chemical transient and we suggest optimal working ranges for technological applications. The importance of the chemical composition at collapse is reflected in the model, including the role of entrapped water vapor. We in particular study the exothermal reactions taking place in H2 and O2 mixtures. At the exact stoichiometric mixture 2:1 the highest internal bubble temperatures are achieved. Copyright © 2013 Elsevier B.V. All rights reserved.

[Short-term efficacy of da Vinci robotic surgical system on rectal cancer in 101 patients].

PubMed

Zeng, Dong-Zhu; Shi, Yan; Lei, Xiao; Tang, Bo; Hao, Ying-Xue; Luo, Hua-Xing; Lan, Yuan-Zhi; Yu, Pei-Wu

2013-05-01

To investigate the feasibility and safety of da Vinci robotic surgical system in rectal cancer radical operation, and to summarize its short-term efficacy and clinical experience. Data of 101 cases undergoing da Vinci robotic surgical system for rectal cancer radical operation from March 2010 to September 2012 were retrospectively analyzed. Evaluation was focused on operative procedure, complication, recovery and pathology. All the 101 cases underwent operation successfully and safely without conversion to open procedure. Rectal cancer radical operation with da Vinci robotic surgical system included 73 low anterior resections and 28 abdominoperineal resections. The average operative time was (210.3±47.2) min. The average blood lose was (60.5±28.7) ml without transfusion. Lymphadenectomy harvest was 17.3±5.4. Passage of first flatus was (2.7±0.7) d. Distal margin was (5.3±2.3) cm without residual cancer cells. The complication rate was 6.9%, including anastomotic leakage(n=2), perineum incision infection(n=2), pulmonary infection (n=2), urinary retention (n=1). There was no postoperative death. The mean follow-up time was(12.9±8.0) months. No local recurrence was found except 2 cases with distant metastasis. Application of da Vinci robotic surgical system in rectal cancer radical operation is safe and patients recover quickly The short-term efficacy is satisfactory.

Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

DOE Office of Scientific and Technical Information (OSTI.GOV)

D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.

2017-04-11

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1.more » Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.« less

Atmospheric Chemistry of the Carbon Capture Solvent Monoethanolamine (MEA): A Theoretical Study

NASA Astrophysics Data System (ADS)

da Silva, G.

2012-12-01

The development of amine solvent technology for carbon capture and storage has the potential to create large new sources of amines to the atmosphere. The atmospheric chemistry of amines generally, and carbon capture solvents in particular, is not well understood. We have used quantum chemistry and master equation modelling to investigate the OH radical initiated oxidation of monoethanolamine (NH2CH2CH2OH), or MEA, the archetypal carbon capture solvent. The OH radical can abstract H atoms from either carbon atom in MEA, with negative reaction barriers. Treating these reactions with a two transition state model can reliably reproduce experimental rate constants and their temperature dependence. The products of the MEA + OH reaction, the NH2CHCH2OH and NH2CH2CHOH radicals, undergo subsequent reaction with O2, which has also been studied. In both cases chemically activated reactions that bypass peroxyl radical intermediates dominate, producing 2-iminoethanol + HO2 (from NH2CHCH2OH) or aminoacetaldehyde + HO2 (from NH2CH2CHOH), making the process HOx-neutral. The operation of chemically activated reaction mechanisms has implications for the ozone forming potential of MEA. The products of MEA photo-oxidation are proposed as important species in the formation of both organic and inorganic secondary aerosols, particularly through uptake of the imine 2-iminoethanol and subsequent hydrolysis to ammonia and glycolaldehyde.

Demonstration of free radical generation in the "stunned" myocardium in the conscious dog and identification of major differences between conscious and open-chest dogs.

PubMed Central

Li, X Y; McCay, P B; Zughaib, M; Jeroudi, M O; Triana, J F; Bolli, R

1993-01-01

Conscious dogs undergoing a 15-min coronary occlusion were given alpha-phenyl N-tert-butyl nitrone (PBN) and the local coronary venous plasma was analyzed by electron paramagnetic resonance spectroscopy. A prolonged myocardial release of PBN radical adducts was observed, which exhibited a burst in the initial minutes of reflow (peaking at 3 min) and then abated but continued for 1-3 h after reperfusion. Computer simulation revealed the presence of at least two PBN adducts (aN = 15.2 G and a beta H = 6.0 G; aN = 14.6 G and a beta H = 3.0 G), both consistent with the trapping of secondary carbon-centered radicals. No appreciable PBN adduct production was observed when collateral flow exceeded 30-40% of nonischemic flow, indicating that a flow reduction of at least 60% is necessary to trigger free radical reactions. There was a direct relationship between the magnitude of PBN adduct production and the severity of contractile dysfunction (r = 0.77), suggesting that the radicals generated upon reperfusion play a causal role in the subsequent stunning. The total release of PBN adducts after 3 h of reperfusion following a 15-min coronary occlusion was found to be approximately five times greater in open-chest compared with conscious dogs; at the same time, the recovery of wall thickening was markedly less in open-chest dogs. This study represents the first application of spin trapping to a conscious animal model of myocardial ischemia. The results demonstrate (a) that free radicals are generated in the stunned myocardium in the absence of the artificial or abnormal conditions associated with previously used models (isolated hearts, open-chest preparations), and (b) that both the severity of postischemic dysfunction and the magnitude of the attendant free radical production are greatly exaggerated in the open-chest dog, implying that previous conclusions derived from this model may not be applicable to conscious animals or to humans. This investigation also provides a method to measure free radicals in awake animals. PMID:8394382

Effect of Regional Hospital Competition and Hospital Financial Status on the Use of Robotic-Assisted Surgery.

PubMed

Wright, Jason D; Tergas, Ana I; Hou, June Y; Burke, William M; Chen, Ling; Hu, Jim C; Neugut, Alfred I; Ananth, Cande V; Hershman, Dawn L

2016-07-01

Despite the lack of efficacy data, robotic-assisted surgery has diffused rapidly into practice. Marketing to physicians, hospitals, and patients has been widespread, but how this marketing has contributed to the diffusion of the technology remains unknown. To examine the effect of regional hospital competition and hospital financial status on the use of robotic-assisted surgery for 5 commonly performed procedures. A cohort study of 221 637 patients who underwent radical prostatectomy, total nephrectomy, partial nephrectomy, hysterectomy, or oophorectomy at 1370 hospitals in the United States from January 1, 2010, to December 31, 2011, was conducted. The association between hospital competition, hospital financial status, and performance of robotic-assisted surgery was examined. The association between hospital competition was measured with the Herfindahl-Hirschman Index (HHI), hospital financial status was estimated as operating margin, and performance of robotic-assisted surgery was examined using multivariate mixed-effects regression models. We identified 221 637 patients who underwent one of the procedures of interest. The cohort included 30 345 patients who underwent radical prostatectomy; 20 802, total nephrectomy; 8060, partial nephrectomy; 134 985, hysterectomy; and 27 445, oophorectomy. Robotic-assisted operations were performed for 20 500 (67.6%) radical prostatectomies, 1405 (6.8%) total nephrectomies, 2759 (34.2%) partial nephrectomies, 14 047 (10.4%) hysterectomies, and 1782 (6.5%) oophorectomies. Use of robotic-assisted surgery increased for each procedure from January 2010 through December 2011. For all 5 operations, increased market competition (as measured by the HHI) was associated with increased use of robotic-assisted surgery. For prostatectomy, the risk ratios (95% CIs) for undergoing a robotic-assisted procedure were 2.20 (1.50-3.24) at hospitals in moderately competitive markets and 2.64 (1.84-3.78) for highly competitive markets compared with noncompetitive markets. For hysterectomy, patients at hospitals in moderately (3.75 [2.26-6.25]) and highly (5.30; [3.27-8.57]) competitive markets were more likely to undergo a robotic-assisted surgery. Increased hospital profitability was associated with use of robotic-assisted surgery only for partial nephrectomy in facilities with medium-high (1.67 [1.13-2.48]) and high (1.50 [0.98-2.29]) operating margins. With analysis limited to patients treated at a hospital that had performed robotic-assisted surgery, there was no longer an association between competition and use of robotic-assisted surgery. Patients undergoing surgery in a hospital in a competitive regional market were more likely to undergo a robotic-assisted procedure. These data imply that regional competition may influence a hospital's decision to acquire a surgical robot.

Randomized clinical trial of new intravenous lipid (SMOFlipid 20%) versus medium-chain triglycerides/long-chain triglycerides in adult patients undergoing gastrointestinal surgery.

PubMed

Wu, Ming-Hsun; Wang, Ming-Yang; Yang, Chin-Yao; Kuo, Min-Liang; Lin, Ming-Tsan

2014-09-01

SMOFlipid 20% is intravenous lipid emulsion (ILE) containing long-chain triglycerides (LCT), medium-chain triglycerides (MCT), olive oil, and fish oil as a mixed emulsion containing α-tocopherol. The aim was to assess the efficacy of this new ILE in gastrointestinal surgery compared with MCT/LCT. In this prospective study, 40 patients were randomized to SMOFlipid 20% or MCT/LCT (Lipovenoes 20%) group. Clinical and biochemistry data were collected. Inflammatory markers (CRP, IL-6, IL-10, TNF-α, TGF-β1) and oxidative stress (ROS and superoxide) were measured. Thirty-five patients (17 males and 18 females) with a mean age of 57 years completed the study. The patients' demographic characteristics (age, gender, height, body weight, and BMI) were similar without significant differences between groups. The increment of triglyceride on day 6 from baseline was significantly lower in SMOFlipid group than in Lipovenoes MCT/LCT group. Inflammatory markers, as well as superoxide radical and total oxygen radical were not different between groups. Despite the comparable effect on inflammatory response, because of its well-balanced fatty acid pattern, relatively low n-6:n-3 ratio, and high vitamin E content, SMOFlipid had a better triglyceride-lowering effect as compared with MCT/LCT in adult patients undergoing gastrointestinal surgery. © 2013 American Society for Parenteral and Enteral Nutrition.

Formation of a Criegee intermediate in the low-temperature oxidation of dimethyl sulfoxide.

PubMed

Asatryan, Rubik; Bozzelli, Joseph W

2008-04-07

Dimethyl sulfoxide (DMSO) is the major sulfur-containing constituent of the Marine Boundary Layer. It is a significant source of H2SO4 aerosol/particles and methane sulfonic acid via atmospheric oxidation processes, where the mechanism is not established. In this study, several new, low-temperature pathways are revealed in the oxidation of DMSO using CBS-QB3 and G3MP2 multilevel and B3LYP hybrid density functional quantum chemical methods. Unlike analogous hydrocarbon peroxy radicals the chemically activated DMSO peroxy radical, [CH3S(=O)CH2OO*]*, predominantly undergoes simple dissociation to a methylsulfinyl radical CH3S*(=O) and a Criegee intermediate, CH2OO, with the barrier to dissociation 11.3 kcal mol(-1) below the energy of the CH3S(=O)CH2* + O2 reactants. The well depth for addition of O2 to the CH3S(=O)CH2 precursor radical is 29.6 kcal mol(-1) at the CBS-QB3 level of theory. We believe that this reaction may serve an important role in atmospheric photochemical and irradiated biological (oxygen-rich) media where formation of initial radicals is facilitated even at lower temperatures. The Criegee intermediate (carbonyl oxide, peroxymethylene) and sulfinyl radical can further decompose, resulting in additional chain branching. A second reaction channel important for oxidation processes includes formation (via intramolecular H atom transfer) and further decomposition of hydroperoxide methylsulfoxide radical, *CH2S(=O)CH2OOH over a low barrier of activation. The initial H-transfer reaction is similar and common in analogous hydrocarbon radical + O2 reactions; but the subsequent very low (3-6 kcal mol(-1)) barrier (14 kcal mol(-1) below the initial reagents) to beta-scission products is not common in HC systems. The low energy reaction of the hydroperoxide radical is a beta-scission elimination of *CH2S(=O)CH2OOH into the CH2=S=O + CH2O + *OH product set. This beta-scission barrier is low, because of the delocalization of the *CH2 radical center through the -S(=O) group, to the -CH2OOH fragment in the transition state structure. The hydroperoxide methylsulfoxide radical can also decompose via a second reaction channel of intramolecular OH migration, yielding formaldehyde and a sulfur-centered hydroxymethylsulfinyl radical HOCH2S*(=O). The barrier of activation relative to initial reagents is 4.2 kcal mol(-1). Heats of formation for DMSO, DMSO carbon-centered radical and Criegee intermediate are evaluated at 298 K as -35.97 +/- 0.05, 13.0 +/- 0.2 and 25.3 +/- 0.7 kcal mol(-1) respectively using isodesmic reaction analysis. The [CH3S*(=O) + CH2OO] product set is shown to form a van der Waals complex that results in O-atom transfer reaction and the formation of new products CH3SO2* radical and CH2O. Proper orientation of the Criegee intermediate and methylsulfinyl radical, as a pre-stabilized pre-reaction complex, assist the process. The DMSO radical reaction is also compared to that of acetonyl radical.

Quality of life in women undergoing urinary diversion for bladder cancer: results of a multicenter study among long-term disease-free survivors.

PubMed

Gacci, Mauro; Saleh, Omar; Cai, Tommaso; Gore, John L; D'Elia, Carolina; Minervini, Andrea; Masieri, Lorenzo; Giannessi, Claudia; Lanciotti, Michele; Varca, Virginia; Simonato, Alchiede; Serni, Sergio; Carmignani, Giorgio; Carini, Marco

2013-03-12

Women undergoing radical cystectomy (RC) and urinary diversion for bladder cancer experience substantial limitations in health-related quality of life (HRQOL). However, the level of discomfort caused by different urinary diversion has been never evaluated in long term survivors. The aim of this multicenter study is to evaluate differences in HRQOL among recurrence-free women undergoing cutaneous ureterostomy (CUS), Bricker's ileal conduit (BK-IC) and Orthotopic neobladder VIP (ONB-VIP) in disease-free females treated with radical cystectomy (RC), with long-term follow up (mean 60.1 months; range 36-122 months). All consecutively treated female patients from two urological institutions who underwent RC and urinary diversion from January 2000 to December 2008, with no evidence of tumor recurrence at a minimum follow up of 36 months, were included. Patients received the European Organisation for Research and Treatment of Cancer (EORTC) generic (QLQ-C30) and bladder cancer-specific instruments (QLQ-BLM30) and the Functional Assessment of Cancer Therapy for Bladder Cancer (FACT-BL). Clinical data and questionnaire results were analyzed in order to evaluate the HRQOL differences among diversion groups. We identified 37 females (median age: 68, range 45-82 years), including 12 status-post CUS, 16 who underwent BK-IC, and 9 who underwent ONB-VIP. Most were healthy (24/37 with no comorbidities, 4/37 Charlson 1-2, 9/37 Charlson 3 or greater - we didn't considered bladder cancer in Charlson evaluation because bladder cancer was the main inclusion criteria). Women undergoing CUS endorsed worse FACT-BL scores compared with BK-IC and ONB-VIP patients, worse HRQOL regarding physical and emotional well-being (p=0.008 and p=0.02, respectively), and a trend toward worse EORTC QLQ-C30 scores for appetite loss and fatigue (p=0.05 for both). In our study long-term disease-free females treated with CUS endorsed worse HRQOL compared with women who underwent BK-IC or ONB-VIP, mostly due to worse physical and emotional perception of their body image.

One-electron redox processes in a cyclic selenide and a selenoxide: a pulse radiolysis study.

PubMed

Singh, Beena G; Thomas, Elizabeth; Kumakura, Fumio; Dedachi, Kenichi; Iwaoka, Michio; Priyadarsini, K Indira

2010-08-19

One-electron redox reactions of cyclic selenium compounds, DL-trans-3,4-dihydroxy-1-selenolane (DHS(red)), and DL-trans-3,4-dihydroxy-1-selenolane oxide (DHS(ox)) were carried out in aqueous solutions using nanosecond pulse radiolysis, and the resultant transients were detected by absorption spectroscopy. Both *OH radical and specific one-electron oxidant, Br(2)(*-) radical reacted with DHS(red) to form similar transients absorbing at 480 nm, which has been identified as a dimer radical cation (DHS(red))(2)(*+). Secondary electron transfer reactions of the (DHS(red))(2)(*+) were studied with 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS(2-)) and superoxide (O(2)(*-)) radicals. The bimolecular rate constants for the electron transfer reaction between (DHS(red))(2)(*+) with ABTS(2-) was determined as 2.4 +/- 0.4 x 10(9) M(-1) s(-1). From this reaction, the yield of (DHS(red))(2)(*+) formed on reaction with *OH radical was estimated in the presence of varying phosphate concentrations. (DHS(red))(2)(*+) reacted with O(2)(*-) radical with a bimolecular rate constant of 2.7 +/- 0.1 x 10(9) M(-1) s(-1) at pH 7. From the same reaction, the positive charge on (DHS(red))(2)(*+) was confirmed by the kinetic salt effect. HPLC analysis of the products formed in the reaction of (DHS(red))(2)(*+) with O(2)(*-) radicals showed formation of the selenoxide, DHS(ox). In order to know if a similar mechanism operated during the reduction of DHS(ox), its reactions with e(aq)(-) were studied at pH 7. The rate constant for this reaction was determined as 5.6 +/- 0.9 x 10(9) M(-1) s(-1), and no transient absorption could be observed in the wavelength region from 280 to 700 nm. It is proposed that the radical anion (DHS(ox))(*-) formed by a one-electron reduction would get protonated to form a hydroxyl radical adduct, which in presence of proton donors, would undergo dehydration to form DHS(*+). Evidence for this mechanism was obtained by converting DHS(*+) to (DHS(red))(2)(*+) with the addition of DHS(red) to the same system. Quantum chemical calculations provided supporting evidence for some of the redox reactions.

Cost analysis of open radical cystectomy versus robot-assisted radical cystectomy.

PubMed

Bansal, Sukhchain S; Dogra, Tara; Smith, Peter W; Amran, Maisarah; Auluck, Ishna; Bhambra, Maninder; Sura, Manraj S; Rowe, Edward; Koupparis, Anthony

2018-03-01

To perform a cost analysis comparing the cost of robot-assisted radical cystectomy (RARC) with open RC (ORC) in a UK tertiary referral centre and to identify the key cost drivers. Data on hospital length of stay (LOS), operative time (OT), transfusion rate, and volume and complication rate were obtained from a prospectively updated institutional database for patients undergoing RARC or ORC. A cost decision tree model was created. Sensitivity analysis was performed to find key drivers of overall cost and to find breakeven points with ORC. Monte Carlo analysis was performed to quantify the variability in the dataset. One RARC procedure costs £12 449.87, or £12 106.12 if the robot was donated via charitable funds. In comparison, one ORC procedure costs £10 474.54. RARC is 18.9% more expensive than ORC. The key cost drivers were OT, LOS, and the number of cases performed per annum. High ongoing equipment costs remain a large barrier to the cost of RARC falling. However, minimal improvements in patient quality of life would be required to offset this difference. © 2017 The Authors BJU International © 2017 BJU International Published by John Wiley & Sons Ltd.

Management of erectile dysfunction post-radical prostatectomy

PubMed Central

Saleh, Alan; Abboudi, Hamid; Ghazal-Aswad, MB; Mayer, Erik K; Vale, Justin A

2015-01-01

Radical prostatectomy is a commonly performed procedure for the treatment of localized prostate cancer. One of the long-term complications is erectile dysfunction. There is little consensus on the optimal management; however, it is agreed that treatment must be prompt to prevent fibrosis and increase oxygenation of penile tissue. It is vital that patient expectations are discussed, a realistic time frame of treatment provided, and treatment started as close to the prostatectomy as possible. Current treatment regimens rely on phosphodiesterase 5 inhibitors as a first-line therapy, with vacuum erection devices and intraurethral suppositories of alprostadil as possible treatment combination options. With nonresponders to these therapies, intracavernosal injections are resorted to. As a final measure, patients undergo the highly invasive penile prosthesis implantation. There is no uniform, objective treatment program for erectile dysfunction post-radical prostatectomy. Management plans are based on poorly conducted and often underpowered studies in combination with physician and patient preferences. They involve the aforementioned drugs and treatment methods in different sequences and doses. Prospective treatments include dietary supplements and gene therapy, which have shown promise with there proposed mechanisms of improving erectile function but are yet to be applied successfully in human patients. PMID:25750901

Sulfate radicals enable a non-enzymatic Krebs cycle precursor

PubMed Central

Keller, Markus A.; Kampjut, Domen; Harrison, Stuart A.; Ralser, Markus

2017-01-01

The evolutionary origins of the tricarboxylic acid cycle (TCA), or Krebs cycle, are so far unclear. Despite a few years ago, the existence of a simple non-enzymatic Krebs-cycle catalyst has been dismissed ‘as an appeal to magic’, citrate and other intermediates have meanwhile been discovered on a carbonaceous meteorite and do interconvert non-enzymatically. To identify the non-enzymatic Krebs cycle catalyst, we used combinatorial, quantitative high-throughput metabolomics to systematically screen iron and sulfate reaction milieus that orient on Archean sediment constituents. TCA cycle intermediates are found stable in water and in the presence of most iron and sulfate species, including simple iron-sulfate minerals. However, we report that TCA intermediates undergo 24 interconversion reactions in the presence of sulfate radicals that form from peroxydisulfate. The non-enzymatic reactions critically cover a topology as present in the Krebs cycle, the glyoxylate shunt and the succinic semialdehyde pathways. Assembled in a chemical network, the reactions achieve more than ninety percent carbon recovery. Our results show that a non-enzymatic precursor for the Krebs cycle is biologically sensible, efficient, and forms spontaneously in the presence of sulfate radicals. PMID:28584880

The First MS-Cleavable, Photo-Thiol-Reactive Cross-Linker for Protein Structural Studies

NASA Astrophysics Data System (ADS)

Iacobucci, Claudio; Piotrowski, Christine; Rehkamp, Anne; Ihling, Christian H.; Sinz, Andrea

2018-04-01

Cleavable cross-linkers are gaining increasing importance for chemical cross-linking/mass spectrometry (MS) as they permit a reliable and automated data analysis in structural studies of proteins and protein assemblies. Here, we introduce 1,3-diallylurea (DAU) as the first CID-MS/MS-cleavable, photo-thiol-reactive cross-linker. DAU is a commercially available, inexpensive reagent that efficiently undergoes an anti-Markovnikov hydrothiolation with cysteine residues in the presence of a radical initiator upon UV-A irradiation. Radical cysteine cross-linking proceeds via an orthogonal "click reaction" and yields stable alkyl sulfide products. DAU reacts at physiological pH and cross-linking reactions with peptides, and proteins can be performed at temperatures as low as 4 °C. The central urea bond is efficiently cleaved upon collisional activation during tandem MS experiments generating characteristic product ions. This improves the reliability of automated cross-link identification. Different radical initiators have been screened for the cross-linking reaction of DAU using the thiol-containing compounds cysteine and glutathione. Our concept has also been exemplified for the biologically relevant proteins bMunc13-2 and retinal guanylyl cyclase-activating protein-2. [Figure not available: see fulltext.

Reaction of 1H-1-oxo-2,4,6,8-tetrakis(tert-butyl)phenoxazine with certain group II-IV metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karsanov, I.V.; Ivakhnenko, E.P.; Khandkarova, V.S.

1987-07-10

It has already been shown that 2-amino-4,6-di(tert-butyl)phenol reacts with 3,5-di(tert-butyl)-o-benzoquinone to form 1H-1-oxo-2,4,6,8-tetrakis(tert-butyl)phenoxazine (I), which is readily reduced by alkali metals to the corresponding semiquinone anion-radical (II), and further to the diamagnetic dianion (IIA). They made use of this ability of (I) to undergo reduction to prepare anion-radical salts with different group II-IV metals in the form of their amalgams. In the EPR spectrum of the anion-radical complex (III) formed in the reduction of (I) by a thallium amalgam, the HFI constants of the unpaired electron with magnetic nuclei of the organic ligand are close to those of the K-saltmore » (II), and a substantial HFI is observed with the /sup 203,205/Tl nuclei. This unequivocally proves that the complex has a semiquinone structure, since an HFI on the /sup 203,205/Tl nuclei of such an order of magnitude is characteristic of o-benzoquinone salts with a thallium cation.« less

Innovative scheme for high-repetition-rate imaging of CN radical.

PubMed

Satija, Aman; Ruesch, Morgan D; Powell, Michael S; Son, Steven F; Lucht, Robert P

2018-02-01

We have employed, to the best of our knowledge, a novel excitation scheme to perform the first high-repetition-rate planar laser-induced fluorescence (PLIF) measurements of a CN radical in combustion. The third harmonic of a Nd:YVO 4 laser at 355 nm due to its relatively large linewidth overlaps with several R branch transitions in a CN ground electronic state. Therefore, the 355 nm beam was employed to directly excite the CN transitions with good efficiency. The CN measurements were performed in premixed CH 4 -N 2 O flames with varying equivalence ratios. A detailed characterization of the high-speed CN PLIF imaging system is presented via its ability to capture statistical and dynamical information in these premixed flames. Single-shot CN PLIF images obtained over a HMX pellet undergoing self-supported deflagration are presented as an example of the imaging system being applied towards characterizing the flame structure of energetic materials.

Efficacy and Safety of Ketamine Added to Local Anesthetic in Modified Pectoral Block for Management of Postoperative Pain in Patients Undergoing Modified Radical Mastectomy.

PubMed

Othman, Ahmed H; El-Rahman, Ahmad M Abd; El Sherif, Fatma

2016-01-01

Breast surgery is an exceedingly common procedure with an increased incidence of acute and chronic pain. Pectoral nerve block is a novel peripheral nerve block alternative to neuro-axial and paravertebral blocks for ambulatory breast surgeries. This study aims to compare the analgesic efficacy and safety of modified Pecs block with ketamine plus bupivacaine versus bupivacaine in patients undergoing breast cancer surgery. A randomized, double-blind, prospective study. Academic medical center. This study is registered at www.clinicaltrials.gov under number: (NCT02620371) after approval by the ethics committee of South Egypt Cancer Institute, Assuit University, Assuit, Egypt. Sixty patients aged 18 - 60 years scheduled for modified radical mastectomy were enrolled and randomly assigned into 2 groups (30 patients each): Control group patients were given ultrasound-guided, Pecs block with 30 mL of 0.25% bupivacaine only. Ketamine group patients were given ultrasound-guided, Pecs block with 30 mL of 0.25% bupivacaine plus ketamine hydrochloride (1 mg/kg). Patients were followed up for 48 hours postoperatively for vital signs, VAS score, first request of rescue analgesia and total morphine consumption, sedation score, and side effects. Ketamine plus bupivacaine in Pecs block compared to bupivacaine alone prolonged the mean time of first request of analgesia (18.25 ± 1.98), (12.56 ± 2.64), respectively (P < 0.001), reduced total morphine consumption (12.50 ± 4.63), (18.86 ± 6.28), respectively (P = 0.016). With no significant difference in hemodynamics, respiratory rate, oxygen saturation, VAS and sedation scores, and side effects observed between the 2 groups (P > 0.05). This study is limited by its sample size. The addition of ketamine to modified Pecs block prolonged the time to first request of analgesia and reduced total opioid consumption without serious side effects in patients who underwent a modified radical mastectomy. Ketamine, bupivacaine, pecs block, postoperative, pain, breast cancer.

Introducing an enhanced recovery programme to an established totally intracorporeal robot-assisted radical cystectomy service.

PubMed

Collins, Justin W; Adding, Christofer; Hosseini, Abolfazl; Nyberg, Tommy; Pini, Giovannalberto; Dey, Linda; Wiklund, Peter N

2016-01-01

The aim of this study was to assess the effect of introducing an enhanced recovery programme (ERP) to an established robot-assisted radical cystectomy (RARC) service. Data were prospectively collected on 221 consecutive patients undergoing totally intracorporeal RARC between December 2003 and May 2014. The ERP was specifically designed to support an evolving RARC service, where increasing proportions of patients requiring radical cystectomy underwent RARC. Patient demographics and outcomes before and after implementation of the ERP were compared. The primary endpoint was length of stay (LOS). Secondary outcomes included age, American Society of Anesthesiologists (ASA) score, preoperative staging, operative time, complications and readmissions. Differences in outcomes between patients before and after implementation of ERP were tested with the Jonckheere-Terpstra trend test and quantile regression with backward selection. Following implementation of the ERP, the demographics of the patients (n = 135) changed, with median age increasing from 66 to 70 years (p < 0.01), higher ASA grade (p < 0.001), higher preoperative stage cancer (pT ≥ 2, p < 0.05) and increased likelihood of undergoing an ileal conduit diversion (p < 0.001). Median LOS before ERP was 9 days [interquartile range (IQR) 8-13 days] and after ERP was 8 days (IQR 6-10 days) (p < 0.001). ASA grade and neoadjuvant chemotherapy also affected LOS (p < 0.05 and p < 0.01, respectively). There was no significant difference in 30 day complication rates, readmission rates or 90 day mortality, with 59% experiencing complications before ERP implementation and 57% after implementation. The majority of complications were low grade. Patient demographics changed as the RARC service evolved from selected patients to a general service. Despite worsening demographics, LOS decreased following ERP implementation. This evidence-based ERP safely standardized perioperative care, resulting in decreased LOS and decreased variability in LOS.

Morbidity and Mortality of Radical Nephrectomy for Patients With Disseminated Cancer: An Analysis of the National Surgical Quality Improvement Program Database.

PubMed

Wallis, Christopher J D; Bjarnason, Georg; Byrne, James; Cheung, Douglas C; Hoffman, Azik; Kulkarni, Girish S; Nathens, Avery B; Nam, Robert K; Satkunasivam, Raj

2016-09-01

To determine the effect of disseminated cancer on perioperative outcomes following radical nephrectomy. We conducted a retrospective cohort study of patients undergoing radical nephrectomy for kidney cancer from 2005 to 2014 using the American College of Surgeons National Surgical Quality Improvement Program, a multi-institutional prospective registry that captures perioperative surgical complications. Patients were stratified according to the presence (n = 657) or absence (n = 7143) of disseminated cancer at the time of surgery. We examined major complications (death, reoperation, cardiac event, or neurologic event) within 30 days of surgery. Secondary outcomes included pulmonary, infectious, venous thromboembolic, and bleeding complications; prolonged length of stay; and concomitant procedures (bowel, liver, spleen, pancreas, and vascular procedures). Adjusted odds ratio (aOR) and 95% confidence interval (95% CI) were calculated using multivariate logical regression models. Patients with disseminated cancer were older and more likely to be male, have greater comorbidities, and have undergone open surgery. Major complications were more common among patients with disseminated cancer (7.8%) than those without disseminated cancer (3.2%; aOR 2.01, 95% CI 1.46-2.86). Mortality was significantly higher in patients with disseminated cancer (3.2%) than those without disseminated cancer (0.5%; P < .0001). Pulmonary (aOR 1.68, 95% CI 1.09-2.59), thromboembolic (aOR 1.72, 95% CI 1.01-2.96), and bleeding complications (aOR 2.12, 95% CI 1.73-2.60) were more common among patients with disseminated cancer as was prolonged length of stay (aOR 1.27, 95% CI 1.06-1.53). Nephrectomy in patients with disseminated cancer is a morbid operation with significant perioperative mortality. These data may be used for preoperative counseling of patients undergoing cytoreductive nephrectomy. Copyright © 2016 Elsevier Inc. All rights reserved.

Photochemically Induced Intramolecular Radical Cyclization Reactions with Imines.

PubMed

Lefebvre, Corentin; Michelin, Clément; Martzel, Thomas; Djou'ou Mvondo, Vaneck; Bulach, Véronique; Abe, Manabu; Hoffmann, Norbert

2018-02-16

The photochemically induced intramolecular hydrogen abstraction or hydrogen atom transfer in cyclic imines 8a,b followed by a cyclization is investigated. Two types of products are observed, one resulting from the formation of a C-C bond, the other from the formation of a C-N bond. A computational study reveals that hydrogen is exclusively transferred to the imine nitrogen leading to a triplet diradical intermediate. After intersystem crossing, the resulting zwitterionic intermediate undergoes cyclization leading to the final product.

Tensile Properties of Poly (N-vinyl caprolactam) Gels

NASA Technical Reports Server (NTRS)

Morgret, Leslie D.; Hinkley, Jeffrey A.

2004-01-01

N-vinyl caprolactam was copolymerized with ethylene glycol dimethacrylate using a free-radical initiator in alcohol/water solution. The resulting gels were thermally-responsive in water, undergoing an approximate fivefold reversible volume shrinkage between room temperature and ca. 50 C. Tensile testing showed that the stress-strain behavior was qualitatively different in the collapsed state above the temperature-induced transition. At the higher temperature, gels were stiffer, more ductile, and showed greater time dependence. Implications for the design of gel actuators are briefly discussed.

Prognostic role of mesenteric lymph nodes involvement in patients undergoing posterior pelvic exenteration during radical or supra-radical surgery for advanced ovarian cancer.

PubMed

Berretta, Roberto; Capozzi, Vito Andrea; Sozzi, Giulio; Volpi, Lavinia; Ceni, Valentina; Melpignano, Mauro; Giordano, Giovanna; Marchesi, Federico; Monica, Michela; Di Serio, Maurizio; Riccò, Matteo; Ceccaroni, Marcello

2018-04-01

The aim of this retrospective study is to analyze the prognostic role and the practical implication of mesenteric lymph nodes (MLN) involvements in advanced ovarian cancer (AOC). A total of 429 patients with AOC underwent surgery between December 2007 and May 2017. We included in the study 83 patients who had primary (PDS) or interval debulking surgery (IDS) for AOC with bowel resection. Numbers, characteristics and surgical implication of MLN involvement were considered. Eighty-three patients were submitted to bowel resection during cytoreduction for AOC. Sixty-seven patients (80.7%) underwent primary debulking surgery (PDS). Sixteen patients (19.3%) experienced interval debulking surgery (IDS). 43 cases (51.8%) showed MLN involvement. A statistic correlation between positive MLN and pelvic lymph nodes (PLN) (p = 0.084), aortic lymph nodes (ALN) (p = 0.008) and bowel infiltration deeper than serosa (p = 0.043) was found. A longer overall survival (OS) and disease-free survival was observed in case of negative MLN in the first 20 months of follow-up. No statistical differences between positive and negative MLN in terms of operative complication, morbidity, Ca-125, type of surgery (radical vs supra-radical), length and site of bowel resection, residual disease and site of recurrence were observed. An important correlation between positive MLN, ALN and PLN was detected; these results suggest a lymphatic spread of epithelial AOC similar to that of primary bowel cancer. The absence of residual disease after surgery is an independent prognostic factor; to achieve this result should be recommended a radical bowel resection during debulking surgery for AOC with bowel involvement.

Peri-operative comparison between daVinci-assisted radical prostatectomy and open radical prostatectomy in obese patients

NASA Astrophysics Data System (ADS)

Le, Carter Q.; Ho, Khai-Linh V.; Slezak, Jeffrey M.; Blute, Michael L.; Gettman, Matthew T.

2007-02-01

Introduction: While the effects of increasing body mass index on prostate cancer epidemiology and surgical approach have recently been studied, its effects on surgical outcomes are less clear. We studied the perioperative outcomes of obese (BMI >= 30) men treated with daVinci-assisted laparoscopic radical prostatectomy (DLP) and compared them to those treated with open radical retropubic prostatectomy (RRP) in a contemporary time frame. Method: After Institutional Review Board approval, we used the Mayo Clinic Radical Prostatectomy database to identify patients who had undergone DLP by a single surgeon and those who had undergone open RRP by a single surgeon between December 2002 and March 2005. Baseline demographics, peri- and post-operative courses, and complications were collected by retrospective chart review, and variables from the two cohorts compared using chi-square method and least-squares method of linear regression where appropriate. Results: 59 patients who had DLP and 76 undergoing RRP were available for study. Baseline demographics were not statistically different between the two cohorts. Although DLP had a significantly lower clinical stage than RRP (p=0.02), pathological stage was not statistically different (p=0.10). Transfusion rates, hospital stay, overall complications, and pathological Gleason were also not significantly different, nor were PSA progression, positive margin rate, or continence at 1 year. After bilateral nerve-sparing, erections suitable for intercourse with or without therapy at 1 year was 88.5% (23/26) for DLP and 61.2% (30/49) for RRP (p=0.01). Follow-up time was similar. Conclusion: For obese patients, DLP appears to have similar perioperative, as well as short-term oncologic and functional outcomes when compared to open RRP.

Quenching mechanisms and diffusional pathways in micellar systems unravelled by time-resolved magnetic-field effects.

PubMed

Goez, Martin; Henbest, Kevin B; Windham, Emma G; Maeda, Kiminori; Timmel, Christiane R

2009-06-08

Magnetic-field effects (MFEs) are used to investigate the photoreaction of xanthone (A) and DABCO (D) in anionic (SDS) or cationic (DTAC) micelles at high pH (DABCO = 1,4-diazabicyclo[2.2.2]octane, SDS = sodium dodecyl sulfate, DTAC = dodecyl trimethyl ammonium chloride). From MFE experiments with nanosecond time resolution, the radical anion A(.)(-) can be observed without any interference from the much more strongly absorbing triplet (3)A*, the different quenching processes can be separated and their rates can be measured. Triplet (3)A* is quenched dynamically both by the SDS micelle (k(1) = 5.0x10(5) s(-1)) and by DABCO approaching from the aqueous phase (k(2) = 2.0x10(9) M(-1) s(-1)). Static quenching by solubilised DABCO (association constant with the SDS micelles, 1.5 M(-1)) also participates at high DABCO concentrations, but is chemically nonproductive and does not lead to MFE generation. The MFEs stemming from the radical ion pairs A(.)(-) D(.)(+) are about 40 times larger in the anionic micelles than in the cationic ones despite a higher yield of free radicals in the latter case. This can be rationalised by different diffusional dynamics: Because of the location of their precursors, A(.)(-) and D(.)(+) are formed at opposite sides of the micelle boundary. Subsequently, the negatively charged Stern layer of the SDS micelle traps the radical cation, which then undergoes surface diffusion, so both the recombination probability and the spin mixing are high; in contrast, the positive surface charge of the DTAC micelle forces the radical cation into the bulk of the solution, thus efficiently blocking a recombination.

Redox- and non-redox-metal-induced formation of free radicals and their role in human disease.

PubMed

Valko, Marian; Jomova, Klaudia; Rhodes, Christopher J; Kuča, Kamil; Musílek, Kamil

2016-01-01

Transition metal ions are key elements of various biological processes ranging from oxygen formation to hypoxia sensing, and therefore, their homeostasis is maintained within strict limits through tightly regulated mechanisms of uptake, storage and secretion. The breakdown of metal ion homeostasis can lead to an uncontrolled formation of reactive oxygen species, ROS (via the Fenton reaction, which produces hydroxyl radicals), and reactive nitrogen species, RNS, which may cause oxidative damage to biological macromolecules such as DNA, proteins and lipids. An imbalance between the formation of free radicals and their elimination by antioxidant defense systems is termed oxidative stress. Most vulnerable to free radical attack is the cell membrane which may undergo enhanced lipid peroxidation, finally producing mutagenic and carcinogenic malondialdehyde and 4-hydroxynonenal and other exocyclic DNA adducts. While redox-active iron (Fe) and copper (Cu) undergo redox-cycling reactions, for a second group of redox-inactive metals such as arsenic (As) and cadmium (Cd), the primary route for their toxicity is depletion of glutathione and bonding to sulfhydryl groups of proteins. While arsenic is known to bind directly to critical thiols, other mechanisms, involving formation of hydrogen peroxide under physiological conditions, have been proposed. Redox-inert zinc (Zn) is the most abundant metal in the brain and an essential component of numerous proteins involved in biological defense mechanisms against oxidative stress. The depletion of zinc may enhance DNA damage by impairing DNA repair mechanisms. Intoxication of an organism by arsenic and cadmium may lead to metabolic disturbances of redox-active copper and iron, with the occurrence of oxidative stress induced by the enhanced formation of ROS/RNS. Oxidative stress occurs when excessive formation of ROS overwhelms the antioxidant defense system, as is maintained by antioxidants such as ascorbic acid, alpha-tocopherol, glutathione (GSH), carotenoids, flavonoids and antioxidant enzymes which include SOD, catalase and glutathione peroxidase. This review summarizes current views regarding the role of redox-active/inactive metal-induced formation of ROS, and modifications to biomolecules in human disease such as cancer, cardiovascular disease, metabolic disease, Alzheimer's disease, Parkinson's disease, renal disease, blood disorders and other disease. The involvement of metals in DNA repair mechanisms, tumor suppressor functions and interference with signal transduction pathways are also discussed.

Combining Manual Lymph Drainage with Physical Exercise after Modified Radical Mastectomy Effectively Prevents Upper Limb Lymphedema.

PubMed

Zhang, Lijuan; Fan, Aiqun; Yan, Jun; He, Yan; Zhang, Huiting; Zhang, Huizhen; Zhong, Qiaoling; Liu, Feng; Luo, Qinghua; Zhang, Liping; Tang, Hailin; Xin, Mingzhu

2016-06-01

Upper limb lymphedema is a common complication after radical mastectomy in patients with breast cancer. In this study, we examined the efficacy of self-manual lymph drainage (MLD) after modified radical mastectomy for the prevention of upper limb lymphedema, scar formation, or shoulder joint dysfunction in breast cancer patients. Breast cancer patients scheduled for modified radical mastectomy were randomly apportioned to undergo physical exercise only (PE group, the control; n = 500) or self-MLD as well as exercise (MLD group; n = 500) after surgery. In the PE group, patients started to undertake remedial exercises and progressive weight training after recovery from anesthesia. In the MLD group, in addition to receiving the same treatments as in the PE group, the patients were trained to perform self-MLD on the surgical incision for 10 min/session, 3 sessions/day, beginning after suture removal and incision closure (10 to 30 days after the surgery). Scar formation was evaluated at one week, and 1, 3, 6, and 12 months after the surgery, respectively. Upper limb circumference and shoulder abduction were measured 24 h before surgery, and at one week, and 1, 3, 6 and 12 months after the surgery. Compared to those in the PE group, patients in MLD group experienced significant improvements in scar contracture, shoulder abduction, and upper limb circumference. Self-MLD, in combination with physical exercise, is beneficial for breast cancer patients in preventing postmastectomy scar formation, upper limb lymphedema, and shoulder joint dysfunction.

Prostaglandin H synthase-catalyzed oxidation of all-trans- and 13-cis-retinoic acid to carbon-centered and peroxyl radical intermediates.

PubMed

Freyaldenhoven, M A; Lloyd, R V; Samokyszyn, V M

1996-06-01

Due to the importance of all-trans-retinoic acid (RA) in the treatment of various dermatological conditions and the wide distribution of prostaglandin H synthase (PGHS) in tissues, we have further examined the mechanisms involved in the hydroperoxide-dependent cooxidation of RA and its isomer, 13-cis-retinoic acid ((13Z)-RA), by PGHS. Hydroperoxide-dependent, PGHS-catalyzed oxidation of RA and (13Z)-RA was shown to form free radical adducts, using electron spin resonance (ESR) spin trapping techniques and 5-phenyl-4-penten-1-yl hydroperoxide (PPHP) or 13-hydroperoxy-9-cis-11-trans-octadecadienoic acid (13-OOH-18:2) as hydroperoxide substrates. Utilization of the spin trap alpha-phenyl-N-tert-butylnitrone (PBN) resulted in the detection of (13Z)-RA-PBN and RA-PBN adducts whose spectra were characterized by hyperfine coupling constants of aH = 4.16/aN = 15.69 and aH = 3.01/aN =15.92, respectively. Identical experiments under anaerobic conditions were carried out using the spin trap 2-methyl-2-nitrosopropane (NtB) which yielded nitroxide adducts whose spectra were characterized by a triplet of doublets with values of aH = 3.49/aN = 15.84 for the (13Z)-RA adduct and aH = 3.49/aN = 15.88 for the RA adduct. These results are indicative of secondary carbon-centered radical formation. We also used (+)-benzo[a]pyrene 7(S),8(S)-dihydrodiol ((+)-BP-7,8-diol) as a peroxyl radical probe. The results demonstrated the formation of (+)-BP-7,8-diol-derived tetrols, with the trans-anti tetrol representing the major oxidation product in systems undergoing PPHP-dependent, PGHS-catalyzed oxidation of (13Z)-RA or RA. These results are consistent with the formation of peroxyl radicals in these systems. In all experiments, the (13Z)-RA isomer appeared to be a better substrate for the enzyme compared to the all-trans isomer. Collectively these results provide further evidence to support the previously proposed mechanism for retinoid oxidation by PGHS involving the intermediacy of C4 carbon-centered radicals which subsequently react with dioxygen, yielding retinoid-derived peroxyl radicals.

Assessment of Physical Therapy Strategies for Recovery of Urinary Continence after Prostatectomy

PubMed Central

Santos, Nivea Adriano de Santana e; Saintrain, Maria Vieira de Lima; Regadas, Rommel Prata; da Silveira, Romulo Augusto; de Menezes, Francisco Julimar Correia

2017-01-01

Introduction: Urinary incontinence is a complication of radical prostatectomy. Pelvic floor exercises can facilitate recovery of continence after surgery; however, there is not sufficient evidence that physical therapy with biofeedback training is effective, particularly with respect to providing a faster recovery. Objective: To analyze the application of physical therapy techniques in the recovery of urinary incontinence after prostatectomy. Methodology: A randomized clinical trial was conducted from April to October 2015 with patients undergoing radical prostatectomy up to three months after surgery at the Santa Casa de Misericordia in Northeastern Brazil. The physical therapy intervention consisted of up to eight individual sessions. Patients were randomized into the intervention group, which performed exercises and received biofeedback training, and the control group, which performed exercises alone. Participants were assessed before, during and after treatment. The initial assessment included a structured instrument addressing sociodemographic and urological data. Frequencies were calculated for all variables and comparisons were checked by the Mann-Whitney test and for correlation significance. Results: The study included 13 patients aged 54-74 years, the majority undergoing retropubic surgery with mild urinary incontinence [11 (84.6%)]. There was a significant difference in the outcome of the pad test before (p=0.070) and after (p=0.015) treatment between the groups, but the reduction of urinary loss and the time to recovery of continence were equivalent for both groups. Conclusion: Both interventions provided improvement in the degree of incontinence within two months of treatment. PMID:28240013

Modulation of oxidative damage by nitroxide free radicals.

PubMed

Dragutan, Ileana; Mehlhorn, Rolf J

2007-03-01

Piperidine nitroxides like 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) are persistent free radicals in non-acidic aqueous solutions and organic solvents that may have value as therapeutic agents in medicine. In biological environments, they undergo mostly reduction to stable hydroxylamines but can also undergo oxidation to reactive oxoammonium compounds. Reactions of the oxoammonium derivatives could have adverse consequences including chemical modification of vital macromolecules and deleterious effects on cell signaling. An examination of their reactivity in aqueous solution has shown that oxoammonium compounds can oxidize almost any organic as well as many inorganic molecules found in biological systems. Many of these reactions appear to be one-electron transfers that reduce the oxoammonium to the corresponding nitroxide species, in contrast to a prevalence of two-electron reductions of oxoammonium in organic solvents. Amino acids, alcohols, aldehydes, phospholipids, hydrogen peroxide, other nitroxides, hydroxylamines, phenols and certain transition metal ions and their complexes are among reductants of oxoammonium, causing conversion of this species to the paramagnetic nitroxide. On the other hand, thiols and oxoammonium yield products that cannot be detected by ESR even under conditions that would oxidize hydroxylamines to nitroxides. These products may include hindered secondary amines, sulfoxamides and sulfonamides. Thiol oxidation products other than disulfides cannot be restored to thiols by common enzymatic reduction pathways. Such products may also play a role in cell signaling events related to oxidative stress. Adverse consequences of the reactions of oxoammonium compounds may partially offset the putative beneficial effects of nitroxides in some therapeutic settings.

Structural features, kinetics and SAR study of radical scavenging and antioxidant activities of phenolic and anilinic compounds

PubMed Central

2013-01-01

Background Phenolic compounds are widely distributed in plant kingdom and constitute one of the most important classes of natural and synthetic antioxidants. In the present study fifty one natural and synthetic structurally variant phenolic, enolic and anilinic compounds were examined as antioxidants and radical scavengers against DPPH, hydroxyl and peroxyl radicals. The structural diversity of the used phenolic compounds includes monophenols with substituents frequently present in natural phenols e.g. alkyl, alkoxy, ester and carboxyl groups, besides many other electron donating and withdrawing groups, in addition to polyphenols with 1–3 hydroxyl groups and aminophenols. Some common groups e.g. alkyl, carboxyl, amino and second OH groups were incorporated in ortho, meta and para positions. Results SAR study indicates that the most important structural feature of phenolic compounds required to possess good antiradical and antioxidant activities is the presence of a second hydroxyl or an amino group in o- or p-position because of their strong electron donating effect in these positions and the formation of a stable quinone-like products upon two hydrogen-atom transfer process; otherwise, the presence of a number of alkoxy (in o or p-position) and /or alkyl groups (in o, m or p-position) should be present to stabilize the resulted phenoxyl radical and reach good activity. Anilines showed also similar structural feature requirements as phenols to achieve good activities, except o-diamines which gave low activity because of the high energy of the resulted 1,2-dimine product upon the 2H-transfer process. Enols with ene-1,2-diol structure undergo the same process and give good activity. Good correlations were obtained between DPPH inhibition and inhibition of both OH and peroxyl radicals. In addition, good correlations were obtained between DPPH inhibition and antioxidant activities in sunflower oil and liver homogenate systems. Conclusions In conclusion, the structures of good anti radical and antioxidant phenols and anilines are defined. The obtained good correlations imply that measuring anti DPPH activity can be used as a simple predictive test for the anti hydroxyl and peroxyl radical, and antioxidant activities. Kinetic measurements showed that strong antioxidants with high activity have also high reaction rates indicating that factors stabilizing the phenoxyl radicals lower also the activation energy of the hydrogen transfer process. PMID:23497653

Toward designed singlet fission: solution photophysics of two indirectly coupled covalent dimers of 1,3-diphenylisobenzofuran.

PubMed

Johnson, Justin C; Akdag, Akin; Zamadar, Matibur; Chen, Xudong; Schwerin, Andrew F; Paci, Irina; Smith, Millicent B; Havlas, Zdeněk; Miller, John R; Ratner, Mark A; Nozik, Arthur J; Michl, Josef

2013-04-25

In order to identify optimal conditions for singlet fission, we are examining the photophysics of 1,3-diphenylisobenzofuran (1) dimers covalently coupled in various ways. In the two dimers studied presently, the coupling is weak. The subunits are linked via the para position of one of the phenyl substituents, in one case (2) through a CH2 linker and in the other (3) directly, but with methyl substituents in ortho positions forcing a nearly perpendicular twist between the two joint phenyl rings. The measurements are accompanied with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. Although in neat solid state, 1 undergoes singlet fission with a rate constant higher than 10(11) s(-1); in nonpolar solutions of 2 and 3, the triplet formation rate constant is less than 10(6) s(-1) and fluorescence is the only significant event following electronic excitation. In polar solvents, fluorescence is weaker because the initial excited singlet state S1 equilibrates by sub-nanosecond charge transfer with a nonemissive dipolar species in which a radical cation of 1 is attached to a radical anion of 1. Most of this charge transfer species decays to S0, and some is converted into triplet T1 with a rate constant near 10(8) s(-1). Experimental uncertainties prevent an accurate determination of the number of T1 excitations that result when a single S1 excitation changes into triplet excitation. It would be one if the charge-transfer species undergoes ordinary intersystem crossing and two if it undergoes the second step of two-step singlet fission. The triplet yield maximizes below room temperature to a value of roughly 9% for 3 and 4% for 2. Above ∼360 K, some of the S1 molecules of 3 are converted into an isomeric charge-transfer species with a shorter lifetime, possibly with a twisted intramolecular charge transfer (TICT) structure. This is not observed in 2.

Evaluation of positive surgical margins in patients undergoing robot-assisted and open radical prostatectomy according to preoperative risk groups.

PubMed

Suardi, Nazareno; Dell'Oglio, Paolo; Gallina, Andrea; Gandaglia, Giorgio; Buffi, Nicolò; Moschini, Marco; Fossati, Nicola; Lughezzani, Giovanni; Karakiewicz, Pierre I; Freschi, Massimo; Lucianò, Roberta; Shariat, Shahrokh F; Guazzoni, Giorgio; Gaboardi, Franco; Montorsi, Francesco; Briganti, Alberto

2016-02-01

Recent studies showed that robot-assisted radical prostatectomy (RARP) represents an oncologically safe procedure in patients with prostate cancer (PCa), where the rate of positive surgical margins (PSMs) might be lower in patients treated with RARP as compared with that of those undergoing the open approach (open RP [ORP]). The aim of this study is to analyze the rate of PSMs according to preoperative risk groups in a large cohort of patients treated with RARP and ORP in a single institution with standardized surgical technique and pathological examination. We evaluated 6,194 consecutive patients with PCa undergoing either ORP (71.1%) or RARP (28.9%) between 1992 and 2014. Logistic regression analyses were used to test the association between type of surgery and PSMs in each preoperative risk group (low vs. intermediate vs. high) after adjusting for confounders. Overall, 21.6% patients had PSMs. RARP was associated with a lower rate of PSMs in low-risk (11.5 vs. 15.4%, P = 0.01), intermediate-risk (18.9 vs. 23.5%, P = 0.008), and high-risk patients (19.7 vs. 30.1%, P<0.001). In multivariable analyses, after stratification according to risk group categories, no difference in PSMs between RARP and ORP was observed for low-risk (odds ratio [OR] = 0.87, P = 0.46) and intermediate-risk patients (OR = 0.84, P = 0.19). Conversely, RARP was associated with lower odds of PSMs in high-risk patients (OR = 0.69, P = 0.04). Similar results were observed when our analyses were repeated after accounting for pathological characteristics, in patients treated between 2006 and 2014 and in a cohort of men treated by high-volume surgeons (all P≤ 0.03). The introduction of RARP at our institution led to a significant reduction in the risk of PSMs in patients with PCa with high-risk disease. Copyright © 2016 Elsevier Inc. All rights reserved.

Impact of marital status in patients undergoing radical cystectomy for bladder cancer.

PubMed

Pruthi, Raj S; Lentz, Aaron C; Sand, Matthew; Kouba, Erik; Wallen, Eric M

2009-08-01

Married (vs. unmarried) individuals have improved health status and longer life expectancies in a variety of benign and malignant disease states, including prostate, breast, head/neck, and lung cancers. We sought to evaluate a cohort of patients undergoing cystectomy for bladder cancer to evaluate the impact of marital status on demographic, peri-operative, and pathological outcomes in order to better understand the factors which may contribute to the survival differences observed. Two-hundred and two patients underwent radical cystectomy and urinary diversion for bladder cancer. Patients were categorized based on marital status as either married or unmarried (widowed, divorced, never married). Correlations were made to demographic factors (age, race, gender, BMI, tobacco use, alcohol use), perioperative factors (pre-op renal function (creatinine), hematocrit, EBL, hospital stay, choice of diversion), and pathological outcomes (organ-confined status, LN positivity). Of the 202 patients, 74% were married. Married individuals (vs. unmarried) were more often male (84 vs. 62%) and had a higher BMI (28.1 vs. 25.9). Married persons had a significantly lower pre-op creatinine (1.1 vs. 1.4) and higher hematocrit (39 vs. 34). Hospital stay was shorter in married patients by a mean of 1.6 days. Regarding operative pathology, married patients had a higher rate of organ-confined disease (59 vs. 47%) (P = 0.05, 0.08 on multivariate) and trended towards a lower rate of LN positivity (15 vs. 21%; P = 0.10, 0.12 multivariate). In patients undergoing cystectomy for bladder cancer, married individuals appear to have improved pre-operative laboratory variables, shorter hospitalization, and improved pathological outcomes versus unmarried patients in our case series. These findings may support the evidence (observed in other tumor types and other disease states) that married persons present earlier than unmarried individuals, and this may help explain the improved survival outcomes that have been observed in married patients with bladder cancer.

Randomized Trial of Studer Pouch versus T-Pouch Orthotopic Ileal Neobladder in Patients with Bladder Cancer.

PubMed

Skinner, Eila C; Fairey, Adrian S; Groshen, Susan; Daneshmand, Siamak; Cai, Jie; Miranda, Gus; Skinner, Donald G

2015-08-01

The need to prevent reflux in the construction of an orthotopic ileal neobladder is controversial. We designed the USC-STAR trial to determine whether the T-pouch neobladder that included an antireflux mechanism was superior to the Studer pouch in patients with bladder cancer undergoing radical cystectomy. This single center, randomized, controlled trial recruited patients with clinically nonmetastatic bladder cancer scheduled to undergo radical cystectomy with neobladder. Eligible patients were randomly assigned to undergo T-pouch or Studer ileal orthotopic neobladder. Treatment assignment was not masked. The primary end point was change in renal function from baseline to 3 years. The CKD-EPI (Chronic Kidney Disease Epidemiology Collaboration) equation was used to calculate the estimated glomerular filtration rate. Between February 2002 and November 2009, 237 patients were randomly assigned to T-pouch ileal orthotopic neobladder and 247 to Studer ileal orthotopic neobladder. Baseline characteristics did not differ between the groups. Between baseline and 3 years the estimated glomerular filtration rate decreased by 6.4 ml/minute/1.73 m(2) in the Studer group and 6.6 ml/minute/1.73 m(2) in the T-pouch group (p=0.35). Multivariable analysis showed that type of ileal orthotopic neobladder was not independently associated with 3-year renal function (p=0.63). However, baseline estimated glomerular filtration rate, age and urinary tract obstruction were independently associated with 3-year decline in renal function. Cumulative risk of urinary tract infection and overall late complications were not different between the groups, but the T-pouch was associated with an increased risk of secondary diversion related surgeries. T-pouch ileal orthotopic neobladder with an antireflux mechanism did not prevent a moderate reduction in renal function observed at 3 years compared to the Studer pouch, but did result in an increase in diversion related secondary surgical procedures. Copyright © 2015 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Characterization of perioperative infection risk among patients undergoing radical cystectomy: Results from the national surgical quality improvement program.

PubMed

Parker, William P; Tollefson, Matthew K; Heins, Courtney N; Hanson, Kristine T; Habermann, Elizabeth B; Zaid, Harras B; Frank, Igor; Thompson, R Houston; Boorjian, Stephen A

2016-12-01

To evaluate the incidence, risk factors, and timing of infections following radical cystectomy (RC). The American College of Surgeons National Surgical Quality Improvement Project database was queried to identify patients undergoing RC for bladder cancer from 2006 to 2013. Characteristics including year of surgery, age, sex body mass index, diabetes, smoking, renal function, steroid usage, preoperative albumin, preoperative hematocrit, perioperative blood transfusion (PBT), and operative time were assessed for association with the risk of infection within 30 days of RC using multivariable logistic regression. A total of 3,187 patients who had undergone RC were identified, of whom 766 (24.0%) were diagnosed with a postoperative infection, at a median of 13 days (interquartile ranges 8-19) after RC. Infections included surgical site infection (SSI) (404; 12.7%), sepsis/septic shock (405; 12.7%), and urinary tract infection (UTI) (309; 9.7%). On multivariable analysis, body mass index≥30kg/m 2 (odds ratios [OR] = 1.52; P<0.01), receipt of a PBT (OR = 1.27; P<0.01), and operative time≥480 minutes (OR = 1.72; P<0.01) were significantly associated with the risk of infection. When the outcomes of UTI, SSI, and sepsis were analyzed separately, operative time≥480 minutes remained independently associated with increased infection risk in each model (OR = 2.11 for UTI, OR = 1.63 for SSI, and OR = 1.80 for sepsis/septic shock; all P<0.05), whereas PBT was associated with SSI and sepsis/septic shock (OR = 1.33 and OR = 1.29, respectively; both P< 0.05). Approximately 25% of patients undergoing RC experience an infection within 30 days of surgery. Several potentially modifiable risk factors for infection were identified, specifically PBT and prolonged operative time, which may represent opportunities for future care improvement. Copyright © 2016 Elsevier Inc. All rights reserved.

The Oxime Portmanteau Motif: Released Heteroradicals Undergo Incisive EPR Interrogation and Deliver Diverse Heterocycles

PubMed Central

2014-01-01

Conspectus Selective syntheses are now available for compounds of many classes, based on C-centered radicals, exploiting a diverse range of mechanisms. The prospect for chemistry based around N- and O-centered radicals is probably more favorable because of the importance of heterocycles as biologically active materials. Heteroradical chemistry is still comparatively underdeveloped due to the need for safe and easy ways of generating them. Oxime esters appeared promising candidates to meet this need because literature reports and our EPR spectroscopic examinations showed they readily dissociated on photolysis with production of a pair of N- and O-centered radicals. It soon became apparent that a whole suite of benign oxime-containing molecules could be pressed into service. The bimodality of the oxime motif meant that by suitable choice of functionality the reactions could be directed to yield selectively products from either the N-centered radicals or from the O-centered radicals. We found that on one hand photolyses of acetophenone oxime esters of carboxylic acids yielded alicyclics. On the other hand, aromatic and heteroaromatic acyl oximes (as well as dioxime oxalates) afforded good yields of phenanthridines and related heterocycles. Easily prepared oxime oxalate amides released carbamoyl radicals, and pleasingly, β-lactams were thereby obtained. Oxime carbonates and oxime carbamates, available via our novel 1,1'-carbonyldiimidazole (CDI)-based preparations, were accessible alternatives for iminyl radicals and hence for phenanthridine preparations. In their second modes, these compounds proved their value as precursors for exotic alkoxycarbonyloxyl and carbamoyloxyl radicals. Microwave-assistance was shown to be a particularly convenient procedure with O-phenyl oxime ethers. The iminyl radicals generated from such precursors with alkene, alkyne, and aromatic acceptor substituents furnished pyrrole, quinoline, phenanthridine, benzonaphthiridine, indolopyridine, and other systems. Microwave irradiations with 2-(aminoaryl)alkanone O-phenyl oximes enabled either dihydroquinazolines or quinazolines to be obtained in very good yields. The fine quality of the EPR spectra, acquired during photolyses of all the O-carbonyl oxime types, marked this as an important complement to existing ways of obtaining such spectra in solution. Quantifications enabled SARs to be obtained for key reaction types of N- and O-centered radicals, thus putting mechanistic chemistry in this area on a much firmer footing. Surprises included the inverse gem-dimethyl effect in 5-exo-cyclizations of iminyls and the interplay of spiro- with ortho-cyclization onto aromatics. Insights into unusual 4-exo-cyclizations of carbamoyl radicals showed the process to be more viable than pent-4-enyl 4-exo-ring closure. Another surprise was the magnitude of the difference in CO2 loss rate from alkoxycarbonyloxyl radicals as compared with acyloxyl radicals. Their rapid 5-exo-cyclization was charted, as was their preferred spiro-cyclization onto aromatics. The first evidence that N-monosubstituted carbamoyloxyls had finite lifetimes was also forthcoming. It is evident that oxime derivatives have excellent credentials as reagents for radical generation and that there is ample room to extend their applications to additional radical types and for further heterocycle syntheses. There is also clear scope for the development of preparative procedures based around the alkoxyl and aminyl radicals that emerge downstream from oxime carbonate and oxime carbamate dissociations. PMID:24654991

Community-based Outcomes of Open versus Robot-assisted Radical Prostatectomy.

PubMed

Herlemann, Annika; Cowan, Janet E; Carroll, Peter R; Cooperberg, Matthew R

2018-02-01

Identifying the optimal surgical approach for patients with localized prostate cancer (PCa) managed in the community setting remains controversial due to the lack of robust, prospective data. To assess surgical outcomes and changes in urinary and sexual quality of life (QOL) over time in patients undergoing radical prostatectomy (RP). Our study included patients enrolled in Cancer of the Prostate Strategic Urologic Research Endeavor (CaPSURE), a large, prospective, mostly community-based, nationwide PCa registry, who underwent RP between 2004 and 2016. Open (ORP) versus robot-assisted radical prostatectomy (RARP) for localized PCa. Demographic and clinicopathologic data and surgical outcomes were compared between ORP and RARP. Self-reported, validated questionnaires (scaled 0-100 with higher numbers indicating better function) were used to evaluate urinary and sexual QOL at different time points. Repeated measures mixed-models assessed changes in function and bother over time in each domain. Among 1892 men (n = 1137 ORP; n = 755 RARP), Cancer of the Prostate Risk Assessment score, Gleason grade at biopsy and RP, and pT-stage were lower in ORP patients (all p < 0.01). Men undergoing RARP had comparable surgical margin rates, lymph node yields, and biochemical recurrence rates. In a subset analysis with 1451 men reporting baseline and follow-up QOL data, ORP patients reported superior scores in urinary incontinence (ORP mean ± standard deviation 69 ± 26 vs RARP 62 ± 27) and bother (ORP 75±29 vs RARP 68±28, both p < 0.01) only in the 1st yr after RP. Differences in sexual outcomes did not differ between groups, nor did any QOL scores beyond 1 yr. Limitations include a decrease in the rate of questionnaire response during follow-up, potential selection biases in terms of patient assignment to ORP versus RARP and survey completion rates, and the fact that RARP cases likely included the initial learning curve for the CaPSURE surgeons. Most patients experienced changes in urinary and sexual QOL in the 1st 3 yr following RP. The pattern of recovery over time was similar between ORP and RARP groups. Patients should not expect different oncologic or QOL outcomes based on surgical approach. Aside from a small, early, and temporary advantage in terms of urinary incontinence and bother favoring open surgery, minimal differences in outcomes are observed when comparing men who undergo open versus robot-assisted prostatectomy in the community setting. Copyright © 2017 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Photo-induced living radical polymerization of acrylates utilizing a discrete copper(II)-formate complex.

PubMed

Anastasaki, Athina; Nikolaou, Vasiliki; Brandford-Adams, Francesca; Nurumbetov, Gabit; Zhang, Qiang; Clarkson, Guy J; Fox, David J; Wilson, Paul; Kempe, Kristian; Haddleton, David M

2015-04-04

A photo-polymerization protocol, utilizing a pre-formed and well-characterized Cu(II) formate complex, [Cu(Me6-Tren)(O2CH)](ClO4), mediated by UV light is described. In the absence of additional reducing agents and/or photosensitizers, ppm concentrations of the oxidatively stable [Cu(Me6-Tren)(O2CH)](ClO4), furnish near-quantitative conversions within 2 h, yielding poly(acrylates) with low dispersities (∼1.10) and exceptional end-group fidelity, capable of undergoing in situ chain extension and block copolymerization.

Enantioselective direct α-amination of aldehydes via a photoredox mechanism: a strategy for asymmetric amine fragment coupling.

PubMed

Cecere, Giuseppe; König, Christian M; Alleva, Jennifer L; MacMillan, David W C

2013-08-07

The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated N-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Importantly, this photoinduced transformation allows direct and enantioselective access to α-amino aldehyde products that do not require postreaction manipulation.

Spindle cell sarcoma of the vulva with myofibroblastic differentiation.

PubMed

Adeleye, Amanda J; Palmeri, Nicholas; Wang, Shih-Hsiu J; Liu-Jarin, Xiaolin; Wright, Jason D

2015-04-01

Primary vulvar sarcomas are rare lesions of the lower genital tract. We report the case of a patient with a spindle cell sarcoma of the vulva. A 44-year-old woman presented with a painless vulvar mass. Vulvar biopsy demonstrated a spindle cell sarcoma with myofibroblastic differentiation. Pretreatment evaluation revealed no evidence of metastatic disease, and magnetic resonance imaging found no local masses. The patient underwent right radical vulvectomy with negative margins and tolerated the procedure well. Women undergoing gynecologic care should have routine evaluation of the vulva to detect these rare neoplasms.

Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

NASA Astrophysics Data System (ADS)

Chang, Hao

A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1}). A much higher energy band was observed in the UV/Vis region, at 520 nm (19,230 cm^{-1}) in acetonitrile for the corresponding bis(hydrazine) radical cation. The width of this band was estimated to be 240 nm (7211 cm^{-1}). The difference in the energies of these absorbance bands, E _{rm op}, reflects the different inner-sphere reorganization energies of the hydrazyl and hydrazine systems. Using Hush analysis, the electron coupling, H_{rm AB} , was calculated to be ca. 3.5 kcal/mol for the bis(hydrazyl) radical cation systems; a smaller value of H_{rm AB} of 1 kcal/mol was obtained for the bis(hydrazine) radical cations. This difference in electronic coupling is consistent with the faster rate of electron transfer, as well as the smaller inner-sphere reorganization energy in the bis(hydrazyl) systems.

The impact of ultra-radical surgery in the management of patients with stage IIIC and IV epithelial ovarian, fallopian tube, and peritoneal cancer.

PubMed

Turnbull, Hilary L; Akrivos, Nikolaos; Wemyss-Holden, Simon; Maiya, Balachandra; Duncan, Timothy J; Nieto, Joaquin J; Burbos, Nikolaos

2017-03-01

The aim of this study is to estimate the percentage of patients with metastatic ovarian, fallopian tube, and primary peritoneal cancer requiring ultra-radical surgery to achieve cytoreduction to less than 1 cm (optimal) or no macroscopic residual disease (complete). Perioperative data were collected prospectively on consecutive patients undergoing elective cytoreductive surgery for metastatic epithelial ovarian, fallopian tube, or primary peritoneal cancer at the Norfolk and Norwich University Hospital, a tertiary referral cancer centre in the United Kingdom from November 2012 to June 2016. Over a 42-month period, 135 consecutive patients underwent cytoreductive surgery for stage IIIC and IV ovarian, fallopian tube, or primary peritoneal cancer. The median age of the patients was 69 years. 47.4% of the patients underwent diaphragmatic peritonectomy and/or resection, 20% underwent splenectomy, 14.1% had excision of disease from porta hepatis and celiac axis, and 5.2% of the patients had gastrectomy. Cytoreduction to no macroscopic visible disease (complete) and to disease with greater tumour diameter of less than 1 cm (optimal) was achieved in 54.1 and 34.1% of the cases, respectively. Without incorporating surgical procedures in the upper abdomen ('ultra-radical'), the combined rate of complete and optimal cytoreduction would be only 33.3%. Up to 50.4% of the patients in this study required at least one surgical procedure classified as ultra-radical, emphasizing the importance of cytoreductive surgery in the upper abdomen in management of women with stage IIIC and IV ovarian, fallopian tube, and primary peritoneal cancer.

The metallic state in neutral radical conductors: dimensionality, pressure and multiple orbital effects.

PubMed

Tian, Di; Winter, Stephen M; Mailman, Aaron; Wong, Joanne W L; Yong, Wenjun; Yamaguchi, Hiroshi; Jia, Yating; Tse, John S; Desgreniers, Serge; Secco, Richard A; Julian, Stephen R; Jin, Changqing; Mito, Masaki; Ohishi, Yasuo; Oakley, Richard T

2015-11-11

Pressure-induced changes in the solid-state structures and transport properties of three oxobenzene-bridged bisdithiazolyl radicals 2 (R = H, F, Ph) over the range 0-15 GPa are described. All three materials experience compression of their π-stacked architecture, be it (i) 1D ABABAB π-stack (R = Ph), (ii) quasi-1D slipped π-stack (R = H), or (iii) 2D brick-wall π-stack (R = F). While R = H undergoes two structural phase transitions, neither of R = F, Ph display any phase change. All three radicals order as spin-canted antiferromagnets, but spin-canted ordering is lost at pressures <1.5 GPa. At room temperature, their electrical conductivity increases rapidly with pressure, and the thermal activation energy for conduction Eact is eliminated at pressures ranging from ∼3 GPa for R = F to ∼12 GPa for R = Ph, heralding formation of a highly correlated (or bad) metallic state. For R = F, H the pressure-induced Mott insulator to metal conversion has been tracked by measurements of optical conductivity at ambient temperature and electrical resistivity at low temperature. For R = F compression to 6.2 GPa leads to a quasiquadratic temperature dependence of the resistivity over the range 5-300 K, consistent with formation of a 2D Fermi liquid state. DFT band structure calculations suggest that the ease of metallization of these radicals can be ascribed to their multiorbital character. Mixing and overlap of SOMO- and LUMO-based bands affords an increased kinetic energy stabilization of the metallic state relative to a single SOMO-based band system.

Length of positive surgical margin after radical prostatectomy as a predictor of biochemical recurrence.

PubMed

Shikanov, Sergey; Song, Jie; Royce, Cassandra; Al-Ahmadie, Hikmat; Zorn, Kevin; Steinberg, Gary; Zagaja, Gregory; Shalhav, Arieh; Eggener, Scott

2009-07-01

Length and location of positive surgical margins are independent predictors of biochemical recurrence after open radical prostatectomy. We assessed their impact on biochemical recurrence in a large robotic prostatectomy series. Data were collected prospectively from 1,398 men undergoing robotic radical prostatectomy for clinically localized prostate cancer from 2003 to 2008 at a single institution. The associations of preoperative prostate specific antigen, pathological Gleason score, pathological stage and positive surgical margin parameters (location, length and focality) with biochemical recurrence rate were evaluated. Margin status and length were measured by a single uropathologist. Biochemical recurrence was defined as serum prostate specific antigen greater than 0.1 ng/ml on 2 consecutive tests. Cox regression models were constructed to evaluate predictors of biochemical recurrence. Of 1,398 consecutive patients who underwent robotic prostatectomy positive margins were present in 243 (17%) (11% of pathological T2 and 41% of T3). Preoperative prostate specific antigen, pathological stage, Gleason score, margin status, and margin length as a continuous and categorical variable (less than 1, 1 to 3, more than 3 mm) were independent predictors of biochemical recurrence. Patients with negative margins and those with a positive margin less than 1 mm had similar rates of biochemical recurrence (log rank test p = 0.18). Surgical margin location was not independently associated with biochemical recurrence. Margin status and length are independent predictors of biochemical recurrence following robotic radical prostatectomy. Although longer followup and validation studies are necessary for confirmation, patients with a positive margin less than 1 mm appear to have similar recurrence rates as those with negative margins.

Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical.

PubMed

Shah, Shaheen; Hao, Ce

2017-07-01

Sulfamethoxypyridazine (SMP) is one of the commonly used sulfonamide antibiotics (SAs). SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants. In this work, SMP was selected as a representative of SAs. We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter, i.e., anions (Br - , Cl - , and NO 3 - ) and cations ions (Ca 2+ , Mg 2+ , and Zn 2+ ) on SMP photodegradation mechanism by quantum chemical methods. In addition, the degradation mechanisms of SMP by hydroxyl radical (OH) were also investigated. The creation of SO 2 extrusion product was accessed with two different energy pathways (pathway-1 and pathway-2) by following two steps (step-I and step-II) in the triplet-sensitized photodegradation of SMP. Due to low activation energy, the pathway-1 was considered as the main pathway to obtain SO 2 extrusion product. Step-II of pathway-1 was measured to be the rate-limiting step (RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step. All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1. The estimated low activation energies of different degradation pathways of SMP with OH radical indicate that OH radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring. Copyright © 2016. Published by Elsevier B.V.

Diffusion of surgical innovation among patients with kidney cancer

PubMed Central

Miller, David C.; Saigal, Christopher S.; Banerjee, Mousumi; Hanley, Jan; Litwin, Mark S.

2009-01-01

Background Despite their potential benefits to patients with kidney cancer, the adoption of partial nephrectomy and laparoscopy has been gradual and asymmetric. To clarify whether this trend reflects differences in kidney cancer patients or differences in surgeon practice styles, we compared the magnitude of surgeon-attributable variance in the use of partial nephrectomy and laparoscopic radical nephrectomy with that attributable to patient and tumor characteristics. Methods Using linked Surveillance, Epidemiology, and End Results-Medicare data, we identified a cohort of 5,483 Medicare beneficiaries treated surgically for kidney cancer between 1997 and 2002. We defined two primary outcomes: (1) use of partial nephrectomy, and (2) use of laparoscopy among patients undergoing radical nephrectomy. Using multilevel models, we estimated surgeon- and patient-level contributions to observed variations in the use of partial nephrectomy and laparoscopic radical nephrectomy. Results Of the 5,483 cases identified, 611(11.1%) underwent partial nephrectomy (43 performed laparoscopically), and 4,872 (88.9%) underwent radical nephrectomy (515 performed laparoscopically). After adjusting for patient demographics, comorbidity, tumor size and surgeon volume, the surgeon-attributable variance was 18.1% for partial nephrectomy and 37.4% for laparoscopy. For both outcomes, the percentage of total variance attributable to surgeon factors was consistently higher than that attributable to patient characteristics. Conclusions For many patients with kidney cancer, the surgery provided depends more on their surgeon’s practice style than on the characteristics of the patient and his or her disease. Consequently, dismantling barriers to surgeon adoption of partial nephrectomy and laparoscopy is an important step toward improving the quality of care for patients with early-stage kidney cancer. PMID:18330868

Magnetic field effect in fluorescence of excited fluorophore equilibrated with exciplex that reversibly dissociates into radical-ion pair undergoing the spin conversion.

PubMed

Dodin, Dmitry V; Ivanov, Anatoly I; Burshtein, Anatoly I

2012-07-14

The fluorescence of the photoexcited electron acceptor, (1)A∗, and the exciplex, (1)[D(+δ)A(-δ)] formed at contact of (1)A∗ with an electron donor (1)D, is known to be very sensitive to a magnetic field, assisting the spin conversion in the resulting geminate radical ion pair (RIP), (1, 3)[D(+)...A(-)]. The relative increase of the fluorescence in the highest magnetic field compared to the lowest one, known as the magnetic field effect, crucially depends on the dielectric constant of the solvent, ɛ. This phenomenon first studied experimentally is at first reproduced here theoretically by means of the so called integral encounter theory. It was shown to be very sensitive to the position of the exciplex energy level relative to the levels of exciplex precursors and the charged products of its dissociation. The results obtained strongly depend on the dielectric properties of the solvents as well as on the exciplex and RIP formation rates.

Robot-assisted radical prostatectomy: advances since 2005.

PubMed

Su, Li-Ming

2010-03-01

To provide an update of recent studies relevant to robot-assisted radical prostatectomy, highlighting technical modifications and associated functional outcomes, mid-term oncologic results and patient perception and satisfaction. Several recent studies have investigated methods of further reducing the morbidities associated with prostatectomy, namely erectile dysfunction and incontinence. These studies provide important anatomic insights into additional mechanisms responsible for potency and incontinence and measures for preserving both. Mid-term oncologic outcomes have also been reported; further substantiating the role of robotics in the treatment of clinically localized prostate cancer. The technique of robotic prostatectomy has evolved over the last decade with significant efforts in improving functional outcomes following surgery. However, aggressive-marketing campaigns and lack of regulation of hospital websites may be contributing to unrealistic expectations in patients who choose to undergo robotic prostatectomy, resulting in dissatisfaction for some patients. National interests in this topic will likely result in the mandate for more stringent studies to assess the comparative effectiveness of robot-assisted prostatectomy with other competing therapies for clinically localized prostate cancer.

Chemotherapy and novel therapeutics before radical prostatectomy for high-risk clinically localized prostate cancer.

PubMed

Cha, Eugene K; Eastham, James A

2015-05-01

Although both surgery and radiation are potential curative options for men with clinically localized prostate cancer, a significant proportion of men with high-risk and locally advanced disease will demonstrate biochemical and potentially clinical progression of their disease. Neoadjuvant systemic therapy before radical prostatectomy (RP) is a logical strategy to improve treatment outcomes for men with clinically localized high-risk prostate cancer. Furthermore, delivery of chemotherapy and other systemic agents before RP affords an opportunity to explore the efficacy of these agents with pathologic end points. Neoadjuvant chemotherapy, primarily with docetaxel (with or without androgen deprivation therapy), has demonstrated feasibility and safety in men undergoing RP, but no study to date has established the efficacy of neoadjuvant chemotherapy or neoadjuvant chemohormonal therapies. Other novel agents, such as those targeting the vascular endothelial growth factor receptor, epidermal growth factor receptor, platelet-derived growth factor receptor, clusterin, and immunomodulatory therapeutics, are currently under investigation. Copyright © 2015 Elsevier Inc. All rights reserved.

Iron-Catalyzed Enantioselective Cross-Coupling Reactions of α-Chloroesters with Aryl Grignard Reagents.

PubMed

Jin, Masayoshi; Adak, Laksmikanta; Nakamura, Masaharu

2015-06-10

The first iron-catalyzed enantioselective cross-coupling reaction between an organometallic compound and an organic electrophile is reported. Synthetically versatile racemic α-chloro- and α-bromoalkanoates were coupled with aryl Grignard reagents in the presence of catalytic amounts of an iron salt and a chiral bisphosphine ligand, giving the products in high yields with acceptable and synthetically useful enantioselectivities (er up to 91:9). The produced α-arylalkanoates were readily converted to the corresponding α-arylalkanoic acids with high optical enrichment (er up to >99:1) via simple deprotections/recrystallizations. The results of radical probe experiments are consistent with a mechanism that involves the formation of an alkyl radical intermediate, which undergoes subsequent enantioconvergent arylation in an intermolecular manner. The developed asymmetric coupling offers not only facile and practical access to various chiral α-arylalkanoic acid derivatives, which are of significant pharmaceutical importance, but also a basis of controlling enantioselectivity in an iron-catalyzed organometallic transformation.

A Comparison of Radical Perineal, Radical Retropubic, and Robot-Assisted Laparoscopic Prostatectomies in a Single Surgeon Series

PubMed Central

Mirza, Moben; Art, Kevin; Wineland, Logan; Tawfik, Ossama; Thrasher, J. Brantley

2011-01-01

Objective. We sought to compare positive surgical margin rates (PSM), estimated blood loss (EBL), and quality of life outcomes (QOL) among perineal (RPP), retropubic (RRP), and robot-assisted laparoscopic (RALP) prostatectomies. Methods. Records from 463 consecutive men undergoing RPP (92), RRP (180), or RALP (191) for clinically localized prostate cancer were retrospectively reviewed. Age, percent tumor volume, Gleason score, stage, EBL, PSM, and QOL using the expanded prostate cancer index composite (EPIC) were compared. Results. PSM were similar when adjusted for stage, grade, and volume. EBL was significantly less in the RALP (189 ml) group compared to both RPP (475 ml) and RRP (999 ml) groups. When corrected for nerve sparing, there were no differences in erectile function and sexual function amongst the three groups. Urinary summary and pad usage scores showed no significant differences. Conclusion. RPP, RRP, and RALP offer similar surgical and QOL outcomes. RALP and RPP demonstrate less EBL compared to RRP. PMID:22111001

[Clinical experience on the use of total parenteral nutrition in patients subjected to radical cystectomy intervention for infiltrating neoplasms of the bladder].

PubMed

Del Boca, C; Furiosi, D; Bolis, C; Ferrari, C

1989-03-01

The Authors report their 7 year follow-up on the use of T.P.N. in 28 patients treated surgically for infiltrating cancer of the bladder. They consider the pathogenetic mechanisms that influence the organism's adaptation to surgical stress with particular reference to the multiple neuroendocrinal and biochemical interconnections. The procedures to define the nutritional/metabolic levels, of the patients undergoing operation are exposed. The T.P.N. is given according to the personal requirements of each patient and is a function of the "performance status", caloric need and to the presence of sepsis. Problems concerning the radical cistectomy such as: time of surgery, extention of exeresis, uroentheroanastomosis, metabolic variations, sepsis, etc., are evaluated. Considering the positive results obtained with this nutritional procedure, the Authors underline the importance of a systematic use of T.P.N. wich should be included, in their opinion, in a multidisciplinar treatment of advanced bladder neoplasms.

Straightforward Method for Coverage of Major Vessels After Modified Radical Neck Dissection.

PubMed

González-García, Raúl; Moreno-García, Carlos; Moreno-Sánchez, Manuel; Román-Romero, Leticia

2017-06-01

A new method for covering the internal jugular vein and carotid artery after exposure of the cervical vascular axis subsequent to neck dissection is presented. To cover the most caudal part of the vascular axis, a platysma coli muscle flap is harvested from its most medial and inferior part of the neck in a caudally based fashion and is slightly rotated posteriorly up to 45°. In addition, a superiorly based sternocleidomastoid muscle flap involving the posterior half of the muscle after detachment of the clavicle head is harvested and rotated 45° anteriorly to cover the upper two thirds of the vascular axis. This technique seems to be a good alternative to the pectoralis major myocutaneous flap for covering cervical major vessels, if no classical radical neck dissection is performed, especially in those oncologic malnourished patients who will undergo adjuvant radiotherapy after surgical treatment. Copyright © 2016 American Association of Oral and Maxillofacial Surgeons. Published by Elsevier Inc. All rights reserved.

Current status of adjuvant chemotherapy after radical cystectomy for deeply invasive bladder cancer.

PubMed

Skinner, D G; Daniels, J R; Lieskovsky, G

1984-07-01

Between March, 1976, and December, 1982, 70 of 157 patients (45%) undergoing single-stage radical cystectomy with pelvic lymphadenectomy and urinary diversion with the intent to cure invasive bladder cancer were found to have pathologic Stage P3B, P4 and/or N + disease. Thirty-four of the 70 patients received adjuvant prophylactic chemotherapy after cystectomy and 36 patients were followed expectantly. From 1976 through 1977 adjuvant chemotherapy consisted of cyclophosphamide 1 Gm/M2 each month for six months; from 1978 through June, 1980, adjuvant chemotherapy consisted of cis-platinum 100 mg/M2 each month for four months with the exception of 1 patient treated more aggressively with combination chemotherapy (CISCA). Since July, 1980, a prospective study has been utilized in which patients were randomized into two groups, Group A receiving combination chemotherapy and Group B followed up expectantly; adjuvant chemotherapy appears to result in a slight delay in time to relapse but no influence in overall survival was observed.

Synthesis of Degradable Poly(vinyl alcohol) by Radical Ring-Opening Copolymerization and Ice Recrystallization Inhibition Activity.

PubMed

Hedir, Guillaume; Stubbs, Christopher; Aston, Phillip; Dove, Andrew P; Gibson, Matthew I

2017-12-19

Poly(vinyl alcohol) (PVA) is the most active synthetic mimic of antifreeze proteins and has extremely high ice recrystallization inhibition (IRI) activity. Addition of PVA to cellular cryopreservation solutions increases the number of recovered viable cells due to its potent IRI, but it is intrinsically nondegradable in vivo . Here we report the synthesis, characterization, and IRI activity of PVA containing degradable ester linkages. Vinyl chloroacetate (VClAc) was copolymerized with 2-methylene-1,3-dioxepane (MDO) which undergoes radical ring-opening polymerization to install main-chain ester units. The use of the chloroacetate monomer enabled selective deacetylation with retention of esters within the polymer backbone. Quantitative IRI assays revealed that the MDO content had to be finely tuned to retain IRI activity, with higher loadings (24 mol %) resulting in complete loss of IRI activity. These degradable materials will help translate PVA, which is nontoxic and biocompatible, into a range of biomedical applications.

Utility of an Australasian registry for children undergoing radiation treatment.

PubMed

Ahern, Verity

2014-12-01

The aim of this study was to evaluate the utility of an Australasian registry ('the Registry') for children undergoing radiation treatment (RT). Children under the age of 16 years who received a course of radiation between January 1997 and December 2010 and were enrolled on the Registry form the subjects of this study. A total of 2232 courses of RT were delivered, predominantly with radical intent (87%). Registrations fluctuated over time, but around one-half of children diagnosed with cancer undergo a course of RT. The most prevalent age range at time of RT was 10-15 years, and the most common diagnoses were central nervous system tumours (34%) and acute lymphoblastic leukaemia (20%). The Registry provides a reflection of the patterns of care of children undergoing RT in Australia and a mechanism for determining the resources necessary to manage children by RT (human, facilities and emerging technologies, such as proton therapy). It lacks the detail to provide information on radiotherapy quality and disease outcomes which should be the subject of separate audit studies. The utility of the Registry has been hampered by its voluntary nature and varying needs for consent. Completion of registry forms is a logical requirement for inclusion in the definition of a subspecialist in paediatric radiation oncology. © 2014 The Royal Australian and New Zealand College of Radiologists.

Surgical treatment for women with breast cancer: do randomized clinical trials represent current medical practices?

PubMed

Frederick, Wayne A I; Ames, Sarah; Downing, Stephanie R; Oyetunji, Tolulope A; Chang, David C; Leffall, Lasalle D

2010-06-01

Randomized clinical trials have not shown survival differences between breast cancer patients who undergo breast-conserving surgery and those who undergo modified radical mastectomy (MRM). Recent studies however, have suggested that these randomized clinical trials findings may not be representative of the entire population or the nature of current patient care. A retrospective analysis of female invasive breast cancer patients who underwent surgery in the Surveillance, Epidemiology, and End Results database (1990-2003) was performed. Survival was compared amongst women who underwent partial mastectomy, partial mastectomy plus radiation (PMR), or MRM. Cox proportional hazards regressions were used to investigate the impact of method of treatment upon survival, after adjusting for patient and tumor characteristics. A total of 218,043 patients, mean age 62 years, were identified. MRM accounted for 51.5 per cent of the study population whereas PMR accounted for 34.9 per cent. On multivariate analyses, significant improvement was observed in patient survival associated with PMR when compared with MRM patients (hazard ratio = 0.71, 95% confidence interval = 0.67-0.74, P < 0.001). This population-based study suggests that there is a survival benefit for women undergoing PMR in the treatment of breast cancer.

Myocardial infarction and subsequent death in a patient undergoing robotic prostatectomy.

PubMed

Thompson, Judy

2009-10-01

A 52-year-old patient, ASA physical status IV, undergoing a radical prostatectomy for cancer with a robotic system had a cardiac arrest 3 hours into the case. All attempts to resuscitate were unsuccessful, and several hours later he was pronounced dead. Underlying patient comorbidity and procedural issues contributed to the patient's death. The patient had a history of coronary artery disease that required the placement of drug-eluting stents 2 years before this surgical procedure. The preoperative cardiac evaluation and pharmacological management of patients with drug-eluting coronary stents are reviewed. There are a number of positional and technical considerations for patients undergoing robotic surgical procedures, especially in relation to the requirement of low-lithotomy and steep Trendelenburg positions. The cardiac and respiratory systems are especially vulnerable to the extreme and lengthy head-down position. The needed positioning, combined with the problems associated with insufflation, presents a unique challenge in anesthetic management. This course reviews the current literature on the surgical implications for patients with drug-eluting stents and the physiologic factors related to position and pneumoperitoneum and their associated stressors. By using a review of the contemporary literature, a best-evidence approach to anesthetic management is reviewed.

Robotic-assisted laparoscopic prostatectomy in umbilical hernia patients: University of California, Irvine, technique for port placement and repair.

PubMed

Kim, William; Abdelshehid, Corollos; Lee, Hak J; Ahlering, Thomas

2012-06-01

To discuss a technique currently used at our institution for the management of umbilical hernias during robot-assisted laparoscopic prostatectomy. As more patients undergo robot-assisted radical prostatectomy, there will be an increase in patients who qualify for robotic surgery with comorbidities. This technique has been utilized in clinically localized prostate cancer patients with umbilical hernias using the da Vinci Surgical System and standard laparoscopic instrumentation. Port placements and closures were performed by a resident assistant and a nurse at the operating table. The prostatectomy was performed by a single experienced surgeon at the console. Currently, no data are available regarding patients with umbilical hernias undergoing robotic prostatectomy. We reviewed our technique of port placement for patients with a pre-existing umbilical hernia undergoing robot-assisted laparoscopic prostatectomy. This technique allows for a reduction of the umbilical hernia, the use of the fascial defect as a robotic port, and the removal of the prostate by way of transverse incision and transverse repair. In our experience, this technique is feasible and reproducible for any small or large umbilical hernia. Copyright © 2012 Elsevier Inc. All rights reserved.

Theoretical description of spin-selective reactions of radical pairs diffusing in spherical 2D and 3D microreactors

NASA Astrophysics Data System (ADS)

Ivanov, Konstantin L.; Sadovsky, Vladimir M.; Lukzen, Nikita N.

2015-08-01

In this work, we treat spin-selective recombination of a geminate radical pair (RP) in a spherical "microreactor," i.e., of a RP confined in a micelle, vesicle, or liposome. We consider the microreactor model proposed earlier, in which one of the radicals is located at the center of the micelle and the other one undergoes three-dimensional diffusion inside the micelle. In addition, we suggest a two-dimensional model, in which one of the radicals is located at the "pole" of the sphere, while the other one diffuses on the spherical surface. For this model, we have obtained a general analytical expression for the RP recombination yield in terms of the free Green function of two-dimensional diffusion motion. In turn, this Green function is expressed via the Legendre functions and thus takes account of diffusion over a restricted spherical surface and its curvature. The obtained expression allows one to calculate the RP recombination efficiency at an arbitrary magnetic field strength. We performed a comparison of the two models taking the same geometric parameters (i.e., the microreactor radius and the closest approach distance of the radicals), chemical reactivity, magnetic interactions in the RP and diffusion coefficient. Significant difference between the predictions of the two models is found, which is thus originating solely from the dimensionality effect: for different dimensionality of space, the statistics of diffusional contacts of radicals becomes different altering the reaction yield. We have calculated the magnetic field dependence of the RP reaction yield and chemically induced dynamic nuclear polarization of the reaction products at different sizes of the microreactor, exchange interaction, and spin relaxation rates. Interestingly, due to the intricate interplay of diffusional contacts of reactants and spin dynamics, the dependence of the reaction yield on the microreactor radius is non-monotonous. Our results are of importance for (i) interpreting experimental data for magnetic field effects on RP recombination in confined space and (ii) for describing kinetics of chemical reactions, which occur predominantly on the surfaces of biomembranes, i.e., lipid peroxidation reactions.

Hydropersulfides: H-Atom Transfer Agents Par Excellence.

PubMed

Chauvin, Jean-Philippe R; Griesser, Markus; Pratt, Derek A

2017-05-10

Hydropersulfides (RSSH) are formed endogenously via the reaction of the gaseous biotransmitter hydrogen sulfide (H 2 S) and disulfides (RSSR) and/or sulfenic acids (RSOH). RSSH have been investigated for their ability to store H 2 S in vivo and as a line of defense against oxidative stress, from which it is clear that RSSH are much more reactive to two-electron oxidants than thiols. Herein we describe the results of our investigations into the H-atom transfer chemistry of RSSH, contrasting it with the well-known H-atom transfer chemistry of thiols. In fact, RSSH are excellent H-atom donors to alkyl (k ∼ 5 × 10 8 M -1 s -1 ), alkoxyl (k ∼ 1 × 10 9 M -1 s -1 ), peroxyl (k ∼ 2 × 10 6 M -1 s -1 ), and thiyl (k > 1 × 10 10 M -1 s -1 ) radicals, besting thiols by as little as 1 order and as much as 4 orders of magnitude. The inherently high reactivity of RSSH to H-atom transfer is based largely on thermodynamic factors; the weak RSS-H bond dissociation enthalpy (∼70 kcal/mol) and the associated high stability of the perthiyl radical make the foregoing reactions exothermic by 15-34 kcal/mol. Of particular relevance in the context of oxidative stress is the reactivity of RSSH to peroxyl radicals, where favorable thermodynamics are bolstered by a secondary orbital interaction in the transition state of the formal H-atom transfer that drives the inherent reactivity of RSSH to match that of α-tocopherol (α-TOH), nature's premier radical-trapping antioxidant. Significantly, the reactivity of RSSH eclipses that of α-TOH in H-bond-accepting media because of their low H-bond acidity (α 2 H ∼ 0.1). This affords RSSH a unique versatility compared to other highly reactive radical-trapping antioxidants (e.g., phenols, diarylamines, hydroxylamines, sulfenic acids), which tend to have high H-bond acidities. Moreover, the perthiyl radicals that result are highly persistent under autoxidation conditions and undergo very rapid dimerization (k = 5 × 10 9 M -1 s -1 ) in lieu of reacting with O 2 or autoxidizable substrates.

Theoretical description of spin-selective reactions of radical pairs diffusing in spherical 2D and 3D microreactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanov, Konstantin L., E-mail: ivanov@tomo.nsc.ru; Lukzen, Nikita N.; Novosibirsk State University, Pirogova St. 2, Novosibirsk 630090

2015-08-28

In this work, we treat spin-selective recombination of a geminate radical pair (RP) in a spherical “microreactor,” i.e., of a RP confined in a micelle, vesicle, or liposome. We consider the microreactor model proposed earlier, in which one of the radicals is located at the center of the micelle and the other one undergoes three-dimensional diffusion inside the micelle. In addition, we suggest a two-dimensional model, in which one of the radicals is located at the “pole” of the sphere, while the other one diffuses on the spherical surface. For this model, we have obtained a general analytical expression formore » the RP recombination yield in terms of the free Green function of two-dimensional diffusion motion. In turn, this Green function is expressed via the Legendre functions and thus takes account of diffusion over a restricted spherical surface and its curvature. The obtained expression allows one to calculate the RP recombination efficiency at an arbitrary magnetic field strength. We performed a comparison of the two models taking the same geometric parameters (i.e., the microreactor radius and the closest approach distance of the radicals), chemical reactivity, magnetic interactions in the RP and diffusion coefficient. Significant difference between the predictions of the two models is found, which is thus originating solely from the dimensionality effect: for different dimensionality of space, the statistics of diffusional contacts of radicals becomes different altering the reaction yield. We have calculated the magnetic field dependence of the RP reaction yield and chemically induced dynamic nuclear polarization of the reaction products at different sizes of the microreactor, exchange interaction, and spin relaxation rates. Interestingly, due to the intricate interplay of diffusional contacts of reactants and spin dynamics, the dependence of the reaction yield on the microreactor radius is non-monotonous. Our results are of importance for (i) interpreting experimental data for magnetic field effects on RP recombination in confined space and (ii) for describing kinetics of chemical reactions, which occur predominantly on the surfaces of biomembranes, i.e., lipid peroxidation reactions.« less

Aortic calcification burden predicts deterioration of renal function after radical nephrectomy.

PubMed

Fukushi, Ken; Hatakeyama, Shingo; Yamamoto, Hayato; Tobisawa, Yuki; Yoneyama, Tohru; Soma, Osamu; Matsumoto, Teppei; Hamano, Itsuto; Narita, Takuma; Imai, Atsushi; Yoneyama, Takahiro; Hashimoto, Yasuhiro; Koie, Takuya; Terayama, Yuriko; Funyu, Tomihisa; Ohyama, Chikara

2017-02-06

Radical nephrectomy for renal cell carcinoma (RCC) is a risk factor for the development of chronic kidney disease (CKD), and the possibility of postoperative deterioration of renal function must be considered before surgery. We investigated the contribution of the aortic calcification index (ACI) to the prediction of deterioration of renal function in patients undergoing radical nephrectomy. Between January 1995 and December 2012, we performed 511 consecutive radical nephrectomies for patients with RCC. We retrospectively studied data from 109 patients who had regular postoperative follow-up of renal function for at least five years. The patients were divided into non-CKD and pre-CKD based on a preoperative estimated glomerular filtration rate (eGFR) of ≥60 mL/min/1.73 m 2 or <60 mL/min/1.73 m 2 , respectively. The ACI was quantitatively measured by abdominal computed tomography before surgery. The patients in each group were stratified between low and high ACIs. Variables such as age, sex, comorbidities, and pre- and postoperative renal function were compared between patients with a low or high ACI in each group. Renal function deterioration-free interval rates were evaluated by Kaplan-Meier analysis. Factors independently associated with deterioration of renal function were determined using multivariate analysis. The median age, preoperative eGFR, and ACI in this cohort were 65 years, 68 mL/min/1.73 m 2 , and 8.3%, respectively. Higher ACI (≥8.3%) was significantly associated with eGFR decline in both non-CKD and pre-CKD groups. Renal function deterioration-free interval rates were significantly lower in the ACI-high than ACI-low strata in both of the non-CKD and pre-CKD groups. Multivariate analysis showed that higher ACI was an independent risk factor for deterioration of renal function at 5 years after radical nephrectomy. Aortic calcification burden is a potential predictor of deterioration of renal function after radical nephrectomy. This study was registered as a clinical trial: UMIN000023577.

[Impact of Gleason score on biochemical recurrence free survival after radical prostatectomy with positive surgical margins].

PubMed

Roux, V; Eyraud, R; Brureau, L; Gourtaud, G; Senechal, C; Fofana, M; Blanchet, P

Research of predictive factors of biochemical recurrence to guide the establishment of an adjuvant treatment after radical prostatectomy for cancer with positive surgical margins. A retrospective cohort of 1577 afro-caribbean patients undergoing radical prostatectomy operated between 1st January 2000 and 1st July 2013 was analyzed. In this cohort, 406 patients had positive surgical margin, we excluded 11 patients who received adjuvant therapy (radiotherapy, hormonotherapy, radio-hormonotherapy) and 2 patients for whom histological analysis of the surgical specimen was for a pT4 pathological stage. After a descriptive analysis, we used a Cox model to look for predictors of survival without biochemical recurrence then, depending on the significant variables, we separated our population into six groups: stage pT2 with Gleason score≤3+4 (group 1), stage pT2 with a score of Gleason≥4+3 (group 2), stage pT3a with a Gleason core≤3+4 (group 3), pT3a stage with a score of Gleason≥4+3 (group 4), stage pT3b with a Gleason score≤3+4 (group 5) and stage pT3b Gleason≥with a score of 4+3 (group 6) and compared survival without biochemical recurrence using a log rank test. After radical prostatectomy with surgical margins with an anatomopathological stage≤pT3b, a Gleason score≥4+3 had a pejorative survival without biochemical recurrence than pathological stage (P<0.001). In multivariate analysis, predictors of survival without biochemical recurrence after radical prostatectomy with positive surgical margins were the majority Gleason postoperative (P<0.0001), pathological stage (P=0.049) adjusted preoperative PSA (P=0.826), with the body mass index (BMI) (P=0.59) and tumor volume (P=0.95). A high postoperatively Gleason score (≥4+3) has a better predictive value of biochemical recurrence than pathological stage pT2 or pT3 at the patients having been treated for prostate cancer by radical prostatectomy with positive surgical margins. 4. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Physical activity and quality of life after radical prostatectomy

PubMed Central

Mina, Daniel Santa; Matthew, Andrew G.; Trachtenberg, John; Tomlinson, George; Guglietti, Crissa L.; Alibhai, Shabbir M.H.; Ritvo, Paul

2010-01-01

Background: There are significant post-surgical reductions in health-related quality of life (HRQOL) in prostate cancer (PCa) patients undergoing radical prostatectomy (RP). Physical activity (PA) interventions have improved treatment outcomes for PCa patients undergoing radiation and hormone therapy, but PA effects have not previously been examined in the RP setting. This study examined the relationship between preoperative PA levels and postoperative HRQOL outcomes in PCa patients treated with RP. Methods: Sixty patients were interviewed regarding lifetime PA and completed preoperative (2 weeks prior to surgery) and postoperative (4 weeks after surgery) HRQOL questionnaires. Aerobic fitness testing was conducted on a subsample of 22 patients. Results: Higher levels of total past-year PA and occupational PA significantly correlated with lesser HRQOL declines from presurgery to 4 weeks post-surgery (Beta = −0.364, p = 0.037 and Beta = −0.243, p = 0.089, respectively) in models adjusted for age, postoperative questionnaire completion date, Gleason score and education. Past-year occupational PA was highly positively correlated with past-year total PA (r = 0.785, p < 0.001). Lifetime total PA was correlated with estimated VO2 max (r = 0.486, p = 0.026) in the 22 patients who were aerobically tested. Lifetime and past-year PA volumes were not correlated with waist circumference or body mass index. Interpretation: Declines in HRQOL after RP may be reduced in patients with higher preoperative levels of self-reported PA. These findings require further study with larger samples to confirm results. If confirmed, findings suggest exercise preoperatively may improve HRQOL outcomes after RP. PMID:20514281

Carcinoma of the ampulla of Vater: patterns of failure following resection and benefit of chemoradiotherapy.

PubMed

Palta, Manisha; Patel, Pretesh; Broadwater, Gloria; Willett, Christopher; Pepek, Joseph; Tyler, Douglas; Zafar, S Yousuf; Uronis, Hope; Hurwitz, Herbert; White, Rebekah; Czito, Brian

2012-05-01

Ampullary carcinoma is a rare malignancy. Despite radical resection, survival rates remain low with high rates of local failure. We performed a single-institution outcomes analysis to define the role of concurrent chemoradiotherapy (CRT) in addition to surgery. A retrospective analysis was performed of all patients undergoing potentially curative pancreaticoduodenectomy for adenocarcinoma of the ampulla of Vater at Duke University Hospitals between 1976 and 2009. Time-to-event analysis was performed comparing all patients who underwent surgery alone to the cohort of patients receiving CRT in addition to surgery. Local control (LC), disease-free survival (DFS), overall survival (OS), and metastases-free survival (MFS) were estimated using the Kaplan-Meier method. A total of 137 patients with ampullary carcinoma underwent Whipple procedure. Of these, 61 patients undergoing resection received adjuvant (n = 43) or neoadjuvant (n = 18) CRT. Patients receiving chemoradiotherapy were more likely to have poorly differentiated tumors (P = .03). Of 18 patients receiving neoadjuvant therapy, 67% were downstaged on final pathology with 28% achieving pathologic complete response (pCR). With a median follow-up of 8.8 years, 3-year local control was improved in patients receiving CRT (88% vs 55%, P = .001) with trend toward 3-year DFS (66% vs 48%, P = .09) and OS (62% vs 46%, P = .074) benefit in patients receiving CRT. Long-term survival rates are low and local failure rates high following radical resection alone. Given patterns of relapse with surgery alone and local control benefit in patients receiving CRT, the use of chemoradiotherapy in selected patients should be considered.

Pathologic implications of prostatic anterior fat pad.

PubMed

Jeong, Jeongyun; Choi, Eun Yong; Kang, Dong I; Ercolani, Matt; Lee, Dong Hyeon; Kim, Wun-Jae; Kim, Isaac Yi

2013-01-01

Lymph node status has significant pathologic implications in patients with prostate cancer. In this study, we have performed pathologic analysis of prostatic anterior fat pad (PAFP) excised during robot-assisted radical prostatectomy (RARP) to investigate the potential role of AFP on pathologic staging of prostate cancer. A total of 258 consecutive patients underwent PAFP excision during RARP between July 2007 and June 2009. PAFP was removed and submitted en bloc to the pathology department and evaluated for the presence of lymphoid tissue and metastatic prostate cancer. Retrospective chart review was performed for all patients. Of the 258 patients, 30 (11.6%) had 1 or 2 PAFP lymph nodes and 228 (88.4%) men showed no lymphoid tissue in their PAFPs. Preoperatively, mean PSA level was higher in the former group. There were no significant pathologic differences between the 2 groups. Among the 30 patients with PAFP lymph nodes, 3 were positive for metastatic prostate cancer. All 3 of these patients had high-risk features preoperatively. In 1 patient, the pelvic lymph nodes were negative for metastatic prostate cancer. At 2-year follow-up, PSA level of this patient was undetectable. Herein, we demonstrated that the PAFP contained lymph nodes in over 11% of the patients undergoing RARP at our institution. Prostate cancer was upstaged in 1 patient as a result of PAFP excision. Since this patient is free of biochemical recurrence at 2 years, routine excision and pathologic analysis of PAFP should be considered in prostate cancer patients undergoing radical prostatectomy. Copyright © 2013 Elsevier Inc. All rights reserved.

Significance of preoperatively observed detrusor overactivity as a predictor of continence status early after robot-assisted radical prostatectomy

PubMed Central

Yanagiuchi, Akihiro; Miyake, Hideaki; Tanaka, Kazushi; Fujisawa, Masato

2014-01-01

Several recent studies have reported the involvement of bladder dysfunction in the delayed recovery of urinary continence following radical prostatectomy (RP). The objective of this study was to investigate the significance of detrusor overactivity (DO) as a predictor of the early continence status following robot-assisted RP (RARP). This study included 84 consecutive patients with prostate cancer undergoing RARP. Urodynamic studies, including filling cystometry, pressure flow study, electromyogram of the external urethral sphincter and urethral pressure profile, were performed in these patients before surgery. Urinary continence was defined as the use of either no or one pad per day as a precaution only. DO was preoperatively observed in 30 patients (35.7%), and 55 (65.5%) and 34 (40.5%) were judged to be incontinent 1 and 3 months after RARP, respectively. At both 1 and 3 months after RARP, the incidences of incontinence in patients with DO were significantly higher than in those without DO. Of several demographic and urodynamic parameters, univariate analyses identified DO and maximal urethral closure pressure (MUCP) as significant predictors of the continence status at both 1 and 3 months after RARP. Furthermore, DO and MUCP appeared to be independently associated with the continence at both 1 and 3 months after RARP on multivariate analysis. These findings suggest that preoperatively observed DO could be a significant predictor of urinary incontinence early after RARP; therefore, it is recommended to perform urodynamic studies for patients who are scheduled to undergo RARP in order to comprehensively evaluate their preoperative vesicourethral functions. PMID:25038181

The safety and efficacy of irreversible electroporation for the ablation of prostate cancer: a multicentre prospective human in vivo pilot study protocol.

PubMed

van den Bos, W; de Bruin, D M; Muller, B G; Varkarakis, I M; Karagiannis, A A; Zondervan, P J; Laguna Pes, M P; Veelo, D P; Savci Heijink, C D; Engelbrecht, M R W; Wijkstra, H; de Reijke, T M; de la Rosette, J J M C H

2014-10-29

Current surgical and ablative treatment options for prostate cancer have a relatively high incidence of side effects, which may diminish the quality of life. The side effects are a consequence of procedure-related damage of the blood vessels, bowel, urethra or neurovascular bundle. Ablation with irreversible electroporation (IRE) has shown to be effective in destroying tumour cells and harbours the advantage of sparing surrounding tissue and vital structures. The aim of the study is to evaluate the safety and efficacy and to acquire data on patient experience of minimally invasive, transperineally image-guided IRE for the focal ablation of prostate cancer. In this multicentre pilot study, 16 patients with prostate cancer who are scheduled for a radical prostatectomy will undergo an IRE procedure, approximately 30 days prior to the radical prostatectomy. Data as adverse events, side effects, functional outcomes, pain and quality of life will be collected and patients will be controlled at 1 and 2 weeks post-IRE, 1 day preprostatectomy and postprostatectomy. Prior to the IRE procedure and the radical prostatectomy, all patients will undergo a multiparametric MRI and contrast-enhanced ultrasound of the prostate. The efficacy of ablation will be determined by whole mount histopathological examination, which will be correlated with the imaging of the ablation zone. The protocol is approved by the ethics committee at the coordinating centre (Academic Medical Center (AMC) Amsterdam) and by the local Institutional Review Board at the participating centres. Data will be presented at international conferences and published in peer-reviewed journals. This pilot study will determine the safety and efficacy of IRE in the prostate. It will show the radiological and histopathological effects of IRE ablations and it will provide data to construct an accurate treatment planning tool for IRE in prostate tissue. Clinicaltrials.gov database: NCT01790451. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

The postoperative clinical outcomes and safety of early enteral nutrition in operated gastric cancer patients.

PubMed

Li, Bing; Liu, Hong-Yi; Guo, Shao-Hua; Sun, Peng; Gong, Fang-Ming; Jia, Bao-Qing

2015-01-01

This study investigated the impact of early enteral nutrition (EEN) on the clinical outcomes of gastric cancer patients after radical gastrectomy. Four hundred gastric cancer patients undergoing radical gastrectomy of any extend with D2 nodal dissection were randomly divided into an experimental and a control group with 200 cases in each group. Patients in the control group received postoperative parenteral nutrition (PN), while patients in the experimental group received postoperative EEN. After treatment, the clinical outcomes, postoperative immune function, and nutritional status of the two groups were evaluated. The postoperative fever time, intestinal function recovery time, anal exhaust time, and the length of hospital stay for patients in the experimental group were significantly shorter than those of the control group. We did not find significant differences in anastomotic leak, postoperative ileus and regurgitation between the two groups. The activities of multiple immune cell types, including CD3⁺, CD4⁺, CD4⁺/CD8⁺, and natural killer (NK) cells, were significantly lower in both groups on postoperative day 1 when compared with the preoperative levels (p<0.05). The level of CD8⁺ was not significantly different between the two groups (p>0.05). After treatment, levels of CD3⁺, CD4⁺, CD4⁺/CD8⁺, and NK cells in the experimental group patients were 35.6 ± 4.2, 42.2 ± 3.0, 1.7 ± 0.3, and 27.3 ± 5.3%, respectively, on postoperative day 7, which were similar to the preoperative levels. The immune cell levels from the control group patients remained significantly lower when compared with preoperative values; in addition, these values were also significantly lower when compared with the EEN patients (p<0.05) CONCLUSION: For gastric cancer patients undergoing radical gastrectomy, the clinical outcome, immune function and nutritional status after EEN were significantly improved. These data suggest the widespread use of EEN in clinical practice.

A Parallel Randomized Clinical Trial Examining the Return of Urinary Continence after Robot-Assisted Radical Prostatectomy with or without a Small Intestinal Submucosa Bladder Neck Sling.

PubMed

Bahler, Clinton D; Sundaram, Chandru P; Kella, Naveen; Lucas, Steven M; Boger, Michelle A; Gardner, Thomas A; Koch, Michael O

2016-07-01

Urinary continence is a driver of quality of life after radical prostatectomy. In this study we evaluated the impact of a biological bladder neck sling on the return of urinary continence after robot-assisted radical prostatectomy. This study compared early continence in patients undergoing robot-assisted radical prostatectomy with a sling and without a sling in a 2-group, 1:1, parallel, randomized controlled trial. Patients were blinded to group assignment. The primary outcome was defined as urinary continence (0 to 1 pad per day) at 1 month postoperatively. Inclusion criteria were organ confined prostate cancer and a prostate specific antigen less than 15 ng/ml. Exclusion criteria were any prior surgery on the prostate, a history of neurogenic bladder and history of pelvic radiation. A chi-squared test was used for the primary outcome. A total of 147 patients were randomized (control 74, sling 73) and 92% were available for primary end point analysis at 1 month. There were no significant differences in baseline or perioperative data except that operating room time was 20.1 minutes longer for the sling group (p=0.04). The continence rate was similar between the control and sling groups at 1 month (47.1% vs 55.2%, p=0.34) and 12 months (86.7% vs 94.5%, p=0.15), respectively. Adverse events were similar between the control and sling groups (10.8% vs 13.7%, p=0.59). The application of an absorbable urethral sling at robot-assisted radical prostatectomy was well tolerated with no increase in obstructive symptoms in this randomized trial. However, the sling failed to show a significant improvement in continence. Copyright © 2016 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Role of radical resection in patients with gallbladder carcinoma and jaundice.

PubMed

Feng, Fei-ling; Liu, Chen; Li, Bin; Zhang, Bai-he; Jiang, Xiao-qing

2012-03-01

Gallbladder carcinoma (GBC) is a commonly-seen malignancy of the biliary tract characterized by difficult early diagnosis, rapid growth, early metastasis, and poor prognosis. Nearly half of GBC patients also have jaundice, which is a mark of the advanced stage of GBC. The role of radical resection in patients of gallbladder carcinoma with jaundice is still a matter of uncertainty, which we attempted to clarify in this study. Totally, 251 GBC patients who received treatment at the Eastern Hepatobiliary Surgery Hospital (EHBH) from December 2002 to January 2010 were recruited into this study. We divided them into group A (jaundice group, n=117) and group B (non-jaundice group, n=134). Clinical records and follow-up data were collected and retrospectively analyzed in both groups. Compared with group A, patients in group B had a longer median survival time ((6.0±0.5) months vs. (15.0±2.6) months, P<0.01). Even in patients with stage III or stage IV GBC, the median survival time in patients without jaundice (n=111), was still longer than that in patients with jaundice (n=116) (P<0.01). The radical resection rate was lower in group A patients than in group B patients with stage III or stage IV GBC; 31.9% vs. 63.1%. However, the median survival time of patients undergoing radical resection did not show a statistical difference between jaundice patients and non-jaundice patients; (12.0±4.3) months vs. (18.0±3.0) months (P>0.05). GBC with jaundice usually implies advanced stage disease and a poor prognosis for the patients. However, our findings indicate that as long as the patient's condition allows, radical resection is still feasible for GBC patients with jaundice, and may achieve a prognosis close to those GBC patients without jaundice.

Bladder neck contracture after robot-assisted laparoscopic radical prostatectomy: evaluation of incidence and risk factors and impact on urinary function.

PubMed

Msezane, Lambda P; Reynolds, W Stuart; Gofrit, Ofer N; Shalhav, Arieh L; Zagaja, Gregory P; Zorn, Kevin C

2008-02-01

Bladder neck contracture (BNC) after radical prostatectomy has been reported to occur in 5% to 32% of men after open radical retropubic prostatectomy (RRP) and 0% to 3% after laparoscopic RRP. Optimal anastomotic closure involves creating a watertight, tension-free anastomosis with well-vascularized, mucosal apposition and correct realignment of the urethra. The cause of BNC is poorly understood; however, it is likely related to multiple factors, including excessive luminal narrowing at the site of reconstruction, local tissue ischemia, failed mucosal apposition, and urinary leakage. In this large series of patients who underwent robot-assisted laparoscopic radical prostatectomy (RLRP), we report the incidence of BNC, evaluate the influence of age, body mass index (BMI), estimated blood loss (EBL), surgical time, and prostate weight on its development and assess follow-up urinary function. Between February 2003 and July 2006, 650 consecutive men underwent RLRP at our institution. Patients with aborted or open conversion procedures were excluded from analysis. The mean overall follow-up for the remaining 634 patients was 19.5 months. Patients presenting with symptoms of outlet obstruction were evaluated with cystoscopy to confirm a BNC. Comparisons of age, BMI, EBL, operative time, and prostate weight were performed using the Student t-test and chi-square analysis. BNC was the diagnosis in seven patients (1.1%), with a mean time of presentation of 4.8 (3-12) months postoperatively. The BNC patients had comparable mean age, BMI, prostate weight, and EBL to the non-BNC cohort. Their operative time, however, was significantly longer (283 v 225 min, P = 0.04). The incidence of BNC after radical prostatectomy is 1.1% in a large series of men undergoing RLRP. The diagnosis was made within 1 year. No significant impact on urinary continence or quality-of-life urinary function was observed after BNC management. A running anastomosis, better visualization, improved instrument maneuverability, and decreased blood loss may account for such a low rate.

Repeat prostate biopsies prior to radical prostatectomy do not impact erectile function recovery and mid- to long-term continence.

PubMed

Furrer, Marc A; Vilaseca, Antoni; Corradi, Renato B; Boxler, Silvan; Thalmann, George N; Nguyen, Daniel P

2018-06-01

A growing number of men undergo repeat biopsies prior to radical prostatectomy for prostate cancer. However, the long-term impact of repeat biopsies on functional outcomes in this patient population remains unelucidated. Thus, we compared functional outcomes between patients who underwent single biopsy versus repeat biopsies before radical prostatectomy. From 1996 to 2015, 1015 consecutive patients underwent radical prostatectomy, and subsequently had urinary continence and erectile function assessed for >2 years follow-up. One-fourth of patients (275; 27%) had ≥2 biopsies before prostatectomy. Logistic regression models tested whether repeat biopsy before prostatectomy predicted continence or erectile function recovery. For the overall cohort, continence rates were 84%, 92%, 96%, and 98% at 3, 6, 12, and 24 months, respectively. Repeat biopsy before prostatectomy was associated with lower continence rate at 3 months compared to single biopsy (P = 0.03); however, no significant differences were observed at 6, 12, or 24 months. In multivariable analyses adjusting for age, body mass index and diabetes/cardiovascular disease/smoking, the association between repeat biopsy and lower likelihood of continence at 3 months remained (odds ratio 0.67, 95% confidence interval 0.47-0.97; P = 0.03). Overall erectile function recovery rates were 16%, 33%, 51%, and 55% at 3, 6, 12, and 24 months, respectively. No difference in erectile function recovery rates was seen at any time point for single biopsy versus repeat biopsy. In multivariable analyses, repeat biopsy was not predictive of erectile function recovery at any time point. Repeat biopsy before radical prostatectomy impairs early continence after surgery. However, erectile function recovery and mid-term to long-term continence are not affected. These data support the current trend towards active surveillance and delayed local treatment in patients with low- to intermediate-risk prostate cancer. © 2018 Wiley Periodicals, Inc.

Unimolecular thermal decomposition of phenol and d5-phenol: Direct observation of cyclopentadiene formation via cyclohexadienone

NASA Astrophysics Data System (ADS)

Scheer, Adam M.; Mukarakate, Calvin; Robichaud, David J.; Nimlos, Mark R.; Carstensen, Hans-Heinrich; Barney Ellison, G.

2012-01-01

The pyrolyses of phenol and d5-phenol (C6H5OH and C6D5OH) have been studied using a high temperature, microtubular (μtubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting the heated reactor (375 K-1575 K) is subject to a free expansion after a residence time in the μtubular reactor of approximately 50-100 μs. The expansion from the reactor into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. We find that the initial decomposition steps at the onset of phenol pyrolysis are enol/keto tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C6H5OH → c-C6H6 = O → c-C5H6 + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C5H6 → c-C5H5 + H → HC≡CH + HCCCH2. At higher temperatures, hydrogen loss from the PhO-H group to form phenoxy radical followed by CO ejection to generate the cyclopentadienyl radical likely contributes to the product distribution; C6H5O-H → C6H5O + H → c-C5H5 + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C6H4-OH) and hydroquinone (p-HO-C6H4-OH) are shown to undergo decarbonylation at the onset of pyrolysis to form hydroxycyclopentadiene. In the case of catechol, we observe that water loss is also an important decomposition channel at the onset of pyrolysis.

[Clinical application of combined hepatic artery resection and reconstruction in surgical treatment for hilar cholangiocarcinoma].

PubMed

Dai, H S; Bie, P; Wang, S G; He, Y; Li, D J; Tian, F; Zhao, X; Chen, Z Y

2018-01-01

Objective: To clarify whether the surgical treatment for hilar cholangiocarcinoma combined with artery reconstruction is optimistic to the patients with hilar cholangiocarcinoma with hepatic artery invasion. Methods: There were 384 patients who received treatment in the First Affiliated Hospital to Army Medical University from January 2008 to January 2016 analyzed retrospectively. There were 27 patients underwent palliative operation, 245 patients underwent radical operation, radical resection account for 63.8%. Patients were divided into four groups according to different operation method: routine radical resection group( n =174), portal vein reconstruction group ( n =47), hepatic artery reconstruction group ( n =24), palliative group( n =27). General information of patients who underwent radical operation treatment was analyzed by chi-square test and analysis of variance. The period of operation time, blood loss, the length of hospital stay and hospitalization expenses of the radical operation patients were analyzed by one-way ANOVA. Comparison among groups was analyzed by LSD- t test. Results: The follow-up ended up in June first, 2016. Each of patients followed for 6 to 60 months, the median follow-up period was 24 months. 1-, 3-, and 5-year survival rates were 81.3%, 44.9% and 13.5% of routine radical operation group, and were 83.0%, 44.7% and 15.1% of portal vein reconstruction group, and were 70.8%, 27.7% and 6.9% of hepatic artery reconstruction group, respectively. And 1-, 3-, and 5-year survival rates of hepatic artery reconstruction group was lower than routine radical group and portal vein reconstruction group significantly ( P <0.05). However, the rate of postoperative complications of the hepatic artery reconstruction group and the routine radical operation group and the portal vein reconstruction group were 62.5%(15/24), 55.3%(96/174) and 51.5%(24/47), respectively. There was no significant difference among them ( P >0.05). The data shows that the ratio of lymphatic metastasis in hepatic artery reconstruction group (70.8%) is much higher than them in routine radical operation group (20.1%) and portal vein reconstruction group (19.1%) significantly ( P <0.05). The presented data also indicate that hepatic artery resection prolongs survival time comparing with patients undergoing palliative therapy for hilar cholangiocarcinoma. Cox regression analysis indicate that hepatic artery resection and reconstruction is a protective factor compare with palliative therapy ( RR =0.38, 95% CI: 0.22-0.67). The significant reason for shorter survival time is a positive correlation between hepatic artery invasion and lymph node metastasis. Conclusion: Hepatic artery resection and reconstruction has beneficial impact on oncologic long-term outcome in patients with advanced stage hilar cholangiocarcinoma.

Resuscitation from experimental traumatic brain injury by magnolol therapy.

PubMed

Wang, Che-Chuan; Lin, Kao-Chang; Lin, Bor-Shyh; Chio, Chung-Ching; Kuo, Jinn-Rung

2013-10-01

The purpose of the present study was to determine whether magnolol, a free radical scavenger, mitigates the deleterious effects of traumatic brain injury (TBI). Traumatic brain injuries were induced in anesthetized male Sprague-Dawley rats using fluid percussion, and the rats were divided into groups treated with magnolol (2 mg/kg, intravenously) or vehicle. A group of rats that did not undergo TBI induction was also studied as controls. Biomarkers of TBI, including glycerol and 2,3-dihydroxybenzoic acid, were evaluated by microdialysis. Infraction volume, extent of neuronal apoptosis, and antiapoptosis factor transforming growth factor β1 (TGF-β1) were also measured. Functional outcomes were assessed by motor assays. Compared with the rats without TBI, the animals with TBI exhibited higher hippocampal glycerol and 2,3-dihydroxybenzoic acid. Relative to the vehicle-treated group, the magnolol-treated group showed decreased hippocampal levels of glycerol and hydroxyl radical levels. The magnolol-treated rats also exhibited decreased cerebral infarction volume and neuronal apoptosis and increased antiapoptosis-associated factor TGF-β1 expression. These effects were translated into improved motor function post TBI. Our results suggest that intravenous magnolol injection mitigates the deleterious effects of TBI in rats based on its potent free radical scavenging capability, and the mechanism of anti-neuronal apoptosis is partly due to an increase in TGF-β1 expression in the ischemic cortex. Copyright © 2013 Elsevier Inc. All rights reserved.

Physician role in physical activity for African-American males undergoing radical prostatectomy for prostate cancer.

PubMed

Williams, Faustine; Imm, Kellie R; Colditz, Graham A; Housten, Ashley J; Yang, Lin; Gilbert, Keon L; Drake, Bettina F

2017-04-01

Physical activity is recognized as a complementary therapy to improve physical and physiological functions among prostate cancer survivors. Little is known about communication between health providers and African-American prostate cancer patients, a high risk population, regarding the health benefits of regular physical activity on their prognosis and recovery. This study explores African-American prostate cancer survivors' experiences with physical activity prescription from their physicians. Three focus group interviews were conducted with 12 African-American prostate cancer survivors in May 2014 in St. Louis, MO. Participants' ages ranged from 49 to 79 years, had completed radical prostatectomy, and their time out of surgery varied from 7 to 31 months. Emerged themes included physician role on prescribing physical activity, patients' perceived barriers to engaging in physical activity, perception of normalcy following surgery, and specific resources survivors' sought during treatment. Of the 12 men who participated, 8 men (67%) expressed that their physicians did not recommend physical activity for them. Although some participants revealed they were aware of the importance of sustained physical activity on their prognosis and recovery, some expressed concerns that urinary dysfunction, incontinence, and family commitments prevented them from engaging in active lifestyles. Transitioning from post radical prostatectomy treatment to normal life was an important concern to survivors. These findings highlight the importance of physical activity communication and prescription for prostate cancer patients.

Risk factors for indications of intraoperative blood transfusion among patients undergoing surgical treatment for colorectal adenocarcinoma.

PubMed

Gonçalves, Iara; Linhares, Marcelo; Bordin, Jose; Matos, Delcio

2009-01-01

Identification of risk factors for requiring transfusions during surgery for colorectal cancer may lead to preventive actions or alternative measures, towards decreasing the use of blood components in these procedures, and also rationalization of resources use in hemotherapy services. This was a retrospective case-control study using data from 383 patients who were treated surgically for colorectal adenocarcinoma at 'Fundação Pio XII', in Barretos-SP, Brazil, between 1999 and 2003. To recognize significant risk factors for requiring intraoperative blood transfusion in colorectal cancer surgical procedures. Univariate analyses were performed using Fisher's exact test or the chi-squared test for dichotomous variables and Student's t test for continuous variables, followed by multivariate analysis using multiple logistic regression. In the univariate analyses, height (P = 0.06), glycemia (P = 0.05), previous abdominal or pelvic surgery (P = 0.031), abdominoperineal surgery (P<0.001), extended surgery (P<0.001) and intervention with radical intent (P<0.001) were considered significant. In the multivariate analysis using logistic regression, intervention with radical intent (OR = 10.249, P<0.001, 95% CI = 3.071-34.212) and abdominoperineal amputation (OR = 3.096, P = 0.04, 95% CI = 1.445-6.623) were considered to be independently significant. This investigation allows the conclusion that radical intervention and the abdominoperineal procedure in the surgical treatment of colorectal adenocarcinoma are risk factors for requiring intraoperative blood transfusion.

[Technological convergence will quickly generate disruptive innovations in oncology].

PubMed

Coucke, Ph A

2016-06-01

Convergence between information and communication technology and recent developments in medical care will totally change the health care sector. The way we perform diagnosis, treatment and follow-up will undergo disruptive changes in a very near future. We intend to highlight this statement by a limited selection of examples of radical innovations, especially in the field of oncology. To be totally disruptive and to illustrate the concept of "lateral power" - especially cognitive distribution - the list of references is only made up of internet links. Anyone - patients included - can easily and instantly access to this information everywhere.

Enantioselective Direct α-Amination of Aldehydes via a Photoredox Mechanism: A Strategy for Asymmetric Amine Fragment Coupling

PubMed Central

Cecere, Giuseppe; Koenig, Christian M.; Alleva, Jennifer L.

2013-01-01

The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated, nitrogen-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Importantly, this photoinduced transformation allows direct and enantioselective access to α-amino aldehyde products that do not require post-reaction manipulation. PMID:23869694

Robotic inferior vena cava surgery.

PubMed

Davila, Victor J; Velazco, Cristine S; Stone, William M; Fowl, Richard J; Abdul-Muhsin, Haidar M; Castle, Erik P; Money, Samuel R

2017-03-01

Inferior vena cava (IVC) surgery is uncommon and has traditionally been performed through open surgical approaches. Renal cell carcinoma with IVC extension generally requires vena cavotomy and reconstruction. Open removal of malpositioned IVC filters (IVCF) is occasionally required after endovascular retrieval attempts have failed. As our experience with robotic surgery has advanced, we have applied this technology to surgery of the IVC. We reviewed our institution's experience with robotic surgical procedures involving the IVC to determine its safety and efficacy. All patients undergoing robotic surgery that included cavotomy and repair from 2011 to 2014 were retrospectively reviewed. Data were obtained detailing preoperative demographics, operative details, and postoperative morbidity and mortality. Ten patients (6 men) underwent robotic vena caval procedures at our institution. Seven patients underwent robotic nephrectomy with removal of IVC tumor thrombus and retroperitoneal lymph node dissection. Three patients underwent robotic explantation of an IVCF after multiple endovascular attempts at removal had failed. The patients with renal cell carcinoma were a mean age of was 65.4 years (range, 55-74 years). Six patients had right-sided malignancy. All patients had T3b lesions at time of diagnosis. Mean tumor length extension into the IVC was 5 cm (range, 1-8 cm). All patients underwent robotic radical nephrectomy, with caval tumor thrombus removal and retroperitoneal lymph node dissection. The average operative time for patients undergoing surgery for renal cell carcinoma was 273 minutes (range, 137-382 minutes). Average intraoperative blood loss was 428 mL (range, 150-1200 mL). The patients with IVCF removal were a mean age of 33 years (range, 24-41 years). Average time from IVCF placement until robotic removal was 35.5 months (range, 4.3-57.3 months). Before robotic IVCF removal, a minimum of two endovascular retrievals were attempted. Average operative time for patients undergoing IVCF removal was 163 minutes (range, 131-202 minutes). Intraoperative blood loss averaged 250 mL (range, 150-350 mL). All procedures were completed robotically. The mean length of stay for all patients was 3.5 days (range, 1-8 days). All patients resumed ambulation on postoperative day 1. Nine patients resumed a regular diet on postoperative day 2. One patient with a renal tumor sustained a colon injury during initial adhesiolysis, before robotic radical nephrectomy, which was recognized at the initial operation and repaired robotically. Robotic radical nephrectomy and caval tumor removal were then completed. No blood transfusions were required intraoperatively, but three patients required blood transfusions postoperatively. Although robotic IVC surgery is uncommon, our initial limited experience demonstrates it is safe and efficacious. Copyright © 2016 Society for Vascular Surgery. Published by Elsevier Inc. All rights reserved.

Accuracy of Pulse Oximeters in Detecting Hypoxemia in Patients with Chronic Thromboembolic Pulmonary Hypertension

PubMed Central

Kohyama, Tomoki; Moriyama, Kiyoshi; Kanai, Riichiro; Kotani, Mariko; Uzawa, Kohji; Satoh, Toru; Yorozu, Tomoko

2015-01-01

Purpose Pulse oximetry is routinely used to continuously and non-invasively monitor arterial oxygen saturation (SaO2). When oxygen saturation by pulse oximeter (SpO2) overestimates SaO2, hypoxemia may be overlooked. We compared the SpO2 - SaO2 differences among three pulse oximeters in patients with chronic thromboembolic pulmonary hypertension (CTEPH) who spent their daily lives in a poor oxygen state. Material and Method This prospective observational study recruited 32 patients with CTEPH undergoing elective cardiac catheterization. As we collected arterial blood samples in the catheter laboratory, SpO2 values were simultaneously recorded. Three pulse oximeters were used on each patient, and SpO2 values were compared with oximetry readings using a blood gas analyzer. To determine the optimal SpO2 value by which to detect hypoxemia (SaO2≦90%), we generated receiver operating characteristic (ROC) curves for each pulse oximeter. Result The root mean square of each pulse oximeter was 1.79 (OLV-3100), 1.64 (N-BS), and 2.50 (Masimo Radical). The mean bias (SpO2 - SaO2) for the 90%–95% saturation range was significantly higher for Masimo Radical (0.19 +/- 1.78% [OLV-3100], 0.18 +/- 1.63% [N-BS], and 1.61 +/- 1.91% [Masimo Radical]; p<0.0001). The optimal SpO2 value to detect hypoxemia (SaO2≦90%) was 89% for OLV-3100, 90% for N-BS, and 92% for Masimo Radical. Conclusion We found that the biases and precision with which to detect hypoxemia differed among the three pulse oximeters. To avoid hypoxemia, the optimal SpO2 should be determined for each pulse oximeter. PMID:25978517

The volume-mortality relation for radical cystectomy in England: retrospective analysis of hospital episode statistics

PubMed Central

Bottle, Alex; Darzi, Ara W; Athanasiou, Thanos; Vale, Justin A

2010-01-01

Objectives To investigate the relation between volume and mortality after adjustment for case mix for radical cystectomy in the English healthcare setting using improved statistical methodology, taking into account the institutional and surgeon volume effects and institutional structural and process of care factors. Design Retrospective analysis of hospital episode statistics using multilevel modelling. Setting English hospitals carrying out radical cystectomy in the seven financial years 2000/1 to 2006/7. Participants Patients with a primary diagnosis of cancer undergoing an inpatient elective cystectomy. Main outcome measure Mortality within 30 days of cystectomy. Results Compared with low volume institutions, medium volume ones had a significantly higher odds of in-hospital and total mortality: odds ratio 1.72 (95% confidence interval 1.00 to 2.98, P=0.05) and 1.82 (1.08 to 3.06, P=0.02). This was only seen in the final model, which included adjustment for structural and processes of care factors. The surgeon volume-mortality relation showed weak evidence of reduced odds of in-hospital mortality (by 35%) for the high volume surgeons, although this did not reach statistical significance at the 5% level. Conclusions The relation between case volume and mortality after radical cystectomy for bladder cancer became evident only after adjustment for structural and process of care factors, including staffing levels of nurses and junior doctors, in addition to case mix. At least for this relatively uncommon procedure, adjusting for these confounders when examining the volume-outcome relation is critical before considering centralisation of care to a few specialist institutions. Outcomes other than mortality, such as functional morbidity and disease recurrence may ultimately influence towards centralising care. PMID:20305302

Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH2OH and CD2OH). I. A theoretical study

NASA Astrophysics Data System (ADS)

Kamarchik, E.; Rodrigo, C.; Bowman, J. M.; Reisler, H.; Krylov, A. I.

2012-02-01

The dissociation of the hydroxymethyl radical, CH2OH, and its isotopolog, CD2OH, following the excitation of high OH stretch overtones is studied by quasi-classical molecular dynamics calculations using a global potential energy surface (PES) fitted to ab initio calculations. The PES includes CH2OH and CH3O minima, dissociation products, and all relevant barriers. Its analysis shows that the transition states for OH bond fission and isomerization are both very close in energy to the excited vibrational levels reached in recent experiments and involve significant geometry changes relative to the CH2OH equilibrium structure. The energies of key stationary points are refined using high-level electronic structure calculations. Vibrational energies and wavefunctions are computed by coupled anharmonic vibrational calculations. They show that high OH-stretch overtones are mixed with other modes. Consequently, trajectory calculations carried out at energies about ˜3000 cm-1 above the barriers reveal that despite initial excitation of the OH stretch, the direct OH bond fission is relatively slow (10 ps) and a considerable fraction of the radicals undergoes isomerization to the methoxy radical. The computed dissociation energies are: D0(CH2OH → CH2O + H) = 10 188 cm-1, D0(CD2OH → CD2O + H) = 10 167 cm-1, D0(CD2OH → CHDO + D) = 10 787 cm-1. All are in excellent agreement with the experimental results. For CH2OH, the barriers for the direct OH bond fission and isomerization are: 14 205 and 13 839 cm-1, respectively.

Electron attachment to C{sub 2} fluorocarbon radicals at high temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A., E-mail: afrl.rvborgmailbox@kirtland.af.mil

Thermal electron attachment to the radical species C{sub 2}F{sub 3} and C{sub 2}F{sub 5} has been studied over the temperature range 300–890 K using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Both radicals exclusively undergo dissociative attachment to yield F{sup −}. The rate constant for C{sub 2}F{sub 5} shows little dependence over the temperature range, remaining ∼4 × 10{sup −9} cm{sup 3} s{sup −1}. The rate constant for C{sub 2}F{sub 3} attachment rises steeply with temperature from 3 × 10{sup −11} cm{sup 3} s{sup −1} at 300 K to 1 × 10{sup −9} cm{sup 3} s{sup −1} at 890 K.more » The behaviors of both species at high temperature are in agreement with extrapolations previously made from data below 600 K using a recently developed kinetic modeling approach. Measurements were also made on C{sub 2}F{sub 3}Br and C{sub 2}F{sub 5}Br (used in this work as precursors to the radicals) over the same temperature range, and, for C{sub 2}F{sub 5}Br as a function of electron temperature. The attachment rate constants to both species rise with temperature following Arrhenius behavior. The attachment rate constant to C{sub 2}F{sub 5}Br falls with increasing electron temperature, in agreement with the kinetic modeling. The current data fall in line with past predictions of the kinetic modeling approach, again showing the utility of this simplified approach.« less

A 10-Year Retrospective Review of a Nonrandomized Cohort of 458 Patients Undergoing Radical Radiotherapy or Cystectomy in Yorkshire, UK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Munro, Nicholas P., E-mail: nic@munron.plus.co; Sundaram, Subramnian K.; Weston, Philip

2010-05-01

Purpose: We have previously reported on the mortality, morbidity, and 5-year survival of 458 patients who underwent radical radiotherapy or surgery for invasive bladder cancer in Yorkshire from 1993 to 1996. We aim to present the 10-year outcomes of these patients and to reassess factors predicting survival. Methods and Materials: The Northern and Yorkshire Cancer Registry identified 458 patients whose cases were subjected to Kaplan-Meier all-cause survival analyses, and a retrospective casenote analysis was undertaken on 398 (87%) for univariate and multivariate Cox proportional hazards modeling. Additional proportional hazards regression modeling was used to assess the statistical significance of variablesmore » on overall survival. Results: The ratio of radiotherapy to cystectomy was 3:1. There was no significant difference in overall 10-year survival between those who underwent radiotherapy (22%) and radical cystectomy (24%). Univariate analyses suggested that female sex, performance status, hydronephrosis and clinical T stage, were associated with an inferior outcome at 10 years. Patient age, tumor grade, treatment delay, and caseload factors were not significant. Multivariate analysis models were created for 0-2 and 2-10 years after treatment. There were no significant differences in treatment for 0-2 years; however, after 2 years follow-up there was some evidence of increased survival for patients receiving surgery compared with radiotherapy (hazard ratio 0.66, 95% confidence interval: 0.44-1.01, p = 0.06). Conclusions: a 10-year minimum follow-up has rarely been reported after radical treatment for invasive bladder cancer. At 10 years, there was no statistical difference in all-cause survival between surgery and radiotherapy treatment modalities.« less

Generation of ROS mediated by mechanical waves (ultrasound) and its possible applications.

PubMed

Duco, Walter; Grosso, Viviana; Zaccari, Daniel; Soltermann, Arnaldo T

2016-10-15

The thermal decomposition of 9,10 diphenylanthracene peroxide (DPAO 2 ) generates DPA and a mix of triplet and singlet molecular oxygen. For DPAO 2 the efficiency to produce singlet molecular oxygen is 0.35. On the other hand, it has shown that many thermal reactions can be carried out through the interaction of molecules with ultrasound. Ultrasound irradiation can create hydrodynamic stress (sonomechanical process), inertial cavitation (pyrolitic process) and long range effects mediated by radicals or ROS. Sonochemical reactions can be originated by pyrolytic like process, shock mechanical waves, thermal reactions and radical and ROS mediated reactions. Sonolysis of pure water can yield hydrogen or hydroxyl radicals and hydrogen peroxide (ROS). When DPAO 2 in 1,4 dioxane solution is treated with 20 or 24kHz and different power intensity the production of molecular singlet oxygen is observed. Specific scavengers like tetracyclone (TC) are used to demonstrate it. The efficiency now is 0.85 showing that the sonochemical process is much more efficient that the thermal one. Another endoperoxide, artemisinin was also studied. Unlike the concept of photosensitizer of photodynamic therapy, in spite of large amount of reported results in literature, the term sonosensitizer and the sonosensitization process are not well defined. We define sonosensitized reaction as one in which a chemical species decompose as consequence of cavitation phenomena producing ROS or other radicals and some other target species does undergo a chemical reaction. The concept could be reach rapidly other peroxides which are now under experimental studies. For artemisinin, an important antimalarian and anticancer drug, was established that ultrasound irradiation increases the effectiveness of the treatment but without any explanation. We show that artemisinin is an endoperoxide and behaves as a sonosensitizer in the sense of our definition. Copyright © 2016 Elsevier Inc. All rights reserved.

Formation, Evaporation, and Hydrolysis of Organic Nitrates from Nitrate Radical Oxidation of Monoterpenes

NASA Astrophysics Data System (ADS)

Ng, N. L.; Takeuchi, M.; Eris, G.; Berkemeier, T.; Boyd, C.; Nah, T.; Xu, L.

2017-12-01

Organic nitrates play an important role in the cycling of NOx and secondary organic aerosol (SOA) formation, yet their formation mechanisms and fates remain highly uncertain. The interactions of biogenic VOCs with NO3 radicals represent a direct way for positively linking anthropogenic and biogenic emissions. Results from ambient studies suggest that organic nitrates have a relatively short lifetime, though corresponding laboratory data are limited. SOA and organic nitrates produced at night may evaporate the following morning due to increasing temperatures or dilution of semi-volatile compounds. Once formed, organic nitrates can also undergo hydrolysis in the presence of particle water. In this work, we investigate the formation, evaporation, and hydrolysis of organic nitrates generated from the nitrate radical oxidation of a-pinene, b-pinene, and limonene. Experiments are conducted in the Georgia Environmental Chamber facility (GTEC) under dry and humid conditions and different temperatures. Experiments are also designed to probe different peroxy radical pathways (RO2+HO2 vs RO2+NO3). Speciated gas-phase and particle-phase organic nitrates are continuously monitored by a Filter Inlet for Gases and AEROsols High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (FIGAERO-HR-ToF-CIMS). Bulk aerosol composition is measured by a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). A large suite of highly oxygenated gas- and particle-phase organic nitrates are formed rapidly. We find a resistance to aerosol evaporation when it is heated. The extent of organic nitrate hydrolysis in the humid experiments is evaluated. The dynamics of the speciated organic nitrates over the course of the experiments will also be discussed. Results from this chamber study provide fundamental data for understanding the dynamics of organic nitrate aerosols over its atmospheric lifetime.

Accuracy of pulse oximeters in detecting hypoxemia in patients with chronic thromboembolic pulmonary hypertension.

PubMed

Kohyama, Tomoki; Moriyama, Kiyoshi; Kanai, Riichiro; Kotani, Mariko; Uzawa, Kohji; Satoh, Toru; Yorozu, Tomoko

2015-01-01

Pulse oximetry is routinely used to continuously and non-invasively monitor arterial oxygen saturation (SaO2). When oxygen saturation by pulse oximeter (SpO2) overestimates SaO2, hypoxemia may be overlooked. We compared the SpO2 - SaO2 differences among three pulse oximeters in patients with chronic thromboembolic pulmonary hypertension (CTEPH) who spent their daily lives in a poor oxygen state. This prospective observational study recruited 32 patients with CTEPH undergoing elective cardiac catheterization. As we collected arterial blood samples in the catheter laboratory, SpO2 values were simultaneously recorded. Three pulse oximeters were used on each patient, and SpO2 values were compared with oximetry readings using a blood gas analyzer. To determine the optimal SpO2 value by which to detect hypoxemia (SaO2≦90%), we generated receiver operating characteristic (ROC) curves for each pulse oximeter. The root mean square of each pulse oximeter was 1.79 (OLV-3100), 1.64 (N-BS), and 2.50 (Masimo Radical). The mean bias (SpO2 - SaO2) for the 90%-95% saturation range was significantly higher for Masimo Radical (0.19 +/- 1.78% [OLV-3100], 0.18 +/- 1.63% [N-BS], and 1.61 +/- 1.91% [Masimo Radical]; p<0.0001). The optimal SpO2 value to detect hypoxemia (SaO2≦90%) was 89% for OLV-3100, 90% for N-BS, and 92% for Masimo Radical. We found that the biases and precision with which to detect hypoxemia differed among the three pulse oximeters. To avoid hypoxemia, the optimal SpO2 should be determined for each pulse oximeter.

Evaluating the learning curve for robot-assisted laparoscopic radical cystectomy.

PubMed

Pruthi, Raj S; Smith, Angela; Wallen, Eric M

2008-11-01

We seek to describe the learning curve of robot-assisted laparoscopic radical cystectomy by evaluating some of the surgical, oncologic, and clinical outcomes in our initial experience with 50 consecutive patients undergoing this novel procedure. Fifty consecutive patients (representing our initial experience with robot-assisted cystectomy) underwent radical cystectomy and urinary diversion from January 2006 to December 2007. Several different metrics were used to evaluate the learning curve of this procedure, including estimated blood loss (EBL), operative (OR) time, pathologic outcomes, and complication rate. We evaluated patients as a continuous variable, divided into five distinct time periods (quintiles), and stratified by first half and second half of robotic experience. EBL was not significantly lower until the third quintile (patients 21-30), after which further significant reductions were not observed. Mean OR time declined between each quintile for the first 30 patients (1-10 v 11-20 v 21-30). No significant declines occurred after the third quintile (21-30). When evaluated as a continuous variable, the statistical cut point at which no further significant reductions were observed was after patient 20 for OR time. No differences were observed with regard to time to flatus, bowel movement, or hospital discharge. Furthermore, complications were not different between the initial 25 patients and the most recent patients. There has been no case of a positive margin, and there was only one inadvertent bladder entry. Lymph node yield has also not significantly changed over time. This report helps to define the learning curve associated with robot-assisted laparoscopic radical cystectomy for bladder cancer. Despite the higher OR times and blood loss that is observed early in the learning curve, no such compromises are observed with regard to these oncologic parameters even early in the experience.

Radical cystectomy in octogenarians--does morbidity outweigh the potential survival benefits?

PubMed

Donat, S Machele; Siegrist, Timothy; Cronin, Angel; Savage, Caroline; Milowsky, Matthew I; Herr, Harry W

2010-06-01

Surveillance, Epidemiology, and End Results data indicate only 19.7% of patients 80 years old or older with muscle invasive bladder cancer undergo radical cystectomy vs 49.4% of those with similar stage disease age 65 to 79 years, reflecting concern for perioperative morbidity. We evaluated the morbidity and survival outcomes of octogenarians treated with radical cystectomy at a tertiary cancer center. We conducted a retrospective review of 1,142 patients entered prospectively into a hospital based complication database between 1995 and 2005 using a modified Clavien system. Complications were classified as minor or major based on the complexity of intervention required. Disease specific and competing risk survival curves for patients younger than 80 years vs 80 years old or older were created. Octogenarians had a nonsignificantly higher rate of minor (55% vs 50%) and major complications (17% vs 13%) than younger patients, respectively (global p = 0.15). After adjusting for baseline characteristics the risk of any complication was roughly flat across all ages (p = 0.9). For major complications risk appeared to increase slightly up to age 65 years and then plateau (p = 0.16). After adjusting for deaths from other causes the cumulative incidence of death from bladder cancer in octogenarians was comparable to that in younger patients (5-year cumulative incidence of death from bladder cancer 26% vs 25%). In our experience radical cystectomy in older patients with bladder cancer provides similar disease control and survival outcomes with risks of high grade perioperative morbidity comparable to those in younger patients, and remains an important treatment option. Copyright 2010 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Effect of routine repeat transurethral resection for superficial bladder cancer: a long-term observational study.

PubMed

Grimm, Marc-Oliver; Steinhoff, Christine; Simon, Xenia; Spiegelhalder, Philipp; Ackermann, Rolf; Vogeli, Thomas Alexander

2003-08-01

We determined the long-term outcome in patients with superficial bladder cancer (Ta and T1) undergoing routine second transurethral bladder tumor resection (ReTURB) in regard to recurrence and progression. We performed an inception cohort study of 124 consecutive patients with superficial bladder cancer undergoing transurethral resection and routine ReTURB (83) between November 1993 and October 1995 at a German university hospital. Immediately after transurethral resection all lesions were documented on a designed bladder map. ReTURB of the scar from initial resection and other suspicious lesions was performed at a mean of 7 weeks. Patients were followed until recurrence or death, or a minimum of 5 years. Residual tumor was found in 33% of all ReTURB cases, including 27% of Ta and 53% of T1 disease, and in 81% at the initial resection site. Five of the 83 patients underwent radical cystectomy due to ReTURB findings. The estimated risk of recurrence after years 1 to 3 was 18%, 29% and 32%, respectively. After 5 years 63% of the patients undergoing ReTURB were still disease-free (mean recurrence-free survival 62 months, median 87). Progression to muscle invasive disease was observed in only 2 patients (3%) after a mean observation of 61 months. These data suggest a favorable outcome regarding recurrence and progression in patients with superficial bladder cancer who undergo ReTURB. ReTURB is suggested at least in those at high risk when bladder preservation is intended.

Retrospective Analysis of Outcome Differences in Preoperative Concurrent Chemoradiation With or Without Elective Nodal Irradiation for Esophageal Squamous Cell Carcinoma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsu, Feng-Ming; Cancer Research Center, National Taiwan University College of Medicine, Taipei, Taiwan; Graduate Institute of Biomedical Electronics and Bioinformatics, National Taiwan University, Taipei, Taiwan

2011-11-15

Purpose: To evaluate the efficacy and patterns of failure of elective nodal irradiation (ENI) in patients with esophageal squamous cell carcinoma (SCC) undergoing preoperative concurrent chemoradiation (CCRT) followed by radical surgery. Methods and Materials: We retrospectively studied 118 patients with AJCC Stage II to III esophageal SCC undergoing preoperative CCRT (median, 36 Gy), followed by radical esophagectomy. Of them, 73 patients (62%) had ENI and 45 patients (38%) had no ENI. Patients with ENI received radiotherapy to either supraclavicular (n = 54) or celiac (n = 19) lymphatics. Fifty-six patients (57%) received chemotherapy with paclitaxel plus cisplatin. The 3-year progression-freemore » survival, overall survival, and patterns of failure were analyzed. Distant nodal recurrence was classified into M1a and M1b regions. A separate analysis using matched cases was conducted. Results: The median follow-up was 38 months. There were no differences in pathological complete response rate (p = 0.12), perioperative mortality rate (p = 0.48), or delayed Grade 3 or greater cardiopulmonary toxicities (p = 0.44), between the groups. More patients in the non-ENI group had M1a failure than in the ENI group, with 3-year rates of 11% and 3%, respectively (p = 0.05). However, the 3-year isolated distant nodal (M1a + M1b) failure rates were not different (ENI, 10%; non-ENI, 14%; p = 0.29). In multivariate analysis, pathological nodal status was the only independent prognostic factor associated with overall survival (hazard ratio = 1.78, p = 0.045). The 3-year overall survival and progression-free survival were 45% and 45%, respectively, in the ENI group, and 52% and 43%, respectively, in the non-ENI group (p = 0.31 and 0.89, respectively). Matched cases analysis did not show a statistical difference in outcomes between the groups. Conclusions: ENI reduced the M1a failure rate but was not associated with improved outcomes in patients undergoing preoperative CCRT for esophageal SCC. Pathological nodal metastasis predicted poor outcome.« less

Intraoperative intravenous lidocaine exerts a protective effect on cell-mediated immunity in patients undergoing radical hysterectomy.

PubMed

Wang, Huan-Liang; Yan, Hong-Dan; Liu, Ya-Yang; Sun, Bao-Zhu; Huang, Rui; Wang, Xiao-Shuang; Lei, Wei-Fu

2015-11-01

Surgical procedures cause a decrease in lymphocyte proliferation rate, an increase in apoptosis and shifts the balance of T‑helper (Th)1/Th2 cells towards anti‑cell‑mediated immunity (CMI) Th2 dominance, which is relevant to the immunosuppressive effects of CMI, postoperative septic complications and the formation of tumor metastasis. Previous studies have revealed that lidocaine exhibits antibacterial actions; regulating inflammatory responses, reducing postoperative pain and affecting the duration spent in hospital. Thus, the present study hypothesized that lidocaine may exert a protective effect on the CMI of patients undergoing surgery for the removal of a primary tumor. A total of 30 adult female patients diagnosed with cervical cancer were recruited to the present study and were randomized into two groups. The lidocaine group received an intravenous bolus dose of 1.5 mg/kg lidocaine, followed by continuous infusion at 1.5 mg/kg/h until discharge from the operating room. The control group received the same volume of normal saline. A 10 ml sample of venous blood was drawn, and the lymphocytes were isolated using Ficoll‑paque 1 day prior to surgery, at discharge from the operating room and 48 h post‑surgery. The proliferation rate of the lymphocytes was assessed using a Cell Counting Kit‑8 assay and was found to be higher in the lidocaine group. The early apoptosis of lymphocytes was attenuated following lidocaine treatment at 48 h post‑surgery, as detected using flow cytometry with Annexin V‑fluorescein isothiocyanate/propidium iodide staining. The level of interferon (IFN)‑γ in the serum at 48 h was significantly decreased following surgery in the control group, compared with the pre‑surgical values (3.782 ± 0.282, vs. 4.089 ± 0.339 pg/ml, respectively) and the ratio of IFN‑γ to interleukin‑4 was well preserved in the lidocaine group. In conclusion, the present study demonstrated that the intraoperative systemic administration of lidocaine exerted a protective effect on CMI in patients with cervical cancer undergoing radical hysterectomy. This may be beneficial in reducing the occurrence of postoperative septic complications and tumor metastasis formation.

Comparison of semi-extended and standard lymph node dissection in radical prostatectomy: A single-institute experience.

PubMed

Hoshi, Senji; Hayashi, Natuho; Kurota, Yuuta; Hoshi, Kiyotsugu; Muto, Akinori; Sugano, Osamu; Numahata, Kenji; Bilim, Vladimir; Sasagawa, Isoji; Ohta, Shoichiro

2015-09-01

Standard lymphadenectomy for prostate cancer is limited to the obturator lymph nodes (LNs), although the internal and external iliac LNs represent the primary landing zone for prostatic lymphatic drainage. We performed anatomically semi-extended pelvic lymph node dissection (PLND) to assess the incidence of LN metastasis in cases of clinically localized prostate cancer. A total of 730 consecutive patients underwent radical prostatectomy with either semi-extended PLND, comprising 6 selective fields, namely the external iliac, internal iliac and obturator LNs bilaterally, or standard LND (obturator LNs alone). A total of 131 patients undergoing semi-extended PLND were compared with 599 patients undergoing standard LND. The patients were stratified into high-risk [prostate-specific antigen (PSA)>20 ng/ml, Gleason score (GS)≥8], intermediate-risk (PSA 10-20 ng/ml, GS=4+3) and low-risk (PSA<10 ng/ml, GS≤3+4) subgroups. Following semi-extended LND, positive LNs were detected in 12/61 (20%) of the high-risk, 1/30 (3%) of the intermediate-risk and 0/40 (0%) of the low-risk cases. Following standard LND, positive LNs were detected in 13/182 (7%) of the high-risk, 1/164 (0.6%) of the intermediate-risk and 0/253 (0%) of the low-risk cases. In high-risk patients, the detection rate of LN metastasis was significantly higher following extended LND compared with standard LND (P<0.01). In 9 of 13 patients (69%), metastases were identified in the internal and external iliac regions, despite negative obturator LNs. There were no significant differences regarding intraoperative and postoperative complications or blood loss in the two groups. There was no lymphocele formation in patients undergoing either standard or semi-extended LND. Extended pelvic LND (PLND) is associated with a high rate of LN metastasis detection outside the fields of standard LND in cases with clinically localized prostate cancer. Therefore, LND including the internal and external iliac LNs should be performed in all patients with high-risk prostate cancer; however, in the low-risk group, PLND may be omitted.

Retrospective analysis of outcome differences in preoperative concurrent chemoradiation with or without elective nodal irradiation for esophageal squamous cell carcinoma.

PubMed

Hsu, Feng-Ming; Lee, Jang-Ming; Huang, Pei-Ming; Lin, Chia-Chi; Hsu, Chih-Hung; Tsai, Yu-Chieh; Lee, Yung-Chie; Chia-Hsien Cheng, Jason

2011-11-15

To evaluate the efficacy and patterns of failure of elective nodal irradiation (ENI) in patients with esophageal squamous cell carcinoma (SCC) undergoing preoperative concurrent chemoradiation (CCRT) followed by radical surgery. We retrospectively studied 118 patients with AJCC Stage II to III esophageal SCC undergoing preoperative CCRT (median, 36 Gy), followed by radical esophagectomy. Of them, 73 patients (62%) had ENI and 45 patients (38%) had no ENI. Patients with ENI received radiotherapy to either supraclavicular (n = 54) or celiac (n = 19) lymphatics. Fifty-six patients (57%) received chemotherapy with paclitaxel plus cisplatin. The 3-year progression-free survival, overall survival, and patterns of failure were analyzed. Distant nodal recurrence was classified into M1a and M1b regions. A separate analysis using matched cases was conducted. The median follow-up was 38 months. There were no differences in pathological complete response rate (p = 0.12), perioperative mortality rate (p = 0.48), or delayed Grade 3 or greater cardiopulmonary toxicities (p = 0.44), between the groups. More patients in the non-ENI group had M1a failure than in the ENI group, with 3-year rates of 11% and 3%, respectively (p = 0.05). However, the 3-year isolated distant nodal (M1a + M1b) failure rates were not different (ENI, 10%; non-ENI, 14%; p = 0.29). In multivariate analysis, pathological nodal status was the only independent prognostic factor associated with overall survival (hazard ratio = 1.78, p = 0.045). The 3-year overall survival and progression-free survival were 45% and 45%, respectively, in the ENI group, and 52% and 43%, respectively, in the non-ENI group (p = 0.31 and 0.89, respectively). Matched cases analysis did not show a statistical difference in outcomes between the groups. ENI reduced the M1a failure rate but was not associated with improved outcomes in patients undergoing preoperative CCRT for esophageal SCC. Pathological nodal metastasis predicted poor outcome. Copyright © 2011 Elsevier Inc. All rights reserved.

Race and risk of metastases and survival after radical prostatectomy: Results from the SEARCH database.

PubMed

Freedland, Stephen J; Vidal, Adriana C; Howard, Lauren E; Terris, Martha K; Cooperberg, Matthew R; Amling, Christopher L; Kane, Christopher J; Aronson, William J

2017-11-01

Black race is associated with prostate cancer (PC) diagnosis and poor outcome. Previously, the authors reported that black men undergoing radical prostatectomy (RP) in equal-access hospitals had an increased risk of biochemical disease recurrence (BCR), but recurrences were equally aggressive as those occurring in white men. The authors examined the association between race and long-term outcomes after RP. Data regarding 1665 black men (37%) and 2791 white men (63%) undergoing RP were analyzed. Using Cox models, the authors tested the association between race and BCR, BCR with a prostate-specific antigen (PSA) doubling time <9 months (aggressive disease recurrence), metastases, PC-specific death, and overall death. At a median follow-up of 102 months, 1566 men (35%) developed BCR, 217 men (5%) experienced aggressive disease recurrence, 193 men (4%) developed metastases, and 1207 men (27%) had died, 107 of whom (2%) died of PC. White men were older and had a lower preoperative PSA level, a lower biopsy and pathological grade group, and more capsular penetration but less seminal vesicle invasion and positive surgical margins versus black men (all P<.05). Black men were found to have a more recent surgery year (P<.001). On univariable analysis, black race was associated with increased BCR (P = .003) and reduced overall death (P = .017). On multivariable analysis, black race was not found to be associated with BCR (hazard ratio [HR], 1.07; P = .26), aggressive recurrence (HR, 1.14; P = .42), metastasis (HR, 1.24; P = .21), PC-specific death (HR, 1.03; P = .91), or overall death (HR, 1.03; P = .67). Among men undergoing RP at equal-access centers, although black men were found to have an increased risk of BCR, they had similar risks of aggressive disease recurrence, metastasis, and PC-specific death compared with white men, and the risk of BCR was found to be similar after controlling for risk parameters. Longer follow-up is needed to confirm these findings. Cancer 2017;123:4199-4206. © 2017 American Cancer Society. © 2017 American Cancer Society.

Differences in microRNA expression during tumor development in the transition and peripheral zones of the prostate

PubMed Central

2013-01-01

Background The prostate is divided into three glandular zones, the peripheral zone (PZ), the transition zone (TZ), and the central zone. Most prostate tumors arise in the peripheral zone (70-75%) and in the transition zone (20-25%) while only 10% arise in the central zone. The aim of this study was to investigate if differences in miRNA expression could be a possible explanation for the difference in propensity of tumors in the zones of the prostate. Methods Patients with prostate cancer were included in the study if they had a tumor with Gleason grade 3 in the PZ, the TZ, or both (n=16). Normal prostate tissue was collected from men undergoing cystoprostatectomy (n=20). The expression of 667 unique miRNAs was investigated using TaqMan low density arrays for miRNAs. Student’s t-test was used in order to identify differentially expressed miRNAs, followed by hierarchical clustering and principal component analysis (PCA) to study the separation of the tissues. The ADtree algorithm was used to identify markers for classification of tissues and a cross-validation procedure was used to test the generality of the identified miRNA-based classifiers. Results The t-tests revealed that the major differences in miRNA expression are found between normal and malignant tissues. Hierarchical clustering and PCA based on differentially expressed miRNAs between normal and malignant tissues showed perfect separation between samples, while the corresponding analyses based on differentially expressed miRNAs between the two zones showed several misplaced samples. A classification and cross-validation procedure confirmed these results and several potential miRNA markers were identified. Conclusions The results of this study indicate that the major differences in the transcription program are those arising during tumor development, rather than during normal tissue development. In addition, tumors arising in the TZ have more unique differentially expressed miRNAs compared to the PZ. The results also indicate that separate miRNA expression signatures for diagnosis might be needed for tumors arising in the different zones. MicroRNA signatures that are specific for PZ and TZ tumors could also lead to more accurate prognoses, since tumors arising in the PZ tend to be more aggressive than tumors arising in the TZ. PMID:23890084

Jaundice as a prognostic factor in patients undergoing radical treatment for carcinomas of the ampulla of Vater.

PubMed

Zhou, Jianguo; Zhang, Qian; Li, Peng; Shan, Yi; Zhao, Dongbing; Cai, Jianqiang

2014-01-01

Carcinomas of the ampulla of Vater (CAV) is a relatively rare malignant gastrointestinal tumor, and its postoperative prognostic factors have been well studied. However, as its first symptom, the impact of jaundice on the prognosis of CAV is not so clear. This study aims to explore the role of jaundice as a prognostic factor in patients undergoing radical treatment for CAV. The clinical data of 195 patients with CAV who were treated in the Cancer Hospital, Chinese Academy of Medical Sciences & Peking Union Medical College, from January 1989 to January 2013 were retrospectively analyzed. Among them, 170 patients with pathologically confirmed CAV entered the statistical analysis. Jaundice was defined as a total bilirubin serum concentration of ≥ 3 mg/dl. Result Of these 170 patients, 99 (58.20%) had jaundice at presentation. Jaundice showed significant correlations with tumor differentiation (P = 0.002), lymph node metastasis (P = 0.016), pancreatic invasion (P = 0.000), elevated preoperative CA199 (P = 0.000), depth of invasion (P = 0.000), and tumor stage (P = 0.000). There were more patients with pancreatic invasion in the jaundice group than in the non-jaundice group. Also, lymph node metastasis was more common in the jaundice group (n = 26) than in the non-jaundice group (n = 8). The non-jaundice group had significant better overall 5-year disease-free survival (72.6%) than the jaundice group (41.2%, P = 0.013). Jaundice was not significantly correlated with the postoperative bleeding (P = 0.050). Jaundice in patients with CAV often predicts more advanced stages and poorer prognoses. Pancreatic invasion and lymph node metastasis are more common in CAV patients with jaundice. Jaundice is not a risk factor for postoperative bleeding and preoperative biliary drainage cannot reduce the incidence of postoperative complications.

Effect of auricular pellet acupressure on antioxidative systems in high-risk diabetes mellitus.

PubMed

Liu, Chi-Feng; Yu, Lee-Fen; Lin, Chia-Hsien; Lin, Song-Chow

2008-04-01

Free radicals and lipid peroxides, both of which are easily formed in the diabetic state, play an important role in the development of diabetic complications. Antioxidative therapy may help prevent diabetic complications caused by lipoperoxidation and free-radical formation in diabetes mellitus (DM). A number of findings suggest that oxidative stress exists in persons with high-risk DM. Auricular pellet acupressure has reportedly been an effective treatment method for a variety of medical conditions, including anxiety, juvenile myopia, essential hypertension, and senile vascular dementia. However, its effects on antioxidative enzymes have not been elucidated. We therefore evaluated the impact of auricular pellet acupressure on antioxidative status in persons with high-risk DM. Our study involved 69 persons with high-risk DM, who were allocated either to undergo acupressure as active treatment for the experimental group or to a control group. The experimental group in the study received auricular pellet acupressure three times daily for 5 consecutive days. After a 2-day rest period, the procedure was performed on the contralateral ear. Acupressure was performed twice on each ear, with each application followed by its application to the contralateral ear, over a total treatment period of 20 days. The control groups did not undergo auricular pellet acupressure. At the end of the 20-day period of treatment of the experimental group, blood was collected from all of the study participants for assay of serum superoxide dismutase (SOD) and catalase concentrations, as was also done for the control group. Serum concentrations of SOD (p < 0.05) and catalase (p < 0.0001) were significantly higher in the experimental group than in the control group. Our findings suggest that auricular pellet acupressure can increase the concentration of antioxidative enzymes in persons with high-risk DM.

Pharmacodynamic and pharmacokinetic neoadjuvant study of hedgehog pathway inhibitor Sonidegib (LDE-225) in men with high-risk localized prostate cancer undergoing prostatectomy.

PubMed

Ross, Ashley E; Hughes, Robert M; Glavaris, Stephanie; Ghabili, Kamyar; He, Ping; Anders, Nicole M; Harb, Rana; Tosoian, Jeffrey J; Marchionni, Luigi; Schaeffer, Edward M; Partin, Alan W; Allaf, Mohamad E; Bivalacqua, Trinity J; Chapman, Carolyn; O'Neal, Tanya; DeMarzo, Angelo M; Hurley, Paula J; Rudek, Michelle A; Antonarakis, Emmanuel S

2017-11-28

To determine the pharmacodynamic effects of Sonidegib (LDE-225) in prostate tumor tissue from men with high-risk localized prostate cancer, by comparing pre-surgical core-biopsy specimens to tumor tissue harvested post-treatment at prostatectomy. We conducted a prospective randomized (Sonidegib vs. observation) open-label translational clinical trial in men with high-risk localized prostate cancer undergoing radical prostatectomy. The primary endpoint was the proportion of patients in each arm who achieved at least a two-fold reduction in GLI1 mRNA expression in post-treatment versus pre-treatment tumor tissue. Secondary endpoints included the effect of pre-surgical treatment with Sonidegib on disease progression following radical prostatectomy, and safety. Fourteen men were equally randomized (7 per arm) to either neoadjuvant Sonidegib or observation for 4 weeks prior to prostatectomy. Six of seven men (86%) in the Sonidegib arm (and none in the control group) achieved a GLI1 suppression of at least two-fold. In the Sonidegib arm, drug was detectable in plasma and in prostatic tissue; and median intra-patient GLI1 expression decreased by 63-fold, indicating potent suppression of Hedgehog signaling. Sonidegib was well tolerated, without any Grade 3-4 adverse events observed. Disease-free survival was comparable among the two arms (HR = 1.50, 95% CI 0.26-8.69, P = 0.65). Hedgehog pathway activity (as measured by GLI1 expression) was detectable at baseline in men with localized high-risk prostate cancer. Sonidegib penetrated into prostatic tissue and induced a >60-fold suppression of the Hedgehog pathway. The oncological benefit of Hedgehog pathway inhibition in prostate cancer remains unclear.

Impact of prostate weight on probability of positive surgical margins in patients with low-risk prostate cancer after robotic-assisted laparoscopic radical prostatectomy.

PubMed

Marchetti, Pablo E; Shikanov, Sergey; Razmaria, Aria A; Zagaja, Gregory P; Shalhav, Arieh L

2011-03-01

To evaluate the impact of prostate weight (PW) on probability of positive surgical margin (PSM) in patients undergoing robotic-assisted radical prostatectomy (RARP) for low-risk prostate cancer. The cohort consisted of 690 men with low-risk prostate cancer (clinical stage T1c, prostate-specific antigen <10 ng/mL, biopsy Gleason score ≤6) who underwent RARP with bilateral nerve-sparing at our institution by 1 of 2 surgeons from 2003 to 2009. PW was obtained from the pathologic specimen. The association between probability of PSM and PW was assessed with univariate and multivariate logistic regression analysis. A PSM was identified in 105 patients (15.2%). Patients with PSM had significant higher prostate-specific antigen (P = .04), smaller prostates (P = .0001), higher Gleason score (P = .004), and higher pathologic stage (P < .0001). After logistic regression, we found a significant inverse relation between PSM and PW (OR 0.97%; 95% confidence interval [CI] 0.96, 0.99; P = .0003) in univariate analysis. This remained significant in the multivariate model (OR 0.98%; 95% CI 0.96, 0.99; P = .006) adjusting for age, body mass index, surgeon experience, pathologic Gleason score, and pathologic stage. In this multivariate model, the predicted probability of PSM for 25-, 50-, 100-, and 150-g prostates were 22% (95% CI 16%, 30%), 13% (95% CI 11%, 16%), 5% (95% CI 1%, 8%), and 1% (95% CI 0%, 3%), respectively. Lower PW is independently associated with higher probability of PSM in low-risk patients undergoing RARP with bilateral nerve-sparing. Copyright © 2011 Elsevier Inc. All rights reserved.

Robotic radical prostatectomy in overweight and obese patients: oncological and validated-functional outcomes.

PubMed

Wiltz, Aimee L; Shikanov, Sergey; Eggener, Scott E; Katz, Mark H; Thong, Alan E; Steinberg, Gary D; Shalhav, Arieh L; Zagaja, Gregory P; Zorn, Kevin C

2009-02-01

To determine the impact of body mass index (BMI) on perioperative functional and oncological outcomes in patients undergoing robotic laparoscopic radical prostatectomy (RLRP) when stratified by BMI. Data were collected prospectively for 945 consecutive patients undergoing RLRP. Patients were evaluated with the UCLA-PCI-SF36v2 validated-quality-of-life questionnaire preoperatively and postoperatively to 24 months. Patients were stratified by BMI as normal weight (BMI < 25 kg/m(2)), overweight (BMI = 25 to < 30 kg/m(2)) and obese (BMI > or = 30 kg/m(2)) for outcomes analysis. Preoperatively, obese men had a significantly greater percentage of medical comorbidities (P < .01) as well as a baseline erectile dysfunction (lower mean baseline Sexual Health Inventory for Men score [P = .01] and UCLA-PCI-SF36v2 sexual function domain scores [P = .01]). Mean operative time was significantly longer in obese patients when compared with normal and overweight men (234 minutes vs 217 minutes vs 214 minutes; P = .0003). Although overall complication rates were comparable between groups, a greater incidence of case abortion caused by pneumoperitoneal pressure with excessive airway pressures was noted in obese men. Urinary continence and potency outcomes were significantly lower for obese men at both 12 and 24 months (all P < .05). In this series, obese men experienced a longer operative time, particularly during the initial robotic experience. As such, surgeons early in their RLRP learning curve should proceed cautiously with surgery in these technically more difficult patients or reserve such cases until the learning curve has been surmounted. These details, including inferior urinary and sexual outcomes, should be discussed with obese patients during preoperative counseling.

Effect of dexmedetomidine on intraocular pressure in patients undergoing robot-assisted laparoscopic radical prostatectomy under total intravenous anesthesia: A randomized, double blinded placebo controlled clinical trial.

PubMed

Kitamura, Sakiko; Takechi, Kenichi; Nishihara, Tasuku; Konishi, Amane; Takasaki, Yasushi; Yorozuya, Toshihiro

2018-06-05

To study the effects of intraoperative dexmedetomidine on the intraocular pressure (IOP) in patients undergoing robot-assisted laparoscopic radical prostatectomy (RALRP) under propofol-remifentanil anesthesia. Double-blind, randomized controlled trial. Operating room. Forty consenting male patients aged ≥20 to <80 years with American Society of Anesthesiologists physical status classes I and II. The patients were randomly assigned to either dexmedetomidine (DEX) (n = 20) or control (n = 20) group. Anesthesia was induced and maintained using propofol, remifentanil, and rocuronium. In the dexmedetomidine group, dexmedetomidine was administered at 0.4 μg/kg/h immediately after anesthesia induction until the end of the surgery, whereas normal saline was administered as placebo in the control group. IOP was measured using a rebound tonometer. Time points of measuring IOP were as follows: T1: before anesthesia induction, T2: 5 min after intubation, T3: 60 min after placing patient in the Trendelenburg position, T4: 120 min after placing patient in the Trendelenburg position, T5: 180 min after placing patient in the Trendelenburg position, T6: 5 min after placing patient in a horizontal position, T7: 5 min after extubation, and T8: 30 min after extubation. A linear mixed model analysis demonstrated a significant intergroup difference in IOP over time and during pneumoperitoneum in the steep Trendelenburg position. IOP at T5 was significantly lower in the dexmedetomidine group than in the control group even after post-hoc analysis in the steep Trendelenburg position periods with Bonferroni correction. Dexmedetomidine combined with propofol decreases IOP in the steep Trendelenburg position during RALRP. Copyright © 2018 Elsevier Inc. All rights reserved.

Multi-institutional analysis of renal function outcomes following radical nephroureterectomy and partial ureterectomy for upper tract urothelial carcinoma.

PubMed

Singla, Nirmish; Gayed, Bishoy A; Bagrodia, Aditya; Krabbe, Laura-Maria; Palazzi, Kerrin L; Mirheydar, Hossein; Harrow, Brian; Jacobs, Corbin; Youssef, Ramy; Darwish, Oussama; Sagalowsky, Arthur; Lotan, Yair; Derweesh, Ithaar; Margulis, Vitaly

2015-06-01

To compare renal function outcomes in patients undergoing radical nephroureterectomy (RNU) or partial (distal) ureterectomy (PU) for upper tract urothelial carcinoma (UTUC). Clinicopathologic data of patients undergoing RNU or PU for UTUC from 1998 to 2012 were compiled. Glomerular filtration rate was calculated preoperatively and postoperatively using the Modification of Diet in Renal Disease equation. We defined "event" as new-onset stage III chronic kidney disease (CKD) or worsening of CKD stage with preexisting CKD. Event-free survival was assessed with Kaplan-Meier methods. Cox regression analyses were performed to identify predictors of events. In total, 193 patients underwent RNU (n = 143) or PU (n = 50) over a median follow-up of 25.9 months. Overall, 15% of patients died of UTUC. High tumor grade (85.9% vs. 66.0%, P = 0.003) and locally advanced stage (>pT2, 37.8% vs. 18.0%, P = 0.014) were significantly more frequent in the RNU cohort. Stage III or higher CKD was present in 61% of RNU patients vs. 48% of PU patients (P = 0.135) at baseline. Although total event rate was higher in the PU cohort (66% vs. 43.4%, P = 0.008), event rates within the first 3 months of surgery were similar between the groups (P = 0.572). Adjuvant chemotherapy was the only predictor of events on Cox regression. Rates of new-onset CKD or worsening of CKD stage were similar in patients treated with RNU and PU. Adjuvant chemotherapy may have a more significant effect on renal outcomes than surgical approach, warranting further investigation. Consideration should be given to preoperative chemotherapy, as adjuvant chemotherapy is limited by decreased renal function following surgery. Copyright © 2015 Elsevier Inc. All rights reserved.

Incidence and perioperative risk factors for early acute kidney injury after radical cystectomy and urinary diversion.

PubMed

Furrer, Marc A; Schneider, Marc P; Burkhard, Fiona C; Wuethrich, Patrick Y

2018-06-01

Early postoperative acute kidney injury (AKI) is associated with increased morbidity and mortality following major surgery. Only few reports exist on postoperative AKI and specifically its risk factors after radical cystectomy (RC) and urinary diversion (UD). We aimed to identify risk factors for AKI in patients undergoing RC and UD. In an observational single-center cohort study, 912 consecutive bladder cancer patients undergoing RC and UD from 2000 to 2016 were evaluated for risk factors for AKI. Multiple logistic regression analysis was performed to model the association between variables and AKI. Early postoperative AKI occurred in 100/912 patients (11%). An increased risk was seen in patients with surgery lasting>400minutes, male and obese patients (>25kg/m²). Independent predictors were duration of surgery (P = 0.020), intraoperative blood loss (P = 0.049), preoperative serum creatinine values (P = 0.004), intraoperative administration of crystalloids (P = 0.032), body mass index (P = 0.031), and fluid balance (P = 0.006). Patients with AKI had a longer hospitalization time (18d vs 17d, P = 0.040). Limitations include the potential bias due to the design as a case series with prospectively collected data with some missing values. An increased risk for AKI was seen in patients with an operative time>400 minutes. Hence, in this group of patients the role of postoperative fluid management for preserving renal function should be considered. Further independent predictors of postoperative AKI were male sex, obesity, intraoperative blood loss, and a low preoperative plasma creatinine. So specially in male and obese patients, optimized perioperative nephroprotective strategies are of importance. Copyright © 2018 Elsevier Inc. All rights reserved.

Comparison of the post-operative analgesic effect of paravertebral block, pectoral nerve block and local infiltration in patients undergoing modified radical mastectomy: A randomised double-blind trial

PubMed Central

Syal, Kartik; Chandel, Ankita

2017-01-01

Background and Aims: Paravertebral block, pectoral nerve (Pecs) block and wound infiltration are three modalities for post-operative analgesia following breast surgery. This study compares the analgesic efficacy of these techniques for post-operative analgesia. Methods: Sixty-five patients with American Society of Anesthesiologists’ physical status 1 or 2 undergoing modified radical mastectomy with axillary dissection were recruited for the study. All patients received 21 mL 0.5% bupivacaine with adrenaline in the technique which was performed at the end of the surgery prior to extubation. Patients in Group 1 (local anaesthetic [LA], n = 22) received infiltration at the incision site after surgery, Group 2 patients (paravertebral block [PVB], n = 22) received ultrasound-guided ipsilateral paravertebral block while Group 3 patients [PECT] (n = 21) received ultrasound-guided ipsilateral Pecs blocks I and II. Patients were evaluated for pain scores at 0, 2, 4, 6, 12 and 24 h, duration of post-operative analgesia and rescue analgesic doses required. Non-normally distributed data were analysed using the Kruskal-Wallis test and Analysis of variance for normal distribution. Results: The post-operative visual analogue scale scores were lower in PVB group compared with others at 0, 2, 4, 12 and 24 h (P < 0.05). Mean duration of analgesia was significantly prolonged in PVB group (P < 0.001) with lesser rescue analgesic consumption up to 24 h. Conclusion: Ultrasound-guided paravertebral block reduces post-operative pain scores, prolongs the duration of analgesia and decreases demands for rescue analgesics in the first 24 h of post-operative period compared to ultrasound-guided Pecs block and local infiltration block. PMID:28890559

Comparison of the post-operative analgesic effect of paravertebral block, pectoral nerve block and local infiltration in patients undergoing modified radical mastectomy: A randomised double-blind trial.

PubMed

Syal, Kartik; Chandel, Ankita

2017-08-01

Paravertebral block, pectoral nerve (Pecs) block and wound infiltration are three modalities for post-operative analgesia following breast surgery. This study compares the analgesic efficacy of these techniques for post-operative analgesia. Sixty-five patients with American Society of Anesthesiologists' physical status 1 or 2 undergoing modified radical mastectomy with axillary dissection were recruited for the study. All patients received 21 mL 0.5% bupivacaine with adrenaline in the technique which was performed at the end of the surgery prior to extubation. Patients in Group 1 (local anaesthetic [LA], n = 22) received infiltration at the incision site after surgery, Group 2 patients (paravertebral block [PVB], n = 22) received ultrasound-guided ipsilateral paravertebral block while Group 3 patients [PECT] ( n = 21) received ultrasound-guided ipsilateral Pecs blocks I and II. Patients were evaluated for pain scores at 0, 2, 4, 6, 12 and 24 h, duration of post-operative analgesia and rescue analgesic doses required. Non-normally distributed data were analysed using the Kruskal-Wallis test and Analysis of variance for normal distribution. The post-operative visual analogue scale scores were lower in PVB group compared with others at 0, 2, 4, 12 and 24 h ( P < 0.05). Mean duration of analgesia was significantly prolonged in PVB group ( P < 0.001) with lesser rescue analgesic consumption up to 24 h. Ultrasound-guided paravertebral block reduces post-operative pain scores, prolongs the duration of analgesia and decreases demands for rescue analgesics in the first 24 h of post-operative period compared to ultrasound-guided Pecs block and local infiltration block.

Return to work following robot-assisted laparoscopic and open retropubic radical prostatectomy: A single-center cohort study to compare duration of sick leave.

PubMed

von Mechow, Stefanie; Graefen, Markus; Haese, Alexander; Tennstedt, Pierre; Pehrke, Dirk; Friedersdorff, Frank; Beyer, Burkhard

2018-06-01

To compare the duration of sick leave in patients with localized prostate cancer after robot-assisted radical prostatectomy (RARP) and open retropubic RP (ORP) at a German high-volume prostate cancer center. The data of 1,415 patients treated with RP at Martini Klinik, Prostate Cancer Center between 2012 and 2016 were, retrospectively, analyzed. Information on employment status, monthly revenues and days of work missed due to sickness were assessed via online questionnaire. Additional data were retrieved from our institutional database. Medians and interquartile ranges (IQR) were reported for continuous data. Cox proportional hazard analysis was performed to compare both surgical techniques for return to work time after RP. Median time elapsed between surgery and return to work comprised 42 days in patients undergoing RARP (IQR: 21-70) and ORP (IQR: 28-84, P = 0.05). In Cox regression analysis, surgical approach showed no impact on return to work time (RARP vs. ORP hazard ratio = 1, 95% CI: 0.91-1.16, P = 0.69). Return to work time was significantly associated with employment status, physical workload and monthly income (all P<0.001). Limitation of this study is the nonrandomized design in a single-center. As the surgical approach did not show any influence on the number of days missed from work in patients undergoing RP, no superiority of either RARP or ORP could be identified for return to work time in a German cohort. Both surgical approaches are safe options usually allowing the patients to resume normal activities including work after an appropriate convalescence period. Copyright © 2018 Elsevier Inc. All rights reserved.

Reconstruction of the pelvic floor and perineum with human acellular dermal matrix and thigh flaps following pelvic exenteration.

PubMed

Said, Hakim K; Bevers, Michael; Butler, Charles E

2007-12-01

Patients who undergo pelvic floor resection as treatment for recurrent cancer following radiation therapy have increased rates of complications, particularly if permanent prosthetic mesh is used for reconstruction. Human acellular dermal matrix (HADM), commonly used for reconstruction in other torso locations, is associated with lower rates of complications (including infection, adhesions and cutaneous exposure) than synthetic mesh. We describe an effective technique to reconstruct the pelvic floor and perineum with HADM and thigh-based flaps following pelvic exenteration and radical vulvectomy. A 75-year-old woman underwent radical resection of the pelvic floor and perineum to treat recurrent vulvar squamous cell carcinoma and osteoradionecrosis. The pelvic floor and perineal soft tissue defect were reconstructed with HADM (AlloDerm; LifeCell Corporation, Branchburg, NJ) and bilateral, thigh-based tissue flaps, respectively. Despite a large resection, previous irradiation therapy and bacterial contamination the wounds healed without complications. Reconstruction of pelvic floor defects using HADM is an option when wound conditions are unfavorable for the use of permanent prosthetic meshes.

Understanding the Reaction Chemistry of 2,2':5',2''-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Understanding the Reaction Chemistry of 2,2':5',2"-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Catalytic routes and oxidation mechanisms in photoreforming of polyols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanwald, Kai E.; Berto, Tobias F.; Eisenreich, Wolfgang

2016-12-01

Photocatalytic reforming of biomass-derived oxygenates leads to H 2 generation and evolution of CO 2 via parallel formation of organic intermediates through anodic oxidations on a Rh/TiO 2 photocatalyst. The reaction pathways and kinetics in the photoreforming of C 3–C 6 polyols were explored. Polyols are converted via direct and indirect hole transfer pathways resulting in (i) oxidative rupture of C–C bonds, (ii) oxidation to a-oxygen functionalized aldoses and ketoses (carbonyl group formation) and (iii) light-driven dehydration. Direct hole transfer to chemisorbed oxygenates on terminal Ti(IV)-OH groups, generating alkoxy-radicals that undergo ß-C–C-cleavage, is proposed for the oxidative C–C rupture. Carbonylmore » group formation and dehydration are attributed to indirect hole transfer at surface lattice oxygen sites [Ti_ _ _O_ _ _Ti] followed by the generation of carbon-centered radicals. Polyol chain length impacts the contribution of the oxidation mechanisms favoring the C–C bond cleavage (internal preferred over terminal) as the dominant pathway with higher polyol carbon number.« less

Light-Induced Toxic Effects of Tamoxifen: A Chemotherapeutic and Chemopreventive Agent.

PubMed

Wang, Lei; Wang, Shuguang; Yin, Jun-Jie; Fu, Peter P; Yu, Hongtao

2009-01-01

Tamoxifen is a powerful drug used to treat breast cancer patients, and more than 500,000 women in the U. S. are being treated with this drug. In our study, tamoxifen is found to be photomutagenic in Salmonella typhimurium TA102 at concentrations as low as 0.08 muM and reaches maximum photomutagenicity at 0.4 muM under a light dose equivalent to 20 min sunlight. These concentrations are comparable to the plasma tamoxifen concentration of 0.4 to 3 muM for patients undergoing tamoxifen therapy. The toxicity seems to be the result of DNA damage and/or lipid peroxidation caused by light irradiation of tamoxifen. The DNA damage caused by irradiation of PhiX174 DNA in the presence of tamoxifen appears to be formation of DNA-tamoxifen covalent adducts, not single strand/double strand cleavages, and there is no oxygen involvement. This is confirmed by EPR experiments that carbon-centerd radicals are formed by light irradiation of tamoxifen and there is no singlet oxygen formation. Although superoxide radical is formed, it is not involved in DNA damage.

NIR photocleavage of the Si-C bond in axial Si-phthalocyanines.

PubMed

Doane, Tennyson; Cheng, Yu; Sodhi, Nipun; Burda, Clemens

2014-11-13

The use of light-triggered photolysis provides a powerful tool for unique syntheses and for applications that require remote operation such as drug delivery or molecular switches. Here, we describe the photochemistry of a recently developed alkylsilicon phthalocyanine Pc 227, which undergoes an exchange of the alkyl ligand for a ligand derived from the solvent when the axial Si-C bond is photolyzed in a solvent with low-energy visible light. In this work with methanol as the solvent, we investigate the formation of the methoxy analogue of the therapeutic drug Pc 4, (termed Pc 233) upon irradiation. Using steady-state spectroscopy and characterization of the photoproducts, the competing pathways between direct ligand exchange on the central silicon atom and delocalization of the radical produced by homolysis on the phthalocyanine ring is observed. The delocalized radical intermediate is quite long-lived. At long times this intermediate decomposes without significant formation of Pc 233. The results of this investigation provide insights into recent work utilizing Pc 227 for drug delivery applications and for future work on the use of phthalocyanines as long-wavelength phototriggers.

Recyclable crosslinked polymer networks with full property recovery made via one-step controlled radical polymerization

NASA Astrophysics Data System (ADS)

Jin, Kailong; Li, Lingqiao; Torkelson, John

Rubber tires illustrate well the issues ranging from economic loss to environmental problems and sustainability issues that arise with spent, covalently crosslinked polymers. A nitroxide-mediated polymerization (NMP) strategy has been developed that allows for one-step synthesis of recyclable crosslinked polymers from monomers or polymers that contain carbon-carbon double bonds amenable to radical polymerization. Resulting materials possess dynamic alkoxyamine crosslinks that undergo reversible decrosslinking as a function of temperature. Using polybutadiene as starting material, and styrene, an appropriate nitroxide molecule and bifunctional initiator for initial crosslinking, a model for tire rubber can be produced by reaction at temperatures comparable to those employed in tire molding. Upon cooling, the crosslinks are made permanent due to the extraordinarily strong temperature dependence of the reverisible nitroxide capping and uncapping reaction. Based on thermomechanical property characterization, when the original crosslinked model rubber is chopped into bits and remolded in the melt state, a well-consolidated material is obtained which exhibits full recovery of properties reflecting crosslink density after multiple recycling steps.

Reduction in PSA messenger-RNA expression and clinical recurrence in patients with prostatic cancer undergoing neoadjuvant therapy before radical prostatectomy

PubMed Central

Grasso, Marco; Lania, Caterina; Blanco, Salvatore; Baruffi, Marco; Mocellin, Simone

2004-01-01

Background We assessed the incidence of micro-metastases at surgical margins (SM) and pelvic lymph nodes (LN) in patients submitted to radical retropubic prostatectomy (RP) after neoadjuvant therapy (NT) or to RP alone. We compared traditional staging to molecular detection of PSA using Taqman-based quantitative real-time PCR (qrt-PCR) never used before for this purpose. Methods 29 patients were assigned to NT plus RP (arm A) or RP alone (arm B). Pelvic LN were dissected for qrt-PCR analysis, together with right and left lateral SM. Results 64,3% patients of arm B and 26.6% of arm A had evidence of PSA mRNA expression in LN and/or SM. 17,2% patients, all of arm B, had biochemical recurrence. Conclusions Qrt-PCR may be more sensitive, compared to conventional histology, in identifying presence of viable prostate carcinoma cells in SM and LN. Gene expression of PSA in surgical periprostatic samples might be considered as a novel and reliable indicator of minimal residual disease after NT. PMID:15104791

On the formation of the ·CH 2CH 2CH=NH 2+ distonic radical cation upon ionization of cyclopropylamine and allylamine

NASA Astrophysics Data System (ADS)

Nguyen, Minh Tho; Creve, Steven; Ha, Tae-Kyu

1998-08-01

Ab initio molecular orbital and density functional theory calculations have been applied to determine the relative stability of the cyclopropylamine 1 and allylamine (CH 2=CHCH 2NH 2+·2) radical cations and their isomers. It is confirmed that, upon ionization, 1 undergoes barrier-free ring-opening giving the distonic species ·CH 2CH 2CH=NH 2+3. 2 also rearranges by a 1,2-H-shift to the more stable 3 (by 70 kJ/mol) which is, however, less stable than the 1-aminopropene ion (CH 3-CH=CH-NH 2+·4) by 60 kJ/mol. The transition structure TS 2/3 lies 40 kJ/mol higher in energy than TS 3/4. Although QCISD and B3LYP calculations of isotropic hyperfine coupling constants agree reasonably with observed values, supporting the presence of the distonic 3 in ESR matrix experiments, the exclusive observation of 3, but not 4, is intriguing. This emphasizes the role of the matrix in stabilizing 3.

Reaction of Pentanol isomers with OH radical – A theoretical perspective

NASA Astrophysics Data System (ADS)

Aazaad, Basheer; Lakshmipathi, Senthilkumar

2018-05-01

The stability of all the three isomeric forms of Pentanol has been examined with relative energy analysis. Even though 2-Pentanol is predicted to be most stable isomeric form, all the three isomeric forms undergo hydrogen atom abstraction reaction with OH radical. Among the proposed 18 different hydrogen atom abstraction reaction, the abstraction from CH2 and CH functional group is found to be a favourable reactive site with low energy barrier in M06-2X/6-311+G(d,p) level of theory. Wiberg bond order analysis shows all the abstraction reactions are concreted but not synchronic in nature. Using force analysis, the calculated work done of individual reaction regions illustrates that structural rearrangements drive the reaction with higher contribution to the energy barrier. The rate constant calculated at M06-2X method for the most favourable reaction is well matched with available experimental data. Using the reported atmospheric OH concentration (1 × 106 molecules/cm3), the life time of 1-Pentanol, 2-Pentanol and 3-Pentanol has calculated to be 18.66, 0.36 and 2.86 days, respectively.

Contemporary management of patients with high-risk non-muscle-invasive bladder cancer who fail intravesical BCG therapy.

PubMed

Yates, D R; Rouprêt, M

2011-08-01

It is advocated that patients with high-risk non-muscle-invasive bladder cancer (NMIBC) receive an adjuvant course of intravesical Bacille Calmette-Guerin (BCG) as first-line treatment. However, a substantial proportion of patients will 'fail' BCG, either early with persistent (refractory) disease or recur late after a long disease-free interval (relapsing). Guideline recommendation in the 'refractory' setting is radical cystectomy, but there are situations when extirpative surgery is not feasible due to competing co-morbidity, a patient's desire for bladder preservation or reluctance to undergo surgery. In this review, we discuss the contemporary management of NMIBC in patients who have failed prior BCG and are not suitable for radical surgery and highlight the potential options available. These options can be categorised as immunotherapy, chemotherapy, device-assisted therapy and combination therapy. However, the current data are still inadequate to formulate definitive recommendations, and data from ongoing trials and maturing studies will give us an insight into whether there is a realistic efficacious second-line treatment for patients who fail intravesical BCG but are not candidates for definitive surgery.

Thermal, photonic and magnetic studies of thiazyl radicals

NASA Astrophysics Data System (ADS)

Beldjoudi, Yassine

Chapter 1 provides an overview of the area of 1,2,3,5-dithiadiazolyl (DTDA) radical chemistry which is central to this thesis, including a review of the crystal engineering principles and the physical properties of DTDA radicals, focusing on structure-property relationships. The magnetic properties of the beta-polymorph of p-NCC 6F4CNSSN have been almost exhaustively studied since 1993 when it was found to exhibit the highest magnetic ordering temperature (T N = 36 K) for an organic magnet. Conversely the structure and physical properties of the alpha-polymorph have barely been explored. The conditions for the selective preparation of alpha and beta-polymorphs of this radical are investigated in Chapter 2. The relative polymorph stability is probed through detailed DSC and PXRD studies and the magnetic properties of the alpha-polymorph fully examined through dc and ac susceptibility measurements coupled with heat capacity studies. In Chapters 3 and 4, systematic structural studies on the variation of substituent groups are undertaken, comprising a series of alkoxy-functionalised perfluorophenyl DTDA radicals, p-ROC6F4CNSSN (R = Me, Et, Pr, Bu) and a comparison of the substitution pattern of the tolyl group on PhDTDA derivatives, MeC6H4C6H 4CNSSN and their polymorphs. These studies use a combination of single crystal and VT-PXRD, SQUID magnetometry and VT EPR spectroscopy combined with DSC measurements and computational studies to probe relative polymorph stabilities and magnetic properties. A new generation of DTDA radicals where the R substituent is "non-innocent" are described in Chapters 5 and 6. In Chapter 5 the synthesis and characterisation of a series of DTDA-functionalised polyaromatic hydrocarbons (PAH) are described and their polymorphism examined as well as their solution and solid state optical properties. These reveal fluorescence quantum efficiencies up to 50%. Radical stability can be enhanced through incorporation into polymer matrices (PMMA and PS) which retard hydrolysis and prototype OLEDs based on a fluorescent DTDA exhibiting a luminance of almost 2000 Cd/m2 is described. Chapter 6 describes two stilbene-based DTDA diradicals in which the potential for thermal and photochemical cis/trans isomerisation, ring closure or [2+2] cycloaddition was explored. Solution photochemistry reactions, monitored by 1H NMR, UV/vis and fluorescence studies and EPR spectroscopy) revealed a trans/cis isomerisation, followed by ring-closure to afford a dihydrophenanthrene intermediate which undergoes H-atom migration with quenching of radical paramagnetism. Subsequent thermal treatment affords a phenanthrene-based diradical species with an increase in sample paramagnetism. Chapter 7 provides a brief overview of the results obtained in this thesis, the insight that these results provide within this research area and the potential for future exploitation.

Photoreduction of Azoalkanes by Direct Hydrogen Abstraction from 1,4-Cyclohexadiene, Alcohols, Stannanes, and Silanes.

PubMed

Adam, Waldemar; Moorthy, Jarugu N.; Nau, Werner M.; Scaiano, J. C.

1997-11-14

A mechanistic investigation of the photoreduction of the n,pi triplet-excited azo chromophore has been carried out on azoalkanes 1, which exhibit efficient intersystem-crossing quantum yields (ca. 0.5). The azoalkanes 1a and 1b undergo facile photoreduction to the corresponding hydrazines in the presence of a variety of hydrogen donors, which include 2-propanol, benzhydrol, 1,4-cyclohexadiene, tributylstannane, and tris(trimethylsilyl)silane. In contrast, the hydrazine yields derived for the azoalkanes 1c and 1d are significantly lower even at high hydrogen donor concentrations due to their lower triplet yields and shorter triplet lifetimes. A clear dependence of the hydrazine yields on the bond dissociation energies of the hydrogen donors has been observed, which is reflected in the quenching rate constants obtained from time-resolved transient absorption spectroscopy. The absolute rate constants for interaction of the triplet azoalkane 1a with hydrogen donors are generally lower (ca. 10-100-fold) than for benzophenone, in line with the less favorable reaction thermodynamics. The comparison of the rate constants for quenching of the triplet-excited azoalkane 1a and of the singlet-excited state of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) reveals a similar reactivity of excited azoalkanes toward hydrogen donors; differences can be accounted for in terms of variations in the energies of the excited states. The interactions of the excited azoalkanes with tributylstannane and benzhydrol produce the radicals characteristic for hydrogen abstraction from these substrates, namely tributylstannyl and hydroxydiphenylmethyl radicals, which were detected through their transient absorptions at 390 and 550 nm, respectively. Interestingly, compared to the photoreduction of benzophenone with benzhydrol, for which the quantum yield for conversion to radicals is unity, between the azoalkane 1a and benzhydrol this efficiency is only ca. 12%. An associative effect through N.H-O bonding is held responsible, which promotes hydrogen transfer versus diffusion out of the caged radical pair. The quenching of the singlet-excited DBO by toluene was also employed to monitor the formation of benzyl radicals (at 317 nm). The photolysis of DBO in tetrahydrofuran as solvent and quencher produced an absorption at ca. 290 nm, which was tentatively assigned to the corresponding hydrazinyl radical.

Double C-H activation of ethane by metal-free SO2*+ radical cations.

PubMed

de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

2010-06-01

The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

A comparison of radical retropubic with perineal prostatectomy for localized prostate cancer within the Uniformed Services Urology Research Group.

PubMed

Lance, R S; Freidrichs, P A; Kane, C; Powell, C R; Pulos, E; Moul, J W; McLeod, D G; Cornum, R L; Brantley Thrasher J

2001-01-01

To review and compare the outcome of patients undergoing radical retropubic prostatectomy (RRP) or radical perineal prostatectomy (RPP) for clinically localized prostate cancer. From 1988 to 1997, 1382 men who were treated by RRP and 316 by RPP were identified from databases of the Uniformed Services Urology Research Group. The following variables were assessed; age, race, prostate-specific antigen (PSA) level before surgery, clinical stage, biopsy Gleason sum, estimated blood loss (EBL), margin-positive rate, pathological stage, biochemical recurrence rate, short and long-term complication rates, impotence and incontinence rates. To eliminate selection bias, the analysis was concentrated on pairs of patients matched by race, preoperative PSA level, clinical stage and biopsy Gleason sum. In the 190 matched patients there were no significant differences between the RRP and RPP groups in either organ-confined (57% vs 55%), margin-positive (39% vs 43%), or biochemical recurrence rates (12.9% vs 17.6% at a mean follow-up of 47.1 vs 42.9 months), respectively. The mean EBL was 1575 mL in the RRP group and 802 mL in the RPP group (P < 0.001). The only significant difference in complication rates was a higher incidence of rectal injury in the RPP group (4.9%) than in the RRP group (none, P < 0.05). In similar populations of patients, RPP offers equivalent organ-confined, margin-positive and biochemical recurrence rates to RRP, while causing significantly less blood loss.

Predictors of new-onset chronic kidney disease in patients managed surgically for T1a renal cell carcinoma: An Australian population-based analysis.

PubMed

Ahn, Thomas; Ellis, Robert J; White, Victoria M; Bolton, Damien M; Coory, Michael D; Davis, Ian D; Francis, Ross S; Giles, Graham G; Gobe, Glenda C; Hawley, Carmel M; Johnson, David W; Marco, David J T; McStea, Megan; Neale, Rachel E; Pascoe, Elaine M; Wood, Simon T; Jordan, Susan J

2018-05-22

New-onset chronic kidney disease (CKD) following surgical management of kidney tumors is common. This study evaluated risk factors for new-onset CKD after nephrectomy for T1a renal cell carcinoma (RCC) in an Australian population-based cohort. There were 551 RCC patients from the Australian states of Queensland and Victoria included in this study. The primary outcome was new-onset CKD (eGFR <60 mL/min per 1.73 m 2 ) and the secondary outcome was new-onset moderate-severe CKD (<45 mL/min per 1.73 m 2 ). Multivariable logistic regression was used to evaluate associations between patient, tumor and health-service characteristics and these outcomes. Forty percent (219/551) of patients developed new-onset CKD, and 12% (68/551) experienced new-onset moderate-severe CKD. Risk factors for new-onset CKD were age, lower preoperative eGFR, tumor size >20 mm, radical nephrectomy, lower hospital caseloads (<20 cases/year), and rural place of residence. The associations between rural place of residence and low center volume were a consequence of higher radical nephrectomy rates. Risk factors for CKD after nephrectomy generally relate to worse baseline health, or likelihood of undergoing radical nephrectomy. Surgeons in rural centres and hospitals with low caseloads may benefit from formalized integration with specialist centers for continued professional development and case-conferencing, to assist in management decisions. © 2018 Wiley Periodicals, Inc.

Secondary organic aerosol formation from isoprene photooxidation

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Ng, N. L.; Murphy, S. M.; Flagan, R. C.; Seinfeld, J. H.

2005-12-01

We report chamber studies of the formation of secondary organic aerosol (SOA) from the oxidation of isoprene (2-methyl-1,3-butadiene). Isoprene is the most abundant non-methane hydrocarbon emitted into the troposphere (source strength of ~500 Tg/year), so even small SOA yields may have a large impact on global SOA production. Reactions are carried out in Caltech's dual 28 m3 Teflon chambers, and aerosol growth is monitored by a differential mobility analyzer (DMA) and an Aerodyne time-of-flight aerosol mass spectrometer (AMS). Isoprene oxidation is initiated by the UV irradiation of isoprene in the presence of hydrogen peroxide, with NO added for high-NOx experiments. These conditions ensure that isoprene oxidation is initiated by reaction with the OH radical, with negligible interference from other oxidants (ozone, nitrate radicals, and O atoms). Aerosol growth is observed under both high-NOx and low-NOx conditions, at isoprene concentrations lower than measured in previous studies (down to 8 ppb). SOA yields are found to be in the range of 1-2%. Yields exhibit a complex dependence on NOx concentration, likely a result of changes in the chemistry of organic peroxy radicals. It is shown that condensable compounds are formed from further reactions of first-generation isoprene oxidation products; the rates and products of such gas-phase reactions are at present poorly understood. Additionally, measurements of SOA composition indicate that these products undergo reactions in the aerosol phase, leading to the formation of low-volatility oligomeric products.

Comparison of post-operative intravesical recurrence and oncological outcomes after open versus laparoscopic nephroureterectomy for upper urinary tract urothelial carcinoma.

PubMed

Zou, Lujia; Zhang, Limin; Zhang, Hu; Jiang, Haowen; Ding, Qiang

2014-04-01

To retrospectively evaluate intravesical recurrence and oncological outcomes after open or laparoscopic radical nephroureterectomy (RNU) for the upper urinary tract urothelial carcinoma (UUT-UC). This study comprised 122 patients diagnosed UUT-UC and subsequently nephroureterectomy was performed on. Several clinical and pathological parameters were emphasized for comparison of clinical outcomes. Among 122 patients with UUT-UC, 101 (82.8 %) and 21 (17.2 %) underwent open or laparoscopic radical nephroureterectomy (ONU or LNU), respectively. In univariable and multivariable Cox regression models, the surgical procedure exerted an impact neither on post-operative intravesical recurrence rate (p = 0.179 and 0.213, respectively) nor on cancer-specific mortality rate (p = 0.561 and 0.159, respectively). The 1-, 2- and 5-year cancer-specific survival (CSS) rates of patients undergoing ONU or LNU were 92.1 versus 95.2 %, 87.1 versus 90.5 %, 79.2 versus 85.7 %, respectively, and the Kaplan–Meier plot illustrated that patients from two groups enjoyed an equivalent survival rate (p = 0.559). Moreover, we added that previous history of bladder tumor and pre-operative hydronephrosis was associated with intravesical recurrence, whereas three prognostic factors, including pathological tumor stage, grade, and lymphovascular invasion, showed possibility to be predictors of cancer-specific mortality. There existed no significant difference of intravesical recurrence and CSS between patients after ONU and LNU. Conclusively, laparoscopic radical nephroureterectomy did not present superiority to open management for patients with UUT-UC.

Comparison of the 7(th) and proposed 8(th) editions of the AJCC/UICC TNM staging system for non-small cell lung cancer undergoing radical surgery.

PubMed

Jin, Ying; Chen, Ming; Yu, Xinmin

2016-09-19

The present study aims to compare the 7(th) and the proposed 8(th) edition of the AJCC/UICC TNM staging system for NSCLC in a cohort of patients from a single institution. A total of 408 patients with NSCLC who underwent radical surgery were analyzed retrospectively. Survivals were analyzed using the Kaplan -Meier method and were compared using the log-rank test. Multivariate analysis was performed by the Cox proportional hazard model. The Akaike information criterion (AIC) and C-index were applied to compare the two prognostic systems with different numbers of stages. The 7(th) AJCC T categories, the proposed 8(th) AJCC T categories, N categories, visceral pleural invasion, and vessel invasion were found to have statistically significant associations with disease-free survival (DFS) on univariate analysis. In the 7(th) edition staging system as well as in the proposed 8(th) edition, T categories, N categories, and pleural invasion were independent factors for DFS on multivariate analysis. The AIC value was smaller for the 8(th) edition compared to the 7(th) edition staging system. The C-index value was larger for the 8(th) edition compared to the 7(th) edition staging system. Based on the data from our single center, the proposed 8(th) AJCC T classification seems to be superior to the 7(th) AJCC T classification in terms of DFS for patients with NSCLC underwent radical surgery.

Atmospheric autoxidation is increasingly important in urban and suburban North America

NASA Astrophysics Data System (ADS)

Praske, Eric; Otkjær, Rasmus V.; Crounse, John D.; Caleb Hethcox, J.; Stoltz, Brian M.; Kjaergaard, Henrik G.; Wennberg, Paul O.

2018-01-01

Gas-phase autoxidation—regenerative peroxy radical formation following intramolecular hydrogen shifts—is known to be important in the combustion of organic materials. The relevance of this chemistry in the oxidation of organics in the atmosphere has received less attention due, in part, to the lack of kinetic data at relevant temperatures. Here, we combine computational and experimental approaches to investigate the rate of autoxidation for organic peroxy radicals (RO2) produced in the oxidation of a prototypical atmospheric pollutant, n-hexane. We find that the reaction rate depends critically on the molecular configuration of the RO2 radical undergoing hydrogen transfer (H-shift). RO2 H-shift rate coefficients via transition states involving six- and seven-membered rings (1,5 and 1,6 H-shifts, respectively) of α-OH hydrogens (HOC-H) formed in this system are of order 0.1 s‑1 at 296 K, while the 1,4 H-shift is calculated to be orders of magnitude slower. Consistent with H-shift reactions over a substantial energetic barrier, we find that the rate coefficients of these reactions increase rapidly with temperature and exhibit a large, primary, kinetic isotope effect. The observed H-shift rate coefficients are sufficiently fast that, as a result of ongoing NOx emission reductions, autoxidation is now competing with bimolecular chemistry even in the most polluted North American cities, particularly during summer afternoons when NO levels are low and temperatures are elevated.

Peculiarities of the photoinitiator-free photopolymerization of pentabrominated and pentafluorinated aromatic acrylates and methacrylates.

PubMed

Daikos, Olesya; Naumov, Sergej; Knolle, Wolfgang; Heymann, Katja; Scherzer, Tom

2016-11-30

Pentabrominated and fluorinated aromatic (meth)acrylates as well as their non-halogenated counterparts have been studied with the aim to avoid conventional photoinitiators and to overcome some negative consequences related to their use. Therefore, RTIR spectroscopy, laser flash photolysis and GC/MS were utilized. Even low concentrations (1 to 5 wt%) of brominated (meth)acrylates in the model varnish lead to initiation of a photopolymerization reaction under exposure to UV light with λ > 300 nm. This is due to the fact that excitation of the aryl moiety leads to the homolysis of bromine-phenyl bonds with a high quantum yield of ∼0.15-0.3. Both, bromine radicals released from either ortho, meta or para position as well as the corresponding tetrabromoaryl radicals, may initiate the polymerization of brominated aromatic (meth)acrylates. In contrast, fluorinated aromatic (meth)acrylates undergo α-cleavage of the carboxyl group (as in the case of non-halogenated aromatic (meth)acrylates), if excitation of the acrylic double bonds is done with UV-C light (λ < 280 nm). Radical formation occurs with a comparable quantum yield of 0.1-0.22 (fluorinated) and 0.16-0.36 (non-halogenated compounds), despite the different pathway of fragmentation. Thus, in all cases the efficiency of initiation is comparable to conventional photoinitiators. Quantum chemical calculations of orbitals involved and of the Gibbs free energy of transients and products support the suggested reaction pathway.

Microstructural study of a nitroxide-mediated poly(ethylene oxide)/polystyrene block copolymer (PEO-b-PS) by electrospray tandem mass spectrometry.

PubMed

Girod, Marion; Phan, Trang N T; Charles, Laurence

2008-08-01

Electrospray ionization tandem mass spectrometry has been used to characterize the microstructure of a nitroxide-mediated poly(ethylene oxide)/polystyrene block copolymer, called SG1-capped PEO-b-PS. The main dissociation route of co-oligomers adducted with lithium or silver cation was observed to proceed via the homolytic cleavage of a C-ON bond, aimed at undergoing reversible homolysis during nitroxide mediated polymerization. This cleavage results in the elimination of the terminal SG1 end-group as a radical, inducing a complete depolymerization process of the PS block from the so-formed radical cation. These successive eliminations of styrene molecules allowed a straightforward determination of the PS block size. An alternative fragmentation pathway of the radical cation was shown to provide structural information on the junction group between the two blocks. Proposed dissociation mechanisms were supported by accurate mass measurements. Structural information on the SG1 end-group could be reached from weak abundance fragment ions detected in the low m/z range of the MS/MS spectrum. Amongst fragments typically expected from PS dissociation, only beta ions were produced. Moreover, specific dissociation of the PEO block was not observed to occur in MS/MS, suggesting that these rearrangement reactions do not compete effectively with dissociations of the odd-electron fragment ions. Information about the PEO block length and the initiated end-group were obtained in MS(3) experiments.

The role of information and communication technology in planning the digital hospital.

PubMed

Lacanna, Giuseppe

2013-01-01

Hospital structure is undergoing radical changes, forced by contemporary market trends, new demands from different stakeholders and a common interest in innovation. Health care expenditure around the globe continues to rise at unsustainable levels. In this context efficiency and optimization become the keywords of the process aimed at lowering costs and increasing the quality of care services. Efficiency and optimization leads to innovation, and innovation in the contemporary age leads to the power of information and communication technology (ICT). This paper discusses how ICT became the new shaping tool for hospital environments and highlights one of the best examples of its implementation.

Acetylene-based pathways for prebiotic evolution on Titan

NASA Astrophysics Data System (ADS)

Abbas, O.; Schulze-Makuch, D.

2002-11-01

Due to Titan's reducing atmosphere and lack of an ozone shield, ionizing radiation penetrates the atmosphere creating ions, radicals and electrons that are highly reactive producing versatile chemical species on Titan's surface. We propose that the catalytic hydrogenation of photochemically produced acetylene may be used as simple metabolic pathway by organisms at or near Titan's surface. While the acetylene may undergo this reaction, it can also undertake several other multi-step synthetic schemes that eventually lead to the production of amino acids or other biologically important molecules. Four model synthetic schemes will be described, and their relevance in relation to prebiotic evolution on Earth is discussed.

Growth factors and renal cancer: characterization and therapeutic implications.

PubMed

Mydlo, J H

1995-01-01

The heterogeneiety renal-cell carcinoma can lead to unpredictable behavior: the ability to achieve a large volume yet not metastasize, the ability to demonstrate late recurrence or spontaneous regression, or the capability to metastasize at a relatively small volume. One-third of all patients who undergo radical nephrectomy for presumed localized disease will eventually have metastasis. Since renal-cell carcinoma is not significantly radio- or chemosensitive, it is important to investigate new avenues for treatment of this tumor once it has spread, specifically at the molecular level. This review discusses the most recent work on growth factors and renal cancer and proposes possible modalities for treatment.

Development and field deployment of an instrument to measure ozone production rates in the troposphere

NASA Astrophysics Data System (ADS)

Sklaveniti, S.; Locoge, N.; Dusanter, S.; Leonardis, T.; Lew, M.; Bottorff, B.; Sigler, P. S. R.; Stevens, P. S.; Wood, E. C. D.; Kundu, S.; Gentner, D. R.

2015-12-01

Ozone is a greenhouse gas and a primary constituent of urban smog, irritating the respiratory system and damaging the vegetation. The current understanding of ozone chemistry in the troposphere indicates that net ozone production P(O3) occurs when peroxy radicals (HO2+RO2) react with NO producing NO2, whose photolysis leads to O3 formation. P(O3) values can be calculated from peroxy radical concentrations, either from ambient measurements or box model outputs. These two estimation methods often disagree for NOx mixing ratios higher than a few ppb, questioning our ability to measure peroxy radicals under high NOx conditions or indicating that there are still unknowns in our understanding of the radical and ozone production chemistry. Direct measurements of ozone production rates will help to address this issue and improve air quality regulations. We will present the development of an instrument for direct measurements of ozone production rates (OPR). The OPR instrument consists of three parts: (i) two quartz flow tubes sampling ambient air ("Ambient" and "Reference" flow tube), (ii) an O3-to-NO2 conversion unit, and (iii) a Cavity Attenuated Phase Shift (CAPS) monitor to measure NO2. The air in the Ambient flow tube undergoes the same photochemistry as in ambient air, while the Reference flow tube is covered by a UV filter limiting the formation of ozone. Exiting the flow tubes, ozone is converted into NO2 and the sum O3+NO2 (Ox) is measured by the CAPS monitor. The difference in Ox between the two flow tubes divided by the residence time yields the Ox production rate, P(Ox). P(O3) is assumed to be equal to P(Ox) when NO2 is efficiently photolyzed during daytime. We will present preliminary results from the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC) campaign in Bloomington, Indiana, during July 2015, where ozone production rates were measured by introducing various amounts of NO inside the flow tubes to investigate the ozone production sensitivity.

Treatment of patients with metastatic renal cell carcinoma undergoing hemodialysis: case report of two patients and short literature review

PubMed Central

2013-01-01

Background Renal cell carcinoma (RCC) may involve both kidneys. When bilateral nephrectomy is necessary renal replacement therapy is mandatory. Treating such patients with sequential therapy based on cytokines, antiangiogenic factors and mammalian target of rapamycin (mTOR) inhibitors is challenging. Case presentation The first case, a 50-year-old Caucasian female, underwent a radical right nephrectomy for RCC. Twelve years later she underwent a radical left nephrectomy along with total hysterectomy including bilateral salpingo-oophorectomy for RCC involving the right kidney and ovary. Hemodialysis was necessary because of bilateral nephrectomy. She relapsed with pulmonary metastases and enlarged mediastinal lymph nodes and received cytokine based therapy along with bevacizumab. Therapy was discontinued despite the partial response because of hemorrhagic gastritis. Therapy was switched to an antiangiogenic factor but the patient manifested a parietal brain hematoma and stopped therapy. Subsequently disease relapsed with malignant pleural effusion and pulmonary nodules and a mammalian target of rapamycin inhibitor was administered which was withdrawn only at patient’s deteriorating performance status. The patient died of the disease 13 years after the initial diagnosis of RCC. The second case, a 51-year-old, Caucasian male, underwent a radical right nephrectomy for a chromophobe RCC. Six months later he underwent a radical left nephrectomy for RCC that proved to be a clear cell RCC. Due to bilateral nephrectomy hemodialysis was obligatory. Following disease recurrence at the anatomical bed of the right kidney therapy with antiangiogenic factor was administered which led to disease regression. However the patient experienced a left temporal-occipital brain hematoma. A radical excision of the recurrence which histologically proved to be a chromophobe RCC was not achieved and the patient received mTOR inhibitor which led to disease complete response. Nine years after the initial diagnosis of RCC he is disease free and leads an active life. Conclusion Patients with RCC are in significant risk to manifest bilateral disease. Renal insufficiency requiring hemodialysis poses therapeutic challenges. Clinicians must be aware of the antiangiogenic factors’ adverse effects, especially bleeding, that may manifest in higher frequency and more severe in this setting. PMID:23587009

Unimolecular Thermal Decomposition of Phenol and d5-Phenol: Direct Observation of Cyclopentadiene Formation via Cyclohexadienone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheer, A. M.; Mukarakate, C.; Robichaud, D. J.

The pyrolyses of phenol and d{sub 5}-phenol (C{sub 6}H{sub 5}OH and C{sub 6}D{sub 5}OH) have been studied using a high temperature, microtubular ({mu}tubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting the heated reactor (375 K-1575 K) is subject to a free expansion after a residence time in the {mu}tubular reactor of approximately 50-100 {micro}s. The expansion from the reactor into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. We find that the initial decomposition steps at themore » onset of phenol pyrolysis are enol/keto tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C{sub 6}H{sub 5}OH {yields} c-C{sub 6}H{sub 6} = O {yields} c-C{sub 5}H{sub 6} + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C{sub 5}H{sub 6} {yields} c-C{sub 5}H{sub 5} + H {yields} HC {triple_bond} CH + HCCCH{sub 2}. At higher temperatures, hydrogen loss from the PhO-H group to form phenoxy radical followed by CO ejection to generate the cyclopentadienyl radical likely contributes to the product distribution; C{sub 6}H{sub 5}O-H {yields} C{sub 6}H{sub 5}O + H {yields} c-C{sub 5}H{sub 5} + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C{sub 6}H{sub 4}-OH) and hydroquinone (p-HO-C{sub 6}H{sub 4}-OH) are shown to undergo decarbonylation at the onset of pyrolysis to form hydroxycyclopentadiene. In the case of catechol, we observe that water loss is also an important decomposition channel at the onset of pyrolysis.« less

Comparison of the One-electron Oxidations of CO-Bridged vs Unbridged Bimetallic Complexes: Electron-transfer Chemistry of Os2Cp2(CO)4 and Os2Cp*2(μ-CO)2(CO)2 (Cp = η5-C5H5, Cp* = η5-C5Me5)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laws, Derek R.; Bullock, R. Morris; Lee, Richmond

The one-electron oxidations of two dimers of half-sandwich osmium carbonyl complexes have been examined by electrochemistry, spectro-electrochemistry, and computational methods. The all-terminal carbonyl complex Os2Cp2(CO)4 (1, Cp = η5-C5H5) undergoes a reversible one-electron anodic reaction at E1/2 = 0.41 V vs ferrocene in CH2Cl2/0.05 M [NBu4][B(C6F5)4], giving a rare example of a metal-metal bonded radical cation unsupported by bridging ligands. The IR spectrum of 1+ is consistent with an approximately 1:1 mixture of anti and gauche structures for the 33 e- radical cation in which it has retained all-terminal bonding of the CO ligands. DFT calculations, including orbital-occupancy-perturbed Mayer bond-ordermore » analyses, show that the HOMOs of anti-1 and gauche-1 are metal-ligand delocalized. Removal of an electron from 1 has very little effect on the Os-Os bond order, accounting for the resistance of 1+ to heterolytic cleavage. The Os-Os bond distance is calculated to decrease by 0.10 Å and 0.06 Å as a consequence of one-electron oxidation of anti-1 and gauche-1, respectively. The CO-bridged complex Os2Cp*2(μ-CO)2(CO)2 (Cp* = η5-C5Me5), trans-2, undergoes a more facile oxidation, E1/2 = - 0.11 V, giving a persistent radical cation shown by solution IR analysis to preserve its bridged-carbonyl structure. However, ESR analysis of frozen solutions of 2+ is interpreted in terms of the presence of two isomers, most likely anti-2+ and trans-2+, at low temperature. Calculations show that the HOMO of trans-2 is highly delocalized over the metal-ligand framework, with the bridging carbonyls accounting for about half of the orbital makeup. The Os-Os bond order again changes very little with removal of an electron, and the Os-Os bond length actually undergoes minor shortening. Calculations suggest that the second isomer of 2+ has both the trans CO-bridged and the anti all-terminal CO structures. DRL and WEG acknowledge the support of the National Science Foundation under grant CHE-0808909. K-WH acknowledges financial support from KAUST. RMB thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences for support. Pacific Northwest National Laboratory is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. We thank Dr. S. I. Gorelsky for the discussion on the OOP analysis.« less

Reduced graphene oxide and porphyrin. An interactive affair in 2-D.

PubMed

Wojcik, Aleksandra; Kamat, Prashant V

2010-11-23

Photoexcited cationic 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP) undergoes charge-transfer interaction with chemically reduced graphene oxide (RGO). Formation of the ground-state TMPyP-RGO complex in solution is marked by the red-shift of the porphyrin absorption band. This complexation was analyzed by Benesi-Hildebrand plot. Porphyrin fluorescence lifetime reduced from 5 to 1 ns upon complexation with RGO, indicating excited-state interaction between singlet excited porphyrin and RGO. Femtosecond transient absorption measurements carried out with TMPyP adsorbed on RGO film revealed fast decay of the singlet excited state, followed by the formation of a longer-living product with an absorption maximum around 515 nm indicating the formation of a porphyrin radical cation. The ability of TMPyP-RGO to undergo photoinduced charge separation was further confirmed from the photoelectrochemical measurements. TMPyP-RGO coated conducting glass electrodes are capable of generating photocurrent under visible excitation. These results are indicative of the electron transfer between photoexcited porphyrin and RGO. The role of graphene in accepting and shuttling electrons in light-harvesting assemblies is discussed.

Intestinal stoma in patients with colorectal cancer from the perspective of 20-year period of clinical observation.

PubMed

Banaszkiewicz, Zbigniew; Woda, Łukasz P; Zwoliński, Tomasz; Tojek, Krzysztof; Jarmocik, Paweł; Jawień, Arkadiusz

2015-01-01

Intestinal stoma is a procedure most often performed in patients with colorectal cancer. To identify the percentage of patients with colorectal cancer in which the intestinal stoma was performed. We retrospectively analysed 443 patients treated during a 20-year period (1994-2013) due to colorectal cancer, in which the intestinal stoma was made during the first surgical intervention. In the second analysed decade, a significant decrease in the percentage of created stomas, definitive stomas in particular, was observed. Stomas were made significantly more often in patients with a tumour located in the rectum, the left half of the colon, and in patients undergoing urgent surgeries. An increased incidence of intestinal stomas was associated with a higher severity of illness and higher proportion of unresectable and non-radical procedures. The definitive stomas were significantly more often made in men and in patients with tumours located in the rectum, whereas temporary stomas were created significantly more often in patients undergoing urgent operations. In the last decade (2004-2013) the number of intestinal stomas in patients operated due to colorectal cancer was significantly reduced.

Mechanisms of redox interactions of bilirubin with copper and the effects of penicillamine.

PubMed

Božić, Bojana; Korać, Jelena; Stanković, Dalibor M; Stanić, Marina; Popović-Bijelić, Ana; Bogdanović Pristov, Jelena; Spasojević, Ivan; Bajčetić, Milica

2017-12-25

Toxic effects of unconjugated bilirubin (BR) in neonatal hyperbilirubinemia have been related to redox and/or coordinate interactions with Cu 2+ . However, the development and mechanisms of such interactions at physiological pH have not been resolved. This study shows that BR reduces Cu 2+ to Cu 1+ in 1:1 stoichiometry. Apparently, BR undergoes degradation, i.e. BR and Cu 2+ do not form stable complexes. The binding of Cu 2+ to inorganic phosphates, liposomal phosphate groups, or to chelating drug penicillamine, impedes redox interactions with BR. Cu 1+ undergoes spontaneous oxidation by O 2 resulting in hydrogen peroxide accumulation and hydroxyl radical production. In relation to this, copper and BR induced synergistic oxidative/damaging effects on erythrocytes membrane, which were alleviated by penicillamine. The production of reactive oxygen species by BR and copper represents a plausible cause of BR toxic effects and cell damage in hyperbilirubinemia. Further examination of therapeutic potentials of copper chelators in the treatment of severe neonatal hyperbilirubinemia is needed. Copyright © 2017 Elsevier B.V. All rights reserved.

Aging and Gene Expression in the Primate Brain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fraser, Hunter B.; Khaitovich, Philipp; Plotkin, Joshua B.

2005-02-18

It is well established that gene expression levels in many organisms change during the aging process, and the advent of DNA microarrays has allowed genome-wide patterns of transcriptional changes associated with aging to be studied in both model organisms and various human tissues. Understanding the effects of aging on gene expression in the human brain is of particular interest, because of its relation to both normal and pathological neurodegeneration. Here we show that human cerebral cortex, human cerebellum, and chimpanzee cortex each undergo different patterns of age-related gene expression alterations. In humans, many more genes undergo consistent expression changes inmore » the cortex than in the cerebellum; in chimpanzees, many genes change expression with age in cortex, but the pattern of changes in expression bears almost no resemblance to that of human cortex. These results demonstrate the diversity of aging patterns present within the human brain, as well as how rapidly genome-wide patterns of aging can evolve between species; they may also have implications for the oxidative free radical theory of aging, and help to improve our understanding of human neurodegenerative diseases.« less

Robot-assisted radical prostatectomy: Multiparametric MR imaging-directed intraoperative frozen-section analysis to reduce the rate of positive surgical margins.

PubMed

Petralia, Giuseppe; Musi, Gennaro; Padhani, Anwar R; Summers, Paul; Renne, Giuseppe; Alessi, Sarah; Raimondi, Sara; Matei, Deliu V; Renne, Salvatore L; Jereczek-Fossa, Barbara A; De Cobelli, Ottavio; Bellomi, Massimo

2015-02-01

To investigate whether use of multiparametric magnetic resonance (MR) imaging-directed intraoperative frozen-section (IFS) analysis during nerve-sparing robot-assisted radical prostatectomy reduces the rate of positive surgical margins. This retrospective analysis of prospectively acquired data was approved by an institutional ethics committee, and the requirement for informed consent was waived. Data were reviewed for 134 patients who underwent preoperative multiparametric MR imaging (T2 weighted, diffusion weighted, and dynamic contrast-material enhanced) and nerve-sparing robot-assisted radical prostatectomy, during which IFS analysis was used, and secondary resections were performed when IFS results were positive for cancer. Control patients (n = 134) matched for age, prostate-specific antigen level, and stage were selected from a pool of 322 patients who underwent nerve-sparing robot-assisted radical prostatectomy without multiparametric MR imaging and IFS analysis. Rates of positive surgical margins were compared by means of the McNemar test, and a multivariate conditional logistic regression model was used to estimate the odds ratio of positive surgical margins for patients who underwent MR imaging and IFS analysis compared with control subjects. Eighteen patients who underwent MR imaging and IFS analysis underwent secondary resections, and 13 of these patients were found to have negative surgical margins at final pathologic examination. Positive surgical margins were found less frequently in the patients who underwent MR imaging and IFS analysis than in control patients (7.5% vs 18.7%, P = .01). When the differences in risk factors are taken into account, patients who underwent MR imaging and IFS had one-seventh the risk of having positive surgical margins relative to control patients (adjusted odds ratio: 0.15; 95% confidence interval: 0.04, 0.61). The significantly lower rate of positive surgical margins compared with that in control patients provides preliminary evidence of the positive clinical effect of multiparametric MR imaging-directed IFS analysis for patients who undergo prostatectomy. © RSNA, 2014.

Dimethylthiourea pretreatment inhibits endotoxin-induced compound exocytosis in goblet cells and plasma leakage of rat small intestine.

PubMed

Liu, Shang-Pin; Chang, Chien-Yu; Huang, Wen-Hung; Fu, Yaw-Syan; Chao, David; Huang, Hung-Tu

2010-01-01

Intravenous application of a high dose of endotoxin, also called lipopoly-saccharide (LPS), results in endotoxemia in animals, that induces production of cytokines and free radicals, systemic inflammation and mucin discharge from mucous tissues. The present study was to investigate (1) whether LPS application increased goblet cell secretion by compound exocytotic activity in mucosal villi and crypts of rat small intestine, and (2) whether hydroxyl radicals were involved in LPS-induced compound exocytosis in goblet cells and plasma leakage. Scanning electron microscopy showed that the numbers of goblet cells undergoing compound exocytosis (cavitated goblet cells) per mm(2) of ileal villus epithelium in rats 5 and 30 min after LPS (15 mg kg(-1)) were 693 +/- 196 (N = 6) and 547 +/- 213 (N = 6), respectively, which were 5.1 and 8.4 times (P < 0.05) the number of saline control. The percentage of villus cavitated goblet cell numbers, in both duodenum and ileum 5 min after LPS and in the ileum 30 min after LPS, increased significantly (P < 0.05). Pretreatment with dimethylthiourea (DMTU), a hydroxyl radical scavenger, decreased the number of cavitated goblet cells to saline control (P > 0.05). Morphometric analysis showed that the percentage of crypt epithelial area in the duodenum and ileum occupied by goblet cell mucin stores in the duodenum and ileum 30 min after LPS were 3.8 +/- 0.2% (N = 6) and 6.9 +/- 0.5 (N = 6), respectively reducing to one half the amount of control (P < 0.01). When DMTU was given prior to LPS the crypt goblet cell mucin stores and the amount of plasma leakage returned to the level of control. It is concluded that hydroxyl radicals were involved in the LPS-induced increase in compound exocytotic activity of goblet cells and the increase in plasma leakage during acute phases of inflammatory response in rat small intestine.

Bladder neck contracture after robot-assisted laparoscopic radical prostatectomy: evaluation of incidence and risk factors and impact on urinary function.

PubMed

Msezane, Lambda P; Reynolds, W Stuart; Gofrit, Ofer N; Shalhav, Arieh L; Zagaja, Gregory P; Zorn, Kevin C

2008-01-01

Bladder neck contracture (BNC) after radical prostatectomy has been reported to occur in 5% to 32% of men after open retropubic prostatectomy (RRP) and in 0% to 3% after laparoscopic RRP. Optimal anastomotic closure involves creating a watertight, tension-free anastomosis with well-vascularized, mucosal apposition and correct realignment of the urethra. The cause of BNC is poorly understood; however, it is likely related to multiple factors, including excessive luminal narrowing at the site of reconstruction, local tissue ischemia, failed mucosal apposition, and urinary leakage. In this large series of patients who underwent robot-assisted laparoscopic radical prostatectomy (RLRP), we report the incidence of BNC, evaluate the influence of age, body mass index (BMI), estimated blood loss (EBL), surgical time, and prostate weight on its development and assess follow-up urinary function. Between February 2003 and July 2006, 650 consecutive men underwent RLRP at our institution. Patients with aborted or open conversion procedures were excluded from analysis. The mean overall follow-up for the remaining 634 patients was 19.5 months. Patients presenting with symptoms of outlet obstruction were evaluated with cystoscopy to confirm a BNC. Comparisons of age, BMI, EBL, operative time, and prostate weight were performed using the Student t-test and chi-square analysis. BNC was the diagnosis in seven patients (1.1%) with a mean time of presentation of 4.8 (3-12) months postoperatively. The BNC patients had comparable mean age, BMI, prostate weight, and EBL to the non-BNC cohort. Their operative time, however, was significantly longer (283 v 225 min., P = 0.04). The incidence of BNC after radical prostatectomy is 2.2% in a large series of men undergoing RLRP. The diagnosis was made within 1 year. No significant impact on urinary continence or quality-of-life urinary function was observed after BNC management. A running anastomosis, better visualization, improved instrument maneuverability, and decreased blood loss may account for such a low rate.

Impact of robotic technique and surgical volume on the cost of radical prostatectomy.

PubMed

Hyams, Elias S; Mullins, Jeffrey K; Pierorazio, Phillip M; Partin, Alan W; Allaf, Mohamad E; Matlaga, Brian R

2013-03-01

Our present understanding of the effect of robotic surgery and surgical volume on the cost of radical prostatectomy (RP) is limited. Given the increasing pressures placed on healthcare resource utilization, such determinations of healthcare value are becoming increasingly important. Therefore, we performed a study to define the effect of robotic technology and surgical volume on the cost of RP. The state of Maryland mandates that all acute-care hospitals report encounter-level and hospital discharge data to the Health Service Cost Review Commission (HSCRC). The HSCRC was queried for men undergoing RP between 2008 and 2011 (the period during which robot-assisted laparoscopic radical prostatectomy [RALRP] was coded separately). High-volume hospitals were defined as >60 cases per year, and high-volume surgeons were defined as >40 cases per year. Multivariate regression analysis was performed to evaluate whether robotic technique and high surgical volume impacted the cost of RP. There were 1499 patients who underwent RALRP and 2565 who underwent radical retropubic prostatectomy (RRP) during the study period. The total cost for RALRP was higher than for RRP ($14,000 vs 10,100; P<0.001) based primarily on operating room charges and supply charges. Multivariate regression demonstrated that RALRP was associated with a significantly higher cost (β coeff 4.1; P<0.001), even within high-volume hospitals (β coeff 3.3; P<0.001). High-volume surgeons and high-volume hospitals, however, were associated with a significantly lower cost for RP overall. High surgeon volume was associated with lower cost for RALRP and RRP, while high institutional volume was associated with lower cost for RALRP only. High surgical volume was associated with lower cost of RP. Even at high surgical volume, however, the cost of RALRP still exceeded that of RRP. As robotic surgery has come to dominate the healthcare marketplace, strategies to increase the role of high-volume providers may be needed to improve the cost-effectiveness of prostate cancer surgical therapy.

Antioxidant and Cytoprotective Effects of Tibetan Tea and Its Phenolic Components.

PubMed

Xie, Hong; Li, Xican; Ren, Zhenxing; Qiu, Weimin; Chen, Jianlan; Jiang, Qian; Chen, Ban; Chen, Dongfeng

2018-01-24

Tibetan tea (Kangzhuan) is an essential beverage of the Tibetan people. In this study, a lyophilized aqueous extract of Tibetan tea ( LATT ) was prepared and analyzed by HPLC. The results suggested that there were at least five phenolic components, including gallic acid, and four catechins (i.e., (+)-catechin, (-)-catechin gallate ( CG ), (-)-epicatechin gallate ( ECG ), and (-)-epigallocatechin gallate). Gallic acid, the four catechins, and LATT were then comparatively investigated by four antioxidant assays: ferric reducing antioxidant power, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide radical (PTIO•) scavenging, 1,1-diphenyl-2-picryl-hydrazl radical scavenging, and 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) radical scavenging assays. In these assays, LATT, along with the five phenolic components, increased their antioxidant effects in a concentration-dependent manner; however, the half maximal scavenging concentrations of ECG were always lower than those of CG . Gallic acid and the four catechins were also suggested to chelate Fe 2+ based on UV-visible spectral analysis. Ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UPLC-ESI-Q-TOF-MS/MS) analysis suggested that, when mixed with PTIO•, the five phenolic components could yield two types of radical adduct formation (RAF) products (i.e., tea phenolic dimers and tea phenolic-PTIO• adducts). In a flow cytometry assay, (+)-catechin and LATT was observed to have a cytoprotective effect towards oxidative-stressed bone marrow-derived mesenchymal stem cells. Based on this evidence, we concluded that LATT possesses antioxidative or cytoprotective properties. These effects may mainly be attributed to the presence of phenolic components, including gallic acid and the four catechins. These phenolic components may undergo electron transfer, H⁺-transfer, and Fe 2+ -chelating pathways to exhibit antioxidative or cytoprotective effects. In these effects, two diastereoisomeric CG and ECG showed differences to which a steric effect from the 2-carbon may contribute. Phenolic component decay may cause RAF in the antioxidant process.

Incidental pT2-T3 gallbladder cancer after a cholecystectomy: outcome of staging at 3 months prior to a radical resection

PubMed Central

Ausania, Fabio; Tsirlis, Theodoris; White, Steven A; French, Jeremy J; Jaques, Bryon C; Charnley, Richard M; Manas, Derek M

2013-01-01

Introduction Patients with incidental pT2-T3 gallbladder cancer (IGC) after a cholecystectomy may benefit from a radical re-resection although their optimal treatment strategy is not well defined. In this Unit, such patients undergo delayed staging at 3 months after a cholecystectomy to assess the evidence of a residual tumour, extra hepatic spread and the biological behaviour of the tumour. The aim of this study was to evaluate the outcome of patients who had delayed staging at 3 months after a cholecystectomy. Methods From July 2003 to July 2011, 56 patients with T2-T3 gallbladder cancer were referred to this Unit of which 49 were diagnosed incidentally on histology after a cholecystectomy. All 49 patients underwent delayed pre-operative staging using multi-detector computed tomography (MDCT) followed selectively by laparoscopy at 3 months after a cholecystectomy. Data were collected from a prospectively held database. The peri-operative and long-term outcomes of patients were analysed. SPSS software was used for statistical analysis. Results There were 38 pT2 and 11 pT3 tumours. After delayed staging, 24/49 (49%) patients underwent a radical resection, 24/49 (49%) were found to be inoperable on pre-operative assessment and 1/49 (2%) patient underwent an exploratory laparotomy and were found to be unresectable. The overall median survival from referral was 20.7 months (54.8 months for the group who had a radical re-resection versus 9.7 months for the group who had unresectable disease, P < 0.001). These results compare favourably with the reported outcome of fast-track management for incidental pT2-T3 gallbladder cancer from other major series in the literature. Conclusion Delayed staging in patients with incidental T2-T3 gallbladder cancer after a cholecystectomy is a useful strategy to select patients who will benefit from a resection and avoid unnecessary major surgery. PMID:23458168

Quality of laparoscopic radical hysterectomy in developing countries: a comparison of surgical and oncologic outcomes between a comprehensive cancer center in the United States and a cancer center in Colombia.

PubMed

Pareja, Rene; Nick, Alpa M; Schmeler, Kathleen M; Frumovitz, Michael; Soliman, Pamela T; Buitrago, Carlos A; Borrero, Mauricio; Angel, Gonzalo; Reis, Ricardo Dos; Ramirez, Pedro T

2012-05-01

To help determine whether global collaborations for prospective gynecologic surgery trials should include hospitals in developing countries, we compared surgical and oncologic outcomes of patients undergoing laparoscopic radical hysterectomy at a large comprehensive cancer center in the United States and a cancer center in Colombia. Records of the first 50 consecutive patients who underwent laparoscopic radical hysterectomy at The University of Texas MD Anderson Cancer Center in Houston (between April 2004 and July 2007) and the first 50 consecutive patients who underwent the same procedure at the Instituto de Cancerología-Clínica las Américas in Medellín (between December 2008 and October 2010) were retrospectively reviewed. Surgical and oncologic outcomes were compared between the 2 groups. There was no significant difference in median patient age (US 41.9 years [range 23-73] vs. Colombia 44.5 years [range 24-75], P=0.09). Patients in Colombia had a lower median body mass index than patients in the US (24.4 kg/m(2) vs. 28.7 kg/m(2), P=0.002). Compared to patients treated in Colombia, patients who underwent surgery in the US had a greater median estimated blood loss (200 mL vs. 79 mL, P<0.001), longer median operative time (328.5 min vs. 235 min, P<0.001), and longer postoperative hospital stay (2 days vs. 1 day, P<0.001). Surgical and oncologic outcomes of laparoscopic radical hysterectomy were not worse at a cancer center in a developing country than at a large comprehensive cancer center in the United States. These results support consideration of developing countries for inclusion in collaborations for prospective surgical studies. Copyright © 2011 Elsevier B.V. All rights reserved.

Atmospheric chemistry of isoflurane, desflurane, and sevoflurane: kinetics and mechanisms of reactions with chlorine atoms and OH radicals and global warming potentials.

PubMed

Sulbaek Andersen, Mads P; Nielsen, Ole J; Karpichev, Boris; Wallington, Timothy J; Sander, Stanley P

2012-06-21

The smog chamber/Fourier-transform infrared spectroscopy (FTIR) technique was used to measure the rate coefficients k(Cl + CF(3)CHClOCHF(2), isoflurane) = (4.5 ± 0.8) × 10(-15), k(Cl + CF(3)CHFOCHF(2), desflurane) = (1.0 ± 0.3) × 10(-15), k(Cl + (CF(3))(2)CHOCH(2)F, sevoflurane) = (1.1 ± 0.1) × 10(-13), and k(OH + (CF(3))(2)CHOCH(2)F) = (3.5 ± 0.7) × 10(-14) cm(3) molecule(-1) in 700 Torr of N(2)/air diluent at 295 ± 2 K. An upper limit of 6 × 10(-17) cm(3) molecule(-1) was established for k(Cl + (CF(3))(2)CHOC(O)F). The laser photolysis/laser-induced fluorescence (LP/LIF) technique was employed to determine hydroxyl radical rate coefficients as a function of temperature (241-298 K): k(OH + CF(3)CHFOCHF(2)) = (7.05 ± 1.80) × 10(-13) exp[-(1551 ± 72)/T] cm(3) molecule(-1); k(296 ± 1 K) = (3.73 ± 0.08) × 10(-15) cm(3) molecule(-1), and k(OH + (CF(3))(2)CHOCH(2)F) = (9.98 ± 3.24) × 10(-13) exp[-(969 ± 82)/T] cm(3) molecule(-1); k(298 ± 1 K) = (3.94 ± 0.30) × 10(-14) cm(3) molecule(-1). The rate coefficient of k(OH + CF(3)CHClOCHF(2), 296 ± 1 K) = (1.45 ± 0.16) × 10(-14) cm(3) molecule(-1) was also determined. Chlorine atoms react with CF(3)CHFOCHF(2) via H-abstraction to give CF(3)CFOCHF(2) and CF(3)CHFOCF(2) radicals in yields of approximately 83% and 17%. The major atmospheric fate of the CF(3)C(O)FOCHF(2) alkoxy radical is decomposition via elimination of CF(3) to give FC(O)OCHF(2) and is unaffected by the method used to generate the CF(3)C(O)FOCHF(2) radicals. CF(3)CHFOCF(2) radicals add O(2) and are converted by subsequent reactions into CF(3)CHFOCF(2)O alkoxy radicals, which decompose to give COF(2) and CF(3)CHFO radicals. In 700 Torr of air 82% of CF(3)CHFO radicals undergo C-C scission to yield HC(O)F and CF(3) radicals with the remaining 18% reacting with O(2) to give CF(3)C(O)F. Atmospheric oxidation of (CF(3))(2)CHOCH(2)F gives (CF(3))(2)CHOC(O)F in a molar yield of 93 ± 6% with CF(3)C(O)CF(3) and HCOF as minor products. The IR spectra of (CF(3))(2)CHOC(O)F and FC(O)OCHF(2) are reported for the first time. The atmospheric lifetimes of CF(3)CHClOCHF(2), CF(3)CHFOCHF(2), and (CF(3))(2)CHOCH(2)F (sevoflurane) are estimated at 3.2, 14, and 1.1 years, respectively. The 100 year time horizon global warming potentials of isoflurane, desflurane, and sevoflurane are 510, 2540, and 130, respectively. The atmospheric degradation products of these anesthetics are not of environmental concern.

The pattern of prognostic and risk indicators among women with breast cancer undergoing modified radical mastectomy in Dar es Salaam, Tanzania.

PubMed

Mwakigonja, Amos R; Rabiel, Happiness; Mbembati, Naboth A; Lema, Leonard E K

2016-01-01

Breast cancer is the commonest female malignancy globally and the second (after uterine cervix) in sub-Saharan Africa including Tanzania. Prognostic indicators reportedly influence post-mastectomy adjuvant therapy by predicting risks on survival and recurrence although in Tanzania this data is lacking. Here, we evaluate the pattern of prognostic and risk indicators among women with breast cancer undergoing modified-radical-mastectomy (MRM) at Muhimbili National Hospital (MNH) and Tumaini Hospital (TH), Dar es Salaam, Tanzania. This hospital-based prospective cross-sectional study included female patients undergoing MRM from April 2011 to January 2012. Clinical stage I-III patients were enrolled after being scheduled for mastectomy. Patients with evidence of distant metastasis (stage IV) were excluded. Mastectomy and axillary lymph nodes biopsies were submitted to the Histopathology laboratory for grade, type, nodal and margins status. Data was collected using a structured questionnaire and analyzed using SPSS. A total of 348 patients were admitted with breast cancer including 86 patients (with 16 from TH having similar demography and presentation) meeting inclusion criteria. Age-range at diagnosis was 28-79 years, mean 52.1 years. Most (89 %) attained menarche after 11 years. About 56 % were postmenopausal. The majority (78 %) were multiparous with positive family history in 14.1 and 37.6 % used hormonal contraceptives. About 27.1 % were social alcohol drinkers. The majority (61 %) had T4b disease, 75.6 % had positive axillary nodes including 42.7 % with 4-9 involved nodes (N2). The commonest (91.9 %) histological type was invasive ductal carcinoma. Lobular, medullary and mucinous carcinomas were rare. Most (83.7 %) of our patients presented with stage III and the rest stage II. Intermediate- and high-grade tumors accounted for 73.5 %. Following MRM, 25 % of our patients had positive surgical margins and similarly for the base. Most of our breast cancer patients present with frequent risks including younger age, multiparity, hormonal contraceptives use, alcohol use and family history. Unfavourable prognostic indicators including late stages, large primary tumor size, skin infiltration, positive surgical margins, positive axillary lymph nodes and a high histological grade were associated. A sustainable screening program by self-examination to allow early diagnosis is needed to reduce morbidity and mortality from this cancer.

[Discussion on standardized implementation of laparoscopic radical lymphadenectomy for distal gastric cancer].

PubMed

Lyu, Zejian; Wang, Junjiang; Li, Yong

2017-08-25

Laparoscopic radical gastrectomy for gastric cancer has been widely applied in clinical practice, and its indications have been extended from early gastric cancer to advanced gastric cancer. It is acknowledged that laparoscopic radical gastrectomy is technically challenging because of the complexity of anatomy, rich blood supply, and extensive lymph node dissection. This paper primarily intends to share the experience of laparoscopic radical D2 gastrectomy for distal gastric cancer with details of choosing the location of Trocar, surgical approaches and the sequence of lymph node dissection. All the surgeries were performed at Department of General Surgery and Gastrointestinal Surgery, Guangdong General Hospital. The finding suggests that a correct laparoscopic Trocar placement is the foundation of adequate surgical field visualization. Under most circumstances, the observation hole should be around 2 cm below the umbilicus and the operating hole should be close to the bilateral clavicle midline. Furthermore, proper surgical approach and sequence of lymph node dissection are the prerequisites for successful laparoscopic radical D2 gastrectomy, as well as the reassurance of dissecting lymph node safely and comprehensively. The position of surgical team adopted in our center is that the surgeon stands to the left of the patient, with laparoscope operator stands in between patient's legs while the first assistant positions himself opposite the surgeon on the right side of the patient. This position correlates to the rules of sequential lymph node dissection, which is "from left to right", "from proximal to distal" and "from inferior to superior". Therefore, it is conductive to inferior and superior pylorus region dissection and it can effectively prevent subsidiary-injury. In our center, the procedure of lymph node dissection has been standardized: the initial step is to undergo station 4sb dissection and greater gastric curvature clearance; then change the patient's position to clean the sub-pyloric lymph node region and cut off the duodenum by linear stapler; followed by the clearance of inferior region of the pylorus and the upper margin of the pancreas; in the final step, the first and the third groups of lymph node dissection is performed. Although varied surgical approaches and sequences of lymph node dissection are applied in different hospitals, the techniques required for laparoscopic D2 radical gastrectomy for gastric cancer are sophisticated and advanced in general. Radical lymph node dissection is complicated, urging surgeons to familiarize themselves with the anatomy of gastric peripheral vascular system and characteristics of lymph node drainage. By designing and implementing effective strategies, such as formulating a regular team, positioning surgical team reasonably, changing a patient's posture during operation, choosing an appropriate surgical approach and following a logically sequence of lymph node dissection, surgeons can standardize the complete surgical procedure, which ultimately reduces bleeding during surgery and shortens the operative time.

[Intracranial plasmocytomas: biology, diagnosis, and treatment].

PubMed

Belov, A I; Gol'bin, D A

2006-01-01

Intracranial plasmocytomas are a rare abnormality in a neurosurgeon's practice. The plasmocytomas may originate from the skull bones or soft tissue intracranial structures; they may be solitary or occur as a manifestation of multiple myeloma, this type being typical of most intracranial plasmocytomas. Progression of solitary plasmocytoma to multiple myeloma is observed in a number of cases. Preoperative diagnosis involves computed tomography or magnetic resonance imaging; angiography is desirable. The final diagnosis of plasmocytoma is chiefly based on a morphological study. Special immunohistochemical studies yield very promising results; these are likely to be of high prognostic value. Intracranial plasmocytomas require a differential approach and a meticulous examination since the presence or absence of multiple myeloma radically affects prognosis. There are well-defined predictors; however, it is appropriate that craniobasal plasmocytomas show a worse prognosis than plasmocytomas of the skull vault and more commonly progress to multiple myeloma. Plasmocytomas respond to radiotherapy very well. The gold standard of treatment for plasmocytoma is its total removal and adjuvant radiation therapy; however, there is evidence for good results when it is partially removed and undergoes radiotherapy or after radical surgery without subsequent radiation. The role of chemotherapy has not been defined today.

UV-tunable laser induced phototransformations of matrix isolated anethole.

PubMed

Krupa, Justyna; Wierzejewska, Maria; Nunes, Cláudio M; Fausto, Rui

2014-03-14

A matrix isolation study of the infrared spectra and structure of anethole (1-methoxy-4-(1-propenyl)benzene) has been carried out, showing the presence of two E conformers (AE1, AE2) of the molecule in the as-deposited matrices. Irradiation using ultraviolet-tunable laser light at 308-307 nm induced conformationally selective phototransformations of these forms into two less stable Z conformers (AZ1, AZ2). The back reactions were also detected upon irradiation at 301 nm. On the whole, the obtained results allow for full assignment of the infrared spectra of all the four experimentally observed anethole isomers and showed that the narrowband UV-induced E-Z photoisomerization is an efficient and selective way to interconvert the two isomers of anethole into each other, with conformational discrimination. Photolysis of anethole was observed as well, with initial methoxyl O-C bond cleavage and formation of CH3 and p-propenylphenoxy (AR) radicals, followed by radical recombination to form 2-methyl-4-propenyl-2,4-cyclohexadienone, which subsequently undergoes ring-opening generating several conformers of long-chain conjugated ketenes. Interpretation of the experimental observations was supported by density functional theory (B3LYP and B2PLYD) calculations.

Cortical astrocytes exposed to tributyltin undergo morphological changes in vitro.

PubMed

Mizuhashi, S; Ikegaya, Y; Nishiyama, N; Matsuki, N

2000-11-01

We investigated the effect of tributyltin (TBT), an endocrine-disrupting chemical, on the morphology and viability of cultured rat cortical astrocytes. Cultured astrocytes exhibited smooth and planiform morphology under normal conditions. Following exposure to TBT, however, they showed rapid morphological changes that are characterized by asteriated cell bodies and process formation in a time- and concentration-dependent manner. Higher concentrations of TBT produced progressive cell death of the astrocytes. In serum-free medium, TBT at a concentration as low as 200 nM induced the stellation. Pharmacological studies revealed that the morphological changes were alleviated by application of diverse free radical scavengers or antioxidants such as catalase, superoxide dismutase, Trolox, ascorbic acid and N-acetyl-L-cysteine, suggesting that TBT-induced stellation is caused by oxidative stress involving free radicals, particularly reactive oxygen species. Furthermore, we found that the astrocyte stellation was abolished by treatment with inhibitors of phospholipase C, mitogen-activated protein kinase kinase or tyrosine phosphatase. The data suggest that TBT causes the stellation through intracellular signaling cascades rather than its non-specific toxicity. These findings provide an important insight for reconciling the problems in assumed aversive actions of this environmental pollutant for mammals.

Ultrafast primary processes of an iron-(III) azido complex in solution induced with 266 nm light.

PubMed

Vennekate, Hendrik; Schwarzer, Dirk; Torres-Alacan, Joel; Krahe, Oliver; Filippou, Alexander C; Neese, Frank; Vöhringer, Peter

2012-05-14

The ultrafast photo-induced primary processes of the iron-(III) azido complex, [Fe(III)N(3)(cyclam-acetato)] PF(6) (1), in acetonitrile solution at room temperature were studied using femtosecond spectroscopy with ultraviolet (UV) excitation and mid-infrared (MIR) detection. Following the absorption of a 266 nm photon, the complex undergoes an internal conversion back to the electronic doublet ground state at a time scale below 2 ps. Subsequently, the electronic ground state vibrationally cools with a characteristic time constant of 13 ps. A homolytic bond cleavage was also observed by the appearance of ground state azide radicals, which were identified by their asymmetric stretching vibration at 1659 cm(-1). The azide radical recombines in a geminate fashion with the iron containing fragment within 20 ps. The cage escape leading to well separated fragments after homolytic Fe-N bond breakage was found to occur with a quantum yield of 35%. Finally, non-geminate recombination at nanosecond time scales was seen to further reduce the photolytic quantum yield to below 20% at a wavelength of 266 nm. This journal is © the Owner Societies 2012

Comprehensive approach for post-prostatectomy incontinence in the era of robot-assisted radical prostatectomy

PubMed Central

Haga, Nobuhiro; Takinami, Ruriko; Tanji, Ryo; Onagi, Akifumi; Matsuoka, Kanako; Koguchi, Tomoyuki; Akaihata, Hidenori; Hata, Junya; Ogawa, Soichiro; Kataoka, Masao; Sato, Yuichi; Ishibashi, Kei; Aikawa, Ken; Kojima, Yoshiyuki

2017-01-01

Abstract Robot-assisted radical prostatectomy (RARP) has enabled steady and stable surgical procedures due to both meticulous maneuvers and magnified, clear, 3-dimensional vision. Therefore, better surgical outcomes have been expected with RARP than with other surgical modalities. However, even in the RARP era, post-prostatectomy incontinence has a relatively high incidence as a bothersome complication. To overcome post-prostatectomy incontinence, it goes without saying that meticulous surgical procedures and creative surgical procedures, i.e., “Preservation”, “Reconstruction”, and “Reinforcement” of the anatomical structures of the pelvis, are most important. In addition, medication and appropriate pad usage might sometimes be helpful for patients with post-prostatectomy incontinence. However, patients who have 1) BMI > 26 kg/m2, 2) prostate volume > 70 mL, 3) eGFR < 60 mL/min, or a 4) Charlson comorbidity index > 2 have a tendency to develop post-prostatectomy incontinence despite undergoing the same surgical procedures. It is important for patients who have a high risk for post-prostatectomy incontinence to be given information about delayed recovery of post-prostatectomy incontinence. Thus, not only the surgical procedures, but also a comprehensive approach, as mentioned above, are important for post-prostatectomy incontinence. PMID:28747618

Can renal dysfunction after infra-renal aortic aneurysm repair be modified by multi-antioxidant supplementation?

PubMed

Wijnen, M H W A; Vader, H L; Van Den Wall Bake, A W L; Roumen, R M H

2002-08-01

Renal failure after lower torso ischemia is a serious problem, partly caused by hypotension and indirect reperfusion injury. This injury is partly due to the formation of oxygen free radicals by activated neutrophils. This injury results in albuminuria and renal function impairment. There are indications that free radical damage in indirect reperfusion injury can be diminished by administering extra antioxidants before and during reperfusion. In this prospective randomised study we have looked at the influence of a multi-antioxidant supplementation on renal function in patients undergoing an elective open infrarenal abdominal aneurysm repair. The patients received either standard treatment (n=22) or standard treatment with additional antioxidants perioperatively (Allopurinol, vitamin E and C, N-acetylcysteine and mannitol). For renal function we have looked at the albumin/creatinine ratio in urine and 24 hr creatinine clearance. Despite significantly increased serum total antioxidant capacity, the group receiving extra antioxidants showed no decrease in the albumin/creatinine ratio in urine. There was however a significantly higher creatinine clearance in this group at day 2. The results indicate that the diminished renal function after infrarenal aneurysm repair may be influenced by antioxidant therapy.

[Surgical treatment and prognosis of Borrmann type IIII( gastric cancer involving the whole stomach].

PubMed

Dong, Ruizeng; Zhang, Zewei; Zhou, Yiming; Hua, Yonghong; Guo, Jianmin

2018-02-25

To explore the surgical treatment and prognosis of Borrmann type IIII( gastric cancer involving the whole stomach. Clinicopathological characteristics and survival data of 223 patients with Borrmann type IIII( gastric cancer involving the whole stomach (defined as the tumor infiltrating 3 regions of the stomach) receiving surgical treatment at the Department of Abdominal Surgery of Zhejiang Cancer Hospital between January 2002 and December 2015 were analyzed retrospectively. The survival time of patients with different clinicopathological features and different treatment methods was compared. Cox regression was used to analyze the independent prognostic factors. Two hundred and twenty-three patients with Borrmann type IIII( gastric cancer involving the whole stomach accounted for 24.0% (223/930) of all Borrmann type IIII( gastric cancer cases undergoing surgical resection at the same period. There were 147 males and 76 females with an average age of 57.8 years. All the patients underwent total gastrectomy. Of these patients, radical resection was performed in 149 cases(66.8%) and palliative resection in 74 cases (33.2%). Combined organ resection was performed in 43 patients (19.3%), including 25 splenectomies, 6 pancreatic body and tail plus spleen and transverse colon resections, 2 transverse colon plus spleen resections, 2 right colon resections, 2 transverse colon resections, 2 ovariectomies, 1 partial jejunal resection, 1 pancreatoduodenectomy, 1 pancreatic tail plus transverse colon resection, and 1 partial pancreatectomy. Postoperative complications occurred in 28 patients(12.6%), including 10 patients with combined organ resection. Esophagojejunal fistula was the most frequent complication, accounting for 39.3%(11/28). Perioperative mortality occurred in 3 patients (1.3%). Thirty-nine patients underwent preoperative adjuvant chemotherapy (clinical stage: cT4aN0M0 in 1 patient, cT4bN1-2M0 in 12 patients, cT4aN1-2M0 in 20 patients, and cT4aN3M0 in 6 patients). Among these 39 patients, post-chemotherapeutic degenerative response was detected in 25 postoperative pathological specimens (64.1%), radical resection was performed in 21 patients (53.8%), distant metastasis was observed in 7 patients (17.9%) and peritoneal metastasis was found in 17 patients (43.6%) during operation. The average maximal tumor diameter was 13.2 cm (range from 6 to 22). Histological types included 23 moderate-poorly differentiated adenocarcinomas (10.3%), 146 poorly differentiated adenocarcinomas (65.5%), 41 signet ring cell carcinomas (18.4%), 11 mucinous adenocarcinomas(4.9%), 1 squamous cell carcinoma (0.4%) and 1 undifferentiated carcinoma (0.4%). Tumor-infiltrating duodenum was found in 57 patients (25.6%) and tumor-infiltrating esophagus in 132 patients (59.2%). The positive margin was found in 66 patients (29.6%): upper margin in 35 patients (15.7%), lower margin in 22 patients (9.9%), and both margins in 9 patients(4.0%). Immunohistochemical positive HER2(3+) was detected in 4 patients (1.8%). Tumor infiltrating into serosa(T4a) was found in 197 patients (88.3%) and infiltrating into adjacent organ (T4b) in 26 patients(11.7%). One hundred and forty-three cases (64.1%) had lymphatic or venous invasion, 187 (83.9%) had neural invasion, and 35 (15.7%) had cancer nodules. Of 149 patients undergoing radical resection, 5 patients were stage II(b, 9 patients were III(a, 20 patients were III(b and 115 patients were III(c. Of 145 patients(65.0%) undergoing postoperative chemotherapy, the average cycles of chemotherapy was 3.6 (median 3 cycles) and only 69 patients (47.6%) completed 4 cycles or more. Patients were followed up for 1-102 months (average 17.3 months). The median overall survival time was 13.8 months and the 1-, 3-, and 5-year survival rate was 57.9%, 14.1% and 6.8% respectively. The median survival time of the 149 cases with radical resection was 16.7 months and the 1-, 3- and 5-year survival rate was 67.5%, 16.5% and 8.4% respectively; the median survival time of the 74 cases with palliative resection was 10.3 months and the 1-, 3- and 5-year survival rate was 42.6%, 8.5% and 1.7% respectively, whose differences were statistically significant (all P=0.000). Multivariate analysis showed that tumor staging (P=0.005), radical resection (P=0.009), lymphatic or venous invasion (P=0.017) and postoperative chemotherapy (P=0.001) were independent prognostic factors. Surgical treatment for Borrmann type IIII( gastric cancer involving the whole stomach is safe. Radical resection can improve the prognosis though the overall survival is poor.

What Aspects of Personal Care Are Most Important to Patients Undergoing Radiation Therapy for Prostate Cancer?

PubMed

Foley, Kimberley A; Feldman-Stewart, Deb; Groome, Patti A; Brundage, Michael D; McArdle, Siobhan; Wallace, David; Peng, Yingwei; Mackillop, William J

2016-02-01

The overall quality of patient care is a function of the quality of both its technical and its nontechnical components. The purpose of this study was to identify the elements of nontechnical (personal) care that are most important to patients undergoing radiation therapy for prostate cancer. We reviewed the literature and interviewed patients and health professionals to identify elements of personal care pertinent to patients undergoing radiation therapy for prostate cancer. We identified 143 individual elements relating to 10 aspects of personal care. Patients undergoing radical radiation therapy for prostate cancer completed a self-administered questionnaire in which they rated the importance of each element. The overall importance of each element was measured by the percentage of respondents who rated it as "very important." The importance of each aspect of personal care was measured by the mean importance of its elements. One hundred eight patients completed the questionnaire. The percentage of patients who rated each element "very important" ranged from 7% to 95% (mean 61%). The mean importance rating of the elements of each aspect of care varied significantly: "perceived competence of caregivers," 80%; "empathy and respectfulness of caregivers," 67%; "adequacy of information sharing," 67%; "patient centeredness," 59%; "accessibility of caregivers," 57%; "continuity of care," 51%; "privacy," 51%; "convenience," 45%; "comprehensiveness of services," 44%; and "treatment environment," 30% (P<.0001). Neither age nor education was associated with importance ratings, but the patient's health status was associated with the rating of some elements of care. Many different elements of personal care are important to patients undergoing radiation therapy for prostate cancer, but the 3 aspects of care that most believe are most important are these: the perceived competence of their caregivers, the empathy and respectfulness of their caregivers, and the adequacy of information sharing. Copyright © 2016 Elsevier Inc. All rights reserved.

Acid proliferation to improve the sensitivity of EUV resists: a pulse radiolysis study

NASA Astrophysics Data System (ADS)

Enomoto, Kazuyuki; Arimitsu, Koji; Yoshizawa, Atsutaro; Yamamoto, Hiroki; Oshima, Akihiro; Kozawa, Takahiro; Tagawa, Seiichi

2011-04-01

The yields of acid have been measured in the electron-beam irradiation of triphenylsulfonium triflate (TPS-Tf) and pinanediol monosulfonates, which consist of tosylate (PiTs), 4-fluorobenzenesulfonate (Pi1F), or 4-trifluoromethylbenzenesulfonate (Pi3F), as an acid amplifier blended in 4-hydroxystyrene matrixes. The acid yields efficiency decreases when PiTs is present, while its efficiency increases in the presence of Pi3F. Reactions of the electrons with TPS-Tf and pinanediol monosulfonates have been studied using pulse radiolysis in liquid tetrahydrofuran (THF) to evaluate the kinetic contributions to acid production. The THF-solvated electrons react with PiTs, Pi1F, and Pi3F to produce the corresponding radical anions; the rate constants are estimated to be 4.1, 5.1, and 9.2 × 1010 M-1 s-1, respectively. Electron transfer from PiTs•-, Pi1F•-, and Pi3F•- radical anions to TPS-Tf occurs with the rate constants of 5.7×1010, 1.2×1011, and 6.3 × 1010 M-1 s-1, respectively. The long-lived Pi3F•- efficiently undergoes the electron transfer to TPS-Tf to form the TPS-Tf•-, which subsequently decompose to generate TfOH. On the other hand, the decay channels of PiTs•- and Pi1F•-, which possess a relatively short lifetime, are presumably dependent on its reactions with solvated protons (charge recombination) rather than the electron transfer to TPS-Tf. The novel acid production pathway via the electron transfer from pinanediol monosulfonate radical anions to TPS-Tf is presented.

Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.

The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and themore » result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.« less

Ionic liquids as an electrolyte for the electro synthesis of organic compounds.

PubMed

Kathiresan, Murugavel; Velayutham, David

2015-12-25

The use of ionic liquids (ILs) as a solvent and an electrolyte for electro organic synthesis has been reviewed. To date several ILs exist, however the ILs based on tetraalkylammonium, pyrrolidinium, piperidinium and imidazolium cations with BF4(-), PF6(-), and TFSI anions have been widely used and explored the most. Electro organic synthesis in ionic liquid media leading to the synthesis of a wide range of organic compounds has been discussed. Anodic oxidation or cathodic reduction will generate radical cation or anion intermediates, respectively. These radicals can undergo self coupling or coupling with other molecules yielding organic compounds of interest. The cation of the IL is known to stabilize the radical anion extensively. This stabilization effect has a specific impact on the electrochemical CO2 reduction and coupling to various organics. The relative stability of the intermediates in IL leads to the formation of specific products in higher yields. Electrochemical reduction of imidazolium or thiazolium based ILs generates N-heterocyclic carbenes that have been shown to catalyze a wide range of base or nucleophile catalyzed organic reactions in IL media, an aspect that falls into the category of organocatalysis. Electrochemical fluorination or selective electrochemical fluorination is another fascinating area that delivers selectively fluorinated organic products in Et3N·nHF or Et4NF·nHF adducts (IL) via anodic oxidation. Oxidative polymerization in ILs has been explored the most; although morphological changes were observed compared to the conventional methods, polymers were obtained in good yields and in some cases ILs were used as dopants to improve the desired properties.

Radical prostatectomy, sparing of the seminal vesicles, and painful orgasm.

PubMed

Mogorovich, Andrea; Nilsson, Andreas E; Tyritzis, Stavros I; Carlsson, Stefan; Jonsson, Martin; Haendler, Leif; Nyberg, Tommy; Steineck, Gunnar; Wiklund, N Peter

2013-05-01

Erectile dysfunction has been widely investigated as the major factor responsible for sexual bother in patients after radical prostatectomy (RP); painful orgasm (PO) is one element of this bother, but little is known about its prevalence and its effects on sexual health. This study aims to investigate the prevalence of PO and to identify potential risk factors. A total of 1,411 consecutive patients underwent open (radical retropubic prostatectomy) or robot-assisted laparoscopic RP between 2002 and 2006. The patients were asked to complete a study-specific questionnaire. Of a total of 145 questions, 5 dealt with the orgasmic characteristics. The questionnaire was also administered to a comparison group of 442 persons, matched for age and area of residency. The response rate was 91% (1,288 patients). A total of 143 (11%) patients reported PO. Among the 834 men being able to have an orgasm, the prevalence was 18% vs. 6% in the comparison group (relative risk [RR] 2.8, 95% confidence interval [CI] 1.7-4.5). When analyzed as independent variables, bilateral seminal vesicle (SV)-sparing approach (RR 2.33, 95% CI 1.0-5.3, P = 0.045) and age <60 years were significantly related to the presence of PO (95% CI 0.5-0.9, P = 0.019). After adjustment for age, bilateral SV-sparing still remained a significant predictor for occurrence of PO. We found that PO occurs significantly more often in patients undergoing bilateral SV-sparing RP when compared with age-matched comparison population. © 2013 International Society for Sexual Medicine.

Tamoxifen metabolism in rat liver microsomes: identification of a dimeric metabolite derived from free radical intermediates by liquid chromatography/mass spectrometry.

PubMed

Jones, R M; Yuan, Z X; Lim, C K

1999-01-01

Tamoxifen has been shown to be a potent liver carcinogen in rats, and generates covalent DNA adducts. On-line high performance liquid chromatography/electrospray ionisation mass spectrometry (HPLC/ESI-MS) has been used to further study the metabolites of tamoxifen formed by rat liver microsomes in the presence of NADPH with a view to identifying potential reactive metabolites which may be responsible for the formation of DNA adducts, and liver carcinogenesis. A metabolite has been detected with a protonated molecule at m/z 773. The mass of this compound is consistent with a dimer of hydroxylated tamoxifen (m/z 388). Analysis of 4-hydroxytamoxifen incubated with a rat liver microsomal preparation showed the formation of a similar metabolite with an apparent MH+ ion at m/z 773, believed to be a dimer of 4-hydroxytamoxifen formed by a free radical reaction. The retention time for this metabolite from 4-hydroxytamoxifen is identical to that of the tamoxifen metabolite, suggesting that these two compounds are the same. The levels of the dimer were higher when 4-hydroxytamoxifen was used as substrate and, in addition, two isomers were detected. It is proposed that tamoxifen was first converted to arene oxides which react with DNA or to 4-hydroxytamoxifen, either directly or via 3,4-epoxytamoxifen, which then undergoes activation via a free radical reaction to give reactive intermediates which can then react with DNA and protein, or with themselves, to give the dimers (m/z 773).

Establishment of a Web-based System for Collection of Patient-reported Outcomes After Radical Prostatectomy in a Statewide Quality Improvement Collaborative.

PubMed

Lucas, Steven M; Kim, Tae-Kyung; Ghani, Khurshid R; Miller, David C; Linsell, Susan; Starr, Jay; Peabody, James O; Hurley, Patrick; Montie, James; Cher, Michael L

2017-09-01

To report on the establishment of a unified, electronic patient-reported outcome (PRO) infrastructure and pilot results from the first 5 practices enrolled in the web-based collection system developed by the Michigan Urological Surgery Improvement Collaborative. Eligible patients were those undergoing radical prostatectomy of 5 academic and community practices. PRO was obtained using a validated 21-item web-based questionnaire, regarding urinary function, erection function, and sexual interest and satisfaction. Data were collected preoperatively, at 3 months, and 6 months postoperatively. Patients were provided a link via email to complete the surveys. Perioperative and PRO data were analyzed as reports for individual patients and summary performance reports for individual surgeons. Among 773 eligible patients, 688 (89%) were enrolled preoperatively. Survey completion rate was 88%, 84%, and 90% preoperatively, at 3 months, and 6 months. Electronic completion rates preoperatively, at 3 months, and 6 months were 70%, 70%, and 68%, respectively. Mean urinary function scores were 18.3, 14.3, and 16.6 (good function ≥ 17), whereas mean erection scores were 18.7, 7.3, and 9.1 (good erection score ≥ 22) before surgery, at 3 months, and 6 months. Variation was noted for erectile function among the practices. Collection of electronic PRO via this unified, web-based format was successful and provided results that reflect expected recovery and identify opportunities for improvement. This will be extended to more practices statewide to improve outcomes after radical prostatectomy. Copyright © 2017 Elsevier Inc. All rights reserved.

Treatment decision-making strategies and influences in patients with localized prostate carcinoma.

PubMed

Gwede, Clement K; Pow-Sang, Julio; Seigne, John; Heysek, Randy; Helal, Mohamed; Shade, Kristin; Cantor, Alan; Jacobsen, Paul B

2005-10-01

Patients diagnosed with localized prostate carcinoma need to interpret complicated medical information to make an informed treatment selection from among treatments that have comparable efficacy but differing side effects. The authors reported initial results for treatment decision-making strategies among men receiving definitive treatment for localized prostate carcinoma. One hundred nineteen men treated with radical prostatectomy (44%) or brachytherapy (56%) consented to participate. Guided by a cognitive-affective theoretic framework, the authors assessed differences in decision-making strategies, and treatment and disease-relevant beliefs and affects, in addition to demographic and clinical variables. Approximately half of patients reported difficulty (49%) and distress (45%) while making treatment decisions, but no regrets (74%) regarding the treatment choice they made. Patients who underwent prostatectomy were younger, were more likely to be employed, had worse tumor grade, and had a shorter time since diagnosis (P < 0.01) compared with patients who did not undergo prostatectomy. In multivariate analyses, compared with patients who received radical prostatectomy, patients who received brachytherapy were more likely to say that they chose this treatment because it was "the least invasive" and they "wanted to avoid surgery" (P < 0.0001). In general, patients who received brachytherapy chose this treatment because of quality of life considerations, whereas "cure" and complete removal of the tumor were the main motivations for patients selecting radical prostatectomy. Long-term data are needed to evaluate distress and decisional regret as patients experience treatment-related chronic side effects and efficacy outcomes. Decision-making aids or other interventions to reduce decisional difficulty and emotional distress during decision making were indicated.

Chemoradiation With Paclitaxel and Carboplatin in High-Risk Cervical Cancer Patients After Radical Hysterectomy: A Korean Gynecologic Oncology Group Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Taek Sang; Kang, Soon Beom, E-mail: tslee70@gmail.com; Kim, Young Tak

Purpose: To evaluate the efficacy and toxicity of concurrent chemoradiation with paclitaxel and carboplatin in patients with high-risk cervical cancer. Methods and Materials: Patients after radical hysterectomy for cervical cancer, with at least 1 high-risk characteristic, were administered paclitaxel 135 mg/m{sup 2}, carboplatin area under the curve = 5 every 3 weeks for 3 cycles concomitant with radiation therapy as adjuvant treatment. Results: This prospective study enrolled 71 consecutive patients. Sixty-six patients (93%) completed the planned treatment. The majority of grade 3/4 neutropenia or nonhematologic toxicities were usually self-limited. Diarrhea grades 3/4 were observed in 4 patients (5.6%). One patientmore » developed anaphylactic shock after infusion of paclitaxel. With a median follow-up of 57 months, recurrences occurred in 16 patients. Multivariable analysis indicated that common iliac lymph node involvement is an independent risk factor for disease recurrence (odds ratio 13.48; 95% confidence interval 2.93-62.03). In the intent-to-treat population (n=71), the estimated 5-year disease-free survival and overall survival rates were 77.3% and 80.3% respectively. In the per-protocol population (n=62), disease-free survival was 78.9% and overall survival was 83.9%. Conclusions: Concurrent chemoradiation with paclitaxel/carboplatin is well tolerated and seems to be effective for patients who undergo radical hysterectomy. Therefore, a prospective, randomized controlled study should be designed to evaluate efficacy of this approach for patients with high-risk cervical cancer.« less

Cost-analysis comparison of robot-assisted laparoscopic radical cystectomy (RC) vs open RC.

PubMed

Lee, Richard; Chughtai, Bilal; Herman, Michael; Shariat, Shahrokh F; Scherr, Douglas S

2011-09-01

• To systematically review and compare the economic burden of open radical cystectomy (ORC) vs robot-assisted laparoscopic radical cystectomy (RALRC) with pelvic lymph node dissection and urinary diversion. • A Medline search was conducted to identify English language articles regarding RC with urinary diversion. The resulting articles were then further restricted by the terms 'laparoscopic', 'robotic', or 'robotic-assisted'.In all, three articles were identified. • Data from each of these articles were then collected on cost performance in addition to relevant clinical variables, such as length of stay (LOS), operative duration, and complication rates. • When possible, data were subdivided by ileal conduit (IC), continent cutaneous diversion (CCD), and orthotopic neobladder (ON) subgroups. • Direct costs resulting from ORC or RALRC with accompanying hospitalization were identified. The indirect costs of complications were considered. • Despite an increased materials cost, RALRC was less expensive than ORC when the cost of complications was considered. • RALRC was less expensive than ORC for IC and CCD, but the cost advantage deteriorated for ON. • The largest cost drivers cited in the published data were LOS, operative durations, and daily hospitalizations costs. • RALRC demonstrated shorter LOS compared with ORC, although this effect was insufficient to offset the increased cost of robotic surgery. • Complications materially affected cost performance. • Despite an increased materials cost, RALRC can be more cost efficient than ORC as a treatment for bladder cancer when the impact of complications are considered. • This effect is most pronounced for patients undergoing IC. © 2011 THE AUTHORS. BJU INTERNATIONAL © 2011 BJU INTERNATIONAL.

Theoretical and experimental evidence of the photonitration pathway of phenol and 4-chlorophenol: a mechanistic study of environmental significance.

PubMed

Bedini, Andrea; Maurino, Valter; Minero, Claudio; Vione, Davide

2012-02-01

Light-induced nitration pathways of phenols are important processes for the transformation of pesticide-derived secondary pollutants into toxic derivatives in surface waters and for the formation of phytotoxic compounds in the atmosphere. Moreover, phenols can be used as ˙NO(2) probes in irradiated aqueous solutions. This paper shows that the nitration of 4-chlorophenol (4CP) into 2-nitro-4-chlorophenol (NCP) in the presence of irradiated nitrate and nitrite in aqueous solution involves the radical ˙NO(2). The experimental data allow exclusion of an alternative nitration pathway by ˙OH + ˙NO(2). Quantum mechanical calculations suggest that the nitration of both phenol and 4CP involves, as a first pathway, the abstraction of the phenolic hydrogen by ˙NO(2), which yields HNO(2) and the corresponding phenoxy radical. Reaction of phenoxyl with another ˙NO(2) follows to finally produce the corresponding nitrated phenol. Such a pathway also correctly predicts that 4CP undergoes nitration more easily than phenol, because the ring Cl atom increases the acidity of the phenolic hydrogen of 4CP. This favours the H-abstraction process to give the corresponding phenoxy radical. In contrast, an alternative nitration pathway that involves ˙NO(2) addition to the ring followed by H-abstraction by oxygen (or by ˙NO(2) or ˙OH) is energetically unfavoured and erroneously predicts faster nitration for phenol than for 4CP. This journal is © The Royal Society of Chemistry and Owner Societies 2012

Preparation and mechanical characterization of a PNIPA hydrogel composite.

PubMed

Liu, Kaifeng; Ovaert, Timothy C; Mason, James J

2008-04-01

A poly (N-isopropylacrylamide) (PNIPA) hydrogel was synthesized by free radical polymerization and reinforced with a polyurethane foam to make a hydrogel composite. The temperature dependence of the elastic modulus of the PNIPA hydrogel and the composite due to volume phase transition was found using a uniaxial compression test, and the swelling property was investigated using an equilibrium swelling ratio experiment. The gel composite preserves the ability to undergo the volume phase transition and its elastic modulus has strong temperature dependence. The temperature dependence of the elastic modulus and swelling ratio of the gel composite were compared to the PNIPA hydrogel. Not surprisingly, the modulus and swelling ratio of the composite were less dramatic than in the gel.

Comparison of the rates of ozonation of biological antioxidants and oleate and linoleate esters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Giamalva, D.; Church, D.F.; Pryor, W.A.

1985-12-17

The rates of reaction with ozone of some biological antioxidants and simple polyunsaturated fatty acids (PUFA) have been measured in water or in aqueous micellar solutions. At pH 7.0 the rate constants are ca. 10(6) M-1 sec-1 for urate, alpha-tocopherol, and PUFA, and 6 X 10(7) M-1 sec-1 for ascorbate. When ozone-containing air is breathed, ascorbate in the lung may undergo direct ozonation. However, alpha-tocopherol is probably spared direct reaction with ozone because it doesn't effectively compete with PUFA in pulmonary membranes; rather, tocopherol is used to scavenge radicals produced from the ozone-PUFA reaction.

Mutations in TP53 are a prognostic factor in colorectal hepatic metastases undergoing surgical resection.

PubMed

Molleví, David G; Serrano, Teresa; Ginestà, Mireia M; Valls, Joan; Torras, Jaume; Navarro, Matilde; Ramos, Emilio; Germà, Josep R; Jaurrieta, Eduardo; Moreno, Víctor; Figueras, Joan; Capellà, Gabriel; Villanueva, Alberto

2007-06-01

The aim of this study was to analyze the prognostic value of TP53 mutations in a consecutive series of patients with hepatic metastases (HMs) from colorectal cancer undergoing surgical resection. Ninety-one patients with liver metastases from colorectal carcinoma were included. Mutational analysis of TP53, exons 4-10, was performed by single-strand conformation polymorphism and sequencing. P53 and P21 protein immunostaining was assessed. Multivariate Cox models were adjusted for gender, number of metastasis, resection margin, presence of TP53 mutations and chemotherapy treatment. Forty-six of 91 (50.05%) metastases showed mutations in TP53, observed mainly in exons 5-8, although 14.3% (n = 13) were located in exons 9 and 10. Forty percent (n = 22) were protein-truncating mutations. TP53 status associated with multiple (> or =3) metastases (65.6%, P = 0.033), advanced primary tumor Dukes' stage (P = 0.011) and younger age (<57 years old, P = 0.03). Presence of mutation associated with poor prognosis in univariate (P = 0.017) and multivariate Cox model [hazard ratio (HR) = 1.80, 95% confidence interval (CI) = 1.07-3.06, P = 0.028]. Prognostic value was maintained in patients undergoing radical resection (R0 series, n = 79, P = 0.014). Mutation associated with a worse outcome in chemotherapy-treated patients (HR = 2.54, 95% CI = 1.12-5.75, P = 0.026). The combination of > or =3 metastases and TP53 mutation identified a subset of patients with very poor prognosis (P = 0.009). P53 and P21 protein immunostaining did not show correlation with survival. TP53 mutational status seems to be an important prognostic factor in patients undergoing surgical resection of colorectal cancer HMs.

Psychotherapy and phosphodiesterase-5 inhibitor in early rehabilitation after radical prostatectomy: a prospective randomised controlled trial.

PubMed

Naccarato, A M E P; Reis, L O; Ferreira, U; Denardi, F

2016-12-01

The aim of this study was to evaluate the impact of group psychotherapy and the use of a phosphodiesterase-5 inhibitor (PDE-5i) in the early rehabilitation stage of patients with prostate cancer undergoing radical prostatectomy (RP). Fifty-six patients undergoing RP for prostate cancer were randomised into four groups, and 53 completed the protocol: Group 1 - control (n = 11), Group 2 - group psychotherapy (n = 16), Group 3 - lodenafil 80 mg/one tablet per week (n = 12) and Group 4 - group psychotherapy + lodenafil 80 mg/one tablet per week (n = 14). The groups were individually evaluated for erectile function (IIEF-5) and quality of life - QoL (SF-36) weekly, with two meetings held a week apart before the RP and 12 weekly meetings after surgery. The ages ranged from 39 to 76 years, average 61.84. There were no significant medication side effects. Only Group 4 showed improvement in intimacy with a partner and satisfaction with their sex life (P = 0.045 and P = 0.013 respectively), and with no significant worsening of the IIEF-5 (P = 0.250) reported. All groups showed worsening in the final result of the role limitations caused by physical problems (P = 0.009) and role limitations caused by emotional problems (P = 0.002) of the SF-36, but Group 4 had a significantly higher score for the role limitations caused by physical problems (P = 0.009) than the other groups. In conclusion, precocious integral treatment involving group psychotherapy and PDE-5i before and after RP led to less deterioration of erectile function and other domains related to physical aspects (SF-36), with improvement in intimacy with their partner and satisfaction in their sex life, being superior to single treatments. © 2016 Blackwell Verlag GmbH.

Multiparametric magnetic resonance imaging and frozen-section analysis efficiently predict upgrading, upstaging, and extraprostatic extension in patients undergoing nerve-sparing robotic-assisted radical prostatectomy

PubMed Central

Bianchi, Roberto; Cozzi, Gabriele; Petralia, Giuseppe; Alessi, Sarah; Renne, Giuseppe; Bottero, Danilo; Brescia, Antonio; Cioffi, Antonio; Cordima, Giovanni; Ferro, Matteo; Matei, Deliu Victor; Mazzoleni, Federica; Musi, Gennaro; Mistretta, Francesco Alessandro; Serino, Alessandro; Tringali, Valeria Maria Lucia; Coman, Ioan; De Cobelli, Ottavio

2016-01-01

Abstract To evaluate the role of multiparametric magnetic resonance imaging (mpMRI) in predicting upgrading, upstaging, and extraprostatic extension in patients with low-risk prostate cancer (PCa). MpMRI may reduce positive surgical margins (PSM) and improve nerve-sparing during robotic-assisted radical prostatectomy (RARP) for localized prostate cancer PCa. This was a retrospective, monocentric, observational study. We retrieved the records of patients undergoing RARP from January 2012 to December 2013 at our Institution. Inclusion criteria were: PSA <10 ng/mL; clinical stage

Multiparametric magnetic resonance imaging and frozen-section analysis efficiently predict upgrading, upstaging, and extraprostatic extension in patients undergoing nerve-sparing robotic-assisted radical prostatectomy.

PubMed

Bianchi, Roberto; Cozzi, Gabriele; Petralia, Giuseppe; Alessi, Sarah; Renne, Giuseppe; Bottero, Danilo; Brescia, Antonio; Cioffi, Antonio; Cordima, Giovanni; Ferro, Matteo; Matei, Deliu Victor; Mazzoleni, Federica; Musi, Gennaro; Mistretta, Francesco Alessandro; Serino, Alessandro; Tringali, Valeria Maria Lucia; Coman, Ioan; De Cobelli, Ottavio

2016-10-01

To evaluate the role of multiparametric magnetic resonance imaging (mpMRI) in predicting upgrading, upstaging, and extraprostatic extension in patients with low-risk prostate cancer (PCa). MpMRI may reduce positive surgical margins (PSM) and improve nerve-sparing during robotic-assisted radical prostatectomy (RARP) for localized prostate cancer PCa.This was a retrospective, monocentric, observational study. We retrieved the records of patients undergoing RARP from January 2012 to December 2013 at our Institution. Inclusion criteria were: PSA <10 ng/mL; clinical stage

Retroperitoneal Laparoscopic Partial Nephrectomy Versus Radical Nephrectomy for Clinical T1 Renal Hilar Tumor: Comparison of Perioperative Characteristics and Short-Term Functional and Oncologic Outcomes.

PubMed

Yang, Chuance; Wang, Zhenlong; Huang, Shanlong; Xue, Li; Fu, Delai; Chong, Tie

2018-04-18

To present our single-center experience with retroperitoneal laparoscopic partial nephrectomy (LPN) and retroperitoneal laparoscopic radical nephrectomy (LRN) for T1 renal hilar tumors and evaluate which one is better. A retrospective review of 63 patients with hilar tumors undergoing retroperitoneal LPN or LRN was performed. The perioperative characteristics, change in estimated glomerular filtration rate (eGFR) from baseline to month 3, and oncologic outcomes were summarized. In total, 25 patients underwent LPN, and 38 patients underwent LRN. The mean tumor size in the LPN and LRN groups was 4.5 and 4.9 cm, respectively. The mean operation time was longer in the LPN group than that in the LRN group (212.5 minutes versus 160.7 minutes, respectively; P < .05). Patients undergoing the LPN had a longer median length of hospital stay after surgery (9 days versus 7 days, P < .05). Four percent of patients in the LPN group experienced postoperative complications compared with 5% of patients in the LRN group, which was not significantly different. Compared with preoperative eGFR, postoperative eGFR at 3 months decreased by 15.2 mL/min/1.73 m 2 and 27.8 mL/min/1.73 m 2 in the LPN and the LRN groups, respectively (P < .05). There was one local recurrence in the LPN group and three local or distant recurrences in the LRN group (P > .05). In experienced hands, although retroperitoneal LRN can result in shorter operation times and shorter lengths of stay, retroperitoneal LPN can preserve renal function better than LRN. Retroperitoneal LPN should be the priority in selected patients with T1 renal hilar tumors, especially for patients with renal insufficiency.

Improving the prediction of pathologic outcomes in patients undergoing radical prostatectomy: the value of prostate cancer antigen 3 (PCA3), prostate health index (phi) and sarcosine.

PubMed

Ferro, Matteo; Lucarelli, Giuseppe; Bruzzese, Dario; Perdonà, Sisto; Mazzarella, Claudia; Perruolo, Giuseppe; Marino, Ada; Cosimato, Vincenzo; Giorgio, Emilia; Tagliamonte, Virginia; Bottero, Danilo; De Cobelli, Ottavio; Terracciano, Daniela

2015-02-01

Several efforts have been made to find biomarkers that could help clinicians to preoperatively determine prostate cancer (PCa) pathological characteristics and choose the best therapeutic approach, avoiding over-treatment. On this effort, prostate cancer antigen 3 (PCA3), prostate health index (phi) and sarcosine have been presented as promising tools. We evaluated the ability of these biomarkers to predict the pathologic PCa characteristics within a prospectively collected contemporary cohort of patients who underwent radical prostatectomy (RP) for clinically localized PCa at a single high-volume Institution. The prognostic performance of PCA3, phi and sarcosine were evaluated in 78 patients undergoing RP for biopsy-proven PCa. Receiver operating characteristic (ROC) curve analyses tested the accuracy (area under the curve (AUC)) in predicting PCa pathological characteristics. Decision curve analyses (DCA) were used to assess the clinical benefit of the three biomarkers. We found that PCA3, phi and sarcosine levels were significantly higher in patients with tumor volume (TV)≥0.5 ml, pathologic Gleason sum (GS)≥7 and pT3 disease (all p-values≤0.01). ROC curve analysis showed that phi is an accurate predictor of high-stage (AUC 0.85 [0.77-0.93]), high-grade (AUC 0.83 [0.73-0.93]) and high-volume disease (AUC 0.94 [0.88-0.99]). Sarcosine showed a comparable AUC (0.85 [0.76-0.94]) only for T3 stage prediction, whereas PCA3 score showed lower AUCs, ranging from 0.74 (for GS) to 0.86 (for TV). PCA3, phi and sarcosine are predictors of PCa characteristics at final pathology. Successful clinical translation of these findings would reduce the frequency of surveillance biopsies and may enhance acceptance of active surveillance (AS). Copyright© 2015 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives† †Electronic supplementary information (ESI) available: Experimental information, synthesis and characterization data, NMR spectra, solid state NMR data, X-ray data, ESR spectra, UV-Vis-NIR spectra, fluorescence spectra, kinetic experiments, theoretical calculations, Tables S1–S8, Scheme S1, Fig. S1–12, References. CCDC 1025063, 1038914, 1049677 and 1040722. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00946d

PubMed Central

Pandit, Palash; Yamamoto, Koji; Nakamura, Toshikazu; Nishimura, Katsuyuki; Kurashige, Yuki; Yanai, Takeshi; Nakamura, Go; Masaoka, Shigeyuki; Furukawa, Ko; Yakiyama, Yumi; Kawano, Masaki

2015-01-01

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt3, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials. PMID:29218181

Ileal conduit vs orthotopic neobladder: Which one offers the best health-related quality of life in patients undergoing radical cystectomy? A systematic review of literature and meta-analysis.

PubMed

Ziouziou, I; Irani, J; Wei, J T; Karmouni, T; El Khader, K; Koutani, A; Iben Attya Andaloussi, A

2018-04-01

Orthotopic neobladder (ONB) and ileal conduit (IC) are the most commonly practiced techniques of urinary diversion (UD) after radical cystectomy (RC) in bladder cancer patients. Data in the literature is still discordant regarding which UD technique offers the best HR-QoL. The objective was to compare HR-QoL in patients undergoing ONB and IC after RC, through a systematic review of the literature and meta-analysis. We performed a literature search of PubMed, ScienceDirect, CochraneLibrary and ClinicalTrials.Gov in September 2017 according to the Cochrane Handbook and the Preferred Reporting Items for Systematic Reviews and Meta-Analyzes. The studies were evaluated according to the "Oxford Center for Evidence-Based Medicine" criteria. The outcome measures evaluated were subdomains' scores of Bladder Cancer Index BCI: urinary function (UF), urinary bother (UB), bowel function (BF), bowel bother (BB), sexual function (SF) and sexual bother (SB). Continuous outcomes were compared using weighted means differences, with 95% confidence intervals. The presence of publication bias was examined by funnel plots. Four studies met the inclusion criteria. The pooled results demonstrated better UF and UB scores in IC patients: differences were -18.17 (95% CI: -27.49, -8.84, P=0.0001) and -3.72 (95% CI: -6.66, -0.79, P=0.01) respectively. There was no significant difference between IC and ONB patients in terms of BF and BB. SF was significantly better in ONB patients: the difference was 12.7 (95% CI, 6.32, 19.08, P<0.0001). However no significant difference was observed regarding SB. This meta-analysis of non-randomized studies demonstrated a better HR-QoL in urinary outcomes in IC patients compared with ONB patients. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Health information quality on the internet for bladder cancer and urinary diversion: a multi-lingual analysis.

PubMed

Corfield, Julia M; Abouassaly, Robert; Lawrentschuk, Nathan

2018-04-01

Bladder cancer patients undergoing radical cystectomy and urinary diversion are faced with difficult decisions regarding mode of urinary diversion. Although these patients may use the Internet as a guide to diagnosis and treatment options, online resources remain largely unregulated leading to a great variation in quality of medical information. Further variation in quality is seen between languages. Fortunately, tools such as an automated toolbar developed by the World Health Organization Health on the Net (HON) Foundation exist to assist physicians in recommending quality online health information to patients. We set out to compare and assess the quality of bladder cancer, ileal conduit and orthotopic neobladder web sites in 2016 on the basis of the HON principles for English language. The Google search engine imbedded with the HON toolbar was used to assess 1350 Web sites using the keywords "bladder cancer", "ileal conduit" and "orthotopic neobladder" in English, Italian and Spanish. The first 150 results of each search were identified and screened. A further analysis was completed comparing results between 2009 and 2016. Less than 20% of English, Italian and Spanish "bladder cancer" and urinary diversion ("ileal conduit" and "orthotopic neobladder") web sites are HON-accredited. HON-accredited web sites featured preferentially in the first 50 search results for bladder cancer (P=0.0001) and ileal conduit (P=0.03) web sites. Comparing 2016 results to 2009, percentage of HON-accreditation has not shown statistically significant change (-13%, P=0.23), while overall number of search results has increased (+44%). A lack of validation of bladder cancer sites is present, which is consistent across modes of urinary diversion (orthotopic neobladder and ileal conduit) and languages. It is important that physicians involved in the care of bladder cancer patients undergoing radical cystectomy and urinary diversion participate in the development of informative, ethical, and reliable health Web sites and direct patients to them.

Lymph node dissection technique is more important than lymph node count in identifying nodal metastases in radical cystectomy patients: a comparative mapping study.

PubMed

Dorin, Ryan P; Daneshmand, Siamak; Eisenberg, Manuel S; Chandrasoma, Shahin; Cai, Jie; Miranda, Gus; Nichols, Peter W; Skinner, Donald G; Skinner, Eila C

2011-11-01

The value of lymph node dissection (LND) in the treatment of bladder urothelial carcinoma is well established. However, standards for the quality of LND remain controversial. We compared the distribution of lymph node (LN) metastases in a two-institution cohort of patients undergoing radical cystectomy (RC) using a uniformly applied extended LND template. Patients undergoing RC at the University of Southern California (USC) Institute of Urology and at Oregon Health Sciences University (OHSU) were included if they met the following criteria: (1) no prior pelvic radiotherapy or LND; (2) lymphatic tissue submitted from all nine predesignated regions, including the paracaval and para-aortic LNs; (3) bladder primary; and (4) category M0 disease. The number and location of LN metastases were prospectively entered into corresponding databases. LN maps were constructed and correlated with preoperative and pathologic characteristics. Kaplan-Meier curves were constructed to estimate overall survival (OS) and recurrence free survival (RFS) among LN-positive (LN+) patients. Inclusion criteria were met by 646 patients (439 USC, 207 OHSU), and 23% had LN metastases at time of cystectomy. Although there was a difference in the median per-patient LN count between institutions, there were no significant interinstitutional differences in the incidence or distribution of positive LNs, which were found in 11% of patients with ≤pT2b and in 44% of patients with ≥pT3a tumors. Among LN+ patients, 41% had positive LNs above the common iliac bifurcation. Estimated 5-yr RFS and OS rates for LN+ patients were 45% and 33%, respectively, and did not differ significantly between institutions. LN metastases in regions outside the boundaries of standard LND are common. Adherence to meticulous dissection technique within an extended template is likely more important than total LN count for achieving optimal oncologic outcomes. Copyright © 2011 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Transversus Abdominis Plane Blockade as Part of a Multimodal Postoperative Analgesia Plan in Patients Undergoing Radical Cystectomy.

PubMed

Matulewicz, Richard S; Patel, Mehul; Jordan, Brian J; Morano, Jacqueline; Frainey, Brendan; Bhanji, Yasin; Bux, Mahreen; Nader, Antoun; Kundu, Shilajit D; Meeks, Joshua J

2018-04-26

Radical cystectomy (RC) is a morbid procedure with frequent complications that may benefit from implementation of an enhanced recovery after surgery (ERAS) protocol. To examine the benefits of a multimodal analgesic plan that uses continuous transversus abdominis plane (TAP) blockade as part of an ERAS protocol after RC. A retrospective comparison of consecutive patients undergoing RC over a 4-year period was conducted. Patients were designated as having surgery either before or after implementation of an ERAS protocol. A major component of the ERAS protocol was a multi-modal analgesia plan with TAP blockade. Patient demographics, comorbidities, operative details, and outcomes, including days to flatus, bowel movement (BM), narcotic usage, and length of stay (LOS) were compared. In total, 171 patients were included: 100 pre-ERAS and 71 ERAS. There were no differences in age, smoking status, operative approach, or diversion type. The patients in the ERAS cohort were less likely to be male, had a higher median BMI, and more likely to have received neoadjuvant chemotherapy. Total and early postoperative narcotic use were lower in the ERAS cohort: 89 vs. 336 mg ( p  < 0.001) and 62 vs 203 mg ( p  = 0.001), respectively. The ERAS cohort had fewer days to flatus (3 vs. 4, p  < 0.001) and fewer days to bowel movement (4 vs. 5, p  < 0.001). Median LOS was shorter in the ERAS cohort (7 vs. 8.5d, p  = 0.001). There were no differences in complications or readmission rates between the two cohorts. TAP blockade as part of an ERAS multi-modal pain plan is associated with low narcotic usage, and significant improvement in time to flatus, BM, and LOS compared to traditional post-RC pain management.

Prospective, Controlled Study of Invasiveness and Post-Aggression Metabolism in Patients Undergoing Robotic-Assisted Radical Prostatectomy.

PubMed

Martinschek, Andreas; Stumm, Lisa; Ritter, Manuel; Heinrich, Elmar; Bolenz, Christian; Trojan, Lutz

2017-01-01

To evaluate in a prospective, controlled, nonrandomized study the surgical stress and acute-phase systemic response in robotic-assisted laparoscopic prostatectomy (RALP) compared to open radical retro-pubic prostatectomy (ORRP) by measuring humoral mediators. Forty consecutive patients undergoing either RALP or ORRP were prospectively included to assess the extent of systemic response. Blood samples were collected before surgery (T1), at the time of prostatectomy (T2), at the time of wound closure (T3), and 12 h (T4), 24 h (T5), and 48 h (T6) after surgery, and assayed for interleukins (IL-6 and IL-10), C-reactive protein (CRP), and hemoglobin. A 2-sided p < 0.05 was considered to indicate significance. Baseline levels of IL-6, IL-10, and CRP were comparable in both arms of the study. IL-6 and IL-10 increased in both groups during surgery and reached maximum levels at 12 and 24 h after surgery. The RALP and RRP groups differed significantly at T2 (p = 0.009), T3 (p = 0.046), T5 (p = 0.05) and T6 (p = 0.0007) for IL-6, and at T3 (p = 0.05) and T4 (p = 0.05) for IL-10. CRP levels differed significantly at 48 h postoperative (p = 0.0053). The maximum levels of all 3 mediators in the RALP group were significantly lower than those in the open surgery group. Patients in the RALP group experienced less pain from day 2 to 4 according to the Visual Analog Scale (p < 0.05). The study suggests that IL-6 and IL-10 are useful objective markers for surgical stress and that tissue trauma and activation of post-aggression metabolism seem to be less in RALP compared to ORRP. © 2017 S. Karger AG, Basel.

Importance of chewing, saliva, and swallowing function in patients with advanced oral cancer undergoing preoperative chemoradiotherapy: a prospective study of quality of life.

PubMed

Nemeth, D; Zaleczna, L; Huremovic, A; Engelmann, J; Poeschl, P W; Strasz, M; Holawe, S; Kornek, G; Laskus, A; Sacher, C; Erovic, B M; Perisanidis, C

2017-10-01

The primary objective of this study was to investigate the quality of life (QOL) of patients with oral squamous cell carcinoma (OSCC) undergoing curative neoadjuvant chemoradiotherapy followed by radical tumour resection and simultaneous oral cavity reconstruction, using two validated questionnaires. A secondary objective was to assess clinical variables predicting post-treatment dysfunction in chewing, saliva, and swallowing. Thirty-five patients with locally advanced OSCC who underwent preoperative chemoradiotherapy were recruited prospectively. All patients completed both the University of Washington Quality of Life version 4 questionnaire (UW-QOL) and the Functional Assessment of Cancer Therapy-Head & Neck version 4 questionnaire (FACT-H&N). UW-QOL and FACT-H&N items were associated with clinical variables. Nearly three-quarters of OSCC patients perceived good to excellent levels of overall QOL after preoperative chemoradiotherapy. Chewing difficulties, decreased salivary function, and swallowing dysfunction were the most frequent complaints of OSCC patients. Items related to food intake were significantly worse in OSCC patients older than 60 years and those with T4 tumours, as well as those without alcohol intake. Chewing, saliva, and swallowing are the most significant issues in patients with OSCC undergoing preoperative chemoradiotherapy. The results of this study may help guide treatment decisions for OSCC patients based on more accurate expectations of adverse effects of cancer treatment. Copyright © 2017 International Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

Health resource use after robot-assisted surgery vs open and conventional laparoscopic techniques in oncology: analysis of English secondary care data for radical prostatectomy and partial nephrectomy.

PubMed

Hughes, David; Camp, Charlotte; O'Hara, Jamie; Adshead, Jim

2016-06-01

To evaluate postoperative health resource utilisation and secondary care costs for radical prostatectomy and partial nephrectomy in National Health Service (NHS) hospitals in England, via a comparison of robot-assisted, conventional laparoscopic and open surgical approaches. We retrospectively analysed the secondary care records of 23 735 patients who underwent robot-assisted (RARP, n = 8 016), laparoscopic (LRP, n = 6 776) or open radical prostatectomy (ORP, n = 8 943). We further analysed 2 173 patients who underwent robot-assisted (RAPN, n = 365), laparoscopic (LPN, n = 792) or open partial nephrectomy (OPN, n = 1 016). Postoperative inpatient admissions, hospital bed-days, excess bed-days and outpatient appointments at 360 and 1 080 days after surgery were reviewed. Patients in the RARP group required significantly fewer inpatient admissions, hospital bed-days and excess bed-days at 360 and 1 080 days than patients undergoing ORP. Patients undergoing ORP had a significantly higher number of outpatient appointments at 1 080 days. The corresponding total costs were significantly lower for patients in the RARP group at 360 days (£1679 vs £2031 for ORP; P < 0.001) and at 1 080 days (£3461 vs £4208 for ORP; P < 0.001). In partial nephrectomy, Patients in the RAPN group required significantly fewer inpatient admissions and hospital bed-days at 360 days compared with those in the OPN group; no significant differences were observed in outcomes at 1 080 days. The corresponding total costs were lower for patients in the RAPN group at 360 days (£779 vs £1242 for OPN, P = 0.843) and at 1 080 days (£2122 vs £2889 for ORP; P = 0.570). For both procedure types, resource utilisation and costs for laparoscopic surgeries lay at the approximate midpoint of those for robot-assisted and open surgeries. Our analysis provides compelling evidence to suggest that RARP leads to reduced long-term health resource utilisation and downstream cost savings compared with traditional open and laparoscopic approaches. Furthermore, despite the limitations that arise from the inclusion of a small sample, these results also suggest that robot-assisted surgery may represent a cost-saving alternative to existing surgical options in partial nephrectomy. Further exploration of clinical cost drivers, as well as an extension of the analysis into subsequent years, could lend support to the wider commissioning of robot-assisted surgery within the NHS. © 2015 The Authors BJU International © 2015 BJU International Published by John Wiley & Sons Ltd.

Fractionation of mercury isotopes by photo-oxidation in aquatic systems

NASA Astrophysics Data System (ADS)

Ghosh, S.; Bergquist, B. A.; Blum, J. D.

2009-12-01

Mercury is a globally distributed pollutant that bioaccumulates in aquatic food webs, even in remote locations. The recent discovery of both large mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) has made the promise of tracing this neurotoxin through the environment by using its isotopes very exciting. So far, the only process demonstrated experimentally to produce large MIF for Hg (similar in magnitude to the MIF observed in natural samples such as fish) is photochemical reduction (Bergquist and Blum, 2007). During photo-reduction, MIF of the odd isotopes was observed with the odd isotopes (199Hg, 201Hg) being preferentially enriched in the aqueous phase. Bergquist and Blum, 2007, suggested that the cause of MIF was the magnetic isotope effect (MIE), which is purely a kinetic phenomenon involving radical pair intermediates. Radical pairs with odd isotopes, which have non-zero nuclear spin and magnetic moments, can undergo spin conversion faster than radical pairs with non-magnetic even isotopes. This allows the odd and even isotopes to be preferentially enriched in different reaction products. MIE is a complex phenomenon that is dependent on several factors including hyperfine coupling, life-time of the radical pair, coupling strength of the radical pair, spin-orbital coupling, diffusion factors, and the solvent cage (space) in which the reaction occurs. Only under rare circumstances will all the factors be suitable for the expression of MIE in natural reactions. The goal of this study was to conduct aqueous photo-oxidation reactions to investigate whether this redox pathway expresses MIF (in the form of MIE) similar to the photo-reduction pathway. In natural systems, net photo-reduction of Hg (II) species results in the release of Hg(0) vapor to the atmosphere. However this net photo-reduction is a combination of both photo-reduction and photo-oxidation. In their experiments, Bergquist and Blum 2007, only investigated the aqueous photo-reduction pathway and suppressed the photo-oxidation reaction. Photochemical oxidation experiments of Hg(0) were performed in quartz reaction chambers using natural sunlight. Solutions of aqueous Hg(0) were prepared by continuously bubbling vapor Hg(0) generated by a gas-liquid separator into the quartz reaction chamber filled with water. Experiments were conducted in the presence of Cl- and other potential oxidants such as semiquinone, hydroxyl radicals and H2O2 to assess if the presence of these different oxidants showed significant differences in the expression of Hg isotopic fractionation during the photo-oxidation process. For experiments run in the presence of Cl- only, ~2% of Hg was oxidized at the end of 7 hours whereas in the presence of both semiquinone radical and Cl- , approximately 20% of Hg was oxidized at the end of 6 hours. In the experiment with hydroxyl radicals present, ~ 7% of Hg was oxidized at the end of 6.5 hours. Another set of experiments were conducted where the net photo-reduction was mimicked, which allowed both photo-oxidation and photo-reduction to occur. Isotopic results and their implications on the redox cycle of mercury obtained from these experiments will be discussed in detail.

ASCA Temperature Maps for Merging and Relaxed Clusters and Physics of the Cluster Gas

NASA Technical Reports Server (NTRS)

Markevitch, M.; Sarazin, C.; Nevalainen, J.; Vikhlinin, A.; Forman, W.

1999-01-01

ASCA temperature maps for several galaxy clusters undergoing strong mergers will be presented. From these maps, it is possible to estimate velocities of the colliding subclusters. I will discuss several interesting implications of these estimates for the physics of the cluster gas and the shape of the gravitational potential. I will also present temperature maps and profiles for several relaxed clusters selected for X-ray mass determination, and present the mass values derived without the assumption of isothermality. The accurate mass-temperature and luminosity-temperature relations will be discussed. This talk will review how AXAF will revolutionize X-ray astronomy through its radically better imaging and spectroscopic resolution. Examples from many fields of astrophysics will be given.

Recurrent Obstructive Giant Inflammatory Polyposis of the Colon

PubMed Central

Budhraja, Vikram

2016-01-01

Inflammatory polyps are relatively common in patients with inflammatory bowel disease. The term giant inflammatory polyposis is used to describe inflammatory polyps greater than 1.5 cm in any dimension. Their clinical presentation can be varied, ranging from asymptomatic, with incidental detection on radiological or endoscopic testing, to symptomatic, with rectal bleeding and colonic obstruction. Although giant inflammatory polyposis is a rare finding, it is of clinical importance, since it is easily mistaken for colon cancer, with patients sometimes undergoing radical surgeries. We describe an unusual case of giant inflammatory polyposis causing recurrent symptomatic obstruction despite multiple segmental colectomies in a patient with indeterminate colitis. This is the first such reported case in English literature to the best of our knowledge. PMID:27807551

Recurrent Obstructive Giant Inflammatory Polyposis of the Colon.

PubMed

Syal, Gaurav; Budhraja, Vikram

2016-08-01

Inflammatory polyps are relatively common in patients with inflammatory bowel disease. The term giant inflammatory polyposis is used to describe inflammatory polyps greater than 1.5 cm in any dimension. Their clinical presentation can be varied, ranging from asymptomatic, with incidental detection on radiological or endoscopic testing, to symptomatic, with rectal bleeding and colonic obstruction. Although giant inflammatory polyposis is a rare finding, it is of clinical importance, since it is easily mistaken for colon cancer, with patients sometimes undergoing radical surgeries. We describe an unusual case of giant inflammatory polyposis causing recurrent symptomatic obstruction despite multiple segmental colectomies in a patient with indeterminate colitis. This is the first such reported case in English literature to the best of our knowledge.

Modernizing the British National Health Service (NHS) -- some ideological and policy considerations.

PubMed

Bradshaw, Peter L

2003-03-01

The British National Health Service (NHS) is undergoing a seemingly unprecedented reorganization. The present Government is attempting to modernize a system of care that has been relatively unchanged for over 50 years amid a great deal of its own publicity about its achievements. This paper begins by briefly examining the ideological basis of these reforms. It proceeds to interrogate the rationale for current health policy from the perspective of the Government. It then analyses the arguments of the detractors who oppose the form these changes are taking. The paper concludes that modernization of the NHS is mainly cosmetic but its significance concerns the stimulation of a broader and radical debate about the future funding and delivery of health care in Britain.

Cancer and intercellular cooperation

PubMed Central

Dieli, Anna Maria

2017-01-01

The major transitions approach in evolutionary biology has shown that the intercellular cooperation that characterizes multicellular organisms would never have emerged without some kind of multilevel selection. Relying on this view, the Evolutionary Somatic view of cancer considers cancer as a breakdown of intercellular cooperation and as a loss of the balance between selection processes that take place at different levels of organization (particularly single cell and individual organism). This seems an elegant unifying framework for healthy organism, carcinogenesis, tumour proliferation, metastasis and other phenomena such as ageing. However, the gene-centric version of Darwinian evolution, which is often adopted in cancer research, runs into empirical problems: proto-tumoural and tumoural features in precancerous cells that would undergo ‘natural selection’ have proved hard to demonstrate; cells are radically context-dependent, and some stages of cancer are poorly related to genetic change. Recent perspectives propose that breakdown of intercellular cooperation could depend on ‘fields’ and other higher-level phenomena, and could be even mutations independent. Indeed, the field would be the context, allowing (or preventing) genetic mutations to undergo an intra-organism process analogous to natural selection. The complexities surrounding somatic evolution call for integration between multiple incomplete frameworks for interpreting intercellular cooperation and its pathologies. PMID:29134064

Potential prevention: Aloe vera mouthwash may reduce radiation-induced oral mucositis in head and neck cancer patients.

PubMed

Ahmadi, Amirhossein

2012-08-01

In recent years, more head and neck cancer patients have been treated with radiotherapy. Radiation-induced mucositis is a common and dose limiting toxicity of radiotherapy among patients with head and neck cancers. Patients undergoing radiation therapy for head and neck cancer are also at increased risk of developing oral candidiasis. A number of new agents applied locally or systemically to prevent or treat radiation-induced mucositis have been investigated, but there is no widely accepted prophylactic or effective treatment for mucositis. Topical Aloe vera is widely used for mild sunburn, frostbites, and scalding burns. Studies have reported the beneficial effects of Aloe gel for wound healing, mucous membrane protection, and treatment of oral ulcers, in addition to antiinflammatory, immunomudulation, antifungal, scavenging free radicals, increasing collagen formation and inhibiting collagenase. Herein the author postulates that oral Aloe vera mouthwash may not only prevent radiation-induced mucositis by its wound healing and antiinflammatory mechanism, but also may reduce oral candidiasis of patients undergoing head and neck radiotherapy due to its antifungal and immunomodulatory properties. Hence, Aloe vera mouthwash may provide an alternative agent for treating radiation-induced oral mucositis and candidiasis in patients with head and neck cancers.

Intestinal stoma in patients with colorectal cancer from the perspective of 20-year period of clinical observation

PubMed Central

Banaszkiewicz, Zbigniew; Woda, Łukasz P.; Tojek, Krzysztof; Jarmocik, Paweł; Jawień, Arkadiusz

2015-01-01

Introduction Intestinal stoma is a procedure most often performed in patients with colorectal cancer. Aim To identify the percentage of patients with colorectal cancer in which the intestinal stoma was performed. Material and methods We retrospectively analysed 443 patients treated during a 20-year period (1994–2013) due to colorectal cancer, in which the intestinal stoma was made during the first surgical intervention. Results In the second analysed decade, a significant decrease in the percentage of created stomas, definitive stomas in particular, was observed. Stomas were made significantly more often in patients with a tumour located in the rectum, the left half of the colon, and in patients undergoing urgent surgeries. An increased incidence of intestinal stomas was associated with a higher severity of illness and higher proportion of unresectable and non-radical procedures. The definitive stomas were significantly more often made in men and in patients with tumours located in the rectum, whereas temporary stomas were created significantly more often in patients undergoing urgent operations. Conclusions In the last decade (2004–2013) the number of intestinal stomas in patients operated due to colorectal cancer was significantly reduced. PMID:25960811

Electrolysis with diamond anodes: Eventually, there are refractory species!

PubMed

Mena, Ismael F; Cotillas, Salvador; Díaz, Elena; Sáez, Cristina; Rodríguez, Juan J; Cañizares, P; Mohedano, Ángel F; Rodrigo, Manuel A

2018-03-01

In this work, synthetic wastewater polluted with ionic liquid 1-butyl-3-methylimidazolium (Bmim) bis(trifluoromethanesulfonyl)imide (NTf 2 ) undergoes four electrolytic treatments with diamond anodes (bare electrolysis, electrolysis enhanced with peroxosulfate promoters, irradiated with UV light and with US) and results obtained were compared with those obtained with the application of Catalytic Wet Peroxide Oxidation (CWPO). Despite its complex heterocyclic structure, Bmim + cation is successfully depleted with the five technologies tested, being transformed into intermediates that eventually can be mineralized. Photoelectrolysis attained the lowest concentration of intermediates, while CWPO is the technology less efficient in their degradation. However, the most surprising result is that concentration of NTf 2 - anion does not change during the five advanced oxidation processes tested, pointing out its strong refractory character, being the first species that exhibits this character in wastewater undergoing electrolysis with diamond. This means that the hydroxyl and sulfate radicals mediated oxidation and the direct electrolysis are inefficient for breaking the C-S, C-F and S-N bounds of the NTf 2 - anion, which is a very interesting mechanistic information to understand the complex processes undergone in electrolysis with diamond. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isomerization and fragmentation reactions of gaseous phenylarsane radical cations and phenylarsanyl cations. A study by tandem mass spectrometry and theoretical calculations.

PubMed

Letzel, Matthias; Kirchhoff, Dirk; Grützmacher, Hans-Friedrich; Stein, Daniel; Grützmacher, Hansjörg

2006-04-28

The unimolecular reactions of radical cations and cations derived from phenylarsane, C6H5AsH2 (1) and dideutero phenylarsane, C6H5AsD2 (1-d2), were investigated by methods of tandem mass spectrometry and theoretical calculations. The mass spectrometric experiments reveal that the molecular ion of phenylarsane, 1*+, exhibits different reactivity at low and high internal excess energy. Only at low internal energy the observed fragmentations are as expected, that is the molecular ion 1*+ decomposes almost exclusively by loss of an H atom. The deuterated derivative 1-d2 with an AsD2 group eliminates selectively a D atom under these conditions. The resulting phenylarsenium ion [C6H5AsH]+, 2+, decomposes rather easily by loss of the As atom to give the benzene radical cation [C6H6]*+ and is therefore of low abundance in the 70 eV EI mass spectrum. At high internal excess energy, the ion 1*+ decomposes very differently either by elimination of an H2 molecule, or by release of the As atom, or by loss of an AsH fragment. Final products of these reactions are either the benzoarsenium ion 4*+, or the benzonium ion [C6H7]+, or the benzene radical cation, [C6H6]*+. As key-steps, these fragmentations contain reductive eliminations from the central As atom under H-H or C-H bond formation. Labeling experiments show that H/D exchange reactions precede these fragmentations and, specifically, that complete positional exchange of the H atoms in 1*+ occurs. Computations at the UMP2/6-311+G(d)//UHF/6-311+G(d) level agree best with the experimental results and suggest: (i) 1*+ rearranges (activation enthalpy of 93 kJ mol(-1)) to a distinctly more stable (DeltaH(r)(298) = -64 kJ mol(-1)) isomer 1 sigma*+ with a structure best represented as a distonic radical cation sigma complex between AsH and benzene. (ii) The six H atoms of the benzene moiety of 1 sigma*+ become equivalent by a fast ring walk of the AsH group. (iii) A reversible isomerization 1+<==>1 sigma*+ scrambles eventually all H atoms over all positions in 1*+. The distonic radical cation 1*+ is predisposed for the elimination of an As atom or an AsH fragment. The calculations are in accordance with the experimentally preferred reactions when the As atom and the AsH fragment are generated in the quartet and triplet state, respectively. Alternatively, 1*(+) undergoes a reductive elimination of H2 from the AsH2 group via a remarkably stable complex of the phenylarsandiyl radical cation, [C6H5As]*+ and an H2 molecule.

Properties of Intermediates in the Catalytic Cycle of Oxalate Oxidoreductase and Its Suicide Inactivation by Pyruvate

PubMed Central

2017-01-01

Oxalate:ferredoxin oxidoreductase (OOR) is an unusual member of the thiamine pyrophosphate (TPP)-dependent 2-oxoacid:ferredoxin oxidoreductase (OFOR) family in that it catalyzes the coenzyme A (CoA)-independent conversion of oxalate into 2 equivalents of carbon dioxide. This reaction is surprising because binding of CoA to the acyl-TPP intermediate of other OFORs results in formation of a CoA ester, and in the case of pyruvate:ferredoxin oxidoreductase (PFOR), CoA binding generates the central metabolic intermediate acetyl-CoA and promotes a 105-fold acceleration of the rate of electron transfer. Here we describe kinetic, spectroscopic, and computational results to show that CoA has no effect on catalysis by OOR and describe the chemical rationale for why this cofactor is unnecessary in this enzymatic transformation. Our results demonstrate that, like PFOR, OOR binds pyruvate and catalyzes decarboxylation to form the same hydroxyethylidine–TPP (HE–TPP) intermediate and one-electron transfer to generate the HE–TPP radical. However, in OOR, this intermediate remains stranded at the active site as a covalent inhibitor. These and other results indicate that, like other OFOR family members, OOR generates an oxalate-derived adduct with TPP (oxalyl-TPP) that undergoes decarboxylation and one-electron transfer to form a radical intermediate remaining bound to TPP (dihydroxymethylidene–TPP). However, unlike in PFOR, where CoA binding drives formation of the product, in OOR, proton transfer and a conformational change in the “switch loop” alter the redox potential of the radical intermediate sufficiently to promote the transfer of an electron into the iron–sulfur cluster network, leading directly to a second decarboxylation and completing the catalytic cycle. PMID:28514140

Primary photophysical properties of moxifloxacin--a fluoroquinolone antibiotic.

PubMed

Lorenzo, Fernando; Navaratnam, Suppiah; Edge, Ruth; Allen, Norman S

2008-01-01

The photophysical properties of the fluoroquinolone antibiotic moxifloxacin (MOX) were investigated in aqueous media. MOX in water, at pH 7.4, shows two intense absorption bands at 287 and 338 nm (epsilon = 44,000 and 17,000 dm(3) mol(-1) cm(-1), respectively). The absorption and emission properties of MOX are pH-dependent, pK(a) values for the protonation equilibria of both the ground (6.1 and 9.6) and excited singlet states (6.8 and 9.1) of MOX were determined spectroscopically. MOX fluoresces weakly, the quantum yield for fluorescence emission being maximum (0.07) at pH 8. Phosphorescence from the excited triplet state in frozen ethanol solution has a quantum yield of 0.046. Laser flash photolysis and pulse radiolysis studies have been carried out to characterize the transient species of MOX in aqueous solution. On laser excitation, MOX undergoes monophotonic photoionization with a quantum yield of 0.14. This leads to the formation of a long-lived cation radical whose absorption is maximum at 470 nm (epsilon(470) = 3400 dm(3) mol(-1) cm(-1)). The photoionization process releases hydrated electron which rapidly reacts (k = 2.8 x 10(10) dm(3) mol(-1) s(-1)) with ground state MOX, yielding a long-lived anion radical with maximum absorption at 390 nm (epsilon(390) = 2400 dm(3) mol(-1) cm(-1)). The cation radical of MOX is able to oxidize protein components tryptophan and tyrosine. The bimolecular rate constants for these reactions are 2.3 x 10(8) dm(3) mol(-1) s(-1) and 1.3 x 10(8) dm(3) mol(-1) s(-1), respectively. Singlet oxygen sensitized by the MOX triplet state was also detected only in oxygen-saturated D(2)O solutions, with a quantum yield of 0.075.

Radical-molecule reaction C3H+H2O: a mechanistic study.

PubMed

Dong, Hao; Ding, Yi-Hong; Sun, Chia-Chung

2005-02-08

Despite the importance of the C(3)H radical in both combustion and interstellar space, the reactions of C(3)H toward stable molecules have never been studied. In this paper, we report our detailed mechanistic study on the radical-molecule reaction C(3)H+H(2)O at the Becke's three parameter Lee-Yang-Parr-B3LYP6-311G(d,p) and coupled cluster with single, double, and triple excitations-CCSD(T)6-311G(2d,p) (single-point) levels. It is shown that the C(3)H+H(2)O reaction initially favors formation of the carbene-insertion intermediates HCCCHOH (1a,1b) rather than the direct H- or OH-abstraction process. Subsequently, the isomers (1a,1b) can undergo a direct H- extrusion to form the well-known product propynal HCCCHO (P(5)). Highly competitively, (1a,1b) can take the successive 1,4- and 1,2-H-shift interconversion to isomer H(2)CCCHO(2a,2b) and then to isomer H(2)CCHCO(3a,3b), which can finally take a direct C-C bond cleavage to give product C(2)H(3) and CO (P(1)). The other products are kinetically much less feasible. With the overall entrance barrier 10.6 kcal/mol, the title reaction can be important in postburning processes. Particularly, our calculations suggest that the title reaction may play a role in the formation of the intriguing interstellar molecule, propynal HCCCHO. The calculated results will also be useful for the analogous C(3)H reactions such as with ammonia and alkanes.

Optimizing outcome reporting after radical cystectomy for organ-confined urothelial carcinoma of the bladder using oncological trifecta and pentafecta.

PubMed

Aziz, Atiqullah; Gierth, Michael; Rink, Michael; Schmid, Marianne; Chun, Felix K; Dahlem, Roland; Roghmann, Florian; Palisaar, Rein-Jüri; Noldus, Joachim; Ellinger, Jörg; Müller, Stefan C; Pycha, Armin; Martini, Thomas; Bolenz, Christian; Moritz, Rudolf; Herrmann, Edwin; Keck, Bastian; Wullich, Bernd; Mayr, Roman; Fritsche, Hans-Martin; Burger, Maximilian; Bastian, Patrick J; Seitz, Christian; Brookman-May, Sabine; Xylinas, Evanguelos; Shariat, Shahrokh F; Fisch, Margit; May, Matthias

2015-12-01

Radical cystectomy (RC) for urothelial carcinoma of the bladder (UCB) is associated with heterogeneous functional and oncological outcomes. The aim of this study was to generate trifecta and pentafecta criteria to optimize outcome reporting after RC. We interviewed 50 experts to consider a virtual group of patients (age ≤ 75 years, ASA score ≤ 3) undergoing RC for a cT2 UCB and a final histology of ≤pT3pN0M0. A ranking was generated for the three and five criteria with the highest sum score. The criteria were applied to the Prospective Multicenter Radical Cystectomy Series 2011. Multivariable binary logistic regression analyses were used to evaluate the impact of clinical and histopathological parameters on meeting the top selected criteria. The criteria with the highest sum score were negative soft tissue surgical margin, lymph node (LN) dissection of at least 16 LNs, no complications according to Clavien-Dindo grade 3-5 within 90 days after RC, treatment-free time between TUR-BT with detection of muscle-invasive UCB and RC <3 months and the absence of local UCB-recurrence in the pelvis ≤12 months. The first three criteria formed trifecta, and all five criteria pentafecta. A total of 334 patients qualified for final analysis, whereas 35.3 and 29 % met trifecta and pentafecta criteria, respectively. Multivariable analyses showed that the relative probability of meeting trifecta and pentafecta decreases with higher age (3.2 %, p = 0.043 and 3.3 %, p = 0.042) per year, respectively. Trifecta and pentafecta incorporate essential criteria in terms of outcome reporting and might be considered for the improvement of standardized quality assessment after RC for UCB.

Surveillance of colorectal cancer: effectiveness of early detection of intraluminal recurrences on prognosis and survival of patients treated for cure.

PubMed

Barillari, P; Ramacciato, G; Manetti, G; Bovino, A; Sammartino, P; Stipa, V

1996-04-01

The authors evaluate the effectiveness of routine colonoscopy and marker evaluation in diagnosis of intraluminal recurrent cancer. Chart review was conducted on 481 patients who underwent curative resection for colorectal cancer between 1980 and 1990. Clinical visits were scheduled and carcinoembryonic antigen evaluation was performed every three months, and colonoscopy was performed preoperatively, 12 to 15 months after surgical treatment, and then with intervals of 12 to 24 months or when symptoms appeared. About 10 percent of patients developed intraluminal recurrences. More than one-half of metachronous lesions arose within the first 24 months, and median time to diagnosis was 25 months. Patients with left-sited tumors in the advanced stage had a higher risk of developing recurrent intraluminal disease. Twenty-nine patients underwent a second surgical operation, of which 17 cases were radical. In this group, the five-year survival was 70.6 percent, although no nonradically treated or nonresected patients survived longer than 31 months. Twenty-two patients were asymptomatic at time of diagnosis of recurrence, and of these, 12 patients underwent radical operation; on the other hand, of the 24 symptomatic patients, only 5 were treated radically. Carcinoembryonic antigen was the first sign of recurrence in eight cases. Colonoscopy must be performed within the first 12 to 15 months after operation, whereas an interval of 24 months between examinations seems sufficient to guarantee early detection of metachronous lesions. Serial tumor marker evaluation is of help in earlier diagnosis of local recurrences. Asymptomatic patients more frequently undergo another operation for cure and thus have a better survival rate.

Planned nerve preservation to reduce positive surgical margins during robot-assisted laparoscopic radical prostatectomy.

PubMed

Zorn, Kevin C; Gofrit, Ofer N; Steinberg, Gary P; Taxy, Jerome B; Zagaja, Gregory P; Shalhav, Arieh L

2008-06-01

The main objective of radical prostatectomy (RP) is optimal oncologic resection with preservation of sexual function (SF). During our initial experience with robot-assisted laparoscopic radical prostatectomy (RLRP), we noted a high rate of posterolateral location of positive surgical margins (PSM) with nerve preservation (NP). With its magnified view of the surgical field and improved instrument precision, one potential advantage of RLRP is the ability to tailor the degree of NP. We evaluated the effect of a protocol for side-specific NP based on preoperative variables on PSM rates and SF outcomes. Between June and November 2006, 150 consecutive RLRPs were performed using a surgical protocol to select side-specific NP techniques (interfascial [IF], partial extrafascial [pEF], and wide extrafascial resection [WEFR]) based on preoperative risk factors (clinical stage, biopsy Gleason score, percentage of positive cores and maximal core cancer percentage, and preoperative PSA). Pathologic and SF outcomes in these patients were compared with those of a control group of 245 consecutive RLRPs in whom non-selective IF dissection was performed. All data were prospectively collected. Mean patient age, PSA, clinical stage, biopsy Gleason score and positive core involvement, pathologic Gleason score, and stage were comparable among the two groups. The overall PSM rate (12.6% nu 20.4%; P = 0.04) and posterolateral location of PSMs (37% nu 70%; P = 0.04) were significantly lower in the study group. At 12 months, potency was reported in 80%, 67%, and 11% of men undergoing bilateral IFNP, partial extrafascial nerve preservation (pEFNP), and WEFR, respectively (P = 0.27). Planning side-specific NP during RLRP, according to selected preoperative variables, can significantly reduce overall and posterolateral PSM rates. Furthermore, partial nerve sparing (pEFNP) also appears to confer favorable early SF outcomes.

Robotic radical prostatectomy learning curve of a fellowship-trained laparoscopic surgeon.

PubMed

Zorn, Kevin C; Orvieto, Marcelo A; Gong, Edward M; Mikhail, Albert A; Gofrit, Ofer N; Zagaja, Gregory P; Shalhav, Arieh L

2007-04-01

Several experienced practitioners of open surgery with limited or no laparoscopic background have adopted robot-assisted laparoscopic radical prostatectomy (RLRP) as an alternative to open radical prostatectomy (RRP), demonstrating outcomes comparable to those in large RRP and laparoscopic prostatectomy series. Thus, the significance of prior laparoscopic skills seems unclear. The learning curve, with respect to operative time and complications, in the hands of a devoted laparoscopic surgeon has not been critically assessed. We evaluated the learning curve of a highly experienced laparoscopic surgeon in achieving expertise with RLRP. We prospectively evaluated 150 consecutive patients undergoing RLRP by a single surgeon between March 2003 and September 2005. The first 25 cases were performed with the assistance of a surgeon experienced in open RRP. Data were compared for the first, second, and third groups of 50 cases. Demographic data were similar for the three groups. Urinary and sexual function data were evaluated subjectively and objectively using the RAND-36v2 Survey and the UCLA PCI preoperatively and at 3, 6, and 12 months postoperatively. The mean operative time, blood loss, and conversion rate decreased significantly with increasing experience. All open conversions occurred during the first 25 cases. Intraoperative and postoperative complication rates were similar among groups. Although the differences were not significant, urinary and sexual function recovery improved with experience. The RLRP learning curve for a fellowship-trained laparoscopic surgeon seems to be similar to that of laparoscopically naive yet experienced practitioners of open RRP. The RLRP is safe and reproducible and even during the learning curve can produce results similar to those reported in large RRP series. The importance of assistance by an experienced open RRP surgeon during the learning curve cannot be overemphasized.

Robotic radical prostatectomy in patients with high-risk disease: a review of short-term outcomes from a high-volume center.

PubMed

Jayram, Gautam; Decastro, Guarionex J; Large, Michael C; Razmaria, Aria; Zagaja, Gregory P; Shalhav, Arieh L; Brendler, Charles B

2011-03-01

Patients with high-risk prostate cancer have historically been treated with multimodal therapy and considered poor candidates for minimally invasive surgery. We reviewed our experiences with robot-assisted radical prostatectomy (RARP) in patients with high-risk clinical features. Clinical database review identified high-risk patients undergoing RARP by two high-volume robotic surgeons. D'Amico's criteria for high-risk prostate cancer were utilized: prostate-specific antigen ≥ 20 ng/mL, clinical stage ≥ T2c, or preoperative Gleason grade ≥ 8. About 148 patients were identified in the study group. Mean age at surgery was 60.9 years, and mean body mass index was 27.9. Mean estimated blood loss was 150 cc and the transfusion rate was 2.7%. Median hospital stay was 1 day and the rate of major complications (Clavien grade ≥ 3) was 3.4%. Bilateral nerve preservation was feasible in 28.4%, and the rate of positive surgical margins was 20.9%. Final pathology demonstrated extra-capsular disease in 54.1% of patients and 12.3% had lymph node involvement. At 2 years of follow-up, 21.3% of patients had experienced biochemical recurrence or had persistent disease after treatment. Continence was 91.2% (1 pad or less) and total impotence (inability to masturbate) was 48.3%. RARP does not compromise oncologic or functional outcomes in patients with high-risk prostate cancer. Although long-term study is necessary to validate oncologic and functional outcomes, our data suggest that the presence of high-risk disease is not a contraindication to a minimally invasive approach for radical prostatectomy at experienced centers.

Photoionization of three isomers of the C9H7 radical.

PubMed

Hemberger, Patrick; Steinbauer, Michael; Schneider, Michael; Fischer, Ingo; Johnson, Melanie; Bodi, Andras; Gerber, Thomas

2010-04-15

Three resonance-stabilized radicals, 1-indenyl (Ind), 1-phenylpropargyl (1PPR), and 3-phenylpropargyl (3PPR), all isomers of the composition C(9)H(7), were generated by jet flash pyrolysis. Their photoionization was examined by VUV synchrotron radiation. The mass spectra show a clean and efficient radical generation when the pyrolysis is turned on. To study the photoionization, photoion yield measurements and threshold photoionization spectroscopy techniques were applied. We determined adiabatic ionization energies (IE(ad)) of 7.53 eV for Ind, 7.20 eV for 3PPR, and 7.4 eV for 1PPR. Ab initio calculations show no major change in geometry upon ionization, in agreement with ionization from a nonbonding molecular orbital. The IEs were also computed and are in agreement with the measured ones. The difference in the IE might allow a distinction of the three isomers in flames. In the indenyl spectrum, an excited a(+) (3)B(2) state of the cation was identified at 8.10 eV, which shows a low-energy vibrational progression of 61 meV. Furthermore, we have examined the dissociative photoionization of the precursors. The indenyl precursor, 1-indenyl bromide, undergoes dissociative photoionization to Ind(+). An appearance energy (AE(0K)) of 10.2 eV was obtained from fitting the experimental breakdown diagram. A binding energy of 1.8 eV can thus be determined for the C-Br bond in 1-indenyl bromide. The phenylpropargyl precursors 1PPBr (1-phenylpropargyl bromide/3-phenyl-3-bromopropyne) and 3PPBr (3-phenylpropargyl bromide/1-phenyl-3-bromopropyne) also lose a bromine atom upon dissociative photoionization. Approximate appearance energies of 9.8 eV for 3PPBr and 9.3 eV for 1PPBr have been determined.

Renal function and urological complications after radical hysterectomy with postoperative radiotherapy and platinum-based chemotherapy for cervical cancer.

PubMed

Okadome, Masao; Saito, Toshiaki; Kitade, Shoko; Ariyoshi, Kazuya; Shimamoto, Kumi; Kawano, Hiroyuki; Minami, Kazuhito; Nakamura, Motonobu; Shimokawa, Mototsugu; Okushima, Kazuhiro; Kubo, Yuichiro; Kunitake, Naonobu

2018-02-01

We aimed to clarify renal functional changes long term and serious urological complications in women with cervical cancer who undergo radical hysterectomy followed by pelvic radiotherapy and/or platinum-based chemotherapy to treat the initial disease. Data on 380 women who underwent radical hysterectomy at the National Kyushu Cancer Center from January 1997 to December 2013 were reviewed. Main outcome measures were the estimated glomerular filtration rate (eGFR) and monitored abnormal urological findings. Postoperative eGFR was significantly lower than preoperative eGFR in 179 women with surgery alone and in 201 women with additional pelvic radiotherapy and/or chemotherapy (both P < 0.01). Two types of univariate analyses for eGFR reduction in women after treatment showed that older age, advanced stage, pelvic radiotherapy, and platinum-based chemotherapy were significant variables on both analyses. Two types of multivariate analyses showed that platinum-based chemotherapy or pelvic radiotherapy were associated with impaired renal function (odds ratio 1.96, 95% confidence interval 1.08-3.54 and odds ratio 2.85, 95% confidence interval 1.12-7.24, for the respective analyses). There was a higher rate of bladder wall thickening in women with pelvic radiotherapy had than those without it (17.4% vs. 2.7%, P < 0.01). One serious urological complication (intraperitoneal rupture of the bladder) occurred among women who underwent pelvic radiotherapy (0.6% vs. 0%). Surgeons should be aware that eGFR is reduced after platinum-based chemotherapy and/or postoperative pelvic radiotherapy. Serious and life-threatening urological complications are rare, but surgeons should be aware of the possibility during the long follow-up. © The Author 2017. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Incidence, predictors and early post-operative course of diabetes insipidus in paediatric craniopharygioma: a comparison with adults.

PubMed

Pratheesh, Ravindran; Swallow, Diane Margaret A; Rajaratnam, Simon; Jacob, K S; Chacko, Geeta; Joseph, Mathew; Chacko, Ari G

2013-06-01

This study aims to determine the incidence, predictors, early post-operative course of diabetes insipidus (DI) in paediatric craniopharyngiomas(CP) and compare the findings with adults. Retrospective analysis of clinical, biochemical, radiological and operative data for 102 consecutive CP surgeries (45 paediatric and 57 adult cases) was done. Bivariate and multivariate analyses were done to determine the predictors of DI. The incidence of the triphasic response and electrolyte abnormalities in the first post-operative week was compared between children and adults. Children had larger tumours and higher incidence of cystic tumours and hydrocephalus. Preoperative DI was close to 15 % in both the age groups. Radical/subtotal excision was achieved in 58 % of children and 53 % of adults. The incidence of post-operative DI was 80 % and 63 % in children and adults, respectively. Children had significantly higher incidence of permanent DI (55.6 %). Radical excision in children (p = 0.000); previous tumour surgery (p = 0.014) and new onset hypopituitarism (p = 0.019) in adults were associated with permanent DI. The triphasic response (23 %), wide intra-day serum sodium fluctuations and hyponatraemia were more common in children. Post-operative DI is a frequent and significant cause of morbidity in children undergoing surgery for CP. Children have a higher incidence of permanent DI. Radical excision is a predictor of permanent DI in children, whereas previous tumour excision and new onset hypopituitarism were predictors of permanent DI among adults. The management of post-operative DI is more difficult in children and the treating physician needs to be alert to detect the triphasic response.

Novel Biomarker of Oxidative Stress Is Associated With Risk of Death in Patients With Coronary Artery Disease.

PubMed

Patel, Riyaz S; Ghasemzadeh, Nima; Eapen, Danny J; Sher, Salman; Arshad, Shawn; Ko, Yi-an; Veledar, Emir; Samady, Habib; Zafari, A Maziar; Sperling, Laurence; Vaccarino, Viola; Jones, Dean P; Quyyumi, Arshed A

2016-01-26

Free radical scavengers have failed to improve patient outcomes, promoting the concept that clinically important oxidative stress may be mediated by alternative mechanisms. We sought to examine the association of emerging aminothiol markers of nonfree radical mediated oxidative stress with clinical outcomes. Plasma levels of reduced (cysteine and glutathione) and oxidized (cystine and glutathione disulphide) aminothiols were quantified by high performance liquid chromatography in 1411 patients undergoing coronary angiography (mean age 63 years, male 66%). All patients were followed for a mean of 4.7 ± 2.1 years for the primary outcome of all-cause death (n=247). Levels of cystine (oxidized) and glutathione (reduced) were associated with risk of death (P<0.001 both) before and after adjustment for covariates. High cystine and low glutathione levels (>+1 SD and <-1 SD, respectively) were associated with higher mortality (adjusted hazard ratio [HR], 1.63; 95% confidence interval [CI], 1.19-2.21; HR, 2.19; 95% CI, 1.50-3.19; respectively) compared with those outside these thresholds. Furthermore, the ratio of cystine/glutathione was also significantly associated with mortality (adjusted HR, 1.92; 95% CI, 1.39-2.64) and was independent of and additive to high-sensitivity C-reactive protein level. Similar associations were found for other outcomes of cardiovascular death and combined death and myocardial infarction. A high burden of oxidative stress, quantified by the plasma aminothiols, cystine, glutathione, and their ratio, is associated with mortality in patients with coronary artery disease, a finding that is independent of and additive to the inflammatory burden. Importantly, these data support the emerging role of nonfree radical biology in driving clinically important oxidative stress. © 2015 The Authors.

Sensory blockade after thoracic paravertebral injection of ropivacaine or bupivacaine.

PubMed

Hura, G; Knapik, P; Misiołek, H; Krakus, A; Karpe, J

2006-08-01

No clinical trials comparing the characteristics of sensory blockade caused by various local anaesthetics in thoracic paravertebral blockade have been published. The aim of this prospective study was a clinical assessment of sensory blockade after paravertebral injection of ropivacaine or bupivacaine in patients undergoing modified radical mastectomy. Seventy ASA I-II patients were randomized to receive a single injection of ropivacaine 0.5% (n = 35) or bupivacaine 0.5% (n = 35) at the T4 level. General anaesthesia with propofol and fentanyl was provided during the procedure and patients were not intubated. The following parameters were analysed: duration and dynamics of the sensory blockade and the patient's and surgeon's assessment. Both ropivacaine and bupivacaine provided a similar level of analgesia. Ropivacaine was characterized by more rapid onset - after only 5 min 53% of patients in this group had the extent of sensory blockade wide enough to perform modified radical mastectomy in comparison to only 20% after bupivacaine (P 9 segments blocked) was noted more often in the ropivacaine group (88% vs. 65%, P < 0.05), lasted longer and appeared to be wider than sensory blockade produced by bupivacaine. Regression of sensory blockade was initially similar, but after 24 h sensory blockade in the ropivacaine group still had a potential to provide analgesia for modified radical mastectomy in 81% of patients in comparison to only 50% of such patients in the bupivacaine group (P < 0.05). Degree of postoperative pain, performance of the cardiovascular system, consumption of medications and complications were all similar between the study groups. Both agents provide satisfactory conditions for mastectomy, but ropivacaine seems to be superior to bupivacaine for thoracic paravertebral blockade during breast cancer surgery.

Risk of in-hospital complications after radical cystectomy for urinary bladder carcinoma: population-based follow-up study of 7608 patients

PubMed Central

Hemelrijck, Mieke; Thorstenson, Andreas; Smith, Philip; Adolfsson, Jan; Akre, Olof

2013-01-01

Objective To evaluate the risk of different in-hospital complications for patients undergoing a radical cystectomy (RC), as limited nationwide population data on short- and long-term complications after RC is available, despite it being the standard treatment for localised muscle-invasive urinary bladder cancer (UBC). Patients and Methods In all, 7608 persons underwent a RC after UBC diagnosis, as registered in the Swedish National Patient Register between 1964 and 2008. We estimated the frequency and incidences and calculated hazard ratios (HR) and 95% confidence intervals (CI) using multivariate Cox proportional hazards models. Results Urinary tract infection/septicaemia was the most common complication following radical cystectomy, with an incidence of 90.4 per 1,000 person years. There was a higher risk of urinary tract infection among patients who had a continent cutaneous reservoir (HR: 1.11 (0.94–1.30) or orthotopic neobladder 1.21 (1.05–1.39) than among those with ileal conduit. Similarly, continent cutaneous reservoir and orthotopic neobladder were associated with increased risks for wound and abdominal wall hernias, stones in the urinary tract, hydronephrosis and nephrostomy tube treatment, and kidney failure. In contrast, risk of bowel obstruction was lower among those with orthotopic neobladder than those with ileal conduit (HR: 0.64 (0.50–0.81)) and those with continent cutaneous reservoir (HR: 0.92 (0.73–1.16). Conclusions In-hospital complications after RC are numerous and continue to accumulate for many years after surgery, indicating the need for life-long follow-up of these patients. Comparison between different types of diversion should, however, be made with care because of potential confounding by indication. PMID:23906011

Evaluation of combined oncologic and functional outcomes after robotic-assisted laparoscopic extraperitoneal radical prostatectomy: trifecta rate of achieving continence, potency and cancer control.

PubMed

Xylinas, Evanguelos; Durand, Xavier; Ploussard, Guillaume; Campeggi, Alexandre; Allory, Yves; Vordos, Dimitri; Hoznek, Andras; Abbou, Claude Clément; de la Taille, Alexandre; Salomon, Laurent

2013-01-01

Outcomes of continence, erectile function, and oncologic control are well-described in isolation especially for the retropubic open approach. However, only few series have yet reported combined results after radical prostatectomy. To determine the proportion of men who are continent, potent, and cancer-free (trifecta rate) 2 years after robot-assisted laparoscopic radical prostatectomy (RALRP). We included patients who underwent a RALRP at our department and who were followed during at least 2 years. Men who were impotent or incontinent before the surgery were excluded from the analysis. Overall, 500 men were included. All patients prospectively completed validated questionnaires (IIEF-5, ICS) before the medical visit and concerning their voiding and sexual disorders, preoperatively, 3, 6, 12, 18, and 24 months after RALRP. Biochemical recurrence was defined as any detectable serum PSA (≥ 0.2 ng/ml). The study end point was the trifecta rate (cancer control, continence, and potency) at 2 years of the surgery. Predictive factors of the trifecta outcome were assessed in univariate and multivariate analyses. Median age and PSA level were 62.2 years and 9.7 ng/mL. A trifecta outcome was achieved in 44% and 53% of men at 12 and 24 months, respectively. The 2-year trifecta rate reached 62% in men undergoing bilateral nerve-sparing surgery and 71% in men < 60 years. Age < 60 years, PSA level < 10 ng/ml, organ-confined disease, and bilateral nerve-sparing procedure were significantly associated with the 2-year trifecta outcome. Two years after RALRP, the trifecta outcome is achieved in 53% of preoperatively potent and continent men. Copyright © 2013 Elsevier Inc. All rights reserved.

[Anastomotic leakage after laparoscopic-assisted radical right hemicolectomy: reason analysis and management].

PubMed

Wu, Xin; Lin, Guole; Qiu, Huizhong; Xiao, Yi; Wu, Bin

2017-06-25

To analyze the clinical features, possible reasons and management of anastomotic leakage after laparoscopic-assisted radical right hemicolectomy. Clinical data of 546 patients undergoing laparoscopic-assisted radical right hemicolectomy in Peking Union Medical College Hospital from October 2010 to September 2016 were retrospectively analyzed. The occurrence of anastomotic leakage and its countermeasures were evaluated. Among 546 patients, 8(1.5%) cases developed anastomotic leakage, including 7 males and 1 female with mean age of (54.3±10.3) years. Six cases of ascending colon cancer, 1 case of phlegmon and 1 case of arterior-venous malformation were confirmed after operation. The incidence of anastomotic leakage after D3 and D2 lymphadenectomy was 2.1%(6/290) and 0.8%(2/256). The time from operation to the diagnosis of anastomotic leakage was (6.6±3.6) days. The clinical manifestation of anastomotic leakage were stool-like drainage in 7 patients, fever in 4 and abdominal pain in 3. Amylase and bilirubin in drainage of 4 patients increased obviously. All the 8 patients underwent secondary ileostomy, including 4 with laparoscopy and 4 with laparotomy. One patient suffered from respiratory failure after re-operation because of severe abdominal infection and was cured by ventilator support treatment. Another one had pelvic encapsulated effusion and was treated by puncture drainage. All the patients discharged from hospital smoothly. Anastomotic leakage after laparoscopic-assisted right hemicolectomy is a quite rare but serious complication, which may be associated with over-cleaning of lymph fatty tissues. Ileostomy should be the first choice of anastomotic leakage after laparoscopy-assisted right hemicolectomy and its efficacy is satisfactory.

A population-based analysis of temporal perioperative complication rates after minimally invasive radical prostatectomy.

PubMed

Schmitges, Jan; Trinh, Quoc-Dien; Abdollah, Firas; Sun, Maxine; Bianchi, Marco; Budäus, Lars; Zorn, Kevin; Perotte, Paul; Schlomm, Thorsten; Haese, Alexander; Montorsi, Francesco; Menon, Mani; Graefen, Markus; Karakiewicz, Pierre I

2011-09-01

Existing population-based reports on complication rates after minimally invasive radical prostatectomy (MIRP) did not address temporal trends. To examine contemporary temporal trends in perioperative MIRP outcomes. Between 2001 and 2007, 4387 patients undergoing MIRP were identified using the Nationwide Inpatient Sample. To examine the rates and trends of intraoperative and postoperative complications, transfusion rates, length of stay in excess of the median, and in-hospital mortality. We tested the effect of the late (2006-2007) versus the early (2001-2005) study period on all outcomes using multivariable logistic regression models controlled for clustering among hospitals. Intraoperative and postoperative complications decreased from 7.0% to 0.8% (p < 0.001) and from 28.5% to 8.7% (p < 0.001), respectively. Transfusion rates decreased from 3.5% to 2.1% (p = 0.3). Hospital length of stay >2 d decreased from 56% to 15% (p < 0.001). In multivariable analyses, intraoperative (odds ratio [OR]: 0.41; p = 0.002) and postoperative (OR: 0.65; p = 0.007) complications were less frequent in the late versus the early study period. Late study period patients were less likely to stay >2 d than early study period patients (OR: 0.34; p > 0.001). Limitations of these findings include the lack of adjustment for several patient variables including disease characteristics, surgeon variables including surgeon caseload, and the restriction to in-hospital events. Our analyses demonstrate that in-hospital complication rates and length of stay after MIRP decreased over time. This implies that temporal differences specific to complication rates after MIRP must be considered when comparisons are made with other radical prostatectomy techniques. Copyright © 2011 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Safety and Efficacy of Robot-assisted Radical Prostatectomy in a Low-volume Center: A 6-year Single-surgeon Experience.

PubMed

DI Pierro, Giovanni Battista; Grande, Pietro; Mordasini, Livio; Danuser, Hansjörg; Mattei, Agostino

2016-08-01

To analyze safety and efficacy of robot-assisted radical prostatectomy (RARP) in a low-volume centre. From 2008 to 2015, 400 consecutive patients undergoing RARP were prospectively enrolled. Complications were classified according to the Modified Clavien System. Biochemical recurrence (BCR) was defined as two consecutive prostate-specific antigen (PSA) values ≥0.2 ng/ml. Functional outcomess were assessed using validated, self-administered questionnaires. Median patient age was 64.5 years. Mean standard deviation (SD) preoperative PSA level was 11.3 (11.7) ng/ml. Median interquartile range (IQR) follow-up was 36 (12-48) months. Overall complication rate was 27.7% (minor complications rate 16.2%). Overall 1-, 3- and 6-year BCR-free survival rates were 85.7%, 77.5% and 53.9%, respectively; these rates were 94.1%, 86.2% and 70.1% in pT2 diseases. At follow-up, 98.4% of patients were fully continent (median (IQR) time to continence was 2 (1-3) months) and 68.2% were potent (median (IQR) time to potency of 3 (3-4) months). RARP appears to be a valuable option for treating clinically localised prostate cancer also in a low-volume institution. Copyright© 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

Mechanistic Study on Electronic Excitation Dissociation of the Cellobiose-Na+ Complex

NASA Astrophysics Data System (ADS)

Huang, Yiqun; Pu, Yi; Yu, Xiang; Costello, Catherine E.; Lin, Cheng

2016-02-01

The recent development of electron activated dissociation (ExD) techniques has opened the door for high-throughput, detailed glycan structural elucidation. Among them, ExD methods employing higher-energy electrons offer several advantages over low-energy electron capture dissociation (ECD), owing to their applicability towards chromophore-labeled glycans and singly charged ions, and ability to provide more extensive structural information. However, a lack of understanding of these processes has hindered rational optimization of the experimental conditions for more efficient fragmentation as well as the development of informatics tools for interpretation of the complex glycan ExD spectra. Here, cellobiose-Na+ was used as the model system to investigate the fragmentation behavior of metal-adducted glycans under irradiation of electrons with energy exceeding their ionization potential, and served as the basis on which a novel electronic excitation dissociation (EED) mechanism was proposed. It was found that ionization of the glycan produces a mixture of radical cations and ring-opened distonic ions. These distonic ions then capture a low-energy electron to produce diradicals with trivial singlet-triplet splitting, and subsequently undergo radical-induced dissociation to produce a variety of fragment ions, the abundances of which are influenced by the stability of the distonic ions from which they originate.

Peroxidase-mediated removal of a polychlorinated biphenyl using natural organic matter as the sole cosubstrate.

PubMed

Colosi, Lisa M; Burlingame, Daniel J; Huang, Qingguo; Weber, Walter J

2007-02-01

Natural organic matter (NOM) of hydroxylated aromatic character can undergo catalyst-mediated self-coupling reactions to form larger molecular aggregates. Indeed, such reactions are central to natural humification processes. Nonhydroxylated persistent aromatic contaminants such as polychlorinated biphenyls (PCBs) are, conversely, inert with respect to such reactions. It is here demonstrated however that significant coincidental coupling and removal of a representative aqueous-phase PCB occurs during horseradish peroxidase (HRP)-catalyzed oxidative coupling reactions of a representative aquatic NOM. Experiments with Suwannee River fulvic acid as a reactive cosubstrate indicate that 2,2'-dichlorobiphenyl (PCB-4) is covalently incorporated into aggregating NOM, likely through fortuitous cross-coupling reactions. To develop a better understanding of potential mechanisms by which the observed phenomenon occurs, two hydroxylated monomeric cosubstrates of known molecular structure, phenol and 4-methoxyphenol, were investigated as alternative cosubstrates. PCB-4 removal appears from these experiments to relate to certain molecular characteristics of the native cosubstrate molecule (reactivity with HRP, favorability for radical attack, and hydrophobicity) and its associated phenoxy radical (stability). The findings reveal potential pathways by which PCBs, and perhaps other polyaromatic contaminants, may be naturally transformed and detoxified in nature. The results further provide a foundation for development of enhanced-humification strategies for remediation of PCB-contaminated environmental systems.

Photodegradation of veterinary ionophore antibiotics under UV and solar irradiation.

PubMed

Sun, Peizhe; Pavlostathis, Spyros G; Huang, Ching-Hua

2014-11-18

The veterinary ionophore antibiotics (IPAs) are extensively used as coccidiostats and growth promoters and are released to the environment via land application of animal waste. Due to their propensity to be transported with runoff, IPAs likely end up in surface waters where they are subject to photodegradation. This study is among the first to investigate the photodegradation of three commonly used IPAs, monensin (MON), salinomycin (SAL) and narasin (NAR), under UV and solar irradiation. Results showed that MON was persistent in a deionized (DI) water matrix when exposed to UV and sunlight, whereas SAL and NAR could undergo direct photolysis with a high quantum yield. Water components including nitrate and dissolved organic matter had a great impact on the photodegradation of IPAs. A pseudosteady state kinetic model was successfully applied to predict IPAs' photodegradation rates in real water matrices. Applying LC/MS/MS, multiple photolytic transformation products of IPAs were observed and their structures were proposed. The direct photolysis of SAL and NAR occurred via cleavage on the ketone moiety and self-sensitized photolysis. With the presence of nitrate, MON was primarily degraded by hydroxyl radicals, whereas SAL showed reactivity toward both hydroxyl and nitrogen-dioxide radicals. Additionally, toxicity tests showed that photodegradation of SAL eliminated its antibiotic properties against Bacillus subtilis.

Noninvasive continuous blood pressure monitoring by the ClearSight system during robot-assisted laparoscopic radical prostatectomy.

PubMed

Sakai, Yoko; Yasuo M, Tsutsumi; Oyama, Takuro; Murakami, Chiaki; Kakuta, Nami; Tanaka, Katsuya

2018-01-01

Robot-assisted laparoscopic radical prostatectomy (RALRP) is commonly performed in the surgical treatment of prostate cancer. However, the steep Trendelenburg position (25) and pneumoperitoneum required for this procedure can sometimes cause hemodynamic changes. Although blood pressure is traditionally monitored invasively during RALRP, the ClearSight system (BMEYE, Amsterdam, The Netherlands) enables a totally noninvasive and simple continuous blood pressure and cardiac output monitoring based on finger arterial pressure pulse contour analysis. We therefore investigated whether noninvasive continuous arterial blood pressure measurements using the ClearSight system were comparable to those obtained invasively in patients undergoing RALRP. Ten patients scheduled for RALRP with American Society of Anesthesiologists physical status I-II were included in this study. At each of the seven defined time points, noninvasive and invasive blood pressure measurements were documented and compared in each patient using Bland-Altman analysis. Although the blood pressure measured with the ClearSight system correlated with that measured invasively, a large difference between the values obtained by the two devices was noted. The ClearSight system was unable to detect blood pressure accurately during RALRP, suggesting that blood pressure monitoring using this device alone is not feasible in this small patient population. J. Med. Invest. 65:69-73, February, 2018.

Awake Craniotomy for Tumor Resection: Further Optimizing Therapy of Brain Tumors.

PubMed

Mehdorn, H Maximilian; Schwartz, Felix; Becker, Juliane

2017-01-01

In recent years more and more data have emerged linking the most radical resection to prolonged survival in patients harboring brain tumors. Since total tumor resection could increase postoperative morbidity, many methods have been suggested to reduce the risk of postoperative neurological deficits: awake craniotomy with the possibility of continuous patient-surgeon communication is one of the possibilities of finding out how radical a tumor resection can possibly be without causing permanent harm to the patient.In 1994 we started to perform awake craniotomy for glioma resection. In 2005 the use of intraoperative high-field magnetic resonance imaging (MRI) was included in the standard tumor therapy protocol. Here we review our experience in performing awake surgery for gliomas, gained in 219 patients.Patient selection by the operating surgeon and a neuropsychologist is of primary importance: the patient should feel as if they are part of the surgical team fighting against the tumor. The patient will undergo extensive neuropsychological testing, functional MRI, and fiber tractography in order to define the relationship between the tumor and the functionally relevant brain areas. Attention needs to be given at which particular time during surgery the intraoperative MRI is performed. Results from part of our series (without and with ioMRI scan) are presented.

Urban Climate Effects on Air Pollution and Atmospheric Chemistry

NASA Astrophysics Data System (ADS)

Rasoul, Tara; Bloss, William; Pope, Francis

2016-04-01

Tropospheric ozone, adversely affects the environment and human health. The presence of chlorine nitrate (ClNO2) in the troposphere can enhance ozone (O3) formation as it undergoes photolysis, releasing chlorine reactive atoms (Cl) and nitrogen dioxide (NO2), both of which enhance tropospheric ozone formation. The importance of new sources of tropospheric ClNO2 via heterogeneous processes has recently been highlighted. This study employed a box model, using the Master Chemical Mechanism (MCM version 3.2) to assess the effect of ClNO2 on air quality in urban areas within the UK. The model updated to include ClNO2 production, photolysis, a comprehensive parameterisation of dinitrogen pentoxide (N2O5) uptake, and ClNO2 production calculated from bulk aerosol composition. The model simulation revealed the presence of ClNO2 enhances the formation of NO2, organic peroxy radical (CH3O2), O3, and hydroxyl radicals (OH) when compared with simulations excluding ClNO2. In addition, the study examined the effect of temperature variation upon ClNO2 formation. The response of ClNO2 to temperature was analysed to identify the underlying drivers, of particular importance when assessing the response of atmospheric chemistry processes under potential future climates.

Generation of gas-phase sodiated arenes such as [(Na3(C6H4)+] from benzene dicarboxylate salts.

PubMed

Attygalle, Athula B; Chan, Chang-Ching; Axe, Frank U; Bolgar, Mark

2010-01-01

Upon collision-induced activation, gaseous sodium adducts generated by electrospray ionization of disodium salts of 1,2- 1,3-, and 1,4-benzene dicarboxylic acids (m/z 233) undergo an unprecedented expulsion of CO(2) by a rearrangement process to produce an ion of m/z 189 in which all three sodium atoms are retained. When isolated in a collision cell of a tandem-in-space mass spectrometer, and subjected to collision-induced dissociation (CID), only the m/z 189 ions derived from the meta and para isomers underwent a further CO(2) loss to produce a peak at m/z 145 for a sodiated arene of formula (Na(3)C(6)H(4))(+). This previously unreported m/z 145 ion, which is useful to differentiate meta and para benzene dicarboxylates from their ortho isomer, is in fact the sodium adduct of phenelenedisodium. Moreover, the m/z 189 ion from all three isomers readily expelled a sodium radical to produce a peak at m/z 166 for a radical cation [(*C(6)H(4)CO(2)Na(2))(+)], which then eliminated CO(2) to produce a peak at m/z 122 for the distonic cation (*C(6)H(4)Na(2))(+). Copyright 2009 John Wiley & Sons, Ltd.

Exploring gay couples' experience with sexual dysfunction after radical prostatectomy: a qualitative study.

PubMed

Hartman, Mary-Ellen; Irvine, Jane; Currie, Kristen L; Ritvo, Paul; Trachtenberg, Lianne; Louis, Alyssa; Trachtenberg, John; Jamnicky, Leah; Matthew, Andrew G

2014-01-01

This exploratory study examines the experience of three gay couples managing sexual dysfunction as a result of undergoing a radical prostatectomy. Semi-structured interviews were conducted as part of a larger study at an urban hospital in Toronto, Ontario, Canada. Interview transcripts were transcribed verbatim, and analyzed using interpretative phenomenological analysis. The authors clustered 18 subordinate themes under 3 superordinate themes: (a) acknowledging change in sexual experience (libido, erectile function, sexual activity, orgasmic function); (b) accommodating change in sexual experience (strategies: emphasizing intimacy, embracing plan B, focus on the other; barriers: side-effect concerns, loss of naturalness, communication breakdown, failure to initiate, trial and failure, partner confounds); and (c) accepting change in sexual experience (indicators: emphasizing health, age attributions, finding a new normal; barriers: uncertain outcomes, treatment regrets). Although gay couples and heterosexual couples share many similar challenges, we discovered that gay men have particular sexual roles and can engage in novel accommodation practices, such as open relationships, that have not been noted in heterosexual couples. All couples, regardless of their level of sexual functioning, highlighted the need for more extensive programming related to sexual rehabilitation. Equitable rehabilitative support is critical to assist homosexual couples manage distress associated with prostatectomy-related sexual dysfunction.

Protective effect of Mangifera indica L. extract (Vimang) on the injury associated with hepatic ischaemia reperfusion.

PubMed

Sánchez, Gregorio Martínez; Rodríguez H, María A; Giuliani, Attilia; Núñez Sellés, Alberto J; Rodríguez, Niurka Pons; León Fernández, Olga Sonia; Re, L

2003-03-01

The effect of Mangifera indica L. extract (Vimang) on treatment of injury associated with hepatic ischaemia/reperfusion was tested. Vimang protects from the oxidative damage induced by oxygen-based free radicals as shown in several in vitro test systems conducted. The ability of Vimang to reduce liver damage was investigated in rats undergoing right-lobe blood fl ow occlusion for 45 min followed by 45 min of reperfusion. The ischaemia/reperfusion model leads to an increase of transaminase (ALT and AST), membrane lipid peroxidation, tissue neutrophil in filtration, DNA fragmentation, loss of protein -SH groups, cytosolic Ca2+ overload and a decrease of catalase activity. Oral administration of Vimang (50, 110 and 250 mg/kg, b.w.) 7 days before reperfusion, reduced transaminase levels and DNA fragmentation in a dose dependent manner (p < 0.05). Vimang also restored the cytosolic Ca2+ levels and inhibited polymorphonuclear migration at a dose of 250 mg/kg b.w., improved the oxidation of total and non protein sulfhydryl groups and prevented modification in catalase activity, uric acid and lipid peroxidation markers (p < 0.05). These data suggest that Vimang could be a useful new natural drug for preventing oxidative damage during hepatic injury associated with free radical generation. Copyright 2003 John Wiley & Sons, Ltd.

Functional Recovery, Oncologic Outcomes and Postoperative Complications after Robot-Assisted Radical Prostatectomy: An Evidence-Based Analysis Comparing the Retzius Sparing and Standard Approaches.

PubMed

Menon, Mani; Dalela, Deepansh; Jamil, Marcus; Diaz, Mireya; Tallman, Christopher; Abdollah, Firas; Sood, Akshay; Lehtola, Linda; Miller, David; Jeong, Wooju

2018-05-01

We report a 1-year update of functional urinary and sexual recovery, oncologic outcomes and postoperative complications in patients who completed a randomized controlled trial comparing posterior (Retzius sparing) with anterior robot-assisted radical prostatectomy. A total of 120 patients with clinically low-intermediate risk prostate cancer were randomized to undergo robot-assisted radical prostatectomy via the posterior and anterior approach in 60 each. Surgery was performed by a single surgical team at an academic institution. An independent third party ascertained urinary and sexual function outcomes preoperatively, and 3, 6 and 12 months after surgery. Oncologic outcomes consisted of positive surgical margins and biochemical recurrence-free survival. Biochemical recurrence was defined as 2 postoperative prostate specific antigen values of 0.2 ng/ml or greater. Median age of the cohort was 61 years and median followup was 12 months. At 12 months in the anterior vs posterior prostatectomy groups there were no statistically significant differences in the urinary continence rate (0 to 1 security pad per day in 93.3% vs 98.3%, p = 0.09), 24-hour pad weight (median 12 vs 7.5 gm, p = 0.3), erection sufficient for intercourse (69.2% vs 86.5%) or postoperative Sexual Health Inventory for Men score 17 or greater (44.6% vs 44.1%). In the posterior vs anterior prostatectomy groups a nonfocal positive surgical margin was found in 11.7% vs 8.3%, biochemical recurrence-free survival probability was 0.84 vs 0.93 and postoperative complications developed in 18.3% vs 11.7%. Among patients with clinically low-intermediate risk prostate cancer randomized to anterior (Menon) or posterior (Bocciardi) approach robot-assisted radical prostatectomy the differences in urinary continence seen at 3 months were muted at the 12-month followup. Sexual function recovery, postoperative complication and biochemical recurrence rates were comparable 1 year postoperatively. Copyright © 2018 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Further insights into the oxidation chemistry and biochemistry of the serotonergic neurotoxin 5,6-dihydroxytryptamine.

PubMed

Singh, S; Dryhurst, G

1990-11-01

The neurodegenerative properties of the serotonergic neurotoxin 5,6-dihydroxytryptamine (5,6-DHT) are widely believed to result from its autoxidation in the central nervous system. The autoxidation chemistry of 5,6-DHT has been studied in aqueous solution at pH 7.2. The reaction is initiated by direct oxidation of the indolamine by molecular oxygen with resultant formation of the corresponding o-quinone 1 and H2O2. A rapid nucleophilic attack by 5,6-DHT on 1 leads to 2,7'-bis(5,6-dihydroxytryptamine) (6) which is more rapidly autoxidized than 5,6-DHT to give the corresponding diquinone 7 along with 2 mol of H2O2. The accumulation of 6 in the reaction solution during the autoxidation of 5,6-DHT despite its more rapid autoxidation indicates that diquinone 7 chemically oxidizes 5,6-DHT (2 mol) to quinone 1 so that an autocatalytic cycle is established. The H2O2 formed as a byproduct of these autoxidation reactions can undergo Fenton chemistry catalyzed by trace transition metal ion contaminants with resultant formation of the hydroxyl radical, HO., which directly oxidizes 5,6-DHT to a radical intermediate (9a/9b). This radical is directly attacked by O2 to yield quinone 1 and superoxide radical anion, O2.-, which further facilitates Fenton chemistry by reducing, inter alia, Fe3+ to Fe2+. A minor side reaction of 1 with water leads to formation of at least two trihydroxytryptamines. Diquinone 7 ultimately reacts with 6, 5,6-DHT, and perhaps trihydroxytryptamines, leading via a sequence of coupling and oxidation reactions to a black indolic melanin polymer. Enzymes such as tyrosinase, ceruloplasmin, and peroxidase and rat brain mitochondria catalyze the oxidation of 5,6-DHT to form dimer 7 and, ultimately, indolic melanin. The role of the autoxidation and the enzyme-mediated and mitochondria-promoted oxidations of 5,6-DHT in expressing the neurodegenerative properties of the indolamine are discussed.

Androgen deprivation therapy for localized prostate cancer and the risk of cardiovascular mortality.

PubMed

Tsai, Henry K; D'Amico, Anthony V; Sadetsky, Natalia; Chen, Ming-Hui; Carroll, Peter R

2007-10-17

We investigated whether androgen deprivation therapy (ADT) use is associated with an increased risk of death from cardiovascular causes in patients treated for localized prostate cancer. From the Cancer of the Prostate Strategic Urologic Research Endeavor database, data on 3262 patients treated with radical prostatectomy and 1630 patients treated with external beam radiation therapy, brachytherapy, or cryotherapy for localized prostate cancer were included in this analysis. Competing risks regression analyses were performed to assess whether use of ADT was associated with a shorter time to death from cardiovascular causes after controlling for age (as a continuous variable) and the presence of baseline cardiovascular disease risk factors. All tests for statistical significance were two-sided. The median follow-up time was 3.8 years (range = 0.1-11.3 years). Among the 1015 patients who received ADT, the median duration of ADT use was 4.1 months (range = 1.0-32.9 months). In a competing risks regression analysis that controlled for age and risk factors for cardiovascular disease, both ADT use (adjusted hazard ratio [HR] = 2.6; 95% confidence interval [CI] = 1.4 to 4.7; P = .002) and age (adjusted HR = 1.07; 95% CI = 1.02 to 1.1; P = .003) were associated with statistically significantly increased risks of death from cardiovascular causes in patients treated with radical prostatectomy. Among patients 65 years or older treated with radical prostatectomy, the 5-year cumulative incidence of cardiovascular death was 5.5% (95% CI = 1.2% to 9.8%) in those who received ADT and 2.0% (95% CI = 1.1% to 3.0%) in those who did not. Among patients 65 years or older treated with external beam radiation therapy, brachytherapy, or cryotherapy, ADT use was associated with a higher cumulative incidence of death from cardiovascular causes, but the difference did not reach statistical significance. The use of ADT appears to be associated with an increased risk of death from cardiovascular causes in patients undergoing radical prostatectomy for localized prostate cancer.

C5a receptor expression is associated with poor prognosis in urothelial cell carcinoma patients treated with radical cystectomy or nephroureterectomy.

PubMed

Wada, Yoshihiro; Maeda, Yoshihiro; Kubo, Tatsuko; Kikuchi, Ken; Eto, Masatoshi; Imamura, Takahisa

2016-11-01

Patients with aggressive urothelial cell carcinoma (UCC) that undergo radical cystectomy or nephroureterectomy exhibit markedly high rates of disease recurrence and mortality. To select appropriate adjuvant thxerapies in addition to radical surgery, the identification of predictive prognostic markers for UCC patients is required. The aim of the present study was to identify such markers, by evaluating the association of UCC complement component 5 (C5) fragment a (C5a)receptor (C5aR) expression, detected using immunohistochemistry, with clinicopathological parameters and survival outcomes of UCC patients. The results revealed that C5aR was expressed in cancer cells, particularly at the invasive front, but not in noncancerous urothelial cells or adjacent cells. The UCC C5aR-positive rate of patients treated with radical surgeries was 73% (38/52) and the rate was 83% (20/24) at stages I-II of disease. No correlation between C5aR expression and any of clinicopathological parameters, which included gender, tumor location, World Health Organization grade, T stage, vessel invasion and stage of disease, was identified. However, univariate and multivariate analyses revealed that C5aR-positive UCC patients exhibited significantly lower overall survival rates [hazard ratio (HR), 3.14; 95% confidence interval (CI), 1.03-9.60; P=0.035 and HR, 3.92; 95% CI, 1.15-13.4; P=0.029, respectively] and 5-year survival rates (0.42 vs. 0.83) compared with C5aR-negative UCC patients. Furthermore, 5-year survival and disease-specific survival rates were lower in patients with C5aR-positive UCC (0.51; 95% CI, 0.30-0.71) than patients with C5aR-negative UCC (0.83; 95% CI, 0.62-1.00). These results indicate that UCC C5aR expression is predictive of poor patient outcomes and thus may lead to the appropriate selection of adjuvant therapies at earlier UCC stages, which could improve patient prognosis.

C5a receptor expression is associated with poor prognosis in urothelial cell carcinoma patients treated with radical cystectomy or nephroureterectomy

PubMed Central

Wada, Yoshihiro; Maeda, Yoshihiro; Kubo, Tatsuko; Kikuchi, Ken; Eto, Masatoshi; Imamura, Takahisa

2016-01-01

Patients with aggressive urothelial cell carcinoma (UCC) that undergo radical cystectomy or nephroureterectomy exhibit markedly high rates of disease recurrence and mortality. To select appropriate adjuvant thxerapies in addition to radical surgery, the identification of predictive prognostic markers for UCC patients is required. The aim of the present study was to identify such markers, by evaluating the association of UCC complement component 5 (C5) fragment a (C5a)receptor (C5aR) expression, detected using immunohistochemistry, with clinicopathological parameters and survival outcomes of UCC patients. The results revealed that C5aR was expressed in cancer cells, particularly at the invasive front, but not in noncancerous urothelial cells or adjacent cells. The UCC C5aR-positive rate of patients treated with radical surgeries was 73% (38/52) and the rate was 83% (20/24) at stages I–II of disease. No correlation between C5aR expression and any of clinicopathological parameters, which included gender, tumor location, World Health Organization grade, T stage, vessel invasion and stage of disease, was identified. However, univariate and multivariate analyses revealed that C5aR-positive UCC patients exhibited significantly lower overall survival rates [hazard ratio (HR), 3.14; 95% confidence interval (CI), 1.03–9.60; P=0.035 and HR, 3.92; 95% CI, 1.15–13.4; P=0.029, respectively] and 5-year survival rates (0.42 vs. 0.83) compared with C5aR-negative UCC patients. Furthermore, 5-year survival and disease-specific survival rates were lower in patients with C5aR-positive UCC (0.51; 95% CI, 0.30–0.71) than patients with C5aR-negative UCC (0.83; 95% CI, 0.62–1.00). These results indicate that UCC C5aR expression is predictive of poor patient outcomes and thus may lead to the appropriate selection of adjuvant therapies at earlier UCC stages, which could improve patient prognosis. PMID:27895761

Nephrectomy for benign disease in the UK: results from the British Association of Urological Surgeons nephrectomy database.

PubMed

Zelhof, Bachar; McIntyre, Iain G; Fowler, Sarah M; Napier-Hemy, Richard D; Burke, Daniel M; Grey, Ben R

2016-01-01

To summarize the practice of UK urologists with regard to nephrectomy for benign disease, documenting the indications, procedural techniques and outcomes. All patients undergoing nephrectomy for a benign condition in 2012 were identified from the British Association of Urological Surgeons (BAUS) nephrectomy database. Recorded variables included the technique of surgery, the type of minimally invasive procedure, operating time, blood loss, transfusion rate, conversion rate, intra- and postoperative complications and mortality rate. Cases were also sub-analysed according to their pathologies to determine the differences in complication rate between stone disease, pyelonephritis, non-functioning kidney and other benign lesions. To contextualize procedural complexity, the simple nephrectomy data were compared with those obtained from the BAUS stage T1 radical nephrectomy audit. A total of 1 093 nephrectomies were performed (537 non-functioning kidneys, 142 stone disease, 129 nephrectomies secondary to pyelonephritis and 285 cases with other benign conditions). Of these, 76% were performed laparoscopically. Blood loss >500 mL was noted in 74 cases with a 4.8% blood transfusion rate. The intra- and postoperative complication rates were 5.2 and 11.9%, respectively. Of the 847 minimally invasive procedures, the conversion rate was 5.9%. Patients with stone disease have the highest intra- and postoperative complications (9.9 and 23.9%, respectively) compared with other benign pathologies. The total number of T1 radical nephrectomies performed was 1 095. In comparison with T1 radical nephrectomy, simple nephrectomy carries an increased risk of conversion to an open procedure (1.8 times), a higher rate of blood transfusion (4.8 vs 2.8%), and a higher risk of intra- and postoperative complications (5.2 vs 3.7% and 11.9 vs 10%, respectively). The present study reports the largest series of nephrectomies performed for benign disease and the resultant data now support the bespoke preoperative counselling of patients. Furthermore, it confirms the commonly held view that simple nephrectomy can be more difficult than its radical counterpart. The authors suggest that the term 'simple nephrectomy' is changed to 'benign nephrectomy'. © 2015 The Authors BJU International © 2015 BJU International Published by John Wiley & Sons Ltd.

Biocompatibility of 4-META/MMA-TBB resin used as a dental luting agent.

PubMed

Nakagawa, Kaori; Saita, Makiko; Ikeda, Takayuki; Hirota, Makoto; Park, Wonhee; Lee, Masaichi Chang-Il; Ogawa, Takahiro

2015-07-01

The bonding and biological properties of currently used luting/cementing materials need to be improved. 4-Acryloyloxyethyl trimellitate anhydride/methyl methacrylate-tri-n-butylborane (4-META/MMA-TBB) resin is primarily used for splinting mobile teeth or treating fractured teeth. It undergoes moisture-resistant polymerization and bonds strongly to dentin and metals. The purpose of this in vitro study was to compare the biological and biochemical properties META/MMA-TBB resin with those of conventional polymethyl methacrylate (PMMA)-MMA resin and other currently used luting materials in order to determine whether it may be a viable dental luting agent. The degree of polymerization of 4-META/MMA-TBB resin, PMMA-MMA autopolymerizing resin, 10-methacryloyloxydecyl dihydrogen phosphate-dimethacrylate (MDP-DMA) adhesive resin, and a glass ionomer cement was measured by Fourier-transformed infrared spectroscopy. Free radical production during setting was evaluated by electron spin resonance (ESR) spectroscopy. Rat dental pulp cells cultured on these materials were examined for cell viability, attachment, proliferation, and functional phenotype. The degree of polymerization of 4-META/MMA-TBB resin was 82% thirty minutes after preparation, compared to 66% for PMMA-MMA autopolymerizing resin. ESR spectroscopy revealed free radical production from 4-META/MMA-TBB resin and glass ionomer cement was equivalent 24 hours after preparation, with no spike in radical generation observed. In contrast, free radical production from PMMA-MMA and MDP-DMA adhesive resins was rapid and sustained and 10 to 20 times greater than that from 4-META/MMA-TBB. The percentage of viable dental pulp cells 24 hours after seeding was considerably higher on MDP-DMA and 4-META/MMA-TBB resin than on glass ionomer cement. Cell number, proliferation, and alkaline phosphatase activity were highest on 4-META/MMA-TBB resin and lowest on the glass ionomer cement. 4-META/MMA-TBB resin is at least as biocompatible, and perhaps even more biocompatible, than other current luting materials, with fast, favorable, and nontoxic polymerization properties. Further in vivo and human studies of 4-META/MMA-TBB resin as a dental luting agent are warranted. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Sarcopenia is an Independent Predictor of Severe Postoperative Complications and Long-Term Survival After Radical Gastrectomy for Gastric Cancer

PubMed Central

Zhuang, Cheng-Le; Huang, Dong-Dong; Pang, Wen-Yang; Zhou, Chong-Jun; Wang, Su-Lin; Lou, Neng; Ma, Liang-Liang; Yu, Zhen; Shen, Xian

2016-01-01

Abstract Currently, the association between sarcopenia and long-term prognosis after gastric cancer surgery has not been investigated. Moreover, the association between sarcopenia and postoperative complications remains controversial. This large-scale retrospective study aims to ascertain the prevalence of sarcopenia and assess its impact on postoperative complications and long-term survival in patients undergoing radical gastrectomy for gastric cancer. From December 2008 to April 2013, the clinical data of all patients who underwent elective radical gastrectomy for gastric cancer were collected prospectively. Only patients with available preoperative abdominal CT scan within 30 days of surgery were considered for analysis. Skeletal muscle mass was determined by abdominal (computed tomography) CT scan, and sarcopenia was diagnosed by the cut-off values obtained by means of optimum stratification. Univariate and multivariate analyses evaluating risk factors of postoperative complications and long-term survival were performed. A total of 937 patients were included in this study, and 389 (41.5%) patients were sarcopenic based on the diagnostic cut-off values (34.9 cm2/m2 for women and 40.8 cm2/m2 for men). Sarcopenia was an independent risk factor for severe postoperative complications (OR = 3.010, P < 0.001), but not for total complications. However, sarcopenia did not show significant association with operative mortality. Moreover, sarcopenia was an independent predictor for poorer overall survival (HR = 1.653, P < 0.001) and disease-free survival (HR = 1.620, P < 0.001). Under the adjusted tumor-node-metastasis (TNM) stage, sarcopenia remained an independent risk factor for overall survival and disease-free survival in patients with TNM stage II and III, but not in patients with TNM stage I. Sarcopenia is an independent predictive factor of severe postoperative complications after radical gastrectomy for gastric cancer. Moreover, sarcopenia is independently associated with overall and disease-free survival in patients with TNM stage II and III, but not in patients with TNM stage I. PMID:27043677

Prospective evaluation of the prevalence and severity of fatigue in patients with prostate cancer undergoing radical external beam radiotherapy and neoadjuvant hormone therapy.

PubMed

Truong, Pauline T; Berthelet, Eric; Lee, Junella C; Petersen, Ross; Lim, Jan T W; Gaul, Catherine A; Pai, Howard; Blood, Paul; Ludgate, Charles M

2006-06-01

To prospectively evaluate the prevalence and severity of fatigue and its impact on quality of life (QOL) during and after radical external beam radiotherapy (RT) for prostate cancer. Twenty-eight men with prostate cancer undergoing RT over 6-8 consecutive weeks were prospectively accrued. The Brief Fatigue Inventory (BFI), a validated fatigue assessment tool, was administered at five time points: baseline (week 1), middle of RT (week 3-4), end of RT (last week of RT), and follow-up (median 6.5 weeks after RT). The BFI contained nine questions, each using 0-10 ratings to quantify fatigue severity and interference with six QOL domains. The prevalence of moderate-severe fatigue was plotted as a function of time. Mean sum and subscale scores at each time point were compared to baseline scores using Wilcoxon tests. Linear regression analyses were performed to assess associations between fatigue scores and age, tumor and treatment characteristics. The median age was 69 years (range 57-84), Gleason score 7 (range 6-10), and presenting PSA 9.0 ng/mL (range 2.5 ng/mL-103.0 ng/mL). Patients were treated once daily to a median dose of 74 Gy (range 60 Gy-78 Gy) over a median of 37 fractions (range 30-39). Hormone therapy was used in all patients (median duration 12.2 months). The prevalence of moderate-severe present fatigue increased from 7% at baseline to 8% at mid-RT and 32% at RT completion. Compared to baseline (mean score 11.5), fatigue increased significantly mid-RT (mean score 14.6, p = 0.03) and peaked at the end of RT (mean score 23.5, p = 0.001). Fatigue significantly interfered with walking ability, normal work, daily chores, and enjoyment of life only at the end of RT. After RT completion, fatigue improved but remained higher compared to baseline at 6.5 weeks of follow-up (mean score 15.0, p = 0.02). On linear regression analysis, age, Gleason score, PSA, T-stage, hormone therapy duration, RT dose and fractions were not significantly associated with mean fatigue scores. Patients undergoing 6-8 weeks of RT experienced significant fatigue adversely affecting QOL persisting after therapy completion. Since walking ability was not affected until the end of RT, a walking exercise intervention to combat fatigue is likely feasible and is being investigated.

What Aspects of Personal Care Are Most Important to Patients Undergoing Radiation Therapy for Prostate Cancer?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foley, Kimberley A.; Department of Public Health Sciences, Queen's University, Kingston, Ontario; Feldman-Stewart, Deb

Purpose/Objective: The overall quality of patient care is a function of the quality of both its technical and its nontechnical components. The purpose of this study was to identify the elements of nontechnical (personal) care that are most important to patients undergoing radiation therapy for prostate cancer. Methods and Materials: We reviewed the literature and interviewed patients and health professionals to identify elements of personal care pertinent to patients undergoing radiation therapy for prostate cancer. We identified 143 individual elements relating to 10 aspects of personal care. Patients undergoing radical radiation therapy for prostate cancer completed a self-administered questionnaire inmore » which they rated the importance of each element. The overall importance of each element was measured by the percentage of respondents who rated it as “very important.” The importance of each aspect of personal care was measured by the mean importance of its elements. Results: One hundred eight patients completed the questionnaire. The percentage of patients who rated each element “very important” ranged from 7% to 95% (mean 61%). The mean importance rating of the elements of each aspect of care varied significantly: “perceived competence of caregivers,” 80%; “empathy and respectfulness of caregivers,” 67%; “adequacy of information sharing,” 67%; “patient centeredness,” 59%; “accessibility of caregivers,” 57%; “continuity of care,” 51%; “privacy,” 51%; “convenience,” 45%; “comprehensiveness of services,” 44%; and “treatment environment,” 30% (P<.0001). Neither age nor education was associated with importance ratings, but the patient's health status was associated with the rating of some elements of care. Conclusions: Many different elements of personal care are important to patients undergoing radiation therapy for prostate cancer, but the 3 aspects of care that most believe are most important are these: the perceived competence of their caregivers, the empathy and respectfulness of their caregivers, and the adequacy of information sharing.« less

Phenotypic modulation of corpus cavernosum smooth muscle cells in a rat model of cavernous neurectomy.

PubMed

Yang, Fan; Zhao, Jian F; Shou, Qi Y; Huang, Xiao J; Chen, Gang; Yang, Ke B; Zhang, Shi G; Lv, Bo D; Fu, Hui Y

2014-01-01

Patients undergoing radical prostatectomy (RP) are at high risk for erectile dysfunction (ED) due to potential cavernous nerve (CN) damage during surgery. Penile hypoxia after RP is thought to significantly contribute to ED pathogenesis. We previously showed that corpora cavernosum smooth muscle cells (CCSMCs) undergo phenotypic modulation under hypoxic conditions in vitro. Here, we studied such changes in an in vivo post-RP ED model by investigating CCSMCs in bilateral cavernous neurectomy (BCN) rats. Sprague-Dawley rats underwent sham (n = 12) or BCN (n = 12) surgery. After 12 weeks, they were injected with apomorphine to determine erectile function. The penile tissues were harvested and assessed for fibrosis using Masson trichrome staining and for molecular markers of phenotypic modulation using immunohistochemistry and western blotting. CCSMC morphological structure was evaluated by hematoxylin-eosin (H&E) staining and transmission electron microscopy (TEM). Erectile function was significantly lower in BCN rats than in sham rats. BCN increased hypoxia-inducible factor-1α and collagen protein expression in corpora cavernous tissue. H&E staining and TEM showed that CCSMCs in BCN rats underwent hypertrophy and showed rough endoplasmic reticulum formation. The expression of CCSMC phenotypic markers, such as smooth muscle α-actin, smooth muscle myosin heavy chain, and desmin, was markedly lower, whereas vimentin protein expression was significantly higher in BCN rats than in control rats. CCSMCs undergo phenotype modulation in rats with cavernous neurectomy. The results have unveiled physiological transformations that occur at the cellular and molecular levels and have helped characterize CN injury-induced ED.

[Feasibility and effectiveness of laparoscopic right colectomy with extracorporeal anastomosis].

PubMed

Feroci, F; Lenzi, E; Kröning, K C; Moraldi, L; Cantafio, S; Borrelli, A; Giaconi, G; Scatizzi, M

2011-02-01

Despite the laparoscopic right hemicolectomy has been validated by many randomized prospective trials, clear evidences on the validity of the totally mini-invasive technique, namely, through intracorporeal anastomosis, are still lacking. The aim of this study was the assessment of short-term outcome within three months from laparoscopic right colectomy with intra- or extra-corporeal anastomosis. With no exclusion, all patients undergoing laparoscopic right hemicolectomy at our institution have been enrolled in this study. Group A included patients undergoing laparoscopic right hemicolectomy with extracorporeal anastomosis (LAC) and Group B, included patients undergoing laparoscopic right hemicolectomy with intracorporeal anastomosis (TLC). Patients' data, surgery details, results of postoperative period and histological tests have been prospectively recorded in a database and analysed. Between December 2006 and December 2008, 45 patients underwent right hemicolectomy, 21 with extracorporeal anastomosis and 24 had intracorporeal ones. As to patients' characteristics and histopathological results there are no difference between the groups. Anastomotic dehiscence occurred one in group A and one in group B (P>0.05). Both patients underwent reoperation. We recorded 6 postoperative ileus with vomiting in the LAC group and only 1 in the TLC group (P<0.05). The incidence of Non-Surgical Site Complications (NSSC) was of 4.54% in LAC group and 8.33% in TLC group (P>0.05). Hospitalization was of 5 days for both groups. In conclusion, we believe that this technique is feasible in terms of safety; it doesn't significatively affect the length of surgical procedure and guarantees maintenance of oncological radicality standards of reference. Besides it significatively improves quality of the post-operative period.

Effects of preemptive analgesia with flurbiprofen ester on lymphocytes and natural killer cells in patients undergoing esophagectomy: A randomized controlled pilot study

PubMed Central

Zhou, Yi; Huang, Jinxi; Bai, Yu; Li, Changsheng

2017-01-01

Background Tumors may induce systemic immune dysfunction, which can be aggravated by surgery and anesthesia/analgesia. Data on the effect of flurbiprofen preemptive analgesia on immune dysfunction is limited. The aim of this study was to investigate the effect of flurbiprofen preemptive analgesia on lymphocytes and natural killer (NK) cells in patients undergoing thoracotomy and thoracoscopy radical esophagectomy, and to explore the analgesic methods suitable for tumor patients. Methods This was a randomized controlled pilot study of 89 patients with esophageal cancer treated with surgery at the Henan Cancer Hospital between January 1, 2015 and December 31, 2016. The patients were divided into three groups: group 1, thoracotomy; group 2, thoracoscopy and laparoscopic surgery; and group 3, flurbiprofen, thoracoscopy, and laparoscopic surgery. CD3+, CD19+, NK, CD4+, and CD8+ cells in whole blood were measured by flow cytometry 30 minutes before surgery (T0), at the end of the thoracic section of the procedure (T1), and at the end of the operation (T2). Results There were no significant differences in CD3+, CD19+, CD8+, NK, and CD4+ cells between the three groups or regarding the time points during the procedure (all P > 0.05). Thoracotomy and thoracoscopy surgery resulted in similar immunological outcomes. Conclusion Flurbiprofen ester preemptive analgesia did not suppress the immune function in patients and could be a safe analgesic method for patients with esophageal cancer undergoing surgery. PMID:28892265

Effects of preemptive analgesia with flurbiprofen ester on lymphocytes and natural killer cells in patients undergoing esophagectomy: A randomized controlled pilot study.

PubMed

Zhou, Yi; Huang, Jinxi; Bai, Yu; Li, Changsheng; Lu, Xihua

2017-11-01

Tumors may induce systemic immune dysfunction, which can be aggravated by surgery and anesthesia/analgesia. Data on the effect of flurbiprofen preemptive analgesia on immune dysfunction is limited. The aim of this study was to investigate the effect of flurbiprofen preemptive analgesia on lymphocytes and natural killer (NK) cells in patients undergoing thoracotomy and thoracoscopy radical esophagectomy, and to explore the analgesic methods suitable for tumor patients. This was a randomized controlled pilot study of 89 patients with esophageal cancer treated with surgery at the Henan Cancer Hospital between January 1, 2015 and December 31, 2016. The patients were divided into three groups: group 1, thoracotomy; group 2, thoracoscopy and laparoscopic surgery; and group 3, flurbiprofen, thoracoscopy, and laparoscopic surgery. CD3+, CD19+, NK, CD4+, and CD8+ cells in whole blood were measured by flow cytometry 30 minutes before surgery (T0), at the end of the thoracic section of the procedure (T1), and at the end of the operation (T2). There were no significant differences in CD3+, CD19+, CD8+, NK, and CD4+ cells between the three groups or regarding the time points during the procedure (all P > 0.05). Thoracotomy and thoracoscopy surgery resulted in similar immunological outcomes. Flurbiprofen ester preemptive analgesia did not suppress the immune function in patients and could be a safe analgesic method for patients with esophageal cancer undergoing surgery. © 2017 The Authors. Thoracic Cancer published by China Lung Oncology Group and John Wiley & Sons Australia, Ltd.

A Comparison of Fentanyl and Flurbiprofen Axetil on Serum VEGF-C, TNF-α, and IL-1ß Concentrations in Women Undergoing Surgery for Breast Cancer.

PubMed

Wen, Yiyun; Wang, Mingde; Yang, Jinfeng; Wang, Yichun; Sun, Huiping; Zhao, Jianghong; Liu, Weizhen; Zhou, Zhengyu; Deng, Hongwu; Castillo-Pedraza, Catalina; Zhang, Yi; Candiotti, Keith A

2015-07-01

Vascular endothelial growth factor-C (VEGF-C), tumor necrosis factor-α (TNF-α), and interleukin-1ß(IL-1ß) have been shown to be associated with the recurrence and metastasis of breast cancer after surgery. This study tested the hypothesis that patients undergoing surgery for breast cancer, who received postoperative analgesia with flurbiprofen axetil combined with small doses of fentanyl (FA), exhibited reduced levels of VEGF-C, TNF-α, and IL-1ß compared with those patients receiving fentanyl alone (F). Forty-women with primary breast cancer undergoing a modified radical mastectomy were randomized to receive postoperative analgesia with flurbiprofen axetil combined with fentanyl or fentanyl alone. Venous blood was sampled before anesthesia, at the end of surgery, and at 48 hours after surgery, and the serum was analyzed. The primary endpoint was changes in the VEGF-C concentrations in serum. Group FA patients reported similar analgesic effects as group F patients at 2, 24, and 48 hours. At 48 hours, mean postoperative concentrations of VEGF-C in group F patients were higher than in group FA patients, 730.9 versus. 354.1 pg/mL (P = 0.003), respectively. The mean postoperative concentrations of TNF-α in group F patients were also higher compared with group FA patients 27.1 vs. 15.8 pg/mL (P = 0.005). Finally, the mean postoperative concentrations of IL-1ß in group F were also significantly higher than in group FA 497.5 vs. 197.7 pg/mL (P = 0.001). In patients undergoing a mastectomy, postoperative analgesia with flurbiprofen axetil, combined with fentanyl, were associated with decreases in serum concentrations of VEGF-C, TNF-α, and IL-1ß compared with patients receiving doses of only fentanyl. © 2014 World Institute of Pain.

Synthesis and characterization of a helicene-based imidazolium salt and its application in organic molecular electronics.

PubMed

Storch, Jan; Zadny, Jaroslav; Strasak, Tomas; Kubala, Martin; Sykora, Jan; Dusek, Michal; Cirkva, Vladimir; Matejka, Pavel; Krbal, Milos; Vacek, Jan

2015-02-02

Herein we demonstrate the synthesis of a helicene-based imidazolium salt. The salt was prepared by starting from racemic 2-methyl[6]helicene, which undergoes radical bromination to yield 2-(bromomethyl)[6]helicene. Subsequent treatment with 1-butylimidazole leads to the corresponding salt 1-butyl-3-(2-methyl[6]helicenyl)-imidazolium bromide. The prepared salt was subsequently characterized by using NMR spectroscopy and X-ray analysis, various optical spectrometric techniques, and computational chemistry tools. Finally, the imidazolium salt was immobilized onto a SiO2 substrate as a crystalline or amorphous deposit. The deposited layers were used for the development of organic molecular semiconductor devices and the construction of a fully reversible humidity sensor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessing clinical competency in medical senior house officers: how and why should we do it?

PubMed Central

Carr, S

2004-01-01

Most consultants are involved in the training and assessment of several grades of doctors in training especially senior house officers (SHOs) and specialist registrars. In the medical and other specialties there is an increasing trend towards assessing junior doctors' competency using the record of in-training assessment process for specialist registrars and using the Royal College of Physicians folder to record competences of medical SHOs. It is necessary to consider why there is a need to assess competency, how it may be done practically, and the advantages and disadvantages of this system of assessment. There are considerable hurdles to the implementation of this system in the medical specialties within today's NHS and the organisation may need to undergo fairly radical change to facilitate this system. PMID:14970290

Ni-Catalyzed Carbon-Carbon Bond-Forming Reductive Amination.

PubMed

Heinz, Christoph; Lutz, J Patrick; Simmons, Eric M; Miller, Michael M; Ewing, William R; Doyle, Abigail G

2018-02-14

This report describes a three-component, Ni-catalyzed reductive coupling that enables the convergent synthesis of tertiary benzhydryl amines, which are challenging to access by traditional reductive amination methodologies. The reaction makes use of iminium ions generated in situ from the condensation of secondary N-trimethylsilyl amines with benzaldehydes, and these species undergo reaction with several distinct classes of organic electrophiles. The synthetic value of this process is demonstrated by a single-step synthesis of antimigraine drug flunarizine (Sibelium) and high yielding derivatization of paroxetine (Paxil) and metoprolol (Lopressor). Mechanistic investigations support a sequential oxidative addition mechanism rather than a pathway proceeding via α-amino radical formation. Accordingly, application of catalytic conditions to an intramolecular reductive coupling is demonstrated for the synthesis of endo- and exocyclic benzhydryl amines.

The crystal structure of a cyanobacterial water-soluble carotenoid binding protein.

PubMed

Kerfeld, Cheryl A; Sawaya, Michael R; Brahmandam, Vishnu; Cascio, Duilio; Ho, Kwok Ki; Trevithick-Sutton, Colleen C; Krogmann, David W; Yeates, Todd O

2003-01-01

Carotenoids undergo a wide range of photochemical reactions in animal, plant, and microbial systems. In photosynthetic organisms, in addition to light harvesting, they perform an essential role in protecting against light-induced damage by quenching singlet oxygen, superoxide anion radicals, or triplet-state chlorophyll. We have determined the crystal structure of a water-soluble orange carotenoid protein (OCP) isolated from the cyanobacterium Arthrospira maxima at a resolution of 2.1 A. OCP forms a homodimer with one carotenoid molecule per monomer. The carotenoid binding site is lined by a striking number of methionine residues. The structure reveals several possible ways in which the protein environment influences the spectral properties of the pigment and provides insight into how the OCP carries out its putative functions in photoprotection.

Lycopene control of benzophenone-sensitized lipid peroxidation

NASA Astrophysics Data System (ADS)

Cvetković, Dragan; Marković, Dejan

2012-05-01

Lycopene antioxidant activity in the presence of two different mixtures of phospholipids in hexane solution, under continuous regime of UV-irradiation from three different ranges (UV-A, UV-B, and UV-C) has been evaluated in this work. Lycopene expected role was to control lipid peroxidation, by scavenging free radicals generated by UV-irradiation, in the presence and in the absence of selected photosensitizer, benzophenone. This work shows that lycopene undergoes to UV-induced destruction (bleaching), highly dependent on the incident photons energy input, more expressed in the presence than in the absence of benzophenone. The further increase ("excess") of its bleaching is undoubtedly related to the further increase of its antioxidant activity in the presence of benzophenone, having the same cause: increase of (phospholipids peroxidation) chain-breaking activities.

Coordination Chemistry of Linear Oligopyrrolic Fragments Inspired by Heme Metabolites

NASA Astrophysics Data System (ADS)

Gautam, Ritika

Linear oligopyrroles are degradation products of heme, which is converted in the presence of heme oxygenase to bile pigments, such as biliverdin and bilirubin. These tetrapyrrolic oligopyrroles are ubiquitously present in biological systems and find applications in the fields of catalysis and sensing. These linear tetrapyrrolic scaffolds are further degraded into linear tripyrrolic and dipyrrolic fragments. Although these lower oligopyrroles are abundantly present, their coordination chemistry requires further characterization. This dissertation focuses mainly on two classes of bioinspired linear oligopyrroles, propentdyopent and tripyrrindione, and their transition metal complexes, which present a rich ligand-based redox chemistry. Chapter 1 offers an overview of heme degradation to different classes of linear oligopyrroles and properties of their transition metal complexes. Chapter 2 is focused on the tripyrrin-1,14-dione scaffold of the urinary pigment uroerythrin, which coordinates divalent transition metals palladium and copper with square planar geometry. Specifically, the tripyrrin-1, 14-dione ligand binds Cu(II) and Pd(II) as a dianionic organic radical under ambient conditions. The electrochemical study confirms the presence of ligand based redox chemistry, and one electron oxidation or reduction reactions do not alter the planar geometry around the metal center. The X-Ray analysis and the electron paramagnetic resonance (EPR) studies of the complexes in the solid and solution phase reveals intermolecular interactions between the ligand based unpaired electrons and therefore formation of neutral pi-pi dimers. In Chapter 3, the antioxidant activity and the fluorescence sensor properties of the tripyrrin-1,14-dione ligand in the presence of superoxide are described. We found that the tripyrrindione ligand undergoes one-electron reduction in the presence of the superoxide radical anion (O2•- ) to form highly fluorescent H3TD1•- radical anion, which emits at 635 nm. This reaction also explains the antioxidant properties of the linear tripyrrin-1,14-dione ligand, which acts as a scavenger of O2•-. In Chapter 4, the zinc binding properties of the tripyrrin-1,14-dione ligand are described. The tripyrrolic ligand coordinates as a dianionic ligand with the divalent Zn(II) ion in both organic and aqueous buffered conditions. The complex formed is highly fluorescent with a long wavelength emission band at 648 nm. The X-Ray crystallography analysis indicates the existence of dinuclear complex [Zn(TD1•)(H2O)]2, featuring a distorted square planar geometry around the Zn(II) center. In Chapter 5, the coordination chemistry of the dipyrrin-1,9-dione fragment of propentdyopent ligand is shown with a series of transition metals like (e.g., Co(II), Ni(II), Cu(II) and Zn(II)), which form homoleptic tetrahedral complexes. The spectroscopic and electrochemical characterization confirms that the complexes shows ligand-based redox chemistry and acts as reservoirs for unpaired electrons. Chapter 6 describes the formation of the fluorescent BODIPY complex of propentdyopent ligand. The dipyrrin-1,9-dione scaffold of heme metabolite propendyopent undergoes a one-pot reaction with borontrifluoride etherate in toluene to form a green fluorescent [(pdp)BF2] complex. Spectroscopic studies reveal that the meso-unsubstituted [(pdp)BF2] complex is stable in tetrahydrofuran and has a quantum yield of 0.13. Electrochemical studies confirm that the complex undergoes ligand-based reduction and acts as a host for an unpaired electron.

Recovery of Baseline Erectile Function in Men Following Radical Prostatectomy for High-Risk Prostate Cancer: A Prospective Analysis Using Validated Measures.

PubMed

Sridhar, Ashwin N; Cathcart, Paul J; Yap, Tet; Hines, John; Nathan, Senthil; Briggs, Timothy P; Kelly, John D; Minhas, Suks

2016-03-01

Recovery of baseline erectile function (EF) after robotic radical prostatectomy in men with high-risk prostate cancer is under-reported. Published studies have selectively reported on low-risk disease using non-validated and poorly defined thresholds for EF recovery. To assess return to baseline EF in men after robotic radical prostatectomy for high-risk prostate cancer. Five hundred thirty-one men underwent robotic radical prostatectomy for high-risk prostate cancer from February 2010 through July 2014. Pre- and postoperative EF was prospectively assessed using the International Index of Erectile Dysfunction (IIEF-5) questionnaire. Multivariate logistic regression analysis determined the effect of age, preoperative function, comorbidities, body mass index, prostate-specific antigen level, cancer stage or grade, nerve-sparing status, adjuvant therapy, and continence on EF return (defined as postoperative return to baseline EF with or without use of phosphodiesterase type 5 inhibitors). Kaplan-Meier analysis and log-rank test were used to analyze return over time. Mann-Whitney U-test was used to compare IIEF-5 scores. Pre- and postoperative EF was assessed using the IIEF-5 Sexual Health Inventory for Men at 3 months, 6 months, 1 year, 2 years, 3 years, and 4 years postoperatively. Overall, return of EF was seen in 23.5% of patients at 18 months. This was significantly increased in men no older than 60 years (P = .024), with a preoperative IIEF-5 score of at least 22 (P = .042), and after undergoing neurovascular bundle preservation (34.9% of patients, P < .001). There was no significant change in IIEF-5 scores from 3 to 36 months in patients who were treated with phosphodiesterase type 5 inhibitors in the non-neurovascular bundle preservation group (P = .87), although there was significant improvement in those receiving second- or third-line therapies (P = .042). Other than preoperative hypertension (P = .03), none of the other comorbidities predicted return of EF. In this study, 23.5% of men recovered to baseline EF. Of those who underwent bilateral neurovascular bundle preservation robotic radical prostatectomy, 70% recovered baseline EF; however, this accounted for only 9.6% of all patients. Only 4% of men who underwent non-neurovascular bundle preservation had baseline recovery with phosphodiesterase type 5 inhibitors up to 36 months. There was significant improvement after use of second- or third-line therapies, indicating the need for earlier institution of these treatment modalities. Copyright © 2016 International Society for Sexual Medicine. Published by Elsevier Inc. All rights reserved.

The accuracy of noninvasive hemoglobin monitoring using the radical-7 pulse CO-Oximeter in children undergoing neurosurgery.

PubMed

Park, Yong-Hee; Lee, Ji-Hyun; Song, Hyun-Gul; Byon, Hyo-Jin; Kim, Hee-Soo; Kim, Jin-Tae

2012-12-01

The most common method for determining the hemoglobin concentration is to draw blood from a patient. However, the Radical-7 Pulse CO-Oximeter (Masimo Corporation, Irvine, CA) can noninvasively provide continuous hemoglobin concentration (SpHb). In our study we compared noninvasive measurements of SpHb with simultaneous laboratory measurements of total hemoglobin in arterial blood samples taken from children (tHb). Arterial blood samples were analyzed using a laboratory CO-oximeter, and SpHb was simultaneously recorded in pediatric patients undergoing neurosurgery. When patients met the criteria for hypovolemia, 10 mL/kg of colloids or red blood cells were administered over 10 minutes. SpHb and tHb data were collected before and after intravascular volume resuscitation. The relationship between SpHb and tHb was assessed using a 4-quadrant plot, linear regression, mixed-effect model, and modified Bland-Altman analyses. One hundred nineteen paired samples were analyzed. The correlation coefficient between SpHb and tHb was 0.53 (P < 0.001), whereas that of change in SpHb versus change in tHb was 0.75 (P < 0.001). The average difference (bias) between tHb and SpHb was 0.90 g/dL (95% confidence interval [CI], 0.48-1.32 g/dL) and 1 standard deviation of the difference (sd) was 1.35 g/dL. The concordance rate (a measure of the number of data points that are in 1 of the 2 quadrants of agreement) determined using a 4-quadrant plot was 93%. The correlation coefficient between SpHb and tHb after intravascular volume resuscitation was 0.58 (P < 0.001), whereas that of changes in SpHb and tHb was 0.87 (P < 0.001). The bias immediately after volume resuscitation was 1.18 g/dL (95% CI, 0.81-1.55 g/dL), and sd was 1.28 g/dL with a concordance rate of 94.4%. The bias was -0.03 g/dL when tHb was ≥11 g/dL, which was significantly lower in comparison with biases when tHb <9 g/dL (1.24 g/dL) and tHb was 9-11 g/dL (1.17 g/dL) (P = 0.004). The Radical-7 Pulse CO-Oximeter can be useful as a trend monitor in children during surgery even immediately after intravascular volume expanders are administered. However, it is advisable to confirm the baseline hemoglobin level and to consider the influence of tHb level on the bias. In addition, one should be cautious with regard to using SpHb alone when making transfusion decisions.

[Comparison of the effects of phosphodiesterase III inhibitors, milrinone and olprinone, in infant corrective cardiac surgery].

PubMed

Sakimura, Shotaro; Yoshino, Jun; Izumi, Kaoru; Jimi, Nobuo; Sumiyoshi, Rieko; Mizuno, Keiichiro

2013-05-01

Clinical characteristics of phosphodiesterase (PDE) III inhibitors, milrinone and olprinone, is not fully understood in infants. We therefore retrospectively examined the hemodynamics, metabolism, and oxygenation of two different PDE III inhibitors in infants undergoing radical correction of ventricular septal defect with pulmonary hypertension. Twenty-six infants with pulmonary hypertension undergoing ventricular septum defect repair were retrospectively allocated to milrinone group (n= 13)and olprinone group(n=13). Hemodynamic parameters, acid-base balance, oxygenation and postoperative mechanical ventilation period were compared between the two groups at induction of anesthesia, weaning from cardiopulmonary bypass and the end of the surgery. The patients' mean age was 4.4 +/- 2.5 months. Demographic data were almost similar between the two groups. Milrinone and olprinone were administered at the rates of 0.5 and 0.3 microg x kg-1 x min-1 at the end of surgery, respectively. Hemodynamic variables, acid-base balance, Pao2 /FIo2 ratio and mechanical ventilation period were not significantly different between the two groups. No adverse side effects were observed during the study period. The effects of the PDE III inhibitors, milrinone and olprinone, on hemodynamic parameters, acid-base balance and oxygenation were similar in these infants. Both milrinone and olprinone could be used safely in infant cardiac surgery.

Direct Functionalization of an Acid-Terminated Nanodiamond with Azide: Enabling Access to 4-Substituted-1,2,3-Triazole-Functionalized Particles

DOE PAGES

Kennedy, Zachary C.; Barrett, Christopher A.; Warner, Marvin G.

2017-03-01

Azides on the periphery of nanodiamond materials (ND) are of great utility because they have been shown to undergo Cu-catalyzed and Cu-free cycloaddition reactions with structurally diverse alkynes, affording particles tailored for applications in biology and materials science. However, current methods employed to access ND featuring azide groups typically require either harsh pretreatment procedures or multiple synthesis steps and use surface linking groups that may be susceptible to undesirable cleavage. Here in this paper we demonstrate an alternative single-step approach to producing linker-free, azide-functionalized ND. Our method was applied to low-cost, detonation-derived ND powders where surface carbonyl groups undergo silver-mediatedmore » decarboxylation and radical substitution with azide. ND with directly grafted azide groups were then treated with a variety of aliphatic, aromatic, and fluorescent alkynes to afford 1-(ND)-4-substituted-1,2,3-triazole materials under standard copper-catalyzed cycloaddition conditions. Surface modification steps were verified by characteristic infrared absorptions and elemental analyses. High loadings of triazole surface groups (up to 0.85 mmol g –1) were obtained as determined from thermogravimetric analysis. The azidation procedure disclosed is envisioned to become a valuable initial transformation in numerous future applications of ND.« less

Discovery and Validation of Predictive Biomarkers of Survival for Non-small Cell Lung Cancer Patients Undergoing Radical Radiotherapy: Two Proteins With Predictive Value

PubMed Central

Walker, Michael J.; Zhou, Cong; Backen, Alison; Pernemalm, Maria; Williamson, Andrew J.K.; Priest, Lynsey J.C.; Koh, Pek; Faivre-Finn, Corinne; Blackhall, Fiona H.; Dive, Caroline; Whetton, Anthony D.

2015-01-01

Lung cancer is the most frequent cause of cancer-related death world-wide. Radiotherapy alone or in conjunction with chemotherapy is the standard treatment for locally advanced non-small cell lung cancer (NSCLC). Currently there is no predictive marker with clinical utility to guide treatment decisions in NSCLC patients undergoing radiotherapy. Identification of such markers would allow treatment options to be considered for more effective therapy. To enable the identification of appropriate protein biomarkers, plasma samples were collected from patients with non-small cell lung cancer before and during radiotherapy for longitudinal comparison following a protocol that carries sufficient power for effective discovery proteomics. Plasma samples from patients pre- and during radiotherapy who had survived > 18 mo were compared to the same time points from patients who survived < 14 mo using an 8 channel isobaric tagging tandem mass spectrometry discovery proteomics platform. Over 650 proteins were detected and relatively quantified. Proteins which showed a change during radiotherapy were selected for validation using an orthogonal antibody-based approach. Two of these proteins were verified in a separate patient cohort: values of CRP and LRG1 combined gave a highly significant indication of extended survival post one week of radiotherapy treatment. PMID:26425690

Kinetics and mechanism for the sonochemical degradation of a nonionic surfactant.

PubMed

Singla, Ritu; Grieser, Franz; Ashokkumar, Muthupandian

2009-03-26

The sonolytic degradation of the nonionic surfactant, octaethylene glycol monododecyl ether (C(12)E(8)), has been studied at various initial concentrations below and above its critical micelle concentration (CMC). It has been observed that the degradation rate increases with an increase in the initial concentration of the surfactant until the CMC is reached. Above the CMC an almost constant degradation rate is observed, suggesting that the surfactant in its monomer form is involved in the degradation process. The degradation process of C(12)E(8) involves two distinct primary processes occurring at the bubble/solution interface: (a) hydroxylation/oxidation of the surfactant and (b) pyrolytic fragmentation of the surfactant. The oxidative cleavage of ethylene oxide units provides evidence for OH radical attack. Hydroxylation of the ethoxy chain gives rise to various short-chain carboxyalkyl-polyethylene glycol intermediates. The polyethylene glycol chain formed, due to the scission of the C(12)E(8) molecule, undergoes rapid hydroxylation/oxidation to yield simple compounds that have the potential to undergo further degradation. The detection of multiple intermediates indicates that several processes affect the complete degradation pathways of the surfactant molecule. TOC analysis, however, indicates that the sonolytic mineralization of the surfactant is difficult to achieve at reasonable rates due to the relatively low surface activity of the degradation products formed during sonolysis.

Evaluation of Mediators Associated with the Inflammatory Response in Prostate Cancer Patients Undergoing Radiotherapy

PubMed Central

Bedini, Nice; Cicchetti, Alessandro; Palorini, Federica; Magnani, Tiziana; Zuco, Valentina; Pennati, Marzia; Campi, Elisa; Allavena, Paola; Pesce, Samantha; Villa, Sergio; Avuzzi, Barbara; Morlino, Sara; Visentin, Maria Emanuela; Zaffaroni, Nadia; Valdagni, Riccardo

2018-01-01

A recent “hot topic” in prostate cancer radiotherapy is the observed association between acute/late rectal toxicity and the presence of abdominal surgery before radiotherapy. The exact mechanism is unclear. Our working hypothesis was that a previous surgery may influence plasma level of inflammatory molecules and this might result in enhanced radiosensitivity. We here present results on the feasibility of monitoring the expression of inflammatory molecules during radiotherapy. Plasma levels of a panel of soluble mediators associated with the inflammatory response were measured in prostate cancer patients undergoing radical radiotherapy. We measured 3 cytokines (IL-1b, IL-6, and TNF alpha), 2 chemokines (CCL2 and CXCL8), and the long pentraxin PTX3. 20 patients were enrolled in this feasibility evaluation. All patients were treated with IMRT at 78 Gy. 3/20 patients reported grade 2 acute rectal toxicity, while 4/20 were scored as grade 2 late toxicity. CCL2 was the most interesting marker showing significant increase during and after radiotherapy. CCL2 levels at radiotherapy end could be modelled using linear regression including basal CCL2, age, surgery, hypertension, and use of anticoagulants. The 4 patients with late toxicity had CCL2 values at radiotherapy end above the median value. This trial is registered with ISRCTN64979094. PMID:29682101

Evaluation of Mediators Associated with the Inflammatory Response in Prostate Cancer Patients Undergoing Radiotherapy.

PubMed

Bedini, Nice; Cicchetti, Alessandro; Palorini, Federica; Magnani, Tiziana; Zuco, Valentina; Pennati, Marzia; Campi, Elisa; Allavena, Paola; Pesce, Samantha; Villa, Sergio; Avuzzi, Barbara; Morlino, Sara; Visentin, Maria Emanuela; Zaffaroni, Nadia; Rancati, Tiziana; Valdagni, Riccardo

2018-01-01

A recent "hot topic" in prostate cancer radiotherapy is the observed association between acute/late rectal toxicity and the presence of abdominal surgery before radiotherapy. The exact mechanism is unclear. Our working hypothesis was that a previous surgery may influence plasma level of inflammatory molecules and this might result in enhanced radiosensitivity. We here present results on the feasibility of monitoring the expression of inflammatory molecules during radiotherapy. Plasma levels of a panel of soluble mediators associated with the inflammatory response were measured in prostate cancer patients undergoing radical radiotherapy. We measured 3 cytokines (IL-1b, IL-6, and TNF alpha), 2 chemokines (CCL2 and CXCL8), and the long pentraxin PTX3. 20 patients were enrolled in this feasibility evaluation. All patients were treated with IMRT at 78 Gy. 3/20 patients reported grade 2 acute rectal toxicity, while 4/20 were scored as grade 2 late toxicity. CCL2 was the most interesting marker showing significant increase during and after radiotherapy. CCL2 levels at radiotherapy end could be modelled using linear regression including basal CCL2, age, surgery, hypertension, and use of anticoagulants. The 4 patients with late toxicity had CCL2 values at radiotherapy end above the median value. This trial is registered with ISRCTN64979094.

Protective Effects of Edaravone in Adult Rats with Surgery and Lipopolysaccharide Administration-Induced Cognitive Function Impairment.

PubMed

Wang, Peiqi; Cao, Jiangbei; Liu, Na; Ma, Li; Zhou, Xueyue; Zhang, Hong; Wang, Yongan

2016-01-01

Postoperative cognitive dysfunction (POCD) is a clinical syndrome characterized by cognitive declines in patients after surgery. Previous studies have suggested that surgery contributed to such impairment. It has been proven that neuroinflammation may exacerbate surgery-induced cognitive impairment in aged rats. The free radical scavenger edaravone has high blood brain barrier permeability, and was demonstrated to effectively remove free radicals from the brain and alleviate the development of POCD in patients undergoing carotid endarterectomy, suggesting its potential role in preventing POCD. For this reason, this study was designed to determine whether edaravone is protective against POCD through its inhibitory effects on inflammatory cytokines and oxidative stress. First, Sprague Dawley adult male rats were administered 3 mg/kg edaravone intraperitoneally after undergoing a unilateral nephrectomy combined with lipopolysaccharide injection. Second, behavioral parameters related to cognitive function were recorded by fear conditioning and Morris Water Maze tests. Last, superoxide dismutase activities and malondialdehyde levels were measured in the hippocampi and prefrontal cortex on postoperative days 3 and 7, and microglial (Iba1) activation, p-Akt and p-mTOR protein expression, and synaptic function (synapsin 1) were also examined 3 and 7 days after surgery. Rats that underwent surgery plus lipopolysaccharide administration showed significant impairments in spatial and working memory, accompanied by significant reductions in hippocampal-dependent and independent fear responses. All impairments were attenuated by treatment with edaravone. Moreover, an abnormal decrease in superoxide dismutase activation, abnormal increase in malondialdehyde levels, significant increase in microglial reactivity, downregulation of p-Akt and p-mTOR protein expression, and a statistically significant decrease in synapsin-1 were observed in the hippocampi and prefrontal cortices of rats at different time points after surgery. All mentioned abnormal changes were totally or partially reversed by edaravone. To our knowledge, few reports have shown greater protective effects of edaravone on POCD induced by surgery plus lipopolysaccharide administration from its anti-oxidative stress and anti-inflammatory effects, as well as maintenance of Akt/mTOR signal pathway activation; these might be closely related to the therapeutic effects of edaravone. Our research demonstrates the potential use of edaravone in the treatment of POCD.

Protective Effects of Edaravone in Adult Rats with Surgery and Lipopolysaccharide Administration-Induced Cognitive Function Impairment

PubMed Central

Liu, Na; Ma, Li; Zhou, Xueyue; Zhang, Hong; Wang, Yongan

2016-01-01

Postoperative cognitive dysfunction (POCD) is a clinical syndrome characterized by cognitive declines in patients after surgery. Previous studies have suggested that surgery contributed to such impairment. It has been proven that neuroinflammation may exacerbate surgery-induced cognitive impairment in aged rats. The free radical scavenger edaravone has high blood brain barrier permeability, and was demonstrated to effectively remove free radicals from the brain and alleviate the development of POCD in patients undergoing carotid endarterectomy, suggesting its potential role in preventing POCD. For this reason, this study was designed to determine whether edaravone is protective against POCD through its inhibitory effects on inflammatory cytokines and oxidative stress. First, Sprague Dawley adult male rats were administered 3 mg/kg edaravone intraperitoneally after undergoing a unilateral nephrectomy combined with lipopolysaccharide injection. Second, behavioral parameters related to cognitive function were recorded by fear conditioning and Morris Water Maze tests. Last, superoxide dismutase activities and malondialdehyde levels were measured in the hippocampi and prefrontal cortex on postoperative days 3 and 7, and microglial (Iba1) activation, p-Akt and p-mTOR protein expression, and synaptic function (synapsin 1) were also examined 3 and 7 days after surgery. Rats that underwent surgery plus lipopolysaccharide administration showed significant impairments in spatial and working memory, accompanied by significant reductions in hippocampal-dependent and independent fear responses. All impairments were attenuated by treatment with edaravone. Moreover, an abnormal decrease in superoxide dismutase activation, abnormal increase in malondialdehyde levels, significant increase in microglial reactivity, downregulation of p-Akt and p-mTOR protein expression, and a statistically significant decrease in synapsin-1 were observed in the hippocampi and prefrontal cortices of rats at different time points after surgery. All mentioned abnormal changes were totally or partially reversed by edaravone. To our knowledge, few reports have shown greater protective effects of edaravone on POCD induced by surgery plus lipopolysaccharide administration from its anti-oxidative stress and anti-inflammatory effects, as well as maintenance of Akt/mTOR signal pathway activation; these might be closely related to the therapeutic effects of edaravone. Our research demonstrates the potential use of edaravone in the treatment of POCD. PMID:27116382

Contemporary use trends and survival outcomes in patients undergoing radical cystectomy or bladder-preservation therapy for muscle-invasive bladder cancer.

PubMed

Cahn, David B; Handorf, Elizabeth A; Ghiraldi, Eric M; Ristau, Benjamin T; Geynisman, Daniel M; Churilla, Thomas M; Horwitz, Eric M; Sobczak, Mark L; Chen, David Y T; Viterbo, Rosalia; Greenberg, Richard E; Kutikov, Alexander; Uzzo, Robert G; Smaldone, Marc C

2017-11-15

The current study was performed to examine temporal trends and compare overall survival (OS) in patients undergoing radical cystectomy (RC) or bladder-preservation therapy (BPT) for muscle-invasive urothelial carcinoma of the bladder. The authors reviewed the National Cancer Data Base to identify patients with AJCC stage II to III urothelial carcinoma of the bladder from 2004 through 2013. Patients receiving BPT were stratified as having received any external-beam radiotherapy (any XRT), definitive XRT (50-80 grays), and definitive XRT with chemotherapy (CRT). Treatment trends and OS outcomes for the BPT and RC cohorts were evaluated using Cochran-Armitage tests, unadjusted Kaplan-Meier curves, adjusted Cox multivariate regression, and propensity score matching, using increasingly stringent selection criteria. A total of 32,300 patients met the inclusion criteria and were treated with RC (22,680 patients) or BPT (9620 patients). Of the patients treated with BPT, 26.4% (2540 patients) and 15.5% (1489 patients), respectively, were treated with definitive XRT and CRT. Improved OS was observed for RC in all groups. After adjustments with more rigorous statistical models controlling for confounders and with more restrictive BPT cohorts, the magnitude of the OS benefit became attenuated on multivariate (any XRT: hazard ratio [HR], 2.115 [95% confidence interval [95% CI], 2.045-2.188]; definitive XRT: HR, 1.870 [95% CI, 1.773-1.972]; and CRT: HR, 1.578 [95% CI, 1.474-1.691]) and propensity score (any XRT: HR, 2.008 [95% CI, 1.871-2.154]; definitive XRT: HR, 1.606 [95% CI, 1.453-1.776]; and CRT: HR, 1.406 [95% CI, 1.235-1.601]) analyses. In the National Cancer Data Base, receipt of BPT was associated with decreased OS compared with RC in patients with stage II to III urothelial carcinoma. Increasingly stringent definitions of BPT and more rigorous statistical methods adjusting for selection biases attenuated observed survival differences. Cancer 2017;123:4337-45. © 2017 American Cancer Society. © 2017 American Cancer Society.

[Effects of preoperative oral glucose on perioperative insulin resistance and plasma proteins of intestinal surgery].

PubMed

Yang, Peng; Feng, Xia; Niu, Li-jun; Yang, Dong-jie; Huang, Wen-qi; Huang, Xiong-qing

2010-11-01

To investigate the effects of oral intake of glucose solution before surgery on the pH at the lower esophagus, perioperative blood glucose level, and plasmic protein in patients undergoing radical resection for colorectal cancer. Between January 2008 and December 2008, 60 patients undergoing radical surgery for colorectal cancer were enrolled and randomized into three groups using the table of random digits. Four patients were withdrawn from the study. Patients in group A (n=19) were given 800 ml of 12.5% glucose solution for oral intake the night before surgery, and 200 ml two hours before surgery. Patients in group B (n=19) were given distilled water instead of glucose. Patients in group C (n=18) were asked to fast for 8-12 hours before operation. Combined general and epidural anesthesia was used. pH at the lower esophagus was monitored during intubation and extubation. Albumin, transferrin, prealbumin, insulin, and fasting blood glucose were measured before surgery and at postoperative day 1, 3, and 7. pH at the lower esophagus was 8.05±0.43 in group A, 7.98±0.41 in group B, and 7.94±0.41 in group C. There were no perioperative acid regurgitations (P>0.05). Serum insulin in group A at postoperative day 1 was (16.32±16.11) μU/L, which was significantly lower than that in group B (30.65±41.74) μU/L and group C (34.01±52.91) μU/L. Log HOMA-IR in group A at postoperative day 1 was significantly lower than that in group B and group C (0.49±0.35 vs. 0.59±0.56 and 0.60±0.63, P<0.05). Transferrin in group C at postoperative day 3 and 7 was significantly lower than that in the other two groups, as was albumin at postoperative day 3 (P<0.05). Oral liquid intake 2 hours before surgery is not associated with increased risk of regurgitation or aspiration during intubation and extubation, and may glucose solution intake reduce insulin resistance and protein degradation after colorectal surgery.

The effect of peroxynitrite decomposition catalyst MnTBAP on aldehyde dehydrogenase-2 nitration by organic nitrates: role in nitrate tolerance.

PubMed

Mollace, Vincenzo; Muscoli, Carolina; Dagostino, Concetta; Giancotti, Luigino Antonio; Gliozzi, Micaela; Sacco, Iolanda; Visalli, Valeria; Gratteri, Santo; Palma, Ernesto; Malara, Natalia; Musolino, Vincenzo; Carresi, Cristina; Muscoli, Saverio; Vitale, Cristiana; Salvemini, Daniela; Romeo, Francesco

2014-11-01

Bioconversion of glyceryl trinitrate (GTN) into nitric oxide (NO) by aldehyde dehydrogenase-2 (ALDH-2) is a crucial mechanism which drives vasodilatory and antiplatelet effect of organic nitrates in vitro and in vivo. Oxidative stress generated by overproduction of free radical species, mostly superoxide anions and NO-derived peroxynitrite, has been suggested to play a pivotal role in the development of nitrate tolerance, though the mechanism still remains unclear. Here we studied the free radical-dependent impairment of ALDH-2 in platelets as well as vascular tissues undergoing organic nitrate ester tolerance and potential benefit when using the selective peroxynitrite decomposition catalyst Mn(III) tetrakis (4-Benzoic acid) porphyrin (MnTBAP). Washed human platelets were made tolerant to nitrates via incubation with GTN for 4h. This was expressed by attenuation of platelet aggregation induced by thrombin (40U/mL), an effect accompanied by GTN-related induction of cGMP levels in platelets undergoing thrombin-induced aggregation. Both effects were associated to attenuated GTN-induced nitrite formation in platelets supernatants and to prominent nitration of ALDH-2, the GTN to NO metabolizing enzyme, suggesting that GTN tolerance was associated to reduced NO formation via impairment of ALDH-2. These effects were all antagonized by co-incubation of platelets with MnTBAP, which restored GTN-induced responses in tolerant platelets. Comparable effect was found under in in vivo settings. Indeed, MnTBAP (10mg/kg, i.p.) significantly restored the hypotensive effect of bolus injection of GTN in rats made tolerants to organic nitrates via chronic administration of isosorbide-5-mononitrate (IS-5-MN), thus confirming the role of peroxynitrite overproduction in the development of tolerance to vascular responses induced by organic nitrates. In conclusion, oxidative stress subsequent to prolonged use of organic nitrates, which occurs via nitration of ALDH-2, represents a key event in GTN tolerance, an effect counteracted both in vitro and in vivo by novel peroxynitrite decomposition catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chemical structure, comparison antioxidant capacity and separation antioxidant of hen, duck and quail egg white protein hydrolysate

NASA Astrophysics Data System (ADS)

Fatah, A.; Meihu, M.; Ning, Q.; Setiani, B. E.; Bintoro, V. P.

2018-01-01

Amino acid linkages as proteins are nutritional substance which important for diet intake. Purification protein procesing undergo heating procedure process followed by additional of proteolytic enzymes or acid had been resulting in protein hydrolysates. A protein hydrolysate describe as many free amino acids bound together through a complex mixture of peptides. Egg white protein hydrolysates is one of subject interested to study for human health or industry product. The objectives of the research are to determine and identification the antioxidant derived from egg white hydrolysate protein. Identification of chemical structure of albumen and albumen protein hydrolysate was examine using IR Spectrophotometry. While comparison of antioxidant capacity and antioxidant separation egg albumen was also investigate using FTIR method (Fourier Transform Infrared Spectroscopy). Hen, duck and quail albumen egg white and on hydrolisate form were used as research materials. The results were showing that different time and enzyme of hydrolysis were not influence at secondary structure of hydrolysate albumen protein. Phytochemical content such as alcohol and hydroxyl compound which have potential as functional group of antioxidant were detected in all of the samples. Their results of radical scavenging activities samples hydrolyzed by pepsin were respectively 89.40%, 50.25% and 85.13%. Whereas the radical scavenging activities of hydrolysates hydrolyzed by papain were 72.85%, 61% and 76.45% respectively.

Gamma Irradiation and Oxidative Degradation of a Silica-Filled Silicone Elastomer

DOE PAGES

Labouriau, Andrea; Cady, Carl Mcelhinney; Gill, John T.; ...

2015-03-21

The radiation oxidative degradation of a commonly used silica-filled silicone elastomer DC745 was investigated by a series of experimental techniques. This elastomer is known to be chemically and thermally stable, but insufficient data exist on the radiation resistance. In the present work, gamma doses up to 200 kGy were applied under air at RT and 1Gy/s. Radiation chemical changes were investigated by NMR, FT-IR, Raman, and mass spectroscopy. DSC and TGA experiments probed thermal transitions and thermal stability changes with exposure dose. SEM probed variations on the surface of the elastomer, and solvent swelling methods were used to investigate changesmore » in the polymer network properties. Electron paramagnetic resonance was employed to detect and identify free radicals. Uniaxial compression load tests at variable temperatures were performed to assess changes in the material’s mechanical response as a function of radiation dose. Results demonstrate that, with increasing exposure, DC745 undergoes changes in chemistry that lead to an increase in thermal stability and cross-link density, formation of free radical species, decrease in heat of fusion and increase in stiffness at low temperatures. Taken together, these results indicate that oxidative cross-linking is the dominant radiolysis mechanism that occurs when this material is exposed to gamma irradiation in air at high dose rates.« less

Improving Hydrophobicity of Glass Surface Using Dielectric Barrier Discharge Treatment in Atmospheric Air

NASA Astrophysics Data System (ADS)

Fang, Zhi; Qiu, Yuchang; Wang, Hui; E, Kuffel

2007-10-01

Non-thermal plasmas under atmospheric pressure are of great interest in industrial applications, especially in material surface treatment. In this paper, the treatment of a glass surface for improving hydrophobicity using the non-thermal plasma generated by dielectric barrier discharge (DBD) at atmospheric pressure in ambient air is conducted, and the surface properties of the glass before and after the DBD treatment are studied by using contact angle measurement, surface resistance measurement and wet flashover voltage tests. The effects of the applied voltage and time duration of DBD on the surface modification are studied, and the optimal conditions for the treatment are obtained. It is found that a layer of hydrophobic coating is formed on the glass surface after spraying a thin layer of silicone oil and undergoing the DBD treatment, and the improvement of hydrophobicity depends on DBD voltage and treating time. It seems that there exists an optimum treating time for a certain applied voltage of DBD during the surface treatment. The test results of thermal aging and chemical aging show that the hydrophobic layer has quite stable characteristics. The interaction mechanism between the DBD plasma and the glass surface is discussed. It is concluded that CH3 and large molecule radicals can react with the radicals in the glass surface to replace OH, and the hydrophobicity of the glass surface is improved accordingly.

Gamma Irradiation and Oxidative Degradation of a Silica-Filled Silicone Elastomer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Labouriau, Andrea; Cady, Carl Mcelhinney; Gill, John T.

The radiation oxidative degradation of a commonly used silica-filled silicone elastomer DC745 was investigated by a series of experimental techniques. This elastomer is known to be chemically and thermally stable, but insufficient data exist on the radiation resistance. In the present work, gamma doses up to 200 kGy were applied under air at RT and 1Gy/s. Radiation chemical changes were investigated by NMR, FT-IR, Raman, and mass spectroscopy. DSC and TGA experiments probed thermal transitions and thermal stability changes with exposure dose. SEM probed variations on the surface of the elastomer, and solvent swelling methods were used to investigate changesmore » in the polymer network properties. Electron paramagnetic resonance was employed to detect and identify free radicals. Uniaxial compression load tests at variable temperatures were performed to assess changes in the material’s mechanical response as a function of radiation dose. Results demonstrate that, with increasing exposure, DC745 undergoes changes in chemistry that lead to an increase in thermal stability and cross-link density, formation of free radical species, decrease in heat of fusion and increase in stiffness at low temperatures. Taken together, these results indicate that oxidative cross-linking is the dominant radiolysis mechanism that occurs when this material is exposed to gamma irradiation in air at high dose rates.« less

Possible role of electric forces in bromine activation during polar boundary layer ozone depletion and aerosol formation events

NASA Astrophysics Data System (ADS)

Tkachenko, Ekaterina

2017-11-01

This work presents a hypothesis about the mechanism of bromine activation during polar boundary layer ozone depletion events (ODEs) as well as the mechanism of aerosol formation from the frost flowers. The author suggests that ODEs may be initiated by the electric-field gradients created at the sharp tips of ice formations as a result of the combined effect of various environmental conditions. According to the author's estimates, these electric-field gradients may be sufficient for the onset of point or corona discharges followed by generation of high local concentrations of the reactive oxygen species and initiation of free-radical and redox reactions. This process may be responsible for the formation of seed bromine which then undergoes further amplification by HOBr-driven bromine explosion. The proposed hypothesis may explain a variety of environmental conditions and substrates as well as poor reproducibility of ODE initiation observed by researchers in the field. According to the author's estimates, high wind can generate sufficient conditions for overcoming the Rayleigh limit and thus can initiate ;spraying; of charged aerosol nanoparticles. These charged aerosol nanoparticles can provoke formation of free radicals, turning the ODE on. One can also envision a possible emission of halogen ion as a result of the ;electrospray; process analogous to that of electrospray ionization mass-spectrometry.

Evaluation of urinary extravasation and results after continence-preserving radical retropubic prostatectomy.

PubMed

Varkarakis, John; Wirtenberger, Walter; Pinggera, Germar-Michael; Berger, Andreas; Harabayashi, Toru; Bartsch, Georg; Horninger, Wolfgang

2004-11-01

To evaluate the feasibility of urinary catheter removal 10 days after a radical retropubic prostatectomy (RRP) by assessing the incidence of urinary extravasation and its effect on postoperative stricture and continence rates. During a 4.5-year period, 619 patients undergoing RRP were evaluated. If no extravasation was detected on gravity cystography, the urinary catheter was removed 10 days after RRP. In patients with significant extravasation the catheter was left in place for 3 weeks. Overall stricture and continence rates were recorded in patients at 3, 6 and 12 months after surgery. There was extravasation during cystography in 29 patients (4.6%). At 3, 6 and 12 months, continence rates after catheter removal at 10 days were 74.9%, 87.9%, and 93.6%, respectively, while in the late-removal group they were 72.4%, 84.6% and 90.9%, respectively, with no significant difference between the groups. At 3 months the overall continence rate was 74.8% and at 12 months up to 93.5%. There was no difference in stricture rates between the groups, with an overall stricture rate of 0.7%. Catheter removal 10 days after RRP is feasible, giving excellent early and late continence rates, with low anastomotic stricture rates obtained using good surgical technique. Extravasation at 10 days was rare and with proper management did not influence the final results.

Characterization analysis for leaves of Leucaena leucocephala by using phytochemical screening assay

NASA Astrophysics Data System (ADS)

Zarina, Z.; Ghazali, C. M. R.; Sam, S. T.

2017-09-01

Leucaena Leucocephala (Lam.) de Wit (Petai Belalang) is a medium plant which belong in group of tropical breed that can survived in hot, dried and warm environment. In Malaysia, the plant is available abundantly. As there are still no commercial used, and no serious intention in finding the benefits of L. Leucocephala, this work come out with the idea to analyze the antioxidants contains in leaves of the plant by undergoes different extraction and chemical testing method. The phytochemical screening assay involved in this study are antioxidant activity by using free radical diphenylpicrylhydrazyl (DPPH) method, total phenolic content by using Folin-Ciocalteu method, total flavonoid content by using colorimetric assay with ascorbic acid and quercetin were used as reference standards while for phosphorus analysis, a molybdenum blue method or also known as ascorbic acid method was used. For antioxidant activity by using free radical diphenylpicrylhydrazyl (DPPH) method, higher concentration was recorded by extraction using methanol (dried sample) which is 8247.0 mg/L, for total phenolic content higher concentration was recorded by extraction using deionized water (dried sample) which is 4276.0 mg/L, for total flavonoid content by using colorimetric assay higher concentration was recorded by extraction using methanol (dried sample) which is 4439.0 mg/L, and for for phosphorus analysis higher concentration was recorded by extraction using methanol (dried sample) which is 71.057 mg/L.

Characterization analysis for leaves of Leucaena Leucocephala by using phytochemical screening assay

NASA Astrophysics Data System (ADS)

Zarina, Z.; Ghazali, C. M. R.; Sam, S. T.

2017-09-01

Leucaena Leucocephala (Lam.) de Wit (Petai Belalang) is a medium plant which belong in group of tropical breed that can survived in hot, dried and warm environment. In Malaysia, the plant is available abundantly. As there are still no commercial used, and no serious intention in finding the benefits of L. Leucocephala, this work come out with the idea to analyze the antioxidants contains in leaves of the plant by undergoes different extraction and chemical testing method. The phytochemical screening assay involved in this study are antioxidant activity by using free radical diphenylpicrylhydrazyl (DPPH) method, total phenolic content by using Folin-Ciocalteu method, total flavonoid content by using colorimetric assay with ascorbic acid and quercetin were used as reference standards while for phosphorus analysis, a molybdenum blue method or also known as ascorbic acid method was used. For antioxidant activity by using free radical diphenylpicrylhydrazyl (DPPH) method, higher concentration was recorded by extraction using methanol (dried sample) which is 8247.0 mg/L, for total phenolic content higher concentration was recorded by extraction using deionized water (dried sample) which is 4276.0 mg/L, for total flavonoid content by using colorimetric assay higher concentration was recorded by extraction using methanol (dried sample) which is 4439.0 mg/L, and for for phosphorus analysis higher concentration was recorded by extraction using methanol (dried sample) which is 71.057 mg/L.

Photoaddition of N-substituted piperazines to C60: an efficient approach to the synthesis of water-soluble fullerene derivatives.

PubMed

Troshina, Olesya A; Troshin, Pavel A; Peregudov, Alexander S; Kozlovski, Viacheslav I; Lyubovskaya, Rimma N

2006-07-17

An oxidative radical photoaddition of mono N-substituted piperazines to [60]fullerene was systematically investigated. Reactions of C60 with piperazines bearing bulky electron-withdrawing groups (2-pyridyl, 2-pyrimidinyl) were found to be the most selective and yielded C60(amine)4O as major products along with small amounts of C60(amine)2. In contrast, interactions of fullerene with N-methylpiperazine and N-(tert-butoxycarbonyl)piperazine were found to have low selectivity due to different side reactions. Tetraaminofullerene derivative C60(N-(2-pyridyl)piperazine)4O was found to react readily with organic and inorganic acids to yield highly water-soluble salts (solubility approximately 150 mg mL(-1)). In contrast, C60(N-(2-pyrimidinyl)piperazine)4O undergoes hydrolysis under the same conditions and results in a complex mixture of compounds with an average composition of C60(N-(2-pyrimidinyl)piperazine)2(OH)2O. Radical photoaddition of N-(2-pyridyl)piperazine to fullerene derivatives can be used as a facile route for their transformation into water-soluble compounds. Two model fullerene cycloadducts (a methanofullerene and a pyrrolidinofullerene) were easily converted into mixtures of regioisomers of A=C60(N-(2-pyridyl)piperazine)4O (A=cyclic addend) that give highly water-soluble salts under acid treatment.