Sample records for total radical d2
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Jiang, Jian-ping; Luo, Zhong-yang; Xuan, Jian-yong; Zhao, Lei; Fang, Meng-xiang; Gao, Xiang
2015-10-01
Pulsed corona discharge in atmosphere has been widely regarded as an efficient flue gas treatment technology for the generation of active radical species, such as the OH radicals. The spatial distribution of OH radicals generated by pulsed corona discharge plays an important role in decomposing pollutants. The two-dimensional (2-D) distribution of OH radicals of positive wire--plate pulsed corona discharge was detected using laser-induced fluorescence (LIF). The influence of relative humidity (RH) and oxygen concentration on the 2-D distribution of OH radicals were investigated. The results indicated that the 2-D distribution of OH radicals was characterized by a fan-shaped distribution from the wire electrode to plate electrode, and both the maximum values of vertical length and horizontal width of the fan area was less than 1 cm. The 2-D distribution area of OH radicals increased significantly with increasing the RH and the optimum condition was 65% RH. The optimal level of the oxygen concentration for the 2-D distribution area of OH radicals was 2%. The process of OH radical generation and 2-D distribution area of OH radicals were significantly interfered when the oxygen concentration was larger than 15%. The total quenching rate coefficients for different RH values and oxygen concentration in this study were used to calculate the fluorescence yield of OH radical. The fluorescence yield, which is the ratio between the emission rate (Einstein coefficient) and the sum of the emission rate and quenching rate, was used to normalize the 2-D distribution area of OH radicals. The fluorescence yield of OH radical decreased with increasing the RH and oxygen concentration linearly and rapidly. It was also found that compared with the RH, the influence of the oxygen concentration had more notable effect on the fluorescence yield of OH radical and 2-D distribution area of OH radicals.
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Perez-Gutierrez, Rosa Martha; Garcia-Campoy, Abraham Heriberto; Muñiz-Ramirez, Alethia
Six new flavonoids 2',4'-dihydroxychalcone-6'-O- β -d-glucopyranoside ( 1 ), α ,3,2',4'-tetrahydroxy-4-methoxy-dihydrochalcone-3'-C- β -glucopyranosy-6'-O- β -d-glucopyranoside ( 2 ), 7-hydroxy-5,8'-dimethoxy-6' α -l-rhamnopyranosyl-8-(3-phenyl-trans-acryloyl)-1-benzopyran-2-one ( 3 ), 6'7-dihydroxy-5,8-dimethoxy-8(3-phenyl-trans-acryloyl)-1-benzopyran-2-one ( 4 ), 9-hydroxy-3,8-dimethoxy-4-prenylpterocarpan ( 5 ), and α ,4,4'-trihydroxydihydrochalcone-2'-O- β -d-glucopyranoside ( 6 ) were isolated from bark of Eysenhardtia polystachya. Antidiabetic activity of compounds 1 - 5 in terms of their cellular antioxidant and free radical scavenging and also in streptozotocin- (STZ-) induced diabetic mice was evaluated on liver transaminases, lipid peroxidation, total bilirubin, total protein, superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (CSH-Px), and glutathione reductase (GSH). Results indicated that 1 - 5 scavenged 2,2-diphenyl-1-picrylhydrazyl (DPPH), hydroxyl ( ∙ OH), nitric oxide radicals (NO ∙ ), superoxide anion radical (O 2 ∙- ), radical cation (ABTS ∙+ ), and hydrogen peroxide (H 2 O 2 ) radical, and protection against H 2 O 2 induced BSA damage was also observed. Furthermore, 1 - 5 showed ability to decrease the oxidative stress in H9c2 cell. Diabetic mice present high levels of lipid peroxide, total protein, SGPT, SGOT, ALP, and TB. However, treatment of STZ-induced diabetes in mice with 1 - 5 reduced levels of these enzymes leading to protector effect of liver. In addition, with treatment with 1 - 5 , increases in radical scavenging enzymes of CSH-Px, SOD, GSH, and CAT have also been observed in diabetic mice. The antioxidant properties of compounds 1 - 5 are a promising strategy for ameliorating therapeutic effects by avoiding disorders in the normal redox reactions in healthy cells which consequently could alleviate complications of diabetes.
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Kumar, Muthusamy Senthil; Chaudhury, Shibani; Balachandran, Srinivasan
2014-12-01
The total phenolic and flavonoid content and percentage of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity of callus and in vivo plant parts of Heliotropium indicum Linn. were estimated. Murashige and Skoog (MS) basal medium supplemented with α-naphthaleneacetic acid (NAA) 2.0 mg/l with benzyladenine (BA) 0.5 mg/l showed the highest amount of callus biomass (1.87 g/tube). The morphology of callus was significantly different according to the plant growth regulators and their concentrations used in the medium. The highest amount of total phenolic (21.70 mg gallic acid equivalent per gram (GAE/g)) and flavonoid (4.90 mg quercetin equivalent per gram (QE/g)) content and the maximum percentage (77.78 %) of radical scavenging activity were estimated in the extract of inflorescence. The synergistic effect of NAA (2.0 mg/l) and BA (0.5 mg/l) enhances the synthesis of total phenolic (9.20 mg GAE/g) and flavonoid (1.25 mg QE/g) content in the callus tissue. The callus produced by the same concentration shows 45.24 % of free radical scavenging activity. While comparing the various concentrations of NAA with 2,4-dichlorophenoxyacetic acid (2,4-D) for the production of callus biomass, total phenolic and flavonoid content and free radical scavenging activity, all the concentrations of NAA were found to be superior than those of 2,4-D.
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Garcia-Campoy, Abraham Heriberto; Muñiz-Ramirez, Alethia
2016-01-01
Six new flavonoids 2′,4′-dihydroxychalcone-6′-O-β-d-glucopyranoside (1), α,3,2′,4′-tetrahydroxy-4-methoxy-dihydrochalcone-3′-C-β-glucopyranosy-6′-O-β-d-glucopyranoside (2), 7-hydroxy-5,8′-dimethoxy-6′α-l-rhamnopyranosyl-8-(3-phenyl-trans-acryloyl)-1-benzopyran-2-one (3), 6′7-dihydroxy-5,8-dimethoxy-8(3-phenyl-trans-acryloyl)-1-benzopyran-2-one (4), 9-hydroxy-3,8-dimethoxy-4-prenylpterocarpan (5), and α,4,4′-trihydroxydihydrochalcone-2′-O-β-d-glucopyranoside (6) were isolated from bark of Eysenhardtia polystachya. Antidiabetic activity of compounds 1–5 in terms of their cellular antioxidant and free radical scavenging and also in streptozotocin- (STZ-) induced diabetic mice was evaluated on liver transaminases, lipid peroxidation, total bilirubin, total protein, superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (CSH-Px), and glutathione reductase (GSH). Results indicated that 1–5 scavenged 2,2-diphenyl-1-picrylhydrazyl (DPPH), hydroxyl (∙OH), nitric oxide radicals (NO∙), superoxide anion radical (O2 ∙−), radical cation (ABTS∙+), and hydrogen peroxide (H2O2) radical, and protection against H2O2 induced BSA damage was also observed. Furthermore, 1–5 showed ability to decrease the oxidative stress in H9c2 cell. Diabetic mice present high levels of lipid peroxide, total protein, SGPT, SGOT, ALP, and TB. However, treatment of STZ-induced diabetes in mice with 1–5 reduced levels of these enzymes leading to protector effect of liver. In addition, with treatment with 1–5, increases in radical scavenging enzymes of CSH-Px, SOD, GSH, and CAT have also been observed in diabetic mice. The antioxidant properties of compounds 1–5 are a promising strategy for ameliorating therapeutic effects by avoiding disorders in the normal redox reactions in healthy cells which consequently could alleviate complications of diabetes. PMID:27668038
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Roy, Subhrajyoti; Dutta, Somit; Chaudhuri, Tapas Kumar
2015-07-01
Diplazium esculentum is the most commonly consumed edible fern throughout Asia and Oceania. Several studies have been performed so far to determine different functional properties of this plant, but there have been no reports on the anticholinesterase and nicotinamide adenine dinucleotide (NADH) oxidase inhibitory activities of this plant. Therefore, the present study was conducted to determine the anticholinesterase and NADH oxidase inhibitory activities of 70% methanolic extract of D. esculentum. The D. esculentum extract was investigated for its acetylcholinesterase and NADH oxidase inhibitory activities as well as its free radical scavenging and total antioxidant activities in the linoleic acid system. The free radical scavenging activity of the extract was determined by the 2,2-diphenyl-1-picryl-hydrazyl (DPPH) method. The total antioxidant activity of the extract was evaluated by ferric thiocyanate (FTC) and thiobarbituric acid (TBA) methods. The D. esculentum extract inhibited acetylcholinesterase and NADH oxidase in a dose-dependent manner, with IC50 values of 272.97±19.38 and 265.81±21.20 μg/mL, respectively. The extract also showed a potent DPPH radical scavenging activity with an IC50 value of 402.88±12.70 μg/mL. Moreover, the extract showed 27.41% and 33.22% of total antioxidant activities determined by FTC and TBA methods, respectively. Results indicated that 70% methanolic extract of D. esculentum effectively inhibited the enzymes acetylcholinesterase and NADH oxidase and acted as a potent antioxidant and free radical scavenger. These in vitro assays indicate that this plant extract is a significant source of natural antioxidants, which may be helpful in preventing the progression of various neurodegenerative disorders associated with oxidative stress.
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Bailey, S M; Fauconnet, A L; Reinke, L A
1997-02-01
Hydroxylation of salicylate and D-phenylalanine was measured to test the usefulness of these compounds for hydroxyl radical (HO(•)) detection in chemical and biological systems. When HO(•) were produced by the photolytic decomposition of hydrogen peroxide, nearly equal amounts of 2,5- and 2,3-dihydroxybenzoic acid (DHBA) were produced from salicylate, with catechol as a minor product. In the photolytic reaction, nearly equal concentrations of p-,m-, and o-tyrosine were formed from D-phenylalanine. When salicylate or D-phenylalanine was present with Fenton reagents or in iron(II) autoxidation systems, the relative proportions of hydroxylated products were similar to those observed after photolysis, although less total products were usually detected. In contrast, when similar experiments were conducted with isolated hepatic microsomes and perfused livers, 2,5-DHBA was the primary product from salicylate, and p-tyrosine was the major product from D-phenylalanine. Cytochrome P-450 enzymes can hydroxylate salicylate to produce 2,5-DHBA, and it is likely that phenylalanine hydroxylase produces most of the p-tyrosine detected in hepatic tissues. Thus, although both salicylate and D-phenylalanine are useful probes for hydroxyl radical formation in chemical systems, hydroxylated products formed from enzymatic reactions complicate interpretation of data from both compounds in vivo.
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Repair Activity of trans-Resveratrol toward 2'-Deoxyguanosine Radicals.
Cheng, Xing; An, Ping; Li, Shujin; Zhou, Liping
2018-04-26
In the present study, the repair activity of trans-resveratrol toward 2'-deoxyguanosine (dGuo) radicals in polar and nonpolar solvents was studied using density functional theory. The hydrogen transfer/proton coupled electron transfer and single electron transfer (SET) mechanisms between trans-resveratrol and dGuo-radicals were considered. Taking into consideration the molar fraction of neutral trans-resveratrol (ROH) and anionic trans-resveratrol (RO - ), the overall rate constants for repairing dGuo-radicals by trans-resveratrol are 9.94 × 10 8 and 2.01 × 10 9 dm 3 mol -1 s -1 in polar and nonpolar solvents, respectively, and the overall rate constant of repairing cation radical (dGuo •+ ) by trans-resveratrol via an SET mechanism is 7.17 × 10 9 dm 3 mol -1 s -1 . The repair activity of RO - toward dGuo-radicals is better than that of ROH, but the repair activity of ROH toward dGuo •+ is better than that of RO - . Unfortunately, neither ROH nor RO - can repair the 2'-deoxyribose radicals of dGuo. It can therefore be concluded that trans-resveratrol is an effective antioxidant for repairing base radicals of dGuo and dGuo •+ . The study can help us understand the repair activity of trans-resveratrol toward dGuo radicals.
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Kubota, Harue; Komarov, Denis A; Yasui, Hironobu; Matsumoto, Shingo; Inanami, Osamu; Kirilyuk, Igor A; Khramtsov, Valery V; Hirata, Hiroshi
2017-06-01
The aim of this study was to demonstrate the feasibility of in vivo three-dimensional (3D) relaxation time T 2 * mapping of a dicarboxy-PROXYL radical using continuous-wave electron paramagnetic resonance (CW-EPR) imaging. Isotopically substituted dicarboxy-PROXYL radicals, 3,4-dicarboxy-2,2,5,5-tetra( 2 H 3 )methylpyrrolidin-(3,4- 2 H 2 )-(1- 15 N)-1-oxyl ( 2 H, 15 N-DCP) and 3,4-dicarboxy-2,2,5,5-tetra( 2 H 3 )methylpyrrolidin-(3,4- 2 H 2 )-1-oxyl ( 2 H-DCP), were used in the study. A clonogenic cell survival assay was performed with the 2 H-DCP radical using squamous cell carcinoma (SCC VII) cells. The time course of EPR signal intensities of intravenously injected 2 H, 15 N-DCP and 2 H-DCP radicals were determined in tumor-bearing hind legs of mice (C3H/HeJ, male, n = 5). CW-EPR-based single-point imaging (SPI) was performed for 3D T 2 * mapping. 2 H-DCP radical did not exhibit cytotoxicity at concentrations below 10 mM. The in vivo half-life of 2 H, 15 N-DCP in tumor tissues was 24.7 ± 2.9 min (mean ± standard deviation [SD], n = 5). The in vivo time course of the EPR signal intensity of the 2 H, 15 N-DCP radical showed a plateau of 10.2 ± 1.2 min (mean ± SD) where the EPR signal intensity remained at more than 90% of the maximum intensity. During the plateau, in vivo 3D T 2 * maps with 2 H, 15 N-DCP were obtained from tumor-bearing hind legs, with a total acquisition time of 7.5 min. EPR signals of 2 H, 15 N-DCP persisted long enough after bolus intravenous injection to conduct in vivo 3D T 2 * mapping with CW-EPR-based SPI.
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Missing Peroxy Radical Sources Within a Rural Forest Canopy
NASA Technical Reports Server (NTRS)
Wolfe, G. M.; Cantrell, C.; Kim, S.; Mauldin, R. L., III; Karl, T.; Harley, P.; Turnipseed, A.; Zheng, W.; Flocke, F.; Apel, E. C.;
2013-01-01
Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a Ponderosa pine forest during the summer 2010 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptv and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Since primary reaction partners for peroxy radicals are either measured (NO) or under-predicted (HO2 and RO2, i.e. self-reaction), missing sources are the most likely explanation for this result. A close comparison of model output with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (approximately 120 and 50 pptv min-1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within forests. We conclude that a similar mechanism may underlie many such observations.
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NASA Astrophysics Data System (ADS)
Kuwabara, M.; Zhang, Z.-Y.; Inanami, O.; Yoshii, G.
Studies concerning the radicals produced in glycerol by reactions with OH radicals have been carried out by investigating deuterated glycerol (glycerol-d 8) by spin-trapping with 2-methyl-2-nitrosopropane. Free radicals produced in linear carbohydrates such as xylitol, dulcitol, D-sorbitol and D-mannitol by reactions with OH radicals as well as by direct γ-radiolysis have been also investigated by spin-trapping. The ESR spectra of the spin-trapped radicals were analysed on the basis of the results from ESR and spin-trapping experiments on glycerol and deuterated glycerol, and the formation of three radical species, CHO-CH-, CH 2-CO- and HO-CH-, due to both OH reactions and direct γ-radiolysis was confirmed for all compounds. The presence of a radical, -CO-CH-, was detected for xylitol, D-sorbitol and D-mannitol. General reactions processes induced by OH reactions or γ-radiolysis in the solid state are discussed.
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Missing Peroxy Radical Sources within a Summertime Ponderosa Pine Forest
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wolfe, G. M.; Cantrell, Chris; Kim, S.
2014-05-13
Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a Ponderosa pine forest during the summer 2010 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen – Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptvmore » and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Peroxy radical sinks are unlikely to be overestimated, suggesting missing sources. A close comparison of model results with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (~120 and 50 pptv min-1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within the forest, and we conclude that a similar mechanism may underlie many such anomalous findings.« less
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Ultraviolet photodissociation dynamics of the benzyl radical.
Song, Yu; Zheng, Xianfeng; Lucas, Michael; Zhang, Jingsong
2011-05-14
Ultraviolet (UV) photodissociation dynamics of jet-cooled benzyl radical via the 4(2)B(2) electronically excited state is studied in the photolysis wavelength region of 228 to 270 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance enhanced multiphoton ionization (REMPI) techniques. In this wavelength region, H-atom photofragment yield (PFY) spectra are obtained using ethylbenzene and benzyl chloride as the precursors of benzyl radical, and they have a broad peak centered around 254 nm and are in a good agreement with the previous UV absorption spectra of benzyl. The H + C(7)H(6) product translational energy distributions, P(E(T))s, are derived from the H-atom TOF spectra. The P(E(T)) distributions peak near 5.5 kcal mol(-1), and the fraction of average translational energy in the total excess energy,
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Marco-Contelles, José; de Opazo, Elsa
2002-05-31
The free radical cyclization (FR) and the ring-closing metathesis (RCM) reaction have been analyzed in order to develop new and original synthetic protocols for the synthesis of enantiomerically pure, highly functionalized, medium-sized carbocycles from carbohydrates. As a result, we report here for the first time examples of the 7-exo FR cyclization of acyclic radical precursors derived from sugars. This process appears to be extremely sensitive to the conformational mobility of the radical species in the transition state. The use of two isopropylidene groups blocking four of the total present hydroxyl groups and a good radical acceptor (as an alpha,beta-unsaturated ester) are mandatory conditions for a successful ring closure protocol. The RCM reaction by using Grubbs' catalyst on selected carbohydrate-derived precursors has afforded variable yields of the expected unsaturated cycloheptane or cycloctane derivatives. The synthesis of the cycloheptitols has been carried out in good yields, regardless of the absolute configuration at the different stereocenters and the nature of the O-functional groups bound in allylic positions to one of the double bonds implicated in the metathesis reaction. Conversely, in the cyclooctane synthesis, we have observed that the success of the reaction depends not only on the absolute configuration at the different stereocenters close to the double bonds but also on the nature of the O-protecting groups on these stereocenters. Finally, the RCM strategy has been used in an attempt to prepare natural (+)-calystegine B(2) from D-glucose. The synthesis of compound 92 from D-glucose constitutes a formal total synthesis of (+)-calystegine B(2), showing the importance of the steric hindrance in allylic positions for a successful RCM reaction.
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Kubrak, Olga I; Atamaniuk, Tetiana M; Husak, Viktor V; Lushchak, Volodymyr I
2013-09-01
This study aims to assess effects of 96 h goldfish exposure to 1, 10 and 100 mg/L of the herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), on metabolic indices and free radical process markers in white muscle of a commercial fish, the goldfish Carassius auratus L. Most oxidative stress markers and antioxidant enzymes were not affected at 2,4-D fish treatment. 2,4-D fish exposure induced the elevated levels of total (by 46% and 40%) and reduced (by 77% and 73%) glutathione in muscles of goldfish of 10 mg/L 2,4-D and recovery (after 100 mg/L of 2,4-D exposure) groups, respectively. However, in muscles of 100 mg/L 2,4-D exposed goldfish these parameters were depleted (by 47% and 64%). None of investigated parameters of protein and carbohydrate metabolisms changed in white muscles of 2,4-D exposed fish, with exception of lactate dehydrogenase activity, which was slightly (by 11-15%) elevated in muscles of goldfish exposed to 10-100 mg/L of 2,4-D, but also recovered. Thus, the short term exposure of goldfish to the selected concentrations of 2,4-D does not substantially affect their white muscle, suggesting the absence of any effect under the environmentally relevant concentrations. Copyright © 2013 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Waring, Michael S.; Wells, J. Raymond
2015-04-01
Indoor chemistry may be initiated by reactions of ozone (O3), the hydroxyl radical (OH), or the nitrate radical (NO3) with volatile organic compounds (VOC). The principal indoor source of O3 is air exchange, while OH and NO3 formation are considered as primarily from O3 reactions with alkenes and nitrogen dioxide (NO2), respectively. Herein, we used time-averaged models for residences to predict O3, OH, and NO3 concentrations and their impacts on conversion of typical residential VOC profiles, within a Monte Carlo framework that varied inputs probabilistically. We accounted for established oxidant sources, as well as explored the importance of two newly realized indoor sources: (i) the photolysis of nitrous acid (HONO) indoors to generate OH and (ii) the reaction of stabilized Criegee intermediates (SCI) with NO2 to generate NO3. We found total VOC conversion to be dominated by reactions both with O3, which almost solely reacted with D-limonene, and also with OH, which reacted with D-limonene, other terpenes, alcohols, aldehydes, and aromatics. VOC oxidation rates increased with air exchange, outdoor O3, NO2 and D-limonene sources, and indoor photolysis rates; and they decreased with O3 deposition and nitric oxide (NO) sources. Photolysis was a strong OH formation mechanism for high NO, NO2, and HONO settings, but SCI/NO2 reactions weakly generated NO3 except for only a few cases.
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Nii, Shota; Shinohara, Koichi; Matsushita, Hiroshi; Noguchi, Yasuyuki; Watanabe, Kazushi; Wakatsuki, Akihiko
2016-07-01
Hepatic effects of estrogen therapy on low-density lipoprotein (LDL) subfraction or oxidative stress have not been previously evaluated. The purpose of the present study was to investigate whether the differential hepatic effects of estrogen affect plasma distribution of small dense LDL and free radical production in postmenopausal women. In all, 45 postmenopausal women were given 0.625 mg/day of oral conjugated equine estrogen (CEE) (n=15), 1.0 mg/day of oral 17β estradiol (E2) (n=15), or 50 μg/day of transdermal 17βE2 (n=15) for 3 months. Subjects received either estrogen alone or with dydrogesterone at 5 mg/day. Plasma concentrations of sex hormone-binding globulin (SHBG), lipids, metallic ions, and derivatives of reactive oxygen metabolites (d-ROMs) were measured. CEE, but not oral 17βE2, increased the plasma concentrations of triglyceride, copper (Cu), and d-ROMs and the ratio of small dense LDL/total LDL cholesterol, a marker for plasma distribution of small dense LDL. Transdermal 17βE2 decreased d-ROMs concentrations but did not significantly change other parameters. Plasma concentrations of SHBG increased in the 3 groups. Estrogen-induced changes in triglyceride correlated positively either with changes in SHBG (R=0.52, P=0.0002) or the ratio of small dense LDL/total LDL cholesterol (R=0.65, P＜0.0001). Changes in Cu also correlated positively either with changes in SHBG (R=0.85, P＜0.0001) or d-ROMs (R=0.86, P＜0.0001). The hepatic effects of different routes or types of estrogen therapy may be associated with plasma distribution of small dense LDL and free radical production in postmenopausal women.
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Jayatilaka, Nayana; Nelson, William H.
2008-01-01
In sodium guanosine dihydrate single crystals, the guanine moiety is deprotonated at N1 due to growth from high-pH (>12) solutions. EPR and ENDOR study of crystals x-irradiated at 10 K detected evidence for three radical forms. Radical R1,characterized by two proton and two nitrogen hyperfine interactions, was identified as the product of net hydrogenation at N7 of the N1-deprotonated guanine unit. R1 exhibited an unusually distorted structure leading to net positive isotropic components of the hydrogen couplings. Radical R2, characterized by one proton and one nitrogen hyperfine coupling was identified as the primary electron loss product. This product is equivalent to that of deprotonation at N1 by the guanine cation and represents the first ENDOR characterization of that product. Radical R3, characterized by a single hydrogen hyperfine coupling, was identified as the product of net dehydrogenation at C1 of the ribose moiety. The identification of radicals R1-R3 was supported by DFT calculations on several possible structures using the B3LYP/6-311G(2df,p)//6-31G(d,p) approach. Radical R4, detected after warming the crystals to room temperature, was identified as the well-known product of net hydrogenation of C8 of the (N1-deprotonated) guanine component. Radical R1, evidently formed by protonation of the primary electron addition product, was present as roughly 60% of the total radicals detected at 10 K. Radical R2 was present as roughly 27% of the total yield, and the concentration of R3 contributed the remaining 13%. R3 is evidently the product of oneelectron oxidation followed by deprotonation; thus, the balance of oxidation and reduction products is approximately equal within experimental uncertainty. PMID:17249824
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Roy, Soumen; Pawar, Sandip; Chowdhary, Abhay
2016-01-01
To evaluate in vitro cytotoxicity and antioxidant activity of Datura metel L. and Cynodon dactylon L. extracts. The extraction of plants parts (datura seed and fruit pulp) and areal parts of durva was carried out using soxhlet and cold extraction method using solvents namely methanol and distilled water. The total phenolic content (TPC) and total flavonoid content (TFC) was determined by established methods. The in vitro cytotoxicity assay was performed in vero cell line by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay method. In vitro antioxidant activity of the extract was performed by 2, 2-diphenyl-1-picrylhydrazyl radical scavenging method. We found that the highest amount of TPC and TFC in methanolic extracts of seed (268.6 μg of gallic acid equivalence/mg of dry plant material) and fruit pulp (8.84 μg of quercetin equivalence/mg dry plant material) of D. metel, respectively prepared by Soxhlet method. The methanolic extract of C. dactylon prepared using soxhlation has shown potent free radical scavenging activity with 50% inhibitory concentration (IC50) value of 100 μg/ml. The IC50 of a methanolic cold extract of datura fruit was found to be 3 mg/ml against vero cell line. We observed that plant parts of C. dactylon and D. metel have a high antioxidant activity. Further research is needed to explore the therapeutic potential of these plant extracts. In the present study we observed a positive correlation was between the phenolic and flavanoid content of the Datura metel and cynodon doctylon (durva) extracts with the free radical scavenging activities. Both were found to have a high antioxidant activity. Abbreviations used: BHA: Butylated hydroxyanisole, BHT: Butylated hydroxytoluene, CC50: 50% cell cytotoxic concentration, CNS: Central nervous system, DPPH: 2, 2-diphenyl-1-picrylhydrazyl, IC50: 50% inhibitory concentration, MTT: 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide), TFC: Total flavonoid content, TPC: Total phenolic content.
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The reactions of HO2 with CO and NO and the reaction of O(1D) with H2O
NASA Technical Reports Server (NTRS)
Simonaitis, R.; Heicklen, J.
1973-01-01
HO2 radicals were generated by the photolysis of N2O at 2139 A in the presence of excess H2O or H2 and smaller amounts of CO and O2. The O(1D) atoms produced from the photolysis of N2O to give HO radicals or H2 to give HO + H. With H2O two HO radicals are produced for each O(1D) removed low pressures (i.e. approximately 20 torr H2O), but the HO yield drops as the pressure is raised. This drop is attributed to the insertion reaction: O(1D) + H2O + M yields H2O2 +M. The HO radicals generated can react with either CO or H2 to produce H atoms which then add to O2 to produce HO2. Two reactions are given for the reactions of the HO radicals, in the absence of NO.
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Wang, Che; Cai, Zheng-Xu; You, Zhong-Lu; Guo, Hui-Shu; Shang, De-Jing; Wang, Xiao-Ling; Zhang, Liang; Ma, Li-Jie; Tan, Jun; Le, Wei-Dong; Li, Song
2014-09-01
There is increasing evidence that free radicals play an important role in neuronal damages induced by diabetes mellitus or cerebral ischemia insults. Antioxidants with free radical scavenging activities have been shown to be beneficial and neuroprotective for these pathological conditions. Here, we report free radical scavenging activity and neuroprotective potential of D138, one copper(II)/zinc(II) Schiff-base complex derived from N,N'-2(2-hydroxynaphthylmethylidene)-1,3-propanediamine. The data from three in vitro assays, 2,2-diphenyl-1-picrylhydrazyl assay, nitro blue tetrazolium assay and hydroxyl radical scavenging assay, indicated that D138 presented a potent free radical scavenging activity. The neuroprotective and antioxidative effects of D138 were further evaluated in vivo using bilateral common carotid artery occlusion (BCCAO) mouse model and streptozotocin (STZ) diabetic mouse model. Our results indicated that treatment of D138 significantly ameliorated the hippocampal neuronal damage and the oxidative stress levels in these animal models. Moreover, D138 also reversed the behavioral deficiencies induced by BCCAO or STZ, as assessed by Y-maze test and fear conditioning test. In conclusion, all these findings support that D138 exerts free radical scavenging and neuroprotective activities and has the potentials to be a potent therapeutic candidate for brain oxidative damage induced by cerebral ischemia or diabetes mellitus.
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NASA Astrophysics Data System (ADS)
Mcavey, K. M.; Groff, C. J.; Xiong, F.; Seeley, J. V.; Starn, T.; Feiner, P. A.; Zhang, L.; Brune, W. H.; Baumann, K.; Misztal, P. K.; Koss, A.; De Gouw, J. A.; Olson, K. F.; Goldstein, A. H.; Bertman, S. B.; Shepson, P. B.
2014-12-01
Organic nitrates (RONO2 + ROONO2) act as an important sink for both organic alkoxy and peroxy and NOx (NO+NO2) radicals, and thus their production can have a significant limiting impact on ozone production. However, there remains significant uncertainty on the formation yields and fates of organic nitrates in the atmosphere. This certainly applies to the biogenic volatile organic compounds (BVOCs), which can often be the dominant reaction partner for OH and thus precursors to the peroxy radicals that produce ozone. Observations of BVOCs and total isoprene and monoterpene nitrates were measured as part of the Southern Oxidant and Aerosol Study in the summer of 2013, at the SEARCH Centreville site in rural, central Alabama. A 0-D box model was constructed to observe the effect of individual and total organic nitrates on ozone production potential, to determine the relative importance of each species in organic nitrate formation. Here we examine the impact of yield uncertainty, and secondary oxidation reactions that might release NOx from the primary organic nitrates.
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NASA Astrophysics Data System (ADS)
Sato-Akaba, Hideo; Fujii, Hirotada; Hirata, Hiroshi
2008-08-01
This article describes a method for reducing the acquisition time in three-dimensional (3D) continuous-wave electron paramagnetic resonance (CW-EPR) imaging. To visualize nitroxyl spin probes, which have a short lifetime in living organisms, the acquisition time for a data set of spectral projections should be shorter than the lifetime of the spin probes. To decrease the total time required for data acquisition, the duration of magnetic field scanning was reduced to 0.5 s. Moreover, the number of projections was decreased by using the concept of a uniform distribution. To demonstrate this faster data acquisition, two kinds of nitroxyl radicals with different decay rates were measured in mice. 3D EPR imaging of 4-hydroxy-2,2,6,6-tetramethylpiperidine-d 17-1- 15N-1-oxyl in mouse head was successfully carried out. 3D EPR imaging of nitroxyl spin probes with a half-life of a few minutes was achieved for the first time in live animals.
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Solecka, Jolanta; Guśpiel, Adam; Postek, Magdalena; Ziemska, Joanna; Kawęcki, Robert; Lęczycka, Katarzyna; Osior, Agnieszka; Pietrzak, Bartłomiej; Pypowski, Krzysztof; Wyrzykowska, Agata
2014-09-30
A series of 3,4-dihydroisoquinoline-3-carboxylic acid derivatives were synthesised and tested for their free-radical scavenging activity using 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radical (ABTS·+), superoxide anion radical (O2·-) and nitric oxide radical (·NO) assays. We also studied d-amino acid oxidase (DAAO), acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) inhibitory activity. Almost each of newly synthesised compounds exhibited radical scavenging capabilities. Moreover, several compounds showed moderate inhibitory activities against DAAO, AChE and BuChE. Compounds with significant free-radical scavenging activity may be potential candidates for therapeutics used in oxidative-stress-related diseases.
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Giese, Ellen C; Gascon, Jacob; Anzelmo, Gianluca; Barbosa, Aneli M; da Cunha, Mário A Alves; Dekker, Robert F H
2015-01-01
β-D-Glucans are known to present antitumor, anticancer, and anti-inflammatory activities that are influenced by their own antioxidant capacity. The antioxidant activity of botryosphaeran, an exopolysaccharide of the (1 → 3;1 → 6)-β-D-glucan type produced by the Botryosphaeria rhodina MAMB-05 was evaluated and compared to some other β-D-glucans (lasiodiplodan an exocellular (1 → 6)-β-D-glucan from Lasiodiplodia theobromae, laminarin and curdlan), and oligosaccharides, disaccharides, and monosaccharides in a study of scavenging activities of free radicals in-vitro. Botryosphaeran displayed high total antioxidant activity (80%) as well as good scavenging activity against hydroxyl radical (90.6%), superoxide anion (37%), hydrogen peroxide (38%), and nitric oxide radical (90%). No reducing power, metal-chelating capacity or inhibition of lipid peroxidation was observed for these β-D-glucans. The results demonstrated that botryosphaeran exhibited effective antioxidant activity as supported by many different assays, suggesting that this β-D-glucan may serve as a source of a new bioactive compound with effective antioxidant activity. Copyright © 2014 Elsevier B.V. All rights reserved.
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The formation of DNA sugar radicals from photoexcitation of guanine cation radicals.
Shukla, Lata I; Pazdro, Robert; Huang, James; DeVreugd, Christopher; Becker, David; Sevilla, Michael D
2004-05-01
In this investigation of radical formation and reaction in gamma- irradiated DNA and model compounds, we report the conversion of the guanine cation radical (one-electron oxidized guanine, G(.+)) to the C1' sugar radical and another sugar radical at the C3' or C4' position (designated C3'(.)/C4'(.)) by visible and UV photolysis. Electron spin resonance (ESR) spectroscopic investigations were performed on salmon testes DNA as well as 5'-dGMP, 3'-dGMP, 2'-deoxyguanosine and other nucleosides/nucleotides as model systems. DNA samples (25- 150 mg/ml D(2)O) were prepared with Tl(3+) or Fe(CN)(3-)(6) as electron scavengers. Upon gamma irradiation of such samples at 77 K, the electron-gain path in the DNA is strongly suppressed and predominantly G(.+) is found; after UV or visible photolysis, the fraction of the C1' sugar radical increases with a concomitant reduction in the fraction of G(.+). In model systems, 3'- dGMP(+.) and 5'-dGMP(+.) were produced by attack of Cl(.-)(2) on the parent nucleotide in 7 M LiCl glass. Subsequent visible photolysis of the 3'-dGMP(+.) (77 K) results predominantly in formation of C1'(.) whereas photolysis of 5'-dGMP(+.) results predominantly in formation of C3'(.)/C4'(.). We propose that sugar radical formation is a result of delocalization of the hole in the electronically excited base cation radical into the sugar ring, followed by deprotonation at specific sites on the sugar.
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Spectroscopic identification of dichlorobenzyl radicals: Jet-cooled 2,3-dichlorobenzyl radical
NASA Astrophysics Data System (ADS)
Chae, Sang Youl; Yoon, Young Wook; Lee, Sang Kuk
2015-07-01
The vibronically excited but jet-cooled 2,3-dichlorobenzyl radical was generated from the corona discharge of precursor 2,3-dichlorotoluene seeded in a large amount of carrier gas He using a pinhole-type glass nozzle. From an analysis of the visible vibronic emission spectrum observed, we obtained the electronic energy of the D1 → D0 transition and vibrational mode frequencies in the D0 state of the 2,3-dichlorobenzyl radical by comparing the observation with the results of ab initio calculations. In addition, we discussed substituent effect of Cls on electronic transition energy in terms of substituent orientation for the first time.
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Antioxidant Capacity and Proanthocyanidin Composition of the Bark of Metasequoia glyptostroboides.
Chen, Fengyang; Zhang, Lin; Zong, Shuling; Xu, Shifang; Li, Xiaoyu; Ye, Yiping
2014-01-01
Metasequoia glyptostroboides Hu et Cheng is the only living species in the genus Metasequoia Miki ex Hu et Cheng (Taxodiaceae), which is well known as a "living fossil" species. In the Chinese folk medicine, the leaves and bark of M. glyptostroboides are used as antimicrobic, analgesic, and anti-inflammatory drug for dermatic diseases. This study is the first to report the free radical scavenging capacity, antioxidant activity, and proanthocyanidin composition of the bark of M. glyptostroboides. We observed total of six extracts and fractions, which were easily obtained by water-ethanol extraction and followed by a further separation with D101 resin column chromatography, had significant DPPH radical, superoxide anion radical, and hydroxyl radical scavenging capacity, total antioxidative capacity (T-AOC), lipid peroxidation inhibitory activity, and metal ions chelating capacity. The fraction MGEB, which was obtained by 60% ethanol extraction and followed by a further separation with D101 resin column chromatograph, possessed the highest proanthocyanidin content and the highest free radical scavenging and antioxidant activities. Furthermore, MGEB could significantly protect against CCl4 induced acute liver injury through inhibition of oxidative stress in mice. In addition, ten proanthocyanidins were isolated from MGEB, and six of them were firstly reported from this plant.
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Wang, Guoying; Shi, Gaofeng; Chen, Xuefu; Chen, Fuwen; Yao, Ruixing; Wang, Zhenju
2013-11-13
A novel free radical reaction combined with liquid chromatography electrospray ionization tandem mass spectrometry (FRR-LC-PDA-ESI/APCI-MS/MS) screening method was developed for the detection and identification of radical-scavenging natural antioxidants. Functionalized graphene was prepared by chemical method for loading free radicals (superoxide radical, peroxyl radical and PAHs free radical). Separation was performed with and without a preliminary exposure of the sample to specific free radicals on the functionalized graphene, which can facilitate reaction kinetics (charge transfers) between free radicals and potential antioxidants. The difference in chromatographic peak areas is used to identify potential antioxidants. The structure of the antioxidants in one sample (Swertia chirayita) is identified using MS/MS and comparison with standards. Thirteen compounds were found to possess potential antioxidant activity, and their free radical-scavenging capacities were investigated. The thirteen compounds were identified as 1,3,5-trihydroxyxanthone-8-O-β-D-glucopyranoside (PD1), norswertianin (PD2), 1,3,5,8-tetrahydroxyxanthone (PD3), 3, 3', 4', 5, 8-penta hydroxyflavone-6-β-D-glucopyranosiduronic acid-6'-pentopyranose-7-O-glucopyranoside (PD4), 1,5,8-trihydroxy-3-methoxyxanthone (PD5), swertiamarin (PS1), 2-C-β-D-glucopyranosyl-1,3,7-trihydroxylxanthone (PS2), 1,3,7-trihydroxylxanthone-8-O-β-D-glucopyranoside (PL1), 1,3,8-trihydroxyl xanthone-5-O-β-D-glucopyranoside (PL2), 1,3,7-trihydroxy-8-methoxyxanthone (PL3), 1,2,3-trihydroxy-7,8-dimethoxyxanthone (PL4), 1,8-dihydroxy-2,6-dimethoxy xanthone (PL5) and 1,3,5,8-tetramethoxydecussatin (PL6). The reactivity and SC50 values of those compounds were investigated, respectively. PD4 showed the strongest capability for scavenging PAHs free radical; PL4 showed prominent scavenging capacities in the lipid peroxidation processes; it was found that all components in S. chirayita exhibited weak reactivity in the superoxide radical scavenging capacity. The use of the free radical reaction screening method based on LC-PDA-ESI/APCI-MS/MS would provide a new approach for rapid detection and identification of radical-scavenging natural antioxidants from complex matrices. Copyright © 2013 Elsevier B.V. All rights reserved.
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Martínez-Flores, Héctor Eduardo; Garnica-Romo, Ma. Guadalupe; Padilla-Ramírez, José Saúl; Saavedra-Molina, Alfredo; Alvarez-Cortes, Osvaldo; Bartolomé-Camacho, María Carmen; Rodiles-López, José Octavio
2018-01-01
Guava leaf (Psidium guajava L.) extracts are used in both traditional medicine and the pharmaceutical industry. The antioxidant compounds in P. guajava leaves can have positive effects including anti-inflammatory, anti-hyperglycemic, hepatoprotective, analgesic, anti-cancer effects, as well as protecting against cardiovascular diseases. In the present study, phenolic compounds and in vitro antioxidant capacity were measured in extracts obtained with polar and non-polar solvents from leaves of two varieties of guava, Calvillo Siglo XXI and Hidrozac. The quantity of total phenolics and total flavonoids were expressed as equivalents of gallic acid and quercetin, respectively. Hydroxyl radical, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and Oxygen Radical Absorbance Capacity using fluorescein (ORAC-FL) in vitro tests were used to assess the radical scavenging abilities of the extracts. The total phenolics were higher in the aqueous fraction of the variety Calvillo Siglo XXI, while in the Hidrozac variety total phenolics were higher in the acetone and chloroform fractions. Total flavonoids were higher in all fractions in the variety Calvillo Siglo XXI. Total phenolics showed a highly positive correlation for ORAC-FL, and a moderately positive correlation with hydroxyl radicals. Finally, total flavonoids showed a slightly positive correlation for ORAC-FL and hydroxyl radicals. Both varieties of guava leaf extract showed excellent antioxidant properties. PMID:29495514
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Camarena-Tello, Julio César; Martínez-Flores, Héctor Eduardo; Garnica-Romo, Ma Guadalupe; Padilla-Ramírez, José Saúl; Saavedra-Molina, Alfredo; Alvarez-Cortes, Osvaldo; Bartolomé-Camacho, María Carmen; Rodiles-López, José Octavio
2018-02-27
Guava leaf ( Psidium guajava L.) extracts are used in both traditional medicine and the pharmaceutical industry. The antioxidant compounds in P. guajava leaves can have positive effects including anti-inflammatory, anti-hyperglycemic, hepatoprotective, analgesic, anti-cancer effects, as well as protecting against cardiovascular diseases. In the present study, phenolic compounds and in vitro antioxidant capacity were measured in extracts obtained with polar and non-polar solvents from leaves of two varieties of guava, Calvillo Siglo XXI and Hidrozac. The quantity of total phenolics and total flavonoids were expressed as equivalents of gallic acid and quercetin, respectively. Hydroxyl radical, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and Oxygen Radical Absorbance Capacity using fluorescein (ORAC-FL) in vitro tests were used to assess the radical scavenging abilities of the extracts. The total phenolics were higher in the aqueous fraction of the variety Calvillo Siglo XXI, while in the Hidrozac variety total phenolics were higher in the acetone and chloroform fractions. Total flavonoids were higher in all fractions in the variety Calvillo Siglo XXI. Total phenolics showed a highly positive correlation for ORAC-FL, and a moderately positive correlation with hydroxyl radicals. Finally, total flavonoids showed a slightly positive correlation for ORAC-FL and hydroxyl radicals. Both varieties of guava leaf extract showed excellent antioxidant properties.
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Gomathi, Duraisamy; Ravikumar, Ganesan; Kalaiselvi, Manokaran; Vidya, Balasubramaniam; Uma, Chandrasekar
2015-06-01
To identify the free radical scavenging activity of ethanolic extract of Evolvulus alsinoides. The free radical scavenging activity was evaluated by in vitro methods like reducing power assay, total antioxidant activity, 2,2-diphenyl-1-picrylhydrazyl (DPPH) reduction, superoxide radical scavenging activity, 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS(+)) scavenging activity, hydroxyl radical scavenging assay, and nitric oxide radical scavenging assay, which were studied by using ascorbic acid as standard. The extract showed significant activities in all antioxidant assays compared with the reference antioxidant ascorbic acid. The total antioxidant activity as well as the reducing power was also found to increase in a dose-dependent manner. Evolvulus alsinoides may act as a chemopreventive agent, providing antioxidant properties and offering effective protection from free radicals.
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Roy, Soumen; Pawar, Sandip; Chowdhary, Abhay
2016-01-01
Aim: To evaluate in vitro cytotoxicity and antioxidant activity of Datura metel L. and Cynodon dactylon L. extracts. Materials and Methods: The extraction of plants parts (datura seed and fruit pulp) and areal parts of durva was carried out using soxhlet and cold extraction method using solvents namely methanol and distilled water. The total phenolic content (TPC) and total flavonoid content (TFC) was determined by established methods. The in vitro cytotoxicity assay was performed in vero cell line by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay method. In vitro antioxidant activity of the extract was performed by 2, 2-diphenyl-1-picrylhydrazyl radical scavenging method. Results: We found that the highest amount of TPC and TFC in methanolic extracts of seed (268.6 μg of gallic acid equivalence/mg of dry plant material) and fruit pulp (8.84 μg of quercetin equivalence/mg dry plant material) of D. metel, respectively prepared by Soxhlet method. The methanolic extract of C. dactylon prepared using soxhlation has shown potent free radical scavenging activity with 50% inhibitory concentration (IC50) value of 100 μg/ml. The IC50 of a methanolic cold extract of datura fruit was found to be 3 mg/ml against vero cell line. Conclusion: We observed that plant parts of C. dactylon and D. metel have a high antioxidant activity. Further research is needed to explore the therapeutic potential of these plant extracts. SUMMARY In the present study we observed a positive correlation was between the phenolic and flavanoid content of the Datura metel and cynodon doctylon (durva) extracts with the free radical scavenging activities. Both were found to have a high antioxidant activity. Abbreviations used: BHA: Butylated hydroxyanisole, BHT: Butylated hydroxytoluene, CC50: 50% cell cytotoxic concentration, CNS: Central nervous system, DPPH: 2, 2-diphenyl-1-picrylhydrazyl, IC50: 50% inhibitory concentration, MTT: 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide), TFC: Total flavonoid content, TPC: Total phenolic content. PMID:27034603
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NASA Astrophysics Data System (ADS)
Yu, Michelle A.; Egawa, Tsuyoshi; Yeh, Syun-Ru; Rousseau, Denis L.; Gerfen, Gary J.
2010-04-01
The reaction intermediates of reduced bovine Cytochrome c Oxidase (CcO) were trapped following its reaction with oxygen at 50 μs-6 ms by innovative freeze-quenching methods and studied by EPR. When the enzyme was reduced with either ascorbate or dithionite, distinct radicals were generated; X-band (9 GHz) and D-band (130 GHz) CW-EPR measurements support the assignments of these radicals to ascorbyl and sulfur dioxide anion radical (SO2-rad), respectively. The X-band spectra show a linewidth of 12 G for the ascorbyl radical and 11 G for the SO2-rad radical and an isotropic g-value of 2.005 for both species. The D-band spectra reveal clear distinctions in the g-tensors and powder patterns of the two species. The ascorbyl radical spectrum displays approximate axial symmetry with g-values of gx = 2.0068, gy = 2.0066, and gz = 2.0023. The SO2-rad>/SUP> radical has rhombic symmetry with g-values of gx = 2.0089, gy = 2.0052, and gz = 2.0017. When the contributions from the ascorbyl and SO2-rad radicals were removed, no protein-based radical on CcO could be identified in the EPR spectra.
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Antioxidant Capacity and Proanthocyanidin Composition of the Bark of Metasequoia glyptostroboides
Chen, Fengyang; Zhang, Lin; Zong, Shuling; Xu, Shifang; Li, Xiaoyu; Ye, Yiping
2014-01-01
Metasequoia glyptostroboides Hu et Cheng is the only living species in the genus Metasequoia Miki ex Hu et Cheng (Taxodiaceae), which is well known as a “living fossil” species. In the Chinese folk medicine, the leaves and bark of M. glyptostroboides are used as antimicrobic, analgesic, and anti-inflammatory drug for dermatic diseases. This study is the first to report the free radical scavenging capacity, antioxidant activity, and proanthocyanidin composition of the bark of M. glyptostroboides. We observed total of six extracts and fractions, which were easily obtained by water-ethanol extraction and followed by a further separation with D101 resin column chromatography, had significant DPPH radical, superoxide anion radical, and hydroxyl radical scavenging capacity, total antioxidative capacity (T-AOC), lipid peroxidation inhibitory activity, and metal ions chelating capacity. The fraction MGEB, which was obtained by 60% ethanol extraction and followed by a further separation with D101 resin column chromatograph, possessed the highest proanthocyanidin content and the highest free radical scavenging and antioxidant activities. Furthermore, MGEB could significantly protect against CCl4 induced acute liver injury through inhibition of oxidative stress in mice. In addition, ten proanthocyanidins were isolated from MGEB, and six of them were firstly reported from this plant. PMID:24772177
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Jet-Cooled Chlorofluorobenzyl Radicals: Spectroscopy and Mechanism
NASA Astrophysics Data System (ADS)
Yoon, Young; Lee, Sang
2016-06-01
Whereas the benzyl radical, a prototypic aromatic free radical, has been the subject of numerous spectroscopic studies, halo-substituted benzyl radicals have received less attention, due to the difficulties associated with production of radicals from precursors. In particular, chloro-substituted benzyl radicals have been much less studied because of the weak visible emission intensity and weak C-Cl bond dissociation energy. The jet-cooled chlorofluorobenzyl radicals were generated in a technique of corona excited supersonic jet expansion using a pinhole-type glass nozzle for the vibronic assignments and measurements of electronic energies of the D_1 → D_0 transition. The 2,4-,2.5-, and 2.6- chlorofluorobenzyl radicals were generated by corona discharge of corresponding precursors, chlorofluorotoluenes seeded in a large amount of helium carrier gas. The vibronic emission spectra were recorded with a long-path monochromator in the visible region. The emission spectra show the vibronic bands originating from two types of benzyl-type radicals, chlorofluorobenzyl and fluorobenzyl benzyl radicals, in which fluorobenzyl radicals were obtained by displacement of Cl by H produced by dissociation of methyl C-H bond. From the analysis of the spectra observed, we could determine the electronic energies in D_1 → D_0 transition and vibrational mode frequencies at the D_0 state of chlorofluorobenzyl radicals, which show the origin band of the electronic transition to be shifted to red region, comparing with the parental benzyl radical. From the quantitative analysis of the red-shift, it has been found that the additivity rule can be applied to dihalo-substituted benzyl radicals. In this presentation, the dissociation process of precursors in corona discharge is discussed in terms of bond dissociation energy as well as the spectroscopic analysis of the radicals. C. S. Huh, Y. W. Yoon, and S. K. Lee, J. Chem. Phys. 136, 174306 (2012). Y. W. Huh, S. Y. Chae, and S. K. Lee, Chem. Phys. Lett. 608, 6 (2014). Y. W. Yoon, S. Y. Chae, M. Lim, and S. K. Lee, Chem. Phys. Lett. 637, 148 (2015).
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Absorption and electroabsorption spectra of carotenoid cation radical and dication
NASA Astrophysics Data System (ADS)
Krawczyk, Stanisław
1998-05-01
Radical cations and dications of two carotenoids astaxanthin and canthaxanthin were prepared by oxidation with FeCl 3 in fluorinated alcohols at room temperature. Absorption and electroabsorption (Stark effect) spectra were recorded for astaxanthin cations in mixed frozen matrices at temperatures about 160 K. The D 0→D 2 transition in cation radical is at 835 nm. The electroabsorption spectrum for the D 0→D 2 transition exhibits a negative change of molecular polarizability, Δ α=-1.2·10 -38 C·m 2/V (-105 A 3), which seems to originate from the change in bond order alternation in the ground state rather than from the electric field-induced interaction of D 1 and D 2 excited states. Absorption spectrum of astaxanthin dication is located at 715-717 nm, between those of D 0→D 2 in cation radical and S 0→S 2 in neutral carotenoid. Its shape reflects a short vibronic progression and strong inhomogeneous broadening. The polarizability change on electronic excitation, Δ α=2.89·10 -38 C·m 2/V (260 A 3), is five times smaller than in neutral astaxanthin. This value reflects the larger energetic distance from the lowest excited state to the higher excited states than in the neutral molecule.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kobayashi, Hirokazu
One-dimensional (1D) molecular chains of 4-substituted-2,2,6,6-tetramethyl-1-piperidinyloxyl (4-X-TEMPO) radicals were constructed in the crystalline 1D nanochannels of 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) used as a template. The ESR spectra of CLPOT inclusion compounds (ICs) using 4-X-TEMPO were examined on the basis of spectral simulation using EasySpin program package for simulating and fitting ESR spectra. The ESR spectra of [(CLPOT){sub 2}-(TEMPO){sub 1.0}] IC were isotropic in the total range of temperatures. The peak-to-peak line width (ΔB{sub pp}) became monotonically narrower from 2.8 to 1.3 mT with increase in temperature in the range of 4.2–298 K. The effect of the rotational diffusion motion of TEMPO radicals inmore » the CLPOT nanochannels for the inter-spin interaction of the [(CLPOT){sub 2}-(TEMPO){sub 1.0}] IC was found to be smaller than the case of [(TPP){sub 2}−(TEMPO){sub 1.0}] IC (TPP = tris(o-phenylenedioxy)cyclotriphosphazene) reported in our previous study. The ΔB{sub pp} of the [(CLPOT){sub 2}-(TEMPO){sub 1.0}] IC in the whole range of temperatures was much narrower than the estimation to be based on the Van Vleck’s formula for the second moment of the rigid lattice model where the electron spin can be considered as fixed; 11 mT of Gaussian line-width component. This suggests the possibility of exchange narrowing in the 1D organic-radical chains of the [(CLPOT){sub 2}-(TEMPO){sub 1.0}] IC. On the other hand, the ESR spectra of [(CLPOT){sub 2}-(MeO-TEMPO){sub 0.41}] IC (MeO-TEMPO = 4-methoxy-TEMPO) were reproduced by a superposition of major broad isotropic adsorption line and minor temperature-dependent modulated triplet component. This suggests that the IC has the part of 1D organic-radical chains and MeO-TEMPO molecules isolated in the CLPOT nanochannels.« less
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Evaluation of In Vitro Antioxidant Potential of Cordia retusa.
Amudha, Murugesan; Rani, Shanmugam
2016-01-01
The present study was carried out to investigate the antioxidant potential, total flavonoid and phenolic content in extracts of aerial parts of Cordia retua (Vahl.) Masam. The samples such as ethyl acetate and ethanol extracts were tested using six in vitro models such as 2,2-diphenyl-1-picrylhydrazyl, nitric oxide radical, iron chelating, hydroxyl radical, superoxide radical scavenging activity and total antioxidant activity to evaluate the in vitro antioxidant potential of C. retusa by spectrophotometrically. Total flavonoid and phenolic content in samples were estimated using aluminum chloride colorimetric and Folin-Ciocalteu method. The results were analyzed statistically by the regression method. Half maximal inhibitory concentration (IC50) of the ethanol extract was found to be 596 μg/ml for DPPH, 597 μg/ml for nitric oxide radical, 554 μg/ml for iron chelating, 580 μg/ml for hydroxyl radical, 562 μg/ml for superoxide radical and 566 μg/ml for total antioxidant capacity. Furthermore, the total flavonoid content and total phenolic content of the ethanol extract were found to be 2.71 mg gallic acid equivalent per gram of extract and 1.86 mg quercetin equivalent per gram of extract, respectively. In all the testing, a significant correlation existed between concentrations of the extract and percentage inhibition of free radicals. The results of the present comprehensive analysis demonstrated that C. retusa possess potent antioxidant activity, high flavonoid and phenolic content. The antioxidant property may be related to the polyphenols and flavonoids present in the extract. These results clearly indicated that C. retusa is effective against free radical mediated diseases as a natural antioxidant.
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Kumar, Anil; Sevilla, Michael D.
2009-01-01
Previous experimental and theoretical work has established that electronic excitation of a guanine cation radical in nucleosides or in DNA itself leads to sugar radical formation by deprotonation from the dexoxyribose sugar. In this work we investigate a ground electronic state pathway for such sugar radical formation in a hydrated one electron oxidized 2′-deoxyguanosine (dG•+ + 7H2O), using density functional theory (DFT) with the B3LYP functional and the 6-31G* basis set. We follow the stretching of the C5′-H bond in dG•+ to gain an understanding of the energy requirements to transfer the hole from the base to sugar ring and then to deprotonate to proton acceptor sites in solution and on the guanine ring. The geometries of reactant (dG•+ + 7H2O), transition state (TS) for deprotonation of C5′ site and product (dG(•C5′, N7-H+) + 7 H2O) were fully optimized. The zero point energy (ZPE) corrected activation energy (TS) for the proton transfer (PT) from C5′ is calculated to be 9.0 kcal/mol and is achieved by stretching the C5′-H bond by 0.13 Å from its equilibrium bond distance (1.099 Å). Remarkably, this small bond stretch is sufficient to transfer the “hole” (positive charge and spin) from guanine to the C5′ site on the deoxyribose group. Beyond the TS, the proton (H+) spontaneously adds to water to form a hydronium ion (H3O+) as an intermediate. The proton subsequently transfers to the N7 site of the guanine (product). The 9 kcal/mol barrier suggests slow thermal conversion of the cation radical to the sugar radical but also suggests that localized vibrational excitations would be sufficient to induce rapid sugar radical formation in DNA base cation radicals. PMID:19754084
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Hsu, Feng-Lin; Huang, Wei-Jan; Wu, Tzu-Hua; Lee, Mei-Hsien; Chen, Lih-Chi; Lu, Hsiao-Jen; Hou, Wen-Chi; Lin, Mei-Hsiang
2012-01-01
Thirteen polyphenolics were isolated from fresh pods of Caesalpinia pulcherrima using various methods of column chromatography. The structures of these polyphenolics were elucidated as gallic acid (1), methyl gallate (2), 6-O-galloyl-d-glucoside (3), methyl 6-O-galloyl-β-d-glucoside (4), methyl 3,6-di-O-galloyl-α-d-glucopyranoside (5), gentisic acid 5-O-α-d-(6′-O-galloyl)glucopyranoside (6), guaiacylglycerol 4-O-β-d-(6′-O-galloyl)glucopyranoside (7), 3-methoxy-4-hydroxyphenol 1-O-β-d-(6′-O-galloyl) glucopyranoside (8), (+)-gallocatechin (9), (+)-catechin (10), (+)-gallocatechin 3-O-gallate (11), myricetin 3-rhamnoside (12), and ampelopsin (13). All isolated compounds were tested for their antioxidant activities in the 1,1-diphenyl-2-picrylhydrazyl (DPPH), hydroxyl, and peroxynitrite radicals scavenging assays. Among those compounds, 11, 12, and 2 exhibited the best DPPH-, hydroxyl-, and peroxynitrite radical-scavenging activities, respectively. Compound 7 is a new compound, and possesses better scavenging activities towards DPPH but has equivalent hydroxyl radical scavenging activity when compared to BHT. The paper is the first report on free radical scavenging properties of components of the fresh pods of Caesalpinia pulcherrima. The results obtained from the current study indicate that the free radical scavenging property of fresh pods of Caesalpinia pulcherrima may be one of the mechanisms by which this herbal medicine is effective in several free radical mediated diseases. PMID:22754350
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Liu, Xi; Zhu, Liancai; Tan, Jun; Zhou, Xuemei; Xiao, Ling; Yang, Xian; Wang, Bochu
2014-01-10
In Chinese traditional medicine, Agrimonia pilosa Ledeb (APL) exhibits great effect on treatment of type 2 diabetes mellitus (T2DM), however its mechanism is still unknown. Considering that T2DM are correlated with postprandial hyperglycemia and oxidative stress, we investigated the α-glucosidase inhibitory activity and the antioxidant activity of flavonoid compound (FC) and triterpenoid compound (TC) from APL. Entire plants of APL were extracted using 95% ethanol and 50% ethanol successively. The resulting extracts were partitioned and isolated by applying liquid chromatography using silica gel column and Sephadex LH 20 column to give FC and TC. The content of total flavonoids in FC and the content of total triterpenoids in TC were determined by using UV spectrophotometry. HPLC analysis was used to identify and quantify the monomeric compound in FC and TC. The α-glucosidase inhibitory activities were determined using the chromogenic method with p-nitrophenyl-α-D-glucopyranoside as substrate. Antioxidant activities were assessed through three kinds of radical scavenging assays (DPPH radical, ABTS radical and hydroxyl radical) & β-carotene-linoleic acid assay. The results indicate FC is abundant of quercitrin, and hyperoside, and TC is abundant of 1β, 2β, 3β, 19α-tetrahydroxy-12-en-28-oic acid (265.2 mg/g) and corosolic acid (100.9 mg/g). The FC & the TC have strong α-glucosidase inhibitory activities with IC50 of 8.72 μg/mL and 3.67 μg/mL, respectively. We find that FC show competitive inhibition against α-glucosidase, while the TC exhibits noncompetitive inhibition. Furthermore, The FC exhibits significant radical scavenging activity with the EC50 values of 7.73 μg/mL, 3.64 μg/mL and 5.90 μg/mL on DPPH radical, hydroxyl radical and ABTS radical, respectively. The FC also shows moderate anti-lipid peroxidation activity with the IC50 values of 41.77 μg/mL on inhibiting β-carotene bleaching. These results imply that the FC and the TC could be responsible for the good clinical effects of APL on T2MD through targeting oxidative stress and postprandial hyperglycaemia. So APL may be good sources of natural antioxidants and α-glucosidase inhibitors exhibiting remarkable potential value for the therapy of T2DM.
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Correia Da Silva, Thiago B; Souza, Vivian Karoline T; Da Silva, Ana Paula F; Lyra Lemos, Rosangela P; Conserva, Lucia M
2010-01-01
In this work, the total phenolic content and antioxidant activity of extracts and four flavonoids isolated from leaves of two Boraginaceae species (Cordia multispicata Cham. and Tournefortia bicolor Sw.) were evaluated using Folin-Ciocalteu reagent, DPPH free radical scavenging and inhibition of peroxidation of linoleic acid by FTC method. For comparison, ascorbic acid, alpha-tocopherol and BHT were used. In general, extracts from T. bicolor (68.8 +/- 0.001 to > 1000 mg/g) showed higher phenolic content than C. multispicata (66.1 +/- 0.009 to 231 +/- 0.07 mg/g), and also scavenged radicals (IC(50) 12.8 +/- 2.5 to 437 +/- 3.5 mg/L) and inhibited lipid peroxide formation (IC(50) 51.2 +/- 2.29 to 89 +/- 0.59 mg/L). For these extracts a good correlation between the phenolic content and antioxidant activity was observed, suggesting that T. bicolor is richer in phenolic compounds and that it could serve as a new source of natural antioxidants or nutraceuticals with potential applications. Chromatographic procedures monitored by antioxidant assays afforded seven compounds, which were identified by spectral analyses (IR, MS and 1D and 2D NMR) and comparison with reported data as being trans-phytol (1), taraxerol (2), 3,7,4'-trimethoxyflavone (3), 5,3'-dihydroxy-3,7,4'-trimethoxyflavone (4), quercetin (5), tiliroside (6), and rutin (7). Compounds (4-7) were also evaluated and were effective as DPPH quenching (IC(50) 7.7 +/- 3.6 to 79.3 +/- 3.4 mg/L) and as inhibition of lipid peroxidation (IC(50) 80.1 +/- 0.98 to 88.7 +/- 3.62 mg/L). This is the first report on the total phenolic content, radical-scavenging and antioxidant activities of these species.
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Li, Wei; Patton, Samuel; Gleason, Jamie M; Mezyk, Stephen P; Ishida, Kenneth P; Liu, Haizhou
2018-06-05
A sequential combination of membrane treatment and UV-based advanced oxidation processes (UV/AOP) has become the industry standard for potable water reuse. Chloramines are used as membrane antifouling agents and therefore carried over into the UV/AOP. In addition, persulfate (S 2 O 8 2- ) is an emerging oxidant that can be added into a UV/AOP, thus creating radicals generated from both chloramines and persulfate for water treatment. This study investigated the simultaneous photolysis of S 2 O 8 2- and monochloramine (NH 2 Cl) on the removal of 1,4-dioxane (1,4-D) for potable-water reuse. The dual oxidant effects of NH 2 Cl and S 2 O 8 2- on 1,4-D degradation were examined at various levels of oxidant dosage, chloride, and solution pH. Results showed that a NH 2 Cl-to-S 2 O 8 2- molar ratio of 0.1 was optimal, beyond which the scavenging by NH 2 Cl of HO • , SO 4 •- , and Cl 2 •- radicals decreased the 1,4-D degradation rate. At the optimal ratio, the degradation rate of 1,4-D increased linearly with the total oxidant dose up to 6 mM. The combined photolysis of NH 2 Cl and S 2 O 8 2- was sensitive to the solution pH due to a disproportionation of NH 2 Cl at pH lower than 6 into less-photoreactive dichloramine (NHCl 2 ) and radical scavenging by NH 4 + . The presence of chloride transformed HO • and SO 4 •- to Cl 2 •- that is less-reactive with 1,4-D, while the presence of dissolved O 2 promoted gaseous nitrogen production. Results from this study suggest that the presence of chloramines can be beneficial to persulfate photolysis in the removal of 1,4-D; however, the treatment efficiency depends on a careful control of an optimal NH 2 Cl dosage and a minimal chloride residue.
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Gallotta, Valerio; Chiantera, Vito; Conte, Carmine; Vizzielli, Giuseppe; Fagotti, Anna; Nero, Camilla; Costantini, Barbara; Lucidi, Alessandro; Cicero, Carla; Scambia, Giovanni; Ferrandina, Gabriella
2017-01-01
To assess the feasibility of total robotic radical surgery (TRRS) in patients with locally advanced cervical cancer (LACC) who receive chemoradiation therapy (CT/RT). A prospective (preplanned) study of a nonrandomized controlled trial (Canadian Task Force classification level 2). Catholic University of the Sacred Hearth, Rome, Italy. Between September 2013 and January 2016, a total of 40 patients with LACC (Fédération Internationale de Gynécologie et d'Obstétrique stage IB2-III) were enrolled in the study. Robotic radical hysterectomy (RRH) plus pelvic and/or aortic lymphadenectomy was attempted within 6 weeks after CT/RT. The feasibility of TRRS as well as the rate, pattern, and severity of early and late postoperative complications were analyzed. After CT/RT, 29 patients (72.5%) underwent type B2 RRH, and 11 (27.5%) underwent type C1 RRH. Pelvic lymphadenectomy was performed in all cases. TRRS was successful in 39 of 40 cases (feasibility rate = 97.5%). In patients successfully completing TRRS, the median operating time was 185 minutes (range, 100-330 minutes), and the median blood loss was 100 mL (range, 50-300 mL). The median time of hospitalization counted from the first postoperative day was 2 days (range, 1-4 days). No intraoperative complications were recorded. During the observation period (median = 18 months; range, 4-28 months), 9 of 40 (22.5%) experienced postoperative complications, for a total number of 12 complications. As of April 2016, recurrence of disease was documented in 5 cases (12.5%). TRRS is feasible in LACC patients administered preoperative CT/RT, providing perioperative outcomes comparable with those registered in early-stage disease, and LACC patients receiving neoadjuvant chemotherapy. Copyright © 2016 AAGL. Published by Elsevier Inc. All rights reserved.
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Evaluation of In Vitro Antioxidant Potential of Cordia retusa
Amudha, Murugesan; Rani, Shanmugam
2016-01-01
The present study was carried out to investigate the antioxidant potential, total flavonoid and phenolic content in extracts of aerial parts of Cordia retua (Vahl.) Masam. The samples such as ethyl acetate and ethanol extracts were tested using six in vitro models such as 2,2-diphenyl-1-picrylhydrazyl, nitric oxide radical, iron chelating, hydroxyl radical, superoxide radical scavenging activity and total antioxidant activity to evaluate the in vitro antioxidant potential of C. retusa by spectrophotometrically. Total flavonoid and phenolic content in samples were estimated using aluminum chloride colorimetric and Folin-Ciocalteu method. The results were analyzed statistically by the regression method. Half maximal inhibitory concentration (IC50) of the ethanol extract was found to be 596 μg/ml for DPPH, 597 μg/ml for nitric oxide radical, 554 μg/ml for iron chelating, 580 μg/ml for hydroxyl radical, 562 μg/ml for superoxide radical and 566 μg/ml for total antioxidant capacity. Furthermore, the total flavonoid content and total phenolic content of the ethanol extract were found to be 2.71 mg gallic acid equivalent per gram of extract and 1.86 mg quercetin equivalent per gram of extract, respectively. In all the testing, a significant correlation existed between concentrations of the extract and percentage inhibition of free radicals. The results of the present comprehensive analysis demonstrated that C. retusa possess potent antioxidant activity, high flavonoid and phenolic content. The antioxidant property may be related to the polyphenols and flavonoids present in the extract. These results clearly indicated that C. retusa is effective against free radical mediated diseases as a natural antioxidant. PMID:27168685
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3,4,5,6-Tetrafluorophenylnitren-2-yl: a ground-state quartet triradical.
Grote, Dirk; Finke, Christopher; Kossmann, Simone; Neese, Frank; Sander, Wolfram
2010-04-19
The photochemistry of 2-iodo-3,4,5,6-tetrafluorophenyl azide (7 d) has been investigated in argon and neon matrices at 4 K, and the products characterized by IR and EPR spectroscopy. The primary photochemical step is loss of a nitrogen molecule and formation of phenyl nitrene 1 d. Further irradiation with UV or visible light results in mixtures of 1 d with azirine 5 d', ketenimine 6 d', nitreno radical 2 d, and azirinyl radical 9. The relative amounts of these products strongly depend on the matrix and on the irradiation conditions. Nitreno radical 2 d with a quartet ground state was characterized by EPR spectroscopy. Electronic structure calculations in combination with the experimental results allow for a detailed understanding of the properties of this unusual new type of organic high-spin molecules. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Total brain death: a reply to Alan Shewmon.
Lee, Patrick; GriseZ, Germain
2012-06-01
D. Alan Shewmon has advanced a well-documented challenge to the widely accepted total brain death criterion for death of the human being. We show that Shewmon’s argument against this criterion is unsound, though he does refute the standard argument for that criterion. We advance a distinct argument for the total brain death criterion and answer likely objections. Since human beings are rational animals--sentient organisms of a specific type--the loss of the radical capacity for sentience (the capacity to sense or to develop the capacity to sense) involves a substantial change, the passing away of the human organism. In human beings total brain death involves the complete loss of the radical capacity for sentience, and so in human beings total brain death is death.
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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.
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Stemp, E D; Barton, J K
2000-08-21
Electron transfer from a protein to oxidatively damaged DNA, specifically from ferrocytochrome c to the guanine radical, was examined using the flash-quench technique. Ru(phen)2dppz2+ (dppz = dipyridophenazine) was employed as the photosensitive intercalator, and ferricytochrome c (Fe3+ cyt c), as the oxidative quencher. Using transient absorption and time-resolved luminescence spectroscopies, we examined the electron-transfer reactions following photoexcitation of the ruthenium complex in the presence of poly(dA-dT) or poly(dG-dC). The luminescence-quenching titrations of excited Ru(phen)2dppz2+ by Fe3+ cyt c are nearly identical for the two DNA polymers. However, the spectral characteristics of the long-lived transient produced by the quenching depend strongly upon the DNA. For poly(dA-dT), the transient has a spectrum consistent with formation of a [Ru(phen)2dppz3+, Fe2+ cyt c] intermediate, indicating that the system regenerates itself via electron transfer from the protein to the Ru(III) metallointercalator for this polymer. For poly(dG-dC), however, the transient has the characteristics expected for an intermediate of Fe2+ cyt c and the neutral guanine radical. The characteristics of the transient formed with the GC polymer are consistent with rapid oxidation of guanine by the Ru(III) complex, followed by slow electron transfer from Fe2+ cyt c to the guanine radical. These experiments show that electron holes on DNA can be repaired by protein and demonstrate how the flash-quench technique can be used generally in studying electron transfer from proteins to guanine radicals in duplex DNA.
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Severino, Joyce Ferreira; Goodman, Bernard A; Kay, Christopher W M; Stolze, Klaus; Tunega, Daniel; Reichenauer, Thomas G; Pirker, Katharina F
2009-04-15
Electron paramagnetic resonance spectroscopy and density functional theory calculations have been used to investigate the redox properties of the green tea polyphenols (GTPs) (-)-epigallocatechin gallate (EGCG), (-)-epigallocatechin (EGC), and (-)-epicatechin gallate (ECG). Aqueous extracts of green tea and these individual phenols were autoxidized at alkaline pH and oxidized by superoxide anion (O(2)(-)) radicals in dimethyl sulfoxide. Several new aspects of the free radical chemistry of GTPs were revealed. EGCG can be oxidized on both the B and the D ring. The B ring was the main oxidation site during autoxidation, but the D ring was the preferred site for O(2)(-) oxidation. Oxidation of the D ring was followed by structural degradation, leading to generation of a radical identical to that of oxidized gallic acid. Alkaline autoxidation of green tea extracts produced four radicals that were related to products of the oxidation of EGCG, EGC, ECG, and gallic acid, whereas the spectra from O(2)(-) oxidation could be explained solely by radicals generated from EGCG. Assignments of hyperfine coupling constants were made by DFT calculations, allowing the identities of the radicals observed to be confirmed.
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Agatonovic-Kustrin, Snezana; Morton, David W; Yusof, Ahmad P
2016-04-15
The aim of this study was to: (a) develop a simple, high performance thin layer chromatographic (HPTLC) method combined with direct 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay to rapidly assess and compare free radical scavenging activity or anti-oxidant activity for major classes of polyphenolics present in wines; and (b) to investigate relationship between free radical scavenging activity to the total polyphenolic content (TPC) and total antioxidant capacity (TAC) in the wine samples. The most potent free radical scavengers that we tested for in the wine samples were found to be resveratrol (polyphenolic non-flavonoid) and rutin (flavonoid), while polyphenolic acids (caffeic acid and gallic acid) although present in all wine samples were found to be less potent free radical scavengers. Therefore, the total antioxidant capacity was mostly affected by the presence of resveratrol and rutin, while total polyphenolic content was mostly influenced by the presence of the less potent free radical scavengers gallic and caffeic acids. Copyright © 2015 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Magne, L.; Pasquiers, S.; Blin-Simiand, N.; Postel, C.
2007-05-01
A photo-triggered discharge has been used to study the production kinetic mechanisms and the reactivity of the hydroxyl radical in a N2/O2 mixture (5% oxygen) containing ethane or ethene for hydrocarbon concentration values in the range 1000-5000 ppm, at 460 mbar total pressure. The discharge (current pulse duration of 60 ns) has allowed the generation of a transient homogeneous non-equilibrium plasma, and the time evolution of the OH density has been measured (relative value) in the afterglow (up to 200 µs) by laser induced fluorescence (LIF). Experimental results have been explained using predictions of a self-consistent 0D discharge and plasma reactivity modelling, and reduced kinetic schemes for OH have been validated. It has been shown that recombination of H- and O-atoms, as well as reaction of O with the hydroperoxy radical HO2, plays a very important role in the production of OH radicals in the mixture with ethane. H is a key species for production of OH and HO2 radicals. As for ethane, O, H and HO2 are key species for the production of OH in the case of ethene, but carbonated radicals, following the partial oxidation of the hydrocarbon molecule by O, also play a non-negligible role. The rate constant for O- and H-atom recombination has been estimated to be 3 × 10-30 cm6 s-1 at near ambient temperature, consistent with LIF measurements on OH for both mixtures with ethane and ethene.
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NASA Astrophysics Data System (ADS)
Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney
2016-07-01
Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H513CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H513CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg
2016-07-05
Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 us. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures upmore » to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 13CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 13CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less
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Kinoshita, Hidefumi; Nakagawa, Ken; Usui, Yukio; Iwamura, Masatsugu; Ito, Akihiro; Miyajima, Akira; Hoshi, Akio; Arai, Yoichi; Baba, Shiro; Matsuda, Tadashi
2015-08-01
Three-dimensional (3D) imaging systems have been introduced worldwide for surgical instrumentation. A difficulty of laparoscopic surgery involves converting two-dimensional (2D) images into 3D images and depth perception rearrangement. 3D imaging may remove the need for depth perception rearrangement and therefore have clinical benefits. We conducted a multicenter, open-label, randomized trial to compare the surgical outcome of 3D-high-definition (HD) resolution and 2D-HD imaging in laparoscopic radical prostatectomy (LRP), in order to determine whether an LRP under HD resolution 3D imaging is superior to that under HD resolution 2D imaging in perioperative outcome, feasibility, and fatigue. One-hundred twenty-two patients were randomly assigned to a 2D or 3D group. The primary outcome was time to perform vesicourethral anastomosis (VUA), which is technically demanding and may include a number of technical difficulties considered in laparoscopic surgeries. VUA time was not significantly shorter in the 3D group (26.7 min, mean) compared with the 2D group (30.1 min, mean) (p = 0.11, Student's t test). However, experienced surgeons and 3D-HD imaging were independent predictors for shorter VUA times (p = 0.000, p = 0.014, multivariate logistic regression analysis). Total pneumoperitoneum time was not different. No conversion case from 3D to 2D or LRP to open RP was observed. Fatigue was evaluated by a simulation sickness questionnaire and critical flicker frequency. Results were not different between the two groups. Subjective feasibility and satisfaction scores were significantly higher in the 3D group. Using a 3D imaging system in LRP may have only limited advantages in decreasing operation times over 2D imaging systems. However, the 3D system increased surgical feasibility and decreased surgeons' effort levels without inducing significant fatigue.
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Attah, Isaac K; Platt, Sean P; Meot-Ner Mautner, Michael; El-Shall, M Samy; Peverati, Roberto; Head-Gordon, Martin
2015-04-02
The binding energy of the naphthalene(+•)(benzene) heterodimer cation has been determined to be 7.9 ± 1 kcal/mol for C10H8(+•)(C6H6) and 8.1 ± 1 kcal/mol for C10H8(+•)(C6D6) by equilibrium thermochemical measurements using the mass-selected drift cell technique. A second benzene molecule binds to the C10H8(+•)(C6D6) dimer with essentially the same energy (8.4 ± 1 kcal/mol), suggesting that the two benzene molecules are stacked on opposite sides of the naphthalene cation in the (C6D6)C10H8(+•)(C6D6) heterotrimer. The lowest-energy isomers of the C10H8(+•)(C6D6) and (C6D6)C10H8(+•)(C6D6) dimer and trimer calculated using the M11/cc-pVTZ method have parallel stacked structures with enthalpies of binding (-ΔH°) of 8.4 and 9.0 kcal/mol, respectively, in excellent agreement with the experimental values. The stacked face-to-face class of isomers is calculated to have substantial charge-transfer stabilization of about 45% of the total interaction energy despite the large difference between the ionization energies of benzene and naphthalene. Similarly, significant delocalization of the positive charge is found among all three fragments of the (C6D6)C10H8(+•)(C6D6) heterotrimer, thus leaving only 46% of the total charge on the central naphthalene moiety. This unexpectedly high charge-transfer component results in activating two benzene molecules in the naphthalene(+•)(benzene)2 heterotrimer cation to associate with a third benzene molecule at 219 K to form a benzene trimer cation and a neutral naphthalene molecule. The global minimum of the C10H8(+•)(C6H6)2 heterotrimer is found to be the one where the naphthalene cation is sandwiched between two benzene molecules. It is remarkable, and rather unusual, that the binding energy of the second benzene molecule is essentially the same as that of the first. This is attributed to the enhanced charge-transfer interaction in the stacked trimer radical cation.
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Hearing Status after Radical Mastoidectomy without Tympanoplasty.
Khan, Shamaila Nawaz; Udaipurwala, Iqbal Hussain; Mehmood, Talat; Rahat, Zahid Mehmood
2017-12-01
To find out the impairment of hearing associated with radical mastoidectomy by measuring the quantitative difference in the functional hearing level before and after radical mastoidectomy operation without tympanoplasty. Cross-sectional comparative study. Department of Otorhinolaryngology and Head Neck Surgery, Bahawal Victoria Hospital, Bahawalpur and PNS Shifa Hospital, Karachi, from November 2009 to January 2013. Eighty-five patients, diagnosed clinically as chronic suppurative otitis media with extensive cholesteatoma having history of ear discharge and hearing impairment for more than 6 weeks duration and requiring radical mastoidectomy for treatment, were included in this study. Pure tone audiogram was done before and after radical mastoidectomy. Hearing impairment was compared in each patient before and after the operation. Among the 85 patients, 54 (63.5%) were males and 31 (36.5%) were females, with the age ranged between 18 to 63 years, mean age being 42.31 4.8 years. The mean increase in hearing loss after radical mastoidectomy in air conduction was 7.19 dB, bone conduction was 4.16 dB, and air-bone gap was 3.75 dB (0.001). The ear became dry and safe in 82 patients (96.5%) out of a total of 85, and only 3 patients required revision surgery at a second stage. Radical mastoidectomy has a least negligible effect on hearing status and one should not limit this technique due to the concern of aggravated hearing in patients with extensive cholesteatoma at the cost of dry and safe ears, which should be of prime importance.
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Marco-Contelles, J; Pozuelo, C; de Opazo, E
2001-06-15
We report the synthesis, free-radical cyclization of precursors 1,2,7-trideoxy-7-iodo-3,4:5,6-di-O-isopropylidene-D-gluco-hept-1-enitol (1), methyl 7-O-acetyl-6-O-benzyl-8-bromo-2,3,8-trideoxy-4,5-O-isopropylidene-D-gluco-oct-2-enonate (2) and 5-O-acetyl-4-O-benzyl-6-bromo-6-deoxy-2,3-O-isopropylidene-D-glucose-O-benzyloxime (3), readily prepared from D-glucose, and some selected transformations of the carbocycles obtained from these intermediates. In compound 1 we have installed a terminal double bond and an iodide as radical acceptor and leaving group, respectively. Compounds 2 and 3 are epsilon-bromo aldehydes substituted with alpha,beta-unsaturated ester and oxime ether functions as radical traps, respectively. The tributyltin hydride mediated ring closure of these radical precursors have afforded a series of interesting, diverse and highly functionalized carbocycles which can be considered useful building blocks for the synthesis of branched-chain cyclitols, aminocyclitols and aminoconduritols. In these processes, a good chemical yield and high stereoselectivity has been found in the newly formed stereocenters. Particularly interesting has been the finding that the stereochemical outcome of the free-radical cyclization is independent of the ratio of isomers (E or Z) in oxime ether 3. These results show the power and the state of art of this strategy for the stereocontrolled synthesis of enantiomerically pure inositols from carbohydrates.
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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
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Collins, Justin W; Sooriakumaran, P; Sanchez-Salas, R; Ahonen, R; Nyberg, T; Wiklund, N P; Hosseini, A
2014-07-01
The aim of this report is to describe our surgical technique of totally intracorporeal robotic assisted radical cystectomy (RARC) with neobladder formation. Between December 2003 and March 2013, a total of 147 patients (118 male, 29 female) underwent totally intracorporeal RARC for urinary bladder cancer. We also performed a systematic search of Medline, Embase and PubMed databases using the terms RARC, robotic cystectomy, robot-assisted, totally intracorporeal RARC, intracorporeal neobladder, intracorporeal urinary diversion, oncological outcomes, functional outcomes, and complication rates. The mean age of our patients was 64 years (range 37-87). On surgical pathology 47% had pT1 or less disease, 27% had pT2, 16% had pT3 and 10% had pT4. The mean number of lymph nodes removed was 21 (range 0-60). 24% of patients had lymph node positive dAQ1isease. Positive surgical margins occurred in 6 cases (4%). Mean follow-up was 31 months (range 4-115 months). Two patients (1.4%) died within 90 days of their operation. Using Kaplan-Meier analysis, overall survival and cancer specific survival at 60 months was 68% and 69.6%, respectively. 80 patients (54%) received a continent diversion with totally intracorporeal neobladder formation. In the neobladder subgroup median total operating time was 420 minutes (range 265-760). Daytime continence and satisfactory sexual function or potency at 12 months ranged between 70-90% in both men and women. Our experience with totally intracorporeal RARC demonstrates acceptable oncological and functional outcomes that suggest this is a viable alternative to open radical cystectomy.
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Maruoka, N; Murata, T; Omata, N; Fujibayashi, Y; Waki, A; Yoshimoto, M; Yano, R; Yonekura, Y; Wada, Y
2001-01-01
Seven-day-old rat brain slices were incubated at 36C in oxygenated Krebs-Ringer solution containing [(18)F]2-fluoro-2-deoxy-D-glucose ([(18)F]FDG), and serial two-dimensional time-resolved images of [(18)F]FDG uptake by the slices were obtained. The Gjedde-Patlak graphical method was applied to the image data, and the duration limit of hypoxia loading that allowed recovery of the fractional rate constant (k3*) of [(18)F]FDG (proportional to the cerebral glucose metabolic rate) after hypoxia loading to the unloaded control level was 50 min, and MK-801 as an N-methyl-D-aspartate antagonist had neuroprotective effects, but PBN as a free radical scavenger was ineffective. In our previous study in adult (7-week-old) rat brains [Murata et al., Exp Neurol 2000, 164:269-279], the limit of the hypoxia loading time was 20 min, and both MK-801 and PBN were effective. In the immature rat brains, the ratio of aerobic glucose metabolism to the total glucose metabolism was low compared with the adult rat brains, suggesting only a slight involvement of free radicals in hypoxic neurotoxicity. These data suggest that the higher resistance of immature brains to hypoxia compared to that of adult brains is attributable to a lower involvement of free radicals due to a lower aerobic glucose metabolic rate. Copyright 2002 S. Karger AG, Basel
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Peroxy Radical Measurements during the IRRONIC Field Project by C2H6 - NO Chemical Amplification
NASA Astrophysics Data System (ADS)
Wood, E. C. D.; Kundu, S.; Deming, B.; Lew, M.; Stevens, P. S.; Sklaveniti, S.; Dusanter, S.
2015-12-01
We present measurements of total peroxy radicals (HO2 + RO2) during the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC) field project in Bloomington, Indiana during July 2015. Peroxy radicals were measured by chemical amplification using ethane and nitric oxide in dual PFA reaction chambers, and the amplification product NO2 was quantified by cavity attenuated phase shift spectroscopy. On sunny days mid-day peroxy radical mixing ratios were typically between 20 and 70 ppt and were well correlated with "HO2*" measured by the Indiana University Laser-Induced Fluorescence with Fluorescence Assay by Gas Expansion (IU-FAGE) instrument. The ratio of total peroxy radicals (UMass) to the IU-FAGE HO2* measurements was greater than two. We also describe results from an informal intercomparison of the two instruments' calibration sources, which are based on acetone photolysis (UMass) and water photolysis (IU). In addition to sampling the IU calibration source in "amplification" mode, the UMass instrument also separately quantified the HO2 mixing ratio in the IU calibration gas by reaction with excess NO and subsequent quantification of the NO2 produced.
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Mass spectrometric studies of trimethylindium pyrolysis
NASA Technical Reports Server (NTRS)
Buchan, N. I.; Larsen, C. A.; Stringfellow, G. B.
1988-01-01
The kinetics of the pyrolysis of trimethylindium (TMIn) in He, D2, and H2 carriers was investigated using the atmospheric pressure flow-tube apparatus described by Larsen et al. (1987) and a time-of-flight mass spectrometer. The rate constant for the pyrolysis of TMIn in He was found to be comparable to that found by Jacko and Price (1964) for TMIn in toluene carrier (a radical scavenger), indicating that TMIn decomposes in He not by radical attack of methyl groups, but by homolytic fission. The decomposition of TMIn is enhanced in D2 and H2 carriers, where the principal products are CH3D and C2H6, and CH4 and C2H6, respectively, indicating that the reaction pathway in these carriers is different from those in He and toluene. The pyrolysis in H2 and D2 is attributed to a radical attack by H or D on TMIn. A reaction mechanism involving a short-lived hypervalent DTMIn species was proposed and was tested using numerical modeling techniques.
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Bonanno, Laura; Zago, Giulia; Marulli, Giuseppe; Del Bianco, Paola; Schiavon, Marco; Pasello, Giulia; Polo, Valentina; Canova, Fabio; Tonetto, Fabrizio; Loreggian, Lucio; Rea, Federico; Conte, PierFranco; Favaretto, Adolfo
2016-01-01
Objectives If concurrent chemoradiotherapy cannot be performed, induction chemotherapy followed by radical-intent surgical treatment is an acceptable option for non primarily resectable non-small-cell lung cancers (NSCLCs). No markers are available to predict which patients may benefit from local treatment after induction. This exploratory study aims to assess the feasibility and the activity of multimodality treatment, including triple-agent chemotherapy followed by radical surgery and/or radiotherapy in locally advanced NSCLCs. Methods We retrospectively collected data from locally advanced NSCLCs treated with induction chemotherapy with carboplatin (area under the curve 6, d [day]1), paclitaxel (200 mg/m2, d1), and gemcitabine (1,000 mg/m2 d1, 8) for three to four courses, followed by radical surgery and/or radiotherapy. We analyzed radiological response and toxicity. Estimated progression-free survival (PFS) and overall survival (OS) were correlated to response, surgery, and clinical features. Results In all, 58 NSCLCs were included in the study: 40 staged as IIIA, 18 as IIIB (according to TNM Classification of Malignant Tumors–7th edition staging system). A total of 36 (62%) patients achieved partial response (PR), and six (10%) progressions were recorded. Grade 3–4 hematological toxicity was observed in 36 (62%) cases. After chemotherapy, 37 (64%) patients underwent surgery followed by adjuvant radiotherapy, and two patients received radical-intent radiotherapy. The median PFS and OS were 11 months and 23 months, respectively. Both PFS and OS were significantly correlated to objective response (P<0.0001) and surgery (P<0.0001 and P=0.002). Patients obtaining PR and receiving local treatment achieved a median PFS and OS of 35 and 48 months, respectively. Median PFS and OS of patients not achieving PR or not receiving local treatment were 5–7 and 11–15 months, respectively. The extension of surgery did not affect the outcome. Conclusion The multimodality treatment was feasible, and triple-agent induction was associated with a considerable rate of PR. Patients achieving PR and receiving radical surgery or radiotherapy (53%) achieved a median OS of 4 years. PMID:27382305
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Bonanno, Laura; Zago, Giulia; Marulli, Giuseppe; Del Bianco, Paola; Schiavon, Marco; Pasello, Giulia; Polo, Valentina; Canova, Fabio; Tonetto, Fabrizio; Loreggian, Lucio; Rea, Federico; Conte, PierFranco; Favaretto, Adolfo
2016-01-01
If concurrent chemoradiotherapy cannot be performed, induction chemotherapy followed by radical-intent surgical treatment is an acceptable option for non primarily resectable non-small-cell lung cancers (NSCLCs). No markers are available to predict which patients may benefit from local treatment after induction. This exploratory study aims to assess the feasibility and the activity of multimodality treatment, including triple-agent chemotherapy followed by radical surgery and/or radiotherapy in locally advanced NSCLCs. We retrospectively collected data from locally advanced NSCLCs treated with induction chemotherapy with carboplatin (area under the curve 6, d [day]1), paclitaxel (200 mg/m(2), d1), and gemcitabine (1,000 mg/m(2) d1, 8) for three to four courses, followed by radical surgery and/or radiotherapy. We analyzed radiological response and toxicity. Estimated progression-free survival (PFS) and overall survival (OS) were correlated to response, surgery, and clinical features. In all, 58 NSCLCs were included in the study: 40 staged as IIIA, 18 as IIIB (according to TNM Classification of Malignant Tumors-7th edition staging system). A total of 36 (62%) patients achieved partial response (PR), and six (10%) progressions were recorded. Grade 3-4 hematological toxicity was observed in 36 (62%) cases. After chemotherapy, 37 (64%) patients underwent surgery followed by adjuvant radiotherapy, and two patients received radical-intent radiotherapy. The median PFS and OS were 11 months and 23 months, respectively. Both PFS and OS were significantly correlated to objective response (P<0.0001) and surgery (P<0.0001 and P=0.002). Patients obtaining PR and receiving local treatment achieved a median PFS and OS of 35 and 48 months, respectively. Median PFS and OS of patients not achieving PR or not receiving local treatment were 5-7 and 11-15 months, respectively. The extension of surgery did not affect the outcome. The multimodality treatment was feasible, and triple-agent induction was associated with a considerable rate of PR. Patients achieving PR and receiving radical surgery or radiotherapy (53%) achieved a median OS of 4 years.
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2014-01-01
Background In Chinese traditional medicine, Agrimonia pilosa Ledeb (APL) exhibits great effect on treatment of type 2 diabetes mellitus (T2DM), however its mechanism is still unknown. Considering that T2DM are correlated with postprandial hyperglycemia and oxidative stress, we investigated the α-glucosidase inhibitory activity and the antioxidant activity of flavonoid compound (FC) and triterpenoid compound (TC) from APL. Methods Entire plants of APL were extracted using 95% ethanol and 50% ethanol successively. The resulting extracts were partitioned and isolated by applying liquid chromatography using silica gel column and Sephadex LH 20 column to give FC and TC. The content of total flavonoids in FC and the content of total triterpenoids in TC were determined by using UV spectrophotometry. HPLC analysis was used to identify and quantify the monomeric compound in FC and TC. The α-glucosidase inhibitory activities were determined using the chromogenic method with p-nitrophenyl-α-D-glucopyranoside as substrate. Antioxidant activities were assessed through three kinds of radical scavenging assays (DPPH radical, ABTS radical and hydroxyl radical) & β-carotene-linoleic acid assay. Results The results indicate FC is abundant of quercitrin, and hyperoside, and TC is abundant of 1β, 2β, 3β, 19α-tetrahydroxy-12-en-28-oic acid (265.2 mg/g) and corosolic acid (100.9 mg/g). The FC & the TC have strong α-glucosidase inhibitory activities with IC50 of 8.72 μg/mL and 3.67 μg/mL, respectively. We find that FC show competitive inhibition against α-glucosidase, while the TC exhibits noncompetitive inhibition. Furthermore, The FC exhibits significant radical scavenging activity with the EC50 values of 7.73 μg/mL, 3.64 μg/mL and 5.90 μg/mL on DPPH radical, hydroxyl radical and ABTS radical, respectively. The FC also shows moderate anti-lipid peroxidation activity with the IC50 values of 41.77 μg/mL on inhibiting β-carotene bleaching. Conclusion These results imply that the FC and the TC could be responsible for the good clinical effects of APL on T2MD through targeting oxidative stress and postprandial hyperglycaemia. So APL may be good sources of natural antioxidants and α-glucosidase inhibitors exhibiting remarkable potential value for the therapy of T2DM. PMID:24410924
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NASA Astrophysics Data System (ADS)
Yoon, Young Wook; Lee, Sang Kuk; Lee, Gi Woo
2011-06-01
The visible vibronic emission spectra were recorded from the corona discharge of precursor tetramethylbenzene with a large amount of inert carrier gas helium using a pinhole-type glass nozzle coupled with corona excited supersonic expansion (CESE) well developed in this laboratory. The spectra showed a series of vibronic bands in the D_1 → D_0 electronic transition of jet-cooled benzyl-type radicals formed from the precursor in a corona excitation. The analysis confirmed that two isomeric radicals, 2,3,4- and 2,3,6-trimethylbenzyl radicals and three isomeric radicals, 3,4,5-, 2,3,5- and 2,4,6-trimethylbenzyl radicals were produced, respectively, from 1,2,3,4- and 1,2,3,5-tetramethylbenzenes as a result of removal of a hydrogen atom from the methyl group at different substitution position. For each isomeric trimethylbenzyl radical generated in the corona discharge of precursor, the electronic transition and a few vibrational mode frequencies were determined in the ground electronic state by comparing with those from both ab initio calculations and the known vibrational data of the precursor. The substitution effect that states the shift of electronic transition depends on the nature, the number, and the position of substituents on the ring has been qualitatively proved for the case of benzyl-type radicals.
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Michael, J Savarimuthu; Kalirajan, A; Padmalatha, C; Singh, A J A Ranjit
2013-09-01
To investigate the in vitro antioxidant activity and total phenolic content of the methanolic leaf extract of Nyctanthes arbor-tristis L. (NA). The sample was tested using five in vitro antioxidant methods (1, 1-diphenyl-2-picryl hydrazine radical scavenging activity (DPPH), hydroxyl radical-scavenging activity (-OH), nitric oxide scavenging activity (NO), superoxide radical-scavenging activity, and total antioxidant activity) to evaluate the in vitro antioxidant potential of NA and the total phenolic content (Folin-Ciocalteu method). The extract showed good free radical scavenging property which was calculated as an IC50 value. IC50 (Half maximal inhibitory concentration) of the methanolic extract was found to be 57.93 μg·mL(-1) for DPPH, 98.61 μg·mL(-1) for -OH, 91.74 μg·mL(-1) for NO, and 196.07 μg·mL(-1) for superoxide radical scavenging activity. Total antioxidant capacity of the extract was found to be (1198 ± 24.05) mg ascorbic acid for the methanolic extract. Free radical scavenging activity observed in the extracts of NA showed a concentration-dependent reaction. The in vitro scavenging tested for free radicals was reported to be due to high phenolic content in the leaf extract. The leaf extract of NA showed the highest total phenolic content with a value of 78.48 ± 4.2 equivalent mg TAE/g (tannic acid equivalent). N. arbor-tristis leaf extract exhibited potent free radical scavenging activity. The finding suggests that N. arbor-tristis leaves could be a potential source of natural antioxidant. Copyright © 2013 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.
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Measuring Atmospheric Free Radicals Using Chemical Amplification
1988-05-01
CH 3Br, H2S, and SO2 [Logan et al., 1981]. Recently, the OH radical has been determined as the dominant loss mechanism for isoprene and monoterpenes ...W. Heaps, D. Philen, and T. McGee, Bondary Layer Measurements of the OH Radical in the Vicinity of an Isolated Power Plant Plume: SO2 and NO2
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Radical-mediated reduction of the dithiocarbamate group under tin-free conditions.
McMaster, Claire; Bream, Robert N; Grainger, Richard S
2012-06-28
Reductive desulfurisation of dithiocarbamates is conveniently achieved using H(3)PO(2)-Et(3)N-ACCN in refluxing dioxane. Fused and spirocyclic β-lactams, prepared through 4-exo trig carbamoyl radical cyclisation-dithiocarbamate group transfer reactions, are reduced without fragmentation of the strained 4-membered ring. Diethyl tetraacetyl-d-glucopyranosyl dithiocarbamate is selectively reduced with or without acyloxy group migration depending on reaction conditions and choice of reductant. Deuterium incorporation from D(3)PO(2)-Et(3)N is observed for a system involving a nucleophilic radical intermediate, but not in the case of the electrophilic radical obtained through acyloxy group migration on a glucose derivative.
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Zhang, Zhi-Peng; Ma, Jun; He, Yuan-Yuan; Lu, Jun; Ren, Di-Feng
2018-06-01
Diospyros lotus, a member of the Ebenaceae family, has long been used as a traditional sedative in China. In this study, the antioxidant and hypoglycemic effects of non-fermented and microorganism-fermented D. lotus were explored. The total phenolic and vitamin C contents of microorganism-fermented D. lotus for 24-72 h were less than those of non-fermented. High-performance liquid chromatography showed that the tannic, catechinic, and ellagic acid contents increased significantly upon fermentation for 24 h. D. lotus fermented with Microbacterium flavum for 24 h exhibited the highest DPPH radical scavenging activity (IC 50 = 4.18 μg mL -1 ), and the highest ABTS radical scavenging activity was exhibited at 72 h of fermentation (IC 50 = 29.18 μg mL -1 ). The anti-α-glucosidase activity of fermented D. lotus was higher (2.06-4.73-fold) than that of non-fermented one. Thus, fermented D. lotus is a useful source of natural antioxidants, and a valuable food, exhibiting antioxidant and hypoglycemic properties. Copyright © 2018 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.
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Schöttker, Ben; Brenner, Hermann; Jansen, Eugène H J M; Gardiner, Julian; Peasey, Anne; Kubínová, Růžena; Pająk, Andrzej; Topor-Madry, Roman; Tamosiunas, Abdonas; Saum, Kai-Uwe; Holleczek, Bernd; Pikhart, Hynek; Bobak, Martin
2015-12-15
The free radical/oxidative stress theory of ageing has received considerable attention, but the evidence on the association of oxidative stress markers with mortality is sparse. We measured derivatives of reactive oxygen metabolite (D-ROM) levels as a proxy for the reactive oxygen species concentration and total thiol levels (TTL) as a proxy for the redox control status in 10,622 men and women (age range, 45-85 years), from population-based cohorts from Germany, Poland, Czech Republic, and Lithuania, of whom 1,702 died during follow-up. Both oxidative stress markers were significantly associated with all-cause mortality independently from established risk factors (including inflammation) and from each other in all cohorts. Regarding cause-specific mortality, compared to low D-ROM levels (≤ 340 Carr U), very high D-ROM levels (>500 Carr U) were strongly associated with both cardiovascular (relative risk (RR), 5.09; 95 % CI, 2.67-9.69) and cancer mortality (RR, 4.34; 95 % CI, 2.31-8.16). TTL was only associated with CVD mortality (RR, 1.30; 95 % CI, 1.15-1.48, for one-standard-deviation-decrease). The strength of the association of TTL with CVD mortality increased with age of the participants (RR for one-standard-deviation-decrease in those aged 70-85 years was 1.65; 95 % CI, 1.22-2.24). In these four population-based cohort studies from Central and Eastern Europe, the oxidative stress serum markers D-ROM and TTL were independently and strongly associated with all-cause and CVD mortality. In addition, D-ROM levels were also strongly associated with cancer mortality. This study provides epidemiological evidence supporting the free radical/oxidative stress theory of ageing and suggests that d-ROMs and TTL are useful oxidative stress markers associated with premature mortality.
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Gu, Jiande; Wang, Jing; Leszczynski, Jerzy
2014-01-30
Computational chemistry approach was applied to explore the nature of electron attachment to cytosine-rich DNA single strands. An oligomer dinucleoside phosphate deoxycytidylyl-3',5'-deoxycytidine (dCpdC) was selected as a model system for investigations by density functional theory. Electron distribution patterns for the radical anions of dCpdC in aqueous solution were explored. The excess electron may reside on the nucleobase at the 5' position (dC(•-)pdC) or at the 3' position (dCpdC(•-)). From comparison with electron attachment to the cytosine related DNA fragments, the electron affinity for the formation of the cytosine-centered radical anion in DNA is estimated to be around 2.2 eV. Electron attachment to cytosine sites in DNA single strands might cause perturbations of local structural characteristics. Visible absorption spectroscopy may be applied to validate computational results and determine experimentally the existence of the base-centered radical anion. The time-dependent DFT study shows the absorption around 550-600 nm for the cytosine-centered radical anions of DNA oligomers. This indicates that if such species are detected experimentally they would be characterized by a distinctive color.
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Polyphenol contents and radical scavenging capacities of red maple (Acer rubrum L.) extracts.
Royer, Mariana; Diouf, Papa Niokhor; Stevanovic, Tatjana
2011-09-01
The crude ethanol and water extracts of different red maple (Acer rubrum L.) tissues: whole branches (WB), wood of branches (BW), bark of branches (BB), stem bark (SB) and whole twigs (T), were examined in order to determine their phenolic contents as well as their radical scavenging capacities. The total phenols (TP), total extractable tanins (TET) and non-precipitable phenols (NPP), were determined by combination of spectrophotometric and precipitation methods, while total flavonoids, hydroxy cinanmic acids and proanthocyanidins were determined spectrophotometrically. The radical scavenging activities of the extracts were determined against five reactive oxygen species (ROS): superoxide anion (O(2)(·-)), hydroxyl radical (HO(·)), peroxyl radical (ROO(·)), hypochlorite ion (ClO(-)), and hydrogen peroxide (H(2)O(2)) and one reactive nitrogen species (RNS): nitric oxide (NO). The extracts of stem bark were significantly more efficient (exhibiting the highest antioxidant efficiencies, AE) than the other studied extracts against all ROS (at p<0.05, Duncan statistical tests), except against NO. The correlation coefficients determined between total phenolic (TP) content and antiradical efficiencies were R(2)=0.12 for O(2)(·-); R(2)=0.29 for HO(·); R(2)=0.40 for H(2)O(2); R(2)=0.86 for ROO(·); R(2)=0.03 for NO(·) and R(2)=0.73 for ClO(-). Our results indicate potential utilisation of extracts as natural antioxidants. Copyright © 2011 Elsevier Ltd. All rights reserved.
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Serwinski, Paul R; Esat, Burak; Lahti, Paul M; Liao, Yi; Walton, Richard; Lan, Jiang
2004-08-06
2-(4-Azidophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (14), 2-(4-azidophenyl)benzimidazole-1-oxide-3-oxyl (16), 2-(4-azidophenyl)-1,2,6-triphenylverdazyl (19), 2-(3-azidophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (21), and (3-azidophenyl)-N-tert-butyl-N-aminoxyl (25) were photolyzed in frozen solution to give S = 3/2 state ESR spectra of the corresponding nitrenophenyl radicals with the following zero-field splitting parameters: |D/hc| = 0.277 cm(-1), |E/hc| < or = 0.002 cm(-1) (7 from 14); |D/hc| = 0.256 cm(-1), |E/hc| < or = 0.002 cm(-1) (8 from 16); |D/hc| = 0.288 cm(-1), |E/hc| < or = 0.002 cm(-1) (9 from 19); |D/hc| = 0.352 cm(-1), |E/hc| = 0.006 cm(-1) (10 from 21); |D/hc| = 0.336 cm(-1), |E/hc| = 0.004 cm(-1) (11 from 25). UB3LYP/6-31G computations and ESR spectroscopic analyses suggest that these are nitreno radicals, even para-linked systems with possible quinonoidal resonance forms. Neat samples of azidophenyl radicals 14 and 21 showed bulk paramagnetic behavior, consistent with the lack of close contacts in their crystal structures. Efforts to make photolabile coordination complexes of 14 and 21 with paramagnetic transition metal ions were unsuccessful: Cu(ClO4)2 x 6H2O instead oxidized them to the corresponding diamagnetic nitrosonium perchlorate salts. Copyright 2004 American Chemical Society
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Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; ...
2016-07-05
Cycloheptatrienyl (tropyl) radical, C 7H 7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. In this study, the pyrolysis products resulting from C 7H 7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C 7H 7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals domore » not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C 7H 7) radicals but rather only benzyl (C 6H 5CH 2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C 6H 5CH 2, C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2. Finally, analysis of the temperature dependence for the pyrolysis of the isotopic species (C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Buckingham, Grant T.; National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden Colorado 80401; Porterfield, Jessica P.
2016-07-07
Cycloheptatrienyl (tropyl) radical, C{sub 7}H{sub 7}, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C{sub 7}H{sub 7} were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C{sub 7}H{sub 7} are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize tomore » benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C{sub 7}H{sub 7}) radicals but rather only benzyl (C{sub 6}H{sub 5}CH{sub 2}). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C{sub 6}H{sub 5}CH{sub 2}, C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less
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NASA Astrophysics Data System (ADS)
Kobayashi, Tsuyoshi; Hashizume, Hiroshi; Ohta, Takayuki; Ishikawa, Kenji; Hori, Masaru; Ito, Masafumi
2015-09-01
The inactivation of microorganisms using nonequilbrium atmospheric pressure plasmas has been attracted much attention due to the low temperature processing and high speed treatment. In this study, we have inactivated E. coli suspended in solutions with neutral pH using an atmospheric-pressure oxygen radical source which can selectively supply electrically neutral oxygen radicals. E. coli cells were suspended with deionized distilled water (DDW) (pH = 6.8) or phosphate buffered saline (PBS) (pH = 7.4) or Citrate-Na buffer (pH = 6.5). The treated samples were diluted and spread on nutrient agar (Nutrient Broth). They were cultured at 37° C. The inactivation effects of oxygen radicals on those cells in solutions were evaluated by colony-counting method. O2 diluted by Ar gas were employed as a working gas for the radical source. The total gas flow rate and the gas mixture ratio of O2/(Ar + O2) were set at 5 slm and 0.6%, respectively. The distance between the radical exit and the suspension surface were set at 10 mm. As a result, the D values for DDW(pH = 6.8), PBS(pH = 7.4) and Citrate-Na buffer(pH = 6.5) were estimated to be 1.4 min, 0.9 min and 16.8 min respectively. The inactivation rates in DDW, PBS were significantly different from that in Citrate-Na buffer. This work was partly supported by JSPS KAKENHI Grant Number 26286072 and project for promoting Research Center in Meijo University.
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NASA Astrophysics Data System (ADS)
Tan, Z.; Lu, K.; Ma, X.; Bohn, B.; Hofzumahaus, A.; Broch, S.; Fuchs, H.; Holland, F.; Liu, Y.; Li, X.; Novelli, A.; Rohrer, F.; Wang, H.; Wu, Y.; Shao, M.; Zeng, L.; Kiendler-Scharr, A.; Wahner, A.; Zhang, Y.
2017-12-01
A comprehensive field campaign was carried out in winter 2016 in the campus of UCAS (University of Chinese Academy of Science), located in a small town 60 km northeast of urban Beijing. Concentrations of OH, HO2 and RO2 radicals as well as the total OH reactivity were measured by a laser induced fluorescence instrument. Maximum hourly averaged OH, HO2 and RO2 radical concentrations were (3±2)×106cm-3, (8±6)×107 cm-3 and (7±5)×107 cm-3, respectively. These radical concentrations were smaller than those observed during summer because of the reduced solar radiation. A chemical modulation device to separate atmospheric OH radicals from any interfering species was applied for few days showing negligible interference for both clean and polluted air masses.HONO and HCHO photolysis were found to be the most important primary sources of ROx radicals. CO and NOx were the important OH reactants which contributed more than half of the total OH reactivity. The relative high OH concentrations in polluted episode enabled a fast oxidation of fresh emitted pollutants and the formation of secondary air products. The observed radical concentrations were compared with the results from a chemical box model. The model is capable of reproducing radical concentrations for moderate NOx conditions but larger discrepancies are observed for both low and high NOx regimes for the peroxy radical concentrations. The underestimation of RO2 radical concentrations for high NOx conditions is discussed in the context of recent campaigns.
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Hwang, Seok Joon; Yoon, Won Byong; Lee, Ok-Hwan; Cha, Seung Ju; Kim, Jong Dai
2014-03-01
The objective of this study was to investigate the radical-scavenging-linked antioxidant properties of the extracts from black chokeberry and blueberry cultivated in Korea. The 70% ethanol extracts were prepared from black chokeberry and blueberry, and evaluated for total phenolic content, total flavonoid content, total proanthocyanidin content, and antioxidative activities, using various in vitro assays, such as DPPH(2,2-diphenyl-1-picrylhydrazyl), ABTS(2,2-azino-bis-(3-ethylenebenzothiozoline-6-sulphonic acid)) radical-scavenging activity, FRAP(ferric-reducing antioxidant power) and reducing power. The major phenolic compounds, including cyanidin-3-galactoside, cyanidin-3-arabinoside, neochlorogenic acid, procyanidin B1, were analysed by HPLC with a photodiode array detector. Results showed that total phenol, flavonoid and proanthocyanidin contents of black chokeberry extract were higher than those of blueberry extract. In addition, black chokeberry extract exhibited higher free radical-scavenging activity and reducing power than did blueberry extract. Cyanidin-3-galactoside was identified as a major phenolic compound, with considerable content in black chokeberry, that correlated with its higher antioxidant and radical-scavenging effects. These results suggest that black chokeberry extracts could be considered as a good source of natural antioxidants and functional food ingredients. Copyright © 2013 Elsevier Ltd. All rights reserved.
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n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions
Zhang, Siyuan; Naab, Benjamin D.; Jucov, Evgheni V.; Parkin, Sean; Evans, Eric G. B.; Millhauser, Glenn L.; Timofeeva, Tatiana V.; Risko, Chad; Brédas, Jean-Luc; Bao, Zhenan; Barlow, Stephen; Marder, Seth R.
2015-01-01
Dimers of 2-substituted N,N'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 {Y = cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)} have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT both indicate a longer C—C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2, yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2) dissociation and of D2-to-A electron transfer, D2 reacts with A to form D+ and A•– by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D+/0.5D2 redox potentials – the effective reducing strengths of the dimers – vary little within the series (ca. –1.9 V vs. FeCp2+/0) due to cancelation of trends in the D+/0 potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. PMID:26088609
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Lee, Wei-Jei; Wang, Weu; Chen, Tai-Chi; Chen, Jung-Chieh; Ser, Kong-Han
2008-08-01
Laparoscopically assisted distal gastrectomy has been used for distal part early gastric cancer resection. However, use of totally laparoscopic gastric cancer resection remains limited because of technical problems, especially when standard D2 nodal dissection was applied. We had reported the first totally laparoscopic Billroth II (BII) subtotal gastrectomy with lymphadenectomy for early gastric cancer in the year 1998. The aim of this study is to determine whether this procedure is superior to conventional open technique. The clinical course of 34 consecutive patients who underwent totally laparoscopic BII gastrectomy using an upper to lower, right to left, and clockwise quadrant-to-quadrant technique was compared with 34 sex-matched and age-matched patients who underwent open gastrectomy. Main outcome measures included operative time, blood loss, length of stay, morbidity and mortality, adequacy of lymphadenectomy, and long-term outcome. In the laparoscopic group, all the operations were completed by laparoscopic technique, but 1 patient required secondary laparotomy for total gastrectomy owing to inadequate resection margin. There was no operation mortality in this study. The postoperative complication rates were similar in these 2 groups. The mean operative time for laparoscopic group was 283+/-122 minutes (range: 186 to 480 min), significantly longer than the 195+/-26 minutes in the conventional group (P<0.001). Laparoscopic group was associated with less intraoperative blood loss (74 vs. 190 mL; P<0.01), early flatus passage (2.9 vs. 4.9 d; P<0.01), less usage of analgesics (3.5 vs. 5.8 doses; P<0.05), and a shorter postoperative hospital stay (8.5 vs. 12.1 d; P<0.01). There was no significant difference between laparoscopic and conventional open radical gastrectomy with regard to ratio of free margin, number of harvested lymph nodes, and survival. Although totally laparoscopic BII gastrectomy using the upper to lower technique required a longer surgical time and was technically more demanding than conventional open surgery, it resulted in shorter recovery time, less analgesic use, and less severe physical discomfort without compromising the operative curability and oncologic outcomes.
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The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings
DOE Office of Scientific and Technical Information (OSTI.GOV)
Buckingham, Grant T.; Ormond, Thomas K.; National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401
2015-01-28
The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C{sub 6}H{sub 5}CH{sub 2}, as well as a set of isotopically labeled radicals: C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C{sub 5}H{submore » 4}=C=CH{sub 2}, H atom, C{sub 5}H{sub 4}—C ≡ CH, C{sub 5}H{sub 5}, HCCCH{sub 2}, and HC ≡ CH. Pyrolysis of the C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2} benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C{sub 6}H{sub 5}CH{sub 2}⇋C{sub 7}H{sub 7}. These labeling studies suggest that there must be other thermal decomposition routes for the C{sub 6}H{sub 5}CH{sub 2} radical that differ from the fulvenallene pathway.« less
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NASA Astrophysics Data System (ADS)
Sudewi, S.; Lolo, W. A.; Warongan, M.; Rifai, Y.; Rante, H.
2017-11-01
Abelmoschus manihot L. has reported to have flavonoids content. This study aims were to determine the ability of A. manihot extract in counteracting free radical DPPH and determine the content of total flavonoids. A. manihot leaf was taken from 2 regions in North Sulawesi, namely Tomohon and Kotamobagu. The maceration was carried out to extract the active compound in a 96% ethanol solvent. Free radical scavenging analysis was carried out by DPPH and determination of its total flavonoid in the extract was measured using spectrophotometri method. The results showed that A. manihot extract from Tomohon and Kotamobagu could counteract free radical of DPPH with value of free radical activity of 88.151 and 88.801 %, respectively. A. manihot leaf from Kotamobagu has higher total flavonoids content 61.763 mg/g compare to Tomohon 46.679 mg/g which presented as quercetin. A. manihot has antioxidant activity.
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Niu, Y; Wan, X L; Zhang, X H; Zhao, L G; He, J T; Zhang, J F; Zhang, L L; Wang, T
2017-04-01
The present study was conducted to investigate the influence of dietary supplementation with different levels of fermented Ginkgo biloba leaves (FGBL) on growth performance, slaughter performance, meat quality, antioxidant enzyme capacity, and free radical scavenging activities of muscles in broiler chickens. A total of 648 one-d-old broiler chickens were randomly allocated into six dietary treatments, including control group (CON group: basal diet), FGBL1, FGBL2, FGBL3, FGBL4, and FGBL5 groups (basal diet containing 1.5, 2.5, 3.5, 4.5, and 5.5 g/kg FGBL, respectively). Body weight gain and feed intake were recorded at 1, 21, and 42 d. At 42 d, 2 birds from each replicate were slaughtered. The results indicated that 3.5 g/kg FGBL diet significantly increased (P < 0.05) ADFI and ADG in 1 to 42 d and ADFI in 22 to 42 d compared with the CON group. In 1 to 21 d, 4.5 g/kg FGBL diet improved (P < 0.05) ADFI and ADG. With dietary FGBL increasing, the feed: gain ratio (F/G) in 1 to 21 d was significantly decreased (P < 0.05). However, birds fed with 5.5 g/kg FGBL had a higher (P < 0.05) F/G compared with other groups in 22 to 42 d and 1 to 42 d. In addition, FGBL3 and FGBL4 showed lower (P < 0.05) L* value in breast muscle, cooking loss in thigh muscle and lower 24 h and 48 h drip loss in both breast and thigh muscles than those of other groups. Furthermore, birds in the FGBL3 and FGBL4 groups increased (P < 0.05) the activity of total superoxide dismutase and total antioxidant capability in muscles, and the scavenging activities of 2,2΄-azino-bis (3-ethylbenzothiazoline-6-sulfonic) acid radical, OH•, and O2•- in thigh muscle, decreased (P < 0.05) malondialdehyde concentration in thigh muscle, as compared to the CON group. In conclusion, FGBL had the potential to improve the growth performance, meat quality and antioxidant status of broiler chickens. The optimal dose in the present study of FGBL in broiler diets was from 3.5 to 4.5 g/kg. © 2016 Poultry Science Association Inc.
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NASA Astrophysics Data System (ADS)
Thangamani, D.; Shankar, R.; Vijayakumar, S.; Kolandaivel, P.
2016-10-01
In the present investigation, the reaction mechanism and kinetics of 2-formylcinnamaldehyde (2-FC) with O3 and hydroxyl OH radicals were studied. The reaction of 2-FC with O3 radical are initiated by the formation of primary ozonide, whereas the reaction of 2-FC with the hydroxyl OH radical are initiated by two different ways: (1). H-atom abstraction by hydroxyl OH radical from the -CHO and -CH = CHCHO group of 2-FC (2). Hydroxyl OH addition to the -CH = CHCHO group to the ring-opened 2-FC. These reactions lead to the formation of an alkyl radical. The reaction pathways corresponding to the reactions between 2-FC with O3 and hydroxyl OH radicals have been analysed using density functionals of B3LYP and M06-2X level of methods with the 6-31+G(d,p) basis set. Single-point energy calculations for the most favourable reactive species are determined by B3LYP/6-311++G(d,p) and CCSD(T)/6-31+G(d,p) levels of theory. From the obtained results, the hydroxyl OH addition at C8 position of 2-FC are most favourable than the C9 position of 2-FC. The subsequent reactions of the alkyl radicals, formed from the hydroxyl OH addition at C8 position, are analysed in detail. The individual and overall rate constant for the most favourable reactions are calculated by canonical variational transition theory with small-curvature tunnelling corrections over the temperature range of 278-350 K. The calculated theoretical rate constants are in good agreement with the available experimental data. The Arrhenius plot of the rate constants with the temperature are fitted and the atmospheric lifetimes of the 2-FC with hydroxyl OH radical reaction in the troposphere calculate for the first time, which can be applied to the study on the atmospheric implications. The condensed Fukui function has been verified for the most favourable reaction sites. This study can be regarded as an attempt to investigate the O3-initiated and hydroxyl OH-initiated reaction mechanisms of 2-FC in the atmosphere.
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Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J
2013-12-27
This work details an ab initio and chemical kinetic study of the hydrogen atom abstraction reactions by the hydroperoxyl radical (HȮ2) on the following esters: methyl ethanoate, methyl propanoate, methyl butanoate, methyl pentanoate, methyl isobutyrate, ethyl ethanoate, propyl ethanoate, and isopropyl ethanoate. Geometry optimizations and frequency calculations of all of the species involved, as well as the hindrance potential descriptions for reactants and transition states, have been performed with the Møller-Plesset (MP2) method using the 6-311G(d,p) basis set. A validation of all of the connections between transition states and local minima was performed by intrinsic reaction coordinate calculations. Electronic energies for all of the species are reported at the CCSD(T)/cc-pVTZ level of theory in kcal mol(-1) with the zero-point energy corrections. The CCSD(T)/CBS (extrapolated from CCSD(T)/cc-pVXZ, in which X = D, T, Q) was used for the reactions of methyl ethanoate + HȮ2 radicals as a benchmark in the electronic energy calculations. High-pressure limit rate constants, in the temperature range 500-2000 K, have been calculated for all of the reaction channels using conventional transition state theory with asymmetric Eckart tunneling corrections. The 1-D hindered rotor approximation has been used for the low frequency torsional modes in both reactants and transition states. The calculated individual and total rate constants are reported for all of the reaction channels in each reaction system. A branching ratio analysis for each reaction site has also been investigated for all of the esters studied in this work.
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Ramadhan, Rico; Phuwapraisirisan, Preecha
2015-10-15
In search of effective antidiabetic agents having therapeutic effect by inhibiting α-glucosidase and preventive effect by scavenging free radicals, Horsfieldia macrobotrys showed promising bioactivity required for the proposed criteria. Bioassay-guided isolation of the stem bark extract resulted in two new arylalkanones named horsfieldone A (1) and maingayone D (2), together with a new flavanone C-glucoside named 8-C-β-d-glucopyranosylpinocembrin (3). Their structures and stereochemistry were determined by spectroscopic techniques as well as Mosher's method. Of isolated compounds, maingayone D (2) was the most potent inhibitors against both α-glucosidases and free radicals. The presence of additional phenolic moieties in 2 clearly indicated their critical roles in inhibitory effects. Further investigation on mechanism underlying α-glucosidase inhibition indicated that maingayone D (2) could retard the enzyme function by both competitive and noncompetitive manners. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Hydroxyl radical mediated DNA base modification by manmade mineral fibres.
Leanderson, P; Söderkvist, P; Tagesson, C
1989-01-01
Manmade mineral fibres (MMMFs) were examined for their ability to hydroxylate 2-deoxyguanosine (dG) to 8-hydroxydeoxyguanosine (8-OH-dG), a reaction that is mediated by hydroxyl radicals. It appeared that (1) catalase and the hydroxyl radical scavengers, dimethylsulphoxide and sodium benzoate, inhibited the hydroxylation, whereas Fe2+ and H2O2 potentiated it; (2) pretreatment of MMMFs with the iron chelator, deferoxamine, or with extensive heat (200-400 degrees C), attenuated the hydroxylation; (3) the hydroxylation obtained by various MMMFs varied considerably; (4) there was no apparent correlation between the hydroxylation and the surface area of different MMMFs, although increasing the surface area of a fibre by crushing it increased its hydroxylating capacity; and (5) there was good correlation between the hydroxylation of dG residues in DNA and the hydroxylation of pure dG in solution for the 16 different MMMFs investigated. These findings indicate that MMMFs cause a hydroxyl radical mediated DNA base modification in vitro and that there is considerable variation in the reactivity of different fibre species. The DNA modifying ability seems to depend on physical or chemical characteristics, or both, of the fibre. PMID:2765416
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Excited state dynamics of the astaxanthin radical cation
NASA Astrophysics Data System (ADS)
Amarie, Sergiu; Förster, Ute; Gildenhoff, Nina; Dreuw, Andreas; Wachtveitl, Josef
2010-07-01
Femtosecond transient absorption spectroscopy in the visible and NIR and ultrafast fluorescence spectroscopy were used to examine the excited state dynamics of astaxanthin and its radical cation. For neutral astaxanthin, two kinetic components corresponding to time constants of 130 fs (decay of the S 2 excited state) and 5.2 ps (nonradiative decay of the S 1 excited state) were sufficient to describe the data. The dynamics of the radical cation proved to be more complex. The main absorption band was shifted to 880 nm (D 0 → D 3 transition), showing a weak additional band at 1320 nm (D 0 → D 1 transition). We found, that D 3 decays to the lower-lying D 2 within 100 fs, followed by a decay to D 1 with a time constant of 0.9 ps. The D 1 state itself exhibited a dual behavior, the majority of the population is transferred to the ground state in 4.9 ps, while a small population decays on a longer timescale of 40 ps. Both transitions from D 1 were found to be fluorescent.
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Kobayashi, Hirokazu; Morinaga, Yuka; Fujimori, Etsuko; Asaji, Tetsuo
2014-07-10
New inclusion compounds (ICs) were prepared using the organic 1D nanochannels of 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) as a nanosized template and nitronyl nitroxide (NN) radicals such as phenylnitronylnitroxide (PhNN) and p-nitrophenylnitronylnitroxide (p-NPNN). ESR measurements below 255 K for the CLPOT ICs diluted with spacer molecules gave rigid limit spectra similar to that for PhNN molecules in a glassy ethanol matrix at low temperature, which suggests isolation of the radical molecules. ESR measurements for them in the range of 290-400 K gave a modulated quintet ESR signal, which suggested uniaxial rotational diffusion of NN radicals in the nanochannels approximately around the principal y-axis of the g-tensors. In the ESR measurements to 430 K for the [(CLPOT)2-(p-NPNN)0.07] IC without spacers, the broader line width than the case in dilution was observed by inter-radical dipolar interaction. In every case, the rotational diffusion activation energies of NN radicals in the CLPOT nanochannels were several times larger than those of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical derivatives (4-X-TEMPO) in CLPOT nanochannels. This is expected due to the larger molecular size of NN radicals than 4-X-TEMPO or stronger interaction between NN radicals and the surrounding host or guest molecules.
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Banu, Rukhsar; Gerding, Jason; Franklin, Cynthia; Sikazwe, Donald; Horton, William; Török, Marianna; Davis, Julian; Cheng, Kwan H; Nakazwe, Muziya; Mochona, Bereket
2017-12-21
The objective of this research is to generate leads for developing our ultimate poly-active molecules with utility in central nervous system (CNS) diseases. Indeed, poly-active molecules capable of mitigating brain free radical damage while enhancing acetylcholine signaling (via cholinesterase inhibition) are still being sought for combating Alzheimer's disease (AD). We differentiate "poly-active" agents from "multi-target" ones by defining them as single molecular entities designed to target only specific contributory synergistic pharmacologies in a disease. For instance, in AD, free radicals either initiate or act in synergy with other pharmacologies, leading to disease worsening. For this preliminary report, a total of 14 (i.e., 4,5-dimethoxy-2-nitrobenzohydrazide plus 1-(1-benzylpiperidin-4-yl)ethan-1-one) derivatives were synthesized and screened, in silico and in vitro, for their ability to scavenge free radicals and inhibit acetylcholinesterase (AChE)/butyrylcholinesterase (BuChE) enzymes. Overall, six derivatives ( 4a , 4d , 4e , 4f , 4g , 9b ) exhibited potent (>30%) antioxidant properties in the oxygen radical absorbance capacity (ORAC) assay. The antioxidant values were either comparable or more potent than the comparator molecules (ascorbic acid, resveratrol, and trolox). Only three compounds ( 4d , 9a , 9c ) yielded modest AChE/BuChE inhibitions (>10%). Please note that a SciFinder substance data base search confirmed that most of the compounds reported herein are new, except 9a and 9c which are also commercially available.
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Sen, Saikat; De, Biplab; Devanna, N; Chakraborty, Raja
2013-03-01
The objective of the present study was to determine the total phenolic and total flavonoid contents, and to evaluate the antioxidant potential of different leaf extracts of Meyna spinosa Roxb. ex Link, a traditional medicinal plant of India. Free radical scavenging and antioxidant potential of the methanol, ethyl acetate, and petroleum ether extracts of Meyna spinosa leaves were investigated using several in vitro and ex vivo assays, including the 2, 2-diphenyl-picrylhydrazyl radical scavenging, superoxide anion scavenging, hydroxyl radical scavenging, nitric oxide radical scavenging, hydrogen peroxide scavenging activity, metal chelating assay, and reducing power ability method. Total antioxidant activity of the extracts was estimated by the ferric thiocyanate method. Inhibition assay of lipid peroxidation and oxidative hemolysis were also performed to confirm the protective effect of the extracts. Total phenolic and total flavonoid contents of the extracts were estimated using standard chemical assay procedures. Methanol extracts showed the highest polyphenolic content and possessed the better antioxidant activity than the other two extracts. Total phenolic and total flavonoid contents in the methanol extract were (90.08 ± 0.44) mg gallic acid equivalents/g and (58.50 ± 0.09) mg quercetin equivalents/g, respectively. The IC50 of the methanol extract in the DPPH(·), superoxide anion, hydroxyl radical, nitric oxide radical, hydrogen peroxide scavenging activity and metal chelating assays were (16.4 ± 0.41), (35.9 ± 0.19), (24.1 ± 0.33), (23.7 ± 0.09), (126.8 ± 2.92), and (117.2 ± 1.01) μg·mL(-1), respectively. The methanol extract showed potent reducing power ability, total antioxidant activity, and significantly inhibit lipid peroxidation and oxidative hemolysis which was similar to that of standards. The results indicated a direct correlation between the antioxidant activity and the polyphenolic content of the extracts, which may the foremost contributors to the antioxidant activity of the plant. The present study confirmed that the methanol extract of Meyna spinosa leaves is a potential source of natural antioxidants. Copyright © 2013 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.
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Antigenotoxic and free radical scavenging activities of extracts from Moricandia arvensis.
Skandrani, I; Sghaier, M Ben; Neffati, A; Boubaker, J; Bouhlel, I; Kilani, S; Mahmoud, A; Ghedira, K; Chekir-Ghedira, L
2007-01-01
This study evaluates genotoxic and antigenotoxic effects of extracts from leaves of Moricandia arvensis, which are used in traditional cooking and medicines. Extracts showed no genotoxicity when tested with the SOS Chromotest using E. coli PQ37 and PQ35 strains, except for the total oligomers flavonoids enriched extract. Petroleum ether and methanol extracts are the most active in reducing nitrofurantoin genotoxicity, whereas methanol and total oligomers flavonoids enriched extracts showed the most important inhibitory effect of H2O2 genotoxicity. In addition, these two extracts showed important free radical scavenging activity toward the DPPH. radical, whereas the chloroform extract exhibited the highest value of TEAC against ABTS+. radical.
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Ding, Xiang; Hou, Yi-ling; Hou, Wan-ru
2012-04-01
In this study, a novel heteropolysaccharide was isolated from the fruiting bodies of Boletus speciosus Forst through DEAE-cellulose column and Sephadex G-200 column. The Boletus speciosus Forst polysaccharide (BSFP-1) had a molecular weight of 1.33×10(4) Da and was mainly composed of l-Man and d-Gal which ratios were 2:1. Structural features of Boletus speciosus Forst polysaccharide (BSFP-1) were investigated by a combination of total hydrolysis, methylation analysis, gas chromatography-mass spectrometry (GC-MS), infrared (IR) spectra and nuclear magnetic resonance (NMR) spectroscopy. The results indicated that Boletus speciosus Forst polysaccharide (BSFP-1) had a backbone of (1→4)-α-l-mannopyranose residues which branches at O-6 based on the experimental results. The branches were mainly composed of one with →1)-α-d-galactopyranose residue. The antioxidant activity of BSFP-1 was evaluated with two biochemical methods, including 1,1-diphenyl-2-picrylhydrazyl (DPPH(-)) radical scavenging, scavenging activity of 2,2'-azino-bis(3-ethylbenzthiazoline-6-suphonic acid)diammonium (ABTS(+)) radical. The results indicated that BSFP-1 showed strong antioxidant. Copyright © 2012 Elsevier B.V. All rights reserved.
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EPR Spectroscopy of Radical Ions of a 2,3-Diamino-1,4-naphthoquinone Derivative.
Tarábek, Ján; Wen, Jin; Dron, Paul I; Pospíšil, Lubomír; Michl, Josef
2018-05-18
We report the electron paramagnetic resonance spectra of the radical cation and radical anion of 1,2,2,3-tetramethyl-2,3-dihydro-1 H-naphtho[2,3- d]imidazole-4,9-dione (1) and its doubly 13 C labeled analogue 2, of interest for singlet fission. The hyperfine coupling constants are in excellent agreement with density functional theory calculations and establish the structures beyond doubt. Unlike the radical cation 1 •+ , the radical anion 1 •- and its parent 1 have pyramidalized nitrogen atoms and inequivalent methyl groups 15 and 16, in agreement with the calculations. The distinction is particularly clear with the labeled analogue 2 •- .
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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.
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Evaluation of Cassia tora Linn. against Oxidative Stress-induced DNA and Cell Membrane Damage
Kumar, R Sunil; Narasingappa, Ramesh Balenahalli; Joshi, Chandrashekar G; Girish, Talakatta K; Prasada Rao, Ummiti JS; Danagoudar, Ananda
2017-01-01
Objective: The present study aims to evaluate antioxidants and protective role of Cassia tora Linn. against oxidative stress-induced DNA and cell membrane damage. Materials and Methods: The total and profiles of flavonoids were identified and quantified through reversed-phase high-performance liquid chromatography. In vitro antioxidant activity was determined using standard antioxidant assays. The protective role of C. tora extracts against oxidative stress-induced DNA and cell membrane damage was examined by electrophoretic and scanning electron microscopic studies, respectively. Results: The total flavonoid content of CtEA was 106.8 ± 2.8 mg/g d.w.QE, CtME was 72.4 ± 1.12 mg/g d.w.QE, and CtWE was 30.4 ± 0.8 mg/g d.w.QE. The concentration of flavonoids present in CtEA in decreasing order: quercetin >kaempferol >epicatechin; in CtME: quercetin >rutin >kaempferol; whereas, in CtWE: quercetin >rutin >kaempferol. The CtEA inhibited free radical-induced red blood cell hemolysis and cell membrane morphology better than CtME as confirmed by a scanning electron micrograph. CtEA also showed better protection than CtME and CtWE against free radical-induced DNA damage as confirmed by electrophoresis. Conclusion: C. tora contains flavonoids and inhibits oxidative stress and can be used for many health benefits and pharmacotherapy. PMID:28584491
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REACTION OF PERFLUOROALKYL RADICALS WITH MOLECULAR HYDROGEN,
reactions with D2 and HD) in which R is some free radical. The discussion below is developed with those systems in mind in which R is a perfluoroalkyl ...photolysis of the appropriate perfluoroketone was used as the radical source. Recently an investigation was made of the reaction, with R = C2F5 and C3F7
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n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions.
Zhang, Siyuan; Naab, Benjamin D; Jucov, Evgheni V; Parkin, Sean; Evans, Eric G B; Millhauser, Glenn L; Timofeeva, Tatiana V; Risko, Chad; Brédas, Jean-Luc; Bao, Zhenan; Barlow, Stephen; Marder, Seth R
2015-07-20
Dimers of 2-substituted N,N'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2 , yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2 ) dissociation and of D2 -to-A electron transfer, D2 reacts with A to form D(+) and A(-) by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D(+) /0.5 D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9 V vs. FeCp2 (+/0) ) (Cp=cyclopentadienyl) due to cancelation of trends in the D(+/0) potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Jan, Shumaila; Khan, Muhammad Rashid; Rashid, Umbreen; Bokhari, Jasia
2013-10-01
This study was conducted to investigate the antioxidant potential of methanol extract and its derived fractions (hexane, ethyl acetate, butanol, and aqueous) of fruits of Monotheca buxifolia (Falc.) Dc., a locally used fruit in Pakistan. Dried powder of the fruit of M. buxifolia was extracted with methanol and the resultant was fractionated with solvents having escalating polarity; n-hexane, chloroform, ethyl acetate, n-butanol and the residual soluble aqueous fraction. Total phenolic and total flavonoid contents were estimated for the methanol and various fractions. These fractions were also subjected to various in vitro assays to estimate the scavenging activity for 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), superoxide, hydroxyl, hydrogen peroxide and reductive ability for ferric ions and phosphomolybdate assay. The n-butanol, aqueous and methanol fractions possessed high amount of phenolics and flavonoids compared with other fractions, and subsequently showed a pronounced scavenging activity on DPPH, ABTS, superoxide, hydroxyl and hydrogen peroxide radicals and had a potent reductive ability on ferric ion and phosphomolybdate assay. There was a found significant correlation between total phenolic and flavonoid contents and EC50 of DPPH, superoxide, hydrogen peroxide radical and phosphomolybdate assays, whereas a nonsignificant correlation was found with the hydroxyl radical and ABTS radical assay. M. buxifolia fruit can be used as natural antioxidant source to prevent damage associated with free radicals.
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π to σ Radical Tautomerization in One-Electron Oxidized 1-Methylcytosine and its Analogs
Adhikary, Amitava; Kumar, Anil; Bishop, Casandra T.; Wiegand, Tyler J.; Hindi, Ragda M.; Adhikary, Ananya; Sevilla, Michael D.
2015-01-01
In this work iminyl σ-radical formation in several one-electron oxidized cytosine analogs including 1-MeC, cidofovir, 2′-deoxycytidine (dCyd), and 2′-deoxycytidine 5′-monophosphate (5′-dCMP) were investigated in homogeneous aqueous (D2O or H2O) glassy solutions at low temperatures employing electron spin resonance (ESR) spectroscopy. Employing density functional theory (DFT) (DFT/B3LYP/6-31G* method), the calculated hyperfine coupling constant (HFCC) values of iminyl σ-radical agree quite well with the experimentally observed ones thus confirming its assignment. ESR and DFT studies show that the cytosine-iminyl σ-radical is a tautomer of the deprotonated cytosine π-cation radical (cytosine π-aminyl radical, C(N4-H)•). Employing 1-MeC samples at various pHs ranging ca. 8 to ca. 11, ESR studies show that the tautomeric equilibrium between C(N4-H)• and the iminyl σ-radical at low temperature is too slow to be established without added base. ESR and DFT studies agree that in the iminyl-σ radical, the unpaired spin is localized to the exocyclic nitrogen (N4) in an in-plane pure p-orbital. This gives rise to an anisotropic nitrogen hyperfine coupling (Azz = 40 G) from N4 and a near isotropic β-nitrogen coupling of 9.7 G from the cytosine ring nitrogen at N3. Iminyl σ-radical should exist in its N3-protonated form as the N3-protonated iminyl σ-radical is stabilized in solution by over 30 kcal/mol (ΔG= −32 kcal/mol) over its conjugate base, the N3-deprotonated form. This is the first observation of an isotropic β-hyperfine ring nitrogen coupling in an N-centered DNA-radical. Our theoretical calculations predict that the cytosine iminyl σ-radical can be formed in dsDNA by a radiation-induced ionization–deprotonation process that is only 10 kcal/mol above the lowest energy path. PMID:26237072
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Antioxidant Activity of Brown Soybean Ethanolic Extracts and Application to Cooked Pork Patties.
Lee, Choong-Hee; Hwang, Ko-Eun; Kim, Hyun-Wook; Song, Dong-Heon; Kim, Yong-Jae; Ham, Youn-Kyung; Choi, Yun-Sang; Jang, Sung-Jin; Jeong, Tae-Jun; Kim, Cheon-Jei
2016-01-01
The brown soybean extract (BE, extracted by distilled water, 50%, 75%, and 95% ethanol) were analyzed for their total phenol, flavonoid, anthocyanin content, and DPPH radical-scavenging activity to determine antioxidant activities. Brown soybean extract with 75% ethanol showed significantly higher DPPH radical scavenging activity, total phenol and anthocyanin content compared to the other treatments (p<0.05). Then, brown soybean extract with 75% ethanol was applied to pork patties at different concentration (0.05%, 0.1%, and 0.2%) and lipid oxidation was evaluated during 15 d of refrigerated storage. Addition of BE significantly increased redness and pH values, respectively (p<0.05). Moreover, TBARS value of pork patties decreased significantly (p<0.05) as BE concentration increased. In sensory evaluation, pork patties with 0.1% BE had significantly higher score than other treatments in flavor and overall acceptability (p<0.05). Consequently, these results indicate that 0.1% BE could be an effective natural antioxidant to inhibit lipid oxidation in pork patties.
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[Survey of cachexia in digestive system cancer patients and its impact on clinical outcomes].
Sun, Yandong; Zhang, Bo; Han, Yusong; Jiang, Yi; Zhuang, Qiulin; Gong, Yuda; Wu, Guohao
2014-10-01
To investigate cachexia in hospitalized patients with digestive system cancer and evaluate its impact on clinical outcomes. By analyzing the clinical data of 5118 hospitalized patients with digestive system cancer in Zhongshan Hospital of Fudan University from January 2012 to December 2013, cachexia was investigated and clinical outcomes between cachexia patients and non-cachexia patients was compared. The total cachexia rate of hospitalized patients with digestive system cancer was 15.7%(803/5118). The highest rate of cachexia was 34.0%(89/262) in patients with pancreatic cancer followed by gastric cancer 22.4%(261/1164), colon cancer 21.7%(146/672), and rectal cancer 20.1%(117/581). In cachexia group and non-cachexia group, the overall completion rate of radical resection was 67.1%(539/803) and 74.5%(3214/4315) respectively(P<0.05). Compared to the non-cachexia group, the cachexia group was associated with longer postoperative hospital stay [(11.5±6.2) d vs. (9.4±4.9) d, P<0.05], slower postoperative recovery of bowel function [(3.4±0.9) d vs. (3.2±0.8) d, P<0.05], longer postoperative time to intake of semifluid [(4.4±1.5) d vs. (3.9±1.1) d, P<0.05], and more postoperative complications within 28 days after radical surgery [8.9%(48/539) vs. 5.8%(186/3214), P<0.05]. After radical surgery, the ICU admission rate of the cachexia group [24.3%(131/539)] was higher than that of the non-cachexia group [20.1%(646/3214)] with significant difference(P<0.05). Compared to non-cachexia group, the reoperation rate [3.2%(17/539) vs. 1.5%(48/3214), P<0.05], ventilator support rate [8.0%(43/539)vs. 5.7%(184/3214), P<0.05] and mortality [2.4%(13/539) vs. 1.1%(35/3214), P<0.05] in the cachexia group were all significantly higher(all P<0.05). Cachexia is commen in patients with digestive system cancer. Cachexia has significant adverse effects on clinical outcomes in hospitalized patients with digestive system cancer.
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NASA Astrophysics Data System (ADS)
Hoffmann, Stanislaw K.; Goslar, Janina; Lijewski, Stefan
2012-08-01
EPR studies of Cu2+ and two free radicals formed by γ-radiation were performed for KHCO3 single crystal at room temperature. From the rotational EPR results we concluded that Cu2+ is chelated by two carbonate molecules in a square planar configuration with spin-Hamiltonian parameters g|| = 2.2349 and A|| = 18.2 mT. Free radicals were identified as neutral HOCOrad with unpaired electron localized on the carbon atom and a radical anion CO3·- with unpaired electron localized on two oxygen atoms. The hyperfine splitting of the EPR lines by an interaction with a single hydrogen atom of HOCOrad was observed with isotropic coupling constants ao = 0.31 mT. Two differently oriented radical sites were identified in the crystal unit cell. Electron spin-lattice relaxation measured by electron spin echo methods shows that both Cu2+ and free radicals relax via two-phonon Raman processes with almost the same relaxation rate. The temperature dependence of the relaxation rate 1/T1 is well described with the effective Debye temperature ΘD = 175 K obtained from a fit to the Debye-type phonon spectrum. We calculated a more realistic Debye temperature value from available elastic constant values of the crystal as ΘD = 246 K. This ΘD-value and the Debye phonon spectrum approximation give a much worse fit to the experimental results. Possible contributions from a local mode or an optical mode are considered and it is suggested that the real phonon spectrum should be used for the relaxation data interpretation. It is unusual that free radicals in KHCO3 relax similarly to the well localized Cu2+ ions, which suggests a small destruction of the host crystal lattice by the ionizing irradiation allowing well coupling between radical and lattice dynamics.
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Plasma Jet (V)UV-Radiation Impact on Biologically Relevant Liquids and Cell Suspension
NASA Astrophysics Data System (ADS)
Tresp, H.; Bussiahn, R.; Bundscherer, L.; Monden, A.; Hammer, M. U.; Masur, K.; Weltmann, K.-D.; Woedtke, Th. V.; Reuter, S.
2014-10-01
In this study the generation of radicals in plasma treated liquids has been investigated. To quantify the contribution of plasma vacuum ultraviolet (VUV) and ultraviolet (UV) radiation on the species investigated, three cases have been studied: UV of plasma jet only, UV and VUV of plasma jet combined, and the plasma effluent including all reactive components. The emitted VUV has been observed by optical emission spectroscopy and its effect on radical formation in liquids has been analyzed by electron spin resonance spectroscopy. Radicals have been determined in ultrapure water (dH2O), as well as in more complex, biorelevant solutions like phosphate buffered saline (PBS) solution, and two different cell culture media. Various compositions lead to different reactive species formation, e.g. in PBS superoxide anion and hydroxyl radicals have been detected, in cell suspension also glutathione thiyl radicals have been found. This study highlights that UV has no impact on radical generation, whereas VUV is relevant for producing radicals. VUV treatment of dH2O generates one third of the radical concentration produced by plasma-effluent treatment. It is relevant for plasma medicine because although plasma sources are operated in open air atmosphere, still VUV can lead to formation of biorelevant radicals. This work is funded by German Federal Ministry of Education a Research (BMBF) (Grant # 03Z2DN12+11).
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Sticking of HO2 on fatty acids aggregates
NASA Astrophysics Data System (ADS)
Vardanega, Delphine; Briquez, Stéphane; Duflot, Denis; Monnerville, Maurice; Toubin, Céline
2015-04-01
Models of atmospheric chemistry are widely used to perform projections of future changes in the chemical composition of the global troposphere, including changes in climate related greenhouse gases and aerosol particles. However, large uncertainties are still associated with the chemistry implemented in these models, which in turn can lead to inaccurate long-term predictions. The proposed work seeks to improve our understanding of the oxidative capacity of the atmosphere, which drives the lifetime of trace gases, and therefore atmospheric composition. Recent measurements [1] of free radicals made in forested environments characterized by low levels of nitrogen oxides (NOx = NO and NO2) indicate that current models of atmospheric chemistry tend to overestimate the concentration of peroxy radicals (HO2 and RO2). An overestimation of peroxy radicals is an important issue since these radicals are the main precursors of the hydroxyl radical (OH), the most important atmospheric oxidant during daytime. This issue could lead to a significant overestimation of the oxidative capacity of the global atmosphere since more than 86% of the Earth surface is covered by forests, oceans, and polar regions. An analysis of this dataset indicates that the missing sink could be due to an underestimation of the rates of RO2+HO2 reactions, and/or the uptake of peroxy radicals onto aerosol particles. A thorough evaluation of scientific studies published in the literature shows that there is a lack of kinetic and mechanistic data to correctly assess the contribution of these two loss pathways of peroxy radicals in low NOx environments. Classical molecular dynamics simulations, using the Gromacs package [2], are performed to study the interaction of HO2 with organic (carboxylic acid) aerosols. The effect of the presence of water molecules on the surface are also be investigated. These calculations provide theoretical values for observable quantities such as uptake and mass accommodation coefficients. Acknowledgments: this research has been supported by the CaPPA project (Chemical and Physical Properties of the Atmosphere), funded by the French National Research Agency (ANR) through the PIA (Programme d'Investissement d'Avenir) under contract ANR-10-LABX-005. References [1] D. Stone, L. K. Whalley and D. E. Heard, Chem. Soc. Rev., 41, 6348 (2012). [2] D. van der Spoel, E. Lindahl, B. Hess, A. R. van Buuren, E. Apol, P. J. Meulenho, D.P. Tieleman, A. L. T. M. Sijbers, K. A. Feenstra, R. van Drunen, and H. J. C. Berendsen, GROMACS User Manual version 5.0.2, 2014, www.gromacs.org.
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NASA Astrophysics Data System (ADS)
Edwards, P. M.; Young, C. J.; Aikin, K.; deGouw, J. A.; Dubé, W. P.; Geiger, F.; Gilman, J. B.; Helmig, D.; Holloway, J. S.; Kercher, J.; Lerner, B.; Martin, R.; McLaren, R.; Parrish, D. D.; Peischl, J.; Roberts, J. M.; Ryerson, T. B.; Thornton, J.; Warneke, C.; Williams, E. J.; Brown, S. S.
2013-03-01
The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3) concentrations above levels harmful to human health for multiple days during the winters of 2009-2010 and 2010-2011. These wintertime O3 pollution episodes occur during cold, stable periods when the ground is snowcovered, and have been linked to emissions from the oil and gas extraction process. The Uintah Basin Winter Ozone Study (UBWOS) was a field intensive in early 2012, whose goal was to address current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. Although elevated O3 concentrations were not observed during the winter of 2011-2012, the comprehensive set of observations tests of our understanding of O3 photochemistry in this unusual emissions environment. A box model, constrained to the observations and using the explicit Master Chemical Mechanism (MCM) V3.2 chemistry scheme, has been used to investigate the sensitivities of O3 production during UBWOS 2012. Simulations identify the O3 production photochemistry to be highly radical limited. Production of OH from O3 photolysis (through reaction of O(1D) with water vapor) contributed only 170 pptv day-1, 8% of the total primary radical source on average. Other radical sources, including the photolysis of formaldehyde (HCHO, 52%), nitrous acid (HONO, 26%), and nitryl chloride (ClNO2, 13%) were larger. O3 production was also found to be highly sensitive to aromatic volatile organic compound (VOC) concentrations, due to radical amplification reactions in the oxidation scheme of these species. Radical production was shown to be small in comparison to the emissions of nitrogen oxides (NOx), such that NOx acted as the primary radical sink. Consequently, the system was highly VOC sensitive, despite the much larger mixing ratio of total non-methane hydrocarbons (230 ppbv (2080 ppbC), 6 week average) relative to NOx (5.6 ppbv average). However, the importance of radical sources which are themselves derived from NOx emissions and chemistry, such as ClNO2 and HONO, make the response of the system to changes in NOx emissions uncertain. These box model simulations provide useful insight into the chemistry controlling winter O3 production in regions of oil and gas extraction.
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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.
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Joffe, Avrum; Mock, Steven; Yun, Byeong Hwa; Kolbanovskiy, Alexander; Geacintov, Nicholas E; Shafirovich, Vladimir
2003-08-01
A simple photochemical approach is described for synthesizing site specific, stable 5-guanidino-4-nitroimidazole (NIm) adducts in single- and double-stranded oligodeoxynucleotides containing single and multiple guanine residues. The DNA sequences employed, 5'-d(ACC CG(1)C G(2)TC CG(3)C G(4)CC) and 5'-d(ACC CG(1)C G(2)TC C), were a portion of exon 5 of the p53 tumor suppressor gene, including the codons 157 (G(2)) and 158 (G(3)) mutation hot spots in the former sequence with four Gs and the codon 157 (G(2)) mutation hot spot in the latter sequence with two Gs. The nitration of oligodeoxynucleotides was initiated by the selective photodissociation of persulfate anions to sulfate radicals induced by UV laser pulses (308 nm). In aqueous solutions, of bicarbonate and nitrite anions, the sulfate radicals generate carbonate anion radicals and nitrogen dioxide radicals by one electron oxidation of the respective anions. The guanine residue in the oligodeoxynucleotide is oxidized by the carbonate anion radical to form the neutral guanine radical. While the nitrogen dioxide radicals do not react with any of the intact DNA bases, they readily combine with the guanine radicals at either the C8 or the C5 positions. The C8 addition generates the well-known 8-nitroguanine (8-nitro-G) lesions, whereas the C5 attack produces unstable adducts, which rapidly decompose to NIm lesions. The maximum yields of the nitro products (NIm + 8-nitro-G) were typically in the range of 20-40%, depending on the number of guanine residues in the sequence. The ratio of the NIm to 8-nitro-G lesions gradually decreases from 3.4 in the model compound, 2',3',5'-tri-O-acetylguanosine, to 2.1-2.6 in the single-stranded oligodeoxynucleotides and to 0.8-1.1 in the duplexes. The adduct of the 5'-d(ACC CG(1)C G(2)TC C) oligodeoxynucleotide containing the NIm lesion in codon 157 (G(2)) was isolated in HPLC-pure form. The integrity of this adduct was established by a detailed analysis of exonuclease digestion ladders by matrix-assisted laser desorption ionization with time-of-flight detection MS techniques.
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Excited states and electrochromism of radical cation of the carotenoid astaxanthin
NASA Astrophysics Data System (ADS)
Krawczyk, Stanisław
1998-09-01
Radical cations of the carotenoid astaxanthin were generated by chemical oxidation with Fe(Cl) 3, and their absorption and electroabsorption (Stark) spectra at temperatures about 150 K were recorded in the spectral range from 5900 to 26000 cm -1 (380 to 1700 nm), covering two absorptive electronic transitions from D 0 (ground) to D 1 and D 2 excited states. The changes in static polarizability are negative and equal -40±10 A 3 for D 0→D 1 and -105±15 A 3 for D 0→D 2, pointing that dominant contribution to polarizabilities results from the coupling of D 1 and D 2 with the ground state. An approximate localization of the next excited state with ground-state parity is estimated based on arguments from perturbation theory.
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NASA Astrophysics Data System (ADS)
Edwards, P. M.; Young, C. J.; Aikin, K.; deGouw, J.; Dubé, W. P.; Geiger, F.; Gilman, J.; Helmig, D.; Holloway, J. S.; Kercher, J.; Lerner, B.; Martin, R.; McLaren, R.; Parrish, D. D.; Peischl, J.; Roberts, J. M.; Ryerson, T. B.; Thornton, J.; Warneke, C.; Williams, E. J.; Brown, S. S.
2013-09-01
The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3) concentrations above levels harmful to human health for multiple days during the winters of 2009-2010 and 2010-2011. These wintertime O3 pollution episodes occur during cold, stable periods when the ground is snow-covered, and have been linked to emissions from the oil and gas extraction process. The Uintah Basin Winter Ozone Study (UBWOS) was a field intensive in early 2012, whose goal was to address current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. Although elevated O3 concentrations were not observed during the winter of 2011-2012, the comprehensive set of observations tests our understanding of O3 photochemistry in this unusual emissions environment. A box model, constrained to the observations and using the near-explicit Master Chemical Mechanism (MCM) v3.2 chemistry scheme, has been used to investigate the sensitivities of O3 production during UBWOS 2012. Simulations identify the O3 production photochemistry to be highly radical limited (with a radical production rate significantly smaller than the NOx emission rate). Production of OH from O3 photolysis (through reaction of O(1D) with water vapor) contributed only 170 pptv day-1, 8% of the total primary radical source on average (primary radicals being those produced from non-radical precursors). Other radical sources, including the photolysis of formaldehyde (HCHO, 52%), nitrous acid (HONO, 26%), and nitryl chloride (ClNO2, 13%) were larger. O3 production was also found to be highly sensitive to aromatic volatile organic compound (VOC) concentrations, due to radical amplification reactions in the oxidation scheme of these species. Radical production was shown to be small in comparison to the emissions of nitrogen oxides (NOx), such that NOx acted as the primary radical sink. Consequently, the system was highly VOC sensitive, despite the much larger mixing ratio of total non-methane hydrocarbons (230 ppbv (2080 ppbC), 6 week average) relative to NOx (5.6 ppbv average). However, the importance of radical sources which are themselves derived from NOx emissions and chemistry, such as ClNO2 and HONO, make the response of the system to changes in NOx emissions uncertain. Model simulations attempting to reproduce conditions expected during snow-covered cold-pool conditions show a significant increase in O3 production, although calculated concentrations do not achieve the highest seen during the 2010-2011 O3 pollution events in the Uintah Basin. These box model simulations provide useful insight into the chemistry controlling winter O3 production in regions of oil and gas extraction.
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NASA Astrophysics Data System (ADS)
Andersson, K. Kristoffer; Barra, Anne-Laure
2002-04-01
Low temperature electron paramagnetic resonance (EPR) spectroscopy with frequencies between 95 and 345 GHz and magnetic fields up to 12 T have been used to study radicals and metal sites in proteins and small inorganic model complexes. We have studied radicals, Fe, Cu and Mn containing proteins. For S=1/2 systems, the high frequency method can resolve the g-value anisotropy. It was used in mouse ribonucleotide reductase (RNR) to show the presence of a hydrogen bond to the tyrosyl radical oxygen. At 285 GHz the type 2 Cu(II) signal in the complex enzyme laccase is clearly resolved from the Hg(II) containing laccase peroxide adduct. For simple metal sites, the systems over S=1/2 can be described by the spin Hamiltonian: HS= BgS+ D[ Sz2- S( S+1)/3+ E/ D ( Sx2- Sy2)]. From the high frequency EPR the D-value can be determined directly by, (I) shifts of geff for half-integer spin systems with large D-values as observed at 345 GHz on an Fe(II)NOEDTA complex, which is best described as S=3/2 system with D=11.5 cm -1, E=0.1 cm -1 and gx= gy= gz=2.0; (II) measuring the outermost signal, for systems with small D values, distant of (2 S-1)*∣ D∣ from the center of the spectrum as observed in S=5/2 Fe(III)EDTA. In Mn(II) substituted mouse RNR R2 protein the weakly interacting Mn(II) at X-band could be observed as decoupled Mn(II) at 285 GHz.
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Esterified dendritic TAM radicals with very high stability and enhanced oxygen sensitivity.
Song, Yuguang; Liu, Yangping; Hemann, Craig; Villamena, Frederick A; Zweier, Jay L
2013-02-15
In this work, we have developed a new class of dendritic TAM radicals (TG, TdG, and dTdG) through a convergent method based on the TAM core CT-03 or its deuterated analogue dCT-03 and trifurcated Newkome-type monomer. Among these radicals, dTdG exhibits the best EPR properties with sharpest EPR singlet and highest O(2) sensitivity due to deuteration of both the ester linker groups and the TAM core CT-03. Like the previous dendritic TAM radicals, these new compounds also show extremely high stability toward various reactive species owing to the dendritic encapsulation. The highly charged nature of these molecules resulting from nine carboxylate groups prevents concentration-dependent EPR line broadening at physiological pH. Furthermore, we demonstrate that these TAM radicals can be easily derivatized (e.g., PEGylation) at the nine carboxylate groups and the resulting PEGylated analogue dTdG-PEG completely inhibits the albumin binding, thereby enhancing suitability for in vivo applications. These new dendritic TAM radicals show great potential for in vivo EPR oximetric applications and provide insights on approaches to develop improved and targeted EPR oximetric probes for biomedical applications.
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Search for Excess Dimuon Production in the Radial Region (1.6 < r < 10) cm at the D0 Experiment
DOE Office of Scientific and Technical Information (OSTI.GOV)
Williams, Mark; Collaboration, for the D0
2009-06-01
We report on a study of dimuon events produced in p{bar p} collisions at {radical}s = 1.96 TeV, using 0.9 fb{sup -1} of data recorded by the D0 experiment during 2008. Using information from the inner-layer silicon tracking detector, we observe 712 {+-} 462 {+-} 942 events in which one or both muons are produced in the range 1.6 < r {approx}< 10 cm, which is expressed as a fraction (0.40 {+-} 0.26 {+-} 0.53)% of the total dimuon sample. We therefore see no significant excess of muons produced a few centimeters away from the interaction point.
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Generation of hydroxyl radicals by urban suspended particulate air matter. The role of iron ions
NASA Astrophysics Data System (ADS)
Valavanidis, Athanasios; Salika, Anastasia; Theodoropoulou, Anna
Recent epidemiologic studies showed statistical associations between particulate air pollution in urban areas and increased morbidity and mortality, even at levels well within current national air quality standards. Inhalable particulate matter (PM 10) can penetrate into the lower airways where they can cause acute and chronic lung injury by generating toxic oxygen free radicals. We tested inhalable total suspended particulates (TSP) from the Athens area, diesel and gasoline exhaust particles (DEP and GED), and urban street dusts, by Electron Paramagnetic Resonance (EPR). All particulates can generate hydroxyl radicals (HO ṡ), in aqueous buffered solutions, in the presence of hydrogen peroxide. Results showed that oxidant generating activity is related with soluble iron ions. Leaching studies showed that urban particulate matter can release large amounts of Fe 3+ and lesser amounts of Fe 2+, as it was shown from other studies. Direct evidence of HO ṡ was confirmed by spin trapping with DMPO and measurement of DMPO-OH adduct by EPR. Evidence was supported with the use of chelator (EDTA), which increases the EPR signal, and the inhibition of the radical generating activity by desferrioxamine or/and antioxidants ( D-mannitol, sodium benzoate).
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Adeleye, Abdulwasiu O; Ajiboye, Taofeek O; Iliasu, Ganiyat A; Abdussalam, Folakemi A; Balogun, Abdulazeez; Ojewuyi, Oluwayemisi B; Yakubu, Musa T
2014-08-01
This study investigated the effect of Dialium guineense pulp phenolic extract on aflatoxin B1 (AFB1)-induced oxidative imbalance in rat liver. Reactive oxygen species (ROS) scavenging potentials of free and bound phenolic extract of D. guineense (0.2-1.0 mg/mL) were investigated in vitro using 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical, superoxide ion (O2(-)), hydrogen peroxide (H2O2), hydroxyl radical, and ferric ion reducing system. In the in vivo study, 35 animals were randomized into seven groups of five rats each. Free and bound phenolic extract (1 mg/mL) produced 66.42% and 93.08%, 57.1% and 86.0%, 62.0% and 90.05%, and 60.11% and 72.37% scavenging effect on DPPH radical, O2(-) radical, H2O2, and hydroxyl radical, while ferric ion was significantly reduced. An AFB1-mediated decrease in the activities of ROS detoxifying enzymes (superoxide dismutase, catalase, glutathione peroxidase, glutathione reductase, and glucose 6 phosphate dehydrogenase) was significantly attenuated (P<.05). AFB1-mediated elevation in the concentrations of oxidative stress biomarkers; malondialdehyde, conjugated dienes, lipid hydroperoxides, protein carbonyl, and percentage DNA fragmentation were significantly lowered by D. guineense phenolic extract (P<.05). Overall, the in vitro and in vivo effects suggest that D. guineense phenolic extract elicited ROS scavenging and detoxification potentials, as well as the capability of preventing lipid peroxidation, protein oxidation, and DNA fragmentation.
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Total free radical species and oxidation equivalent in polluted air.
Wang, Guoying; Jia, Shiming; Niu, Xiuli; Tian, Haoqi; Liu, Yanrong; Chen, Xuefu; Li, Lan; Zhang, Yuanhang; Shi, Gaofeng
2017-12-31
Free radicals are the most important chemical intermediate or agent of the atmosphere and influenced by thousands of reactants. The free radicals determine the oxidizing power of the polluted air. Various gases present in smog or haze are oxidants and induce organ and cellular damage via generation of free radical species. At present, however, the high variability of total free radicals in polluted air has prevented the detection of possible trends or distributions in the concentration of those species. The total free radicals are a kind of contaminants with colorless, tasteless characteristics, and almost imperceptible by human body. Here we present total free radical detection and distribution characteristics, and analyze the effects of total free radicals in polluted air on human health. We find that the total free radical values can be described by not only a linear dependence on ozone at higher temperature period, but also a linear delay dependence on particulate matter at lower temperature period throughout the measurement period. The total free radical species distribution is decrease from west to east in Lanzhou, which closely related to the distribution of the air pollutants. The total free radical oxidation capacity in polluted air roughly matches the effects of tobacco smoke produced by the incomplete combustion of a controlled amount of tobacco in a smoke chamber. A relatively unsophisticated chromatographic fingerprint similarity is used for indicating preliminarily the effect of total free radicals in polluted air on human health. Copyright © 2017 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kasiviswanathan, Shiva; Rudelson, Mark; Smith, Adam
2009-01-01
Contingency tables are the method of choice of government agencies for releasing statistical summaries of categorical data. In this paper, we consider lower bounds on how much distortion (noise) is necessary in these tables to provide privacy guarantees when the data being summarized is sensitive. We extend a line of recent work on lower bounds on noise for private data analysis [10, 13. 14, 15] to a natural and important class of functionalities. Our investigation also leads to new results on the spectra of random matrices with correlated rows. Consider a database D consisting of n rows (one per individual),more » each row comprising d binary attributes. For any subset of T attributes of size |T| = k, the marginal table for T has 2{sup k} entries; each entry counts how many times in the database a particular setting of these attributes occurs. Imagine an agency that wishes to release all (d/k) contingency tables for a given database. For constant k, previous work showed that distortion {tilde {Omicron}}(min{l_brace}n, (n{sup 2}d){sup 1/3}, {radical}d{sup k}{r_brace}) is sufficient for satisfying differential privacy, a rigorous definition of privacy that has received extensive recent study. Our main contributions are: (1) For {epsilon}- and ({epsilon}, {delta})-differential privacy (with {epsilon} constant and {delta} = 1/poly(n)), we give a lower bound of {tilde {Omega}}(min{l_brace}{radical}n, {radical}d{sup k}{r_brace}), which is tight for n = {tilde {Omega}}(d{sup k}). Moreover, for a natural and popular class of mechanisms based on additive noise, our bound can be strengthened to {Omega}({radical}d{sup k}), which is tight for all n. Our bounds extend even to non-constant k, losing roughly a factor of {radical}2{sup k} compared to the best known upper bounds for large n. (2) We give efficient polynomial time attacks which allow an adversary to reconstruct sensitive infonnation given insufficiently perturbed contingency table releases. For constant k, we obtain a lower bound of {tilde {Omega}}(min{l_brace}{radical}n, {radical}d{sup k}{r_brace}) that applies to a large class of privacy notions, including K-anonymity (along with its variants) and differential privacy. In contrast to our bounds for differential privacy, this bound (a) is shown only for constant k, but (b) is tight for all values of n when k is constant. (3) Our reconstruction-based attacks require a new lower bound on the least singular values of random matrices with correlated rows. For a constant k, consider a matrix M with (d/k) rows which are formed by taking all possible k-way entry-wise products of an underlying set of d random vectors. We show that even for nearly square matrices with d{sup k}/log d columns, the least singular value is {Omega}({radical}d{sup k}) with high probability - asymptotically, the same bound as one gets for a matrix with independent rows. The proof requires several new ideas for analyzing random matrices and could be of independent interest.« less
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The products of the gas-phase reactions of the OH radical with n-butyl methyl ether and 2-isopropoxyethanol in the presence of NO have been investigated at 298 ? 2 K and 740 Torr total pressure of air by gas chromatography and in situ atmospheric pressure ionization...
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Vinholes, Juliana; Vizzotto, Márcia
2017-01-01
Background: Camellia sinensis, the most consumed and popular beverages worldwide, and Eugenia uniflora, a Brazilian native species, have been already confirmed to have beneficial effects in the treatment of diabetes mellitus. However, their potential acting together against an enzyme linked to this pathology has never been exploited. Objective: The aim of this study was to evaluate the inhibitory properties of individual and combined ethanolic extracts of the leaves of C. sinensis and E. uniflora over alpha-glucosidase, a key digestive enzyme used on the Type 2 diabetes mellitus (T2DM) control. In addition, their inhibitory activity against 2,2-diphenyl-1-picrylhydrazyl radical (DPPH•) and peroxyl radicals was also assayed. Materials and Methods: Enzyme inhibition and antioxidant potential were assessed based on in vitro assays. Total phenolic compounds, carotenoids, and chlorophylls A and B were achieved using spectrophotometric methods. Results: E. uniflora was almost 40 times more active on alpha-glucosidase than C. sinensis and combined extracts showed a significant synergistic effect with an obtained IC50 value almost 5 times lower than the theoretical value. C. sinensis extract was twice more active than E. uniflora concerning DPPH•, in contrast, E. uniflora was almost 10 times more effective than C. sinensis on inhibition of peroxyl radicals with a significant synergistic effect for combined extracts. The extracts activities may be related with their phytochemicals, mainly phenolic compounds, and chlorophylls. Conclusion: Combined C. sinensis and E. uniflora ethanolic extracts showed synergistic effect against alpha-glucosidase and lipid peroxidation. These herbal combinations can be used to control postprandial hyperglycemia and can also provide antioxidant defenses to patients with T2DM. SUMMARY Alfa-glucosidase and antioxidant Interaction between Camellia sinensis L. Kuntze and Eugenia uniflora L. ethanolic extracts was investigated.Extracts showed synergistic effect over alpha-glucosidase and peroxyl radicals.Total phenolic, carotenoids and chlorophylls A and B can be responsible by the observed activities.Extracts could be used as alternative to control postprandial hyperglycemia.Extracts could increase antioxidant defenses to patients with T2DM. Abbreviations Used: T2DM: Type 2 diabetes mellitus; DPPH: 2,2-diphenyl-1-picrylhydrazyl radical; PNPG: 4-Nitrophenyl β-D-glucuronide; LOO: Lipid peroxidation; SEM: Standard error of the mean; CAE: Chlorogenic acid equivalent PMID:28250662
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Sjöberg, B M; Gräslund, A; Eckstein, F
1983-07-10
The B2 subunit of ribonucleotide reductase from Escherichia coli contains a tyrosine radical which is essential for enzyme activity. In the reaction between ribonucleotide reductase and the substrate analogue 2'-azido-2'-deoxycytidine 5'-diphosphate a new transient radical is formed. The EPR characteristics of this new radical species are consistent with a localization of the unpaired electron at the sugar moiety of the nucleotide. The radical shows hyperfine couplings to a hydrogen and a nitrogen nucleus, the latter probably being part of the azide substituent. The formation of the nucleotide radical in this suicidal reaction is concomitant with the decay of the tyrosine radical of the B2 subunit. Kinetic data argue for a first (pseudosecond) order decay of the B2 radical via generation of the nucleotide radical followed by a slower first order decay of the nucleotide radical. End products in the reaction are cytosine and radical-free protein B2. In the reaction between bacteriophage T4 ribonucleotide reductase and 2'-azido-2'-deoxycytidine 5'-diphosphate an identical nucleotide radical is formed. The present results are consistent with the hypothesis that the appearance and structure of the transient radical mimic stages in the normal reaction pathway of ribonucleotide reductase, postulated to proceed via 3'-hydrogen abstraction and cation radical formation of the substrate nucleotide (Stubbe, J., and Ackles, D. (1980) J. Biol. Chem. 255, 8027-8030). The nucleotide radical described here might be equivalent to such a cation radical intermediate.
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Milhøj, Birgitte O; Sauer, Stephan P A
2015-06-18
The accessibility of all possible reaction paths for the reaction between the nucleobase adenine and the (•)OH radical is investigated through quantum chemical calculations of barrier heights and rate constants at the ωB97X-D/6-311++G(2df,2pd) level with Eckart tunneling corrections. First the computational method is validated by considering the hydrogen abstraction from the heterocyclic N9 nitrogen in adenine as a test system. Geometries for all molecules in the reaction are optimized with four different DFT exchange-correlation functionals (B3LYP, BHandHLYP, M06-2X, and ωB97X-D), in combination with Pople and Dunning basis sets, all of which have been employed in similar investigations in the literature. Improved energies are obtained through single point calculations with CCSD(T) and the same basis sets, and reaction rate constants are calculated for all methods both without tunneling corrections and with the Wigner, Bell, and Eckart corrections. In comparison to CCSD(T)//BHandHLYP/aug-cc-pVTZ reference results, the ωB97X-D/6-311++G(2df,2pd) method combined with Eckart tunneling corrections provides a sensible compromise between accuracy and time. Using this method, all subreactions of the reaction between adenine and the (•)OH radical are investigated. The total rate constants for hydrogen abstraction and addition for adenine are predicted with this method to be 1.06 × 10(-12) and 1.10 × 10(-12) cm(3) molecules(-1) s(-1), respectively. Abstractions of H61 and H62 contribute the most, while only addition to the C8 carbon is found to be of any significance, in contrast to previous claims that addition is the dominant reaction pathway. The overall rate constant for the complete reaction is found to be 2.17 × 10(-12) cm(3) molecules(-1) s(-1), which agrees exceptionally well with experimental results.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Inbar, S.; Linschitz, H.; Cohen, S.G.
Nanosecond flash photolysis, steady irradiation, and deuterium substitution studies have been carried out on solutions of benzophenone with added reductants. Quantum yields (phi/sub ketyl/) for reduction in benzene of benzophenone triplet to ketyl radical, based on phi = 2 for benzhydrol (I), were approx. 1 for cyclohexane (II), tert-butylamine (III), 2-aminobutane (IV), cyclohexylamine (V), di-n-propylamine (VI), and triethylamine (VII), approx. 0.7 for 1,4-diazabicyclo(2.2.2)octane (VIII), and approx. 0 for tert-butyl alcohol (IX). Thus, quenching, without radical formation by H abstraction from N and/or ..cap alpha..-C, does not occur with common aliphatic amines but does with Dabco (VIII). The latter quenching ismore » markedly increased by small additions of acetonitrile; the flash spectrum from this compound indicates formation of a triplet amine CT complex or radical ion pair. Triplet-reductant interaction rate constants, k/sur ir/, are high for the amines (approx. 10/sup 8/-10/sup 9/ M/sup -1/ s/sup -1/) but also show significant deuterium kinetic isotope effects: 1.9 with III-N-d/sub 2/; 1.4 with IV-N-d/sub 2/; 1.2-1.3 with IV-..cap alpha..-C-d. It is proposed that k/sub ir/ measures H atom abstraction, favored in the transition state by an initial charge-transfer interaction. Overall steady irradiation quantum yields of reduction by amines, phi/sub Red/, are much lower than phi/sub ketyl/. This is attributed to disproportionationreactions of ketyl and alkylaminyl radicals for primary and secondary amines, and, possibly, aminoalkyl radicals for tertiary amines. In the case of tert-butylamine, the rate constant for disproportionation is obtained from the decay kinetics of ketyl radical and leads to phi/sub Red/ in agreement with that directly measured.« less
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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.
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NASA Astrophysics Data System (ADS)
Kermani, Majid; Mohammadi, Farzad; Kakavandi, Babak; Esrafili, Ali; Rostamifasih, Zeinab
2018-06-01
Herein, a sulfate radical (SO4rad -)-based oxidation process was utilized for simultaneous degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) herbicides using mesoporous hematite-based natural semi-conductor minerals (HM-NSMs) as efficient activators of persulfate (PS). The features of the catalyst were characterized using field emission scanning electron microscopy (FESEM); Brunauer, Emmett and Teller (BET) analysis; X-ray diffraction (XRD); and energy-dispersive X-ray spectroscopy (EDS). The effect of some operational parameters, including solution pH, catalyst loading, PS dosage and temperature, on the performance system of PS/HM-NSMs was examined. A plausible oxidation mechanism for degradation of both pollutants was also proposed. Increasing the removal efficiency of herbicides follows the order of PS/HM-NSM > HM-NSM > PS. In all experiments, the 2,4-D removal rates were slightly lower than those for MCPA, indicating that 2,4-D has a more recalcitrant nature than MCPA. Under optimized conditions, degradation rates of 68.1% and 74.5% were achieved for 2,4-D and MCPA, respectively, during a 120-min reaction. HM-NSM displays a highly synergistic effect on the degradation of herbicides in the presence of PS. The trapping experiments demonstrated that both OHrad and SO4rad - radicals contribute significantly during the degradation of 2,4-D and MCPA and that sulfate radicals were the dominant species. A mineralization degree of 36% was obtained under optimum conditions. In conclusion, the coupling of PS and HM-NSM is a promising and effective technique to degrade organic matter for the treatment of herbicide-contaminated waters and wastewaters under real conditions.
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Yang, Jun; Ou, Boxin; Wise, Mitchell L; Chu, YiFang
2014-10-01
To better understand mechanisms underlying the health benefits of oats, the free radical scavenging capacities of oat avenanthramides 2c, 2f, and 2p and their ability to inhibit NF-κB activation were evaluated. The antioxidant capacities of 2c, 2f, and 2p against peroxyl radicals, hydroxyl radicals, superoxide anion, singlet oxygen, and peroxynitrite were determined by using ORAC, HORAC, SORAC, SOAC, and NORAC assays, respectively. The total antioxidant capacity of 2c was approximately 1.5-fold those of 2f and 2p. Total antioxidant capacity was primarily attributable to SORAC and ORAC for 2c (>77%, p<0.05), and to ORAC and SOAC for 2f. ORAC accounted for approximately 32% of total antioxidant capacity in 2p. EC50 values for inhibiting TNF-α-induced NF-κB activation in C2C12 cells were 64.3, 29.3, and 9.10 μM for 2c, 2f, and 2p, respectively. Differences in antioxidant capacities and ability to inhibit NF-κB among the avenanthramides could be ascribed to structural variations. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Piccolella, Simona; Fiorentino, Antonio; Pacifico, Severina; D'Abrosca, Brigida; Uzzo, Piera; Monaco, Pietro
2008-03-26
Many edible plant metabolites are known to be useful as cellular antioxidants. In the search for antioxidative chemicals from native fruits of the Campania region of Italy, Prunus cerasus L., an acidic cherry widely used for culinary purposes, has been studied. Fruit crude extracts (MeOH, EtOAc, and hexane) were submitted to an antioxidative screening using specific assay media characterized from the presence of highly reactive radical species (DPPH*, ABTS*+, O2*-, NO) or lipoperoxidation markers. The reducing power of the samples was also determined. It was observed that the most polar extracts in MeOH and EtOAc were able to exercise a massive and dose-increasing antioxidative capacity. The peculiar efficacy of the same extracts was revealed by investigating their protein and deoxyribose oxidation capacity. A preliminary analysis of total phenol, flavonoid, and anthocyanin contents together with biological screening data put the basis on P. cerasus fruit phytochemical investigation of methanolic extract. Twenty secondary metabolites were isolated and characterized by spectroscopic (especially 1D and 2D NMR) and spectrometric techniques. 1-(4-Hydroxyphenyl)-1,2-ethanediol-1,2-bis-1-O-beta-D-glucopyranoside (3), (4-hydroxy-3-methoxyphenyl)methanol-1-O-beta-D-gentiobioside (4), epicatechin-3-malate (14), and epicatechin-3-(1''-methyl)malate (15) were isolated for the first time. All of the compounds were evaluated for their radical scavenging activity on DPPH*, O2*-, and NO. Flavonoids and quinic acid derivatives were found to be the more antioxidative substances.
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The reaction of peroxy radicals with OH: rate constants and HO2 yields
NASA Astrophysics Data System (ADS)
Fittschen, C. M.; Assaf, E.; Schoemaecker, C.; Vereecken, L.
2017-12-01
Peroxy radicals, RO2, are key species in the atmosphere. They are formed from a reaction of OH radicals with hydrocarbon: RH + OH + O2 → RO2 + H2O In polluted environments, RO2 radicals react predominantly with NO, leading to formation of NO2 and eventually through photolysis of NO2 to formation of O3. At low NOx concentrations such as in the marine boundary layer or the background troposphere, the lifetime of RO2 radicals increases and other reaction pathways become competitive. Atmospheric chemistry models have considered until recently only the self- and cross reaction with other RO2 radicals or with HO2 radicals as the major fate for RO2 radicals under low NOx conditions. Recently, the rate constants for the reaction of peroxy radicals with OH radicals RO2 + OH → products has been measured for CH3O2 [1, 2] and C2H5O2 [3] and it was shown to become competitive to other sinks [4]. However, in order to evaluate the impact of this so far neglected sink for peroxy radicals on the composition of remote atmospheres, the reaction products must be known. A recently improved experimental set-up combining laser photolysis with two simultaneous cw-CRDS detections in the near IR allowing for a time resolved, absolute quantification of OH and RO2 radicals has been used for a further investigation of this class of reactions. High-repetition rate LIF is used for determining relative OH profiles. For CH3O2 radicals, HO2 has been determined as major product recently [5]. Currently, we study the next larger perxoy, C2H5O2, using different radical precursors (C2H5I, (COCl)2/C2H6, XeF2/C2H6) and also deuterated C2D5I in order to elucidate the product yield. Preliminary results show a much lower HO2 yield for C2H5O2 compared to CH3O2. The most recent results will be presented at the conference. [1] A. Bossolasco, E. Faragó, C. Schoemaecker, and C. Fittschen, CPL, 593, 7, (2014). [2] E. Assaf, B. Song, A. Tomas, C. Schoemaecker, C. Fittschen, JPC A, 120, 8923 (2016) [3] Eszter Faragó, Coralie Schoemaecker, Bela Viskolcz, and Christa Fittschen, CPL, 619, 196, (2015). [4] Christa Fittschen, Lisa Whalley, and Dwayne Heard, EST, 118, 7700, (2014). [5] E. Assaf, L. Sheps, L. Whalley, D. Heard, A. Tomas, C. Schoemaecker, C. Fittschen, EST, 51, 2170 (2017)
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Catalytic and Thermal 1,2-Rearrangement of (α-Mercaptobenzyl)trimethylsilane
NASA Astrophysics Data System (ADS)
Zhang, Jie; Cui, Mengzhong; Feng, Shengyu; Sun, Xiaomin; Feng, Dacheng
2009-09-01
The mechanisms of catalytic and thermal 1,2-rearrangement of (α-mercaptobenzyl)trimethylsilane were studied by using density functional theory (DFT) at the MP2/6-31+G(d,p)//B3LYP/6-31G(d) levels. The results show that (α-mercaptobenzyl)trimethylsilane rearranges to (benzylthio)trimethylsilane through a trimethylsilyl group migration from C to S atom via a transition state of pentacoordinate Si atom with or without radical initiators. The low reaction activation energy (15.1 kcal/mol) is responsible for the fast rearrangement in the presence of radical initiators. Both radical and nonradical thermal rearrangement mechanisms were suggested, and the radical mechanism dominates through its self-catalyzing. These results are consistent with the experiment results. The activation energy (ΔHact = 15.1 kcal/mol) for the rate-determining step within the self-catalytic cycle is low enough to make (trimethylsilylbenzyl)thiyl radical be a reasonable catalyst for the thermal rearrangement. The catalytic and thermal 1,2-rearrangement mechanisms of (α-mercaptobenzyl)trimethylsilane, especially the self-catalytic radical mechanism, were revealed for the first time. The comparison of the rearrangement mechanisms between (α-mercaptobenzyl)trimethylsilane and silylmethanethiol discloses the factors in determining the reaction mechanism of such kinds of mercaptoalkyl-functionalized organosilanes. The phenyl group is found to be favorable for the radical rearrangement, thus making (α-mercaptobenzyl)trimethylsilane instable.
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OH Radical Reactions with Nitroimidazole and Nitrotriazole Derivatives
NASA Astrophysics Data System (ADS)
Gümüş, Selçuk
2012-04-01
The reactions between hydroxyl radical and 5-nitro-1H-imidazole (A), 2-nitro-1H-imidazole (B), and 3-nitro-4H-1,2,4-triazole (C) were theoretically investigated using B3LYP/6-31G(d,p) level of theory. The OH radical additions to double bonds were explored in bulk solvent (water). The data presented show that the barriers to reaction were very low, 3-7 kcal/mol, indicating fast reactions. Thermodynamically, OH addition to position 2 of structure A leads to the most stable radical product. The main geometrical parameters are reported for reactants, transition states, and radical products together with some energetic data of the nitro-imidazolone-type final compounds.
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Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J
2014-12-26
We have performed a systematic, theoretical chemical kinetic investigation of H atom abstraction by Ḣ atoms and ȮH, HȮ2, and ĊH3 radicals from aldehydes (methanal, ethanal, propanal, and isobutanal) and acids (methanoic acid, ethanoic acid, propanoic acid, and isobutanoic acid). The geometry optimizations and frequencies of all of the species in the reaction mechanisms of the title reactions were calculated using the MP2 method and the 6-311G(d,p) basis set. The one-dimensional hindered rotor treatment for reactants and transition states and the intrinsic reaction coordinate calculations were also determined at the MP2/6-311G(d,p) level of theory. For the reactions of methanal and methanoic acid with Ḣ atoms and ȮH, HȮ2, and ĊH3 radicals, the calculated relative electronic energies were obtained with the CCSD(T)/cc-pVXZ (where X = D, T, and Q) method and were extrapolated to the complete basis set limit. The electronic energies obtained with the CCSD(T)/cc-pVTZ method were benchmarked against the CCSD(T)/CBS energies and were found to be within 1 kcal mol(-1) of one another. Thus, the energies calculated using the less expensive CCSD(T)/cc-pVTZ method were used in all of the reaction mechanisms and in calculating our high-pressure limit rate constants for the title reactions. Rate constants were calculated using conventional transition state theory with an asymmetric Eckart tunneling correction, as implemented in Variflex. Herein, we report the individual and average rate constants, on a per H atom basis, and total rate constants in the temperature range 500-2000 K. We have compared some of our rate constant results to available experimental and theoretical data, and our results are generally in good agreement.
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Investigation of radical locations in various sesame seeds by CW EPR and 9-GHz EPR imaging.
Nakagawa, K; Hara, H
2015-01-01
We investigated the location of radical in various sesame seeds using continuous-wave (CW) electron paramagnetic resonance (EPR) and 9-GHz EPR imaging. CW EPR detected persistent radicals (single line) for various sesame seeds. The EPR linewidth of black sesame seeds was narrower than that of the irradiated white sesame seeds. A very small signal was detected for the white sesame seeds. Two-dimensional (2D) imaging using a 9-GHz EPR imager showed that radical locations vary for various sesame seeds. The paramagnetic species in black sesame seeds were located on the seed coat (skin) and in the hilum region. The signal with the highest intensity was obtained from the hilum part. A very low-intensity image was observed for the white sesame seeds. In addition, the 2D imaging of the irradiated white sesame seeds showed that free radicals were located throughout the entire seed. For the first time, CW EPR and 9-GHz EPR imaging showed the exact location of radical species in various sesame seeds.
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Kowalska, Iwona; Pecio, Lukasz; Ciesla, Lukasz; Oleszek, Wieslaw; Stochmal, Anna
2014-11-19
Fourteen phenolic compounds (flavonoids and phenolic acids) were isolated and 19 were identified in the aerial parts of Triticum aestivum L. The structures of these compounds were established on the basis of the data obtained by electrospray ionization-mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) techniques. T. aestivum L. was found to be rich in flavones, especially in luteolin derivatives. Three of the isolated compounds, including luteolin 6-C-[6Glc″-O-E-caffeoyl-β-D-glucopyranosyl(1″→2)-β-glucopyranoside], luteolin 6-C-[5Rib″-O-E-feruoyl-β-D-ribofuranosyl(1″→2)-β-glucopyranoside], and 3',4',5'-O-trimethyltricetin 7-O-[β-D-glucuropyranosyl(1″→2)-β-D-glucopyranoside], have been reported for the first time in the plant kingdom. The amount of individual phenolics, in winter wheat, was also determined. Additionally, the free radical scavenging potential of the isolated compounds was tested in a simple and rapid thin-layer chromatography-2,2-diphenyl-1-picrylhydrazyl radical test (TLC-DPPH•) with image processing.
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Ben Ammar, Rebai; Miyamoto, Tomofumi; Chekir-Ghedira, Leila; Ghedira, Kamel; Lacaille-Dubois, Marie-Aleth
2018-03-13
From the butanolic and the ethyl acetate extracts of Rhamnus alaternus L root bark and leaves, three new anthraquinone glycosides, alaternosides A-C (1,4,6,8 tetrahydroxy-3 methyl anthraquinone 1-O-ß-D-glucopyranosyl-4,6-di-O-α-L-rhamnopyranoside (1); 1,2,6,8 tetrahydroxy-3 methyl anthraquinone 8-O-ß-D-glucopyranoside (2) and 1, 6 dihydroxy-3 methyl 6 [2'-Me (heptoxy)] anthraquinone (3)) were isolated and elucidated together with the two known anthraquinone glycosides, Physcion-8-O-rutinoside (4) and emodin-6-O-α-L-rhamnoside (5) as well as with the known kaempferol-7-methylether (6), β-sitosterol (7) and β-sitosterol-3-O-glycoside (8). Their chemical structures were elucidated using spectroscopic methods (1D-, 2D-NMR and FAB-MS). Free radical scavenging activity of the isolated compounds was evaluated by their ability to scavenge DPPH . free radicals. Compounds (3), (4) and (6) showed the highest activity with IC 50 values of 9.46, 27.68 and 2.35 μg/mL, respectively.
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Byer, Amanda S; Yang, Hao; McDaniel, Elizabeth C; Kathiresan, Venkatesan; Impano, Stella; Pagnier, Adrien; Watts, Hope; Denler, Carly; Vagstad, Anna; Piel, Jörn; Duschene, Kaitlin S; Shepard, Eric M; Shields, Thomas P; Scott, Lincoln G; Lilla, Edward A; Yokoyama, Kenichi; Broderick, William E; Hoffman, Brian M; Broderick, Joan B
2018-06-28
Radical S-adenosyl-L-methionine (SAM) en-zymes comprise a vast superfamily catalyzing diverse reactions essential to all life through ho-molytic SAM cleavage to liberate the highly-reactive 5-deoxyadenosyl radical (5-dAdo•). Our recent observation of a catalytically compe-tent organometallic intermediate Ω that forms dur-ing reaction of the radical SAM (RS) enzyme py-ruvate formate-lyase activating-enzyme (PFL-AE) was therefore quite surprising, and led to the question of its broad relevance in the superfamily. We now show that Ω in PFL-AE forms as an in-termediate under a variety of mixing order condi-tions, suggesting it is central to catalysis in this enzyme. We further demonstrate that Ω forms in a suite of RS enzymes chosen to span the totality of superfamily reaction types, implicating Ω as essential in catalysis across the RS superfamily. Finally, EPR and electron nuclear double reso-nance spectroscopy establish that Ω involves an Fe-C5 bond between 5-dAdo• and the [4Fe-4S] cluster. An analogous organometallic bond is found in the well-known adenosylcobalamin (co-enzyme B12) cofactor used to initiate radical reac-tions via a 5'-dAdo• intermediate. Generation of a 5'-dAdo• intermediate via homolytic metal-carbon bond cleavage thus appears to be similar for Ω and coenzyme B12. However coenzyme B12 is involved in enzymes catalyzing of only a small number (~12) of distinct reactions, while the RS superfamily has more than 100,000 distinct se-quences and over 80 reaction types character-ized to date. The appearance of Ω across the RS superfamily therefore dramatically enlarges the sphere of bio-organometallic chemistry in Nature.
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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.
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Stefanić, I; Ljubić, I; Bonifacić, M; Sabljić, A; Asmus, K-D; Armstrong, D A
2009-04-07
A pulse radiolysis study was carried out of the reaction rate constants and kinetic isotope effects of hydroxyl-radical-induced H/D abstraction from the most-simple alpha-amino acid glycine in its anionic form in water. The rate constants and yields of three predominantly formed radical products, glycyl (NH2-*CH-CO2-), aminomethyl (NH2-*CH2), and aminyl (*NH-CH2-CO2-) radicals, as well as of their partially or fully deuterated analogs, were found to be of comparable magnitude. The primary, secondary, and primary/secondary H/D kinetic isotope effects on the rate constants were determined with respect to each of the three radicals. The unusual variety of products for such an elementary reaction between two small and simple species indicates a complex mechanism with several reactions taking place simultaneously. Thus, a theoretical modeling of the reaction mechanism and kinetics in the gas- and aqueous phase was performed by using the unrestricted density functional theory with the BB1K functional (employing the polarizable continuum model for the aqueous phase), unrestricted coupled cluster UCCSD(T) method, and improved canonical variational theory. Several hydrogen-bonded prereaction complexes and transition states were detected. In particular, the calculations pointed to a significant mechanistic role of the three-electron two-orbital (sigma/sigma* N therefore O) hemibonded prereaction complexes in the aqueous phase. A good agreement with the experimental rate constants and kinetic isotope effects was achieved by downshifting the calculated reaction barriers by 3 kcal mol(-1) and damping the NH(D) stretching frequency by a factor of 0.86.
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NASA Astrophysics Data System (ADS)
Takahashi, Wataru; Miyake, Yusuke; Hirata, Hiroshi
2014-10-01
This article describes an improved method for suppressing image artifacts in the visualization of 14N- and 15N-labeled nitroxyl radicals in a single image scan using electron paramagnetic resonance (EPR). The purpose of this work was to solve the problem of asymmetric EPR absorption spectra in spectral processing. A hybrid function of Gaussian and Lorentzian lineshapes was used to perform spectral line-fitting to successfully separate the two kinds of nitroxyl radicals. This approach can process the asymmetric EPR absorption spectra of the nitroxyl radicals being measured, and can suppress image artifacts due to spectral asymmetry. With this improved visualization method and a 750-MHz continuous-wave EPR imager, a temporal change in the distributions of a two-phase paraffin oil and water/glycerin solution system was visualized using lipophilic and hydrophilic nitroxyl radicals, i.e., 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16-DOXYL stearic acid) and 4-hydroxyl-2,2,6,6-tetramethylpiperidine-d17-1-15N-1-oxyl (TEMPOL-d17-15N). The results of the two-phase separation experiment verified that reasonable artifact suppression could be achieved by the present method that deals with asymmetric absorption spectra in the EPR imaging of 14N- and 15N-labeled nitroxyl radicals.
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Evaluated rate constants for selected HCFC's and HFC's with OH and O((sup)1D)
NASA Technical Reports Server (NTRS)
Hampson, Robert F.; Kurylo, Michael J.; Sander, Stanley P.
1990-01-01
The chemistry of HCFC's and HFC's in the troposphere is controlled by reactions with OH in which a hydrogen atom is abstracted from the halocarbon to form water and a halo-alkyl radical. The halo-alkyl radical subsequently reacts with molecular oxygen to form a peroxy radical. The reactions of HCFC's and HFC's with O(exp1D) atoms are unimportant in the troposphere, but may be important in producing active chlorine of OH in the stratosphere. Here, the rate constants for the reactions of OH and O(exp1D) with many HFC's and HCFC's are evaluated. Recommendations are given for the five HCFC's and three HFC's specified by AFEAS as primary alternatives as well as for all other isomers of C1 and C2 HCFC's and HFC's where rate data exist. In addition, recommendations are included for CH3CCl3, CH2Cl2, and CH4.
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2012-01-01
Background Sonchus asper (SA) is traditionally used for the treatment of various ailments associated with liver, lungs and kidneys. This study was aimed to investigate the therapeutic potential of nonpolar (hexane, SAHE; ethyl acetate, SAEE and chloroform, SACE) and polar (methanol, SAME) crude extracts of the whole plant. Methods To achieve these goals, several parameters including free-radical (DPPH•, ABTS•+, H2O2 and •OH) scavenging, iron chelating activity, scavenging of superoxide radicals, total flavonoids and total phenolic content (TPC) were examined. Results The SA extracts presented a remarkable capacity to scavenge all the tested reactive species with IC50 values being found at the μg ⁄ ml level. The SAME was shown to have the highest TPCs while lowest IC50 values for the DPPH•, ABTS•+ radical scavenging capacities and iron chelating scavenging efficiency, moreover, SAME had best activities in scavenging of superoxide radicals and hydrogen peroxide as well as potently scavenged the hydroxyl radicals. Conclusion These results suggest the potential of S. asper as a medicine against free-radical-associated oxidative damage. PMID:22305477
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NASA Astrophysics Data System (ADS)
Cho, Myoung Lae; Lee, Dong-Jin; Lee, Hyi-Seung; Lee, Yeon-Ju; You, Sang Guan
2013-12-01
The nitric oxide inhibitory (NOI) and antioxidant (ABTS and DPPH radical scavenging effects with reducing power) activities of the ethanol (EtOH) extracts and solvent partitioned fractions from Scytosiphon lomentaria, Chorda filum, Agarum cribrosum, and Desmarestia viridis were investigated, and the correlation between biological activity and total phenolic (TP) and phlorotannin (TPT) content was determined by PCA analysis. The yield of EtOH extracts from four brown seaweeds ranged from 2.6 to 6.6% with the highest yield from D. viridis, and the predominant compounds in their solvent partitioned fractions had medium and/or less polarity. The TP and TPT content of the EtOH extracts were in the ranges of 25.0-44.1 mg GAE/g sample and 0.2-4.6 mg PG/g sample, respectively, which were mostly included in the organic solvent partitioned fractions. Strong NOI activity was observed in the EtOH extracts and their solvent partitioned fractions from D. viridis and C. filum. In addition, the EtOH extract and its solvent partitioned fractions of D. viridis exhibited little cytotoxicity to Raw 264.7 cells. The most potent ABTS and DPPH radical scavenging capacity was shown in the EtOH extracts and their solvent partitioned fractions from S. lomentaria and C. filum, and both also exhibited strong reducing ability. In the PCA analysis the content of TPT had a good correlation with DPPH ( r = 0.62), ABTS ( r = 0.69) and reducing power ( r = 0.65), however, an unfair correlation was observed between the contents of TP and TPT and NOI, suggesting that the phlorotannins might be responsible for the DPPH and ABTS radical scavenging activities.
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Han, Ding-Pei; Lu, Ai-Guo; Feng, Hao; Wang, Pu-Xiong-Zhi; Cao, Qi-Feng; Zong, Ya-Ping; Feng, Bo; Zheng, Min-Hua
2013-05-01
To study the feasibility, safety, and short-/long-term outcomes of laparoscopy-assisted right hemicolectomy with D3 lymphadenectomy for colon cancer. The clinical data of 177 cases that underwent laparoscopy-assisted radical right hemicolectomy with D3 lymphadenectomy for colon cancer between Jun 2003 and Sep 2010 was collected; the safety of operation, status of recovery, complication, oncological outcomes, and results of short-/long-term follow-up were analyzed. No case died in this study; five cases (2.82 %) were converted to open surgery. Four cases (2.26 %) underwent hand-assisted laparoscopic right hemicolectomy. The average operation time was 133 ± 36 min, and the blood loss was 94 ± 34 ml. The average time for passage of flatus, liquid food eating, and hospitalization were 2.1 ± 0.7, 3.2 ± 0.5, and 10.4 ± 2.7 day, respectively. The total number of lymph nodes removed was 15.2 ± 10.1. Postoperative complications were observed in 23 of 177 patients (12.99 %). The median follow-up period was 54 months; port-site recurrence was observed in one patient; local recurrence was found in five cases (2.82 %); distant metastasis was found in 21 cases (11.86 %). The cumulative overall survival of all stages at 12, 36, 60, and 72 months was 97.18 %, 83.73 %, 70.37 %, and 68.99 %, respectively. The cancer-specific survival was 98.73 % (12 months), 87.81 % (36 months), and 80.17 % (60 months). Laparoscopy-assisted right hemicolectomy with D3 lymphadenectomy can be successfully performed for right colon cancer with the advantages of minimally invasive surgery. Moreover, the results implied appropriate short- and long-term outcomes.
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Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie
2015-01-01
ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500
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Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew
2015-07-01
Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D 4 and D 5 with the OH radical are 1.9 × 10 -12 (95% confidence interval (CI): (1.7-2.2) × 10 -12 ) and 2.6 × 10 -12 (CI: (2.3-2.9) × 10 -12 ) cm 3 molecule -1 s -1 , respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D 6 is 2.8 × 10 -12 (CI: (2.5-3.2) × 10 -12 ) cm 3 molecule -1 s -1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D 5 were 33% higher than for D 4 (CI: 30-37%), whereas the rates for D 6 were only 8% higher than for D 5 (CI: 5-10%). The activation energies of the reactions of D 4 , D 5 , and D 6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.
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Zhao, Chunjian; Li, Chunying; Liu, Shuaihua; Yang, Lei
2014-01-01
Total polyphenol content, catechins content, and antioxidant capacities of green, dark, oolong, and black teas made from Camellia sinensis in China were evaluated. The total polyphenol content of 20 samples of tea was in the range of 7.82–32.36%. Total catechins content was in the range of 4.34–24.27%. The antioxidant capacity of tea extract was determined by the oxygen radical absorbance capacity (ORAC) test and the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging test. Total polyphenol content, catechins content, and antioxidant capacity decreased in the following order: green > oolong > black > dark tea. A positive correlation existed between the antioxidant capacity and total polyphenol content or catechins content (R 2 = 0.67–0.87). The antioxidant capacities of five major catechins (epigallocatechin gallate (EGCG), epicatechin gallate (ECG), epicatechin, epigallocatechin, and catechin) were determined by online HPLC DPPH radical-scavenging; the antioxidant activity of tea was mainly attributed to the esterified catechins (EGCG or ECG). PMID:25243234
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Suarez, Javier; Ranguelova, Kalina; Jarzecki, Andrzej A.; Manzerova, Julia; Krymov, Vladimir; Zhao, Xiangbo; Yu, Shengwei; Metlitsky, Leonid; Gerfen, Gary J.; Magliozzo, Richard S.
2009-01-01
A mechanism accounting for the robust catalase activity in catalase-peroxidases (KatG) presents a new challenge in heme protein enzymology. In Mycobacterium tuberculosis, KatG is the sole catalase and is also responsible for peroxidative activation of isoniazid, an anti-tuberculosis pro-drug. Here, optical stopped-flow spectrophotometry, rapid freeze-quench EPR spectroscopy both at the X-band and at the D-band, and mutagenesis are used to identify catalase reaction intermediates in M. tuberculosis KatG. In the presence of millimolar H2O2 at neutral pH, oxyferrous heme is formed within milliseconds from ferric (resting) KatG, whereas at pH 8.5, low spin ferric heme is formed. Using rapid freeze-quench EPR at X-band under both of these conditions, a narrow doublet radical signal with an 11 G principal hyperfine splitting was detected within the first milliseconds of turnover. The radical and the unique heme intermediates persist in wild-type KatG only during the time course of turnover of excess H2O2 (1000-fold or more). Mutation of Met255, Tyr229, or Trp107, which have covalently linked side chains in a unique distal side adduct (MYW) in wild-type KatG, abolishes this radical and the catalase activity. The D-band EPR spectrum of the radical exhibits a rhombic g tensor with dual gx values (2.00550 and 2.00606) and unique gy (2.00344) and gz values (2.00186) similar to but not typical of native tyrosyl radicals. Density functional theory calculations based on a model of an MYW adduct radical built from x-ray coordinates predict experimentally observed hyperfine interactions and a shift in g values away from the native tyrosyl radical. A catalytic role for an MYW adduct radical in the catalase mechanism of KatG is proposed. PMID:19139099
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Nemeria, Natalia S.; Ambrus, Attila; Patel, Hetalben; Gerfen, Gary; Adam-Vizi, Vera; Tretter, Laszlo; Zhou, Jieyu; Wang, Junjie; Jordan, Frank
2014-01-01
Herein are reported unique properties of the human 2-oxoglutarate dehydrogenase multienzyme complex (OGDHc), a rate-limiting enzyme in the Krebs (citric acid) cycle. (a) Functionally competent 2-oxoglutarate dehydrogenase (E1o-h) and dihydrolipoyl succinyltransferase components have been expressed according to kinetic and spectroscopic evidence. (b) A stable free radical, consistent with the C2-(C2α-hydroxy)-γ-carboxypropylidene thiamin diphosphate (ThDP) cation radical was detected by electron spin resonance upon reaction of the E1o-h with 2-oxoglutarate (OG) by itself or when assembled from individual components into OGDHc. (c) An unusual stability of the E1o-h-bound C2-(2α-hydroxy)-γ-carboxypropylidene thiamin diphosphate (the “ThDP-enamine”/C2α-carbanion, the first postdecarboxylation intermediate) was observed, probably stabilized by the 5-carboxyl group of OG, not reported before. (d) The reaction of OG with the E1o-h gave rise to superoxide anion and hydrogen peroxide (reactive oxygen species (ROS)). (e) The relatively stable enzyme-bound enamine is the likely substrate for oxidation by O2, leading to the superoxide anion radical (in d) and the radical (in b). (f) The specific activity assessed for ROS formation compared with the NADH (overall complex) activity, as well as the fraction of radical intermediate occupying active centers of E1o-h are consistent with each other and indicate that radical/ROS formation is an “off-pathway” side reaction comprising less than 1% of the “on-pathway” reactivity. However, the nearly ubiquitous presence of OGDHc in human tissues, including the brain, makes these findings of considerable importance in human metabolism and perhaps disease. PMID:25210035
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Characterization of Jamaican Delonix regia and Cassia fistula Seed Extracts
Reid, Raymond; Rattray, Vaughn; Williams, Ruth; Denny, Marcel
2016-01-01
Delonix regia and Cassia fistula seed extracts were evaluated for their antioxidant activity, total phenolics, ash, zinc and fatty acid content. Fourier Transform Infrared Spectroscopy (FTIR) was utilized to assess the chemical functionalities present within the seeds. Antioxidant activity was determined by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) and Trolox equivalent antioxidant capacity (TEAC) assays. Total phenolics were determined by the Folin-Ciocalteu assay. Lipid extracts were characterized by nuclear magnetic resonance spectroscopy and gas chromatography/mass spectrometry. Zinc concentration was determined by atomic absorption spectroscopy. Extracts from the seeds of C. fistula had a higher antioxidant activity, free radical scavenging activity, and phenolic content than D. regia. FTIR revealed that the seeds are a rich source of protein with small quantities of fat. C. fistula extracts contained a higher percentage of total fat than D. regia. Palmitic acid was identified as the predominant saturated fatty acid in both extracts. Oleic acid and linoleic acid were identified in smaller quantities. Seed extracts may be considered for use in food and nutraceutical applications. PMID:27034834
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Biochemistry of free radicals: from electrons to tissues.
Boveris, A
1998-01-01
Free radicals are chemical species with an unpaired electron in the outer valence orbitals. The unpaired electron makes them paramagnetic (physics) and relatively reactive (chemistry). The free radicals that are normal metabolites in aerobic biological systems have varied reactivities, ranging from the high reactivity of hydroxyl radical (t1/2 = 10(-9) s) to the low reactivity of melanins (t1/2 = days). The univalent reduction of oxygen that takes place in mammalian organs produces superoxide radicals at a rate of about 2% of the total oxygen uptake. The primary production of superoxide radicals sustains a free radical chain reaction involving a series of reactive oxygen species (hydrogen peroxide, hydroxyl and peroxyl radical and singlet oxygen). Nitric oxide is almost unreactive as free radical except for its termination reaction with superoxide radical to yield the strong oxidant peroxynitrite. Nitric oxide also reacts with ubiquinol in a redox reaction, with cytochrome oxidase competitively with oxygen, and oxymyoglobin and oxyhemoglobin displacing oxygen. Septic shock and endotoxemia produce muscle dysfunction and oxidative stress due to increased steady state concentrations of reactive oxygen and nitrogen species.
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Chang, Chia Lin; Lin, Che San; Lai, Guia Hung
2012-01-01
The objective of this study was to determine phytochemical characteristics, chemiluminescence antioxidant capacities, and neuroprotective effects on PC12 cells for methanol extracts of Spatholobus suberectus, Uncaria rhynchophylla, Alpinia officinarum, Drynaria fortunei, and Crataegus pinnatifida. The C. pinnatifida extract (CPE) afforded the greatest yield and total phenolic content. The S. suberectus extract (SSE) yielded the greatest total flavonoid content. The U. rhynchophylla extract (URE) produced the greatest total tannin content, and the A. officinarum extract (AOE) produced the greatest total triterpenoid content. The D. fortunei extract, assayed using horseradish peroxidase-luminol-hydrogen peroxide (H2O2), and AOE using pyrogallol-luminol assay each exhibited better antioxidant activity than the L-ascorbic acid and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid did. The CPE, SSE, and URE presented neurogrowth effects and neuroprotective activities on H2O2-induced PC12 cell death at 0.5–5.0 μg/mL. The CPE represents a promising medicinal plant source for the treatment of H2O2-induced neurodegenerative disease, because of its useful phytochemical characteristics. PMID:21845204
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Kobayashi, Hirokazu; Asaji, Tetsuo; Tani, Atsushi
2012-03-01
The molecular orientation and dynamics of the organic stable radicals such as 2,2,6,6-tetramethyl-1-piperidinyl-1-oxyl (TEMPO) or 4-hydroxy-TEMPO (TEMPOL) included in the one-dimensional (1-D) organic nanochannels of 2,4,6-tris-4-(chlorophenoxy)-1,3,5-triazine (CLPOT) were investigated by examining the inclusion compounds (ICs) diluted by the co-inclusion of non-radicals using ESR spectroscopy. Spectral simulation showed that the axial rotation of TEMPO or TEMPOL molecules is excited in the nanochannels with activation energies of 8 and 7 kJ mol(-1) , respectively. The rotation axis was estimated to be tilted towards the principal x direction in the axis system of the g-tensor of the respective radicals. This is quite different from that for similar ICs in the nanochannels of tris(o-phenylenedioxy)cyclotriphosphazene (TPP), in which the radicals are axially rotating around the principal axis y of the g-tensor. The difference is attributed to the larger nanospace of the CLPOT nanochannels. Copyright © 2012 John Wiley & Sons, Ltd.
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Tsegaw, Yetsedaw Andargie; Sander, Wolfram; Kaiser, Ralf I
2016-03-10
Thin films of nitromethane (CH3NO2) along with its isotopically labeled counterpart D3-nitromethane (CD3NO2) were photolyzed at discrete wavelength between 266 nm (4.7 eV) and 121 nm (10.2 eV) to explore the underlying mechanisms involved in the decomposition of model compounds of energetic materials in the condensed phase at 5 K. The chemical modifications of the ices were traced in situ via electron paramagnetic resonance, thus focusing on the detection of (hitherto elusive) reaction intermediates and products with unpaired electrons. These studies revealed the formation of two carbon-centered radicals [methyl (CH3), nitromethyl (CH2NO2)], one oxygen-centered radical [methoxy (CH3O)], two nitrogen-centered radicals [nitrogen monoxide (NO), nitrogen dioxide (NO2)], as well as atomic hydrogen (H). The decomposition products of these channels and the carbon-centered nitromethyl (CH2NO2) radical in particular represent crucial reaction intermediates leading via sequential molecular mass growth processes in the exposed nitromethane samples to complex organic molecules as predicted previously by dynamics calculations. The detection of the nitromethyl (CH2NO2) radical along with atomic hydrogen (H) demonstrated the existence of a high-energy decomposition pathway, which is closed under collisionless conditions in the gas phase.
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ClO radical yields in the reaction of O(1D) with Cl2, HCl, chloromethanes, and chlorofluoromethanes.
Feierabend, Karl J; Papanastasiou, Dimitrios K; Burkholder, James B
2010-11-18
Absolute ClO radical product yields in the gas-phase reactions of O((1)D) with Cl(2), HCl, CCl(4), CHCl(3), CH(2)Cl(2), CH(3)Cl, CFCl(3), CF(2)Cl(2), CF(3)Cl, CHFCl(2), and CHF(2)Cl are reported. Product yields were measured using pulsed-laser photolysis of O(3) to produce O((1)D) in the presence of excess reactant combined with dual wavelength differential cavity ring-down spectroscopic detection of the ClO radical. ClO radical absorption cross sections for the A(2)Π(v = 10) ← X(2)Π(v = 0) transition band head near 280 nm were determined between 200 and 296 K as part of this work. The ClO product yields obtained at room temperature were Cl(2) (0.77 ± 0.10), HCl (0.20 ± 0.04), CCl(4) (0.79 ± 0.04), CHCl(3) (0.77 ± 0.04), CH(2)Cl(2) (0.73 ± 0.04), CH(3)Cl (0.46 ± 0.06), CFCl(3) (0.79 ± 0.04), CF(2)Cl(2) (0.76 ± 0.06), CF(3)Cl (0.82 ± 0.06), CHFCl(2) (0.73 ± 0.05), and CHF(2)Cl (0.56 ± 0.03), where the quoted error limits are 2σ of the measurement precision. ClO product yields in the O((1)D) + Cl(2) and CFCl(3) reactions were found to be independent of temperature between 200 and 296 K, within the precision of the measurements. The absolute ClO yields obtained in this study are compared with previously reported values determined using relative and indirect methods.
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Stefanović, Olgica D; Tešić, Jelena D; Čomić, Ljiljana R
2015-09-01
Melilotus albus Medic. and Dorycnium herbaceum Vill. (Fabaceae) acetone, ethyl acetate, and ethanol extracts were investigated for their in vitro antimicrobial, antibiofilm, and antioxidant activity with quantification of phenolic compound contents. In general, D. herbaceum extracts showed better antibacterial and antioxidant activity than M. albus extracts. Bacteria Bacillus subtilis, Staphylococcus aureus ATCC 25923, Pseudomonas aeruginosa, and Proteus mirabilis were the most susceptible with the minimum inhibitory concentrations (MICs), determined by microdilution method, between 1.25-10 mg/mL. Antifungal activity was lower with the detectable MICs at 10 mg/mL and 20 mg/mL. The plant extracts, using the crystal violet assay, inhibit P. aeruginosa biofilm formation in concentration range from 5 mg/mL to 20 mg/mL whereas the effect on mature bacterial biofilm was lower. The antioxidant activity was evaluated using 2, 2-diphenyl-1-picrylhydrazyl (DPPH) radicals scavenging and reducing power model systems. The intensity of DPPH radicals scavenging activity, expressed as half maximal effective concentration (EC 50 ) values, was from 84.33 μg/mL to >1000 μg/mL. The extracts demonstrated reduced power in a concentration-dependent manner, with ethanol extract as the most active. The total phenols, flavonoids, and proanthocyanidins were determined spectrophotometrically while total extractable tannins were obtained by precipitation method. The phenolic compounds showed differences in their total contents depending on solvents polarities and plant species. Although the plants M. albus and D. herbaceum have not yet been fully explored, these results contribute better understanding of their biotic properties and potential application as antimicrobial and antioxidant agents. Copyright © 2015. Published by Elsevier B.V.
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Activity-Guided Identification of in Vitro Antioxidants in Beer.
Spreng, Stefan; Hofmann, Thomas
2018-01-24
In order to locate the key antioxidants contributing to oxidative stability of beer, activity-guided fractionation in combination with the oxygen radical absorbance capacity (ORAC) assay, hydrogen peroxide scavenging (HPS) assay, and linoleic acid (LA) assay was applied to a pilsner-type beer. LC-MS and 1D/2D NMR experiments led to the identification of a total of 31 antioxidants, among which 3-methoxy-4-hydroxyphenyl-β-d-glucopyranoside (tachioside), 4-(2-formylpyrrol-1-yl)butyric acid, 4-[2-formyl-5-(hydroxymethyl)pyrrol-1-yl]butyric acid, n-multifidol-3-O-β-d-glucoside, quercetin-3-O-(6″-malonyl)-glucoside, 4-feruloylquinic acid, syringaresinol, saponarin, and hordatines A-C have been isolated from beer for the first time. On a molar comparison, the hordatines A-C, saponarin, and quercetin-3-O-β-d-(6″-malonyl)glucoside were evaluated with the highest antioxidant activities of all identified beer constituents, reaching values of 10-17.5 (ORAC), 2.0-4.1 (HPS), and 1.1-6.1 μmol TE/μmol (LA) for hordatines A-C.
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Rawat, Sandeep; Jugran, Arun; Giri, Lalit; Bhatt, Indra D.; Rawal, Ranbeer S.
2011-01-01
Crude extract of Myrica esculenta fruits, a wild edible species of Indian Himalayan Region, was evaluated for phenolic compounds and antioxidant properties. Results revealed significant variation in total phenolic and flavonoid contents across populations. Among populations, total phenolic content varied between 1.78 and 2.51 mg gallic acid equivalent/g fresh weight (fw) of fruits and total flavonoids ranged between 1.31 and 1.59 mg quercetin equivalent/g fw. Antioxidant activity determined by 2,2′-azinobis(3-ethylbenzothiazoline-6-sulphonic acid) radical scavenging, 1,1-diphenyl-2-picrylhydrazyl radical scavenging and ferric reducing antioxidant power (FRAP) exhibited considerable antioxidant potential and showed significant positive correlation with total phenolic and total flavonoids content. High performance liquid chromatography analysis revealed significant variation (P < .01) in phenolic compounds (i.e., gallic acid, catechin, hydroxybenzioc acid and ρ-coumaric acid) across populations. This study provides evidences to establish that consumption of M. esculenta fruits while providing relished taste would also help in reduction of free radicals. Therefore, this wild edible species deserves promotion in the region through horticulture and forestry interventions. PMID:21785629
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Lee, Sang Hoon; Oh, Seung Hee; Hwang, In Guk; Kim, Hyun Young; Woo, Koan Sik; Woo, Shun Hee; Kim, Hong Sig; Lee, Junsoo; Jeong, Heon Sang
2016-06-01
This study was performed to evaluate and compare the antioxidant substance content and antioxidant activities of white (Superior) and colored (Hongyoung, Jayoung, Jasim, Seohong, and Jaseo) potatoes. The potatoes were extracted with 80% ethanol and were evaluated for the total polyphenol, flavonoid, and anthocyanin contents and for 1,1-diphenyl- 2-picrylhydrazyl (DPPH)/2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) radical scavenging activity, reducing power, and ferrous metal ion chelating effect. The total polyphenol, flavonoid, and anthocyanin contents of Hongyoung and Jayoung were higher than white and other colored potatoes. All colored potato extracts, except for Jaseo and Seohong, showed higher ABTS radical scavenging activities than the general white potato extract. Hongyoung and Jayoung had the highest ABTS and DPPH radical scavenging activities. Optical density values for the reducing power of Jayoung and Jaseo at concentration of 2 mg/mL were 0.148 and 0.090, respectively. All colored potato extracts had lower ferrous metal ion chelating effect than the white potato. A significant (P<0.05) positive correlation was observed between total polyphenol content and total flavonoid content (r=0.919), anthocyanin content (r=0.992), and ABTS radical scavenging activity (r=0.897). Based on these results, this research may be useful in developing the Hongyoung and Jayoung cultivars with high antioxidant activities.
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Zhao, Lei; Gao, Xiang; Luo, Zhong-Yang; Xuan, Jian-Yong; Jiang, Jian-Ping; Cen, Ke-Fa
2011-11-01
Streamer plays a key role in the process of OH radical generation. The propagation of primary and secondary streamers of positive wire-plate pulsed corona discharge was observed using a short gate ICCD in air environment. The influence of the applied voltage on the properties was investigated. It was shown that the primary streamer propagation velocity, electric coverage and length of secondary streamer increased significantly with increasing the applied voltage. Then 2-D OH distribution was investigated by the emission spectrum. With the analysis of the OH emission spectra, the distribution of OH radicals showed a trend of decreasing from the wire electrode to its circumambience. Compared with the streamer propagation trace, the authors found that OH radical distribution and streamer are in the same area. Both OH radical concentration and the intensity of streamer decreased when far away from the wire electrode.
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Wu, Adam; Mader, Elizabeth A.; Datta, Ayan; Hrovat, David A.; Borden, Weston Thatcher; Mayer, James M.
2009-01-01
Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO• (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO• (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl (tBu2NO•), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and tBu2NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of nitroxyl radicals. The HAT reactions all have |ΔGo| ≤ 1.4 kcal mol−1 and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO• + TEMPO-H → 4-oxo-TEMPO-H + TEMPO• occurs with k2H,MeCN = 10 ± 1 M−1 s−1 in MeCN at 298 K (K2H,MeCN = 4.5 ± 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k2D,MeCN = 0.44 ± 0.05 M−1 s−1 with k2H,MeCN/k2D,MeCN = 23 ± 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH2Cl2, 23 ± 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO• with 4-MeO-TEMPO-H(D) also has a large KIE, k3H/k3D = 21 ± 3 in MeCN. For these three reactions, the EaD – EaH values, between 0.3 ± 0.6 and 1.3 ± 0.6 kcal mol−1, and the log(AH/AD) values, between 0.5 ± 0.7 and 1.1 ± 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of tBu2NO• + TEMPO-H(D) in MeCN has a large KIE, 16 ± 3 in MeCN, and very unusual isotopic activation parameters, EaD – EaH = −2.6 ± 0.4 and log(AH/AD) = 3.1 ± 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH3)2NO• + (CH3)2NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO(•/H), tBu2NO(•/H), and Ph2NO(•/H) self-exchange reactions reveal why the phenyl groups make the last of these reactions several orders of magnitude faster than the first two. By inference, the calculations also suggest why tunneling appears to be more important in the self-exchange reactions of dialkylhydroxylamines than of arylhydroxylamines. PMID:19618933
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Aschmann, Sara M; Arey, Janet; Atkinson, Roger
2002-02-15
Alkanes are important constituents of gasoline fuel and vehicle exhaust, with branched alkanes comprising a significant fraction of the total alkanes observed in urban areas. Products of the gas-phase reactions of OH radicals with 2,2,4-trimethylpentane and 2,2,4-trimethylpentane-d18 in the presence of NO at 298+/-2 K and atmospheric pressure of air have been investigated using gas chromatography with flame ionization detection (GC-FID), combined gas chromatography-mass spectrometry (GC-MS), and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS). Acetone, 2-methylpropanal, and 4-hydroxy-4-methyl-2-pentanone were identified and quantified by GC-FID from 2,2,4-trimethylpentane with molar formation yields of 54+/-7%, 26+/-3%, and 5.1+/-0.6%, respectively; upper limits to the formation yields of acetaldehyde, 2,2-dimethylpropanal, and 4,4-dimethyl-2-pentanone were obtained. Additional products observed from 2,2,4-trimethylpentane by API-MS and API-MS/MS analyses using positive and negative ion modes were hydroxy products of molecular weight 130 and 144, a product of molecular weight 128 (attributed to a C8-carbonyl), and hydroxynitrates of molecular weight 135, 177, and 191 (attributed to HOC4H8ONO2, HOC7H14ONO2, and HOC8H16-ONO2, respectively). Formation of HOC8H16ONO2 and HOC7H14-ONO2 is consistent with the observation of products of molecular weight 207 (HOC8D16ONO2) and 191 (HOC7D14-ONO2), respectively, in the API-MS analyses of the 2,2,4-trimethylpentane-d18 reaction (-OD groups rapidly exchange to -OH groups under our experimental conditions). These product data allow the reaction pathways to be delineated to a reasonable extent, and the reaction mechanism is discussed.
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Quality of life in advanced maxillary sinus cancer after radical versus conservative maxillectomy.
Liu, Liting; Liu, Dan; Guo, Qiyun; Shen, Bin
2013-07-01
A study of patients with advanced maxillary sinus cancer who underwent radical or conservative maxillectomy was performed to show the differences between the 2 groups in patients' survival rate and quality of life (QOL). A total of 61 advanced maxillary sinus cancer patients from Weifang People's Hospital in China were traced: 27 radical maxillectomy and 34 conservative maxillectomy. Survival rate was compared between the 2 groups. Quality of life assessments were performed at the time of preoperation as well as 6, 12, and 18 months after the operation. Measures included the University of Washington-QOL scale (UW-QOL) and the Hospital Anxiety and Depression Scale. The UW-QOL scale scores of the composite score, appearance, activity, recreation, swallowing, speech, and chewing in the conservative surgical group were much higher than those in the radical surgical group. However, there is no big difference in total survival rate between these 2 groups. Also, no significant difference can be seen in the scores of pain, employment, and shoulder between the 2 groups. At the 6-month follow-up, the radical maxillectomy had more effects on anxiety than the conservative maxillectomy, while they are almost equally effective on depression. The 12-month and 18-month follow-ups showed that the radical maxillectomy made a greater impact on both anxiety and depression than the conservative maxillectomy. Conservative maxillectomy is more effective than radical maxillectomy to preserve the QOL of patients with advanced maxillary sinus cancer.
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Mediani, Ahmed; Abas, Faridah; Tan, Chin Ping; Khatib, Alfi
2014-05-07
The present study was conducted to determine the effect of air (AD), oven (OD) and freeze drying (FD) on the free radical scavenging activity and total phenolic content (TPC) of Cosmos caudatus and the effect of storage time by the comparison with a fresh sample (FS). Among the three drying methods that were used, AD resulted in the highest free radical scavenging activity against 1,1-diphenyl-2-picrylhydrazyl (DPPH) (IC50 = 0.0223 mg/mL) and total phenolic content (27.4 g GAE/100 g), whereas OD produced the lowest scavenging activity and TPC value. After three months of storage, the dried samples showed a high and consistent free radical scavenging activity when compared to stored fresh material. The drying methods could preserve the quality of C. caudatus during storage and the stability of its bioactive components can be maintained.
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Mediani, Ahmed; Abas, Faridah; Tan, Chin Ping; Khatib, Alfi
2014-01-01
The present study was conducted to determine the effect of air (AD), oven (OD) and freeze drying (FD) on the free radical scavenging activity and total phenolic content (TPC) of Cosmos caudatus and the effect of storage time by the comparison with a fresh sample (FS). Among the three drying methods that were used, AD resulted in the highest free radical scavenging activity against 1,1-diphenyl-2-picrylhydrazyl (DPPH) (IC50 = 0.0223 mg/mL) and total phenolic content (27.4 g GAE/100 g), whereas OD produced the lowest scavenging activity and TPC value. After three months of storage, the dried samples showed a high and consistent free radical scavenging activity when compared to stored fresh material. The drying methods could preserve the quality of C. caudatus during storage and the stability of its bioactive components can be maintained. PMID:26784876
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Lambe, Andrew; Massoli, Paola; Zhang, Xuan; ...
2017-06-22
Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O 3) is photolyzed at 254 nm to produce O( 1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O 3 hinders the ability of oxidation flow reactors to simulate NO x-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NO x (NO+NO 2) to nitric acid (HNO 3), making it impossible to sustain NOmore » x at levels that are sufficient to compete with hydroperoxy (HO 2) radicals as a sink for organic peroxy (RO 2) radicals. We developed a new method that is well suited to the characterization of NO x-dependent SOA formation pathways in oxidation flow reactors. NO and NO 2 are produced via the reaction O( 1D) + N 2O → 2NO, followed by the reaction NO + O 3 → NO 2+O 2. Laboratory measurements coupled with photochemical model simulations suggest that O( 1D) + N 2O reactions can be used to systematically vary the relative branching ratio of RO 2 + NO reactions relative to RO 2 + HO 2 and/or RO 2 + RO 2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO 3 -) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NO x-influenced environments and in laboratory chamber experiments.« less
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NASA Astrophysics Data System (ADS)
Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William
2017-06-01
Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Lambe, Andrew; Massoli, Paola; Zhang, Xuan
Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O 3) is photolyzed at 254 nm to produce O( 1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O 3 hinders the ability of oxidation flow reactors to simulate NO x-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NO x (NO+NO 2) to nitric acid (HNO 3), making it impossible to sustain NOmore » x at levels that are sufficient to compete with hydroperoxy (HO 2) radicals as a sink for organic peroxy (RO 2) radicals. We developed a new method that is well suited to the characterization of NO x-dependent SOA formation pathways in oxidation flow reactors. NO and NO 2 are produced via the reaction O( 1D) + N 2O → 2NO, followed by the reaction NO + O 3 → NO 2+O 2. Laboratory measurements coupled with photochemical model simulations suggest that O( 1D) + N 2O reactions can be used to systematically vary the relative branching ratio of RO 2 + NO reactions relative to RO 2 + HO 2 and/or RO 2 + RO 2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO 3 -) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NO x-influenced environments and in laboratory chamber experiments.« less
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NASA Technical Reports Server (NTRS)
Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John;
2017-01-01
Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO+NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D)+N2O->2NO, followed by the reaction NO+O3->NO2+O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D)+N2O reactions can be used to systematically vary the relative branching ratio of RO2 +NO reactions relative to RO2 +HO2 and/or RO2+RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO-3 ) reagent ion to detect gas-phase oxidation products of isoprene and -pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.
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Effects of oxygen radicals in low-pressure surface-wave plasma on sterilization
NASA Astrophysics Data System (ADS)
Nagatsu, Masaaki; Terashita, Fumie; Nonaka, Hiroyuki; Xu, Lei; Nagata, Toshi; Koide, Yukio
2005-05-01
The effects of oxygen radicals on sterilization were studied using a 2.45GHz surface-wave oxygen plasma. A population of 1.5×106 Bacillus stearothermophilus spores was irradiated for 3min or more with oxygen plasma, generated at pressures between 6 and 14Pa. The decimal reduction value (D value), a measure of the effectiveness of sterilization, was determined to be about 15-25s. Using only oxygen radicals, excluding all charged particles, the 1.5×106 spores were sterilized with a D value of 30-45s after 5min or more of irradiation. On scanning electron microscopy, the length and width of the spores changed significantly due to chemical etching by oxygen radicals.
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NASA Astrophysics Data System (ADS)
Krishna, Rahul; Titus, Elby
2017-12-01
Here, we demonstrate for the first time the structural evolution of 1D graphene nanotubes (GNTs) by the cutting of two dimensional (2D) graphene oxide (GO) sheet in reducing environment at ambient conditions in presence of Ni metal in acidic environment. We observed that in-situ generated radical hydrogen (Hrad) responsible for cutting of graphene sheets and re-structuring of 2D sheet structure to one 1D nanotubes. Structural evolution of GNTs was confirmed by using of transmission electron microscopy (TEM) technique. The current vs. voltage (I-V) characteristics of GNTs displayed room temperature (RT) negative differential resistance (NDR) effect which is typical in nanowires, suggested the applicability of nanomaterial for various kind of electronics applications such as memory devices and transistors fabrication.
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Search for first-generation scalar leptoquarks in p anti-p collisions at s**(1/2) = 1.96-TeV
DOE Office of Scientific and Technical Information (OSTI.GOV)
Abazov, V.M.; Abbott, B.; Abolins, M.
2004-12-01
The authors report on a search for pair production of first-generation scalar leptoquarks (LQ) in p{bar p} collisions at {radical}s = 1.96 TeV using an integrated luminosity of 252 pb{sup -1} collected at the Fermilab Tevatron collider by the D0 detector. They observe no evidence for LQ production in the topologies arising from LQ{ovr LQ} {yields} eqeq and LQ{ovr LQ} {yields} eqvq, and derive 95% C.L. lower limits on the LQ mass as a function of {beta}, where {beta} is the branching fraction for LQ {yields} eq. The limits are 241 and 218 GeV/c{sup 2} for {beta} = 1 andmore » 0.5, respectively. These results are combined with those obtained by D0 at {radical}s = 1.8 TeV, which increases these LQ mass limits to 256 and 234 GeV/c{sup 2}.« less
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Lissi, E A; Modak, B; Torres, R; Escobar, J; Urzua, A
1999-06-01
Total reactive antioxidant potential (TRAP) of resinous exudates from Heliotropium species was evaluated by measuring the bleaching of stable free radicals. The antioxidant capacity of the resinous exudates in Trolox equivalents, evaluated from the bleaching of ABTS derived radical cations, ranged from 2.0 M (H. huascoense) to 5.2 M (H. stenophyllum), indicating a very high concentration of phenolic compounds. Considerably smaller values were obtained by measuring the bleaching of DPPH radicals. The ratio between the values obtained employing ABTS derived radicals and DPPH, ranged from 37 (H. megalanthum) to 4.5 (H. chenopodiaceum variety typica). The magnitude of the difference can be considered as an indication of the relative reactivity of the antioxidants present in the exudates. Similar ratios were observed when stoichiometric coefficients were evaluated for representative purified flavonoids obtained from the resinous exudates.
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Code of Federal Regulations, 2011 CFR
2011-07-01
.... (1985). (13) Mill T., Hendry D.G., Richardson H. “Free radical oxidants in natural waters.” Science, 207...)(7) of this section); peroxy radicals (RO2−) (Mill et al. (1981) under paragraph (f)(9) of this section; Mill et al. (1983) under paragraph (f)(8) of this section); hydroxyl radicals (HO−) (Mill et al...
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Code of Federal Regulations, 2010 CFR
2010-07-01
.... (1985). (13) Mill T., Hendry D.G., Richardson H. “Free radical oxidants in natural waters.” Science, 207...)(7) of this section); peroxy radicals (RO2−) (Mill et al. (1981) under paragraph (f)(9) of this section; Mill et al. (1983) under paragraph (f)(8) of this section); hydroxyl radicals (HO−) (Mill et al...
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Physocalycoside, a new phenylethanoid glycoside from Phlomis physocalyx Hub.-Mor.
Ersöz, Tayfun; Alipieva, Kalina Iv; Yalçin, Funda Nuray; Akbay, Pinar; Handjieva, Nedjalka; Dönmez, Ali A; Popov, Simeon; Caliş, Ihsan
2003-01-01
A new phenylethanoid tetraglycoside, physocalycoside (2), was isolated from the aerial parts of Phlomis physocalyx. Its structure was identified as 3-hydroxy-4-methoxy-beta-phenylethoxy-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)]-4-O-feruloyl-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranoside, on the basis of spectroscopic evidence. In addition, one known iridoid glucoside, lamiide (1) and five known phenylethanoid glycosides, wiedemannioside C (3), verbascoside (= acteoside) (4), leucosceptoside A (5), martynoside (6), and forsythoside B (7) were also characterized. Compounds 2-7 demonstrated radical scavenging properties towards the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical.
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Semi-Continuous Fermentation of Onion Vinegar and Its Functional Properties.
Lee, Sulhee; Lee, Jin-A; Park, Gwi-Gun; Jang, Jae-Kweon; Park, Young-Seo
2017-08-08
For the fermentation of vinegar using onion, acetic acid bacteria and yeast strains with high fermentation ability were screened. Among them, Saccharomyces cerevisiae 1026 was selected as a starter for ethanol production and Acetobacter orientalis MAK88 was selected as a vinegar producer. When the two-stage fermentation of onion vinegar was performed at 28 °C, the titratable acidity reached 4.80% at 24 h of fermentation. When semi-continuous fermentation proceeded to charge-discharge consisting of three cycles, the acetic acid content reached 4.35% at 48 h of fermentation. At this stage, the fermentation efficiency, acetic acid productivity, and specific product formation rate were 76.71%, 17.73 g/(L·d), and 20.58 g/(g·h), respectively. The process in this study significantly reduced the fermentation time and simplified the vinegar production process. The content of total flavonoids and total polyphenols in onion vinegar were 104.36 and 455.41 μg/mL, respectively. The antioxidant activities of onion vinegar in terms of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic) acid (ABTS⁺) radical scavenging activity, and reducing power were 75.33%, 98.88%, and 1.28, respectively. The nitrite scavenging abilities of onion vinegar were 95.38 at pH 1.2. The onion vinegar produced in this study showed higher organoleptic acceptability than commercial onion vinegar.
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Melen, Rebecca L; Less, Robert J; Pask, Christopher M; Rawson, Jeremy M
2016-11-21
The synthesis and structural characterization of a series of perfluoroaryldiselenadiazolyls [DSeDA; p-XC 6 F 4 CNSeSeN (X = F, Cl, Br, CF 3 , NO 2 , and CN for 2a-2f, respectively)] are described. Concentration-dependent solution UV/vis measurements on 2a follow the Beer-Lambert law and the transitions assigned through time-dependent density functional theory (TD-DFT) studies, indicating little propensity for dimerization in solution (10 -3 -10 -4 M). Solution electron paramagnetic resonance (EPR) spectra reveal that these radicals exhibit a broad featureless singlet around g = 2.04 but form well-resolved anisotropic EPR spectra in frozen solution, from which spin densities were determined and found to reflect an increase in the spin density at the chalcogen in relation to the corresponding dithiadiazolyl (DTDA) radicals, p-XC 6 F 4 CNSSN. The solid-state structures of 2a and 2d-2f all adopt spin-paired cis-cofacial dimers in which the dimers are held together via multicenter π*-π* "pancake bonding" interactions. Conversely, 2b and 2c exhibit an orthogonal mode of association, which is unique to DSeDA chemistry but which also affords a singlet ground state evidenced by SQUID magnetometry. The more sterically demanding diselenadiazolyl radical 2f was also prepared and exhibits a trans-antarafacial dimerization mode. DFT studies [UPBE0-D3 ccPVTZ-PP(-F)++] on the model radical HCNSeSeN confirm that each dimer is a stable energy minimum on the potential energy surface, reproducing well the experimental geometric parameters with relative stability in the order cis-cofacial > orthogonal > trans-antarafacial. Computational studies reflect stronger dimerization for DSeDA radicals in relation to their sulfur analogues, consistent with the experimental observation: While 2a and 2d are isomorphous with their corresponding DTDA radicals, 2b, 2c, and 2e-2g are all dimeric, in contrast to their DTDA analogues, which are monomeric in the solid-state. A study on 2f reveals that significant geometric strain accumulates in order to support the propensity for both cis dimerization and intermolecular CN···Se interactions. Conversely, p-NCC 6 F 4 CNSSN likely forfeits dimerization in the analogous packing motif in order to release strain but retains the favorable intermolecular CN···S interactions.
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Champion, Guillaume; Lalioti, Nikolia; Tangoulis, Vassilis; Arrio, Marie-Anne; Sainctavit, Philippe; Villain, Françoise; Caneschi, Andrea; Gatteschi, Dante; Giorgetti, Christine; Baudelet, François; Verdaguer, Michel; Cartier dit Moulin, Christophe
2003-07-09
We report here the X-ray magnetic circular dichroism (XMCD) study at the Gd M(4,5)- and L(2,3)-edges of two linear magnetic chains involving Gd(III) cations bridged by nitronyl nitroxide radicals. This spectroscopy directly probes the magnetic moments of the 4f and 5d orbitals of the gadolinium ions. We compare macroscopic magnetic measurements and local XMCD signals. The M(4,5)-edges results are in agreement with the J values extracted from the fits of the SQUID magnetic measurements. The L(2,3)-edges signals show that the electronic density in the Gd 5d orbitals depends on the neighbors of the gadolinium cations. Nevertheless, the 5d orbitals do not seem to play any role in the superexchange pathway between radicals through the metal ion proposed to explain the particular magnetic exchange interactions between the radicals in these chains.
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Cheel, José; Schmeda-Hirschmann, Guillermo; Jordan, Miguel; Theoduloz, Cristina; Rodríguez, Jaime A; Gerth, André; Wilken, Dirk
2007-01-01
An in vitro propagation system was developed to obtain shoot and root cultures from the Andean spice Sanicula graveolens (Apiaceae). Propagation of shoots, roots and plantlets was achieved by the temporary immersion system. The free radical scavenging effect of the methanol/water (7:3 v/v) extracts was determined by the discoloration of the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH). Total phenolic, flavonoid, chlorogenic acid (CA) and quercetin 3-O-glucoside content in the samples was assessed by spectrophotometry and DAD-HPLC analysis, respectively. On a dry weight basis, the crude extracts showed total phenolic values ranging from 3.57 to 6.93%, with highest content for the root culture sample. Total flavonoid content ranged from 1.23 to 2.23% and was lower for the root culture. Chlorogenic acid and neochlorogenic acid were identified by TLC in all samples. Highest free radical scavenging effect was observed for the root culture which also presented the highest CA content. Two of the shoot culture samples, with similar IC50 values in the DPPH discoloration assay, also presented close quercetin-3-O-glucoside content.
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Water accelerated transformation of d-limonene induced by ultraviolet irradiation and air exposure.
Li, Li Jun; Hong, Peng; Jiang, Ze Dong; Yang, Yuan Fan; Du, Xi Ping; Sun, Hao; Wu, Li Ming; Ni, Hui; Chen, Feng
2018-01-15
d-Limonene is a fragrant chemical that widely exists in aromatic products. Isotopic labelling of water molecules plus GC-MS and GC-PCI-Q-TOF analyses were used to investigate the influence of water molecules on chemical transformation of d-limonene induced by UV irradiation and air exposure. The results showed that the synergistic effect of UV irradiation, air exposure and water presence could facilitate d-limonene transformation into the limonene oxides: p-mentha-2,8-dienols, hydroperoxides, carveols, l-carvone and carvone oxide. UV irradiation, air exposure, or water alone, however, caused negligible d-limonene transformation. With the aid of isotopic labelling of water and oxygen molecules, it was found that water molecules were split into hydrogen radicals and hydroxyl radicals, and the hydrogen radicals, in particular, promoted the transformation reactions. This study has elucidated the mechanism and factors that influence the transformation of d-limonene, which will benefit industries involved in production and storage of d-limonene-containing products. Copyright © 2017 Elsevier Ltd. All rights reserved.
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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.
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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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hernandez, Federico J.; INFIQC, Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Centro Láser de Ciencias Moleculares, Universidad Nacional de Córdoba, Ciudad Universitaria, Pabellón, X5000HUA Córdoba; Brice, Joseph T.
2015-10-28
Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH–H{sub 2}O and OH(D{sub 2}O){sub n} clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH–H{sub 2}O and OH–D{sub 2}O binary complexes, revealing amore » 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D{sub 2}O){sub 2}, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for “up-up” and “up-down” structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D{sub 2}O molecules are observed shifted approximately 300 cm{sup −1} to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D{sub 2}O){sub 3}.« less
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McCullough, Karey D; Bartfay, Wally J
2007-04-01
Genetic disorders of iron metabolism such as primary and secondary hemochromatosis affect thousands of individuals worldwide and are major causes of liver dysfunction, morbidity, and mortality. Although the exact mechanism of hepatic injury associated with these genetic disorders is not fully understood, the propagation of excess concentrations of iron-catalyzed oxygen free radicals (OFRs) may play a role. The authors hypothesized that chronic iron burden would result in dose-dependent (a) increases in hepatic iron stores, (b) increases in hepatic OFR-mediated hepatic cellular injury as quantified by the cytotoxic aldehydes malondialdehyde (MDA) and hexanal, and (c) decreases in protective antioxidant reserve status as quantified by plasma vitamin E (alpha-tocopherol) levels in a murine model. Twenty B(6)D(2)F1 male mice were randomized to the (a) saline control (0.05 mL intraperiotoneal [i.p.]/mouse/day, n = 5), (b) 100 mg total iron burden (n = 5), (c) 200 mg total iron burden (n = 5), or (d) 400 mg total iron burden (n = 5) group. Iron burden was achieved by daily injections of iron dextran (Imferon, 0.05 mL i.p./mouse/day). In comparison to control mice and in support of the hypothesis, the authors observed significant dose-dependent increases in total hepatic iron burden (p < .001) with corresponding increases in MDA and hexanal concentrations (p < .001) and decreases in the protective plasma antioxidant vitamin E (p < .001). These findings suggest that iron-catalyzed OFR-mediated damage may play a role in damaging the liver in chronic states of iron burden.
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NASA Astrophysics Data System (ADS)
Whalley, Lisa K.; Stone, Daniel; Dunmore, Rachel; Hamilton, Jacqueline; Hopkins, James R.; Lee, James D.; Lewis, Alastair C.; Williams, Paul; Kleffmann, Jörg; Laufs, Sebastian; Woodward-Massey, Robert; Heard, Dwayne E.
2018-02-01
Measurements of OH, HO2, RO2i (alkene and aromatic-related RO2) and total RO2 radicals taken during the ClearfLo campaign in central London in the summer of 2012 are presented. A photostationary steady-state calculation of OH which considered measured OH reactivity as the OH sink term and the measured OH sources (of which HO2+ NO reaction and HONO photolysis dominated) compared well with the observed levels of OH. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2, however, highlighted a substantial discrepancy between radical observations under lower NOx conditions ([NO] < 1 ppbv), typically experienced during the afternoon hours, and indicated that the model was missing a significant peroxy radical sink; the model overpredicted HO2 by up to a factor of 10 at these times. Known radical termination steps, such as HO2 uptake on aerosols, were not sufficient to reconcile the model-measurement discrepancies alone, suggesting other missing termination processes. This missing sink was most evident when the air reaching the site had previously passed over central London to the east and when elevated temperatures were experienced and, hence, contained higher concentrations of VOCs. Uncertainties in the degradation mechanism at low NOx of complex biogenic and diesel related VOC species, which were particularly elevated and dominated OH reactivity under these easterly flows, may account for some of the model-measurement disagreement. Under higher [NO] (> 3 ppbv) the box model increasingly underpredicted total [RO2]. The modelled and observed HO2 were in agreement, however, under elevated NO concentrations ranging from 7 to 15 ppbv. The model uncertainty under low NO conditions leads to more ozone production predicted using modelled peroxy radical concentrations ( ˜ 3 ppbv h-1) versus ozone production from peroxy radicals measured ( ˜ 1 ppbv h-1). Conversely, ozone production derived from the predicted peroxy radicals is up to an order of magnitude lower than from the observed peroxy radicals as [NO] increases beyond 7 ppbv due to the model underprediction of RO2 under these conditions.
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Kirk, Benjamin B.; Savee, John D.; Trevitt, Adam J.; ...
2015-07-16
The reaction of small hydrocarbon radicals (i.e. ˙CN, ˙C 2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C 2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC≡C˙), a likely product frommore » the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d 4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (–H = 27%, –CH 3 = 73%) and (–H = 14%, –CH 3 = 86%), respectively. Altogether, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.« less
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Kirk, Benjamin B; Savee, John D; Trevitt, Adam J; Osborn, David L; Wilson, Kevin R
2015-08-28
The reaction of small hydrocarbon radicals (i.e.˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC[triple bond, length as m-dash]C˙), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (-H = 27%, -CH3 = 73%) and (-H = 14%, -CH3 = 86%), respectively. Together, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kirk, Benjamin B.; Savee, John D.; Trevitt, Adam J.
The reaction of small hydrocarbon radicals (i.e. ˙CN, ˙C 2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C 2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC≡C˙), a likely product frommore » the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d 4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (–H = 27%, –CH 3 = 73%) and (–H = 14%, –CH 3 = 86%), respectively. Altogether, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.« less
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Yuh, Bertram E; Nazmy, Michael; Ruel, Nora H; Jankowski, Jason T; Menchaca, Anita R; Torrey, Robert R; Linehan, Jennifer A; Lau, Clayton S; Chan, Kevin G; Wilson, Timothy G
2012-11-01
Comprehensive and standardized reporting of adverse events after robot-assisted radical cystectomy (RARC) and urinary diversion for bladder cancer is necessary to evaluate the magnitude of morbidity for this complex operation. To accurately identify and assess postoperative morbidity after RARC using a standardized reporting system. A total of 241 consecutive patients underwent RARC, extended pelvic lymph node dissection, and urinary diversion between 2003 and 2011. In all, 196 patients consented to a prospective database, and they are the subject of this report. Continent diversions were performed in 68% of cases. All complications within 90 d of surgery were defined and categorized by a five-grade and 10-domain modification of the Clavien system. Univariable and multivariable logistic regression analyses were used to identify predictors of complications. Grade 1-2 complications were categorized as minor, and grade 3-5 complications were categorized as major. All blood transfusions were recorded as grade ≥2. Eighty percent of patients (156 of 196 patients) experienced a complication of any grade ≤90 d after surgery. A total of 475 adverse events (113 major) were recorded, with 365 adverse events (77%) occurring ≤30 d after surgery. Sixty-eight patients (35%) experienced a major complication within the first 90 d. Other than blood transfusions given (86 patients [43.9%]), infectious, gastrointestinal, and procedural complications were the most common, at 16.2%, 14.1%, and 10.3%, respectively. Age, comorbidity, preoperative hematocrit, estimated blood loss, and length of surgery were predictive of a complication of any grade, while comorbidity, preoperative hematocrit, and orthotopic diversion were predictive of major complications. The 90-d mortality rate was 4.1%. The main limitation is lack of a control group. Analysis of postoperative morbidity following RARC demonstrates a considerable complication rate, though the rate is comparable to contemporary open series that followed similar reporting guidelines. This finding reinforces the need for complete and standardized reporting when evaluating surgical techniques and comparing published series. Copyright © 2012 European Association of Urology. Published by Elsevier B.V. All rights reserved.
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Zamani, Mehdi; Moradi Delfani, Ali; Jabbari, Morteza
2018-05-03
The radical scavenging performance and antioxidant activity of γ-alumina nanoparticles towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical were investigated by spectroscopic and computational methods. The radical scavenging ability of γ-alumina nanoparticles in the media with different polarity (i.e. i-propanol and n-hexane) was evaluated by measuring the DPPH absorbance in UV-Vis absorption spectra. The structure and morphology of γ-alumina nanoparticles before and after adsorption of DPPH were studied using XRD, FT-IR and UV-Vis spectroscopic techniques. The adsorption of DPPH free radical on the clean and hydrated γ-alumina (1 1 0) surface was examined by dispersion corrected density functional theory (DFT-D) and natural bond orbital (NBO) calculations. Also, time-dependent density functional theory (TD-DFT) was used to predict the absorption spectra. The adsorption was occurred through the interaction of radical nitrogen N and NO 2 groups of DPPH with the acidic and basic sites of γ-alumina surface. The high potential for the adsorption of DPPH radical on γ-alumina nanoparticles was investigated. Interaction of DPPH with Brønsted and Lewis acidic sites of γ-alumina was more favored than Brønsted basic sites. The following order for the adsorption of DPPH over the different active sites of γ-alumina was predicted: Brønsted base < Lewis acid < Brønsted acid. These results are of great significance for the environmental application of γ-alumina nanoparticles in order to remove free radicals. Copyright © 2018. Published by Elsevier B.V.
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Ji, Xinjian; Li, Yongzhen; Ding, Wei; Zhang, Qi
2015-07-27
NosL is a radical S-adenosyl-L-methionine (SAM) enzyme that converts L-Trp to 3-methyl-2-indolic acid, a key intermediate in the biosynthesis of a thiopeptide antibiotic nosiheptide. In this work we investigated NosL catalysis by using a series of Trp analogues as the molecular probes. Using a benzofuran substrate 2-amino-3-(benzofuran-3-yl)propanoic acid (ABPA), we clearly demonstrated that the 5'-deoxyadenosyl (dAdo) radical-mediated hydrogen abstraction in NosL catalysis is not from the indole nitrogen but likely from the amino group of L-Trp. Unexpectedly, the major product of ABPA is a decarboxylated compound, indicating that NosL was transformed to a novel decarboxylase by an unnatural substrate. Furthermore, we showed that, for the first time to our knowledge, the dAdo radical-mediated hydrogen abstraction can occur from an alcohol hydroxy group. Our study demonstrates the intriguing promiscuity of NosL catalysis and highlights the potential of engineering radical SAM enzymes for novel activities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Antioxidant ability and mechanism of rhizoma Atractylodes macrocephala.
Li, Xican; Lin, Jian; Han, Weijuan; Mai, Wenqiong; Wang, Li; Li, Qiang; Lin, Miaofang; Bai, Mingsong; Zhang, Lishan; Chen, Dongfeng
2012-11-13
Rhizoma Atractylodes macrocephala (AM) has been used in Traditional Chinese Medicine (TCM) for about 2,000 years. In the study, we firstly determined the antioxidant levels of five AM extracts by •OH-scavenging, •O2−-scavenging, Fe2+-chelating, Cu2+-chelating, DPPH·-scavenging, and ABTS+·-scavenging assays. After measurement of the chemical contents in five AM extracts, we quantitatively analyzed the correlations between antioxidant levels and chemical contents. It was observed that total phenolics and total flavonoids had significant positive correlations with antioxidant levels (R = 0.685 and 0.479, respectively). In contrast, total sugars and total saponins presented lower correlations with antioxidant levels (R=−0.272 and 0.244, respectively). It means that antioxidant activity of AM should be attributed to total phenolics (including phenolic acids and flavonoids), and not total sugars and total saponins. Further analysis indicated that phenolic acids exhibited higher R values with radical-scavenging assays (R=0.32–1.00), while flavonoids showed higher R values with metal-chelating assays (R=0.86 and 0.90). In conclusion, AM exerts its antioxidant effect through metal-chelating, and radical-scavenging which is via donating hydrogen atom and donating electron. Its metal-chelating may result from flavonoids, while its radical-scavenging can be attributed to phenolic acids, especially caffeic acid, ferulic acid, and protocatechuic acid.
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NASA Astrophysics Data System (ADS)
Pan, Huilin; Liu, Kopin
2018-01-01
(2 + 1) resonance-enhanced multiphoton ionization (REMPI) detection of methyl radicals, in particular that via the intermediate 3p Rydberg states, has shown to be a powerful method and thus enjoyed a wide range of applications. Methyl has six vibrational modes. Among them—including partially and fully deuterated isotopologs—four out of twenty vibrational frequencies in the intermediate 3p states have so far eluded direct spectroscopic determination. Here, by exploiting the imaging spectroscopy approach to a few judiciously selected chemical reactions, the four long-sought REMPI bands—CHD2(611), CH2D(311), CH2D(511), and CH2D(611)—are discovered, which complete the REMPI identification for probing any vibrational mode of excitation of methyl radical and its isotopologs. These results, in conjunction with those previously reported yet scattered in the literature, are summarized here for ready reference, which should provide all necessary information for further spectral assignments and future studies of chemical dynamics using this versatile REMPI scheme.
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Kelly, Christopher B; Patel, Niki R; Primer, David N; Jouffroy, Matthieu; Tellis, John C; Molander, Gary A
2017-03-01
Visible-light-activated photoredox catalysts provide synthetic chemists with the unprecedented capability to harness reactive radicals through discrete, single-electron transfer (SET) events. This protocol describes the synthesis of two transition metal complexes, [Ir{dF(CF 3 ) 2 ppy} 2 (bpy)]PF 6 (1a) and [Ru(bpy) 3 ](PF 6 ) 2 (2a), that are activated by visible light. These photoredox catalysts are SET agents that can be used to facilitate transformations ranging from proton-coupled electron-transfer-mediated cyclizations to C-C bond constructions, dehalogenations, and H-atom abstractions. These photocatalysts have been used in the synthesis of medicinally relevant compounds for drug discovery, as well as the degradation of biological polymers to access fine chemicals. These catalysts are prepared from IrCl 3 and RuCl 3 , respectively, in three chemical steps. These steps can be described as a series of two ligand modifications followed by an anion metathesis. Using the cost-effective, scalable procedures described here, the ruthenium-based photocatalyst 2a can be synthesized in a 78% overall yield (∼8.1 g), and the iridium-based photocatalyst 1a can be prepared in a 56% overall yield (∼4.4 g). The total time necessary for the complete protocols ranges from ∼2 d for 2a to 5-7 d for 1a. Procedures for applying each catalyst in representative photoredox/Ni cross-coupling to form C sp 3-C sp 2 bonds using the appropriate radical precursor-organotrifluoroborates with 1a and bis(catecholato)alkylsilicates with 2a-are described. In addition, more traditional photoredox-mediated transformations are included as diagnostic tests for catalytic activity.
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Radical observations during the Clean air for London project
NASA Astrophysics Data System (ADS)
Whalley, L. K.; Stone, D.; Clancy, N.; Lee, J. D.; Laufs, S.; Kleffmann, J.; Heard, D. E.
2012-12-01
With greater than 50 % of the global population residing in urban conurbations, poor urban air quality has a demonstrable effect on human health. OH and HO2 radicals, (collectively termed HOx) together with RO2 radicals, mediate virtually all of the oxidative chemistry in the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3 and particulates. Understanding the chemistry of free-radicals in the atmosphere is essential in improving predictions of the lifetimes of pollutants and spatial scales of their transport within urban areas. Results from earlier field campaigns in urban and polluted regions have demonstrated the significance of HONO photolysis and alkene ozonolysis in the production of HOx radicals. In many cases, however, measurements of HONO have not been made, reducing the ability to evaluate model successes for OH in these environments. Here we present measurements of OH, HO2, RO2 and OH reactivity taken during the wintertime (January - February, 2012) and summertime (July - August, 2012) as part of the Clean air for London (ClearfLo) project in London. RO2 was detected using a newly developed flow-reactor laser-induced fluorescence technique which is able to discriminate between HO2 and organic peroxy radicals [1]. Low concentrations of radicals were observed during the wintertime, midday [OH], [HO2] and [RO2] were ~ 0.04, 0.8 and 1.5 pptv respectively, comparable to observations of radicals at other urban locations in winter [2,3,4], and which displayed a negative correlation with NO concentrations. OH reactivity was high and largely tracked the diurnal profiles of NOx and CO, with the highest reactivity ~100 s-1 observed during the morning rush hour. Analysis of factors controlling OH concentrations during the wintertime suggests that the formation of OH from the photolysis of O3 and subsequent reaction of O(1D) with H2O is a minor contribution both under high and low NOx conditions owing to the low rate of photolysis experienced and instead OH from photolysis of HONO (measured during ClearfLo using the LOPAP technique) [5], ozonolysis of alkenes and the reaction of HO2 with NO dominated the oxidative capacity of this urban location. Summertime observations coincided with the London 2012 Olympics. During this observational period, a number of high pollution events were observed where meteorological conditions favoured sustained, elevated ozone production (peaking at 100 ppbv). Radical concentrations were elevated during these episodes, with [OH], [HO2] and [RO2] peaking at ~ 0.16, 14 and 10 pptv respectively. The influence of HO2 and RO2 radicals on ozone production during these episodes will be presented along with a comparison of factors influencing modelled radical concentrations during the summer and wintertime. [1] Fuchs, H. et al., Review of Scientific Instruments, 79, 084104, 2008 [2] Heard, D.E. et al., Geophysical Research Letters, 13, L18112, 2004 [3] Ren, X. et al., Atmospheric Environment, 40, S252-S263, 2006 [4] Kanaya, Y. et al., Journal of Geophysical Research - Atmospheres, 112, D21312, 2007 [5] Kleffmann, J. et al., Atmospheric Environment, 40, 3640-3652, 2006
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Tang, Weizhi; Dong, Mingsheng; Wang, Weilu; Han, Shuo; Rui, Xin; Chen, Xiaohong; Jiang, Mei; Zhang, Qiuqin; Wu, Junjun; Li, Wei
2017-10-01
Three released exopolysaccharide fractions (r-EPS1, r-EPS2 and r-EPS3) were isolated from the fermented milk of Lactobacillus delbrueckii ssp. bulgaricus SRFM-1 and purified by anion exchange chromatography, and characterizations of the structures were conducted. The r-EPS1 and r-EPS2 were homogenous with the average molecular weights of 3.97×10 5 Da and 3.86×10 5 Da, respectively. Three r-EPS fractions were composed of galactose and glucose with a molar ratio of 1.23: 1.00, 1.33: 1.00 and 1.00: 1.34, respectively. Structural characterization indicated that the r-EPS1 contained a backbone of →6-β-d-Galp-(1→4)-β-d-Glcp-(1→4)-α-d-Galp-(1→4)-β-d-Galp-(1→6)-β-d-Galp-(1→4)-β-d-Glcp-(1→4)-α-d-Galp-(1→4)-β-d-Galp-(1→4)-α-d-Glcp-(1→, and had three branching points which existed in terminal with D-Glcp residues with α/β-d-(1→6) linkages. The r-EPS2 was composed of →6-β-d-Galp-(1→4)-β-d-Glcp-(1→6)-α-d-Galp-(1→ as the backbone chain with a branching point which also existed in terminal D-Glcp residue with β-(1→6) linkage. In addition, three r-EPS fractions exhibited strong scavenging activities on superoxide radical, hydroxyl radical, DPPH radical and chelating activity on ferrous ion, and their antioxidant activities decreased in the order of r-EPS1>r-EPS2>r-EPS3. Copyright © 2017 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Yamaoki, Rumi; Kimura, Shojiro; Ohta, Masatoshi
2015-12-01
The relationship between electron spin resonance (ESR) signal intensity of irradiated plant materials and sugar content was investigated by spectral analysis using peony roots. A weak background signal near g=2.005 was observed in the roots. After a 10 kGy irradiation, the ESR line broadened and the intensity increased, and the spectral characteristics were similar to a typical spectrum of irradiated food containing crystalline sugars. The free radical concentration was nearly stable 30 days after irradiation. The spectrum of peony root 30 days after irradiation was simulated using the summation of the intensities of six assumed components: radical signals derived from (a) sucrose, (b) glucose, (c) fructose, (d) cellulose, (e) the background signal near g=2.005 and (f) unidentified component. The simulated spectra using the six components were in agreement with the observed sample spectra. The intensity of sucrose radical signal in irradiated samples increased proportionally up to 20 kGy. In addition, the intensity of sucrose radical signals was strongly correlated with the sucrose contents of the samples. The results showed that the radiation sensitivity of sucrose in peony roots was influenced little by other plant constituents. There was also a good correlation between the total area of the spectra and the sucrose content, because the sucrose content was higher than that of other sugars in the samples. In peony roots, estimation of the absorbed dose from the ESR signal intensity may be possible by a calibration method based on the sucrose content.
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Nakagawa, Kouichi; Maeda, Hayato
2017-02-01
We investigated the location and distribution of paramagnetic species in dry black, brown, and yellow (normal) soybean seeds using electron paramagnetic resonance (EPR), X-band (9 GHz) EPR imaging (EPRI), and HPLC. EPR primarily detected two paramagnetic species in black soybean. These two different radical species were assigned as stable organic radical and Mn 2+ species based on the g values and hyperfine structures. The signal from the stable radical was noted at g ≈ 2.00 and was relatively strong and stable. Subsequent noninvasive two-dimensional (2D) EPRI of the radical present in black soybean revealed that the stable radical was primarily located in the pigmented region of the soybean coat, with very few radicals observed in the soybean cotyledon (interior). Pigments extracted from black soybean were analyzed using HPLC. The major compound was found to be cyanidin-3-glucoside. Multi-EPR and HPLC results indicate that the stable radical was only found within the pigmented region of the soybean coat, and it could be cyanidin-3-glucoside or an oxidative decomposition product.
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Theoretical investigations of the gas phase reaction of limonene (C10H16) with OH radical
NASA Astrophysics Data System (ADS)
Ranjan Dash, Manas; Rajakumar, B.
2015-11-01
The rate coefficients of hydroxyl radical (OH) reaction with limonene were computed using canonical variational transition state theory with small-curvature tunnelling between 275 and 400 K. The geometries and frequencies of all the stationary points are calculated using hybrid density functional theory methods M06-2X and MPWB1K with 6-31+G(d,p), 6-311++G(d,p), and 6-311+G(2df,2p) basis sets. Both addition and abstraction channels of the title reaction were explored. The rate coefficients obtained over the temperature range of 275-400 K were used to derive the Arrhenius expressions: k(T) = 4.06×10-34 T7.07 exp[4515/T] and k(T) = 7.37×10-25 T3.9 exp[3169/T] cm3 molecule-1 s-1 at M06-2X/6-311+G(2df,2p) and MPWB1K/6-311+G(2df,2p) levels of theory, respectively. Kinetic study indicated that addition reactions are major contributors to the total reaction in the studied temperature range. The atmospheric lifetime (τ) of limonene due to its reactions with various tropospheric oxidants was calculated and concluded that limonene is lost in the atmosphere within a few hours after it is released. The ozone production potential of limonene was computed to be (14-18) ppm, which indicated that degradation of limonene would lead to a significant amount of ozone production in the troposphere.
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Effects of oxygen radicals in low-pressure surface-wave plasma on sterilization
DOE Office of Scientific and Technical Information (OSTI.GOV)
Nagatsu, Masaaki; Terashita, Fumie; Nonaka, Hiroyuki
2005-05-23
The effects of oxygen radicals on sterilization were studied using a 2.45 GHz surface-wave oxygen plasma. A population of 1.5x10{sup 6} Bacillus stearothermophilus spores was irradiated for 3 min or more with oxygen plasma, generated at pressures between 6 and 14 Pa. The decimal reduction value (D value), a measure of the effectiveness of sterilization, was determined to be about 15-25 s. Using only oxygen radicals, excluding all charged particles, the 1.5x10{sup 6} spores were sterilized with a D value of 30-45 s after 5 min or more of irradiation. On scanning electron microscopy, the length and width of themore » spores changed significantly due to chemical etching by oxygen radicals.« less
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Captopril and 6-mercaptopurine: whose SH possesses higher antioxidant ability?
Li, Guo-Xiang; Liu, Zai-Qun
2009-12-01
Antioxidant capacities of captopril (CAP), 6-mercaptopurine (6-MP) and 9-(beta-D-ribofuranosyl)-6-mercaptopurine (6-MPR) were investigated by interacting them with 2,2'-diphenyl-1-picrylhydrazyl (DPPH), galvinoxyl radical, and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cation radical (ABTS(+)(*)), and by protecting DNA and erythrocyte against 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH) induced oxidation. It was found that CAP possessed the highest ability to donate the hydrogen atom in -SH to DPPH and galvinoxyl, while 6-MPR had the strongest ability to reduce ABTS(+)(*). In the process of protecting DNA and erythrocytes against AAPH-induced oxidation, CAP can trap 0.5 and 1.3 radicals, 6-MP can trap 0.6 and 2.2, and 6-MPR can trap 1.0 and 3.0 radicals, respectively. CAP can also protect erythrocytes against hemin-induced hemolysis.
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Young, Cora J; Washenfelder, Rebecca A; Roberts, James M; Mielke, Levi H; Osthoff, Hans D; Tsai, Catalina; Pikelnaya, Olga; Stutz, Jochen; Veres, Patrick R; Cochran, Anthony K; VandenBoer, Trevor C; Flynn, James; Grossberg, Nicole; Haman, Christine L; Lefer, Barry; Stark, Harald; Graus, Martin; de Gouw, Joost; Gilman, Jessica B; Kuster, William C; Brown, Steven S
2012-10-16
Photolabile nighttime radical reservoirs, such as nitrous acid (HONO) and nitryl chloride (ClNO(2)), contribute to the oxidizing potential of the atmosphere, particularly in early morning. We present the first vertically resolved measurements of ClNO(2), together with vertically resolved measurements of HONO. These measurements were acquired during the California Nexus (CalNex) campaign in the Los Angeles basin in spring 2010. Average profiles of ClNO(2) exhibited no significant dependence on height within the boundary layer and residual layer, although individual vertical profiles did show variability. By contrast, nitrous acid was strongly enhanced near the ground surface with much smaller concentrations aloft. These observations are consistent with a ClNO(2) source from aerosol uptake of N(2)O(5) throughout the boundary layer and a HONO source from dry deposition of NO(2) to the ground surface and subsequent chemical conversion. At ground level, daytime radical formation calculated from nighttime-accumulated HONO and ClNO(2) was approximately equal. Incorporating the different vertical distributions by integrating through the boundary and residual layers demonstrated that nighttime-accumulated ClNO(2) produced nine times as many radicals as nighttime-accumulated HONO. A comprehensive radical budget at ground level demonstrated that nighttime radical reservoirs accounted for 8% of total radicals formed and that they were the dominant radical source between sunrise and 09:00 Pacific daylight time (PDT). These data show that vertical gradients of radical precursors should be taken into account in radical budgets, particularly with respect to HONO.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Turro, N.J.; Khudyakov, I.V.; Bossmann, S.H.
1993-02-11
Time-resolved electron spin resonance (TR ESR) has been used to investigate the chemically induced dynamic electron polarization (CIDEP) generated by the interaction of stable free radicals with the triplet states of benzophenone, benzil, and 2-acetylnaphthalene. The stable radicals were mono-, di-, tri-, and tetranitroxyl free radicals possessing the 2,2,6,6-tetramethylpiperidine-N-oxyl moiety. All of the stable radical systems investigated were found to be emissively polarized by interaction with the triplet states, and the phase of polarization was independent of the sign of zero-field splitting (D) of the interacting triple molecule. Possible and likely mechanisms of polarization transfer (creation) resulting from the interactionmore » of photoexcited triplet molecules with nitroxyls in the strong electron exchange are discussed. The emissive CIDEP of nitroxyls observed in the interactions with triplet benzil, which has D > 0, provides strong support for the operation of the radical-triplet pair mechanism. Within the time scale of TR ESR experiments ([approximately]10[sup [minus]7]--10[sup [minus]6] s) no significant variation in the shape of the CIDEP spectra of the nitroxyls was observed, either in viscous media or in micelles. It is concluded that intramolecular spin exchange (or conformational change) of polynitroyls occurs much faster than the time resolution of the experiment. 24 refs., 6 figs., 1 tab.« less
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Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues.
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.
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NASA Astrophysics Data System (ADS)
Kobayashi, Sumire; Bonaventura, Zdeněk; Tholin, Fabien; Popov, Nikolay A.; Bourdon, Anne
2017-07-01
This paper presents 2D simulations of nanosecond discharges between two point electrodes for four different H2-air mixtures defined by their equivalence ratios ϕ (i.e. φ =0, air, φ =0.3, lean mixture, φ =1, stoichiometric mixture and φ =1.5, rich mixture) at atmospheric pressure and at an initial temperature of 1000 K. In a first step, we have shown that the mixture composition has only a very small influence on the discharge dynamics and structure during the streamer phase and up to the formation of the plasma channel between the two point electrodes in H2-air mixtures with φ \\in [0,1.5]. However, as the plasma channel is formed slightly earlier as the equivalence ratio increases, for a given voltage pulse, the duration of the nanosecond spark phase increases as the equivalence ratio increases. As expected, we have shown that excited states of N2 (and in particular N2(A)) and radicals (and in particular O(D), O(P), H and OH) are very efficiently produced during the voltage pulse after the start of the spark phase. After the voltage pulse, and up to 100 ns, the densities of excited states of N2 and of O(D) decrease. Conversely, most of the O(P), H and OH radicals are produced after the voltage pulse due to the dissociative quenching of electronically excited N2. As for radicals, the gas temperature starts increasing after the start of the spark phase. For all studied mixtures, the density of O(P) atoms and the gas temperature reach their maxima after the end of the voltage pulse and the densities of O(P), H and OH radicals and the maximal gas temperature increase as the equivalence ratio increases. We have shown that the production of radicals is the highest on the discharge axis and the distribution of species after the voltage pulse and up to 100 ns has a larger diameter between the electrodes than close to both electrode tips. As for species, the temperature distribution presents two hot spots close to the point electrode tips. The non-uniform distributions of radical densities and gas temperature obtained after the nanosecond voltage pulse provide accurate initial conditions for 2D reactive flow codes to study the combustion ignition on longer timescales and compare with experiments.
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The antioxidant and radical scavenging activities of black pepper (Piper nigrum) seeds.
Gülçin, Ilhami
2005-11-01
Water and ethanol crude extracts from black pepper (Piper nigrum) were investigated for their antioxidant and radical scavenging activities in six different assay, namely, total antioxidant activity, reducing power, 1,1-Diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, and metal chelating activities. Both water extract (WEBP) and ethanol extract (EEBP) of black pepper exhibited strong total antioxidant activity. The 75 microg/ml concentration of WEBP and EEBP showed 95.5% and 93.3% inhibition on peroxidation of linoleic acid emulsion, respectively. On the other hand, at the same concentration, standard antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and alpha-tocopherol exhibited 92.1%, 95.0%, and 70.4% inhibition on peroxidation of linoleic acid emulsion, respectively. Also, total phenolic content in both WEBP and EEBP were determined as gallic acid equivalents. The total phenolics content of water and ethanol extracts were determined by the Folin-Ciocalteu procedure and 54.3 and 42.8 microg gallic acid equivalent of phenols was detected in 1 mg WEBP and EEBP.
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Antioxidant activity of selected plant species; potential new sources of natural antioxidants.
Nićiforović, N; Mihailović, V; Masković, P; Solujić, S; Stojković, A; Pavlović Muratspahić, D
2010-11-01
The aim of this study was to examine six plants from Serbia for their potential antioxidant activity. Therefore, six antioxidant activity assays were carried out, including: total antioxidant capacity, DPPH free-radical scavenging, the inhibitory activity toward lipid peroxidation, Fe(3+)- reducing power, Fe(2+)- chelating ability and hydroxyl radical scavenging activity. Total phenolic and flavonoid contents were also determined for each alcoholic extract. Cotinus coggygria extract contained the highest amount of total phenols (413mg GAE /g dry extract), while the highest proportion of flavonoids was found in the Echium vulgare methanol extract (105 mg RU/g). Cotinus coggygria and Halacsya sendtneri alcoholic extracts showed the highest total antioxidant capacity (313 and 231 mg AA/g dry extract), as well as DPPH free-radical scavenging (IC(50)=9 and 99 μg/ml), inhibitory activity toward lipid peroxidation (IC(50)=3 and 17 μg/ml) and reducing power. Whereas, the greatest hydroxyl radical scavenging activity, as well as ferrous ion chelating ability showed Echium vulgare, Echium rubrum and Halacsya sendtneri. Copyright © 2010 Elsevier Ltd. All rights reserved.
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Two new flavanone glycosides of Jasminum lanceolarium and their anti-oxidant activities.
Sun, Jia-Ming; Yang, Jun-Shan; Zhang, Hui
2007-03-01
Two new flavanone glucosides, (2S)-5,7,3',5'-tetrahydroxy-flavanone 7-O-beta-D-allopyranoside (1) and (2S)-5,7,3',5'-tetrahydroxy-flavanone 7-O-beta-D-glucopyranosie (2) were isolated from the stems and leaves of Jasminum lanceolarium, along with five known compounds: Betulinaldehyde (3), betulinic acid (4), betulin (5), syringin (6) and Liriodendrin (7). Their structures were determined on the basis of spectroscopic and chemical methods. The isolated compounds were screened for their in vitro antioxidant activity through DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging assay. Compounds 2 demonstrated significant radical scavenging activity.
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Xu, Libin; Korade, Zeljka; Porter, Ned A.
2010-01-01
Free radical chain oxidation of highly oxidizable 7-dehydrocholesterol (7-DHC) initiated by 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) was carried out at 37°C in benzene for 24 hours. Fifteen oxysterols derived from 7-DHC were isolated and characterized with 1D- and 2D-NMR spectroscopy and mass spectrometry. A mechanism that involves abstraction of hydrogen atoms at C-9 and/or C-14 is proposed to account for the formation of all of the oxysterols and the reaction progress profile. In either the H-9 or H-14 mechanism, a pentadienyl radical intermediate is formed after abstraction of H-9 or H-14 by a peroxyl radical. This step is followed by the well-precedented transformations observed in peroxidation reactions of polyunsaturated fatty acids such as oxygen addition, peroxyl radical 5-exo cyclization, and SHi carbon radical attack on the peroxide bond. The mechanism for peroxidation of 7-DHC also accounts for the formation of numerous oxysterol natural products isolated from fungal species, marine sponges, and cactaceous species. In a cell viability test, the oxysterol mixture from 7-DHC peroxidation was found to be cytotoxic to Neuro2a neuroblastoma cells in the micromolar concentration range. We propose that the high reactivity of 7-DHC and the oxysterols generated from its peroxidation may play important roles in the pathogenesis of Smith-Lemli-Opitz syndrome (SLOS), X-linked dominant chondrodysplasia punctata (CDPX2), and cerebrotendinous xanthomatosis (CTX), all of these being metabolic disorders having an elevated level of 7-DHC. PMID:20121089
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[Effects of vitamin E and selenium on the metabolism of free radicals in broilers].
Xu, Jian-Xiong; Wang, Jing; Wang, Tian
2007-08-01
Taking 200 healthy broilers at 14 d of age as test materials, the free radicals in their blood and tissues were detected by electron spin resonance (ESR) and biochemical methods, aimed to investigate the effects of vitamin E (V(E)) and selenium (Se) on the metabolism of different free radicals and their dynamic changes in the broilers. The results showed that the content of NO free radicals in broilers tissues decreased with increasing supplementing level of V(E), while high supplementation of Se tended to induce the production of NO free radicals. High supplementation of V(E) and Se in feeds improved the GSH-Px and SOD activities in broilers serum and liver significantly. With the extension of experimental period, the SOD activity in tissues decreased, while GSH-PX activity increased gradually, implying that the deficiency of V(E) and/or Se might induce the overproduction of O2*- and H2O2 free radicals. H2O2 free radicals might be produced largely at early stage of V(E) and Se deficiency and declined then, while the over-production of O2*- free radicals could maintain for a long time. The deficiency of V(E) and/or Se could improve the MDA content significantly, and Se deficiency had higher effects than V(E) deficiency. There were synergic effects in the metabolism of NO, O2 and H2O2 free radicals.
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Nishikawa, Masatomo; Watanabe, Hiromitsu; Kurahashi, Toshifumi
2017-09-01
To evaluate the impact of metabolic syndrome on the early recovery of urinary continence after robot-assisted radical prostatectomy. The present study included a total of 302 consecutive Japanese patients with clinically localized prostate cancer who underwent robot-assisted radical prostatectomy. In this study, postoperative urinary continence was defined as no leak or the use of a security pad. The continence status was assessed by interviews before and 1 and 3 months after robot-assisted radical prostatectomy. Metabolic syndrome was defined as follows: body mass index ≥25 kg/m 2 and two or more of the following: hypertension, diabetes mellitus and dyslipidemia. The effect of the presence of metabolic syndrome on the continence status of these patients was retrospectively examined. A total of 116 (38.4%) and 203 (67.2%) of the 302 patients were continent at 1 and 3 months after robot-assisted radical prostatectomy, respectively. A total of 31 (10.3%) patients were judged to have metabolic syndrome. Despite the operative time being longer in patients with metabolic syndrome, no significant differences were observed in the remaining preoperative, intraoperative or postoperative variables between patients with or without metabolic syndrome. On multivariate logistic regression analysis, metabolic syndrome and the duration of hospitalization were significantly correlated with the 1-month continence status. Similarly, metabolic syndrome and estimated blood loss during surgery were independent predictors of continence rates at 3 months after robot-assisted radical prostatectomy. These findings suggest that the presence of metabolic syndrome could have a significant impact on the early recovery of urinary continence after robot-assisted radical prostatectomy. © 2017 The Japanese Urological Association.
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Fourier-transform MW spectroscopy of the SH({sup 2}{Pi}{sub i})-Ar and SD-Ar radical complexes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sumiyoshi, Yoshihiro; Endo, Yasuki; Ohshima, Yasuhiro
1996-12-31
The authors have studied the SH({sup 2}{Pi}{sub i})-Ar and SD-Ar radical complexes with FTMW spectroscopy. The complexes were produced in a supersonic free jet by a pulsed discharge of H{sub 2}S or D{sub 2}S, which was diluted to 0.35% in Ar with a stagnation pressure of 2 atm. R-branch transitions in the lower spin-orbit component ({Omega}=3/2) for the linear {sup 2}{Pi}{sub i} radicals were observed for J{double_prime} = 3/2 to J{double_prime} = 15/2 in the 8-26 GHz region. The transitions were split into two parity components owing to the parity doubling. Each parity component was split further due to themore » magnetic hyperfine interaction associated with the H/D nucleus. Rotational constants for SH-Ar and SD-Ar were determined to be 1569.656(2) and 1567.707(2)MHz respectively. The value for SH-Ar agrees well with that of a previous LIF study. From the SH/SD data, it was confirmed that the argon atom is located at the hydrogen side of the SH radical. With an assumption that the S-H bond length is equal to that in the monomer, the H-Ar distance is calculated to be 2.900 {Angstrom}, which is about 0.1 {Angstrom} longer than that in OH-Ar. The effective D{sub J} constants of SH-Ar and SD-Ar were found to have negative values of -58.4(7) and -50.7(6), kHz respectively.« less
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Mat Taha, Rosna; Banisalam, Behrooz
2015-01-01
In the present study the extracts of in vivo and in vitro grown plants as well as callus tissue of red clover were tested for their antioxidant activities, using different extraction solvent and different antioxidant assays. The total flavonoid and phenolic contents as well as extraction yield of the extracts were also investigated to determine their correlation with the antioxidant activity of the extracts. Among all the tested extracts the highest amounts of total phenolic and total flavonoids content were found in methanol extract of in vivo grown plants. The antioxidant activity of tested samples followed the order in vivo plant extract > callus extract > in vitro extract. The highest reducing power, 2,2-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radical scavenging, and chelating power were found in methanol extracts of in vivo grown red clover, while the chloroform fraction of in vivo grown plants showed the highest 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging, superoxide anion radical scavenging and hydrogen peroxide scavenging compared to the other tested extracts. A significant correlation was found between the antioxidant activity of extracts and their total phenolic and total flavonoid content. According to the findings, the extract of in vitro culture of red clover especially the callus tissue possesses a comparable antioxidant activity to the in vivo cultured plants' extract. PMID:26064936
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Lowrance, William T.; Eastham, James A.; Savage, Caroline; Maschino, A. C.; Laudone, Vincent P.; Dechet, Christopher B.; Stephenson, Robert A.; Scardino, Peter T.; Sandhu, Jaspreet S.
2012-01-01
Purpose We describe current trends in robotic and open radical prostatectomy in the United States after examining case logs for American Board of Urology certification. Materials and Methods American urologists submit case logs for initial board certification and recertification. We analyzed logs from 2004 to 2010 for trends and used logistic regression to assess the impact of urologist age on robotic radical prostatectomy use. Results A total of 4,709 urologists submitted case logs for certification between 2004 and 2010. Of these logs 3,374 included 1 or more radical prostatectomy cases. Of the urologists 2,413 (72%) reported performing open radical prostatectomy only while 961 (28%) reported 1 or more robotic radical prostatectomies and 308 (9%) reported robotic radical prostatectomy only. During this 7-year period we observed a large increase in the number of urologists who performed robotic radical prostatectomy and a smaller corresponding decrease in those who performed open radical prostatectomy. Only 8% of patients were treated with robotic radical prostatectomy by urologists who were certified in 2004 while 67% underwent that procedure in 2010. Median age of urologists who exclusively performed open radical prostatectomy was 43 years (IQR 38–51) vs 41 (IQR 35–46) for those who performed only robotic radical prostatectomy. Conclusions While the rate was not as high as the greater than 85% industry estimate, 67% of radical prostatectomies were done robotically among urologists who underwent board certification or recertification in 2010. Total radical prostatectomy volume almost doubled during the study period. These data provide nonindustry based estimates of current radical prostatectomy practice patterns and further our understanding of the evolving surgical treatment of prostate cancer. PMID:22498227
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Lowrance, William T; Eastham, James A; Savage, Caroline; Maschino, A C; Laudone, Vincent P; Dechet, Christopher B; Stephenson, Robert A; Scardino, Peter T; Sandhu, Jaspreet S
2012-06-01
We describe current trends in robotic and open radical prostatectomy in the United States after examining case logs for American Board of Urology certification. American urologists submit case logs for initial board certification and recertification. We analyzed logs from 2004 to 2010 for trends and used logistic regression to assess the impact of urologist age on robotic radical prostatectomy use. A total of 4,709 urologists submitted case logs for certification between 2004 and 2010. Of these logs 3,374 included 1 or more radical prostatectomy cases. Of the urologists 2,413 (72%) reported performing open radical prostatectomy only while 961 (28%) reported 1 or more robotic radical prostatectomies and 308 (9%) reported robotic radical prostatectomy only. During this 7-year period we observed a large increase in the number of urologists who performed robotic radical prostatectomy and a smaller corresponding decrease in those who performed open radical prostatectomy. Only 8% of patients were treated with robotic radical prostatectomy by urologists who were certified in 2004 while 67% underwent that procedure in 2010. Median age of urologists who exclusively performed open radical prostatectomy was 43 years (IQR 38-51) vs 41 (IQR 35-46) for those who performed only robotic radical prostatectomy. While the rate was not as high as the greater than 85% industry estimate, 67% of radical prostatectomies were done robotically among urologists who underwent board certification or recertification in 2010. Total radical prostatectomy volume almost doubled during the study period. These data provide nonindustry based estimates of current radical prostatectomy practice patterns and further our understanding of the evolving surgical treatment of prostate cancer. Copyright © 2012 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.
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Olugbami, J O; Gbadegesin, M A; Odunola, O A
2014-09-01
Plant-derived antioxidants with free radical scavenging activities can be relevant as chemopreventive agents against the numerous diseases associated with free radicals and reactive oxygen species. Some phytoconstituents possess antioxidant activities in biological systems. On this basis, we evaluated the antioxidant potential, and determined the total phenolic and flavonoid contents of the e thanol e xtract of the s tem bark of A nogeissus l eiocarpus [ EESAL ]. Antioxidant assays carried out include: 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging, phosphomolybdate, β-carotene bleaching, ferric reducing, and hydroxyl radical scavenging activities. Results of DPPH assay showed no significant difference ( p < 0.001) between EESAL and butylated hydroxyanisole [BHA], while EESAL exhibited a significantly ( p < 0.001) higher activity than BHT [butylated hydroxytoluene]. Phosphomolybdate method recorded a total antioxidant capacity of 190.00 ± 70.53 µg butylated hydroxytoluene equivalents [BHTE]/mg dry extract, while β-carotene bleaching assay gave percent antioxidant activities of both EESAL and BHT as 81.46±1.62 and 80.90±1.39 respectively. Ferric reducing abilities of both EESAL and ascorbic acid increased in a concentration-dependent manner with EESAL displaying a significantly ( p < 0.001) higher reductive activity than vitamin C. EESAL displayed a significantly higher hydroxyl radical scavenging activity as compared with BHT at the lowest concentration with no significant difference at the highest concentration. Total phenolic and flavonoid contents of EESAL were obtained as 608.10 ± 2.12 µg GAE/mg and 78.96 ± 3.37 µg QE/mg respectively. Taken together, the free radical scavenging and antioxidant activity of EESAL is likely due to its high phenolic content with complementary effects of the flavonoid components.
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Antioxidant and free radical-scavenging activity of constituents from two Scorzonera species.
Milella, Luigi; Bader, Ammar; De Tommasi, Nunziatina; Russo, Daniela; Braca, Alessandra
2014-10-01
The aim of this study was to investigate the secondary metabolites content of Scorzonera papposa DC., an edible plant eaten in the desert region of Jordan and to assess its antioxidant and free radical-scavenging activity. By using this bioassay-oriented approach nine compounds, including the new natural compounds (6-trans-p-coumaroyl)-3-O-β-D-glucopyranosyl-2-deoxy-D-riburonic acid (1), (6-cis-p-coumaroyl)-3-O-β-D-glucopyranosyl-2-deoxy-D-riburonic acid (2a), (6-trans-p-coumaroyl)-3-O-β-D-glucopyranosyl-2-deoxy-D-riburonic acid methyl ester (3), and (6-trans-p-coumaroyl)-3-O-β-D-glucopyranosyl-(5-acetyl)-2-deoxy-D-riburonic acid (4), having the rare deoxy-D-riburonic acid moiety, were isolated. Their structures were elucidated by UV, MS, (1)H and (13)C NMR and 2D NMR. The antioxidant activity of the S. papposa pure compounds and of related derivatives isolated from another Scorzonera species (S. judaica Eig.) was also tested. The Relative Antioxidant Capacity Index (RACI) was applied as an integrated method to compare the antioxidant activities obtained using different chemical methods. Copyright © 2014 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Tan, Zhaofeng; Lu, Keding; Ma, Xuefei; Birger, Bohn; Broch, Sebastian; Fuchs, Hendrik; Hofzumahaus, Andreas; Holland, Frank; Li, Xin; Liu, Yuhan; Novelli, Anna; Rohrer, Franz; Shao, Min; Wang, Haichao; Wu, Yusheng; Zeng, Limin; Kiendler-Scharr, Astrid; Wahner, Andreas; Zhang, Yuanhang
2017-04-01
A comprehensive field campaign was carried out in winter 2016 in Huairou, a small town located 60 km northeast of Beijing downtown. Concentrations of OH, HO2and RO2 radicals were measured by a laser induced fluorescence instrument. Radical concentrations were smaller than during summer because of reduced solar radiation. Maximum hourly averaged OH, HO2 and RO2 radical concentrations were (3±2)×106cm-3, (8±6)×107 cm-3 and (7±5)×107 cm-3, respectively. Chemical modulation measurements were applied on a few days showing no significant OH interference for different chemical conditions. HONO and HCHO photolysis were found to be the most important primary source of ROx radicals. OH reactivity, the inverse of the OH radical lifetime, was also measured by a laser-photolysis and laser induced fluorescence instrument. In general, CO and NOx were the dominated OH reactants which contributed more than half of the total OH reactivity. The relative high OH concentrations in polluted episode enabled a fast oxidation of fresh emitted pollutants and the formation of secondary products. The observed radical concentrations were compared with the results from a chemical box model. The model is capable of reproducing radical concentrations in the moderate NOx conditions but has difficulty in both the low and high NOx regimes. The underestimation of RO2 radical concentrations in the high NOx conditions indicate a missing RO2 source.
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Radical-induced purine lesion formation is dependent on DNA helical topology.
Terzidis, Michael A; Prisecaru, Andreea; Molphy, Zara; Barron, Niall; Randazzo, Antonio; Dumont, Elise; Krokidis, Marios G; Kellett, Andrew; Chatgilialoglu, Chryssostomos
2016-11-01
Herein we report the quantification of purine lesions arising from gamma-radiation sourced hydroxyl radicals (HO • ) on tertiary dsDNA helical forms of supercoiled (SC), open circular (OC), and linear (L) conformation, along with single-stranded folded and non-folded sequences of guanine-rich DNA in selected G-quadruplex structures. We identify that DNA helical topology and folding plays major, and unexpected, roles in the formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxo-dG) and 8-oxo-7,8-dihydro-2'-deoxyadenosine (8-oxo-dA), along with tandem-type purine lesions 5',8-cyclo-2'-deoxyguanosine (5',8-cdG) and 5',8-cyclo-2'-deoxyadenosine (5',8-cdA). SC, OC, and L dsDNA conformers together with folded and non-folded G-quadruplexes d[TGGGGT] 4 (TG4T), d[AGGG(TTAGGG) 3 ] (Tel22), and the mutated tel24 d[TTGGG(TTAGGG) 3 A] (mutTel24) were exposed to HO • radicals and purine lesions were then quantified via stable isotope dilution LC-MS/MS analysis. Purine oxidation in dsDNA follows L > OC ≫ SC indicating greater damage towards the extended B-DNA topology. Conversely, G-quadruplex sequences were significantly more resistant toward purine oxidation in their unfolded states as compared with G-tetrad folded topologies; this effect is confirmed upon comparative analysis of Tel22 (∼50% solution folded) and mutTel24 (∼90% solution folded). In an effort to identify the accessibly of hydroxyl radicals to quadruplex purine nucleobases, G-quadruplex solvent cavities were then modeled at 1.33 Å with evidence suggesting that folded G-tetrads may act as potential oxidant traps to protect against chromosomal DNA damage.
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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.
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Ding, Xiang; Hou, Yiling; Zhu, Yuanxiu; Wang, Panpan; Fu, Lei; Zhu, Hongqing; Zhang, Nan; Qin, Hang; Qu, Wei; Wang, Fang; Hou, Wanru
2015-06-01
A novel heteropolysaccharide from the fruiting bodies of Gomphus clavatus Gray was isolated through Sephadex G-200 and DEAE-cellulose columns. The Gomphus clavatus Gray polysaccharide (GCG-1) was mainly composed of β-D-glucosepyranose (β-D-Glu) and α-D-galactopyranose (α-D-Gal) in a ratio of 3:2 and had a molecular weight of ~50,000 Da. The structure of GCG-1 was investigated by a combination of total hydrolysis, gas chromatography-mass spectrometry, methylation analysis, nuclear magnetic resonance spectroscopy and infrared spectra. The results indicated that GCG-1 had a backbone of (1 → 4)-β-D-glucosepyranose residues with branches at O-6 and the branches consisted of two with (1 → 3)-α-D-galactopyranose residue. Antioxidation test in vitro showed that it possessed strong free radical scavenging activity, which may be comparable to vitamin C and butylated hydroxytoluene. GCG-1 also induced the apoptosis of HepG-2 cells and affected the mRNA expression of various housekeeping genes in the HepG-2 cells. The results indicated that Gomphus clavatus Gray may be an ideal sources for antioxidant and anticancer agents.
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Investigating Pigment Radicals in Black Rice Using HPLC and Multi-EPR.
Nakagawa, Kouichi; Maeda, Hayato
2017-01-01
We investigated the location and distribution of paramagnetic species in black and white rice using electron paramagnetic resonance (EPR), X-band (9 GHz) EPR imaging (EPRI), and HPLC. EPR primarily detected two paramagnetic species in black rice, which were identified as a stable radical and Mn 2+ species, based on the g values and hyperfine components of the EPR signals. The signal from the stable radical appeared at g ≈ 2.00 and was relatively strong and stable. Subsequent noninvasive two-dimensional (2D) EPRI revealed that this stable radical was primarily located in the pigmented region of black rice, while very few radicals were observed in the rice interior. Pigments extracted from black rice were analyzed using HPLC; the major compound was found to be cyanidin-3-glucoside. EPR and HPLC results indicate that the stable radical was only found within the pigmented region of the rice, and that it could either be cyanidin-3-glucoside, or one of its oxidative decomposition products.
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A barrier-free atomic radical-molecule reaction: N (2D) NO2 (2A1) mechanistic study
NASA Astrophysics Data System (ADS)
Zuo, Ming-Hui; Liu, Hui-Ling; Huang, Xu-Ri; Zhan, Jin-Hui; Sun, Chia-Chung
The reaction of N (2D) radical with NO2 molecule has been studied theoretically using density functional theory and ab initio quantum chemistry method. Singlet electronic state [N2O2] potential energy surfaces (PES) are calculated at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311+G(d) + ZPE and G3B3 levels of theory. All the involved transition states for generation of (2NO) and (O2 + N2) lie much lower than the reactants. Thus, the novel reaction N + NO2 can proceed effectively even at low temperatures and it is expected to play a role in both combustion and interstellar processes. On the basis of the analysis of the kinetics of all pathways through which the reactions proceed, we expect that the competitive power of reaction pathways may vary with experimental conditions for the title reaction.
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Konovalov, A N; Vikhert, T M; Korshunov, A G; Gorelyshev, S K
1988-01-01
The authors compared the evaluation of the extent of radicalism of removal of craniopharyngiomas of the third ventricle during the operation and in postmortem examination in 17 cases. They found that the transcallosal approach provides greater possibility for radical removal and correct appraisal of the volume of the removed tumor. Growth of connective-tissue fibres of the capsule of the craniopharyngioma into the walls of the third ventricle hinders total removal of the tumor. Other possible sources of recurrences may be microscopie areas of the glial capsule whose fibres grow into the brain matter together with craniopharyngioma epithelial cell complexes, as well as microcraniopharyngiomas growing independently in the depths of the hypophysis which are not related to the removed tumor.
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21 CFR 82.2051 - Lakes (Ext. D&C).
Code of Federal Regulations, 2010 CFR
2010-04-01
..., titanium dioxide, zinc oxide, talc, rosin, aluminum benzoate, calcium carbonate, or on any combination of... is a salt in which is combined the basic radical sodium, potassium, barium, or calcium; or (ii) a... color with the basic radical sodium, potassium, aluminum, barium, calcium, strontium, or zirconium. (2...
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21 CFR 82.2051 - Lakes (Ext. D&C).
Code of Federal Regulations, 2012 CFR
2012-04-01
..., titanium dioxide, zinc oxide, talc, rosin, aluminum benzoate, calcium carbonate, or on any combination of... is a salt in which is combined the basic radical sodium, potassium, barium, or calcium; or (ii) a... color with the basic radical sodium, potassium, aluminum, barium, calcium, strontium, or zirconium. (2...
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21 CFR 82.2051 - Lakes (Ext. D&C).
Code of Federal Regulations, 2013 CFR
2013-04-01
..., titanium dioxide, zinc oxide, talc, rosin, aluminum benzoate, calcium carbonate, or on any combination of... is a salt in which is combined the basic radical sodium, potassium, barium, or calcium; or (ii) a... color with the basic radical sodium, potassium, aluminum, barium, calcium, strontium, or zirconium. (2...
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21 CFR 82.2051 - Lakes (Ext. D&C).
Code of Federal Regulations, 2014 CFR
2014-04-01
..., titanium dioxide, zinc oxide, talc, rosin, aluminum benzoate, calcium carbonate, or on any combination of... is a salt in which is combined the basic radical sodium, potassium, barium, or calcium; or (ii) a... color with the basic radical sodium, potassium, aluminum, barium, calcium, strontium, or zirconium. (2...
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21 CFR 82.2051 - Lakes (Ext. D&C).
Code of Federal Regulations, 2011 CFR
2011-04-01
..., titanium dioxide, zinc oxide, talc, rosin, aluminum benzoate, calcium carbonate, or on any combination of... is a salt in which is combined the basic radical sodium, potassium, barium, or calcium; or (ii) a... color with the basic radical sodium, potassium, aluminum, barium, calcium, strontium, or zirconium. (2...
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13 C dynamic nuclear polarization using isotopically enriched 4-oxo-TEMPO free radicals.
Niedbalski, Peter; Parish, Christopher; Kiswandhi, Andhika; Lumata, Lloyd
2016-12-01
The nitroxide-based free radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) is a widely used polarizing agent in NMR signal amplification via dissolution dynamic nuclear polarization (DNP). In this study, we have thoroughly investigated the effects of 15 N and/or 2 H isotopic labeling of 4-oxo-TEMPO free radical on 13 C DNP of 3 M [1- 13 C] sodium acetate samples in 1 : 1 v/v glycerol : water at 3.35 T and 1.2 K. Four variants of this free radical were used for 13 C DNP: 4-oxo-TEMPO, 4-oxo-TEMPO- 15 N, 4-oxo-TEMPO-d 16 and 4-oxo-TEMPO- 15 N,d 16 . Our results indicate that, despite the striking differences seen in the electron spin resonance (ESR) spectral features, the 13 C DNP efficiency of these 15 N and/or 2 H-enriched 4-oxo-TEMPO free radicals are relatively the same compared with 13 C DNP performance of the regular 4-oxo-TEMPO. Furthermore, when fully deuterated glassing solvents were used, the 13 C DNP signals of these samples all doubled in the same manner, and the 13 C polarization buildup was faster by a factor of 2 for all samples. The data here suggest that the hyperfine coupling contributions of these isotopically enriched 4-oxo-TEMPO free radicals have negligible effects on the 13 C DNP efficiency at 3.35 T and 1.2 K. These results are discussed in light of the spin temperature model of DNP. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.
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Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.
Sebbar, N; Bozzelli, J W; Bockhorn, H
2014-01-09
Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.
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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.
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NASA Astrophysics Data System (ADS)
Barzegar, Abolfazl; Rezaei-Sadabady, Rogaie
2017-10-01
Five galvinoxyl radicals (Grad) reduction by one polyphenolic myricetin (Myc, 3,3‧,4‧,5,5‧,7-Hexahydroxyflavone) molecule-using EPR method-demonstrated that each Myc should donate at least five H atoms resulted in multiradicals Myc5rad (5 Grad + 1Myc → 5 GH + 1 Myc5rad). The process that five H atoms donation occurs from different OH sites of Myc lead to appearing of five unpaired valence electrons of Myc5rad via two possible different mechanisms. First; concerted five H atoms donation from five different OH groups that directly results in Myc5rad radicals (Myc → Myc5rad). Second; the step-wise radical formation in five different OH groups of Myc (Myc → Mycrad → Myc2rad → Myc3rad → Myc4rad → Myc5rad). Computational DFT method was used to analyze all the six different OH groups of Myc which involved in free radical reactions for the purposes of clarification the stable multiradicals Myc5rad formation mechanism. The fast semi-empirical combined quantum method, AM1/DFT, as well as full DFT geometry optimization approaches of B3LYP functional DFT/DFT with different basis sets of 6-31G (d), 6-311 + G (d,p) and 6-311 + G (2d,2p) confirmed the stepwise H atom abstraction trend on the main three hydroxyl sites as 4‧-Orad → 4‧-Orad3-Orad → 4‧-Orad3-Orad-7Orad both in the gas and water phase. Spin delocalization over the entire Myc, adding the co-planarity, contributed to the stabilization of respective radical species. The excellent stability of Myc radicals should give an effective chain-breaking antioxidant activity for Myc in biological environment which is expected to have far fewer side effects. These findings may be useful to elucidate the radical scavenging mechanism of other flavonoids regarding to design novel antioxidants.
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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.
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NASA Technical Reports Server (NTRS)
Wine, P. H.; Hynes, A. J.; Nicovich, J. M.
1997-01-01
Results are presented and discussed for a number of gas phase free radical reactions where H/D isotope effects provide valuable mechanistic insights. The cases considered are (1) the reactions of OH, NO3, and Cl with atmospheric reduced sulfur compounds, (2) the reactions of OH and OD with CH3CN and CD3CN, and (3) the reactions of alkyl radicals with HBr and DBr.
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Hydrogen exchange equilibria in thiols.
Hofstetter, Dustin; Thalmann, Basil; Nauser, Thomas; Koppenol, Willem H
2012-09-17
Cysteine, cysteinyl-glycine, glutathione, phenylalanyl-cysteinyl-glycine, and histidyl-cysteinyl-glycine were dissolved in acidic and neutral D(2)O in the presence of the radical generator 2,2'-azobis(2-methylpropionamidine) dihydrochloride and radical mediator compounds (benzyl alcohol and 2-propanol). An exchange of H-atoms by D-atoms took place in these peptides due to intramolecular H-abstraction equilibria. NMR measurements allow one to follow the extent of H-D exchanges and to identify the sites where these exchanges take place. Significant exchanges occur in acidic media in GSH at positions Glu-β and Glu-γ, in Phe-Cys-Gly at positions Phe ortho, Phe-β, Cys-α, Cys-β, and Gly-α, and in His-Cys-Gly at positions His H1, His H2, His β, Cys β, and Gly α. In neutral media, exchanges occur in Cys-Gly at position Cys β and in GSH at position Cys α. Phe-Cys-Gly and His-Cys-Gly were not examined in neutral media. Sites participating in the radical exchange equilibria are highly dependent on structure and pH; the availability of electron density in the form of lone pairs appears to increase the extent of exchange. Interestingly, and unexpectedly, 2D NMR experiments show that GSH rearranges itself in acidic solution: the signals shift, but their patterns do not change. The formation of a thiolactone from Gly and Cys residues matches the changes observed.
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Kolodziejczyk-Czepas, Joanna; Nowak, Pawel; Kowalska, Iwona; Stochmal, Anna
2014-10-01
Clovers were chosen on the basis of traditional medicine recommendations, agricultural value, or available information on their promising chemical profiles. This study evaluates and compares free radical scavenging and antioxidant properties of six clover species: Trifolium alexandrinum L. (Leguminosae), Trifolium fragiferum L., Trifolium hybridum L., Trifolium incarnatum L., Trifolium resupinatum var. majus Boiss., and Trifolium resupinatum var. resupinatum L. Free radical scavenging activity of the extracts (1.5-50 µg/ml) was estimated by reduction of 1,1-diphenyl-2-picrylhydrazyl (DPPH(•)) and 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonic) acid (ABTS(•)) radicals. The Trifolium extract effects on total antioxidant capacity of blood plasma were determined by the reduction of ABTS(•+) and DPPH(•) radicals, as well as with the use of the ferric reducing ability of plasma (FRAP) assay. The UPLC analysis of chemical profiles of the examined extracts showed the presence of three or four groups of phenolic substances, including phenolic acids, clovamides, isoflavones, and other flavonoids. The measurements of free radical scavenging and ferric reducing ability of the examined clover extracts revealed the strongest effect for T. alexandrinum. Furthermore, antioxidant activity assays in human plasma have shown protective effects of all extracts against peroxynitrite-induced reduction of total antioxidant capacity. Trifolium plants may be a rich source of bioactive substances with antioxidant properties. The examined extracts displayed free radical scavenging action and partly protected blood plasma against peroxynitrite-induced oxidative stress; however, the beneficial effects of T. alexandrinum and T. incarnatum seem to be slightly higher.
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Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...
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Zhao, Long; Yang, Tao; Kaiser, Ralf I; Troy, Tyler P; Ahmed, Musahid; Ribeiro, Joao Marcelo; Belisario-Lara, Daniel; Mebel, Alexander M
2017-02-16
We investigated temperature-dependent products in the pyrolysis of helium-seeded n-dodecane, which represents a surrogate of the n-alkane fraction of Jet Propellant-8 (JP-8) aviation fuel. The experiments were performed in a high temperature chemical reactor over a temperature range of 1200 K to 1600 K at a pressure of 600 Torr, with in situ identification of the nascent products in a supersonic molecular beam using single photon vacuum ultraviolet (VUV) photoionization coupled with the analysis of the ions in a reflectron time-of-flight mass spectrometer (ReTOF). For the first time, the initial decomposition products of n-dodecane-including radicals and thermally labile closed-shell species-were probed in experiments, which effectively exclude mass growth processes. A total of 15 different products were identified, such as molecular hydrogen (H 2 ), C2 to C7 1-alkenes [ethylene (C 2 H 4 ) to 1-heptene (C 7 H 14 )], C1-C3 radicals [methyl (CH 3 ), ethyl (C 2 H 5 ), allyl (C 3 H 5 )], small C1-C3 hydrocarbons [acetylene (C 2 H 2 ), allene (C 3 H 4 ), methylacetylene (C 3 H 4 )], as well as the reaction products [1,3-butadiene (C 4 H 6 ), 2-butene (C 4 H 8 )] attributed to higher-order processes. Electronic structure calculations carried out at the G3(CCSD,MP2)//B3LYP/6-311G(d,p) level of theory combined with RRKM/master equation of rate constants for relevant reaction steps showed that n-dodecane decomposes initially by a nonterminal C-C bond cleavage and producing a mixture of alkyl radicals from ethyl to decyl with approximately equal branching ratios. The alkyl radicals appear to be unstable under the experimental conditions and to rapidly dissociate either directly by C-C bond β-scission to produce ethylene (C 2 H 4 ) plus a smaller 1-alkyl radical with the number of carbon atoms diminished by two or via 1,5-, 1,6-, or 1,7- 1,4-, 1,9-, or 1,8-H shifts followed by C-C β-scission producing alkenes from propene to 1-nonene together with smaller 1-alkyl radicals. The stability and hence the branching ratios of higher alkenes decrease as temperature increases. The C-C β-scission continues all the way to the propyl radical (C 3 H 7 ), which dissociates to methyl (CH 3 ) plus ethylene (C 2 H 4 ). In addition, at higher temperatures, another mechanism can contribute, in which hydrogen atoms abstract hydrogen from C 12 H 26 producing various n-dodecyl radicals and these radicals then decompose by C-C bond β-scission to C3 to C11 alkenes.
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Effect of curcumin against oxidation of biomolecules by hydroxyl radicals.
Borra, Sai Krishna; Mahendra, Jaideep; Gurumurthy, Prema; Jayamathi; Iqbal, Shabeer S; Mahendra, Little
2014-10-01
Among various reactive oxygen species, hydroxyl radicals have the strongest chemical activity, which can damage a wide range of essential biomolecules such as lipids, proteins, and DNA. The objective of this study was to investigate the beneficial effects of curcumin on prevention of oxidative damage of biomolecules by hydroxyl radicals generated in in vitro by a Fenton like reaction. We have incubated the serum, plasma and whole blood with H2O2/Cu2+/ Ascorbic acid system for 4 hours at 37 0C and observed the oxidation of biomolecules like albumin, lipids, proteins and DNA. Curcumin at the concentrations of 50,100 and 200 μmoles, prevented the formation of ischemia modified albumin, MDA, protein carbonyls, oxidized DNA and increased the total antioxidant levels and GSH significantly. These observations suggest the hydroxyl radical scavenging potentials of curcumin and protective actions to prevent the oxidation of biomolecules by hydroxyl radicals.
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High-resolution one-photon absorption spectroscopy of the D2Σ- ← X2 Π system of radical OH and OD
NASA Astrophysics Data System (ADS)
Heays, A. N.; de Oliveira, N.; Gans, B.; Ito, K.; Boyé-Péronne, S.; Douin, S.; Hickson, K. M.; Nahon, L.; Loison, J. C.
2018-01-01
Vacuum-ultraviolet (VUV) photoabsorption spectra were recorded of the A2Σ+(v‧ = 0) ← X2 Π(v‧‧ = 0) , D2Σ-(v‧ = 0) ← X2 Π(v‧‧ = 0) and D2Σ-(v‧ = 1) ← X2 Π(v‧‧ = 0) bands of the OH and OD radicals generated in a plasma-discharge source using synchrotron radiation as a background continuum coupled with the VUV Fourier-transform spectrometer on the DESIRS beamline of synchrotron SOLEIL. High-resolution spectra permitted the quantification of transition frequencies, relative f-values, and natural line broadening. The f-values were absolutely calibrated with respect to a previous measurement of A2Σ+(v‧ = 0) ← X2 Π(v‧‧ = 0) (Wang et al., 1979). Lifetime broadening of the excited D2Σ-(v = 0) and D2Σ-(v = 1) levels is measured for the first time and compared with previous experimental limits, and implies a lifetime 5 times shorter than a theoretical prediction (van der Loo and Groenenboom, 2005). A local perturbation of the D2Σ-(v = 0) level in OH was found.
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Yatagai, Tomonori; Ohkawa, Yoshiko; Kubo, Daichi; Kawase, Yoshinori
2017-01-02
The hydroxyl radical generation in an electro-Fenton process with a gas-diffusion electrode which is strongly linked with electro-chemical generation of hydrogen peroxide and iron redox cycle was studied. The OH radical generation subsequent to electro-chemical generations of H 2 O 2 was examined under the constant potential in the range of Fe 2+ dosage from 0 to 1.0 mM. The amount of generated OH radical initially increased and gradually decreased after the maximum was reached. The initial rate of OH radical generation increased for the Fe 2+ dosage <0.25 mM and at higher Fe 2+ dosages remained constant. At higher Fe 2+ dosages the precipitation of Fe might inhibit the enhancement of OH radical generation. The experiments for decolorization and total organic carbon (TOC) removal of azo-dye Orange II by the electro-Fenton process were conducted and the quick decolorization and slow TOC removal of Orange II were found. To quantify the linkages of OH radical generation with dynamic behaviors of electro-chemically generated H 2 O 2 and iron redox cycle and to investigate effects of OH radical generation on the decolorization and TOC removal of Orange II, novel reaction kinetic models were developed. The proposed models could satisfactory clarify the linkages of OH radical generation with electro-chemically generated H 2 O 2 and iron redox cycle and simulate the decolorization and TOC removal of Orange II by the electro-Fenton process.
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Thotneosides A, B and C: potent antioxidants from nepalese crude drug, leaves of Aconogonon molle.
Joshi, Khem Raj; Devkota, Hari Prasad; Watanabe, Takashi; Yahara, Shoji
2014-01-01
Three new glycosides: thotneoside A (quercetin 3-O-(6″-O-phenylacetyl)-β-D-galactopyranoside) (1), thotneoside B (quercetin 3-O-(6″-O-phenylacetyl)-β-D-glucopyranoside) (2) and thotneoside C (3-methyl-2-butenoic acid 1-O-β-D-glucopyranoside) (3), together with nine known compounds; quercetin (4), quercetin 3-O-β-D-galactopyranoside (5), quercetin 3-O-(6″-O-galloyl)-β-D-galactopyranoside (6), quercetin 3-O-β-D-galacturonopyranoside (7), quercetin 3-O-β-D-glucuronopyranoside (8), quercetin 3-O-α-L-rhamnopyranoside (9), rutin (10), quercetin 3-O-α-L-arabinopyranoside (11) and 2,4,6-trihydroxyacetophenone 2-O-β-D-glucopyranoside (12) have been isolated from the shade dried leaves of Aconogonon molle, commonly known as "Thotne″ in Nepal. The structures were elucidated on the basis of chemical and spectroscopic methods. All of these compounds were isolated for the first time from A. molle and their in vitro antioxidant activity was evaluated by 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging assay. Quercetin (4) and its glycosides (1-2, 5-11) showed potent free radical scavenging activity.
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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.
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CYCLOOXYGENASE COMPETITIVE INHIBITORS ALTER TYROSYL RADICAL DYNAMICS IN PROSTAGLANDIN H SYNTHASE-2†
Wu, Gang; Tsai, Ah-Lim; Kulmacz, Richard J.
2009-01-01
Reaction of prostaglandin H synthase (PGHS) isoforms 1 or 2 with peroxide forms a radical at Tyr385 that is required for cyclooxygenase catalysis, and another radical at Tyr504, whose function is unknown. Both tyrosyl radicals are transient and rapidly dissipated by reductants, suggesting that cyclooxygenase catalysis might be vulnerable to suppression by intracellular antioxidants. Our initial hypothesis was that the two radicals are in equilibrium and that their proportions and stability are altered upon binding of fatty acid substrate. As a test, we examined the effects of three competitive inhibitors (nimesulide, flurbiprofen and diclofenac) on the proportions and stability of the two radicals in PGHS-2 pretreated with peroxide. Adding nimesulide after ethyl peroxide led to some narrowing of the tyrosyl radical signal detected by EPR spectroscopy, consistent with a small increase in the proportion of the Tyr504 radical. Neither flurbiprofen nor diclofenac changed the EPR linewidth when added after peroxide. In contrast, the effects of cyclooxygenase inhibitors on the stability of the preformed tyrosyl radicals were dramatic. The half-life of total tyrosyl radical was 4.1 min in the control, >10 hr with added nimesulide, 48 min with flurbiprofen, and 0.8 min with diclofenac. Stabilization of the tyrosyl radicals was evident even at substoichiometric levels of nimesulide. Thus, the inhibitors had potent, structure-dependent, effects on the stability of both tyrosyl radicals. This dramatic modulation of tyrosyl radical stability by cyclooxygenase site ligands suggests a mechanism for regulating the reactivity of PGHS tyrosyl radicals with cellular antioxidants. PMID:19894761
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Lugemwa, Fulgentius Nelson; Snyder, Amanda L.; Shaikh, Koonj
2013-01-01
Thirty eight bottles of red wine (Carbanet Sauvignon) were randomly selected based on vintage, region, price, and age (number of months in a barrel). The total phenolic content of each wine was determined using Folin-Ciocalteau assay. The radical scavenging activity was evaluated using 2,2-diphenyl-1-picryhydrazyl (DPPH) assay. Apart from a few bottles that exhibited above average radical scavenging activity and phenolic content, there was no good correlation of those two quantities with region, price or vintage. The average phenolic amount was 2874 mg/L. The lowest phenolic content was found to be 1648 mg/L for an eight dollar wine. Wine with the highest amount of phenol of 4495 mg/L was a 2007, nine dollar bottle from South America. High amount of phenols did not translate into high radical scavenging activity. Barrel-aging did not increase the amount of phenols or the radical scavenging activity of wine. In order to discover new and potent sources of antioxidants from plants, the following spices were studied: ginger, cilantro, cumin, anise, linden, eucalyptus, marjoram, oregano, sage, thyme and rosemary. Whole spices were crushed and extracted for 96 h at room temperature using a combination of ethyl acetate, ethyl alcohol and water in the ratio of 4.5:4.5:1 (v/v/v). The radical scavenging activity of extracts was evaluated using 2,2-diphenyl-1-picryhydrazyl (DPPH) assay. The total phenolic content of each spice was also determined using the Folin-Ciocalteau assay. Eucalyptus was found to be the most potent antioxidant with an LC50 of 324.1 mg of phenol/L, followed by marjoram with an LC50 of 407.5 mg of phenol/L, and rosemary with an LC50 of 414.0 mg/L. The least potent antioxidants were ginger and cilantro with LC50 of 7604 mg/L of phenol and 7876 mg of phenol/L, respectively. PMID:26784340
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Berndt, Torsten; Richters, Stefanie; Kaethner, Ralf; Voigtländer, Jens; Stratmann, Frank; Sipilä, Mikko; Kulmala, Markku; Herrmann, Hartmut
2015-10-15
The gas-phase reaction of ozone with C5-C8 cycloalkenes has been investigated in a free-jet flow system at atmospheric pressure and a temperature of 297 ± 1 K. Highly oxidized RO2 radicals bearing at least 5 O atoms in the molecule and their subsequent reaction products were detected in most cases by means of nitrate-CI-APi-TOF mass spectrometry. Starting from a Criegee intermediate after splitting-off an OH-radical, the formation of these RO2 radicals can be explained via an autoxidation mechanism, meaning RO2 isomerization (ROO → QOOH) and subsequently O2 addition (QOOH + O2 → R'OO). Time-dependent RO2 radical measurements concerning the ozonolysis of cyclohexene indicate rate coefficients of the intramolecular H-shifts, ROO → QOOH, higher than 1 s(-1). The total molar yield of highly oxidized products (predominantly RO2 radicals) from C5-C8 cycloalkenes in air is 4.8-6.0% affected with a calibration uncertainty by a factor of about two. For the most abundant RO2 radical from cyclohexene ozonolysis, O,O-C6H7(OOH)2O2 ("O,O" stands for two O atoms arising from the ozone attack), the determination of the rate coefficients of the reaction with NO2, NO, and SO2 yielded (1.6 ± 0.5) × 10(-12), (3.4 ± 0.9) × 10(-11), and <10(-14) cm(3) molecule(-1) s(-1), respectively. The reaction of highly oxidized RO2 radicals with other peroxy radicals (R'O2) leads to detectable accretion products, RO2 + R'O2 → ROOR' + O2, which allows to acquire information on peroxy radicals not directly measurable with the nitrate ionization technique applied here. Additional experiments using acetate as the charger ion confirm conclusively the existence of highly oxidized RO2 radicals and closed-shell products. Other reaction products, detectable with this ionization technique, give a deeper insight in the reaction mechanism of cyclohexene ozonolysis.
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NASA Astrophysics Data System (ADS)
Leicht, Daniel; Kaufmann, Matin; Pal, Nitish; Schwaab, Gerhard; Havenith, Martina
2017-03-01
The infrared spectrum of allyl:water clusters embedded in helium nanodroplets was recorded. Allyl radicals were produced by flash vacuum pyrolysis and trapped in helium droplets. Deuterated water was added to the doped droplets, and the infrared spectrum of the radical water aggregates was recorded in the frequency range 2570-2820 cm-1. Several absorption bands are observed and assigned to 1:1 and 1:2 allyl:D2O clusters, based on pressure dependent measurements and accompanying quantum chemical calculations. The analysis of the 1:1 cluster spectrum revealed a tunneling splitting as well as a combination band. For the 1:2 cluster, we observe a water dimer-like motif that is bound by one π-hydrogen bond to the allyl radical.
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Radical production inside an acoustically driven microbubble.
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.
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Panebianco, Valeria; Sciarra, Alessandro; Osimani, Marcello; Lisi, Danilo; Ciccariello, Mauro; Salciccia, Stefano; Gentile, Vincenzo; Di Silverio, Franco; Passariello, Roberto
2009-01-01
The aim of this study was to assess the capability of a 3D isotropic MRI T2-weighted sequence (3D T2 ISO) in the depiction of changes of neurovascular bundles (NVBs) after bilateral nerve-sparing radical retropubic prostatectomy (RRP). Furthermore, our aim was also to introduce a new MRI classification score of the NVB alteration patterns using the International Index Erectile Function Five-Item (IIEF-5) score as standard of reference. Fifty-three consecutive patients were postoperatively submitted to two MR examinations, including both 2D TSE T2-weighted (2D T2) and 3D T2 ISO sequences. Image findings were scored using a relative five-point classification and correlated with the postoperative IIEF-5 score. Radiologists attributed 13.2% of patients to class 0, 11.3% to class I, 34% to class II, 24.5% to class III, and 16.9% to class IV. With 3D T2 ISO images, the same radiologists determined 43.3% class 0, 32% class I, 11.4% class II, 7.5% class III, and 5.7% class IV. In all cases, the correlation and regression analysis between the 3D T2 ISO and IIEF-5 score resulted in higher coefficients values. The 3D sequence correlated most closely with patients' grading of erectile function.
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Warncke, Kurt
2005-03-08
Molecular structural features of the product radical in the Co(II)-product radical pair catalytic intermediate state in coenzyme B(12)- (adenosylcobalamin-) dependent ethanolamine deaminase from Salmonella typhimurium have been characterized by using X-band three-pulse electron spin-echo envelope modulation (ESEEM) spectroscopy in the disordered solid state. The Co(II)-product radical pair state was prepared by cryotrapping holoenzyme during steady-state turnover on excess 1,1,2,2-(2)H(4)-aminoethanol or natural abundance, (1)H(4)-aminoethanol. Simulation of the (2)H/(1)H quotient ESEEM (obtained at two microwave frequencies, 8.9 and 10.9 GHz) from the interaction of the unpaired electron localized at C2 of the product radical with nearby (2)H nuclei requires four types of coupled (2)H, which are assigned as follows: (a) a single strongly coupled (effective dipole distance, r(eff) = 2.3 A) (2)H in the C5' methyl group of 5'-deoxyadenosine, (b) two weakly coupled (r(eff) = 4.2 A) (2)H in the C5' methyl group, (c) one (2)H coupling from a beta-(2)H bonded to C1 of the product radical (isotropic hyperfine coupling, A(iso) = 4.7 MHz), and (d) a second type of C1 beta-(2)H coupling (A(iso) = 7.7 MHz). The two beta-(2)H couplings are proposed to arise from two C1-C2 rotamer states of the product radical that are present in approximately equal proportion. A model is presented, in which C5' is positioned at a distance of 3.3 A from C2, which is comparable with the C1-C5' distance in the Co(II)-substrate radical pair intermediate. Therefore, the C5'methyl group remains in close (van der Waals) contact with the substrate and product radical species during the radical rearrangement step of the catalytic cycle, and the C5' center is the sole mediator of radical pair recombination in ethanolamine deaminase.
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Cho, Jin-Gyeong; Song, Na-Young; Nam, Tae-Gyu; Shrestha, Sabina; Park, Hee-Jung; Lyu, Ha-Na; Kim, Dae-Ok; Lee, Gihwan; Woo, Young-Min; Jeong, Tae-Sook; Baek, Nam-In
2013-10-30
The transgenic rice cultivar of Oryza sativa spp. japonica cv. Hwa-Young, C1/R-S transgenic rice (C1/R-S rice), is a flavonoid-rich cultivar of rice. The grains of C1/R-S rice were extracted with aqueous MeOH, and the concentrated extract was partitioned with EtOAc, n-BuOH, and H2O, successively. Repeated silica gel, octadecyl silica gel (ODS), and Sephadex LH-20 column chromatographies for the EtOAc and n-BuOH fractions afforded four new flavonoids (compounds 2, 3, 7, and 8) along with four known flavonoids: (+)-3'-O-methyltaxifolin (1), brassicin (4), isorhamnetin-4'-O-β-D-glucosyranoside (5), and 3'-O-methyltaxifolin-5-O-β-D-glucopyranoside (6). The new flavonoids were identified as 3'-O-methyltaxifolin-7-O-β-D-glucopyranoside (2), 3'-O-methyltaxifolin-4'-O-β-D-glucopyranoside (3), isorhamnetin-7-O-β-D-cellobioside (brassicin-4″-O-β-D-glucopyranoside) (7), and brassicin-4'-O-β-D-glucosyranoside (8) from the result of spectroscopic data including nuclear magnetic resonance spectrometry (NMR), mass spectrometry (MS), and infrared spectroscopy (IR). Also, quantitative analysis of major flavonoids (compounds 2, 3, and 8) in C1/R-S rice, O. sativa spp. japonica cv. Hwa-Young (HY), and a hybrid of two cultivar (C1/R-S rice/HY) extracts was performed using HPLC experiment. The isolated flavonoids were evaluated for their radical-scavenging effect on DPPH and ABTS radicals.
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Kinetics of the reduction of cobalt(III) amine complexes by 1-hydroxy-1-methylethyl radicals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kusaba, K.; Ogino, Hiroshi; Bakac, A.
1989-03-08
In order to better understand the rate constants for the reduction of several cobalt complexes by 1-hydroxy-1-methylene radicals ({sup {sm bullet}}C(CH{sub 3}){sub 2}OH), the reactions of {sup {sm bullet}}(CH{sub 3}){sub 2}OH with several cobalt(III) complexes of bidentate amines have been studied. The Marcus-Hush theory was deemed the most appropriate for analysis of the kinetic data. The correlation between the kinetics of the reduction of the Co(III) amines by C(CH{sub 3}){sub 2}OH and the reduction of the first d-d band for Co(III) complexes is discussed. 21 refs., 2 figs., 1 tab.
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Peukert, S L; Michael, J V
2013-10-10
The shock tube technique has been used to study the hydrogen abstraction reactions D + CH3OH → CH2O + H + HD (A) and CH3 + CH3OH → CH2O + H + CH4 (B). For reaction A, the experiments span a T-range of 1016 K ≤ T ≤ 1325 K, at pressures 0.25 bar ≤ P ≤ 0.46 bar. The experiments on reaction B, CH3 + CH3OH, cover a T-range of 1138 K ≤ T ≤ 1270 K, at pressures around 0.40 bar. Reflected shock tube experiments, monitoring the depletion of D-atoms by applying D-atom atomic resonance absorption spectrometry (ARAS), were performed on reaction A using gas mixtures of C2D5I and CH3OH in Kr bath gas. C2D5I was used as precursor for D-atoms. For reaction B, reflected shock tube experiments monitoring H-atom formation with H-ARAS, were carried out using gas mixtures of diacetyl ((CH3CO)2) and CH3OH in Kr bath gas. (CH3CO)2 was used as the source of CH3-radicals. Detailed reaction models were assembled to fit the D-atom and H-atom time profiles in order to obtain experimental rate constants for reactions A and B. Total rate constants from the present experiments on D + CH3OH and CH3 + CH3OH can be represented by the Arrhenius equations kA(T) = 1.51 × 10(-10) exp(-3843 K/T) cm(3) molecules(-1) s(-1) (1016 K ≤ T ≤ 1325 K) and kB(T) = 9.62 × 10(-12) exp(-7477 K/T) cm(3) molecules(-1) s(-1) (1138 K ≤ T ≤ 1270 K). The experimentally obtained rate constants were compared with available rate data from the literature. The results from quantum chemical studies on reaction A were found to be in good agreement with the present results. The present work represents the first direct experimental study on these bimolecular reactions at combustion temperatures and is important to the high-temperature oxidation of CH3OH.
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Protective effects of buckwheat honey on DNA damage induced by hydroxyl radicals.
Zhou, Juan; Li, Peng; Cheng, Ni; Gao, Hui; Wang, Bini; Wei, Yahui; Cao, Wei
2012-08-01
To understand the antioxidant properties of buckwheat honeys, we investigated their antioxidant effects on hydroxyl radical-induced DNA breaks in the non-site-specific and site-specific systems, the physicochemical properties, antioxidant activities (1,1-diphenyl-2-picrylhydrazyl (DPPH), hydroxyl radical scavenging activity, chelating, and reducing power assays), total phenolic content and individual phenolic acids were also determined. Total phenolic content of buckwheat honeys ranged from 774 to 1694 mg PA/kg, and p-hydroxybenzoic and p-coumaric acids proved to be the main components in buckwheat honeys. All the buckwheat honey samples possess stronger capability to protect DNA in the non-site-specific systems than in the site-specific systems from being damaged by hydroxyl radicals. In the non-site-specific and site-specific system, buckwheat honeys samples prevented ()OH-induced DNA breaks by 21-78% and 5-31% over control value, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.
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Asim, Sumreen; Zhu, Yunqing; Batool, Aisha; Hailili, Reshalaiti; Luo, Jianmin; Wang, Yuanhao; Wang, Chuanyi
2017-10-01
2, 4-dichlorophenol (2, 4-DCP) is considered to be a highly toxic, mutagenic, and possibly carcinogenic pollutant. This study is focused on the electrochemical oxidation of 2, 4-DCP on nanostructured 3D-porous Ti/Sb-SnO 2 -Gr anodes, with the aim of presenting a comprehensive elucidation of mineralization process through the investigation of influential kinetics, the reactivity of hydroxyl radical's and analysis of intermediates. High efficiency was achieved at pH of 3 using Na 2 SO 4 electrolytes at a current density of 30 mA cm -2 . Under the optimized conditions, a maximum removal of 2, 4-DCP of up to 99.9% was reached, whereas a TOC removal of 81% was recorded with the lowest EC TOC (0.49 kW h g -1 ) within 40 min of electrolysis. To explore the stability of the 3D-Ti/Sb-SnO 2 -Gr electrodes, a continuous electrochemical operation was established, and the consistent mineralization results indicated the effectiveness of the 3D-Ti/Sb-SnO 2 -Gr system concerning its durability and practical utilization. EPR studies demonstrated the abundant generation of OH radicals on 3D-Ti/Sb-SnO 2 -Gr, resulting in fast recalcitrant pollutant incineration. From dechlorination and the reactivity of the OH radicals, several intermediates including six cyclic byproducts and three aliphatic carboxylic acids were detected, and two possible degradation pathways were proposed that justify the complete mineralization of 2, 4-DCP. Copyright © 2017 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Javed, M. U.; Hens, K.; Martinez, M.; Kubistin, D.; Novelli, A.; Beygi, Z. H.; Axinte, R.; Nölscher, A. C.; Sinha, V.; Song, W.; Johnson, A. M.; Auld, J.; Bohn, B.; Sander, R.; Taraborrelli, D.; Williams, J.; Fischer, H.; Lelieveld, J.; Harder, H.
2016-12-01
Peroxy radicals play a key role in ozone (O3) production and hydroxyl (OH) recycling influencing the self-cleansing capacity and air quality. Organic peroxy radical (RO2) concentrations are estimated by three different approaches for a boreal forest, based on the field campaign HUMPPA-COPEC 2010 in Southern Finland. RO2 concentrations were simulated by a box model constrained by the comprehensive dataset from the campaign and cross-checked against the photostationary state (PSS) of NOx [= nitric oxide (NO) + nitrogen dioxide (NO2)] calculations. The model simulated RO2 concentrations appear too low to explain the measured PSS of NOx. As the atmospheric RO2 production is proportional to OH loss, the total OH loss rate frequency (total OH reactivity) in the model is underestimated compared to the measurements. The total OH reactivity of the model is tuned to match the observed total OH reactivity by increasing the biogenic volatile organic compound (BVOCs) concentrations for the model simulations. The new-found simulated RO2 concentrations based on the tuned OH reactivity explain the measured PSS of NOx reasonably well. Furthermore, the sensitivity of the NOx lifetime and the catalytic efficiency of NOx (CE) in O3 production, in the context of organic alkyl nitrate (RONO2) formation, was also investigated. Based on the campaign data, it was found that the lifetime of NOx and the CE are reduced and are sensitive to the RONO2 formation under low-NOx conditions, which matches a previous model-based study.
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Sarkar, Biswatrish; Kumar, Dhananjay; Sasmal, Dinakar; Mukhopadhyay, Kunal
2014-01-01
Anthocyanin extracts (AEs) from Ocimum tenuiflorum (leaf), Hibiscus rosa-sinensis (petal) and Hibiscus sabdariffa (calyx) were investigated and compared for in vitro antioxidant activity and DNA damage protective property. Total phenolic content (TPC) and total anthocyanin content (TAC) of the AEs were determined and the major anthocyanins were characterised. In vitro antioxidant activities were assessed by ferric-reducing antioxidant power (FRAP) assay, 2,2-diphenyl-1-picryl hydrazyl (DPPH) radical-scavenging activity, 2-deoxy-D-ribose degradation assay and lipid peroxidation assay. The protective property of the AEs was also examined against oxidative DNA damage by H2O2 and UV using pUC19 plasmid. All the AEs particularly those from O. tenuiflorum demonstrated efficient antioxidant activity and protected DNA from damage. Strong correlation between antioxidant capacity and TPC and TAC was observed. Significant correlation between antioxidant capacity and TPC and TAC ascertained that phenolics and anthocyanins were the major contributors of antioxidant activity.
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Laser induced fluorescence of HCCO (DCCO) radical formed in O+C2H2 (C2D2) reaction
NASA Astrophysics Data System (ADS)
Inoue, Gen; Suzuki, Makoto
1986-04-01
Laser induced fluorescence of HCCO (DCCO) radical have been obtained in the reaction of O(3P)+C2H2(C2D2) for the first time (X 2A'-2A`). The laser excitation spectra have been obtained over the wavelength region from 310 to 370 nm. The collision-free lifetimes for HCCO and DCCO are 0.14 and 3.8 μs, respectively. From the excitation and dispersed fluorescence spectra, some vibrational energies have been obtained in cm-1 unit: 1762 (1727), 150-140 (n.a.), and 2334 (1901) for the ground state HCCO (DCCO), and 1183 (1167), 866 (607), and 2862 (2075) for the excited state HCCO (DCCO). The band origin ν00 is 28 296.7 cm-1.
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Nakagawa, Kouichi; Minakawa, Satoko; Sawamura, Daisuke; Hara, Hideyuki
2017-01-01
Continuous wave electron paramagnetic resonance (CW EPR) and X-band (9 GHz) EPR imaging (EPRI) were used to nondestructively investigate the possible differentiation between malignant melanoma (MM) and nevus pigmentosus (NP) melanin radicals in paraffin-embedded specimens. The EPR spectra of both samples were analyzed using linewidth, spectral pattern, and X-band EPRI. The CW-EPR spectra of the MM showed an additional signal overlap. Eumelanin- and pheomelanin-related radicals were observed in the MM specimens. The EPR results revealed that the peak-to-peak linewidths (ΔH pp ) of paraffin-embedded MM and NP samples were 0.65 ± 0.01 and 0.69 ± 0.01 mT, respectively. The g-value was 2.005 for both samples. Moreover, the two-dimensional (2D) EPRI of the MM showed different signal intensities at the different tumor stages, unlike the NP, which displayed fewer variations in signal intensity. Thus, the present results suggest that EPR and 2D EPRI can be useful for characterization of the two melanin radicals in the MM and for determination of their size and concentration.
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Low-temperature chemistry between water and hydroxyl radicals: H/D isotopic effects
NASA Astrophysics Data System (ADS)
Lamberts, T.; Fedoseev, G.; Puletti, F.; Ioppolo, S.; Cuppen, H. M.; Linnartz, H.
2016-01-01
Sets of systematic laboratory experiments are presented - combining Ultra High Vacuum cryogenic and plasma-line deposition techniques - that allow us to compare H/D isotopic effects in the reaction of H2O (D2O) ice with the hydroxyl radical OD (OH). The latter is known to play a key role as intermediate species in the solid-state formation of water on icy grains in space. The main finding of our work is that the reaction H2O + OD → OH + HDO occurs and that this may affect the HDO/H2O abundances in space. The opposite reaction D2O + OH → OD + HDO is much less effective, and also given the lower D2O abundances in space not expected to be of astronomical relevance. The experimental results are extended to the other four possible reactions between hydroxyl and water isotopes and are subsequently used as input for Kinetic Monte Carlo simulations. This way we interpret our findings in an astronomical context, qualitatively testing the influence of the reaction rates.
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Asikin, Yonathan; Takahashi, Makoto; Mizu, Masami; Takara, Kensaku; Oku, Hirosuke; Wada, Koji
2016-03-15
Sugarcane molasses is a potential by-product of the sugarcane manufacturing industry that is rich in antioxidant materials. The present study aimed to obtain antioxidative compounds from sugarcane molasses and to evaluate their ability to protect DNA from oxidative damage. Two neolignan glucosides were isolated from sugarcane molasses using bioassay and UV spectra monitoring-guided fractionation. The compounds were elucidated as (7R,8S)-dehydrodiconiferyl alcohol-4-O-β-d-glucoside (1) and (7S,8R)-simulanol-9'-O-β-d-glucoside (2). Neolignan glucoside 2 protected against DNA damage caused by free radicals more effectively than did neolignan glucoside 1 (13.62 and 9.08 µmol L(-1) for peroxyl and hydroxyl radicals, respectively, compared to 48.07 and 14.42 µmol L(-1) ). Additionally, neolignan glucoside 2 exhibited superior DNA protection against free radicals compared with various known antioxidative compounds, including p-coumaric acid, ferulic acid, vanillic acid and epigallocatechin gallate. The isolated neolignan glucosides from sugarcane molasses are able to protect DNA from oxidative damage caused by free radicals. This is the first identification of these two compounds in sugarcane molasses. The sugarcane molasses can therefore be used as potential nutraceutical preventative agents, and the findings may foster the utilization of this by-product as a bioresource-based product. © 2015 Society of Chemical Industry. Copyright © 2015 Society of Chemical Industry.
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Erkekoglou, Ioannis; Nenadis, Nikolaos; Samara, Efrosini; Mantzouridou, Fani Th
2017-06-01
The phenolic content/composition and antioxidant activity of hot/cold infusion and decoction from the leaves of Arbutus unedo were studied for the first time. 1,1-diphenyl-2-picrylhydrazyl (DPPH ● ), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) radical cation (ABTS ●+ ), crocin-bleaching, copper-reducing, and liposome accelerated oxidation assays were used for the evaluation of the activity in vitro. In vivo, the extracts were examined for their ability to protect S. cerevisiae cells from H 2 O 2 induced oxidative stress. An on-line high-performance liquid chromatography-DPPH ● assay was applied to identify potent radical scavengers and comment on their contribution to the total activity. The addition of leaves to boiling water (decoction) was the most appropriate practice to apply since the highest phenol intake (220.2 mg gallic acid/cup served) was obtained. Additionally, its antioxidant activity was equal or superior to that of the other extracts. Flavonols (~51-61 mg/g dry extract) were the main phenols in all the extracts, with quercitrin accounting for ~20% of the total phenol amount. The on-line DPPH ● method verified the high potency of the decoction and indicated as the most active radical scavengers, two galloylquinic acid derivatives and myricitrin, accounting for ~28-45% and ~11-13% of the total scavenging, respectively. Present data may contribute to the future exploitation of A. unedo leaves by the food industry for health-promoting herbal tea preparations and dietary supplements.
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Dong, Guohui; Ai, Zhihui; Zhang, Lizhi
2014-12-01
In this study, nanoscale zero-valent copper (nZVC) was synthesized with a facile solvothermal method and used for the aerobic removal of azo contaminants at neutral pH for the first time. We found that both Cu(I) and OH generated during the nZVC induced molecular oxygen activation process accounted for the rapid total destruction of azo contaminants in the nZVC/Air system, where nZVC could activate molecular oxygen to produce H2O2, and also release Cu(I) to break the -NN- bond of azo contaminants via the sandmeyer reaction for the generation of carbon center radicals. The in-situ generated carbon center radicals would then react with OH produced by the Cu(I) catalyzed decomposition of H2O2, resulting in the generation of low molecular weight organic acids and their subsequent mineralization. The indispensible role of Cu(I) catalyzed sandmeyer reaction and the promotion effect of in-situ generated carbon center radicals on the rapid total destruction of azo contaminants in the nZVC/Air system were confirmed by gas chromatography-mass spectrometry analysis. This study can deepen our understanding on the degradation of organic pollutant with molecular oxygen activated by zero valent metal, and also provide a new method to remove azo contaminants at neutral pH. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Location and magnetic relaxation properties of the stable tyrosine radical in photosystem II.
Innes, J B; Brudvig, G W
1989-02-07
Dipolar interactions with neighboring metal ions can cause enhanced spin-lattice relaxation of free radicals. We have applied the theory of dipolar relaxation enhancement and shown that the dependence of the enhanced relaxation on the protein structure surrounding the free radical can be used to obtain distances from the free radical to the protein surface. To test the theoretical predictions, we have examined the effect of added Dy3+ complexes on the microwave power saturation of free radicals in two protein complexes of known structure: myoglobin nitroxide and the reaction center from Rhodobacter sphaeroides. Three cases have been considered: (1) metal ions bound to a specific site, (2) metal ions bound randomly over the protein surface, and (3) metal ions distributed randomly in solution. Only case 3, which assumes no specific binding, gave good agreement between the distances obtained by using the two model systems. The effect of added Dy3+ complexes on the microwave power saturation of signal IIslow from photosystem II (PSII) was used to determine the location of the stable tyrosine radical giving rise to signal IIslow. Assuming that the surface of a membrane-bound protein can be approximated as planar, we have obtained distances from the tyrosine radical to the membrane surface in thylakoids, in PSII membranes, and in Tris-washed PSII membranes. The distances we have determined are in good agreement with those predicted on the basis of a structural homology between the D1 and D2 subunits of PSII and the structurally characterized L and M subunits of the reaction center from purple non-sulfur bacteria. We have also examined the temperature dependence of the microwave power at half-saturation (P1/2) of signal IIslow from 4 to 200 K in dark-adapted PSII membranes. Above 70 K, the P1/2 increases as T2.5, which is consistent with a Raman relaxation mechanism.(ABSTRACT TRUNCATED AT 250 WORDS)
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Manir, Md Maniruzzaman; Kim, Jeong Kee; Lee, Byeong-Gon; Moon, Surk-Sik
2012-04-01
Four new quercetin acylglycosides, designated camelliquercetisides A-D, quercetin 3-O-[α-L-arabinopyranosyl(1→3)][2-O″-(E)-p-coumaroyl][β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→6)]-β-D-glucoside (17), quercetin 3-O-[2-O″-(E)-p-coumaroyl][β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→6)]-β-D-glucoside (18), quercetin 3-O-[α-L-arabinopyranosyl(1→3)][2-O″-(E)-p-coumaroyl][α-L-rhamnopyranosyl(1→6)]-β-d-glucoside (19), and quercetin 3-O-[2-O″-(E)-p-coumaroyl][α-L-rhamnopyranosyl(1→6)]-β-D-glucoside (20), together with caffeine and known catechins, and flavonoids (1-16) were isolated from the leaves of Camellia sinensis. Their structures were determined by spectroscopic (1D and 2D NMR, IR, and HR-TOF-MS) and chemical methods. The catechins and flavonoidal glycosides exhibited yeast alcohol dehydrogenase (ADH) inhibitory activities in the range of IC(50) 8.0-70.3μM, and radical scavenging activities in the range of IC(50) 1.5-43.8 μM, measured by using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. Copyright © 2012 Elsevier Ltd. All rights reserved.
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Kimmig, Rainer; Aktas, Bahriye; Buderath, Paul; Wimberger, Pauline; Iannaccone, Antonella; Heubner, Martin
2013-08-16
The technique of compartment-based radical hysterectomy was originally described by M Höckel as total mesometrial resection (TMMR) for standard treatment of stage I and II cervical cancer. However, with regard to the ontogenetically-defined compartments of tumor development (Müllerian) and lymph drainage (Müllerian and mesonephric), compartments at risk may also be defined consistently in endometrial cancer. This is the first report in the literature on the compartment-based surgical approach to endometrial cancer. Peritoneal mesometrial resection (PMMR) with therapeutic lymphadenectomy (tLNE) as an ontogenetic, compartment-based oncologic surgery could be beneficial for patients in terms of surgical radicalness as well as complication rates; it can be standardized for compartment-confined tumors. Supported by M Höckel, PMMR was translated to robotic surgery (rPMMR) and described step-by-step in comparison to robotic TMMR (rTMMR). Patients (n = 42) were treated by rPMMR (n = 39) or extrafascial simple hysterectomy (n = 3) with/without bilateral pelvic and/or periaortic robotic therapeutic lymphadenectomy (rtLNE) for stage I to III endometrial cancer, according to International Federation of Gynecology and Obstetrics (FIGO) classification. Tumors were classified as intermediate/high-risk in 22 out of 40 patients (55%) and low-risk in 18 out of 40 patients (45%), and two patients showed other uterine malignancies. In 11 patients, no adjuvant external radiotherapy was performed, but chemotherapy was applied. No transition to open surgery was necessary. There were no intraoperative complications. The postoperative complication rate was 12% with venous thromboses, (n = 2), infected pelvic lymph cyst (n = 1), transient aphasia (n = 1) and transient dysfunction of micturition (n = 1). The mean difference in perioperative hemoglobin concentrations was 2.4 g/dL (± 1.2 g/dL) and one patient (2.4%) required transfusion. During follow-up (median 17 months), one patient experienced distant recurrence and one patient distant/regional recurrence of endometrial cancer (4.8%), but none developed isolated locoregional recurrence. There were two deaths from endometrial cancer during the observation period (4.8%). We conclude that rPMMR and rtLNE are feasible and safe with regard to perioperative morbidity, thus, it seems promising for the treatment of intermediate/high-risk endometrial cancer in terms of surgical radicalness and complication rates. This could be particularly beneficial for morbidly obese and seriously ill patients.
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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.
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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
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Bicarbonate-activated persulfate oxidation of acetaminophen.
Jiang, Mengdi; Lu, Junhe; Ji, Yuefei; Kong, Deyang
2017-06-01
Persulfate (PS) is widely used as an oxidant for in situ chemical remediation of contaminated groundwater. In this study we demonstrated for the first time that PS could be activated by bicarbonate. Acetaminophen was used as the probe compound to examine the reactivity of PS/bicarbonate system. It was found that acetaminophen could be effectively transformed and the reaction rate appeared pseudo-first-order to the concentrations of both acetaminophen and PS. Radical scavenger tests indicated that neither free radicals (SO 4 - and HO) nor superoxide (O 2 - ) was responsible for acetaminophen transformation. Generation of singlet oxygen ( 1 O 2 ) was verified using furfuryl alcohol (FFA) as a probe. Formation of 1 O 2 was further quantified in D 2 O fortified solution based on kinetic solvent isotopic effect (KSIE) but it was found that 1 O 2 contributed only 51.4% of the total FFA transformation. The other 48.6% was presumed to be ascribed to the reaction with peroxymonocarbonate (HCO 4 - ). However, the transformation of acetaminophen was mostly due to the reaction with HCO 4 - but not 1 O 2 . Instead of degradation, HCO 4 - oxidized acetaminophen via a one-electron abstraction mechanism resulting in the generation of acetaminophen radicals which coupled to each other to form dimers and trimers. HCO 4 - also hydrolyzed rapidly to form hydrogen peroxide (H 2 O 2 ) which led to the formation of 1 O 2 , during which O 2 - was a key intermediates. Because bicarbonate is ubiquitously presented in groundwater, the findings of this research provide important insights into the fundamental processes involved in PS oxidation in subsurface. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Hudzik, Jason M; Bozzelli, Joseph W; Simmie, John M
2014-10-09
Standard enthalpies of formation (ΔH°f 298) of methyl, ethyl, primary and secondary propyl, and n-butyl radicals are evaluated and used in work reactions to determine internal consistency. They are then used to calculate the enthalpy of formation for the tert-butyl radical. Other thermochemical properties including standard entropies (S°(T)), heat capacities (Cp(T)), and carbon-hydrogen bond dissociation energies (C-H BDEs) are reported for n-pentane, n-heptane, 2-methylhexane, 2,3-dimethylpentane, and several branched higher carbon number alkanes and their radicals. ΔH°f 298 and C-H BDEs are calculated using isodesmic work reactions at the B3LYP (6-31G(d,p) and 6-311G(2d,2p) basis sets), CBS-QB3, CBS-APNO, and G3MP2B3 levels of theory. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level for contributions to entropy and heat capacities. Enthalpy calculations for these hydrocarbon radical species are shown to have consistency with the CBS-QB3 and CBS-APNO methods using all work reactions. Our recommended ideal gas phase ΔH°f 298 values are from the average of all CBS-QB3, CBS-APNO, and for G3MP2B3, only where the reference and target radical are identical types, and are compared with literature values. Calculated values show agreement between the composite calculation methods and the different work reactions. Secondary and tertiary C-H bonds in the more highly branched alkanes are shown to have bond energies that are several kcal mol(-1) lower than the BDEs in corresponding smaller molecules often used as reference species. Entropies and heat capacities are calculated and compared to literature values (when available) when all internal rotors are considered.
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Improved radical stability of viologen anolytes in aqueous organic redox flow batteries.
Hu, Bo; Tang, Yijie; Luo, Jian; Grove, Grant; Guo, Yisong; Liu, T Leo
2018-05-09
A high voltage (1.38 V) total organic aqueous redox flow battery is reported using 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium tetrachloride ((NPr)2V) as an anolyte and 4-trimethylammonium-TEMPO chloride (NMe-TEMPO) as a catholyte. The exceptional radical stability of [(NPr)2V]+˙ enabled the flow battery in achieving 97.48% capacity retention for 500 cycles and a power density of 128.2 mW cm-2.
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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.
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Scavenging capacity of strawberry tree (Arbutus unedo L.) leaves on free radicals.
Oliveira, Ivo; Coelho, Valentim; Baltasar, Raquel; Pereira, José Alberto; Baptista, Paula
2009-07-01
Despite strawberry tree (Arbutus unedo L.) leaves had a long use in traditional medicine due to its antiseptic, diuretic, astringent and depurative properties, the potential of their antioxidant activity are still lacking. Our study goals to assess the antioxidant and free radical scavenging potential of water, ethanol, methanol and diethyl ether extracts of A. unedo leaves. Total phenols content was achieved spectrophotometrically using Folin-Ciocalteau reagent with gallic acid as standard. Antioxidant activity was evaluated using three different methods: reducing power of iron (III)/ferricyanide complex assay, scavenging effect on DPPH (2,2-diphenyl-1-picrylhydrazyl) radicals and scavenging effect on superoxide radicals by using the PMS-NADH-nitroblue tetrazolium system. Ethanol extracts of A. unedo leaves were the highest in reducing power (IC(50) 232.7 microg/mL) and DPPH scavenging effect (IC(50) 63.2 microg/mL) followed by water extracts (with IC(50) of 287.7 and 73.7 microg/mL, respectively); whereas diethyl ether extracts were the lowest. In the scavenging on superoxide radical assay, methanol extracts obtained the best results (IC(50) 6.9 microg/mL). For all the methods tested the antioxidant activity was concentration dependent. In accordance with antioxidant activity, highest total phenols content were found in ethanol, followed by water, methanol and diethyl ether extract. The results indicated that A. unedo leaves are a potential source of natural antioxidants.
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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.
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Suessenbacher, Astrid; Lass, Achim; Mayer, Bernd; Brunner, Friedrich
2002-04-01
Oxygen-derived free radicals and oxidants (reactive oxygen intermediates, ROI) have been implicated in cardiovascular diseases. The protective role of nitric oxide (NO) against ROI-mediated tissue injury is not resolved. We tested the effects of exogenous NO, L- and D-arginine and a NO synthase inhibitor on electrolysis-induced cardiac injury and the generation of ROI by electrolysis. Superoxide dismutase (SOD) and catalase were used for comparison. Hearts ( n=7) from male rats (350+/-30 g) were perfused in vitro at 10 ml min(-1) g(-1), ROI generated by electrolysis of the perfusion medium (15 mA, 10 s), and cardiac function and the level of isoluminol-derived chemiluminescence in electrolysed perfusion medium documented for 15 min ( n=4). The ROI-induced maximal reduction of left ventricular developed pressure to 55+/-5% of baseline, and a 2.2+/-0.1-fold rise in coronary perfusion pressure 3 min after electrolysis, were prevented by SOD (50 U ml(-1)), catalase (100 U ml(-1)), S-nitroso- N-acetyl- D,L-penicillamine (SNAP, 100 nmol l(-1)); L-arginine (1 mmol l(-1)), N(G)-nitro- L-arginine (L-NNA, 200 micromol l(-1)) or D-arginine (1 mmol l(-1)). The effect of L-arginine was concentration dependent. In all cases, the beneficial effects were closely matched by a near-total reduction of ROI in the perfusion medium.We conclude that, besides mimicking or enhancing NO activity, L-arginine and donor-derived exogenous NO are cardioprotective by reducing ROI-mediated tissue injury. The protective effect of L-NNA and D-arginine implies that the protection results from a direct chemical interaction between the drug and the oxidizing species.
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2012-01-01
Background The aim of this study was to screen various solvent extracts of whole plant of Torilis leptophylla to display potent antioxidant activity in vitro and in vivo, total phenolic and flavonoid contents in order to find possible sources for future novel antioxidants in food and pharmaceutical formulations. Material and methods A detailed study was performed on the antioxidant activity of the methanol extract of whole plant of Torilis leptophylla (TLM) and its derived fractions {n-hexane (TLH), chloroform (TLC) ethyl acetate (TLE) n-butanol (TLB) and residual aqueous fraction (TLA)} by in vitro chemical analyses and carbon tetrachloride (CCl4) induced hepatic injuries (lipid peroxidation and glutathione contents) in male Sprague-Dawley rat. The total yield, total phenolic (TPC) and total flavonoid contents (TFC) of all the fractions were also determined. TLM was also subjected to preliminary phytochemical screening test for various constituents. Results The total phenolic contents (TPC) (121.9±3.1 mg GAE/g extract) of TLM while total flavonoid contents (TFC) of TLE (60.9 ±2.2 mg RTE/g extract) were found significantly higher as compared to other solvent fractions. Phytochemical screening of TLM revealed the presence of alkaloids, anthraquinones, cardiac glycosides, coumarins, flavonoids, saponins, phlobatannins, tannins and terpenoids. The EC50 values based on the DPPH (41.0±1 μg/ml), ABTS (10.0±0.9 μg/ml) and phosphomolybdate (10.7±2 μg/ml) for TLB, hydroxyl radicals (8.0±1 μg/ml) for TLC, superoxide radicals (57.0±0.3 μg/ml) for TLM and hydrogen peroxide radicals (68.0±2 μg/ml) for TLE were generally lower showing potential antioxidant properties. A significant but marginal positive correlation was found between TPC and EC50 values for DPPH, hydroxyl, phosphomolybdate and ABTS, whereas another weak and positive correlation was determined between TFC and EC50 values for superoxide anion and hydroxyl radicals. Results of in vivo experiment revealed that administration of CCl4 caused a significant increase in lipid peroxidation (TBARS) while decrease in GSH contents of liver. In contrast, TLM (200 mg/kg bw) and silymarin (50 mg/kg bw) co-treatment effectively prevented these alterations and maintained the antioxidant status. Conclusion Data from present results revealed that Torilis leptophylla act as an antioxidant agent due to its free radical scavenging and cytoprotective activity. PMID:23153304
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Atmospheric Hydroxyl Radical Production from Electronically Excited NO2 and H2O
NASA Astrophysics Data System (ADS)
Li, Shuping; Matthews, Jamie; Sinha, Amitabha
2008-03-01
Hydroxyl radicals are often called the “detergent” of the atmosphere because they control the atmosphere’s capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.
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Atmospheric hydroxyl radical production from electronically excited NO2 and H2O.
Li, Shuping; Matthews, Jamie; Sinha, Amitabha
2008-03-21
Hydroxyl radicals are often called the "detergent" of the atmosphere because they control the atmosphere's capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.
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Rahman, Md Mahbubur; Islam, Md Badrul; Biswas, Mohitosh; Khurshid Alam, A H M
2015-10-30
In humans, many diseases are associated with the accumulation of free radicals. Antioxidants can scavenge free radicals and minimize their impact. Therefore, the search for naturally occurring antioxidants of plant origin is imperative. Here, we aimed to investigate the antioxidant and free radical scavenging properties of methanolic extracts from Tabebuia pallida (T. pallida) stem bark (TPSB), root bark (TPRB), leaves (TPL), and flowers (TPF). The antioxidant and free radical scavenging activity were determined by several standard methods using spectrophotomer. Total phenolic and flavonoid contents were estimated using Folin-Ciocalteu reagent and aluminum chloride colorimetric assay methods, respectively. Among the extracts, TPL showed the highest total antioxidant capacity followed by TPRB, TPF, and TPSB. Based on DPPH and hydroxyl radical scavenging activity, TPL showed strong scavenging activity (91.05 ± 1.10 and 62.00 ± 0.57) with IC50 of 9.20 ± 0.28 and 46.00 ± 2.84 μg/mL, respectively when compared with standard BHT (IC50 of 7.00 ± 0.25 μg/mL) and CA (75.00 ± 0.14 μg/mL). These results suggest that TPL had the highest radical scavenging activity among the extractives that closely resembled the standard's. In lipid peroxidation inhibition assay, TPL exhibited the most potent inhibitory activity (83.18 ± 2.12 %) with IC50 of 12.00 ± 2.12 μg/mL, which closely resembled standard CA (IC50 of 10.50 ± 0.28 μg/mL). Also, the reducing capacity on ferrous ion was in the following order: TPL > TPRB > TF > TPSB. The phenolic and flavonoid contents of TPL were higher than other extractives. A positive correlation (p value <0.001) was observed between phenolic content and free radical (DPPH(·) and (·)OH) scavenging efficiencies and lipid peroxidation inhibition activity. Methanolic extract of T. pallida leaf is a potential source of natural antioxidants and serves as an effective free radical scavenger and/or inhibitor. Hence, T. pallida might be a good plant-based pharmaceutical product for several diseases caused by free radicals.
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Photodissociation of anisole and absolute photoionization cross-section of the phenoxy radical.
Xu, Hong; Pratt, S T
2013-11-21
We have studied the photodissociation dynamics of anisole (C6H5OCH3) at 193 nm and determined the absolute photoionization cross-section of the phenoxy radical at 118.2 nm (10.486 eV) relative to the known cross-section of the methyl radical. Even at this energy, there is extensive fragmentation of the phenoxy radical upon photoionization, which is attributed to ionizing transitions that populate low-lying excited electronic states of the cation. For phenoxy radicals with less than ∼1 eV of internal energy, we find a cross-section for the production of the phenoxy cation of 14.8 ± 3.8 Mb. For radicals with higher internal energy, dissociative ionization is the dominant process, and for internal energies of ∼2.7-3.7 eV, we find a total cross-section (photoionization plus dissociative ionization) of 22.3 ± 4.1 Mb. The results are discussed relative to the recently reported photoionization cross-section of phenol.
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Li, Xiao-Mei; Yan, Hong; Zhou, Kai-Na; Dang, Shao-Nong; Wang, Duo-Lao; Zhang, Yin-Ping
2011-07-01
Music therapy has been used in multiple health care settings to reduce patient pain, anxiety, and stress. However, few available studies have investigated its effect on pain among breast cancer patients after radical mastectomy. The aim of this study was to explore the effects of music therapy on pain reduction in patients with breast cancer after radical mastectomy. This randomized controlled trial was conducted at the Surgical Department of Oncology Center, First Affiliated Hospital of Xi'an Jiaotong University from March to November 2009. A total of 120 breast cancer patients who received Personal Controlled Analgesia (PCA) following surgery (mastectomy) were randomly allocated to two groups, an intervention group and a control group (60 patients in each group). The intervention group accepted music therapy from the first day after radical mastectomy to the third admission to hospital for chemotherapy in addition to the routine nursing care, while the control group received only routine nursing care. Pain scores were measured at baseline and three post-tests using the General Questionnaire and Chinese version of Short-Form of McGill Pain Questionnaire. The primary endpoint was the change in the Pain Rating Index (PRI-total) score from baseline. Music therapy was found to reduce the PRI-total score in the intervention group significantly compared with the control group with a mean difference (95% CI) of -2.38 (-2.80, -1.95), -2.41 (-2.85, -1.96), and -1.87 (-2.33, -1.42) for the 1st, 2nd, and 3rd post-tests, respectively. Similar results were found for Visual Analogue Scale (VAS) and Present Pain Intensity (PPI) scores. The findings of the study provide some evidence that music therapy has both short- and long-term positive effects on alleviating pain in breast cancer patients following radical mastectomy.
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The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K
NASA Technical Reports Server (NTRS)
Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.
2004-01-01
The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.
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Becerra Bachino, Virginia; Cots, Francesc; Guedea, Ferran; Pera, Joan; Boladeras, Ana; Aguiló, Ferran; Suárez, José Francisco; Gallo, Pedro; Murgui, Lluis; Pont, Angels; Cunillera, Oriol; Pardo, Yolanda; Ferrer, Montserrat
2011-01-01
To compare the initial costs of the three most established treatments for clinically localized prostate cancer according to risk, age and comorbidity groups, from the healthcare provider's perspective. We carried out a cost comparison study in a sample of patients consecutively recruited between 2003 and 2005 from a functional unit for prostate cancer treatment in Catalonia (Spain). The use of services up to 6 months after the treatment start date was obtained from hospital databases and direct costs were estimated by micro-cost calculation. Information on the clinical characteristics of patients and treatments was collected prospectively. Costs were compared by using nonparametric tests comparing medians (Kruskall-Wallis) and a semi-logarithmic multiple regression model. Among the 398 patients included, the cost difference among treatments was statistically significant: medians were € 3,229.10, € 5,369.00 and € 6,265.60, respectively, for the groups of patients treated with external 3D conformal radiotherapy, brachytherapy and radical retropublic prostatectomy, (p<0.001). In the multivariate analysis (adjusted R(2)=0.8), the average costs of brachytherapy and external radiotherapy were significantly lower than that of prostatectomy (coefficient -0.212 and -0.729, respectively). Radical prostatectomy proved to be the most expensive treatment option. Overall, the estimated costs in our study were lower than those published elsewhere. Most of the costs were explained by the therapeutic option and neither comorbidity nor risk groups showed an effect on total costs independent of treatment. Copyright © 2010 SESPAS. Published by Elsevier Espana. All rights reserved.
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Terahertz Spectroscopy of Deuterated Methylene Bi-Radical CD_2
NASA Astrophysics Data System (ADS)
Ozeki, Hiroyuki; Bailleux, Stephane
2015-06-01
Methylene, the parent of the carbene compounds, plays a crucial role in many chemical reactions. This bi-radical is a known interstellar molecule that has been detected towards hot cores in dense interstellar clouds. CH_2 is also thought to be present in cometary atmospheres. In the gas phase chemical models of both dense and diffuse molecular clouds, CH_2 is a key intermediate in interstellar carbon chemistry which is produced primarily by dissociative recombination of the methyl ion, CH^+_3. Recently tentative detection of the mono-deuterated methyl ion, CH_2D^+ has been reported toward an infrared source in the vicinity of Orion. Deuterated methylene CHD and CD_2 can be produced from this ion or its counterpart CHD^+_2 by dissociative recombination with an electron: CH2D+ + e- → CHD+ H or {CH2 + D}, CHD2+ ~+ e- → CHD+ D or CD2 + H. Thus, both CHD and CD_2 can be observed in warm interstellar clouds, where the deuterium fractionation process is important. Precise laboratory reference data are desirable for radioastronomical observation of these molecules. Here we report on our high-resolution spectroscopic investigation on the deuterated methylene radical, CD_2 (X ^3B_1) up to 1.45 THz. At present time, eleven out of the twelve fine-structure components of four pure rotational transitions have been newly recorded, and these measurements double the number of previously observed transitions. CD_2 was generated in a discharge in CD_2CO which was obtained from the flash pyrolysis of acetic anhydride-d6 ((CD_3CO)_2O). Effort is currently made to measure the astronomically important 111 - 000 transition whose fine-structure components are predicted to occur at 1.224,1.228 and 1.234 THz. D. C. Lis, P. F. Goldsmith, E. A. Bergin et al. 2009, in Submillimeter Astrophysics and Technology, ASP Conf. Ser., 417, 23. H. Ozeki and S. Saito J. Chem. Phys. 1996, 104, 2167.
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Effect of Curcumin Against Oxidation of Biomolecules by Hydroxyl Radicals
Mahendra, Jaideep; Gurumurthy, Prema; Jayamathi; Iqbal, Shabeer S; Mahendra, Little
2014-01-01
Background: Among various reactive oxygen species, hydroxyl radicals have the strongest chemical activity, which can damage a wide range of essential biomolecules such as lipids, proteins, and DNA. Objective: The objective of this study was to investigate the beneficial effects of curcumin on prevention of oxidative damage of biomolecules by hydroxyl radicals generated in in vitro by a Fenton like reaction. Materials and Methods: We have incubated the serum, plasma and whole blood with H2O2/Cu2+/ Ascorbic acid system for 4 hours at 37 0C and observed the oxidation of biomolecules like albumin, lipids, proteins and DNA. Results: Curcumin at the concentrations of 50,100 and 200 μmoles, prevented the formation of ischemia modified albumin, MDA, protein carbonyls, oxidized DNA and increased the total antioxidant levels and GSH significantly. Conclusion: These observations suggest the hydroxyl radical scavenging potentials of curcumin and protective actions to prevent the oxidation of biomolecules by hydroxyl radicals. PMID:25478334
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Sreelatha, S; Padma, P R
2009-12-01
Antioxidants play an important role in inhibiting and scavenging free radicals, thus providing protection to human against infections and degenerative diseases. Current research is now directed towards natural antioxidants originated from plants due to safe therapeutics. Moringa oleifera is used in Indian traditional medicine for a wide range of various ailments. To understand the mechanism of pharmacological actions, antioxidant properties of the Moringa oleifera leaf extracts were tested in two stages of maturity using standard in vitro models. The successive aqueous extract of Moringa oleifera exhibited strong scavenging effect on 2, 2-diphenyl-2-picryl hydrazyl (DPPH) free radical, superoxide, nitric oxide radical and inhibition of lipid per oxidation. The free radical scavenging effect of Moringa oleifera leaf extract was comparable with that of the reference antioxidants. The data obtained in the present study suggests that the extracts of Moringa oleifera both mature and tender leaves have potent antioxidant activity against free radicals, prevent oxidative damage to major biomolecules and afford significant protection against oxidative damage.
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Trinuclear Mn(II) complex with paramagnetic bridging 1,2,3-dithiazolyl ligands.
Sullivan, David J; Clérac, Rodolphe; Jennings, Michael; Lough, Alan J; Preuss, Kathryn E
2012-11-18
The first metal coordination complex of a radical ligand based on the 1,2,3-dithiazolyl heterocycle is reported. 6,7-Dimethyl-1,4-dioxo-naphtho[2,3-d][1,2,3]dithiazolyl acts as a bridging ligand in the volatile trinuclear Mn(hfac)(2)-Rad-Mn(hfac)(2)-Rad-Mn(hfac)(2) complex (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato-). The Mn(II) and radical ligand spins are coupled anti-ferromagnetically (AF) resulting in an S(T) = 13/2 spin ground state.
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Wang, Liying; Ding, Long; Wang, Ying; Zhang, Yan; Liu, Jingbo
2015-02-16
Corn gluten meal, a corn processing industry by-product, is a good source for the preparation of bioactive peptides due to its special amino acid composition. In the present study, the in vitro and cellular free radical scavenging activities of corn peptide fractions (CPFs) were investigated. Results indicated that CPF1 (molecular weight less than 1 kDa) and CPF2 (molecular weight between 1 and 3 kDa) exhibited good hydroxyl radical, superoxide anion radical and 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonicacid) diammonium salt (ABTS) radical scavenging activity and oxygen radical absorbance capacity (ORAC). Meanwhile, the in vitro radical scavenging activity of CPF1 was slightly higher than that of CPF2. Both CPF1 and CPF2 also exhibited significant cytoprotective effects and intracellular reactive oxygen species scavenging activity in Caco-2 cells exposed to hydrogen peroxide (H2O2). The amino acid composition analysis revealed that the CPF were rich in hydrophobic amino acids, which comprised of more than 45% of total amino acids. An antioxidant peptide sequence of Tyr-Phe-Cys-Leu-Thr (YFCLT) was identified from CPF1 using matrix-assisted laser desorption/ionization time-of-flight/time-of-flight mass spectrometry (MALDI TOF/TOF MS). The YFCLT exhibited excellent ABTS radical scavenging activity with a 50% effective concentration (EC50) value of 37.63 µM, which was much lower than that of Trolox. In conclusion, corn gluten meal might be a good source to prepare antioxidant peptides.
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The millimeter-wave spectrum of the MgH and MgD radicals
NASA Technical Reports Server (NTRS)
Ziurys, L. M.; Barclay, W. L., Jr.; Anderson, M. A.
1993-01-01
The pure rotational spectrum of MgH radical (X 2 Sigma (+)) in its ground state v = 0 and v = 1 vibrational modes has been observed in the laboratory using millimeter/submillimeter direct absorption spectroscopy. The rotational spectra of two isotopically substituted species, MgD and (Mg-26)H, have been detected as well. All six hyperfine components of the N = 0 -1 transition of MgH in its v = 0 and v = 1 states have been directly measured to an accuracy of +/-50 kHz, and the five components have been observed for (Mg-26)H. The N = 0 +/-1 and N = 1 -2 transitions of MgD have also been detected. Rotational, fine structure, and hyperfine constants were determined for all species from a nonlinear least-squared fit to the data using a 2 Sigma Hamiltonian.
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Multi-State Vibronic Interactions in Fluorinated Benzene Radical Cations.
NASA Astrophysics Data System (ADS)
Faraji, S.; Köppel, H.
2009-06-01
Conical intersections of potential energy surfaces have emerged as paradigms for signalling strong nonadiabatic coupling effects. An important class of systems where some of these effects have been analyzed in the literature, are the benzene and benzenoid cations, where the electronic structure, spectroscopy, and dynamics have received great attention in the literature. In the present work a brief overview is given over our theoretical treatments of multi-mode and multi-state vibronic interactions in the benzene radical cation and some of its fluorinated derivatives. The fluorobenzene derivatives are of systematic interest for at least two different reasons. (1) The reduction of symmetry by incomplete fluorination leads to a disappearance of the Jahn-Teller effect present in the parent cation. (2) A specific, more chemical effect of fluorination consists in the energetic increase of the lowest σ-type electronic states of the radical cations. The multi-mode multi-state vibronic interactions between the five lowest electronic states of the fluorobenzene radical cations are investigated theoretically, based on ab initio electronic structure data, and employing the well-established linear vibronic coupling model, augmented by quadratic coupling terms for the totally symmetric vibrational modes. Low-energy conical intersections, and strong vibronic couplings are found to prevail within the set of tilde{X}-tilde{A} and tilde{B}-tilde{C}-tilde{D} cationic states, while the interactions between these two sets of states are found to be weaker and depend on the particular isomer. This is attributed to the different location of the minima of the various conical intersections occurring in these systems. Wave-packet dynamical simulations for these coupled potential energy surfaces, utilizing the powerful multi-configuration time-dependent Hartree method are performed. Ultrafast internal conversion processes and the analysis of the MATI and photo-electron spectra shed new light on the spectroscopy and fluorescence dynamics of these species. W. Domcke, D. R. Yarkony, and H. Köppel, Advanced Series in Physical Chemistry, World Scientific, Singapore (2004). M. H. Beck and A. Jäckle and G. A. Worth and H. -D. Meyer, Phys. Rep. 324, 1 (2000). S. Faraji, H. Köppel, (Part I) ; S. Faraji, H. Köppel, H.-D. Meyer, (Part II) J. Chem. Phys. 129, 074310 (2008).
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Ghosh, Sougata; Derle, Abhishek; Ahire, Mehul; More, Piyush; Jagtap, Soham; Phadatare, Suvarna D.; Patil, Ajay B.; Jabgunde, Amit M.; Sharma, Geeta K.; Shinde, Vaishali S.; Pardesi, Karishma; Dhavale, Dilip D.; Chopade, Balu A.
2013-01-01
Gnidia glauca and Dioscorea bulbifera are traditional medicinal plants that can be considered as sources of natural antioxidants. Herein we report the phytochemical analysis and free radical scavenging activity of their sequential extracts. Phenolic and flavonoid content were determined. Scavenging activity was checked against pulse radiolysis generated ABTS•+ and OH radical, in addition to DPPH, superoxide and hydroxyl radicals by biochemical methods followed by principal component analysis. G. glauca leaf extracts were rich in phenolic and flavonoid content. Ethyl acetate extract of D. bulbifera bulbs and methanol extract of G. glauca stem exhibited excellent scavenging of pulse radiolysis generated ABTS•+ radical with a second order rate constant of 2.33×106 and 1.72×106, respectively. Similarly, methanol extract of G. glauca flower and ethyl acetate extract of D. bulbifera bulb with second order rate constants of 4.48×106 and 4.46×106 were found to be potent scavengers of pulse radiolysis generated OH radical. G. glauca leaf and stem showed excellent reducing activity and free radical scavenging activity. HPTLC fingerprinting, carried out in mobile phase, chloroform: toluene: ethanol (4: 4: 1, v/v) showed presence of florescent compound at 366 nm as well as UV active compound at 254 nm. GC-TOF-MS analysis revealed the predominance of diphenyl sulfone as major compound in G. glauca. Significant levels of n-hexadecanoic acid and octadecanoic acid were also present. Diosgenin (C27H42O3) and diosgenin (3á,25R) acetate were present as major phytoconstituents in the extracts of D. bulbifera. G. glauca and D. bulbifera contain significant amounts of phytochemicals with antioxidative properties that can be exploited as a potential source for herbal remedy for oxidative stress induced diseases. These results rationalize further investigation in the potential discovery of new natural bioactive principles from these two important medicinal plants. PMID:24367520
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Ghosh, Sougata; Derle, Abhishek; Ahire, Mehul; More, Piyush; Jagtap, Soham; Phadatare, Suvarna D; Patil, Ajay B; Jabgunde, Amit M; Sharma, Geeta K; Shinde, Vaishali S; Pardesi, Karishma; Dhavale, Dilip D; Chopade, Balu A
2013-01-01
Gnidia glauca and Dioscorea bulbifera are traditional medicinal plants that can be considered as sources of natural antioxidants. Herein we report the phytochemical analysis and free radical scavenging activity of their sequential extracts. Phenolic and flavonoid content were determined. Scavenging activity was checked against pulse radiolysis generated ABTS(•+) and OH radical, in addition to DPPH, superoxide and hydroxyl radicals by biochemical methods followed by principal component analysis. G. glauca leaf extracts were rich in phenolic and flavonoid content. Ethyl acetate extract of D. bulbifera bulbs and methanol extract of G. glauca stem exhibited excellent scavenging of pulse radiolysis generated ABTS(•+) radical with a second order rate constant of 2.33 × 10(6) and 1.72 × 10(6), respectively. Similarly, methanol extract of G. glauca flower and ethyl acetate extract of D. bulbifera bulb with second order rate constants of 4.48 × 10(6) and 4.46 × 10(6) were found to be potent scavengers of pulse radiolysis generated OH radical. G. glauca leaf and stem showed excellent reducing activity and free radical scavenging activity. HPTLC fingerprinting, carried out in mobile phase, chloroform: toluene: ethanol (4: 4: 1, v/v) showed presence of florescent compound at 366 nm as well as UV active compound at 254 nm. GC-TOF-MS analysis revealed the predominance of diphenyl sulfone as major compound in G. glauca. Significant levels of n-hexadecanoic acid and octadecanoic acid were also present. Diosgenin (C₂₇H₄₂O₃) and diosgenin (3á,25R) acetate were present as major phytoconstituents in the extracts of D. bulbifera. G. glauca and D. bulbifera contain significant amounts of phytochemicals with antioxidative properties that can be exploited as a potential source for herbal remedy for oxidative stress induced diseases. These results rationalize further investigation in the potential discovery of new natural bioactive principles from these two important medicinal plants.
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Differential Cytochrome P450 2D Metabolism Alters Tafenoquine Pharmacokinetics
Vuong, Chau; Xie, Lisa H.; Potter, Brittney M. J.; Zhang, Jing; Zhang, Ping; Duan, Dehui; Nolan, Christina K.; Sciotti, Richard J.; Zottig, Victor E.; Nanayakkara, N. P. Dhammika; Tekwani, Babu L.; Walker, Larry A.; Smith, Philip L.; Paris, Robert M.; Read, Lisa T.; Li, Qigui; Pybus, Brandon S.; Sousa, Jason C.; Reichard, Gregory A.; Smith, Bryan
2015-01-01
Cytochrome P450 (CYP) 2D metabolism is required for the liver-stage antimalarial efficacy of the 8-aminoquinoline molecule tafenoquine in mice. This could be problematic for Plasmodium vivax radical cure, as the human CYP 2D ortholog (2D6) is highly polymorphic. Diminished CYP 2D6 enzyme activity, as in the poor-metabolizer phenotype, could compromise radical curative efficacy in humans. Despite the importance of CYP 2D metabolism for tafenoquine liver-stage efficacy, the exact role that CYP 2D metabolism plays in the metabolism and pharmacokinetics of tafenoquine and other 8-aminoquinoline molecules has not been extensively studied. In this study, a series of tafenoquine pharmacokinetic experiments were conducted in mice with different CYP 2D metabolism statuses, including wild-type (WT) (reflecting extensive metabolizers for CYP 2D6 substrates) and CYPmouse 2D knockout (KO) (reflecting poor metabolizers for CYP 2D6 substrates) mice. Plasma and liver pharmacokinetic profiles from a single 20-mg/kg of body weight dose of tafenoquine differed between the strains; however, the differences were less striking than previous results obtained for primaquine in the same model. Additionally, the presence of a 5,6-ortho-quinone tafenoquine metabolite was examined in both mouse strains. The 5,6-ortho-quinone species of tafenoquine was observed, and concentrations of the metabolite were highest in the WT extensive-metabolizer phenotype. Altogether, this study indicates that CYP 2D metabolism in mice affects tafenoquine pharmacokinetics and could have implications for human tafenoquine pharmacokinetics in polymorphic CYP 2D6 human populations. PMID:25870069
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Antinephrolithiatic and antioxidative efficacy of Dolichos biflorus seeds in a lithiasic rat model.
Saha, Sarmistha; Verma, Ramtej J
2015-01-01
Dolichos biflorus sensu auct non L. (Fabaceae) is widely used for the treatment of kidney stones, leucorrhoea, urinary disorders, and menstrual troubles, and is known for its antioxidant activity. To evaluate the preventive effect of hydro-alcoholic extract of Dolichos biflorus seeds (DBE) in ethylene glycol induced nephrolithiasis. In vitro antioxidative capacity of DBE was estimated in terms of reducing power, superoxide radical, 2,2- diphenyl-1-picrylhydrazyl radical, and nitric oxide scavenging activity. A validated HPLC method was used for standardization using quercetin as a marker. Adult female Wistar rats were administered with DBE (150 and 300 mg/kg body weight/day) along with ethylene glycol (0.75%, v/v) for 28 d. The various biochemical parameters were measured in urine, serum, and kidney followed by histochemistry. Ethylene glycol caused a significant increase in calcium, oxalate, phosphate, and total protein in urine as well as in kidney whereas decrease in calcium, sodium, and magnesium in serum was observed (p < 0.001). Ethylene glycol also caused a significant increase in lipid peroxidation and concurrent decrease in activities of antioxidant enzymes in kidney (p < 0.001). However, the seed extract of D. biflorus caused significant restoration of all these parameters (p < 0.001). Histopathological and histochemical studies also showed the reduced calcifications in kidney of seed extract treated rats. These results indicated that seeds of D. biflorus have significant prophylactic effect in preventing the nephrolithiasis, which might be due to the antioxidant activity of the active compounds of the plant.
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Biondi, Roberto; Ambrosio, Giuseppe; Liebgott, Tibaud; Cardounel, Arturo J; Bettini, Marco; Tritto, Isabella; Zweier, Jay L
2006-07-15
Research in the pathophysiology of ischemia/reperfusion or redox signaling is hindered by lack of simple methodology to measure short-lived oxygen radicals. In the presence of hydroxyl radical ((*)OH), d-phenylalanine (d-Phe) yields para-, meta- and ortho-tyrosine. We have previously demonstrated that d-Phe can accurately detect (*)OH formation in chemical, enzymatic and cellular systems by simple HPLC methodology [Anal Biochem 290:138;2001]. In the present study, we tested whether d-Phe hydroxylation can be used to detect (*)OH formation in intact organs. Rat hearts were perfused with buffer containing 5 mM d-Phe and subjected to 30 min of total global ischemia at 37 degrees C followed by 45 min of reperfusion. Quantitative analysis of the three hydroxytyrosine isomers was achieved by HPLC-based electrochemical detection of cardiac venous effluent, with the analytical cells operating in the oxidative mode. The detection limit of this assay was <10 fmol. Under baseline conditions, hydroxytyrosine release from the heart was very low ( congruent with0.8 nmol/min/g). However, a prominent tyrosine burst occurred immediately upon post-ischemic reflow. In cardiac effluent collected 40 s into reperfusion, the hydroxytyrosine concentration was more than 40 times greater than at baseline; hydroxytyrosine concentration then progressively declined, to return to pre-ischemic values by 5 min of reperfusion. In parallel experiments, formation of hydroxytyrosines was markedly reduced in hearts reperfused in the presence of the (*)OH scavenger mannitol. Inclusion of 5 mm d-Phe in the perfusion medium altered neither basal cardiac function nor coronary vascular tone, but it enhanced recovery of myocardial function during post-ischemic reperfusion, consistent with direct reaction with (*)OH. Our results demonstrate that d-Phe is a sensitive method for detection of (*)OH generation in the heart. Since d-Phe is not a substrate for endogenous enzymes, it can be exploited as a reliable method to measure (*)OH formation under a variety of pathophysiological conditions.
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Growing up Radical: Investigation of Benzyl-Like Radicals with Increasing Chain Lengths
NASA Astrophysics Data System (ADS)
Korn, Joseph A.; Jawad, Khadija M.; Hewett, Daniel M.; Zwier, Timothy S.
2015-06-01
Combustion processes involve complex chemistry including pathways leading to polyaromatic hydrocarbons (PAHs) from small molecule precursors. Resonance stabilized radicals (RSRs) likely play an important role in the pathways to PAHs due to their unusual stability. Benzyl radical is a prototypical RSR that is stabilized by conjugation with the phenyl ring. Earlier work on α-methyl benzyl radical showed perturbations to the spectroscopy due to a hindered methyl rotor. If the alkyl chain is lengthened then multiple conformations become possible. This talk will discuss the jet-cooled spectroscopy of α-ethyl benzyl radical and α-propyl benzyl radical produced from the discharge of 1-phenyl propanol and 1-phenyl butanol respectively. Electronic spectra were obtained via resonant two-photon ionization, and IR spectra were obtained by resonant ion-dip infrared spectroscopy. Kidwell, N. M.; Reilly, N. J.; Nebgen, B.; Mehta-Hurt, D. N.; Hoehn, R. D.; Kokkin, D. L.; McCarthy, M. C.; Slipchenko, L. V.; Zwier, T. S. The Journal of Physical Chemistry A 2013, 117, 13465.
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Durand, Grégory; Choteau, Fanny; Pucci, Bernard; Villamena, Frederick A
2008-12-04
Nitrones have exhibited pharmacological activity against radical-mediated pathophysiological conditions and as analytical reagents for the identification of transient radical species by electron paramagnetic resonance (EPR) spectroscopy. In this work, competitive spin trapping, stopped-flow kinetics, and density functional theory (DFT) were employed to assess and predict the reactivity of O(2)(*-) and HO(2)(*) with various para-substituted alpha-phenyl-N-tert-butylnitrone (PBN) spin traps. Rate constants of O(2)(*-) trapping by nitrones were determined using competitive UV-vis stopped-flow method with phenol red (PR) as probe, while HO(2)(*) trapping rate constants were calculated using competition kinetics with 5,5-dimethylpyrroline N-oxide (DMPO) by employing EPR spectroscopy. The effects of the para substitution on the charge density of the nitronyl-carbon and on the free energies of nitrone reactivity with O(2)(*-) and HO(2)(*) were computationally rationalized at the PCM/B3LYP/6-31+G(d,p)//B3LYP/6-31G(d) level of theory. Theoretical and experimental data show that the rate of O(2)(*-) addition to PBN derivatives is not affected by the polar effect of the substituents. However, the reactivity of HO(2)(*) follows the Hammett equation and is increased as the substituent becomes more electron withdrawing. This supports the conclusion that the nature of HO(2)(*) addition to PBN derivatives is electrophilic, while the addition of O(2)(*-) to PBN-type compounds is only weakly electrophilic.
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Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range.
Yan, Chao; Kocevska, Stefani; Krasnoperov, Lev N
2016-08-11
Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH → CH3O + HO2 (1a) and CH3O2 + OH → CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k1a+1b = (8.4 ± 1.7) × 10(-11)(T/298 K)(-0.81) cm(3) molecule(-1) s(-1) (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%.
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Phase 2 Clinical Trials: D-Methionine to Reduce Noise-Induced Hearing Loss
2016-07-01
no lapses in regulatory reports or approvals (IRB, HRPO, FDA). KEYWORDS: D-methionine, noise, protection, hearing loss , antioxidant, free radicals...25, 2012 2012“D-methionine (D-met) Pre- Loading Prior to Noise Exposure Significantly Reduces Temporary and Permanent Noise-Induced Hearing Loss ...1 AWARD NUMBER: W81XWH-11-C-0033 TITLE: Phase 2 Clinical Trials: D-Methionine to Reduce Noise-induced Hearing Loss PRINCIPAL INVESTIGATOR
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NASA Astrophysics Data System (ADS)
Sommariva, R.; Brown, S. S.; Roberts, J. M.; Monks, P. S.; Parker, A. E.; Osthoff, H. D.; Ravishankara, A. R.; Trainer, M.
2006-12-01
Chemistry of free radicals in the marine boundary layer was investigated during two cruises of the NOAA Research Vessel Ronald H. Brown as parts of the NEAQS-ITCT 2004 and TexAQS-GoMACCS 2006 campaigns. The nitrate radical (NO{_3}) and dinitrogen pentoxide (N{_2}O{_5}) were measured during the NEAQS campaign by Cavity Ring-Down Spectroscopy (CaRDS). NO{_3} abundances measured under the conditions encountered during the cruise were investigated using a zero-dimensional model based upon the Master Chemical Mechanism (MCMv3.1, http://mcm.leeds.ac.uk). The model was constrained to measurements of chemical and physical parameters taken during the campaign. The high level of chemical detail in the MCM allowed us to calculate abundances of the alkyl peroxy radicals that were to be expected and to study the interactions during the night between these alkyl peroxy radicals (RO{_2}) and NO{_3}. In particular, the importance of the reaction between RO{_2} and NO{_3} as a sink for NO{_3} under different conditions was assessed. CaRDS NO{_3} measurements during TexAQS campaign were made in conjunction with measurements of total peroxy radicals (HO{_2}+RO{_2}) by a chemical amplification technique (PERCA), allowing for experimental verification of the relationships between these radicals at night. The preliminary measurements taken during TeXAQS 2006 will be presented and they will be used to investigate the night-time chemistry of the peroxy radicals, and especially the interactions between NO{_3} and peroxy radical in a polluted nighttime environment.
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In vitro antioxidant activity of pet ether extract of black pepper
Singh, Ramnik; Singh, Narinder; Saini, B.S.; Rao, Harwinder Singh
2008-01-01
Objective: To investigate the in vitro antioxidant activity of different fractions (R1, R2 and R3) obtained from pet ether extract of black pepper fruits (Piper nigrum Linn.) Materials and Methods: The fractions R1, R2 and R3 were eluted from pet ether and ethyl acetate in the ratio of 6:4, 5:5 and 4:6, respectively. 1,1-Diphenyl-2-picryl-hydrazyl (DPPH) radical, superoxide anion radical, nitric oxide radical, and hydroxyl radical scavenging assays were carried out to evaluate the antioxidant potential of the extract. Results: The free radical scavenging activity of the different fractions of pet ether extract of P. nigrum (PEPN) increased in a concentration dependent manner. The R3 and R2 fraction of PEPN in 500 µg/ml inhibited the peroxidation of a linoleic acid emulsion by 60.48±3.33% and 58.89±2.51%, respectively. In DPPH free radical scavenging assay, the activity of R3 and R2 were found to be almost similar. The R3 (100µg/ml) fraction of PEPN inhibited 55.68±4.48% nitric oxide radicals generated from sodium nitroprusside, whereas curcumin in the same concentration inhibited 84.27±4.12%. Moreover, PEPN scavenged the superoxide radical generated by the Xanthine/Xanthine oxidase system. The fraction R2 and R3 in the doses of 1000µg/ml inhibited 61.04±5.11% and 63.56±4.17%, respectively. The hydroxyl radical was generated by Fenton's reaction. The amounts of total phenolic compounds were determined and 56.98 µg pyrocatechol phenol equivalents were detected in one mg of R3. Conclusions: P. nigrum could be considered as a potential source of natural antioxidant. PMID:20040947
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Protection of cadmium chloride induced DNA damage by Lamiaceae plants
Thirugnanasampandan, Ramaraj; Jayakumar, Rajarajeswaran
2011-01-01
Objective To analyze the total phenolic content, DNA protecting and radical scavenging activity of ethanolic leaf extracts of three Lamiaceae plants, i.e. Anisomelos malabarica (A. malabarica), Leucas aspera (L. aspera) and Ocimum basilicum (O. basilicum). Methods The total polyphenols and flavonoids were analyzed in the ethanolic leaf extracts of the lamiaceae plants. To determine the DNA protecting activity, various concentrations of the plant extracts were prepared and treated on cultured HepG2 human lung cancer cells. The pretreated cells were exposed to H2O2 to induce DNA damage through oxidative stress. Comet assay was done and the tail length of individual comets was measured. Nitric oxide and superoxide anion scavenging activities of lamiaceae plants were analyzed. Results Among the three plant extracts, the highest amount of total phenolic content was found in O. basilicum (189.33 mg/g), whereas A. malabarica showed high levels of flavonoids (10.66 mg/g). O. basilicum also showed high levels of DNA protecting (85%) and radical scavenging activity. Conclusions The results of this study shows that bioactive phenols present in lamiaceae plants may prevent carcinogenesis through scavenging free radicals and inhibiting DNA damage. PMID:23569799
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Wan, X L; Song, Z H; Niu, Y; Cheng, K; Zhang, J F; Ahmad, H; Zhang, L L; Wang, T
2017-04-01
An experiment was conducted to evaluate the effects of including enzymatically treated Artemisia annua L. (EA) in broiler diets on growth performance, meat quality, and oxidative stability of breast and thigh muscles. A total of 256 one-d-old Arbor Acres broiler chicks were randomly allotted into four groups with eight replicates of eight birds each. Broilers in the four groups were offered basal diet supplemented with 0.0, 0.5, 1.0, and 1.5 g/kg EA during the 42-d experiment, respectively. The ADG, ADFI, and feed/gain ratio (F:G) were measured at 42 d of age. Breast and thigh muscle samples from eight birds per treatment were obtained at 42 d to determine meat quality, free radical scavenging activity, and lipid peroxidation. All treatment groups had similar ADG, ADFI, and F:G during the 42 d experiment (P > 0.05). Drip loss at 24 h and shearing force of breast muscle were linearly (P < 0.05) and quadratically (P < 0.05) decreased by EA addition. The drip loss at 24 h and 48 h, cooking loss and shearing force of thigh muscle followed the same fashion. The supplementation of EA quadratically increased 2, 2-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) diammonium salt (ABTS) (P = 0.004) and 2, 2-diphenyl-1-picrylhydrazyl (DPPH) (P = 0.035) free radical scavenging activities in breast muscle, and linearly (P < 0.05) and quadratically (P < 0.05) increased ABTS and DPPH scavenging activities of thigh muscle. Increasing levels of EA linearly (P < 0.05) or quadratically (P < 0.05) or both decreased the malondialdehyde (MDA) concentrations in breast and thigh muscle samples during 15 d of storage at 4°C. The results indicated that EA supplementation improved meat quality and oxidative stability of breast and thigh muscles in broilers. The inclusion level of 1.0 g/kg EA in broiler diet was recommended. © 2016 Poultry Science Association Inc.
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Favoring D2-Lymphadenectomy in Gastric Cancer
Karavokyros, Ioannis; Michalinos, Adamantios
2018-01-01
The role of extended lymphadenectomy in the surgical treatment of gastric cancer has been debated for many years. So far six prospective randomized trials and a number of meta-analyses comparing D1- to D2-lymphadenectomy in open surgery have been published with contradicting results. The possible oncologic benefit of radical lymphadenectomy has been blurred by a number of reasons. In most of the trials the strategies under comparison were made similar after protocol violations. Imperfect design of the trials could not exclude the influence of cofounding factors. Inappropriate endpoints could not detect evidently the difference between the two surgical strategies. On the other hand radical lymphadenectomy was characterized by increased morbidity and mortality. This was mostly caused by the addition of pancreatico-splenectomy in all D2-dissections, even when not indicated. A careful analysis of the available evidence indicates that D2-lymphadenectomy performed by adequately trained surgeons without resection of the pancreas and/or spleen, unless otherwise indicated, decreases Gastric Cancer Related Deaths and increases Disease Specific Survival. This evidence is not compelling but cannot be ignored. D2-lymphadendctomy is nowadays considered to be the standard of care for resectable gastric cancer. PMID:29930941
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Favoring D2-Lymphadenectomy in Gastric Cancer.
Karavokyros, Ioannis; Michalinos, Adamantios
2018-01-01
The role of extended lymphadenectomy in the surgical treatment of gastric cancer has been debated for many years. So far six prospective randomized trials and a number of meta-analyses comparing D 1 - to D 2 -lymphadenectomy in open surgery have been published with contradicting results. The possible oncologic benefit of radical lymphadenectomy has been blurred by a number of reasons. In most of the trials the strategies under comparison were made similar after protocol violations. Imperfect design of the trials could not exclude the influence of cofounding factors. Inappropriate endpoints could not detect evidently the difference between the two surgical strategies. On the other hand radical lymphadenectomy was characterized by increased morbidity and mortality. This was mostly caused by the addition of pancreatico-splenectomy in all D 2 -dissections, even when not indicated. A careful analysis of the available evidence indicates that D 2 -lymphadenectomy performed by adequately trained surgeons without resection of the pancreas and/or spleen, unless otherwise indicated, decreases Gastric Cancer Related Deaths and increases Disease Specific Survival. This evidence is not compelling but cannot be ignored. D 2 -lymphadendctomy is nowadays considered to be the standard of care for resectable gastric cancer.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Guldi, D.M.
A series of water-soluble isomer bis(pyrrolidinium) salts, with C{sub 60}(C{sub 4}H{sub 10}N{sup +}){sub 2} as cationic moiety (2a--2d), were probed in radical- and light-induced reduction studies and compared to bis(carboxylates) C{sub 60}[C(COO{sup {minus}}){sub 2}]{sub 2} and to {gamma}-CD-encapsulated C{sub 60}. Pulse radiolytic reduction of 2a--2d with hydrated electrons and (CH{sub 3}){sub 2}{sup {sm{underscore}bullet}}COH radicals leads to the formation of the fullerene {pi}-radical anion, exhibiting fingerprint absorption characteristics in the near-IR region. Because of the electron-withdrawing nature of the pyrrolidinium groups the electron-acceptor properties of the investigated bis(pyrrolidinium) salts are markedly improved relative to the bis(carboxylates) (C{sub 60}[C(COO{sup {minus}}){sub 2}]{sub 2})more » and also relative to C{sub 60}. For example, the rate constants for the fullerene reduction of 2a--2d with hydrated electrons ((0.88--2.2) x 10{sup 10} M{sup {minus}1} s{sup {minus}1}) and (CH{sub 3}){sub 2}{sm{underscore}bullet}COH radicals ((4.7--7.1) x 10{sup 8} M{sup {minus}1} s{sup {minus}1}) are clearly faster than those noted for C{sub 60}[C(COO{sup {minus}}){sub 2}]{sub 2} (e{sub aq}{sup {minus}}: (0.19--0.34) x 10{sup 10} M{sup {minus}1} s{sup {minus}1}; (CH{sub 3}){sub 2}{sup {sm{underscore}bullet}}COH: (0.9--2.2) x 10{sup 8}M{sup {minus}1} s{sup {minus}1}), and C{sub 60} (e{sub aq}{sup {minus}}: 1.8 x 10{sup 10} M{sup {minus}1} s{sup {minus}1}; (CH{sub 3}){sub 2}{sup {sm{underscore}bullet}}COH: 2.7 x 10{sup 8} M{sup {minus}1} s{sup {minus}1}). Photolysis of 2a--2d gives rise to singlet excited state absorptions that closely resemble earlier observations for the pyrrolidine precursor, e.g., C{sub 60}(C{sub 3}H{sub 7}N){sub 2} (1a--1d) in deoxygenated toluene solutions. The triplet lifetimes of 2a--2d, as measured by nanosecond-resolved photolysis, are typically around 33 {mu}s, similar to the triplet lifetimes of truly monomeric fullerene solutions. Quenching experiments with diszabicyclooctane (DABCO), involving the triplet excited states of 2a--2d, yielded rate constants which vary between 2.5 x 10{sup 6} and 4.7 x 10{sup 6} M{sup {minus}1} s{sup {minus}1} and reveal a slow-down relative to C{sub 60}(7.4 x 10{sup 7} M{sup {minus}1} s{sup {minus}1}).« less
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NASA Technical Reports Server (NTRS)
Salawitch, R. J.; Wofsy, S. C.; We-Nnberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.
1994-01-01
In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower statosphere during SPADE are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for (OH) and (HO2) are reduced if we allow for higher yields of O((1)D) from O2 photolysis and for heterogeneous production of HNO2. The data suggest more efficent catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommendend rates and cross sections. Increased in (O3) in the lower stratosphere may be larger in response to inputs of NO(y) from supersonic aircraft than estimated by current assessment models.
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Hexapole-selected supersonic beams of reactive radicals: CF3, SiF3, SH, CH, and C2H
NASA Astrophysics Data System (ADS)
Weibel, Michael A.; Hain, Toby D.; Curtiss, Thomas J.
1998-02-01
A supersonic corona discharge source was used to produce molecular beams of plasma particles. Neutral, polar components of the plasma mixture were selectively focused by an electrostatic hexapole, thereby "simplifying" the chemical and rotational state composition of the beam. Careful choice of a radical precursor, combined with control of discharge and hexapole voltage allowed the production of pure beams of CF3, SiF3, and SH (purity typically better than 90%), with no noticeable signal arising from undissociated precursor, ions, or other radicals. Focused beams from a hydrocarbon plasma contained a radical mixture of predominantly CH and C2H. Radical beams were characterized by rotationally and translationally cold temperatures (typically TR<20 K and TS<20 K, respectively) and high intensities (typically 1011-1012cm-2 s-1). Simulated focusing spectra using classical trajectory calculations showed generally good agreement with the experimental data, leading to the first experimental measurement of the permanent electric dipole moment of SiF3 (μ=1.2±0.1 D).
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Karthikeyan, S; Sekaran, G
2014-03-07
The objective of this investigation is to evaluate the hydroxyl radical (˙OH) generation using nanoporous activated carbon (NPAC), derived from rice husk, and dissolved oxygen in water. The in situ production of the ˙OH radical was confirmed through the DMPO spin trapping method in EPR spectroscopy and quantitative determination by a deoxyribose assay procedure. NPAC served as a heterogeneous catalyst to degrade 2-deoxy-d-ribose (a reference compound) using hydroxyl radical generated from dissolved oxygen in water at temperatures in the range 313-373 K and pH 6, with first order rate constants (k = 9.2 × 10(-2) min(-1), k = 1.2 × 10(-1) min(-1), k = 1.3 × 10(-1) min(-1) and k = 1.68 × 10(-1) min(-1)). The thermodynamic constants for the generation of hydroxyl radicals by NPAC and dissolved oxygen in water were ΔG -1.36 kJ mol(-1) at 313 K, ΔH 17.73 kJ mol(-1) and ΔS 61.01 J mol(-1) K(-1).
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Lee, Na-Ri; Lee, Sang-Mee; Cho, Kwang-Sik; Jeong, Seong-Yun; Hwang, Dae-Youn; Kim, Dong-Seob; Hong, Chang-Oh; Son, Hong-Joo
2014-06-01
The objectives of this study was to improve poly-γ-glutamic acid (γ-PGA) production by Bacillus subtilis D7 isolated from a Korean traditional fermented food and to assess its antioxidant activity for applications in the cosmetics and pharmaceutical industries. Strain D7 produced γ-PGA in the absence of L-glutamic acid, indicating L-glutamic acid-independent production. However, the addition of L-glutamic acid increased γ-PGA production. Several tricarboxylic acid cycle intermediates and amino acids could serve as the metabolic precursors for γ-PGA production, and the addition of pyruvic acid and D-glutamic acid to culture medium improved the yield of γ-PGA markedly. The maximum yield of γ-PGA obtained was 24.93 ± 0.64 g/l in improved medium, which was about 5.4-fold higher than the yield obtained in basal medium. γ-PGA was found to have 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity (46.8 ± 1.5 %), hydroxyl radical scavenging activity (52.0 ± 1.8 %), 2,2'-azinobis-3-ethylbenzothiazoline-6-sulfonate (ABTS) radical scavenging activity (42.1 ± 1.8 %), nitric oxide scavenging activity (35.1 ± 1.3 %), reducing power (0.304 ± 0.008), and metal chelating activity (91.3 ± 3.5 %). These results indicate that γ-PGA has a potential use in the food, cosmetics, and biomedical industries for the development of novel products with radical scavenging activity. As far as we are aware, this is the first report to describe the antioxidant activityof γ-PGA produced by bacteria.
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Anticancer and antioxidant tannins from Pimenta dioica leaves.
Marzouk, Mohamed S A; Moharram, Fatma A; Mohamed, Mona A; Gamal-Eldeen, Amira M; Aboutabl, Elsayed A
2007-01-01
Two galloylglucosides, 6-hydroxy-eugenol 4-O-(6'-O-galloyl)-beta-D-4C1-glucopyranoside (4) and 3-(4-hydroxy-3-methoxyphenyl)-propane-1,2-diol-2-O-(2',6'-di-O-galloyl)-beta-D -4C1-glucopyranoside (7), and two C-glycosidic tannins, vascalaginone (10) and grandininol (14), together with fourteen known metabolites, gallic acid (1), methyl gallate (2), nilocitin (3), 1-O-galloyl-4,6-(S)-hexahydroxydiphenoyl-(alpha/beta)-D-glucopyranose (5), 4,6-(S)-hexahydroxydiphenoyl-(alpha/beta)-D-glucopyranose (6), 3,4,6-valoneoyl-(alpha/beta)-D-glucopyranose (8), pedunculagin (9), casuariin (11), castalagin (12), vascalagin (13), casuarinin (15), grandinin (16), methyl-flavogallonate (17) and ellagic acid (18), were identified from the leaves of Pimenta dioica (Merr.) L. (Myrtaceae) on the basis of their chemical and physicochemical analysis (UV, HRESI-MS, 1D and 2D NMR). It was found that 9 is the most cytotoxic compound against solid tumour cancer cells, the most potent scavenger against the artificial radical DPPH and physiological radicals including ROO*, OH*, and O2-*, and strongly inhibited the NO generation and induced the proliferation of T-lymphocytes and macrophages. On the other hand, 3 was the strongest NO inhibitor and 16 the highest stimulator for the proliferation of T-lymphocytes, while 10 was the most active inducer of macrophage proliferation.
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Abd Aziz, Maheran; Stanslas, Johnson; Abdul Kadir, Mihdzar
2013-01-01
The present paper focused on antioxidant and cytotoxicity assessment of crude and total saponin fraction of Chlorophytum borivilianum as an important medicinal plant. In this study, three different antioxidant activities (2,2-diphenyl-1-picrylhydrazyl radical scavenging (DPPH), ferrous ion chelating (FIC), and β-carotene bleaching (BCB) activity) of crude extract and total saponin fraction of C. borivilianum tubers were performed. Crude extract was found to possess higher free radical scavenging activity (ascorbic acid equivalents 2578 ± 111 mg AA/100 g) and bleaching activity (IC50 = 0.7 mg mL−1), while total saponin fraction displayed higher ferrous ion chelating (EC50 = 1 mg mL−1). Cytotoxicity evaluation of crude extract and total saponin fraction against MCF-7, PC3, and HCT-116 cancer cell lines using 3-(4,5-dimethylthiazol-2-yl)-2,5 diphenyltetrazolium bromide (MTT) cell viability assay indicated a higher cytotoxicity activity of the crude extract than the total saponin fraction on all cell lines, being most effective and selective on MCF-7 human breast cancer cell line. PMID:24223502
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Sugahara, Shintaro; Ueda, Yuto; Fukuhara, Kumiko; Kamamuta, Yuki; Matsuda, Yasushi; Murata, Tatsuro; Kuroda, Yasuhiro; Kabata, Kiyotaka; Ono, Masateru; Igoshi, Keiji; Yasuda, Shin
2015-11-01
Yacon (Smallanthus sonchifolius), a native Andean plant, has been cultivated as a crop and locally used as a traditional folk medicine for the people suffering from diabetes and digestive/renal disorders. However, the medicinal properties of this plant and its processed foods have not been completely established. This study investigates the potent antioxidative effects of herbal tea leaves from yacon in different free radical models and a ferric reducing model. A hot-water extract exhibited the highest yield of total polyphenol and scavenging effect on 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical among four extracts prepared with hot water, methanol, ethanol, and ethylacetate. In addition, a higher reducing power of the hot-water extract was similarly demonstrated among these extracts. Varying concentrations of the hot-water extract resulted in different scavenging activities in four synthetic free radical models: DPPH radical (EC50 28.1 μg/mL), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) cation radical (EC50 23.7 μg/mL), galvinoxyl radical (EC50 3.06 μg/mL), and chlorpromazine cation radical (EC50 475 μg/mL). The yacon tea-leaf extract further demonstrated superoxide anion (O2(-)) radical scavenging effects in the phenazine methosulfate-NADH-nitroblue tetrazolium (EC50 64.5 μg/mL) and xanthine oxidase assay systems (EC50 20.7 μg/mL). Subsequently, incubating human neutrophilic cells in the presence of the tea-leaf extract could suppress the cellular O2(-) radical generation (IC50 65.7 μg/mL) in a phorbol 12-myristate 13-acetate-activated cell model. These results support yacon tea leaves may be a good source of natural antioxidants for preventing O2(-) radical-mediated disorders. Yacon has been considered to be a potent alternative food source for patients who require a dietary cure in regional area, while the leaf part has been provided and consumed as an herbal tea in local markets. We demonstrated here potent antioxidative effects of the tea leaves from yacon in different free radical assays, reducing power assay, and cellular superoxide anion radical generation assay. Results support yacon tea leaves may be a good source of natural antioxidants for preventing O2(-) radical-mediated disorders. © 2015 Institute of Food Technologists®
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NASA Technical Reports Server (NTRS)
Salawitch, R. J.; Wofsy, S. C.; Wennberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.;
1994-01-01
In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for [OH] and [HO2] are reduced if we allow for higher yields of O(sup 1)D) from 03 photolysis and for heterogeneous production of HNO2. The data suggest more efficient catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [O3] in the lower stratosphere may be larger in response to inputs of NO(sub y) from supersonic aircraft than estimated by current assessment models.
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NASA Astrophysics Data System (ADS)
Rousseau, Denis
2012-02-01
The reaction of hydrogen peroxide (H2O2) with oxidized bovine cytochrome c oxidase (bCcO) was studied by electron paramagnetic resonance (EPR) to determine the properties of radical intermediates. Two distinct radicals with widths of 12 and 46 G are directly observed by X-band CW-EPR in the reaction of bCcO with H2O2 at pH 6 and pH 8. High-frequency EPR (D-band) provides assignments to tyrosine for both radicals based on well-resolved g-tensors. The 46 G wide radical has extensive hyperfine structure and can be fit with parameters consistent with Y129. However, the 12 G wide radical has minimal hyperfine structure and can be fit using parameters unique to the post-translationally modified Y244 in CcO. The results are supported by mixed quantum mechanics and molecular mechanics calculations. This study reports spectroscopic evidence of a radical formed on the modified tyrosine in CcO and resolves the much debated controversy of whether the wide radical seen at low pH in the bovine system is a tyrosine or tryptophan. A model is presented showing how radical formation and migration may play an essential role in proton translocation. This work was done in collaboration with Michelle A. Yu, Tsuyoshi Egawa, Syun-Ru Yeh and Gary J. Gerfen from Albert Einstein College of Medicine; Kyoko Shinzawa-Itoh and Shinya Yoshikawa from the University of Hyogo; and Victor Guallar from the Barcelona Supercomputing Center.
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Effects of Kombucha on oxidative stress induced nephrotoxicity in rats
2009-01-01
Background Trichloroethylene (TCE) may induce oxidative stress which generates free radicals and alters antioxidants or oxygen-free radical scavenging enzymes. Methods Twenty male albino rats were divided into four groups: (1) the control group treated with vehicle, (2) Kombucha (KT)-treated group, (3) TCE-treated group and (4) KT/TCE-treated group. Kidney lipid peroxidation, glutathione content, nitric oxide (NO) and total blood free radical concentrations were evaluated. Serum urea, creatinine level, gamma-glutamyl transferase (GGT) and lactate dehydrogenase (LDH) activities were also measured. Results TCE administration increased the malondiahyde (MDA) and NO contents in kidney, urea and creatinine concentrations in serum, total free radical level in blood and GGT and LDH activities in serum, whereas it decreased the glutathione (GSH) level in kidney homogenate. KT administration significantly improved lipid peroxidation and oxidative stress induced by TCE. Conclusion The present study indicates that Kombucha may repair damage caused by environmental pollutants such as TCE and may be beneficial to patient suffering from renal impairment. PMID:19943946
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Effects of Kombucha on oxidative stress induced nephrotoxicity in rats.
Gharib, Ola Ali
2009-11-27
Trichloroethylene (TCE) may induce oxidative stress which generates free radicals and alters antioxidants or oxygen-free radical scavenging enzymes. Twenty male albino rats were divided into four groups: (1) the control group treated with vehicle, (2) Kombucha (KT)-treated group, (3) TCE-treated group and (4) KT/TCE-treated group. Kidney lipid peroxidation, glutathione content, nitric oxide (NO) and total blood free radical concentrations were evaluated. Serum urea, creatinine level, gamma-glutamyl transferase (GGT) and lactate dehydrogenase (LDH) activities were also measured. TCE administration increased the malondiahyde (MDA) and NO contents in kidney, urea and creatinine concentrations in serum, total free radical level in blood and GGT and LDH activities in serum, whereas it decreased the glutathione (GSH) level in kidney homogenate. KT administration significantly improved lipid peroxidation and oxidative stress induced by TCE. The present study indicates that Kombucha may repair damage caused by environmental pollutants such as TCE and may be beneficial to patient suffering from renal impairment.
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Relative stability of radicals derived from artemisinin: A semiempirical and DFT study
NASA Astrophysics Data System (ADS)
Arantes, C.; de Araujo, M. T.; Taranto, A. G.; de M. Carneiro, J. W.
The semiempirical AM1 and PM3 methods, as well as the density functional (DFT/B3LYP) approach using the 6-31g(d) basis set, were employed to calculate the relative stability of intermediate radicals derived from artemisinin, a sesquiterpene lactone having an endoperoxide bridge that is essential for its antimalarial activity. The compounds studied have their nonperoxidic oxygen atom of the trioxane ring and/or the carbonyl group replaced by a CH2 unit. Relative stabilities were calculated by means of isodesmic equations using artemisinin as reference. It was found that replacement of oxygen atoms decreases the relative stability of the anionic radical intermediates. In contrast, for compounds with inverted stereochemistry the intermediate radicals were found to be more stable than those with the artemisinin-like stereochemistry. These relative stabilities may modulate the antimalarial potency. Radicals centered on carbon are always more stable than the corresponding radicals centered on oxygen.
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Luo, Qiu-Lian; Tang, Zhuan-Hui; Zhang, Xue-Feng; Zhong, Yong-Hong; Yao, Su-Zhi; Wang, Li-Sheng; Lin, Cui-Wu; Luo, Xuan
2016-08-01
In this report, a water-soluble polysaccharide was obtained from the dried stems of Dendrobium officinale Kimura et Migo by hot-water (70-75°C) extraction and 85% ethanol precipitation, and successively purification by DEAE-cellulose anion-exchange chromatography and gel-permeation chromatography. The D. officinale polysaccharide (DOP) has a molecular weight of 8500Da. Monosaccharide composition analysis reveals that DOP is composed of mannose, glucose, and arabinose with a trace of galacturonic acid in a molar ratio of 6.2:2.3:2.1:0.1. Periodate oxidation-smith degradation and 1D and 2D NMR spectroscopy analysis suggest the predominance of mannose and glucose, and it contains a 2-O-acetylglucomannan and (1→4)-linked-β-d-mannopyranosyl and (1→4)-linked-β-d-glucopyranosyl residues. Atomic force microscope shows that DOP mainly exists as rod-shaped chains, supporting high degrees of polymerization. The antioxidant activities of the polysaccharide in vitro assay indicate that DOP has good scavenging activity of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, higher scavenging activity of hydroxyl radical, and metal chelating activities. Copyright © 2016 Elsevier B.V. All rights reserved.
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Kayano, Shin-ichi; Kikuzaki, Hiroe; Ikami, Takao; Suzuki, Tomoo; Mitani, Takahiko; Nakatani, Nobuji
2004-04-01
Isolation and structural elucidation of prune constituents were performed and total 10 compounds were determined by NMR and MS analyses. A novel compound was identified to be 2-(5-hydroxymethyl-2',5'-dioxo-2',3',4',5'-tetrahydro-1'H-1,3'-bipyrrole)carbaldehyde, and 7 phenolic compounds were isolated from prunes for the first time. In addition, antioxidant activity of them was evaluated on the basis of the oxygen radical absorbance capacity (ORAC).
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Wasila, Humaira; Li, Xuan; Liu, Linwei; Ahmad, Imran; Ahmad, Sajjad
2013-08-01
Pomegranate peel was used in juicing to find out its effects on the juice products' (storable juice and wine) sensory property, polyphenols composition, and antioxidant ability. Macroporous resin was used to purify the polyphenols, and 6 different in vitro assays were used to comprehensively determine the antioxidant activity of each. The results showed that juicing with peel made the juice bitter and astringent, but contributed better sensory quality to wine. Peel contributed higher total polyphenols and flavonoids, but lower anthocyanins to the juice products, and caused the phenolics content to fluctuate more dramatically during making wine than the storable juice. Polyphenols purified from the juice products containing peel showed higher total reducing ability and 2,2-diphenyl-1-picrylhydrazyl and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid radical elimination abilities, but their clearance activity of hydroxyl radicals was not positive, and their superoxide anion radical elimination ability showed no significant difference when compared to polyphenols purified from juice products without peel. © 2013 Institute of Food Technologists®
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Anti-inflammatory Hydrolyzable Tannins from Myricaria bracteata.
Liu, Jia-Bao; Ding, Ya-Si; Zhang, Ying; Chen, Jia-Bao; Cui, Bao-Song; Bai, Jin-Ye; Lin, Ming-Bao; Hou, Qi; Zhang, Pei-Cheng; Li, Shuai
2015-05-22
Twelve hydrolyzable tannins were obtained from the twigs of Myricaria bracteata, including two new hellinoyl-type dimers, bracteatinins D1 (1) and D2 (2); a new hellinoyl-type trimer, bracteatinin T1 (3); two known monomers, nilotinin M4 (4) and 1,3-di-O-galloyl-4,6-O-(aS)-hexahydroxydiphenoyl-β-d-glucose (5); six known dimers, tamarixinin A (6), nilotinin D8 (7), hirtellins A (10), B (9), and E (8), and isohirtellin C (11); and a known trimer, hirtellin T3 (12). The structures of the tannins were elucidated by spectroscopic data analysis and comparisons to known tannins. All compounds were evaluated as free radical scavengers using 1,1-diphenyl-2-picrylhydrazyl and hydroxy radicals and compared to the activity of BHT and Trolox. Compound 6 showed a significant anti-inflammatory effect on croton oil-induced ear edema in mice (200 mg/kg, inhibition rate 69.8%) and on collagen-induced arthritis in DBA/1 mice (20 mg/kg, inhibition rate 46.0% at day 57).
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Joshi, Khem Raj; Devkota, Hari Prasad; Watanabe, Takashi; Yahara, Shoji
2014-01-01
Eleven phenolic compounds, quercetin (1), quercetin 3-O-β-d-galactopyranoside (2), quercetin 3-O-(6″-O-galloyl)-β-d-galactopyranoside (3), quercetin 3-O-(6″-O-caffeoyl)-β-d-galactopyranoside (4), quercetin 3-O-β-d-glucopyranoside (5), rutin (6) quercetin 3-O-α-l-arabinopyranoside (7), quercetin 3-O-α-l-arabinofuranoside (8), protocatechulic acid (9), gallic acid (10) and chlorogenic acid (11), were isolated from the flowers of Aconogonon molle, a Nepalese medicinal plant. Structures of these compounds were elucidated on the basis of spectroscopic methods. All these compounds were isolated for the first time from flowers, and five compounds (4, 5, 8, 9 and 11) were isolated for the first time from A. molle. All of these isolated compounds were evaluated for their in vitro antioxidant activity by using the 1,1-diphenyl-2-picrylhydrazyl radical-scavenging method. Quercetin (1), quercetin glycosides (2-8) and gallic acid (10) exhibited potent antioxidant activity.
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NASA Technical Reports Server (NTRS)
Richardson, D.
1975-01-01
The inhibitory effects are investigated of d,1-alpha-tocopherol and d,1-alpha-tocopheryl acetate on the free radical deterioration of cellular membranes. The level of toxicity of d,1-alpha-tocopherol and d,1-alpha-tocopheryl acetate in mice is determined.
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Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes
2015-01-01
We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C–H bonds over tertiary C–H bonds and even occur at primary C–H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 °C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO)2 at 100 °C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C–H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C–H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product. PMID:24405209
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Staluszka, Justyna; Steblecka, Malgorzata; Szajdzinska-Pietek, Ewa; Kohl, Ingrid; Salzmann, Christoph G; Hallbrucker, Andreas; Mayer, Erwin
2008-09-18
Hyperquenched glassy water (HGW) has been suggested as the best model for liquid water, to be used in low-temperature studies of indirect radiation effects on dissolved biomolecules (Bednarek et al. J. Am. Chem. Soc. 1996, 118, 9387). In the present work, these effects are examined by X-band electron spin resonance spectroscopy (ESR) in gamma-irradiated HGW matrix containing 2'-deoxyguanosine-5'-monophosphate. Analysis of the complex ESR spectra indicates that, in addition to OH(*) and HO2(*) radicals generated by water radiolysis, three species are trapped at 77 K:(i) G(C8)H(*) radical, the H-adduct to the double bond at C8; (ii) G(- *) radical anion, the product of electron scavenging by the aromatic ring of the base; and (iii) dR(-H)(*) radicals formed by H abstraction from the sugar moiety, predominantly at the C'5 position. We discuss the yields of the radicals, their thermal stability and transformations, as well as the effect of photobleaching. This study confirms our earlier suggestion that in HGW the H atom addition/abstraction products are created at 77 K in competition with HO2(*) radicals, in a concerted process following ionization of water molecule at L-type defect sites of the H-bonded matrix. The lack of OH(*) reactivity toward the solute suggests that the H-bonded structure in HGW is much more effective in recombining OH(*) radicals than that of aqueous glasses obtained from highly concentrated electrolyte solutions. Furthermore, complementary experiments for the neat matrix have provided evidence that HO2(*) radicals are not the product of H atom reaction with molecular oxygen, possibly generated by ultrasounds used in the process of sample preparation.
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Zhou, Yiying; Nelson, William H
2011-10-27
With K-band EPR (Electron Paramagnetic Resonance), ENDOR (Electron-Nuclear DOuble Resonance), and EIE (ENDOR-induced EPR) techniques, three free radicals (RI-RIII) in L-lysine hydrochloride dihydrate single crystals X-irradiated at 298 K were detected at 298 K, and six radicals (R1, R1', R2-R5) were detected if the temperature was lowered to 66 K from 298 K. R1 and RI dominated the central portion of the EPR at 66 and 298 K, respectively, and were identified as main chain deamination radicals, (-)OOCĊH(CH(2))(4)(NH(3))(+). R1' was identified as a main chain deamination radical with the different configuration from R1 at 66 K, and it probably formed during cooling the temperature from 298 to 66 K. The configurations of R1, R1', and RI were analyzed with their coupling tensors. R2 and R3 each contain one α- and four β-proton couplings and have very similar EIEs at three crystallographic axes. The two-layer ONIOM calculations (at B3LYP/6-31G(d,p):PM3) support that R2 and R3 are from different radicals: dehydrogenation at C4, (-)OOCCH(NH(3))(+)CH(2)ĊH(CH(2))(2)(NH(3))(+), and dehydrogenation at C5, (-)OOCCH(NH(3))(+)(CH(2))(2)ĊHCH(2)(NH(3))(+), respectively. The comparisons of the coupling tensors indicated that R2 (66 K) is the same radical as RII (298 K), and R3 is the same as RIII. Thus, RII and RIII also are the radicals of C4 and C5 dehydrogenation. R4 and R5 are minority radicals and were observed only when temperature was lowered to 66 K. R4 and R5 were only tentatively assigned as the side chain deamination radical, (-)OOCCH (NH(3))(+)(CH(2))(3)ĊH(2), and the radical dehydrogenation at C3, (-)OOCCH(NH(3))(+)ĊH(CH(2))(3)(NH(3))(+), respectively, although the evidence was indirect. From simulation of the EPR (B//a, 66 K), the concentrations of R1, R1', and R2-R5 were estimated as: R1, 50%; R1', 11%; R2, 14%; R3, 16%; R4, 6%; R5, 3%.
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Electron spin resonance detection of oxygen radicals released by UVA-irradiated human fibroblasts
NASA Astrophysics Data System (ADS)
Souchard, J. P.; Pierlot, G.; Barbacanne, M. A.; Charveron, M.; Bonafé, J.-L.; Nepveu, F.
1999-01-01
This work reports the electron spin resonance (ESR) detection of oxygenated radicals (OR) released by cultured human fibroblasts after UVA (365 nm) exposure. 5,5-dimethyl-pyrroline-N-oxide (DMPO) was used as spin trap. After a UVA irradiation of one hour, followed by a latent period of at least 45 min., and an incubation time of 30 min. in a trapping medium containing DMPO, glucose, Na^+, K+ and Ca2+ an ESR signal was recorded. By contrast, an ESR signal was produced after only 15 min. incubation when calcium ionophore A23187 was used. Although the ESR signal was characteristic of the hydroxyl adduct DMPO-OH, the use of catalase and superoxide dismutase (SOD) revealed that UVA stimulated fibroblasts released the superoxide anion O2- in the medium. SOD, vitamin C and (+)-catechin inhibited the release of superoxide generated by human fibroblasts stimulated with A23187 calcium ionophore at 5 units/ml, 10-5 M and 2× 10-4 M, respectively. Dans ce travail nous présentons la détection par résonance de spin électronique (RSE) de radicaux oxygénés (RO) libérés par des fibroblastes humains en culture après irradiation aux UVA (365 nm). Le 5,5-diméthyl-1-pyrroline-N-oxyde (DMPO) a été utilisé comme piégeur de spin. Après une irradiation aux UVA d'une heure, suivie d'une période de latence d'au moins 45 min. et d'une incubation de 30 min. dans un milieu de piégeage composé de DMPO, glucose, Na^+, K+ et Ca2+, un signal RPE est enregistré. L'ionophore calcique A23187 entraîne l'apparition d'un signal RPE après seulement 15 min. d'incubation. Bien que le signal RPE obtenu corresponde à l'adduit DMPO-OH du radical hydroxyle, l'utilisation de catalase et de superoxyde dismutase (SOD) a révélé que les fibroblastes libéraient l'anion superoxyde dans le milieu de culture. Sur ce modèle cellulaire la SOD, la vitamine C et la (+) catéchine inhibent la production du radical superoxyde aux concentrations respectivement de 5 unités/ml, 10-5 M et 2× 10-4M.
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NASA Astrophysics Data System (ADS)
Urban, Rolf-Dieter; Jones, Harold
1991-03-01
The infrared spectrum of the manganese deuteride radical has been observed in its ground electronic state ( 7Σ) using a diode-laser spectrometer. The hyperfine structure of a number of infrared transitions in the bands ν=1←0, ν=2←1 and ν=3←2 were measured with a nominal accuracy of ±0.001 cm -1. In all cases, the complete structure was easily resolved. Dunham parameters, spin—rotation and spin—spin coupling parameters were determined from the MnD data. A simultaneous fit of these data with those determined previously for MnH was carried out to determine mass-independent parameters and mass-scaling coefficients.
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Bergenin Content and Free Radical Scavenging Activity of Bergenia Extracts. .
Hendrychová, Helena; Martin, Jan; Tůmová, Lenka; Kočevar-Glavač, Nina
2015-07-01
Our research was focused on the evaluation of bergenin content and free radical scavenging activity of extracts prepared from three different species of Bergenia - B. crassifolia (L.) Fritsch., B. ciliata (Haw.) Sternb. and B. x ornata Stein. collected during different seasons. Using an HPLC method, the highest total amount of bergenin was revealed in the leaves of B. x ornata and B. crassifolia (4.9 - 5.1 mg x g(-1)). Free radical scavenging power was determined by two methods--FRAP and NADH. The best free radical scavengers were B. crassifolia (FRAP: 6.7 - 15.9 mg GAE. 100g(-1); NADH: 20.3 - 50.9%) and B. ornata (FRAP: 13.7 - 15.2 mg GAE. 100g(-1); NADH: 29.3 - 31.1%). The lowest content of bergenin and the weakest radical scavenger was B. ciliata (bergenin: 3.1 mg x g(-1); FRAP: 5.5 - 11.0 mg GAE.100g(-1); NADH: 23.2 - 25.6%). The presence of a large percentage of bergenin is responsible for the radical scavenging activity, as shown by the results from the FRAP and NADH assays. Significant, positive correlation was found between bergenin content and radical scavenging activity in both methods.
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Differential cytochrome P450 2D metabolism alters tafenoquine pharmacokinetics.
Vuong, Chau; Xie, Lisa H; Potter, Brittney M J; Zhang, Jing; Zhang, Ping; Duan, Dehui; Nolan, Christina K; Sciotti, Richard J; Zottig, Victor E; Nanayakkara, N P Dhammika; Tekwani, Babu L; Walker, Larry A; Smith, Philip L; Paris, Robert M; Read, Lisa T; Li, Qigui; Pybus, Brandon S; Sousa, Jason C; Reichard, Gregory A; Smith, Bryan; Marcsisin, Sean R
2015-07-01
Cytochrome P450 (CYP) 2D metabolism is required for the liver-stage antimalarial efficacy of the 8-aminoquinoline molecule tafenoquine in mice. This could be problematic for Plasmodium vivax radical cure, as the human CYP 2D ortholog (2D6) is highly polymorphic. Diminished CYP 2D6 enzyme activity, as in the poor-metabolizer phenotype, could compromise radical curative efficacy in humans. Despite the importance of CYP 2D metabolism for tafenoquine liver-stage efficacy, the exact role that CYP 2D metabolism plays in the metabolism and pharmacokinetics of tafenoquine and other 8-aminoquinoline molecules has not been extensively studied. In this study, a series of tafenoquine pharmacokinetic experiments were conducted in mice with different CYP 2D metabolism statuses, including wild-type (WT) (reflecting extensive metabolizers for CYP 2D6 substrates) and CYPmouse 2D knockout (KO) (reflecting poor metabolizers for CYP 2D6 substrates) mice. Plasma and liver pharmacokinetic profiles from a single 20-mg/kg of body weight dose of tafenoquine differed between the strains; however, the differences were less striking than previous results obtained for primaquine in the same model. Additionally, the presence of a 5,6-ortho-quinone tafenoquine metabolite was examined in both mouse strains. The 5,6-ortho-quinone species of tafenoquine was observed, and concentrations of the metabolite were highest in the WT extensive-metabolizer phenotype. Altogether, this study indicates that CYP 2D metabolism in mice affects tafenoquine pharmacokinetics and could have implications for human tafenoquine pharmacokinetics in polymorphic CYP 2D6 human populations. Copyright © 2015, American Society for Microbiology. All Rights Reserved.
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Spectroscopic Identification of p-CHLORO-α-METHYLBENZYL Radical in the Gas Phase
NASA Astrophysics Data System (ADS)
Lee, Seung Woon; Lee, Gi Woo; Lee, Sang Kuk
2009-06-01
We report the first spectroscopic identification of the p-fluoro-α-methylbenzyl radical in the gas phase. Precursor p-fluoro-ethylbenzene seeded in a large amount of inert carrier gas helium was electrically discharged to produce the benzyl-type radicals in a corona excited supersonic expansion using a pinhole-type glass nozzle, from which the vibronic emission spectrum was recorded in the visible region using a long path monochromator. From an analysis of the spectrum observed, we found the formation of p-fluoro-α-methylbenzyl radical as well as p-fluorobenzyl radical in the jet from the precursor. After eliminating the bands belonging to p-fluorobenzyl radical using the known data, we identified spectroscopically the formation of the p-fluoro-α-methylbenzyl radical, in which the energy of the D_1 → D_0 electronic transition and a few vibrational mode frequencies in the ground electronic state were determined by comparison with those from an ab initio calculation and with those from the known data of the precursor. S. K. Lee and D. Y. Baek Chem. Phys. Lett. 301(3-4), 407-412 (1999).
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Cheng, Ni; Wang, Yuan; Gao, Hui; Yuan, Jialing; Feng, Fan; Cao, Wei; Zheng, Jianbin
2013-09-01
The protective effect of extract of Crataegus pinnatifida (Rosaceae) pollen (ECPP) on the DNA damage response to oxidative stress was investigated and assessed with an alkaline single-cell gel electrophoresis (SCGE) assay and pBR322 plasmid DNA breaks in site-specific and non-site-specific systems. Total phenolic content, total flavonoid content, individual phenolic compounds, antioxidant activities (1,1-diphenyl-2-picrylhydrazyl (DPPH), radical scavenging activity, FRAP, and chelating activity) were also determined. The results showed that ECPP possessed a strong ability to protect DNA from being damaged by hydroxyl radicals in both the site-specific system and the non-site-specific system. It also exhibited a cytoprotection effect in mouse lymphocytes against H₂O₂-induced DNA damage. These protective effects may be related to its high total phenolic content (17.65±0.97 mg GAE/g), total flavonoid content (8.04±0.97 mg rutin/g), strong free radical scavenging activity and considerable ferrous ion chelating ability (14.48±0.21 mg Na₂EDTA/g). Copyright © 2013 Elsevier Ltd. All rights reserved.
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Alaşalvar, Can; Soylu, Mustafa Serkan; Güder, Aytaç; Albayrak, Çiğdem; Apaydın, Gökhan; Dilek, Nefise
2014-05-05
In this study, (E)-4,6-dibromo-3-methoxy-2-[(3-methoxyphenylimino)methyl]phenol has been synthesized and characterized by using X-ray technique and FT-IR experimentally and using B3LYP/6-31G(d,p) and HF/6-31G(d,p) methods theoretically. The intermolecular and intramolecular interactions of the title compound have been determined according to X-ray results. The molecular geometry, vibrational frequencies of the title compound in the ground state have been calculated using the density functional B3LYP and HF method with the 6-31G(d,p) basis set and calculated bond parameters and vibrational frequencies values show good agreement with experimental values. Theoretical and experimental results show that tautomeric form of the structure is phenol-imine form. Besides HOMO-LUMO energy gap, molecular electrostatic potential map were performed at B3LYP/6-31G(d,p) level. It is worthy note of that, the free radical scavenging activities of the title compound were assessed using DPPH˙, DMPD˙(+), and ABTS˙(+) assays. The obtained results show that the title compound has effective DPPH˙ (SC50 2.61±0.09 μg/mL), DMPD˙(+) (SC50 2.82±0.14 μg/mL), and ABTS˙(+) (SC50 4.91±0.18 μg/mL) radical scavenging activities when compared with standard antioxidants (BHA, rutin, and trolox). Copyright © 2014 Elsevier B.V. All rights reserved.
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Cai, S J; Wu, C X; Gong, L M; Song, T; Wu, H; Zhang, L Y
2012-10-01
This study was conducted to investigate the effect of nano-selenium (nano-Se) on performance, meat quality, immune function, oxidation resistance, and tissue selenium content in broilers. A total of five hundred forty 1-d-old male Arbor Acres broilers were randomly allotted to 1 of 5 treatments with each treatment being applied to 6 replicates of 18 chicks. The 5 treatments consisted of corn-soybean meal-based diets supplemented with 0.0, 0.3, 0.5, 1.0, or 2.0 mg/kg of nano-Se. The selenium content of the unsupplemented control diet was 0.09 mg/kg for the starter phase (0 to 21 d) and 0.08 mg/kg for the grower phase (22 to 42 d). There were no significant differences (P > 0.05) in performance, meat color, or immune organ index (thymus, bursa, and spleen) due to supplementation with nano-Se. On d 42, a significant quadratic effect of nano-Se was observed on glutathione peroxidase activity, free radical inhibition, contents of IgM, glutathione, and malondialdehyde in serum, on glutathione peroxidase activity, free radical inhibition in liver, and on glutathione peroxidase activity in muscle, with birds fed 0.30 mg/kg of nano-Se exhibiting the best effect and birds fed 2.0 mg/kg of nano-Se showing the worst effect on these parameters. Liver and muscle selenium content increased linearly and quadratically as the dietary nano-Se level increased (P < 0.01), and reached the highest value when 2.0 mg/kg of nano-Se was fed. Based on a consideration of all experiment indexes, 0.3 to 0.5 mg/kg is suggested to be the optimum level of supplementation of nano-Se, and the maximum supplementation of nano-Se could not be more than 1.0 mg/kg in broilers.
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NASA Technical Reports Server (NTRS)
Bosco, S. R.
1982-01-01
The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.
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Jaafarzadeh, Nematollah; Ghanbari, Farshid; Ahmadi, Mehdi
2017-02-01
2,4-Dichlorophenoxyacetic acid (2,4-D) is one of the most applicable herbicides in the world. Therefore, its residue in aquatic environment threatens the human health and ecosystems. In this study, Fe 2 O 3 (hematite) nanoparticles (HNPs) were synthesized, and the characteristics of the obtained HNPs were determined using X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) technique, and particle size analyzer (PSA). The catalytic activity of HNPs was evaluated for the activation of peroxymonosulfate (PMS) for the degradation of 2,4-D. The effects of the operating parameters were studied for the PMS/HNPs system. The results showed that the acidic condition provided higher efficiency, while overdosing of PMS had a scavenging effect. The PMS/HNPs showed high efficiency in comparison with the homogeneous forms of iron (Fe 2+ and Fe 3+ ). Reusability of HNPs was studied in five consequent usages. The presence of the anions (chloride, nitrate, and hydrogen phosphate) reduced the 2,4-D degradation. Moreover, the catalytic activity of HNPs was also investigated in the presence of other oxidants. UV irradiation increased the function of PMS/HNPs and its mechanism was described. The order of 2,4-D removal for the oxidants was PMS > persulfate > H 2 O 2 > percarbonate. A total of 29.7% of 2,4-D chlorine content was released during the destruction of 2,4-D. The quenching study showed that sulfate radical was the major agent in the degradation of 2,4-D. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Lung biodurability and free radical production of cellulose nanomaterials
Stefaniak, Aleksandr B.; Seehra, Mohindar S.; Fix, Natalie R.; Leonard, Stephen S.
2015-01-01
The potential applications of cellulose nanomaterials in advanced composites and biomedicine makes it imperative to understand their pulmonary exposure to human health. Here, we report the results on the biodurability of three cellulose nanocrystal (CNC), two cellulose nanofibril (CNF) and a benchmark cellulose microcrystal (CMC) when exposed to artificial lung airway lining fluid (SUF, pH 7.3) for up to 7 days and alveolar macrophage phagolysosomal fluid (PSF, pH 4.5) for up to 9 months. X-ray diffraction analysis was used to monitor biodurability and thermogravimetry, surface area, hydrodynamic diameter, zeta potential and free radical generation capacity of the samples were determined (in vitro cell-free and RAW 264.7 cell line models). The CMC showed no measurable changes in crystallinity (xCR) or crystallite size D in either SUF or PSF. For one CNC, a slight decrease in xCR and D in SUF was observed. In acidic PSF, a slight increase in xCR with exposure time was observed, possibly due to dissolution of the amorphous component. In a cell-free reaction with H2O2, radicals were observed; the CNCs and a CNF generated significantly more ●OH radicals than the CMC (p<0.05). The ●OH radical production correlates with particle decomposition temperature and is explained by the higher surface area to volume ratio of the CNCs. Based on their biodurability, mechanical clearance would be the primary mechanism for lung clearance of cellulose materials. The production of ●OH radicals indicates the need for additional studies to characterize the potential inhalation hazards of cellulose. PMID:25265049
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Kyriakopoulou, I; Magiatis, P; Skaltsounis, A L; Aligiannis, N; Harvala, C
2001-08-01
A new phenylethanoid glycoside, samioside, was isolated from the aerial parts of Phlomis samia and identified as 1-O-3,4-(dihydroxyphenyl)ethyl beta-D-apiofuranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->3)-4-O-caffeoyl-beta-D-glucopyranoside (1). In addition, one known phenylethanoid glycoside and three known flavonoids were identified as acteoside (2), apigenin, chrysoeriol, and ermanin, respectively. The structure of 1 was elucidated on the basis of its spectroscopic data. Samioside (1) demonstrated scavenging properties toward the DPPH radical and antimicrobial activity against Gram-positive and -negative bacteria.
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Aliyu, Abubakar B; Ibrahim, Mohammed A; Musa, Aliyu M; Musa, Aisha O; Kiplimo, Joyce J; Oyewale, Adebayo O
2013-01-01
Antioxidants activities from plants sources have attracted a wide range of interest across the world in recent times. This is due to growing concern for safe and alternative sources of antioxidants. The free radical scavenging activity using 1,1-diphenyl-2-picrylhydrazyl radical (DPPH), reducing power assay, total antioxidant capacity of the phosphomolybdenum method and the total phenolics content using the Folin-Ciocalteu reagent were carried out on the acetone, n-butanol and methanol root extracts of Anchomanes difformis. The results of the total phenolics content expressed in mg/100 g of gallic acid equivalent (GAE) showed that the n-butanol extract has significantly (p < 0.05) higher phenolics content (381 +/- 1.13) than the methanol and acetone extracts. All the extracts displayed strong concentration dependent radical scavenging activity. It was also observed that the n-butanol extract showed higher activity of 70.87% and 78.59% at low concentrations of 31.25 microg/mL and 62.5 microg/mL, respectively, than methanol and acetone extracts. The results also showed that the n-butanol extract has strongest reducing ability which is comparable to that of gallic acid at all the concentrations tested. Phytochemical screening on the extracts revealed the presence of flavonoids, saponins, and tannins. The results suggest that n-butanol extract of the plant is very rich in antioxidant compounds worthy of further investigations.
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Boosting effect of ortho-propenyl substituent on the antioxidant activity of natural phenols.
Marteau, Clémentine; Guitard, Romain; Penverne, Christophe; Favier, Dominique; Nardello-Rataj, Véronique; Aubry, Jean-Marie
2016-04-01
Seven new antioxidants derived from natural or synthetic phenols have been designed as alternatives to BHT and BHA antioxidants. Influence of various substituents at the ortho, meta and para positions of the aromatic core of phenols on the bond dissociation enthalpy of the ArO-H bond was evaluated using a DFT method B3LYP/6-311++G(2d,2p)//B3LYP/6-311G(d,p). This prediction highlighted the ortho-propenyl group as the best substituent to decrease the bond dissociation enthalpy (BDE) value. The rate constants of hydrogen transfer from these phenols to DPPH radical in a non-polar and non-protic solvent have been measured and were found to be in agreement with the BDE calculations. For o-propenyl derivatives from 2-tert-butyl-4-methylphenol, BHA, creosol, isoeugenol and di-o-propenyl p-cresol, fewer radicals were trapped by a single phenol molecule, i.e. a lower stoichiometric number. Reaction mechanisms involving the evolution of the primary phenoxyl radical ArO are proposed to rationalise these effects. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Shabbir, Maria; Khan, Muhammad Rashid; Saeed, Naima
2013-06-22
Maytenus royleanus is traditionally used in gastro-intestinal disorders. The aim of this study was to evaluate the methanol extract of leaves and its derived fractions for various antioxidant assays and for its potential against lipid peroxidation and hemolytic activity. Various parameters including scavenging of free-radicals (DPPH, ABTS, hydroxyl and superoxide radical), hydrogen peroxide scavenging, Fe3+ to Fe2+ reducing capacity, total antioxidant capacity, anti-lipid peroxidation and anti-hemolytic activity were investigated. Methanol extract and its derived fractions were also subjected for chemical constituents. LC-MS was also performed on the methanol extract. Qualitative analysis of methanol extract exhibited the presence of alkaloids, anthraquinones, cardiac glycosides, coumarins, flavonoids, saponins, phlobatannins, tannins and terpenoids. LC-MS chromatogram indicated the composition of diverse compounds including flavonoids, phenolics and phytoestrogens. Methanol extract, its ethyl acetate and n-butanol fractions constituted the highest amount of total phenolic and flavonoid contents and showed a strong correlation coefficient with the IC50 values for the scavenging of DPPH, hydrogen peroxide radicals, superoxide radicals, anti-lipid peroxidation and anti-hemolytic efficacy. Moreover, n-butanol fraction showed the highest scavenging activity for ABTS radicals and for reduction of Fe3+ to Fe2+. Present results suggested the therapeutic potential of Maytenus royleanus leaves, in particular, methanol extract, ethyl acetate and n-butanol fraction as therapeutic agent against free-radical associated damages. The protective potential of the extract and or fraction may be attributed due to the high concentration of phenolic, flavonoid, tannins and terpenoids.
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Total flavonoid content and formulation antioxidant cream stem of jatropha multifida l.
NASA Astrophysics Data System (ADS)
Dwi Franyoto, Yuvianti; Kusmita, Lia; Mutmainah; Demma Angrena, Riega
2018-05-01
Free radical induced oxidative stress that influences the occurrence of various degenerative diseases such as cancer, coronary heart disease and premature aging. Stems of Jatropha multifida L are known to contain flavanoid compounds have antioxidant activity. A study has been carried out to determine antioxidant potential of stems of Jatropha multifida L. Initially, material was macerated gradually with ethanol. The extract obtained was filtered and evaporated. Determination of total flavanoid contents (TFC) using spectrophotometric methods. The antioxidant potential of this extract was evaluated by 2, 2-diphenyl-1- picrylhydrazyl (DPPH) radical scavenging assay. In the DPPH radical-scavenging activities, the extract had the antioxidant activity (IC50 = 72 ± 0.01 μg/ml). The results showed the extracts of Jatropha multifida L. could be considered as natural antioxidants and may be useful for curing diseases arising from oxidative deterioration. The formulation comprises with 5% of extract and was formulated using fusion method. The evaluation of the formulated cream showed good results and can be good potential for cosmetic product development.
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Jang, Su-Chan; Choi, Jong-Ho
2014-11-21
The gas-phase radical-radical reaction dynamics of ground-state atomic oxygen O((3)P) with vinyl radicals C2H3 has been studied by combining the results of vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed beam configuration with ab initio calculations. The two radical reactants O((3)P) and C2H3 were produced by photolysis of NO2 and supersonic flash pyrolysis of C2H3I, respectively. Doppler profile analysis of the kinetic energy release of the nascent H-atom products from the title reaction O((3)P) + C2H3→ H((2)S) + CH2CO (ketene) revealed that the average translational energy of the products and the average fraction of the total available energy were 7.03 ± 0.30 kcal mol(-1) and 7.2%. The empirical data combined with CBS-QB3 level ab initio theory and statistical calculations demonstrated that the title oxygen-hydrogen exchange reaction is a major reaction channel, through an addition-elimination mechanism involving the formation of a short-lived, dynamical complex on the doublet potential energy surface. On the basis of systematic comparison with several exchange reactions of hydrocarbon radicals, the observed kinetic energy release can be explained in terms of the weak impulse at the moment of decomposition in the loose transition state with a product-like geometry and a small reverse barrier along the exit channel.
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NASA Astrophysics Data System (ADS)
Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Michoud, V.; Gilman, J. B.; Kuster, W. C.; Veres, P. R.; Graus, M.; de Gouw, J. A.; Roberts, J.; Young, C.; Washenfelder, R.; Brown, S. S.; Thalman, R.; Waxman, E.; Volkamer, R.; Tsai, C.; Stutz, J.; Flynn, J. H.; Grossberg, N.; Lefer, B.; Alvarez, S. L.; Rappenglueck, B.; Mielke, L. H.; Osthoff, H. D.; Stevens, P. S.
2016-04-01
Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex-LA 2010 campaign using the laser-induced fluorescence-fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero-dimensional model using the Regional Atmospheric Chemical Mechanism-2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.
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Hellwig, Petra; Yano, Takahiro; Ohnishi, Tomoko; Gennis, Robert B
2002-08-27
During turnover of cytochrome bo(3) from Escherichia coli, a semiquinone radical is stabilized in a high-affinity binding site. To identify binding partners of this radical, site-directed mutants have been designed on the basis of a recently modeled quinone binding site (Abramson et al., 2000). The R71H, H98F, D75H, and I102W mutant enzymes were found to show very little or no quinol oxidase activity. The thermodynamic and EPR spectroscopic properties of semiquinone radicals in these mutants were characterized. For the H98F and the R71H mutants, no EPR signal of the semiquinone radical was observed in the redox potential range from -100 to 250 mV. During potentiometric titration of the D75H mutant enzyme, a semiquinone signal was detected in the same potential range as that of the wild-type enzyme. However, the EPR spectrum of the D75H mutant lacks the characteristic hyperfine structure of the semiquinone radical signal observed in the wild-type oxidase, indicating that D75 or the introduced His, interacts with the semiquinone radical. For the I102W mutant, a free radical signal was observed with a redox midpoint potential downshifted by about 200 mV. On the basis of these observations, it is suggested that R71, D75, and H98 residues are involved in the stabilization of the semiquinone state in the high-affinity binding site. Details of the possible binding motif and mechanistic implications are discussed.
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Miao, Fang; Shi, Ying; Fan, Zhi-Feng; Jiang, Shan; Xu, Shi-Zheng; Lei, Tie-Chi
2016-01-01
Safe and effective ingredients capable of removing undesired hyperpigmentation from facial skin are urgently needed for both pharmaceutical and cosmetic purposes. Deoxyarbutin (4-[(tetrahydro-2H-pyran-2-yl) oxy] phenol, D-Arb) is a glucoside derivative of hydroquinone. Here, we investigated the toxicity and efficacy of D-Arb at the sub-cellular level (directly on melanosomes) and skin pigmentation using in vivo and in vitro models to compare with its parent compound hydroquinone (1,4-benzenediol, HQ). At first, we examined the ultrastructural changes of melanosomes in hyperpigmented guinea pig skin induced by 308-nm monochromatic excimer lightand/or treated with HQ and D-Arb using transmission electron microscopy. The results showed that prominent changes in the melanosomal membrane, such as bulb-like structure and even complete rupture of the outer membranes, were found in the skin after topical application of 5% HQ for 10 days. These changes were barely observed in the skin treated with D-Arb. To further clarify whether membrane toxicity of HQ was a direct result of the compound treatment, we also examinedultrastructural changes of individual melanosomes purified from MNT1 human melanoma cells. Similar observations were obtained from the naked melanosome model in vitro. Finally, we determined the effects of melanosomal fractions exposed to HQ or D-Arb on hydroxyl radical generation in the Fenton reaction utilizing an electron spin resonance assay. D-Arb-treated melanosomesexhibit a moderate hydroxyl radical-scavenging activity, whereas HQ-treated melanosomessignificantly generate more hydroxyl free radicals. This study suggests that D-Arb possesses a potent ability in skin lightening and antioxidation with less melanosome cytotoxicity.
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Bystrom, Laura M; Lewis, Betty A; Brown, Dan L; Rodriguez, Eloy; Obendorf, Ralph L
2009-06-01
Edible fruits of the native South American tree Melicoccus bijugatus Jacq. are consumed fresh or in traditional food, drink and medicinal preparations. Some therapeutic effects of these fruits may be due to phenolics and sugars. Aqueous acetone, methanol or ethanol tissue extracts of different cultivars or collections of M. bijugatus fruits from the Dominican Republic and Florida were analyzed for total phenolics and free radical scavenging activity by UV-vis spectroscopy, sugars by gas chromatography, and antimicrobial activity by the disc diffusion assay. Total phenolics and free radical scavenging activities ranked: seed coat > embryo > pulp extracts. Montgomery cultivar fruits had the highest total phenolics. For sugars: pulp > embryo and highest in Punta Cana fruit pulp. In all extracts: sucrose > glucose and fructose. Glucose:fructose ratios were 1:1 (pulp) and 0.2:1 (embryo). Pulp extracts had dose-response antibacterial activity and pulp and embryo extracts had antifungal activity against one yeast species. Phenolics and sugars were confirmed with thin-layer chromatography and nuclear magnetic resonance. Sugar-free pulp fractions containing phenolics had slightly more antimicrobial activity than H2O-soluble pulp fractions with sugars. Results indicate M. bijugatus fruits contain phenolics, sugars and other H2O-soluble compounds consistent with therapeutic uses.
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In vitro evaluation of free radical scavenging activity of Codariocalyx motorius root extract.
Chidambaram, Uma; Pachamuthu, Vanitha; Natarajan, Suganya; Elango, Bhakkiyalakshmi; Suriyanarayanan; Ramkumar, Kunga Mohan
2013-03-01
To determine the phenolic content in Codariocalyx motorius root extract and to evaluate its antioxidant properties using various in vitro assay systems. The antioxidant activity was evaluated based on scavenging of 1,1-diphenyl-2-picrylhydrazyl, hydroxyl radicals, superoxide anions, nitric oxide, hydrogen peroxide, peroxynitrite, reducing power and by inhibition of lipid peroxidation which was estimated in terms of thiobarbituric acid reactive substances. The root extract of the Codariocalyx motorius (C. motorius) exhibited potent total antioxidant activity that increased with increasing amount of extract concentration, which was compared with standard drug such as quercetin, butylated hydroxytoluene, tocopherol at different concentrations. The different concentrations of the extracts showed inhibition on lipid peroxidation. In addition, the extracts had effective reducing power, free radical scavenging, super oxide anion scavenging, nitric oxide scavenging, lipid peroxidation, and total phenolic content depending on concentration. High correlation between total phenolic contents and scavenging potential of different reactive oxygen species (r(2)=0.831-0.978) indicated the polyphenols as the main antioxidants. Codariocalyx motorius (C. motorius) root possess the highly active antioxidant substance which can be used for the treatment of oxidative stress-related diseases. Copyright © 2013 Hainan Medical College. Published by Elsevier B.V. All rights reserved.
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Free Radical Scavenging Properties of Annona squamosa
Vikas, Biba; Akhil B, S; P, Remani; Sujathan, K
2017-10-26
Annona squamosa has extensively been used in the traditional and folkloric medicine and found to possess many biological activities. Different solvents, petroleum ether, chloroform, ethyl acetate and methanol extracts of Annona squamosa seeds (ASPE, ASCH, ASEA, ASME) have been used to prepare plant extracts. The present investigations dealt with the free radical scavenging activity of four extracts using various techniques such as total reducing power estimation, total phenolic count, 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging effect, evaluation of ABTS cation decolorisation capacity, FRAP assay, hdroxyl radical scavenging assay, super oxide assay and Nitric oxide radical scavenging assay of the extracts. The results showed that the four extracts of Annona squamosa showed significant reducing power in four extracts. The total phenolic contents in petroleum ether, chloroform, ethyl acetate, methanol extracts and positive control were 0.64±0.17, 0.54±0.27, 0.49±0.24, 0.57±0.22 and 0.66±0.33. The antioxidant capacity by ABTS assay of ASPE, ASCH, ASEA, ASME and positive control, trolox showed 77.75±0.5,73.25±1.7,78.5± 1.2 , 80 ± 0.8 μg/ml and 94.2 ± 0.9 respectively. The (50 % scavenging activity) SA50 of ASPE and ASCH, ASEA and ASME was found to be 34.4 μg/ml, 43.8 μg/ml 34.7 μg/m and 28.8 μg/ml respectively by DPPH assay. The percentage of hydroxyl radical scavenging increased with the increasing concentration of the extracts. ASPE, ASCH, ASEA and ASME showed superoxide radical scavenging activity, as indicated by their values 66 ± 0.5, 68 ± 1 ,63 ± 1 and 70 ± 0.5 μg/ml respectively compared to gallic acid which was 97 ± 0.5 μg/ml. The values for scavenging of nitric oxide for ASPE, ASCH, ASEA and ASME were 91.0 ± 1.0, 66.75 ± 0.5, 71.75 ± 1.1 and 75.75 ± 1.15 μg/ml while value for standard ascorbic acid was 91.0 ± 1.0 μg/ml. The results revealed strong antioxidants in four extracts may lead to the development of potent antioxidant agents from Annona squamosa seeds. Creative Commons Attribution License
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NASA Astrophysics Data System (ADS)
Martinez, Raul A., III
The main objective of this work was to examine food additives and spices (from the Apiaceae family) to determine their antioxidant properties to counteract oxidative stress (damage) caused by Environmental pollutants. Environmental pollutants generate Reactive Oxygen species and Reactive Nitrogen species. Star anise essential oil showed lower antioxidant activity than extracts using DPPH scavenging. Dill Seed -- Anethum Graveolens -the monoterpene components of dill showed to activate the enzyme glutathione-S-transferase , which helped attach the antioxidant molecule glutathione to oxidized molecules that would otherwise do damage in the body. The antioxidant activity of extracts of dill was comparable with ascorbic acid, alpha-tocopherol, and quercetin in in-vitro systems. Black Cumin -- Nigella Sativa: was evaluated the method 1,1-diphenyl2-picrylhhydrazyl (DPPH) radical scavenging activity. Positive correlations were found between the total phenolic content in the black cumin extracts and their antioxidant activities. Caraway -- Carum Carvi: The antioxidant activity was evaluated by the scavenging effects of 1,1'-diphenyl-2-picrylhydrazyl (DPPH). Caraway showed strong antioxidant activity. Cumin -- Cuminum Cyminum - the major polyphenolic were extracted and separated by HPTLC. The antioxidant activity of the cumin extract was tested on 1,1'-diphenyl-2- picrylhydrazyl (DPPH) free radical scavenging. Coriander -- Coriandrum Sativum - the antioxidant and free-radical-scavenging property of the seeds was studied and also investigated whether the administration of seeds curtails oxidative stress. Coriander seed powder not only inhibited the process of Peroxidative damage, but also significantly reactivated the antioxidant enzymes and antioxidant levels. The seeds also showed scavenging activity against superoxides and hydroxyl radicals. The total polyphenolic content of the seeds was found to be 12.2 galic acid equivalents (GAE)/g while the total flavonoid content was found to be 12.6 quercetin equivalents/g. The Maximum free radical-scavenging action and free radical reducing power of coriander seed extract was observed at a concentration of 50microg galic acid equivalents (GAE) (Sharma Om P. et al 2009) Anise - Pimpinella Anisum - the seeds of anise were investigated and the extracts showed marked antioxidant activity, both linoleic acid and liposome model systems. The antioxidant activity of alcohol extracts decreased in the order chamomile flowers > gtill seeds>gtnise seeds. The extract also showed good free radical-scavenging 2,2'-diphenyl-l-picrylhydrazyl (DPPH) activity, indicating that they act as hydrogen donors. (Sharma, Om P. et al 2009) Carrot Seed-- Daucus Carota --carrot seed is known for containing potent amounts of antioxidants. It is known for its phenomenal free-radical scavenging and oxygen radical absorbing abilities. It contains high levels of carotenoids and components of vitamin A and powerful antioxidants. It also has high levels of tocopherol, a fat soluble form of vitamin E Carrot seed is a natural antioxidant. Total Phenolic content in extracts was measured by the Folin-Ciocalteu (FC) reagent method. Results were expressed as micrograms of galic acid equivalents (GAE). Celery Seed -- Apium Graveolens - Celery contains well known antioxidants like vitamin C and flavonoids. Scientists have identified at least a dozen other types of antioxidants in celery. Celery is an important food source of conventional antioxidant nutrients, including vitamin C, beta-carotene, and manganese. But its claim to fame may very well be its phytonutrients. Many of these phytonutrients fall into the category of phenolic antioxidants and have been shown to provide anti-inflammatory benefits as well. Celery is an excellent source of vitamin K and molybdenum. It is a very good source of folate, potassium, dietary fiber, manganese, and pantothenic acid. Celery is also a good source of vitamin B2, copper, vitamin C, vitamin A, and vitamin E. The total phenolic content was measured by the Folin-Ciocalteu (FC) reagent method. Fennel--- Foeniculum Vulgare : Like many of its fellow spices contains its own unique combinations of phytonutrients -- including the flavonoids rutin, quercetin, and various kaempferol glycosides -- that give it strong antioxidant activity. The phytonutrients in fennel extracts compare favorably in research studies to BHT (butylated hydroxytoluene), a potentially toxic antioxidant commonly added to processed food. The most fascinating phytonutrients compound in fennel, may be anethole - the primary component of its volatile oil. In addition to its unusual phytonutrients, fennel bulb is an excellent source of vitamin C Vitamin C is the body's primary water-soluble antioxidant, able to neutralize free radicals in all aqueous environments of the body. The vitamin C found in fennel bulb is directly antimicrobial and is also needed for the proper function of the immune system. The total phenolic content was measured by the Folin-Ciocalteu reagent method Cilantro Powder -- Coriandrum Sativum - Cilantro herb is very low in calories and contains no cholesterol. However its deep-green leaves possess good amounts of antioxidants, essential oils, vitamins, and dietary fiber, which help reduce LDL or "bad cholesterol" while raising HDL or "good cholesterol" levels. Its leaves and seeds contain many essential volatile oils. The leaves and stem are also rich in numerous antioxidant polyphenolic Flavonoids such as quercetin, kaempferel, rhamnetin, and epigenin. The herb is a good source of minerals like potassium, calcium manganese, iron, and magnesium. Carrot Powder -- Daucus Carota : Carrot is known for containing potent amounts of antioxidants. It is known for its phenomenal free-radical scavenging and oxygen radical absorbing abilities. It contains high levels of carotenoids and components of vitamin A and powerful antioxidants. It also has high levels of tocopherol, a fat soluble form of vitamin E Carrot seed is a natural antioxidant. Total Phenolic content in extracts was measured by the Folin-Ciocalteu (FC) reagent method. Results were expressed as micrograms of galic acid equivalents (GAE). Weed -- Anethum Graveolens: Dill weed contains numerous plant derived chemical compounds that are known to have been anti-oxidant, disease preventing, and health promoting properties. This popular herb contains no cholesterol and low in calories. Nonetheless, it holds many antioxidants, vitamins like niacin, pyridoxine, etc. and dietary fibers. Dill seeds contain many essential volatile oils such as d-carvone, clillapiol, DHC, eugenol, limonene, terpinene, and myristicin. Dill is also rich in many vital vitamins, including folic acid, riboflavin, vitamin A, 13-carotene, vitamin C, that is essential for optimum metabolism in the human body. Dill weed is a good source of minerals like potassium, calcium manganese, iron, and magnesium. Ammi -- Ammi visnaga L.: Eleven flavonols have been isolated from the aerial parts of Ammi visnaga L. from which four aglycones, four monoglycosides, two diglycosides and one triglycoside. Ammi oil evaluation was done by the antioxidant power of 1,11-diphenyl-2picrylhydrazal (DPPH) radical scavenging activity. DPPH is a stable free radical, which changes its colour from violet to yellow upon reduction by the process of electron donation. The scavenging potential of the antioxidants present in E.O.A seeds can thus be determined by their degree of discoloration to yellow. As per data obtained through experiment, it was seen that scavenging effect of DPPH radical increased with increasing the concentration of essential oil (1.25-10micro1).E.O.A. The E.O.A. has shown considerable reducing power) They exhibited moderate scavenging activity when compared with ascorbic acid (standards). The ability of samples to scavenge DPPH radical was determined on the basis of their concentration providing % effect. Parsley Seed -- Petroselinum Sativum: The flavonoids in parsley -- especially luteolin -- have been shown to function as antioxidants that combine with highly reactive oxygen-containing molecules (oxygen radicals) and help prevent oxidative damage. In addition to its volatile oils and flavonoids, parsley is an excellent source of vitamin C and a good source of vitamin A (notably through its concentration of the pro-vitamin A carotenoids, beta-carotene). Vitamin C has many different functions. It is the body's primary water-soluble antioxidant, rendering harmless dangerous free radicals in all water soluble areas of the body. Beta carotene, another important antioxidant, works in the fat soluble areas of the body. (Bate-Smith et al 1962).
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Chen, Ji-Peng; He, Wei; Yang, Zhen-Yu; Yao, Zhu-Jun
2015-07-17
An efficient synthesis of the tricyclo[4,3,1,0(1, 5)]decane core (B/C/D rings) of plumisclerin A, a unique cytotoxic marine diterpenoid, is described. A Pauson-Khand reaction and a SmI2-mediated radical 1,4-conjugate addition successfully served as key reactions for construction of the fully functionalized 5,6-fused rings and the highly strained cyclobutanol moiety with correct relative stereochemistries, respectively.
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In vitro antioxidant potential of dicliptera roxburghiana
2013-01-01
Background Stress caused by free radicals accumulation result into many hazardous diseases. A number of investigations are focusing to find out the plant oriented natural antioxidant moieties. The basic aim of this research was to investigate the antioxidant potential, total Phenolic and flavonoids contents and photochemical screening of the crude methanol extract and its derived various fractions Dicliptera roxburghiana of Acanthaceae family. Methods Crude methanol extract of aerial parts of Dicliptera roxburghiana (DRME) was partitioned in to n-hexane (DRHF), chloroform (DRCF), ethyl acetate (DREF), n-butanol (DRBF) and the remaining soluble portion as residual aqueous fraction (DRAF). We evaluated the antioxidant activities of the extract and various fractions through different analytical methods such as DPPH, superoxide anion, ABTS, H2O2, hydroxyl radical and phosphomolybdate radical inhibition. In vitro lipid peroxidation and reducing power of the plant was also analyzed. Total flavonoid and phenolic contents of the extract and all fractions were also quantified. Plant was also subjected for preliminary phytochemical screening to confirm the presence or absence of various constituents in the plant. Results Phytochemical screening confirmed the presence of flavonoids, phenolics, tannins, alkaloids, saponins, terpenoids and coumarines. Quantitative analysis revealed the maximum amount of total phenolic and flavonoid contents in DRME while lowest in DRHF. Methanol extract, DREF, DRCF and DRBF exhibited promising antioxidant potential for DPPH, ABTS, H2O2, phosphomolybdate, superoxide anion and hydroxyl radical scavenging capabilities, while these were not appreciable for DRHF and DRAF. All fractions except DRHF and DRAF possess strong reducing power ability and showed appreciable lipid peroxidation inhibition. Conclusion These research investigations revealed that Dicliptera roxburghiana is a potent source of natural antioxidants. Hence the plant can be used for management of different stress and anxiety related ailments. PMID:23777321
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Use of aspartame-based sweetener tablets in emergency dosimetry using EPR.
Maghraby, A; Salama, E
2010-06-01
Accident dosimetry aims to evaluate the unplanned radiation doses delivered to individuals through one of the objects exist in the area of the accident. The gamma dose response of free radicals generated in irradiated aspartame tablets and its usability for emergency dosimetry was studied. EPR spectra of unirradiated and irradiated aspartame-based sweetener were recorded. Two signals arise after irradiating, S(1) at g (S(1)) = 2.00229 +/- 0.00097 and S(2) at g (S(2)) = 2.00262 +/- 0.00088. Some EPR parameters were studied for radiation-induced radicals in aspartame sweeteners tablets, such as the microwave saturation behaviour, the effect of magnetic field modulation amplitude on the peak-to-peak height and peak-to-peak line width for both of S(1) and S(2). Responses of S(1) and S(2) to different radiation doses were studied and resulted in linear relationships, radicals persistence curves were plotted over a 49-d storage period. It was found that Aspartame sweeteners tablets are useful in the range from 0.96 to 39.96 Gy. Radiation-induced radicals possess reasonable stability.
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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.
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Ji, Xinjian; Mandalapu, Dhanaraju; Cheng, Jinduo; Ding, Wei; Zhang, Qi
2018-03-30
The radical S-adenosylmethionine (SAM) superfamily enzymes cleave SAM reductively to generate a highly reactive 5'-deoxyadenosyl (dAdo) radical, which initiates remarkably diverse reactions. Unlike most radical SAM enzymes, the class C radical SAM methyltransferase NosN binds two SAMs in the active site, using one SAM to produce a dAdo radical and the second as a methyl donor. Here, we report a mechanistic investigation of NosN in which an allyl analogue of SAM (allyl-SAM) was used. We show that NosN cleaves allyl-SAM efficiently and the resulting dAdo radical can be captured by the olefin moieties of allyl-SAM or 5'-allylthioadenosine (ATA), the latter being a derivative of allyl-SAM. Remarkably, we found that NosN produced two distinct sets of products in the presence and absence of the methyl acceptor substrate, thus suggesting substrate-triggered production of ATA from allyl-SAM. We also show that NosN produces S-adenosylhomocysteine from 5'-thioadenosine and homoserine lactone. These results support the idea that 5'-methylthioadenosine is the direct methyl donor in NosN reactions, and demonstrate great potential to modulate radical SAM enzymes for novel catalytic activities. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies.
Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun
2016-07-13
Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions.
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Bizuayehu, Dereje; Atlabachew, Minaleshewa; Ali, Mirtachew Tihar
2016-01-01
Eight brands of tea (Camellia sinensis),which are cultivated and commercially available in Ethiopian market, were analyzed for estimation of their total secondary metabolites (polyphenols, flavonoids and tannins) content and free radical scavenging activity which is expressed on dry weight basis. In this present study, the total polyphenols, tannin and flavonoid contents were studied spectrophotometrically using Folin-Dennis, Folin-Dennis/protein precipitation and aluminium chloride methods respectively. The free radical scavenging activity was determined by using DPPH radical assay. Results of the analysis revealed that the total polyphenol content varied from 21.3 ± 0.24 to 31.6 ± 0.31 mg of gallic acid equivalent/g of dry matter. Total flavonoids content in the tea samples varied from 8.17 ± 0.68 to 23.2 ± 0.68 mg of catechin equivalent/g of dry weight and tannin content varied from 5.64 ± 0.39 7.45 ± 0.27 mg tannic acid equivalent/g of dry weight basis. The free radical scavenging activity among the tea brand samples ranged from 28.8 ± 1.86 to 80.0 ± 0.63 mg ascorbic acid equivalent/g and the half maximal inhibitory concentration (IC50%) values varied from 7.3 ± 1.35 to 64.0 ± 2.81 µg/mL of extract. The correlation between the antioxidant activity with total polyphenol content (R = 0.91325), with flavonoids (R = 0.80658) and with tannin (R = 0.73125) was calculated and maximum correlation value was found between polyphenol content and the free radical scavenging activity of the tea samples. The results in this study also revealed that green tea had the higher polyphenolic content and found to have the most promising antioxidant activity. This study further confirmed that Ethiopia tea is reach in phenolic compounds as compared to some overseas tea cultivars/varieties.
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Haywood, Rachel; Volkov, Arsen; Andrady, Carima; Sayer, Robert
2012-03-01
The in vitro star system used for sunscreen UVA-testing is not an absolute measure of skin protection being a ratio of the total integrated UVA/UVB absorption. The in vivo persistent-pigment-darkening method requires human volunteers. We investigated the use of the ESR-detectable DMPO protein radical-adduct in solar-simulator-irradiated skin substitutes for sunscreen testing. Sunscreens SPF rated 20+ with UVA protection, reduced this adduct by 40-65% when applied at 2 mg/cm(2). SPF 15 Organic UVA-UVB (BMDBM-OMC) and TiO(2)-UVB filters and a novel UVA-TiO(2) filter reduced it by 21, 31 and 70% respectively. Conventional broad-spectrum sunscreens do not fully protect against protein radical-damage in skin due to possible visible-light contributions to damage or UVA-filter degradation. Anisotropic spectra of DMPO-trapped oxygen-centred radicals, proposed intermediates of lipid-oxidation, were detected in irradiated sunscreen and DMPO. Sunscreen protection might be improved by the consideration of visible-light protection and the design of filters to minimise radical leakage and lipid-oxidation.
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Kumari, Shweta; Chang, Sam K C
2016-07-01
Soy sprouts possess health benefits and is required to be cooked before consumption. The effects of cooking on the phenolic components and antioxidant properties of soy sprouts with different germination days were investigated. A food-grade cultivar Prosoy with a high protein content was germinated for 1, 2, 3, 5, and 7 d and cooked till palatable for 20, 20, 5, 5, and 7 min, respectively. Total phenolic content (TPC), total flavonoids content (TFC), condensed tannins content (CTC), individual phenolic acids, isoflavones, DPPH, ferric-reducing antioxidant power (FRAP), and oxygen radical absorbance capacity (ORAC) of raw and cooked sprouts were measured. Cooking caused significant losses in phenolic content and antioxidant activities, and maximum loss was on day 3 > 5 > 7, including TPC (32%, 23%, and 15%), TFC (50%, 44%, and 20%), CTC (73%, 47%, and 12%), DPPH (31%, 15%, and 5%), FRAP (34%, 25%, and 1%), and ORAC (34%, 22%, 32%), respectively. Cooking caused significant losses in most individual phenolic acid, benzoic group, cinnamic group, total phenolic composition, individual isoflavones, and total isoflavones. The losses of phenolic acids such as gallic, protocatechuic, hydroxybenzoic, syringic, chlorogenic, or sinapic acids during cooking were not compensated by the increases in trihydroxybenzoic, vanillic or coumaric acids on certain days of germination. Cooking caused minimal changes in phenolic acid composition of day 1 and 2 sprouts compared to 3, 5, and 7 d sprouts. © 2016 Institute of Food Technologists®
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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.
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Optimization of selenizing conditions for Seleno-Lentinan and its characteristics.
Ren, Guangming; Li, Koukou; Hu, Yang; Yu, Min; Qu, Juanjuan; Xu, Xiuhong
2015-11-01
Lentinan was successfully modified with nitric acid-sodium selenite method based on L9(3(4)) orthogonal experiments. The optimum selenizing conditions were obtained according to selenium conversion rate as follows: Lentinan of 1.0g, pH of 4.5, temperature of 70°C and sodium selenite of 1.50g. The antioxidant activity assays in vitro (DPPH, reducing power, superoxide radicals and hydroxyl radicals) proved that Lentinan had stronger antioxidant activity after selenizing. The elevations of serum alanine aminotransferase and aspartate aminotransferase, as well as the abnormal hepatic architecture, verified that oral administration of Seleno-Lentinan (SL2-1) markedly alleviated oxidative damage in the liver of mice induced by D-gal. In addition, SL2-1 significantly increased total antioxidant capacity, activities and protein expressions of catalase and glutathione peroxidase and lowered malondialdehyde levels in serum and liver. Fourier transform infrared spectroscopy analysis indicated that selenium of SL2-1 was mostly existed as the formations of OSeO, SeO and SeOC. Scanning electron microscope coupled with energy dispersive X-ray spectroscopy analysis revealed that the surface structure and elemental components of Lentinan significantly changed after selenizing. The results are instructive for the development of organic selenium-supplement resource. Copyright © 2015 Elsevier B.V. All rights reserved.
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Kumar, Ashutosh; Chen, Shih-Heng; Kadiiska, Maria B.; Hong, Jau-Shyong; Zielonka, Jacek; Kalyanaraman, Balaraman; Mason, Ronald P.
2014-01-01
Microglia are the resident immune cells in the brain. Microglial activation is characteristic of several inflammatory and neurodegenerative diseases including Alzheimer’s disease, multiple sclerosis, and Parkinson’s disease. Though LPS-induced microglial activation in models of Parkinson’s disease (PD) is well documented, the free radical-mediated protein radical formation and its underlying mechanism during LPS-induced microglial activation is not known. Here we have used immuno-spin trapping and RNA interference to investigate the role of inducible nitric oxide synthase (iNOS) in peroxynitrite-mediated protein radical formation in murine microglial BV2 cells treated with LPS. Treatment of BV2 cells with LPS resulted in morphological changes, induction of iNOS and increased protein radical formation. Pretreatments with FeTPPS (a peroxynitrite decomposition catalyst), L-NAME (total NOS inhibitor), 1400W (iNOS inhibitor) and apocynin significantly attenuated LPS-induced protein radical formation and tyrosine nitration. Results obtained with coumarin-7-boronic acid, a highly specific probe for peroxynitrite detection, correlated with LPS-induced tyrosine nitration, which demonstrated involvement of peroxynitrite in protein radical formation. A similar degree of protection conferred by 1400W and L-NAME led us to conclude that only iNOS, and no other forms of NOS, are involved in LPS-induced peroxynitrite formation. Subsequently, siRNA for iNOS, the iNOS-specific inhibitor 1400W, the NF-kB inhibitor PDTC and the P38 MAPK inhibitor SB202190 were used to inhibit iNOS directly or indirectly. Inhibition of iNOS precisely correlated with decreased protein radical formation in LPS-treated BV2 cells. The time course of protein radical formation also matched the time course of iNOS expression. Taken together, these results prove the role of iNOS in peroxynitrite-mediated protein radical formation in LPS-treated microglial BV2 cells. PMID:24746617
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NASA Astrophysics Data System (ADS)
Zhang, Ji-Dong; Zhang, Li-Li
2017-12-01
The decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO2 radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO2 + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO2 + FOX-7 results in the formation of NO3 radical, which has never been detected experimentally during the decomposition of FOX-7.
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NASA Astrophysics Data System (ADS)
Saheb, Vahid; Maleki, Samira
2018-03-01
The hydrogen abstraction reactions from CH3Cl2F (R-141b) and CH3CClF2 (R-142b) by OH radicals are studied theoretically by semi-classical transition state theory. The stationary points for the reactions are located by using KMLYP density functional method along with 6-311++G(2 d,2 p) basis set and MP2 method along with 6-311+G( d, p) basis set. Single-point energy calculations are performed by the CBS-Q and G4 combination methods on the geometries optimized at the KMLYP/6-311++G(2 d,2 p) level of theory. Vibrational anharmonicity coefficients, x ij , which are needed for semi-classical transition state theory calculations, are computed at the KMLYP/6-311++G(2 d,2 p) and MP2/6-311+G( d, p) levels of theory. The computed barrier heights are slightly sensitive to the quantum-chemical method. Thermal rate coefficients are computed over the temperature range from 200 to 2000 K and they are shown to be in accordance with available experimental data. On the basis of the computed rate coefficients, the tropospheric lifetime of the CH3CCl2F and CH3CClF2 are estimated to be about 6.5 and 12.0 years, respectively.
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LABORATORY STUDIES ON THE FORMATION OF FORMIC ACID (HCOOH) IN INTERSTELLAR AND COMETARY ICES
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bennett, Chris J.; Kim, Yong Seol; Kaiser, Ralf I.
2011-01-20
Mixtures of water (H{sub 2}O) and carbon monoxide (CO) ices were irradiated at 10 K with energetic electrons to simulate the energy transfer processes that occur in the track of galactic cosmic-ray particles penetrating interstellar ices. We identified formic acid (HCOOH) through new absorption bands in the infrared spectra at 1690 and 1224 cm{sup -1} (5.92 and 8.17 {mu}m, respectively). During the subsequent warm-up of the irradiated samples, formic acid is evident from the mass spectrometer signal at the mass-to-charge ratio, m/z = 46 (HCOOH{sup +}) as the ice sublimates. The detection of formic acid was confirmed using isotopically labeledmore » water-d2 with carbon monoxide, leading to formic acid-d2 (DCOOD). The temporal fits of the reactants, reaction intermediates, and products elucidate two reaction pathways to formic acid in carbon monoxide-water ices. The reaction is induced by unimolecular decomposition of water forming atomic hydrogen (H) and the hydroxyl radical (OH). The dominating pathway to formic acid (HCOOH) was found to involve addition of suprathermal hydrogen atoms to carbon monoxide forming the formyl radical (HCO); the latter recombined with neighboring hydroxyl radicals to yield formic acid (HCOOH). To a lesser extent, hydroxyl radicals react with carbon monoxide to yield the hydroxyformyl radical (HOCO), which recombined with atomic hydrogen to produce formic acid. Similar processes are expected to produce formic acid within interstellar ices, cometary ices, and icy satellites, thus providing alternative processes for the generation of formic acid whose abundance in hot cores such as Sgr-B2 cannot be accounted for solely by gas-phase chemistry.« less
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Particle phase photosensitized radical production and aerosol aging.
Corral-Arroyo, Pablo; Bartels-Rausch, Thorsten; Alpert, Peter Aaron; Dumas, Stephane; Perrier, Sebastien; George, Christian; Ammann, Markus
2018-06-13
Atmospheric aerosol particles may contain light absorbing (brown carbon, BrC), triplet forming organic compounds that can sustain catalytic radical reactions and thus contribute to oxidative aerosol aging. We quantify UVA induced radical production initiated by imidazole-2-carboxaldehyde (IC), benzophenone (BPh) and 4-Benzoylbenzoic acid (BBA) in the presence of the non-absorbing organics citric acid (CA), shikimic acid (SA) and syringol (Syr) at varying mixing ratios. We observed a maximum HO 2 release of 10 13 molecules min -1 cm -2 at a mole ratio Χ BPh <0.02 for BPh in CA. Mixtures of either IC or BBA with CA resulted in 10 11 -10 12 molecules min -1 cm -2 of HO 2 at mole ratios (Χ IC and Χ BBA ) between 0.01 and 0.15. HO 2 release was affected by relative humidity (RH) and film thickness suggesting coupled photochemical reaction and diffusion processes. Quantum yields of HO 2 formed per absorbed photon for IC, BBA and BPh were between 10 -7 and 5∙10 -5 . The non-photoactive organics, Syr and SA, increased HO 2 production due to the reaction with the triplet excited species ensuing ketyl radical production. Rate coefficients of the triplet of IC with Syr and SA measured by laser flash photolysis experiments were k Syr =9.4±0.3∙10 8 M -1 s -1 and k SA =2.7±0.5∙10 7 M -1 s -1 . A simple kinetic model was used to assess total HO 2 and organic radical production in the condensed phase and to upscale to ambient aerosol, indicating that BrC induced radical production may amount to an upper limit of 20 and 200 M day -1 of HO 2 and organic radical respectively, which is greater or in the same order of magnitude as the internal radical production from other processes, previously estimated to be around 15 M per day.
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Double C-H activation of ethane by metal-free SO2*+ radical cations.
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.
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Jahromi, Alireza Raayat; Rasooli, Rokhsana; Kamali, Younes; Ahmadi, Nasrollah; Sattari, Ehsan
2017-01-01
Antioxidants are potent scavengers of free radicals and have beneficial effects on human health. The aim of this study was to investigate the potential protective antioxidant activity of the edible portion of date fruit extract in an experimental testicular torsion/detorsion (T/D) model in rats. To investigate the potential protective effects of date palm (DP), 30 male Spraque-Dawley rats were divided into three groups: sham-operated, T/D, and T/D + DP-treated (500 mg/kg, PO) groups. Testicular ischemia was induced via keeping the left testis under 720° clockwise torsion for 2 h (h), afterward, detorsion was performed. All rats were sacrificed 4 h after detorsion. Serum malondialdehyde (MDA) concentration, total oxidative status (TOS), total antioxidant status (TAS), oxidative stress index (OSI), and histopathological damage score were evaluated. Serum MDA, TOS, and OSI levels rose significantly in the T/D group. These values were lower in the T/D + DP group. TAS values decreased significantly in T/D group and rose in T/D + DP group. Severe injury was seen in the twisted testes of T/D group. In contrast, ipsilateral-twisted testicular tissue in the DP-treated group showed moderate-to-mild changes. Contralateral testicular tissue in the T/D group had a mild-to-moderate tissue injury; meanwhile, treated group revealed normal-to-mild changes. Spermatogenesis was significantly improved in DP-treated group when compared with the T/D group. The findings suggest a possible protective effect of DP against testicular oxidative damage induced by T/D; however, more detailed studies are warranted. Given the presence of several phenolic compounds possessing high antioxidant activity in DP, it could potentially be used to reduce testis ischemia/reperfusion-induced damage. Abbreviations Used : TAS: Total antioxidant status,TOS: Total oxidative status; OSI: Oxidative stress index; MDA: Malondialdehyde; C: Congestion; H: Hemorrhage, E: Edema; SG: Sloughed germinal cells; SA: Spermatogenesis arrest; STD: Seminiferous tubules disorganization; STA: Seminiferous tubules atrophy; G: Giant cells; T/D: Torsion/detorsion; DP: Date palm.
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Biondi, R; Xia, Y; Rossi, R; Paolocci, N; Ambrosio, G; Zweier, J L
2001-03-01
Hydroxylation of l-phenylalanine (Phe) by hydroxyl radical (*OH) yields 4-, 3-, and 2-hydroxyl-Phe (para-, meta-, and ortho-tyrosine, respectively). Phe derivative measurements have been employed to detect *OH formation in cells and tissues, however, the specificity of this assay is limited since Phe derivatives also arise from intracellular Phe hydroxylase. d-Phe, the d-type enantiomer, is not hydroxylated by Phe hydroxylase. We evaluate whether d-Phe reacts with *OH as well as l-Phe, providing a more reliable probe for *OH generation in biological systems. With *OH generated by a Fenton reaction or xanthine oxidase, d- and l-Phe equally gave rise to p, m, o-tyr and this could be prevented by *OH scavengers. Resting human neutrophils (PMNs) markedly converted l-Phe to p-tyr, through non-oxidant-mediated reactions, whereas d-Phe was unaffected. In contrast, when PMNs were stimulated in the presence of redox cycling iron the *OH formed resulted in more significant rise of p-tyr from d-Phe (9.4-fold) than l-Phe (3.6-fold) due to the significant background formation of p-tyr from l-Phe. Together, these data indicated that d- and l-Phe were equally hydroxylated by *OH. Using d-Phe instead of l-Phe can eliminate the formation of Phe derivatives from Phe hydroxylase and achieve more specific, sensitive measurement of *OH in biological systems.
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NASA Technical Reports Server (NTRS)
Zhao, Yi-Lei; Laufer, Allan H.; Halpern, Joshua B.; Fahr, Askar
2007-01-01
Photodissociation channels and the final product yields from the 193 nm photolysis of propene-h6 (CH2=CHCH3) and propene-d6 (CD2=CDCD3) have been investigated, employing gas chromatography, mass spectroscopy, and flame ionization (GC/MS/FID) detection methods. The yields of methane as well as butadiene relative to ethane show considerable variations when propene-h6 or propene-d6 are photolyzed. This suggests significant variances in the relative importance of primary photolytic processes and/or secondary radical reactions, occurring subsequent to the photolysis. Theoretical calculations suggest the potential occurrence of an intramolecular dissociation through a mechanism involving vinylidene formation, accompanied by an ethylenic H-migration through the pi-orbitals. This process affects the final yields of methane-h4 versus methane-d4 with respect to other products. The product yields from previous studies of the 193 nm photolysis of methyl vinyl ketone-h6 and -d6 (CH2=CHCOCH3, CD2=CDCOCD3), alternative precursors for generating methyl and vinyl radicals, are compared with the current results for propene.
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Summertime photochemistry during CAREBeijing-2007: ROx budgets and O3 formation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Zhen; Wang, Y.; Gu, Dasa
2012-08-28
We analyze summertime photochemistry near the surface in Beijing, China, using a 1-D photochemical model (Regional chEmical and trAnsport Model, REAM-1D) constrained by in situ observations, focusing on the budgets of ROx (OH + HO2 + RO2) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O3 in the planetary boundary layer are also discussed. In terms of daytime average, the total ROx primary production rate near the surface in Beijing is 6.6 ppbv per hour (ppbv h{sup 1}, among the highest found in urban atmospheres. The largest primary ROxmore » source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO2 and RO2 at 2.5 ppbv h{sup 1}1 and 1.7 ppbv h{sup 1}, respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2 ppbv h{sup 1}, much larger than that of O1D+H2O (0.4 ppbv h{sup 1}). The largest ROx sink is via OH + NO2 reaction (1.6 ppbv h{sup 1}), followed by formation of RO2NO2 (1.0 ppbv h{sup 1}) and RONO2 (0.7 ppbv h{sup 1}). Due to the large aerosol surface area, aerosol uptake of HO2 appears to be another important radical sink, although the estimate of its magnitude is highly variable depending on the uptake coefficient value used. The daytime average O3 production and loss rates near the surface are 32 ppbv h{sup 1} and 6.2 ppbv h{sup 1}, respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO transformation leads to considerable O3 loss and reduction of its lifetime. Our observation-constrained modeling analysis suggests that oxidation of VOCs (especially aromatics) and heterogeneous reactions (e.g. HONO formation and aerosol uptake HO2) play potentially critical roles in the primary radical budget and O3 formation in Beijing. One important ramification is that O3 production is neither NOx nor VOC limited, but in a transition regime where reduction of either NOx or VOCs could result in reduction of O3 production. The transition regime implies more flexibility in the O3 control strategies than a binary system of either NOx or VOC limited regime. The co-benefit of concurrent reduction of both NOx and VOCs in reducing column O3 production integrated in the planetary boundary layer is significant. Further research on the spatial extent of the transition regime over the polluted eastern China is critically important for controlling regional O3 pollution.« less
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Hwang, Eun-Sun; Thi, Nhuan Do
2014-01-01
Laver is one of the most consumed edible red algae seaweeds in the genus Porphyra. Laver is primarily prepared in the form of dried, roasted, and seasoned products. We investigated the total polyphenol and flavonoid contents of laver products, and evaluated the in vitro antioxidant properties of solvent extracts from commercially processed laver products. Significant differences in the concentration of phenolic compounds were found among differently processed laver. The total phenolic content for laver extracts ranged from 10.81 mg gallic acid equivalent (GAE)/g extract to 32.14 mg GAE/g extract, depending on extraction solvent and temperature. Laver extracts contained very few flavonoids (0.55 mg catechin equivalent/g extracts to 1.75 mg catechin equivalent/g extracts). 2,2-Diphenyl-1-picrylhydrazyl (DPPH), 2,2′-azino-bis-3-ethylbenzothiazoline-6-sulphonic acid (ABTS), hydroxyl radical, and superoxide anion scavenging assays were used to determine the radical scavenging capacities of laver extracts. These assays revealed that the processing method and extraction condition affected the antioxidant potentials of laver. Antioxidant activity of dried laver, roasted laver, and seasoned laver increased in a concentration-dependent manner (100~1,000 μg/mL). The radical scavenging activities of 37°C and 100°C water extracts were lower than that of a 37°C 70% ethanol extract. The highest radical scavenging capacity was observed in the 37°C 70% ethanol extracts of dried laver, roasted laver, and seasoned laver. Overall, these results support that notion that laver contains bioactive compounds, such as polyphenols and flavonoids, which may have a positive effect on health. PMID:24772408
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Hwang, Eun-Sun; Thi, Nhuan Do
2014-01-01
Laver is one of the most consumed edible red algae seaweeds in the genus Porphyra. Laver is primarily prepared in the form of dried, roasted, and seasoned products. We investigated the total polyphenol and flavonoid contents of laver products, and evaluated the in vitro antioxidant properties of solvent extracts from commercially processed laver products. Significant differences in the concentration of phenolic compounds were found among differently processed laver. The total phenolic content for laver extracts ranged from 10.81 mg gallic acid equivalent (GAE)/g extract to 32.14 mg GAE/g extract, depending on extraction solvent and temperature. Laver extracts contained very few flavonoids (0.55 mg catechin equivalent/g extracts to 1.75 mg catechin equivalent/g extracts). 2,2-Diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulphonic acid (ABTS), hydroxyl radical, and superoxide anion scavenging assays were used to determine the radical scavenging capacities of laver extracts. These assays revealed that the processing method and extraction condition affected the antioxidant potentials of laver. Antioxidant activity of dried laver, roasted laver, and seasoned laver increased in a concentration-dependent manner (100~1,000 μg/mL). The radical scavenging activities of 37°C and 100°C water extracts were lower than that of a 37°C 70% ethanol extract. The highest radical scavenging capacity was observed in the 37°C 70% ethanol extracts of dried laver, roasted laver, and seasoned laver. Overall, these results support that notion that laver contains bioactive compounds, such as polyphenols and flavonoids, which may have a positive effect on health.
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Haupa, Karolina A; Johnson, Britta A; Sibert, Edwin L; Lee, Yuan-Pern
2017-10-21
The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C 3v to C s provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CH 2 DO in a matrix of p-H 2 has been recorded. This species was prepared by irradiating a p-H 2 matrix containing deuterated d 1 -nitritomethane (CH 2 DONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CH 2 DO reacts with H 2 with a rate coefficient (3.5 ± 1.0) × 10 -3 s -1 . Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + C s -CH 2 DOH, which was demonstrated by an additional experiment on irradiation of a CH 2 DOH/Cl 2 /p-H 2 matrix with ultraviolet and IR light to induce the H + CH 2 DOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ∼10 cm -1 , the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d 2 -methoxy radical (CHD 2 O) was obtained upon irradiation of d 2 -nitritomethane (CHD 2 ONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHD 2 O reacts with H 2 with a rate coefficient (6.0 ± 1.4) × 10 -3 s -1 ; CD 2 OH was produced as a major product because the barrier for the formation of CHDOH from H + CHD 2 OH is greater by ∼400 cm -1 . Rate coefficients of the decays of CH 3 O, CH 2 DO, CHD 2 O, and CD 3 O and their corresponding potential energy surfaces are compared.
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NASA Astrophysics Data System (ADS)
Haupa, Karolina A.; Johnson, Britta A.; Sibert, Edwin L.; Lee, Yuan-Pern
2017-10-01
The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C3v to Cs provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CH2DO in a matrix of p-H2 has been recorded. This species was prepared by irradiating a p-H2 matrix containing deuterated d1-nitritomethane (CH2DONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CH2DO reacts with H2 with a rate coefficient (3.5 ± 1.0) × 10-3 s-1. Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + Cs-CH2DOH, which was demonstrated by an additional experiment on irradiation of a CH2DOH/Cl2/p-H2 matrix with ultraviolet and IR light to induce the H + CH2DOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ˜10 cm-1, the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d2-methoxy radical (CHD2O) was obtained upon irradiation of d2-nitritomethane (CHD2ONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHD2O reacts with H2 with a rate coefficient (6.0 ± 1.4) × 10-3 s-1; CD2OH was produced as a major product because the barrier for the formation of CHDOH from H + CHD2OH is greater by ˜400 cm-1. Rate coefficients of the decays of CH3O, CH2DO, CHD2O, and CD3O and their corresponding potential energy surfaces are compared.
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NASA Technical Reports Server (NTRS)
Leventis, Nicholas; Oh, Woon Su; Gao, Xue-Rong; Rawashdeh, Abdel Monem M.
2003-01-01
At the potential range where both decamethylferrocene (dMeFc) and ferrocene (Fc) are oxidized with rates controlled by linear diffusion, electrogenerated Fc(+) radicals diffusing outwards from the electrode react quantitatively (K23 C=5.8 x 10(exp 8) with dMeFc diffusing towards the electrode and produce Fc and dMeFc. That reaction replaces dMeFc with Fc, whose diffusion coefficient is higher than that of dMeFc(+), and the total mass-transfer limited current from the mixture is increased by approximately 10%. Analogous observations are made when mass-transfer is controlled by convective-diffusion as in RDE voltammetry. Similar results have been obtained with another, and for all practical purposes randomly selected pair of redox-active substances, [Co(bipy)3](2+) and N - methylphenothiazine (MePTZ); reaction of MePTZ(+) with [Co(bipy)3](2+) replaces the latter with MePTZ, which diffuses faster and the current increases by approximately 20%. The experimental voltammograms have been simulated numerically and the role of (a) the rate constant of the homogeneous reaction; (b) the relative concentrations; and, (c) the diffusion coefficients of all species involved have been studied in detail. Importantly, it was also identified that within any given redox system the dependence of the mass-transfer limited current on the bulk concentrations of the redox-active species is expected to be non-linear. These findings are discussed in terms of their electroanalytical implications.
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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.
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Thermochemical properties for isooctane and carbon radicals: computational study.
Snitsiriwat, Suarwee; Bozzelli, Joseph W
2013-01-17
Thermochemical properties for isooctane, its internal rotation conformers, and radicals with corresponding bond energies are determined by use of computational chemistry. Enthalpies of formation are determined using isodesmic reactions with B3LYP density function theory and composite CBS-QB3 methods. Application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations for the lowest energy conformer. Internal rotor potentials are determined for the isooctane parent and for the primary, secondary, and tertiary radicals in order to identify isomer energies. Intramolecular interactions are shown to have a significant effect on the enthalpy of formation of the isooctane parent and its radicals. The computed standard enthalpy of formation for the lowest energy conformers of isooctane from this study is -54.40 ± 1.60 kcal mol(-1), which is 0.8 kcal mol(-1) lower than the evaluated experimental value -53.54 ± 0.36 kcal mol(-1). The standard enthalpy of formation for the primary radical for a methyl on the quaternary carbon is -5.00 ± 1.69 kcal mol(-1), for the primary radical on the tertiary carbon is -5.18 ± 1.69 kcal mol(-1), for the secondary isooctane radical is -9.03 ± 1.84 kcal mol(-1), and for the tertiary isooctane radical is -12.30 ± 2.02 kcal mol(-1). Bond energy values for the isooctane radicals are 100.64 ± 1.73, 100.46 ± 1.73, 96.41 ± 1.88 and 93.14 ± 2.05 kcal mol(-1) for C3•CCCC2, C3CCCC2•, C3CC•CC2, and C3CCC•C2, respectively. Entropy and heat capacity values are reported for the lowest energy homologues.
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Lee, Jai-Sung; Bae, Inhyu
2018-02-01
Effects of quality, physicochemical properties and antioxidants in Camembert cheese added with red ginseng powder (RGP) were investigated. Cheese samples were prepared with 0.05%, 0.10%, 0.15% and 0.20% RGP. and then monitored during ripening at 14°C for 28 d. The pH of the RGP amended treatment groups increased during the ripening period relative to the control ( p <0.05). Moreover, the 1,2-Diphenyl-1-picrylhydrazyle (DPPH) was highest in the 0.15% RGP group from 21 d to 28 d. ABTS + radical scavenging activity was increased just like DPPH as the ripening period passed, 0.10% treatment was highest at from 7 d to 21 d. 0.15% RGP was contents of ginsenosides : 10,999.7 ppm. The Free fatty acids (FFA), controls with 0.15% treatment, while the total fat (TF) and monounsaturated fat (MuSF) were higher in the control than the 0.15% RGP group ( p <0.05). The total free amino acid (FAA) was increased in the control, and 0.15% RGP, and control was highest at then 0.15% RGP. The samples had average contents of fat and protein were 29% and 18-20% respectively. Additionally, the L* value decreased, while the a* and b* values increased as the amount of RGP added increased. Sensory evaluation revealed that texture and total acceptability were higher in the control group at 12 d. Although the addition of RGP did not exert a better effect on the ripening of the camembert cheese, but the ripening grade was similar to that of the common camembert cheese, and the additional function of the cheese was reinforced. Functional cheese could be developed.
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Lee, Jai-Sung; Bae, Inhyu
2018-01-01
Effects of quality, physicochemical properties and antioxidants in Camembert cheese added with red ginseng powder (RGP) were investigated. Cheese samples were prepared with 0.05%, 0.10%, 0.15% and 0.20% RGP. and then monitored during ripening at 14°C for 28 d. The pH of the RGP amended treatment groups increased during the ripening period relative to the control (p<0.05). Moreover, the 1,2-Diphenyl-1-picrylhydrazyle (DPPH) was highest in the 0.15% RGP group from 21 d to 28 d. ABTS+ radical scavenging activity was increased just like DPPH as the ripening period passed, 0.10% treatment was highest at from 7 d to 21 d. 0.15% RGP was contents of ginsenosides : 10,999.7 ppm. The Free fatty acids (FFA), controls with 0.15% treatment, while the total fat (TF) and monounsaturated fat (MuSF) were higher in the control than the 0.15% RGP group (p<0.05). The total free amino acid (FAA) was increased in the control, and 0.15% RGP, and control was highest at then 0.15% RGP. The samples had average contents of fat and protein were 29% and 18-20% respectively. Additionally, the L* value decreased, while the a* and b* values increased as the amount of RGP added increased. Sensory evaluation revealed that texture and total acceptability were higher in the control group at 12 d. Although the addition of RGP did not exert a better effect on the ripening of the camembert cheese, but the ripening grade was similar to that of the common camembert cheese, and the additional function of the cheese was reinforced. Functional cheese could be developed. PMID:29725225
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Adefegha, Stephen Adeniyi; Oboh, Ganiyu
2012-07-01
Spices have been used as food adjuncts and in folklore for ages. Inhibition of key enzymes (α-amylase and α-glucosidase) involved in the digestion of starch and protection against free radicals and lipid peroxidation in pancreas could be part of the therapeutic approach towards the management of hyperglycemia and dietary phenolics have shown promising potentials. This study investigated and compared the inhibitory properties of aqueous extracts of some tropical spices: Xylopia aethiopica [Dun.] A. Rich (Annonaceae), Monodora myristica (Gaertn.) Dunal (Annonaceae), Syzygium aromaticum [L.] Merr. et Perry (Myrtaceae), Piper guineense Schumach. et Thonn (Piperaceae), Aframomum danielli K. Schum (Zingiberaceae) and Aframomum melegueta (Rosc.) K. Schum (Zingiberaceae) against α-amylase, α-glucosidase, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals and sodium nitroprusside (SNP)-induced lipid peroxidation in rat pancreas--in vitro using different spectrophotometric method. Aqueous extract of the spices was prepared and the ability of the spice extracts to inhibit α-amylase, α-glucosidase, DPPH radicals and SNP-induced lipid peroxidation in rat pancreas--in vitro was investigated using various spectrophotometric methods. All the spice extracts inhibited α-amylase (IC(50) = 2.81-4.83 mg/mL), α-glucosidase (IC(50) = 2.02-3.52 mg/mL), DPPH radicals (EC(50) = 15.47-17.38 mg/mL) and SNP-induced lipid peroxidation (14.17-94.38%), with the highest α-amylase & α-glucosidase inhibitory actions and DPPH radical scavenging ability exhibited by X. aethiopica, A. danielli and S. aromaticum, respectively. Also, the spices possess high total phenol (0.88-1.3 mg/mL) and flavonoid (0.24-0.52 mg/mL) contents with A. melegueta having the highest total phenolic and flavonoid contents. The inhibitory effects of the spice extracts on α-amylase, α-glucosidase, DPPH radicals and SNP-induced lipid peroxidation in pancreas (in vitro) could be attributed to the presence of biologically active phytochemicals such as phenolics and some non-phenolic constituents of the spices. Furthermore, these spices may exert their anti-diabetic properties through the mechanism of enzyme inhibition, free radicals scavenging ability and prevention of lipid peroxidation.
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Ismail, Hassan Fahmi; Hashim, Zanariah; Soon, Wong Tet; Rahman, Nur Syukriah Ab; Zainudin, Ain Nabihah; Majid, Fadzilah Adibah Abdul
2017-10-01
Natural antioxidants derived from plants have shown a tremendous inhibitory effect on free radicals in actively metabolizing cells. Overproduction of free radicals increases the risk factor of chronic diseases associated with diabetes, cancer, arthritis and cardiovascular disease. Andrographis paniculata, Cinnamon zeylanicum, Curcuma xanthorrhiza, Eugenia polyantha and Orthosiphon stamineus are ethnomedicinal plants used in the Asian region to treat various illnesses from a common fever to metabolic disease. In this study, we have quantified the total phenolic (TPC) and flavonoid content (TFC) in these plants and its inhibitory effect on 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) free radicals as well as the cytotoxicity effect on cell lines proliferation and zebrafish embryogenesis. Results showed that Cinnamon zeylanicum and E. polyantha have the highest phenolic and flavonoid content. Furthermore, both herbs significantly inhibited the formation of DPPH and ABTS free radicals. Meanwhile, O. stamineus exhibited minimum cytotoxicity and embryotoxicity on tested models. Good correlation between IC50 of 3T3-L1 cells and LC50 embyrotoxicity was also found. This study revealed the potent activity of antioxidant against free radical and the toxicology levels of the tested herbal plants.
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Patel, DK; Kumar, R; Prasad, SK; Hemalatha, S
2011-01-01
Objective To examine the antioxidant activity and total phenolic content of different solvent fractions of Pedalium murex (P. murex) Linn fruits (Family: Pedaliaceae) as well as the correlation between the total antioxidant capacity and total phenolic content. Methods In the present study, the antioxidant activities of P. murex were evaluated using six in-vitro assays, namely total antioxidant assay, DPPH assay, reducing power, nitric oxide scavenging, hydrogen peroxide scavenging and deoxyribose scavenging assays, and total phenol contents were also investigated. Results The ethyl acetate (EA) fraction was found to have high levels of phenolic content (298.72±2.09 mg GAE/g). The EA fraction exhibit higher total antioxidant capacity, higher percentage of DPPH radical scavenging activity (135.11±2.95µg/mL), nitric oxide (200.57±4.51µg/mL), hydrogen peroxide (217.91±6.12 µg/mL), deoxyribose (250.01±4.68µg/mL) and higher reducing power. Correlation coefficient (r2=0.914) was found to be significant between total phenolic content and total antioxidant activity. Conclusions In general, the results indicate that the EA fractions are rich in phenolic antioxidants with potent free radical scavenging activity implying their importance to human health. PMID:23569800
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NASA Astrophysics Data System (ADS)
Remusat, L.; Robert, F.; Meibom, A.; Mostefaoui, S.; Delpoux, O.; Binet, L.; Gourier, D.; Derenne, S.
2007-12-01
Insoluble organic matter (IOM) in primitive carbonaceous chondrites is known to be enriched in deuterium, with D/H ratios > 300×10 -6. It is also characterized by a high degree of isotopic heterogeneity, as demonstrated by the observation of D-rich "hot spots" in NanoSIMS ion microprobe images [1] and by GC-irMS studies [2]. Understanding the origin of this heterogeneity represents a fundamental challenge with implications for the origin and distribution of organics in the interstellar medium and in the protoplanetary disk from which our planetary system formed. We have determined the carrier of the isotopically anomalous hydrogen in IOM isolated from the carbonaceous chondrite Orgueil. Electron Paramagnetic Resonance spectroscopy has shown that hydrogen in the benzylic bond of organic radicals has a deuterium to hydrogen (D/H) ratio of 1.5±0.5×10-2 in Orgueil IOM, which is the highest solar system D/H ratio ever reported [3]. By combining these data with quantitative image analysis recorded at a high spatial resolution with the NanoSIMS, we are able to prove that the organic radicals can account for the deuterium excess in the IOM D-rich "hot spots". Furthermore, the radicals fall on a well-defined trend between D/H ratio and C-H bond energy [2], consistent with a new interpretation of the hydrogen isotopic variations in solar system organics according to which pre-existing organics exchange their D with highly deuterated gaseous molecules, such as H2D+ or HD2+. The distributions of these deuterated species has been theoritically mapped in protostellar disks [4]. This conclusion runs contrary to previous interpretations, according to which the IOM is an interstellar product reprocessed in the protosolar gas and deuterium-rich "hot spot" relics of pristine interstellar organic matter, which escaped solar nebula or parent body processes. [1] Busemann et al (2006) Science 312, 727-730; [2] Remusat L. et al. (2006) Earth Planet. Sci. Let. 243, 15-25 ; [3] Delpoux O. et al. (2007) 38th LPSC, #1138. [4] Ceccarelli C. and Dominik C. (2005) A&A 440, 583-593.
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Sharma, Kiran K; Razskazovskiy, Yuriy; Purkayastha, Shubhadeep; Bernhard, William A
2009-06-11
The question of how NA base sequence influences the yield of DNA strand breaks produced by the direct effect of ionizing radiation was investigated in a series of oligodeoxynucleotides of the form (d(CG)(n))(2) and (d(GC)(n))(2). The yields of free base release from X-irradiated DNA films containing 2.5 waters/nucleotide were measured by HPLC as a function of oligomer length. For (d(CG)(n))(2), the ratio of the Gua yield to Cyt yield, R, was relatively constant at 2.4-2.5 for n = 2-4 and it decreased to 1.2 as n increased from 5 to 10. When Gua was moved to the 5' end, for example going from d(CG)(5) to d(GC)(5), R dropped from 1.9 +/- 0.1 to 1.1 +/- 0.1. These effects are poorly described if the chemistry at the oligomer ends is assumed to be independent of the remainder of the oligomer. A mathematical model incorporating charge transfer through the base stack was derived to explain these effects. In addition, EPR was used to measure the yield of trapped-deoxyribose radicals at 4 K following X-irradiation at 4 K. The yield of free base release was substantially greater, by 50-100 nmol/J, than the yield of trapped-deoxyribose radicals. Therefore, a large fraction of free base release stems from a nonradical intermediate. For this intermediate, a deoxyribose carbocation formed by two one-electron oxidations is proposed. This reaction pathway requires that the hole (electron loss site) transfers through the base stack and, upon encountering a deoxyribose hole, oxidizes that site to form a deoxyribose carbocation. This reaction mechanism provides a consistent way of explaining both the absence of trapped radical intermediates and the unusual dependence of free base release on oligomer length.
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Brand variation in oxidant production in mainstream cigarette smoke: Carbonyls and free radicals.
Reilly, Samantha M; Goel, Reema; Trushin, Neil; Elias, Ryan J; Foulds, Jonathan; Muscat, Joshua; Liao, Jason; Richie, John P
2017-08-01
Oxidative stress/damage resulting from exposure to cigarette smoke plays a critical role in the development of tobacco-caused diseases. Carbonyls and free radicals are two major classes of oxidants in tobacco smoke. There is little information on the combined delivery of these oxidants across different cigarette brands; thus, we set out to measure and compare their levels in mainstream smoke from popular US cigarettes. Mainstream smoke from 28 different cigarette brands produced by smoking (FTC protocol) was analyzed for five important, abundant carbonyls, and levels were compared to previously determined free radical for the same brands. Overall, there were large variations (3- to 6-fold) in carbonyl levels across brands with total carbonyl levels ranging from 275 to 804 μg/cigarette, which persisted even after adjusting for ventilation. Individual carbonyl levels were highly correlated with each other (r 2 : 0.40-0.95, P < 0.003) except for formaldehyde. Both gas-phase (r 2 : 0.37, P = 0.006) and particulate-phase (r 2 : 0.27, P = 0.005) free radicals were correlated to total carbonyl content; however, this correlation disappeared after adjusting for ventilation. These data show that overall oxidant production varies widely by cigarette brand and the resulting difference in oxidant burden could potentially lead to differences in disease risk. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Bhauso, Tengale Dipak; Radhakrishnan, Thankappan; Kumar, Abhay; Mishra, Gyan Prakash; Dobaria, Jentilal Ramjibhai; Patel, Kirankumar; Rajam, Manchikatla Venkat
2014-01-01
In the changing global environmental scenarios, water scarcity and recurrent drought impose huge reductions to the peanut (Arachis hypogaea L.) crop yield. In plants, osmotic adjustments associated with efficient free radical scavenging ability during abiotic stress are important components of stress tolerance mechanisms. Mannitol, a compatible solute, is known to scavenge hydroxyl radicals generated during various abiotic stresses, thereby conferring tolerance to water-deficit stress in many plant species. However, peanut plant is not known to synthesize mannitol. Therefore, bacterial mtlD gene coding for mannitol 1-phosphate dehydrogenase under the control of constitutive promoter CaMV35S was introduced and overexpressed in the peanut cv. GG 20 using Agrobacterium tumefaciens-mediated transformation. A total of eight independent transgenic events were confirmed at molecular level by PCR, Southern blotting, and RT-PCR. Transgenic lines had increased amount of mannitol and exhibited enhanced tolerance in response to water-deficit stress. Improved performance of the mtlD transgenics was indicated by excised-leaf water loss assay and relative water content under water-deficit stress. Better performance of transgenics was due to the ability of the plants to synthesize mannitol. However, regulation of mtlD gene expression in transgenic plants remains to be elucidated. PMID:25436223
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Lipid metabolites with free-radical scavenging activity from Euphorbia helioscopia L.
Cateni, F; Zilic, J; Altieri, T; Zacchigna, M; Procida, G; Gaggeri, R; Rossi, D; Collina, S
2014-07-01
The methanolic extract of the plant Euphorbia helioscopia L. exhibited an interesting free-radical scavenging activity. From the aerial parts of Euphorbia helioscopia L. (Euphorbiaceae), a complex mixture of seven cerebrosides together with glucoclionasterol, a digalactosyldiacylglycerol and a diacylmonogalactosylglycerol were identified. The structures of the cerebrosides were characterized as 1-O-β-D-glucosides of phytosphingosines, which comprised (2S, 3S, 4E, 8E)-2-amino-4(E),8(E)-octadecadiene-1,3-diol, (2S, 3S, 4E, 8Z)-2-amino-4(E),8(Z)-octadecadiene-1,3-diol, (2S, 3S, 4R, 8Z)-2-amino-8(Z)-octadecene-1,3,4-triol as long chain bases with seven 2-hydroxy fatty acids of varying chain lengths (C16, C24:1, C26:1, C24, C26, C28:1) linked to the amino group. The glycosylglycerides were characterized as (2S)-2,3-O-di-(9,12,15-octadecatrienoyl)-glyceryl-6-O-(α-D-galactopyranosyl)-β-D-galactopyranoside and (2S)-2,3-O-di-(9,12,15-octadecatrienoyl)-glyceryl-1-O-β-D-galactopyranoside. The structures were established on the basis of spectroscopic data and chemical reactions. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.
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Comparative Study of Erythrina indica Lam. (Febaceae) Leaves Extracts for Antioxidant Activity
Sakat, SS; Juvekar, AR
2010-01-01
The present study was designed to investigate the antioxidant activity of aqueous and methanol extracts of Erythrina indica Lam leaves by in vitro methods viz. 1, 1-Diphenyl-2-Picrylhydrazyl, nitric oxide radical scavenging activity, and inhibition of lipid peroxidation by thiobarbituric acid reactive substances (TBARS) method on isolated rat liver tissues. Quantitative analysis of antioxidative components like total amount of phenolics, flavonoids, and flavonols were estimated using the spectrophotometric method. Linear regression analysis was used to calculate the IC50 value. Results showed that the aqueous and methanol extracts exhibited significant DPPH radicals scavenging activity with an IC50 value 342.59 ± 19.59, 283.24 ± 12.28 µg/mL respectively. Nitric oxide radicals were significantly scavenged by the aqueous and methanol extracts (IC50 = 250.12 ± 10.66; 328.29 ± 3.74 µg/mL). Lipid peroxidation induced by the Fe2+ was inhibited by the aqueous extract with low IC50 value (97.29 ± 2.05 µg/mL) as compared to methanol extract (IC50 = 283.74 ± 5.70 µg/mL). Both the extracts were exhibited similar quantities of total phenolics. Total flavonoids were found to be in higher quantities than total flavonols in aqueous extract as compared to methanol extract. From the results, it is concluded that the aqueous and methanol extracts of E. indica leaves possesses significant antioxidant activity that may be due to the presence of flavonoids and related polyphenolic compounds. PMID:21331194
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NASA Astrophysics Data System (ADS)
Stoesser, Reinhard; Klein, Jeannette; Peschke, Simone; Zehl, Andrea; Cämmerer, Bettina; Kroh, Lothar W.
2007-08-01
During the early stage of the Maillard reaction pyrazinium radical cations were detected by ESR within the reaction system D-glucose/glycine. The spectra were characterized by completely resolved hyperfine structure. The partial pressure of oxygen and the radical concentrations were measured directly in the reaction mixture by ESR using solutions of the spin probe TEMPOL and of DPPH, respectively. There are quantitative and qualitative relations of the actual concentration of the radical ions to the partial pressure of oxygen, the temperature-time regime and the mechanical mixing of the reaction system. These macroscopic parameters significantly affect both the induction period and the velocity of the time-dependent formation of free radicals. From in situ variations of p(O 2) and p(Ar) including the connected mixing effects caused by the passing the gases through the reaction mixture, steric and chemical effects of the stabilization of the radical ions were established. The determination of suitable and relevant conditions for stabilization and subsequent radical reactions contributes to the elucidation of the macroscopically known antioxidant activity of Maillard products.
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Wang, Yong; Wen, Xin; Cui, Xin; Wojtas, Lukasz; Zhang, X Peter
2017-01-25
Donor-substituted diazo reagents, generated in situ from sulfonyl hydrazones in the presence of base, can serve as suitable radical precursors for Co(II)-based metalloradical catalysis (MRC). The cobalt(II) complex of D 2 -symmetric chiral porphyrin [Co(3,5-Di t Bu-Xu(2'-Naph)Phyrin)] is an efficient metalloradical catalyst that is capable of activating different N-arylsulfonyl hydrazones for asymmetric radical cyclopropanation of a broad range of alkenes, affording the corresponding cyclopropanes in high yields with effective control of both diastereo- and enantioselectivity. This Co(II)-based metalloradical system represents the first catalytic protocol that can effectively utilize donor-type diazo reagents for asymmetric olefin cyclopropanation.
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New chalcanonol glycoside from the seeds of saw palmetto: antiproliferative and antioxidant effects.
Abdel Bar, Fatma M
2015-01-01
A new chalcanonol glycoside dimer, bis-O-[(I-4') → (II-6')]-α-hydroxyphloretin-2'-O-β-glucoside (1), in addition to six known compounds, namely (-)-epicatechin (2) and (-)-epiafzelechin (3), 4-hydroxybenzoic acid (4), protocatechuic acid (5), methylgallate (6), β-sitosterol (7) and β-sitosterol-3-O-glucoside (8), was isolated from the seeds of saw palmetto. The structures of the isolated compounds were established from the analysis of their MS and 1D and 2D NMR spectroscopic data. The antiproliferative activities of the isolated compounds towards PC3, the human prostate cancer cells were investigated. Amongst the isolated compounds, the new compound and the sterolic derivatives showed antiproliferative effects. Screening of the antioxidant effects of the isolated compounds by 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid radical assay revealed that the isolated phenolics were active free radical scavengers.
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Pawar, Amol Ashok; Halivni, Shira; Waiskopf, Nir; Ben-Shahar, Yuval; Soreni-Harari, Michal; Bergbreiter, Sarah; Banin, Uri; Magdassi, Shlomo
2017-07-12
Additive manufacturing processes enable fabrication of complex and functional three-dimensional (3D) objects ranging from engine parts to artificial organs. Photopolymerization, which is the most versatile technology enabling such processes through 3D printing, utilizes photoinitiators that break into radicals upon light absorption. We report on a new family of photoinitiators for 3D printing based on hybrid semiconductor-metal nanoparticles. Unlike conventional photoinitiators that are consumed upon irradiation, these particles form radicals through a photocatalytic process. Light absorption by the semiconductor nanorod is followed by charge separation and electron transfer to the metal tip, enabling redox reactions to form radicals in aerobic conditions. In particular, we demonstrate their use in 3D printing in water, where they simultaneously form hydroxyl radicals for the polymerization and consume dissolved oxygen that is a known inhibitor. We also demonstrate their potential for two-photon polymerization due to their giant two-photon absorption cross section.
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Lumata, Lloyd L; Martin, Richard; Jindal, Ashish K; Kovacs, Zoltan; Conradi, Mark S; Merritt, Matthew E
2015-04-01
We sought to build a dynamic nuclear polarization system for operation at 4.6 T (129 GHz) and evaluate its efficiency in terms of (13)C polarization levels using free radicals that span a range of ESR linewidths. A liquid helium cryostat was placed in a 4.6 T superconducting magnet with a 150-mm warm bore diameter. A 129-GHz microwave source was used to irradiate (13)C enriched samples. Temperatures close to 1 K were achieved using a vacuum pump with a 453-m(3)/h roots blower. A hyperpolarized (13)C nuclear magnetic resonance (NMR) signal was detected using a saddle coil and a Varian VNMRS console operating at 49.208 MHz. Samples doped with free radicals BDPA (1,3-bisdiphenylene-2-phenylallyl), trityl OX063 (tris{8-carboxyl-2,2,6,6-benzo(1,2-d:4,5-d)-bis(1,3)dithiole-4-yl}methyl sodium salt), galvinoxyl ((2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy), 2,2-diphenylpicrylhydrazyl (DPPH) and 4-oxo-TEMPO (4-Oxo-2,2,6,6-tetramethyl-1-piperidinyloxy) were assayed. Microwave dynamic nuclear polarization (DNP) spectra and solid-state (13)C polarization levels for these samples were determined. (13)C polarization levels close to 50 % were achieved for [1-(13)C]pyruvic acid at 1.15 K using the narrow electron spin resonance (ESR) linewidth free radicals trityl OX063 and BDPA, while 10-20 % (13)C polarizations were achieved using galvinoxyl, DPPH and 4-oxo-TEMPO. At this field strength free radicals with smaller ESR linewidths are still superior for DNP of (13)C as opposed to those with linewidths that exceed that of the (1)H Larmor frequency.
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NASA Astrophysics Data System (ADS)
Demaison, J.
This document is part of Part 1 of Subvolume D 'Asymmetric Top Molecules' of Volume 29 'Molecular Constants Mostly from Microwave, Molecular Beam, and Sub-Doppler Laser Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1996-06-01
The goal of this work is to study the behavior of the angular distribution of the electron from the decay of the W boson in a specific rest frame of the W, the Collins-Soper frame. More specifically, the parameter {alpha}{sub 2} from the expression d{sigma}/d(P{sub T}{sup W}){sup 2} d cos {theta}* = k(1 + {alpha}{sub 2} cos {theta}* + {alpha}{sup 2}(cos {theta}*){sup 2}), corresponding to the distribution of cos {theta}* in the Collins-Soper frame, was measured. The experimental value of {alpha}P{sub 2} was compared with the predictions made by E. Mirkes [11] who included the radiative QCD perturbations in themore » weak-interaction B{sub boson} {r_arrow} lepton + lepton. This experimental value was extracted for the first time using knowledge about how the radiative QCD perturbations will modify the predictions given by the Electro-Weak process only.« less
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NASA Astrophysics Data System (ADS)
Gour, Nand Kishor; Begum, Saheen Shehnaz; Deka, Ramesh Chandra
2018-06-01
Degradation of 1,1-Dichlorodimethylether by NO3 radical in the troposphere has been modelled theoretically by employing Gaussian09 suite at BHandHLYP/6-311++G(d,p) level. Energies of all optimized electronic structures have been further refined at CCSD(T) method along with the same basis set to characterize stationary points on the potential energy surface including transition states. The rate constants of the titled reaction are obtained over the temperature range 200-450 K. Results show that H-abstraction is highly favourable for sbnd CHCl2 group of CH3OCHCl2. The atmospheric lifetime and global warming potential of the titled molecule have been reported. The thermal decomposition of CH3OC(Orad)Cl2 has also been explored.
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Qin, Peiyou; Wei, Aichun; Zhao, Degang; Yao, Yang; Yang, Xiushi; Dun, Baoqing; Ren, Guixing
2017-06-01
This study aimed to investigate the effects of different concentrations of sodium bicarbonate (NaHCO 3 ) on the accumulation of flavonoids, total phenolics and d-chiro-inositol (DCI), as well as the antioxidant and α-glucosidase inhibitory activities, in tartary buckwheat sprouts. Treatment with low concentrations of NaHCO 3 (0.05, 0.1, and 0.2%) resulted in an increase in flavonoids, total phenolic compounds and DCI concentrations, and improved DPPH radical-scavenging and α-glucosidase inhibition activities compared with the control (0%). The highest levels of total flavonoids (26.69mg/g DW), individual flavonoids (rutin, isoquercitrin, quercetin, and kaempferol), total phenolic compounds (29.31mg/g DW), DCI (12.56mg/g DW), as well as antioxidant and α-glucosidase inhibition activities, were observed in tartary buckwheat sprouts treated with 0.05% NaHCO 3 for 96h. These results indicated that appropriate treatment with NaHCO 3 could improve the healthy benefits of tartary buckwheat sprouts. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Kabir, Faisal; Sultana, Mosammad Shahin; Kurnianta, Heri
2015-09-01
Grape pomace is an abundant source of underutilized winery by-products. Polyphenols were extracted from grape pomace using cellulase and gluco-amylase enzymes. 2,2-diphenyl-1-picrylhydrazyl (DPPH) and Folin-Ciocalteu's assays were used to measure antioxidant activity and total polyphenolic contents. Both cellulase, and gluco-amylase digested grape pomace showed efficient radical scavenging activity. In addition, the total polyphenolic contents of cellulase digested grape pomace showed lower concentrations were effective compared to higher concentrations, whereas gluco-amylase enzyme did not show remarkable variations. The DPPH radical scavenging activity and total polyphenolic contents were significantly higher in the cellulase digested grape pomace compared to the gluco-amylase digested and the not digested grape pomace. It is notable that enzymatic digestions were efficient for extracting polyphenols from grape pomace. The underutilized grape pomace polyphenols can be further used for food safety as a natural antioxidant.
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Kabir, Faisal; Sultana, Mosammad Shahin; Kurnianta, Heri
2015-01-01
Grape pomace is an abundant source of underutilized winery by-products. Polyphenols were extracted from grape pomace using cellulase and gluco-amylase enzymes. 2,2-diphenyl-1-picrylhydrazyl (DPPH) and Folin-Ciocalteu’s assays were used to measure antioxidant activity and total polyphenolic contents. Both cellulase, and gluco-amylase digested grape pomace showed efficient radical scavenging activity. In addition, the total polyphenolic contents of cellulase digested grape pomace showed lower concentrations were effective compared to higher concentrations, whereas gluco-amylase enzyme did not show remarkable variations. The DPPH radical scavenging activity and total polyphenolic contents were significantly higher in the cellulase digested grape pomace compared to the gluco-amylase digested and the not digested grape pomace. It is notable that enzymatic digestions were efficient for extracting polyphenols from grape pomace. The underutilized grape pomace polyphenols can be further used for food safety as a natural antioxidant. PMID:26451359
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Physicochemical characterisation and radical-scavenging activity of Cucurbitaceae seed oils.
Jorge, Neuza; da Silva, Ana Carolina; Malacrida, Cassia Roberta
2015-01-01
Oils extracted from Cucurbitaceae seeds were characterised for their fatty acid and tocopherol compositions. In addition, some physicochemical characteristics, total phenolic contents and the radical-scavenging activities were determined. Oil content amounted to 23.9% and 27.1% in melon and watermelon seeds, respectively. Physicochemical characteristics were similar to those of other edible oils and the oils showed significant antioxidant activities. Fatty acid composition showed total unsaturated fatty acid content of 85.2-83.5%, with linoleic acid being the dominant fatty acid (62.4-72.5%), followed by oleic acid (10.8-22.7%) and palmitic acid (9.2-9.8%). The oils, especially watermelon seed oil, showed high total tocopherol and phenolic contents. The γ-tocopherol was the predominant tocopherol in both oils representing 90.9 and 95.6% of the total tocopherols in melon and watermelon seed oils, respectively. The potential utilisation of melon and watermelon seed oils as a raw material for food, chemical and pharmaceutical industries appears to be favourable.
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Antioxidant activity of Caesalpinia digyna root.
Srinivasan, R; Chandrasekar, M J N; Nanjan, M J; Suresh, B
2007-09-05
The antioxidant properties of three successive extracts of Caesalpinia digyna Rottler root and the isolated compound, bergenin, were tested using standard in vitro and in vivo models. The amount of the total phenolic compounds present was also determined. The successive methanol extract of Caesalpinia digyna root (CDM) exhibited strong scavenging effect on 2,2-diphenyl-2-picryl hydrazyl (DPPH) free radical, 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulphonic acid) diammonium salt (ABTS) radical cation, hydrogen peroxide, nitric oxide, hydroxyl radical and inhibition of lipid peroxidation. The free radical scavenging effect of CDM was comparable with that of reference antioxidants. The CDM having the highest content of phenolic compounds and strong free radical scavenging effect when administered orally to male albino rats at 100, 200 and 400mg/kg body weight for 7 days, prior to carbontetrachloride (CCl(4)) treatment, caused a significant increase in the levels of catalase (CAT) and superoxide dismutase (SOD) and significant decrease in the levels of lipidperoxidation (LPO) in serum, liver and kidney in a dose dependent manner, when compared to CCl(4) treated control. These results clearly indicate the strong antioxidant property of Caesalpinia digyna root. The study provides a proof for the ethnomedical claims and reported biological activities. The plant has, therefore, very good therapeutic potential.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Jin, Bing; Clouthier, Dennis J., E-mail: dclaser@uky.edu; Sheridan, Phillip M.
2015-03-28
In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X{sub 2}BY (X = H, halogen, Y = O, S) free radicals have been predicted using high level ab initio theory. The theoretical results have been used to calculate the electronic absorption and single vibronic level (SVL) emission spectra of the radicals under typical jet-cooled conditions. Using these diagnostic predictions, the previously unknown F{sub 2}BS and Cl{sub 2}BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF{sub 3}more » or BCl{sub 3} and CS{sub 2} vapor to an electric discharge at the exit of a pulsed molecular beam valve. The B{sup ~2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} laser-induced fluorescence spectra were found within 150 cm{sup −1} of their theoretically predicted positions with vibronic structure consistent with our Franck-Condon simulations. The B{sup ~2}A{sub 1} state emits down to the ground state and to the low-lying A{sup ~2}B{sub 1} excited state and the correspondence between the observed and theoretically derived SVL emission Franck-Condon profiles was used to positively identify the radicals and make assignments. Excited state Coriolis coupling effects complicate the emission spectra of both radicals. In addition, a forbidden component of the electronically allowed B{sup ~}–X{sup ~} band system of Cl{sub 2}BS is evident, as signaled by the activity in the b{sub 2} modes in the spectrum. Symmetry arguments indicate that this component gains intensity due to a vibronic interaction of the B{sup ~2}A{sub 1} state with a nearby electronic state of {sup 2}B{sub 2} symmetry.« less
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Chen, Chu; Xu, Xue-Min; Chen, Yang; Yu, Meng-Yao; Wen, Fei-Yan; Zhang, Hao
2013-12-01
A novel acylated flavonol glycoside: isorhamnetin (3-O-[(6-O-E-sinapoyl)-β-D-glucopyranosyl-(1→2)]-β-D-glucopyranosyl-7-O-α-L-rhamnopyranoside) (1), together with two known acylated flavonol glycosides: quercetin (3-O-[(6-O-E-sinapoyl)-β-D-glucopyranosyl-(1→2)]-β-D-glucopyranosyl-7-O-α-L-rhamnopyranoside) (2) and kaempferol (3-O-[(6-O-E-sinapoyl)-β-D-glucopyranosyl-(1→2)]-β-D-glucopyranosyl-7-O-α-L-rhamnopyranoside) (3) were isolated from the n-butanol fraction of sea buckthorn (Hippophae rhamnoides ssp. sinensis) berries for the first time by chromatographic methods, and their structures were elucidated using UV, MS, (1)H and (13)C NMR, and 2D NMR. Compounds 1-3 showed good scavenging activities, with respective IC50 values of 8.91, 4.26 and 30.90 μM toward the 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical; respective Trolox equivalent antioxidant capacities of 2.89, 4.04 and 2.44 μM μM(-1) toward 2,2'-azino-bis-3-ethyl-benzothiazoline-6-sulphonate (ABTS) radical. The quantitative analysis of the isolated acylated flavonol glycosides was performed by HPLC-DAD method. The contents of compounds 1-3 were in the range of 12.2-31.4, 4.0-25.3, 7.5-59.7 mg/100 g dried berries and 9.1-34.5, 75.1-182.1, 29.2-113.4 mg/100 g dried leaves, respectively. Copyright © 2013. Published by Elsevier Ltd.
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Videolaparoscopic radical hysterectomy approach: a ten-year experience.
Campos, Luciana Silveira; Limberger, Leo Francisco; Kalil, Antonio Nocchi; de Vargas, Gabriel Sebastião; Damiani, Paulo Agostinho; Haas, Fernanda Feltrin
2009-01-01
Because of the advancements in surgical techniques and laparoscopic instruments, total laparoscopic radical hysterectomy can now be performed for the treatment of uterine cervical carcinoma. We assessed the feasibility, complications, and survival rates of patients who underwent total laparoscopic radical hysterectomy with pelvic lymphadenectomy. We retrospectively collected data from the medical charts of 29 patients who had undergone surgery between 1998 and 2008. The following data were assessed: age, staging, histological type, number of lymph nodes retrieved, parametrial measures, operative time, length of hospital stay, surgical complications, and disease-free time. The mean patient age was 37.07+/-10.45 years. Forty percent of the patients had previously undergone abdominal or pelvic surgeries. Mean operative time was 228.96+/-60.41 minutes, and mean retrieved lymph nodes was 16.9+/-8.12. All patients had free margins. No conversions to laparotomy were necessary. Median time until hospital dismissal was 6.5 days (range 3-38 days). Four patients had intraoperative complications: 2 lacerations of the rectum, 1 laceration of the bladder, and 1 lesion of the ureter. Three patients developed bladder or ureteral fistulas postoperatively that were successfully corrected surgically. Laparoscopic radical hysterectomy is feasible and has acceptable complications. The radicalism of the surgery must be considered, bearing in mind the parametrial measures and the number of lymph nodes retrieved.
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Antioxidative Activity of Colostrum and Human Milk: Effects of Pasteurization and Storage.
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.
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Ali, Nasser A. Awadh; Chhetri, Bhuwan K.; Dosoky, Noura S.; Shari, Khola; Al-Fahad, Ahmed J. A.; Wessjohann, Ludger; Setzer, William N.
2017-01-01
Background: Ocimum forskolei and Teucrium yemense (Lamiaceae) are used in traditional medicine in Yemen. Methods: The chemical composition, antimicrobial, antioxidant and cytotoxic activities of the essential oils isolated from the leaves of Ocimum forskolei Benth. (EOOF) and two different populations of Teucrium yemense Deflers., one collected from Dhamar province (EOTY-d), and another collected from Taiz (EOTY-t) were investigated. The antimicrobial activities of the oils were evaluated against several microorganisms with the disc diffusion test or the broth microdilution test. The essential oils were screened for in-vitro cytotoxic activity against human tumor cells. EOOF and EOTY-d were screened for free-radical-inhibitory activity using the DPPH radical scavenging assay. Results: Sixty-four compounds were identified in (EOOF) representing 100% of the oil content with endo-fenchol (31.1%), fenchone (12.2%), τ-cadinol (12.2%), and methyl (E)-cinnamate (5.1%) as the major compounds. In EOTY-d, 67 compounds were identified, which made up 91% of the total oil. The most abundant constituents were (E)-caryophyllene (11.2%), α-humulene (4.0.%), γ-selinene (5.5%), 7-epi-α-selinene (20.1%), and caryophyllene oxide (20.1%), while the major compounds in EOTY-t were α-pinene (6.6%), (E)-caryophyllene (19.1%) α-humulene (6.4%), δ-cadinene (6.5%), caryophyllene oxide (4.3%), α-cadinol (9.5%), and shyobunol (4.6%). The most sensitive microorganisms for EOOF were B. subtilis, S. aureus, and C. albicans with inhibition zones of 34, 16, and 24 mm and MIC values of, 4.3 mg/mL, 4.3 mg/mL, and 8.6 mg/mL, respectively. EOTY-t showed antimicrobial activity against S. aureus, B. cereus, A. niger, and B. cinerea with MIC values of 0.156, 0.156, 0.313 and 0.313 mg/mL, respectively. Neither essential oil showed remarkable radical inhibition (IC50 = 31.55 and 31.41 μL/mL). EOTY-d was active against HT-29 human colorectal adenocarcinoma cell lines with IC50 = 43.7 μg/mL. Consistent with this, EOTY-t was active against both MCF-7 and MDA-MB-231 human breast adenocarcinoma cells. Conclusions: The antimicrobial activity of Ocimum forskolei essential oil against B. subtilis and C. albicans is consistent with its traditional use in Yemeni traditional medicine to treat skin infections. Both O. forskolei and T. yemense show wide variations in their respective essential oil compositions; there remains a need to investigate both species botanically, genetically, and phytochemically more comprehensively. PMID:28930232
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NASA Astrophysics Data System (ADS)
Bennett, Chris J.; Ennis, Courtney P.; Kaiser, Ralf I.
2014-02-01
The formation of water (H2O) in the interstellar medium is intrinsically linked to grain-surface chemistry; thought to involve reactions between atomic (or molecular) hydrogen with atomic oxygen (O), molecular oxygen (O2), and ozone (O3). Laboratory precedent suggests that H2O is produced efficiently when O2 ices are exposed to H atoms (~100 K). This leads to the sequential generation of the hydroxyperoxyl radical (HO2), then hydrogen peroxide (H2O2), and finally H2O and a hydroxyl radical (OH); despite a barrier of ~2300 K for the last step. Recent detection of the four involved species toward ρ Oph A supports this general scenario; however, the precise formation mechanism remains undetermined. Here, solid O2 ice held at 12 K is exposed to a monoenergetic beam of 5 keV D+ ions. Products formed during the irradiation period are monitored through FTIR spectroscopy. O3 is observed through seven archetypal absorptions. Three additional bands found at 2583, 2707, and 1195 cm -1 correspond to matrix isolated DO2 (ν1) and D2O2 (ν1, ν5), and D2O (ν2), respectively. During subsequent warming, the O2 ice sublimates, revealing a broad band at 2472 cm-1 characteristic of amorphous D2O (ν1, ν3). Sublimating D2, D2O, D2O2, and O3 products were confirmed through their subsequent detection via quadrupole mass spectrometry. Reaction schemes based on both thermally accessible and suprathermally induced chemistries were developed to fit the observed temporal profiles are used to elucidate possible reaction pathways for the formation of D2-water. Several alternative schemes to the hydrogenation pathway (O2→HO2→H2O2→H2O) were identified; their astrophysical implications are briefly discussed.
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In vitro antioxidant potential of selected aphrodisiac medicinal plants.
Riaz, M; Shahid, M; Jamil, A; Saqib, M
2017-01-01
The present study aimed to evaluate the antioxidant activity of six selected aphrodisiac medicinal plants. Useful parts of the selected medicinal plants were collected and extracted in methanolic solvent. The antioxidant activity of selected plant extract was determined through different antioxidant assays, namely DPPH radical scavenging assay and ferric reducing antioxidant assay. Moreover, antioxidant compounds, like total phenolics and total flavonoids contents, were also determined. Results showed that Mucuna pruriens seed extract displayed high contents of phenolic compounds with total phenolic content of 683.15±4.28 mg GAE/g dry plant material while the least phenolic content was observed in Asparagus racemosus (195.5±3.02 mg GAE/g dry plant material). Highest total flavonoids content was found in Anacyclus pyrethrum roots (156.58±4.01 μg CE/g) and the least content was found in Asparagus racemosus roots. Among the studied plant extracts, the highest radical scavenging activity was shown by Mucuna pruriens seed extract (82.05±0.55%) and the least percent scavenging activity was observed in Tribulus terrestris extract (36.40±2.01%). Vitamin C was used as positive control for antioxidant assays showing 93.54±0.9% radical scavenging activity. The plant extract also exhibited a strong reducing potential against free radicals. Therefore, the present study concluded that all the studied medicinal plants possess varying concentrations of secondary active metabolites responsible for the antioxidant properties of the tested plant extracts.
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NASA Technical Reports Server (NTRS)
Anderson, James G.
1996-01-01
A summary of the first order scientific conclusions that emerged from the research done under this grant are as follows: (1) For the first time, the concentration of the key hydrogen and halogen radicals OH, H02, ClO and BrO were determined on a global scale extending from the arctic circle to the antarctic circle, over the altitude domain of the ER-2. That domain extends from 15-20 km altitude, covering a critical part of the lower stratosphere; (2) Simultaneous, in situ measurements of the concentrations of OH, H02, ClO, BrO, NO and NO2 demonstrate the predominance of odd-hydrogen and halogen free radical catalysis in determining the rate of removal of ozone in the lower stratosphere over the complete ASHOE mission. This extends to the global scale the "first look" data obtained during the NASA Stratospheric Photochemistry and Dynamics Experiment (SPADE), executed out of Ames Research Center in June 1993. This represents a major rearrangement of our understanding with respect to the hierarchy of dominant catalytic cycles controlling ozone loss in the lower stratosphere. For the past twenty years, it has been assumed that nitrogen radicals dominate the destruction rate of ozone in the lower stratosphere; (3) Throughout the altitude and latitude range covered by ASHOE, it was determined that a single catalytic cycle, HO2 + O3 yields OH + 2O2, accounted for one half of the total O3 removal in this region of the atmosphere. Halogen radical catalytic cycles were found to account for one third of the ozone loss, and nitrogen radicals were found to account for 20% of the loss; (4) Simultaneous observations of the full complement of radicals, tracers, ozone, and water vapor during ASHOE demonstrated quantitatively the coupling that exists between the rate limiting radicals and other reactive species in the photochemical reaction network. Specifically, the concentrations of ClO and HO2 are inversely correlated with the concentration of NOx. This carries the implication that the NOx effluent from the proposed High Speed Civil Transport may be less destructive to stratospheric ozone than had previously been thought. ASHOE brought this conclusion forward for the first time on a global basis; and (5) The density of BrO was measured on a global scale during ASHOE in the lower stratosphere. It was found that bromine is responsible for 55-65% of the local rate of catalytic destruction of ozone by reactions involving bromine and chlorine. Normalizing calculated loss rates to total available inorganic bromine and chlorine explicitly demonstrates that bromine is 60-80 times more efficient than chlorine in removing ozone in the lower stratosphere. An inferred value of total inorganic bromine is in excellent agreement with measurements of their source species, organic bromine compounds in the troposphere.
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Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies
Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun
2016-01-01
Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions. PMID:27405843
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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
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Fan, Zhi-Feng; Jiang, Shan; Xu, Shi-Zheng; Lei, Tie-Chi
2016-01-01
Safe and effective ingredients capable of removing undesired hyperpigmentation from facial skin are urgently needed for both pharmaceutical and cosmetic purposes. Deoxyarbutin (4-[(tetrahydro-2H-pyran-2-yl) oxy] phenol, D-Arb) is a glucoside derivative of hydroquinone. Here, we investigated the toxicity and efficacy of D-Arb at the sub-cellular level (directly on melanosomes) and skin pigmentation using in vivo and in vitro models to compare with its parent compound hydroquinone (1,4-benzenediol, HQ). At first, we examined the ultrastructural changes of melanosomes in hyperpigmented guinea pig skin induced by 308-nm monochromatic excimer lightand/or treated with HQ and D-Arb using transmission electron microscopy. The results showed that prominent changes in the melanosomal membrane, such as bulb-like structure and even complete rupture of the outer membranes, were found in the skin after topical application of 5% HQ for 10 days. These changes were barely observed in the skin treated with D-Arb. To further clarify whether membrane toxicity of HQ was a direct result of the compound treatment, we also examinedultrastructural changes of individual melanosomes purified from MNT1 human melanoma cells. Similar observations were obtained from the naked melanosome model in vitro. Finally, we determined the effects of melanosomal fractions exposed to HQ or D-Arb on hydroxyl radical generation in the Fenton reaction utilizing an electron spin resonance assay. D-Arb-treated melanosomesexhibit a moderate hydroxyl radical-scavenging activity, whereas HQ-treated melanosomessignificantly generate more hydroxyl free radicals. This study suggests that D-Arb possesses a potent ability in skin lightening and antioxidation with less melanosome cytotoxicity. PMID:27776184
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Rokhlenko, Yekaterina; Geacintov, Nicholas E; Shafirovich, Vladimir
2012-03-14
The exposure of guanine in the oligonucleotide 5'-d(TCGCT) to one-electron oxidants leads initially to the formation of the guanine radical cation G(•+), its deptotonation product G(-H)(•), and, ultimately, various two- and four-electron oxidation products via pathways that depend on the oxidants and reaction conditions. We utilized single or successive multiple laser pulses (308 nm, 1 Hz rate) to generate the oxidants CO(3)(•-) and SO(4)(•-) (via the photolysis of S(2)O(8)(2-) in aqueous solutions in the presence and absence of bicarbonate, respectively) at concentrations/pulse that were ∼20-fold lower than the concentration of 5'-d(TCGCT). Time-resolved absorption spectroscopy measurements following single-pulse excitation show that the G(•+) radical (pK(a) = 3.9) can be observed only at low pH and is hydrated within 3 ms at pH 2.5, thus forming the two-electron oxidation product 8-oxo-7,8-dihydroguanosine (8-oxoG). At neutral pH, and single pulse excitation, the principal reactive intermediate is G(-H)(•), which, at best, reacts only slowly with H(2)O and lives for ∼70 ms in the absence of oxidants/other radicals to form base sequence-dependent intrastrand cross-links via the nucleophilic addition of N3-thymidine to C8-guanine (5'-G*CT* and 5'-T*CG*). Alternatively, G(-H)(•) can be oxidized further by reaction with CO(3)(•-), generating the two-electron oxidation products 8-oxoG (C8 addition) and 5-carboxamido-5-formamido-2-iminohydantoin (2Ih, by C5 addition). The four-electron oxidation products, guanidinohydantoin (Gh) and spiroiminodihydantoin (Sp), appear only after a second (or more) laser pulse. The levels of all products, except 8-oxoG, which remains at a low constant value, increase with the number of laser pulses.
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Lin, Kun-Yi Andrew; Lai, Hong-Kai; Tong, Shaoping
2018-03-15
Two-dimensional (2D) planar cobalt-containing materials are promising catalysts for activating peroxymonosulfate (PMS) to degrade contaminants because 2D sheet-like morphology provides large reactive surfaces. However, preparation of these sheet-supported cobaltic materials typically involves multiple steps and complex reagents, making them less practical for PMS activation. In this study, a cobalt-based nanosheet (CoNS) is particularly developed using a one-step hydrothermal process with a single reagent in water. The resulting CoNS can exhibit a thickness as thin as a few nanometers and 2-D morphology. CoNS is also primarily comprised of cobalt species in a coordinated form of Prussian Blue analogue, which consists of both Co 3+ and Co 2+ . These features make CoNS promising for activating PMS in aqueous systems. As degradation of an emerging contaminant, caffeine, is selected as a representative reaction, CoNS not only successfully activates PMS to fully degrade caffeine in 20 min but also exhibits a much higher catalytic activity than the most common PMS activator, Co 3 O 4 . Via studying inhibitive effects of radical scavengers, caffeine degradation by CoNS-activated PMS is primarily attributed to sulfate radicals and hydroxyl radicals to a lesser extent. The degradation products of caffeine by CoNS-activated PMS are also identified and a potential degradation pathway is proposed. Moreover, CoNS could be also re-used to activate PMS for caffeine degradation without activity loss. These results indicate that CoNS is a conveniently prepared and highly effective and stable 2-D catalyst for aqueous chemical oxidation reactions. Copyright © 2017. Published by Elsevier Inc.
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Formaldehyde Production from Isoprene Oxidation Across NOx Regimes
NASA Technical Reports Server (NTRS)
Wolfe, G. M.; Kaiser, J.; Hanisco, T. F.; Keutsch, F. N.; de Gouw, J. A.; Gilman, J. B.; Graus, M.; Hatch, C. D.; Holloway, J.; Horowitz, L. W.;
2015-01-01
The chemical link between isoprene and formaldehyde (HCHO) is a strong, non-linear function of NOx (= 27 NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the Southeast U.S., we quantify HCHO production across the urban-rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly-emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1 - 2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9), while background HCHO increases by more than a factor of 2 (from 1.5 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D chemical box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models under-estimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or under-estimated hydroxyl radical concentrations. Moreover, we find that the total organic peroxy radical production rate is essentially independent of NOx, as the increase in oxidizing capacity with NOx is largely balanced by a decrease in VOC reactivity. Thus, the observed NOx dependence of HCHO mainly reflects the changing fate of organic peroxy radicals.
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NASA Astrophysics Data System (ADS)
Whalley, Lisa; Stone, Daniel; Sharp, Thomas; Garraway, Shani; Bannan, Thomas; Percival, Carl; Hopkins, James; Holmes, Rachel; Hamilton, Jacqui; Lee, James; Laufs, Sebastian; Kleffmann, Jörg; Heard, Dwayne
2014-05-01
With greater than 50 % of the global population residing in urban conurbations, poor urban air quality has a demonstrable effect on human health. OH and HO2 radicals, (collectively termed HOx) together with RO2 radicals, mediate virtually all of the oxidative chemistry in the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3 and particulates. Here we present measurements of OH, HO2, partially speciated RO2 (distinguishing smaller alkane related RO2 from larger alkane/alkene/aromatic related RO2), ClNO2 and OH reactivity measurements taken during the ClearfLo campaign in central London in the summer of 2012. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2 tested our ability to reproduce radical levels, and enabled detailed radical budgets to be determined, highlighting for example the important role of the photolysis of nitrous acid (HONO) and carbonyl species as radical sources. Speciation of RO2 enabled the break-down of ozone production from different classes of VOCs to be calculated directly and compared with model calculations. Summertime observations of radicals have helped to identify that increases in photolytic sources of radicals on warm, sunny days can significantly increase local ozone concentrations leading to exceedances of EU air quality recommendations of 60 ppbV. The photolytic breakdown of ClNO2 to Cl atoms can more than double radical concentrations in the early morning; although the integrated increase in radical concentrations over a 24 hr period in model runs when ClNO2 photolysis is included is more modest. On average we calculate just under a 1 ppb increase in ozone due to the presence of ClNO2 in London air. OH reactivity was found to be greatest during morning and evening rush hours. Good agreement between the modelled OH reactivity and observations could be achieved when reactivity associated with model generated photo-oxidation products was considered in addition to the measured primary OH reactants. Carbonyl species such as formaldehyde, acetaldehyde and acetone have been identified as the VOC class dominating organic OH reactivity. As such, together with the direct radical source contribution by photolysis, these species dominate local ozone production in London. Modelling studies comparing the observed carbonyl concentrations with model predictions suggest that over 50% of the total concentration may be directly emitted and, hence, London's in-situ chemistry may be considered to contribute significantly to the ozone levels observed.
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Wang, Jing; Zheng, Meizhu; Chen, Lina; Liu, Zhiqiang; Zhang, Yuchi; Liu, Chun-Ming; Liu, Shu
2016-11-01
Hydroxyl radicals are the most reactive free radical of human body, a strong contributor to tissue damage. In this study, liquid chromatography coupled to electrospray ionization mass spectrometry was applied to screen and identify hydroxyl radical scavengers from the total flavonoids of Ginkgo biloba leaves, and high-performance counter current chromatography was used to separate and isolate the active compounds. Furthermore, molecular devices were used to determine hydroxyl radical scavenging activities of the obtained hydroxyl radical scavengers and other flavonoids from G. biloba leaves. As a result, six compounds were screened as hydroxyl radical scavengers, but only three flavonoids, namely, rutin, cosmos glycosides and apigenin-7-O-Glu-4'-O-Rha, were isolated successfully from total flavonoids by high-performance counter current chromatography. The purities of the three obtained compounds were over 90%, respectively, as determined by liquid chromatography. Molecular devices with 96-well microplates evaluation indicated that the 50% scavenging concentration values of screened compounds were lower than that of other flavonoids, they performed greater hydroxyl radical scavenging activity, and the evaluation effects were consistent with the liquid chromatography with mass spectrometry screening results. Therefore, chromatography combined with molecular devices is a feasible and an efficient method for systematic screening, identification, isolation, and evaluation of bioactive components in mixture of botanical medicines. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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German-Báez, L J; Valdez-Flores, M A; Félix-Medina, J V; Norzagaray-Valenzuela, C D; Santos-Ballardo, D U; Reyes-Moreno, C; Shelton, L M; Valdez-Ortiz, A
2017-12-01
The production of photosynthetic biofuels using microalgae is a promising strategy to combat the use of non-renewable energy sources. The microalgae residual biomass is a waste by-product of biofuel production; however, it could prove to have utility in the development of sustainable nutraceuticals and functional foods. In this study, a comprehensive characterisation of the under-utilised Phaeodactylum tricornutum microalgae residual biomass is presented. Proximal composition, antioxidant capacity (using three different antioxidant assays; oxygen radical absorbance capacity; radical cation activity, ABTS; and radical scavenging activity, DPPH), and total phenolic content of free and bound polyphenols were determined. Additionally, the physicochemical properties of water activity, pH, water absorption index, water solubility index, and dispersibility were evaluated. Results revealed that P. tricornutum microalgae residual biomass exhibits a relatively high protein and carbohydrate content, with values of 36.67% and 46.78%, respectively; and most carbohydrates were found as total dietary fibre (45.57%), of which insoluble dietary fibre was the most predominant (43.54%). Antioxidant capacity values for total phytochemicals of 106.22, 67.93, 9.54 µM TE g -1 dw were determined by oxygen radical absorbance capacity, ABTS, and DPPH assays, respectively. Total phenolic content was found to be 2.90 mg GAE g -1 dw. Interestingly, antioxidant capacity and total phenolic content were higher in bound than in free phytochemical extracts. The physicochemical analysis showed P. tricornutum microalgae residual biomass to have suitable properties for the generation of a beverage with Aw, pH, water absorption index, water solubility index, and dispersibility values of 0.45, 7.12, 3.40 g gel g -1 dw, 2.5 g solids 100 g -1 dw, and 90%, respectively. Hence, P. tricornutum microalgae residual biomass could be considered a potential source of bioactive compounds suitable for the production of functional food exhibiting antioxidant capacity and high dietary fibre content.
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Balucani, Nadia; Casavecchia, Piergiorgio
2006-12-01
We have investigated gas-phase reactions of N((2)D) with the most abundant hydrocarbons in the atmosphere of Titan by the crossed molecular beam technique. In all cases, molecular products containing a novel CN bond are formed, thus suggesting possible routes of formation of gas-phase nitriles in the atmosphere of Titan and primordial Earth. The same approach has been recently extended to the study of radical-radical reactions, such as the reaction of atomic oxygen with the CH(3) and C(3)H(5) radicals. Products other than those already considered in the modeling of planetary atmospheres and interstellar medium have been identified.
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Roques, Nans; Maspoch, Daniel; Wurst, Klaus; Ruiz-Molina, Daniel; Rovira, Concepció; Veciana, Jaume
2006-12-13
The synthesis of a three-dimensional, six-connecting, organic building block based on a robust, rigid, and open-shell polychlorotriphenylmethyl (PTM) unit (radical 1) is reported, and its self-assembly properties are described in detail. The tendencies of this highly polar molecule and its hydrogenated precursor, compound 4, to form hydrogen bonds with oxygenated solvents ([1THF(6)] and [4THF(6)]) were reduced by replacing THF with diethyl ether in the crystallization process to yield two-dimensional (2D) hydrogen-bonded structures ([1(Et(2)O)(3)] and [4(Et(2)O)(3)]). The presence of direct hydrogen bonds between the radicals in the latter phase of 1 gives rise to very weak ferromagnetic intermolecular interactions at low temperatures, whereas when the radicals are isolated by THF molecules these interactions are antiferromagnetic and very weak. The role played by the carboxylic groups not only in the self-assembly properties but also in the transmission of the magnetic interactions has been illustrated by determination of the crystal structure and measurement of the magnetic properties of the corresponding hexaester radical 6, in which the close packing of molecular units gives rise to weak antiferromagnetic intermolecular interactions. Attempts to avoid solvation of the molecules in the solid state and to increase the structural and magnetic dimensionality were pursued by recrystallization of both compounds 1 and 4 from concentrated nitric acid, affording two three-dimensional (3D) robust hydrogen-bonded structures. While the structure obtained with compound 4 is characterized by the presence of polar channels and boxes containing water guest molecules along the c axis, radical 1 was oxidized to the corresponding fuchsone 10, which presented a completely different close-packed, guest-free structure.
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Adam, Waldemar; Roschmann, Konrad J; Saha-Möller, Chantu R; Seebach, Dieter
2002-05-08
cis-Stilbene (1) has been epoxidized by a set of diverse oxygen donors [OxD], catalyzed by the Mn(III)(salen)X complexes 3 (X = Cl, PF(6)), to afford a mixture of cis- and trans-epoxides 2. The cis/trans ratios range from 29:71 (extensive isomerization) to 92:8, which depends both on the oxygen source [OxD] and on the counterion X of the catalyst. When (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)-benzene (4) is used as substrate, a mechanistic probe which differentiates between radical and cationic intermediates, no cationic ring-opening products are found in this epoxidation reaction; thus, isomerized epoxide product arises from intermediary radicals. The dependence of the diastereoselectivity on the oxygen source is rationalized in terms of a bifurcation step in the catalytic cycle, in which concerted Lewis-acid-activated oxygen transfer competes with stepwise epoxidation by the established Mn(V)(oxo) species. The experimental counterion effect is attributed to the computationally assessed ligand-dependent reaction profiles and stereoselectivities of the singlet, triplet, and quintet spin states available to the manganese species.
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Ogusucu, Renata; Rettori, Daniel; Netto, Luis E S; Augusto, Ohara
2009-02-27
Peroxiredoxins are receiving increasing attention as defenders against oxidative damage and sensors of hydrogen peroxide-mediated signaling events. In the yeast Saccharomyces cerevisiae, deletion of one or more isoforms of the peroxiredoxins is not lethal but compromises genome stability by mechanisms that remain under scrutiny. Here, we show that cytosolic peroxiredoxin-null cells (tsa1Deltatsa2Delta) are more resistant to hydrogen peroxide than wild-type (WT) cells and consume it faster under fermentative conditions. Also, tsa1Deltatsa2Delta cells produced higher yields of the 1-hydroxyethyl radical from oxidation of the glucose metabolite ethanol, as proved by spin-trapping experiments. A major role for Fenton chemistry in radical formation was excluded by comparing WT and tsa1Deltatsa2Delta cells with respect to their levels of total and chelatable metal ions and of radical produced in the presence of chelators. The main route for 1-hydroxyethyl radical formation was ascribed to the peroxidase activity of Cu,Zn-superoxide dismutase (Sod1), whose expression and activity increased approximately 5- and 2-fold, respectively, in tsa1Deltatsa2Delta compared with WT cells. Accordingly, overexpression of human Sod1 in WT yeasts led to increased 1-hydroxyethyl radical production. Relevantly, tsa1Deltatsa2Delta cells challenged with hydrogen peroxide contained higher levels of DNA-derived radicals and adducts as monitored by immuno-spin trapping and incorporation of (14)C from glucose into DNA, respectively. The results indicate that part of hydrogen peroxide consumption by tsa1Deltatsa2Delta cells is mediated by induced Sod1, which oxidizes ethanol to the 1-hydroxyethyl radical, which, in turn, leads to increased DNA damage. Overall, our studies provide a pathway to account for the hypermutability of peroxiredoxin-null strains.
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Zeng, QingMin; Lei, Fuming; Gao, ZhaoYa; Wang, YanZhao; Gao, Qing Kun
2017-09-22
The purpose of this study is to compare and evaluate the security and efficacy of 3D vs 2D laparoscopy in rectal cancer treatment. Forty-six patients who suffered from rectal cancer and went on laparoscopic radical resection of rectal carcinoma in Peking University Shougang Hospital from Feb. 2015 to Mar. 2016 were included in the study. They were randomly divided into two groups. The 23 patients operated with the 3D system were compared with 23 patients operated with the 2D system by perioperative data. There were no significant differences in age, sex, pathological type, tumor differentiation, TNM staging, and surgical procedures (P > 0.05). The average operating time of 3D laparoscopic surgery group (172.2 ± 27.5 min) was shorter than that of 2D group (192.6 ± 22.3) (P < 0.05); the rate of transfer to laparotomy is lower in 2D group (72.7%) than in 3D group (86.4%), but they have no significant difference; and the intraoperative blood loss (247.0 ± 173.6 ml vs 282.6 ± 195.6 ml), postoperative passage of flatus (2.8 ± 0.8 days vs 3.1 ± 1.0 days), and indwelling catheter time (5.6 ± 1.9 days vs 6.3 ± 2.0 days) in 3D group and 2D group (P > 0.05) were not significantly different. There were no differences in other complications between the two groups. No significantly different recrudescence and death rates were found between the two groups (P > 0.05). The 3D laparoscopy shortens the operation time of rectum cancer. 3D laparoscopic surgery is more efficient in treatment of rectal cancer than 2D laparoscopy and is worth of being generalized.
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The Reaction Mechanism and Kinetics for the Reaction of OH Radicals with Atmospheric Metolachlor
NASA Astrophysics Data System (ADS)
Chen, Chao; Zhou, Qin; Zheng, Jian; Jin, Xinhui; Ma, Wanyong; Zhou, Jianhua
2018-07-01
Metolachlor [2-chloro- N-(2-ethyl-6-methylphenyl)- N-(2-methoxy-1-methylethyl)acetamide], has been used as a chloroacetanilide herbicide to control annual grass weeds and broadleaf weeds in corn, cotton, peanuts, soybeans and beans. In this paper, aRS-metolachlor has been used as a model to investigate the reaction of OH radicals with atmospheric metolachlor. The reaction mechanism was obtained at the MPWB1K/6-311 + g(3 df,2 p)//MPWB1K/6-31 + g( d, p) level of theory and the rate constants were deduced over the temperature range of 180-370 K using canonical variational transition state (CVT) theory with the small curvature tunneling (SCT) method. The atmospheric lifetime of aRS-metolachlor determined by OH radicals is about 3.97 h, which indicates that it can be degradaded in the gas phase easily and doesn't have the potential for long-range transport.
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Zuo, Ai-Ren; Yu, Yan-Ying; Shu, Qing-Long; Zheng, Li-Xiang; Wang, Xiao-Min; Peng, Shu-Hong; Xie, Yan-Fei; Cao, Shu-Wen
2014-06-01
Acute liver damage is primarily induced by one of several causes, among them viral exposure, alcohol consumption, and drug and immune system issues. Agents with the ability to inhibit tyrosinase and protect against DNA damage caused by reactive oxygen species (ROS) may be therapeutically useful for the prevention or treatment of ROS-related diseases. This investigation examined the hepatoprotective effects of phloretin and phloretin isonicotinyl hydrazone (PIH) on d-galactosamine (D-GalN)-induced acute liver damage in Kunming mice, as well as the possible mechanisms. The serum levels of alanine aminotransferase (ALT), aspartate aminotransferase (AST), γ-glutamyl transferase (γ-GT), alkaline phosphatase (ALP), and total bilirubin (TB) as well as the histopathological changes in mouse liver sections were determined. The antioxidant effects of phloretin, quercetin, and PIH on lipid peroxidation in rat liver mitochondria in vitro, 1,1-diphenyl-2-picrylhydrazyl (DPPH) or 2,2-azino-bis-(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) free radical scavenging activity in vitro, and supercoiled pBR322 plasmid DNA were confirmed. The experiment also examined the antityrosinase activity, inhibition type, and inhibition constant of phloretin and PIH. Phloretin, quercetin, or PIH significantly prevented the increase in serum ALT, AST, γ-GT, ALP, and TB in acute liver damage induced by D-GalN, and produced a marked reduction in the histopathological hepatic lesions. Phloretin, quercetin, or PIH also exhibited antioxidant effects on lipid peroxidation in rat liver mitochondria in vitro, DPPH or ABTS free radical scavenging activity in vitro, and supercoiled pBR322 plasmid DNA. Phloretin, quercetin, or PIH also exhibited good antityrosinase activity. To the best of our knowledge, this was the first study of the hepatoprotective effects of phloretin and PIH on D-GalN-induced acute liver damage in Kunming mice as well as the possible mechanisms. This was also the first study of the lipid peroxidation inhibition activity of phloretin and PIH in liver mitochondria induced by the Fe(2+)/vitamin C (Vc) system in vitro, the protective effects on supercoiled pBR322 plasmid DNA, and the antityrosinase activity of phloretin and PIH. Copyright © 2014. Published by Elsevier B.V.
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Exercise-induced brachial artery vasodilation: role of free radicals.
Richardson, Russell S; Donato, Anthony J; Uberoi, Abhimanyu; Wray, D Walter; Lawrenson, Lesley; Nishiyama, Steven; Bailey, Damian M
2007-03-01
Originally thought of as simply damaging or toxic "accidents" of in vivo chemistry, free radicals are becoming increasingly recognized as redox signaling molecules implicit in cellular homeostasis. Indeed, at the vascular level, it is plausible that oxidative stress plays a regulatory role in normal vascular function. Using electron paramagnetic resonance (EPR) spectroscopy, we sought to document the ability of an oral antioxidant cocktail (vitamins C, E, and alpha-lipoic acid) to reduce circulating free radicals, and we employed Doppler ultrasound to examine the consequence of an antioxidant-mediated reduction in oxidative stress on exercise-induced vasodilation. A total of 25 young (18-31 yr) healthy male subjects partook in these studies. EPR spectroscopy revealed a reduction in circulating free radicals following antioxidant administration at rest ( approximately 98%) and as a consequence of exercise ( approximately 85%). Plasma total antioxidant capacity and vitamin C both increased following the ingestion of the antioxidant cocktail, whereas vitamin E levels were not influenced by the ingestion of the antioxidants. Brachial artery vasodilation during submaximal forearm handgrip exercise was greater with the placebo (7.4 +/- 1.8%) than with the antioxidant cocktail (2.3 +/- 0.7%). These data document the efficacy of an oral antioxidant cocktail in reducing free radicals and suggest that, in a healthy state, the aggressive disruption of the delicate balance between pro- and antioxidant forces can negatively impact vascular function. These findings implicate an exercise-induced reliance upon pro-oxidant-stimulated vasodilation, thereby revealing an important and positive vascular role for free radicals.
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Lipid peroxidation inhibition and antiradical activities of some leaf fractions of Mangifera indica.
Badmus, Jelili A; Adedosu, Temitope O; Fatoki, John O; Adegbite, Victor A; Adaramoye, Oluwatosin A; Odunola, Oyeronke A
2011-01-01
This study was undertaken to assess in vitro lipid peroxidation inhibitions and anti-radical activities of methanolic, chloroform, ethyl acetate and water fractions of Mangifera indica leaf. Inhibition of Fe(2+)-induced lipid peroxidation (LPO) in egg, brain, and liver homogenates, 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroxyl (OH-) radical scavenging activities were evaluated. Total phenol was assessed in all fractions, and the reducing power of methanolic fraction was compared to gallic acid and ascorbic acid. The results showed that Fe2+ induced significant lipid peroxidation (LPO) in all the homogenates. Ethyl acetate fraction showed the highest percentage inhibition of LPO in both egg yolk (68.3%) and brain (66.3%), while the aqueous fraction exerted the highest inhibition in liver homogenate (89.1%) at a concentration of 10 microg/mL. These observed inhibitions of LPO by these fractions were higher than that of ascorbic acid used as a standard. The DPPH radical scavenging ability exhibited by ethyl acetate fraction was found to be the highest with IC50 value of 1.5 microg/mL. The ethyl acetate and methanolic fractions had the highest OH- radical scavenging ability with the same IC50 value of 5 microg/mL. The total phenol content of ethyl acetate fraction was the highest with 0.127 microg/mg gallic acid equivalent (GAE). The reductive potential of methanolic fraction showed a concentration-dependent increase. This study showed that inhibition of LPO and the DPPH and OH- radicals scavenging abilities of Mangifera indica leaf could be related to the presence of phenolic compounds. Therefore, the ethyl acetate fraction of the leaf may be a good source of natural antioxidative agent.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Acosta, D.; Adelman, J.; Affolder, T.
We present a new measurement of the inclusive and differential production cross sections of J/{psi} mesons and b-hadrons in proton-antiproton collisions at {radical}s = 1960 GeV. The data correspond to an integrated luminosity of 39.7 pb{sup -1} collected by the CDF Run II detector. We find the integrated cross section for inclusive J/{psi} production for all transverse momenta from 0 to 20 GeV/c in the rapidity range |y| < 0.6 to be 4.08 {+-} 0.02(stat){sub -0.33}{sup +0.36}(syst) {mu}b. We separate the fraction of J/{psi} events from the decay of the long-lived b-hadrons using the lifetime distribution in all events withmore » p{sub T} (J/{psi}) > 1.25 GeV/c. We find the total cross section for b-hadrons, including both hadrons and anti-hadrons, decaying to J/{psi} with transverse momenta greater than 1.25 GeV/c in the rapidity range |y(J/{psi})| < 0.6, is 0.330 {+-} 0.005(stat){sub -0.033}{sup +0.036}(syst) {mu}b. Using a Monte Carlo simulation of the decay kinematics of b-hadrons to all final states containing a J/{psi}, we extract the first measurement of the total single b-hadron cross section down to zero transverse momentum at {radical}s = 1960 GeV. We find the total single b-hadron cross section integrated over all transverse momenta for b-hadrons in the rapidity range |y| < 0.6 to be 17.6 {+-} 0.4(stat){sub -2.3}{sup +2.5}(syst) {mu}b.« less
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Dastmalchi, Keyvan; Wang, Isabel; Stark, Ruth E
2016-11-01
The need for safe, effective preservatives is a prominent issue in the food and drug industries, reflecting demand for natural alternatives to synthetic chemicals viewed as harmful to consumers and the environment. Thus, this study determined the identities and scavenging capacities of antioxidant metabolites produced as a response to potato tuber wounding, using activity-guided fractionation of polar extracts from a Yukon Gold cultivar that had previously exhibited exceptionally high radical-scavenging activity. Activity-guided fractionation using the ABTS(+) radical scavenging assay and LC-MS with TOF-MS for compositional analysis of the most potent antioxidant fractions yielded identification of nine constituents: coumaroylputrescine; feruloylquinic acid; isoferuloylputrescine; ferulic acid; 22,25-dimethoxy-3-[[2,3,4-tri-O-methyl-6-O-(2,3,4,6-tetra-O-methyl-β-d-glucopyranosyl)-β-d-glucopyranosyl]oxy]-(3β)-lanost-9(11)-en-24-one; 4-(2Z)-2-decen-1-yl-5-[1-(4-hydroxyphenyl)decyl]-1,2-benzenediol; 8-[(2E)-3,7-dimethyl-2,6-octadien-1-yl]-5-hydroxy-2,8-dimethyl-6-(3-methyl-2-buten-1-yl)-2H-1-benzopyran-4,7(3H,8H)-dione; 3-[(2-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy]-20-[(6-O-β-d-xylopyranosyl-β-d-glucopyranosyl)oxy]-dammar-24-en-19-al; (3β)-28-oxo-28-(phenylmethoxy)oleanan-3-yl 2-O-β-d-galactopyranosyl-3-O-(phenylmethyl)-, butyl ester β-d-glucopyranosiduronic acid. A positive correlation was observed between the scavenging activities and the polarities of the active fractions. The antioxidant capacities of the fractions were also characterised by monitoring the activity throughout a 45-minute assay period. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Dastmalchi, Keyvan; Wang, Isabel; Stark, Ruth E.
2016-01-01
The need for safe, effective preservatives is a prominent issue in the food and drug industries, reflecting demand for natural alternatives to synthetic chemicals viewed as harmful to consumers and the environment. Thus, this study determined the identities and scavenging capacities of antioxidant metabolites produced as a response to potato tuber wounding, using activity-guided fractionation of polar extracts from a Yukon Gold cultivar that had previously exhibited exceptionally high radical-scavenging activity. Activity-guided fractionation using the ABTS•+ radical scavenging assay and LC-MS with TOF-MS for compositional analysis of the most potent antioxidant fractions yielded identification of nine constituents: coumaroylputrescine; feruloylquinic acid; isoferuloylputrescine; ferulic acid; 22,25-dimethoxy-3-[[2,3,4-tri-O-methyl-6-O-(2,3,4,6-tetra-O-methyl-β-D-glucopyranosyl)-β-D-glucopyranosyl]oxy]-(3β)-lanost-9(11)-en-24-one; 4-(2Z)-2-decen-1-yl-5-[1-(4-hydroxyphenyl)decyl]-1,2-benzenediol; 8-[(2E)-3,7-dimethyl-2,6-octadien-1-yl]-5-hydroxy-2,8-dimethyl-6-(3-methyl-2-buten-1-yl)-2H-1-benzopyran-4,7(3H,8H)-dione; 3-[(2-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]-20-[(6-O-β-D-xylopyranosyl-β-D-glucopyranosyl)oxy]-dammar-24-en-19-al; (3β)-28-oxo-28-(phenylmethoxy)oleanan-3-yl 2-O-β-D-galactopyranosyl-3-O-(phenylmethyl)-, butyl ester β-D-glucopyranosiduronic acid. A positive correlation was observed between the scavenging activities and the polarities of the active fractions. The antioxidant capacities of the fractions were also characterised by monitoring the activity throughout a 45-minute assay period. PMID:27211673
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Antioxidant activity of Syzygium cumini leaf gall extracts
Eshwarappa, Ravi Shankara Birur; Iyer, Raman Shanthi; Subbaramaiah, Sundara Rajan; Richard, S Austin; Dhananjaya, Bhadrapura Lakkappa
2014-01-01
Introduction: Free radicals are implicated in several metabolic diseases and the medicinal properties of plants have been explored for their potent antioxidant activities to counteract metabolic disorders. This research highlights the chemical composition and antioxidant potential of leaf gall extracts (aqueous and methanol) of Syzygium cumini (S. cumini), which have been extensively used in traditional medications to treat various metabolic diseases. Methods: The antioxidant activities of leaf gall extracts were examined using diphenylpicrylhydrazyl (DPPH), nitric oxide scavenging, hydroxyl scavenging and ferric reducing power (FRAP) methods. Results: In all the methods, the methanolic extract showed higher antioxidant potential than the standard ascorbic acid. The presence of phenolics, flavonoids, phytosterols, terpenoids, and reducing sugars was identified in both the extracts. When compared, the methanol extract had the highest total phenolic and flavonoid contents at 474±2.2 mg of GAE/g d.w and 668±1.4 mg of QUE/g d.w, respectively. The significant high antioxidant activity can be positively correlated to the high content of total polyphenols/flavonoids of the methanol extract. Conclusion: The present study confirms the folklore use of S. cumini leaves gall extracts as a natural antioxidant and justifies its ethnobotanical use. Further, the result of antioxidant properties encourages the use of S. cumini leaf gall extracts for medicinal health, functional food and nutraceuticals applications. PMID:25035854
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Cavalleri, A; Colombo, C; Venturelli, E; Miceli, R; Mariani, L; Cornelli, U; Pala, V; Berrino, F; Secreto, G
2004-01-01
Measuring the free radical activity in serum samples from prospective studies is the best way to investigate the association between oxidative stress and human diseases. Prospective studies require the analysis of serum samples that have often been stored for a long time. Our study was designed to determine the effect of storage at -30 degrees C and -80 degrees C for two years on free radical activity. We analyzed the free radical activity by measuring circulating hydroperoxides in a pool of sera at baseline and after one day, one week, one month and 25 months of storage, using a photometric method (d-ROMs test). Measurements were performed in aliquots thawed only once at each time point and in aliquots frozen and thawed repeatedly over the study period. After two years we observed a small but statistically significant 4% decrease in the hydroperoxide concentration, which was substantially unaffected by storage temperatures and repeated freeze-thaw cycles. We also carried out the d-ROMs test in sera from ten apparently healthy volunteers at 2, 8, 24, and 48 hours after collection and storage at 4 degrees C and did not observe any significant variation. In conclusion, the d-ROMs test is a simple method suitable to evaluate the free radical activity in frozen serum samples after long-term storage.
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Hata, Kuniki; Urushibara, Ayumi; Yamashita, Shinichi; Lin, Mingzhang; Muroya, Yusa; Shikazono, Naoya; Yokoya, Akinari; Fu, Haiying; Katsumura, Yosuke
2015-01-01
Reactions of edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) with deoxyguanosine monophosphate (dGMP) hydroxyl radical adducts were investigated by pulse radiolysis technique. Edaravone was found to reduce the dGMP hydroxyl radical adducts through electron transfer reactions. The rate constants of the reactions were greater than 4 × 108 dm3 mol−1 s−1 and similar to those of the reactions of ascorbic acid, which is a representative antioxidant. Yields of single-strand breaks, base lesions, and abasic sites produced in pUC18 plasmid DNA by gamma ray irradiation in the presence of low concentrations (10–1000 μmol dm−3) of edaravone were also quantified, and the chemical repair activity of edaravone was estimated by a method recently developed by the authors. By comparing suppression efficiencies to the induction of each DNA lesion, it was found that base lesions and abasic sites were suppressed by the chemical repair activity of edaravone, although the suppression of single-strand breaks was not very effective. This phenomenon was attributed to the chemical repair activity of edaravone toward base lesions and abasic sites. However, the chemical repair activity of edaravone for base lesions was lower than that of ascorbic acid. PMID:25212600
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Peroxy radical detection by chemical amplification (PERCA)
NASA Technical Reports Server (NTRS)
Stedman, D. H.
1986-01-01
Important reactions of atmospheric free radicals are the chain oxidation of NO and CO. Thus: H2O + NO yields OH + NO2; OH + CO yields H + CO2; H + O2 + M yields HO2 + M. In most models, the need to know the free radical concentration could also be described as the need to know the rate of the above oxidation chain in the atmosphere. It is the total rate of this chain (also carried by RO2 and RO) which was measured using the PERCA. The PERCA is thus essentially a RO sub X meter. The PERCA works by adding excess CO (10%) and NO (5ppm) to a stream of air and measuring the NO2 produced after 3s of reaction time. Since other processes produce NO2, the chain reaction is modulated by switching the CO for N2. The chain length is limited by the reaction OH + NO yields HONO and is modeled to be somewhat over 1000. Measured chain lengths agree with the modeled numbers.
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Photooxidation of carbofuran by a polychromatic UV irradiation without and with hydrogen peroxide
DOE Office of Scientific and Technical Information (OSTI.GOV)
Benitez, F.J.; Beltran-Heredia, J.; Gonzalez, T.
The photodegradation of carbofuran aqueous solutions has been conducted with direct photolysis provided by a polychromatic UV radiation source and by the combination of this UV radiation with hydrogen peroxide. In both processes, the decomposition level obtained as a function of the operating variables is reported, and the presence of tert-butyl alcohol, a scavenger of free radicals, is discussed. While the contribution of hydroxyl radicals is negligible in the direct photolysis, its reactions in the UV/H{sub 2}O{sub 2} system clearly increase the carbofuran decomposition and therefore must be taken into account in the reaction rate equation for the total degradation.more » From the mechanisms proposed, the quantum yields for the direct photolysis and the kinetic constants for the reaction between carbofuran and the hydroxyl radicals generated in the H{sub 2}O{sub 2} photolysis in the combined process are respectively evaluated.« less
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The reaction of O(1 D) with H2O and the reaction of OH with C3H6
NASA Technical Reports Server (NTRS)
Simonaitis, R.; Heicklen, J.
1972-01-01
The N2O was photolyzed at 2139 A to produce O(1 D) atoms in the presence of H2O and CO. The O(1 D) atoms react with H2O to produce HO radicals, as measured by CO2 production from the reaction of OH with CO. The relative rate constant for O(1 D) removal by H2O compared to that by N2O is 2.1. In the presence of C3H6, the OH can be removed by reaction with either CO or C3H6.
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Measurements of free radicals in a megacity during the Clean Air for London Project
NASA Astrophysics Data System (ADS)
Heard, Dwayne; Whalley, Lisa; Stone, Daniel; Clancy, Noel; Lee, James; Kleffman, Jorg; Laufs, Sebastian; Bandy, Brian
2013-04-01
Free radicals control the photo-oxidative chemistry of the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3, multifunctional species and particulates. Here we present measurements of OH, HO2 and RO2 radicals and OH reactivity recorded at North Kensington, Central London, during two Intensive Operational Periods (IOPs) of the Clear Air for London (Clearflo) project in the summer and winter of 2012. OH and HO2 were measured using laser-induced fluorescence (LIF) spectroscopy at low pressure (the FAGE technique), and RO2 was measured using the recently developed ROXLIF technique, which utilises an external flow-reactor interfaced to FAGE, and which is able to discriminate between HO2 and organic peroxy radicals. Through control of reagent gases we are further able to provide a separate measurement of those RO2 species which are known to give an interference for HO2 measurements (namely alkene, aromatic and large-chain alkane derived RO2). OH reactivity was measured using laser-flash photolysis combined with FAGE. Low concentrations of radicals were observed during the winter IOP, with mixing ratios of [OH] ~ 0.04 pptv, [HO2] ~ 0.4 pptv, and [RO2] ~ 1.6 pptv at noon, all displaying a negative correlation with NO. The photolysis of O3 and subsequent reaction of O(1D) with H2O vapour was only a minor contribution to radical production in winter, with photolysis of HONO a major radical source. The summer IOP coincided with the London Olympic Games, with a number of pollution events, with ozone peaking at 100 ppbv (exceeding EU air quality directives) and elevated radical concentrations (peak [OH] ~ 0.14 pptv, [HO2] ~ 4 pptv, [RO2] ~ 6.4 pptv) being observed. The net rate of ozone production was calculated from radical observations and agreed well with measured ozone production, suggesting that advection/dilution by continental air-masses was not playing a significant role in determining ozone concentrations in London at that time. The ability to partially speciate RO2 enabled the contribution towards ozone production from different types of parent VOCs to be assessed. Steady-state analyses, using OH reactivity measurements to constrain the rate of loss of OH, gave reasonable agreement for [OH] but an additional HO2 sink was required to match [HO2]. The photolysis of HONO and carbonyl species and the decomposition of PAN were the dominant sources of radicals in London in summer.
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NASA Astrophysics Data System (ADS)
Dilek Özçelik, Nefise; Tunç, Tuncay; Çatak Çelik, Raziye; Erzengin, Mahmut; Özışık, Hacı
2017-05-01
We report in this paper the synthesis, spectroscopic, crystal structure, biological activities and theoretical results of the title compound. The crystal structure was defined by the X-ray diffraction (XRD) method. In addition, this newly synthesized hydrazone derivative was also subjected to its possible antioxidant activity with free radical scavenging ability of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals using butylated hydroxytoluene (BHT) as standard antioxidant. The structural calculations were performed by the density functional theory using the B3LYP method with 6-311++G(2d,2p) basis set. The calculated values were compared with experimental results.
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Antioxidant Activity of Three Honey Samples in relation with Their Biochemical Components
Rahaman, Norul Liza A.; Adnan, Nur Ardawati; Eddie Tan, Ti Tjih
2013-01-01
The antioxidant activities based on the free radical scavenging, reducing power, and bleaching inhibition were investigated for the three commonly used honeys in Malaysia, namely, tualang, gelam, and acacia honey. The antioxidant capacity of the honey samples was correlated with their biochemical constituents such as total phenol, total flavonoid content, and total water-soluble vitamins (vitamin B1, B2, B3, B9, B12, and vitamin C). The total flavonoid content of honey samples was strongly correlated with the three antioxidative processes (r = 0.9276–0.9910). In contrast, the total water-soluble vitamins was found to be well correlated with the free radical scavenging activity (r = 0.8226). Vitamin B3 was likely to be in the highest concentration, which covered for 69–80% of the total vitamin content. A number of five phenolic acids, three flavonoids, and two organic acids had also been detected from the honey samples using UPLC-MS/MS, without sugar-removal procedure. PMID:24027653
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Excited state properties of the astaxanthin radical cation: A quantum chemical study
NASA Astrophysics Data System (ADS)
Dreuw, Andreas; Starcke, Jan Hendrik; Wachtveitl, Josef
2010-07-01
Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT rad + ) are investigated. While the optically allowed excited D 1 and D 3 states are typical ππ∗ excited states, the D 2 and D 4 states are nπ∗ states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ∗ states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.
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Bender, Güneş; Poyner, Russell R; Reed, George H
2008-10-28
Rapid-mix freeze-quench (RMFQ) methods and electron paramagnetic resonance (EPR) spectroscopy have been used to characterize the steady-state radical in the deamination of ethanolamine catalyzed by adenosylcobalamin (AdoCbl)-dependent ethanolamine ammonia-lyase (EAL). EPR spectra of the radical intermediates formed with the substrates, [1-13C]ethanolamine, [2-13C]ethanolamine, and unlabeled ethanolamine were acquired using RMFQ trapping methods from 10 ms to completion of the reaction. Resolved 13C hyperfine splitting in EPR spectra of samples prepared with [1-13C]ethanolamine and the absence of such splitting in spectra of samples prepared with [2-13C]ethanolamine show that the unpaired electron is localized on C1 (the carbinol carbon) of the substrate. The 13C splitting from C1 persists from 10 ms throughout the time course of substrate turnover, and there was no evidence of a detectable amount of a product like radical having unpaired spin on C2. These results correct an earlier assignment for this radical intermediate [Warncke, K., et al. (1999) J. Am. Chem. Soc. 121, 10522-10528]. The EPR signals of the substrate radical intermediate are altered by electron spin coupling to the other paramagnetic species, cob(II)alamin, in the active site. The dipole-dipole and exchange interactions as well as the 1-13C hyperfine splitting tensor were analyzed via spectral simulations. The sign of the isotropic exchange interaction indicates a weak ferromagnetic coupling of the two unpaired electrons. A Co2+-radical distance of 8.7 A was obtained from the magnitude of the dipole-dipole interaction. The orientation of the principal axes of the 13C hyperfine splitting tensor shows that the long axis of the spin-bearing p orbital on C1 of the substrate radical makes an angle of approximately 98 degrees with the unique axis of the d(z2) orbital of Co2+.
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Spectroscopic studies on the antioxidant activity of ellagic acid
NASA Astrophysics Data System (ADS)
Kilic, Ismail; Yeşiloğlu, Yeşim; Bayrak, Yüksel
2014-09-01
Ellagic acid (EA, C14H6O8) is a natural dietary polyphenol whose benefits in a variety of diseases shown in epidemiological and experimental studies involve anti-inflammation, anti-proliferation, anti-angiogenesis, anticarcinogenesis and anti-oxidation properties. In vitro radical scavenging and antioxidant capacity of EA were clarified using different analytical methodologies such as total antioxidant activity determination by ferric thiocyanate, hydrogen peroxide scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging, 2,2‧-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging activity and superoxide anion radical scavenging, ferrous ions (Fe2+) chelating activity and ferric ions (Fe3+) reducing ability. EA inhibited 71.2% lipid peroxidation of a linoleic acid emulsion at 45 μg/mL concentration. On the other hand, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), α-tocopherol and ascorbic acid displayed 69.8%, 66.8%, 64.5% and 59.7% inhibition on the peroxidation of linoleic acid emulsion at the same concentration, respectively. In addition, EA had an effective DPPH• scavenging, ABTSrad + scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, ferric ions (Fe3+) reducing power and ferrous ions (Fe2+) chelating activities. Also, those various antioxidant activities were compared to BHA, BHT, α-tocopherol and ascorbic acid as references antioxidant compounds. These results suggested that EA can be used in the pharmacological, food industry and medicine because of these properties.
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Spectroscopic studies on the antioxidant activity of p-coumaric acid
NASA Astrophysics Data System (ADS)
Kiliç, Ismail; Yeşiloğlu, Yeşim
2013-11-01
p-coumaric acid (4-hydroxycinnamic acid), a phenolic acid, is a hydroxyl derivative of cinnamic acid. It decreases low density lipoprotein (LDL) peroxidation and reduces the risk of stomach cancer. In vitro radical scavenging and antioxidant capacity of p-coumaric acid were clarified using different analytical methodologies such as total antioxidant activity determination by ferric thiocyanate, hydrogen peroxide scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging, 2,2‧-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) radical scavenging activity and superoxide anion radical scavenging, ferrous ions (Fe2+) chelating activity and ferric ions (Fe3+) reducing ability. p-Coumaric acid inhibited 71.2% lipid peroxidation of a linoleic acid emulsion at 45 μg/mL concentration. On the other hand, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), α-tocopherol and ascorbic acid displayed 66.8%, 69.8%, 64.5% and 59.7% inhibition on the peroxidation of linoleic acid emulsion at the same concentration, respectively. In addition, p-coumaric acid had an effective DPPHrad scavenging, ABTSrad + scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, ferric ions (Fe3+) reducing power and ferrous ions (Fe2+) chelating activities. Also, those various antioxidant activities were compared to BHA, BHT, α-tocopherol and ascorbic acid as references antioxidant compounds. These results suggested that p-coumaric acid can be used in the pharmacological and food industry because of these properties.
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C2H4ArF2 1,2-Difluoroethane - argon (1/1)
NASA Astrophysics Data System (ADS)
Demaison, J.
This document is part of Part 1 of Subvolume D 'Asymmetric Top Molecules' of Volume 29 'Molecular Constants Mostly from Microwave, Molecular Beam, and Sub-Doppler Laser Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.
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Ademosun, Ayokunle O.
2014-01-01
This study sought to investigate the effect of infusions from green tea (Camellia sinensis) and some citrus peels [shaddock (Citrus maxima), grapefruit (Citrus paradisi), and orange (Citrus sinensis)] on key enzymes relevant to the management of neurodegenerative conditions [monoamine oxidase (MAO) and butyrylcholinesterase (BChE)]. The total phenol contents and antioxidant activities as typified by their 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) radicals scavenging abilities, ferric reducing antioxidant properties, and Fe2+ chelating abilities were also investigated. Green tea had the highest total phenol (43.3 mg/g) and total flavonoid (16.4 mg/g) contents, when compared to orange [total phenol (19.6 mg/g), total flavonoid (6.5 mg/g)], shaddock [total phenol (16.3 mg/g), total flavonoid (5.2 mg/g)], and grapefruit [total phenol (17.7 mg/g), total flavonoid (5.9 mg/g)]. Orange (EC50 = 1.78 mg/mL) had the highest MAO inhibitory ability, while green tea had the least MAO inhibitory ability (EC50 = 2.56 mg/mL). Similarly, green tea had the least BChE inhibitory ability (EC50 = 5.43 mg/mL) when compared to the citrus peels' infusions. However, green tea infusions had the strongest highest ABTS radical scavenging ability, reducing power, and Fe2+ chelating ability. The inhibition of MAO and BChE activities by the green tea and citrus peels infusions could make them good dietary means for the prevention/management of neurodegenerative conditions. PMID:25243093
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Ifesan, B O T; Siripongvutikorn, S; Hutadilok-Towatana, N; Voravuthikunchai, S P
2009-09-01
The scavenging activities of crude ethanolic extract from Eleutherine americana, on 2,2-diphenyl-1-picrylhydrazyl (DPPH) and hydroxyl free radicals were investigated. The results revealed that the extract produced IC(50) values of 8.4 microg/mL and 0.78 mg/mL on DPPH and hydroxyl free radicals, respectively. The total phenolic content of the extract was determined using the Folin-Ciocalteu reagent and the crude extract yielded high phenolic content of 4.56 mumol gallic acid equivalent per milligram dried extract. The extract, at different concentrations, was incorporated into pork, cooked in the microwave, and stored at 4 degrees C for 9 d. The crude extract demonstrated antioxidant activity, which increases with increased extract concentrations and retarded lipid oxidation in the cooked pork. Antibacterial activity of the extract against Staphylococcus aureus in the cooked pork revealed that at a concentration of 10.8 mg/100 g, the extract reduced the bacterial population by 0.57 log compared to control at 9 d of storage. The sensory results revealed that the pork samples treated with the extract and the control sample were not significantly different from day 0 to 6; however, on day 9 the treatments were significantly scored higher than the control. Furthermore, addition of the extract led to an increase in the redness values of the pork and this was acceptable from the sensory point of view. E. americana crude extract could be a promising novel antioxidant to prevent lipid oxidation and a potential natural color enhancer of red meat and meat products.
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Amicangelo, Jay C; Lee, Yuan-Pern
2017-11-22
The reaction of chlorine atoms (Cl) with isoprene (2-methyl-1,3-butadiene, C 5 H 8 ) in solid para-hydrogen (p-H 2 ) matrices at 3.2 K was studied using infrared (IR) spectroscopy. Mixtures of C 5 H 8 and Cl 2 were codeposited in p-H 2 at 3.2 K, followed by irradiation with ultraviolet light at 365 nm to induce the photodissociation of Cl 2 and the subsequent reaction of the Cl atoms with C 5 H 8 . Upon 365 nm photolysis, a multitude of new lines appeared in the IR spectrum, and, based on the secondary photolysis behavior, it was determined that the majority of the new lines belong to two distinct chemical species, designated as set A (intense lines at 1237.9, 807.8, and 605.6/608.2 cm -1 , and several other weaker lines) and set B (intense lines at 942.4, 1257.7, 796.7/798.5, 667.9, and 569.7 cm -1 , and several other weaker lines). Quantum-chemical calculations were performed at the B3PW91/6-311++G(2d,2p) level for ·C 5 H 7 and the four possible isomers of the ·C 5 H 8 Cl radicals, produced from the addition of the Cl atom to the four distinct sites of carbon atoms in C 5 H 8 , to determine the relative energetics and predict IR spectra for each radical. The newly observed lines of sets A and B are assigned to the 1-chloromethyl-2-methylallyl radical (addition to carbon 4) and the 1-chloromethyl-1-methylallyl radical (addition to carbon 1) according to comparison with predicted IR spectra of possible products. The 1-chloromethyl-2-methylallyl radical and 1-chloromethyl-1-methylallyl radicals were predicted to be the most stable, with the latter ∼8 kJ mol -1 lower in energy than the former. The ratio of the 1-chloromethyl-1-methylallyl to the 1-chloromethyl-2-methylallyl radicals is estimated to be (1.2 ± 0.5):1.0, indicating that the two radicals are produced in approximately equal amounts. The exclusive production of the radicals involving the addition of the Cl atom to the two terminal carbons of isoprene is analogous to what was previously observed for the reaction of Cl atoms with trans-1,3-butadiene in solid p-H 2 .
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Kauf, Teresa L; Svatek, Robert S; Amiel, Gilad; Beard, Timothy L; Chang, Sam S; Fergany, Amr; Karnes, R Jeffrey; Koch, Michael; O'Hara, Jerome; Lee, Cheryl T; Sexton, Wade J; Slaton, Joel W; Steinberg, Gary D; Wilson, Shandra S; Techner, Lee; Martin, Carolyn; Moreno, Jessica; Kamat, Ashish M
2014-06-01
We evaluated the effect of alvimopan treatment vs placebo on health care utilization and costs related to gastrointestinal recovery in patients treated with radical cystectomy in a randomized, phase 4 clinical trial. Resource utilization data were prospectively collected and evaluated by cost consequence analysis. Hospital costs were estimated from 2012 Medicare reimbursement rates and medication wholesale acquisition costs. Differences in base case mean costs between the study cohorts for total postoperative ileus related costs (hospital days, study drug, nasogastric tubes, postoperative ileus related concomitant medication and postoperative ileus related readmissions) and total combined costs (postoperative ileus related, laboratory, electrocardiograms, nonpostoperative ileus related concomitant medication and nonpostoperative ileus related readmission) were evaluated by probabilistic sensitivity analysis using a bootstrap approach. Mean hospital stay was 2.63 days shorter for alvimopan than placebo (mean±SD 8.44±3.05 vs 11.07±8.23 days, p=0.005). Use of medications or interventions likely intended to diagnose or manage postoperative ileus was lower for alvimopan than for placebo, eg total parenteral nutrition 10% vs 25% (p=0.001). Postoperative ileus related health care costs were $2,340 lower for alvimopan and mean total combined costs were decreased by $2,640 per patient for alvimopan vs placebo. Analysis using a 10,000-iteration bootstrap approach showed that the mean difference in postoperative ileus related costs (p=0.04) but not total combined costs (p=0.068) was significantly lower for alvimopan than for placebo. In patients treated with radical cystectomy alvimopan decreased hospitalization cost by reducing the health care services associated with postoperative ileus and decreasing the hospital stay. Copyright © 2014 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.
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Beliaev, A M; Bagnenko, S F; Kabanov, M Iu; Vashetko, R V; Surov, D A; Zakharenko, A A; Babkov, O V; Koshevoĭ, A A; Novitskaia, N Iu; Rumiantsev, V N
2011-01-01
In order to improve radicalism of emergency surgical interventions an appropriate method of total mesocolonectomy and D3-lymph node dissection in the medial-lateral direction and the principle of "no-touch technique" were used in 14 patients. This technique is safe, effective, does not prolong the duration of operation and postoperative period, is not followed by increased number of complications and lethality.
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Comprehensive assessment of phenolics and antiradical potential of Rumex hastatus D. Don. roots
2014-01-01
Background Roots of Rumex hastatus (Polygonaceae) are traditionally used for the treatment of various ailments including liver and lung diseases. In this study, various solvent extracts of R. hastatus roots, like methanolic, n-hexane, ethyl acetate, chloroform, butanol and aqueous fractions were assessed through their antioxidant properties in vitro and determination of phenolic contents. Methods Several parameters like DPPH˙, ABTS˙+, ˙OH, H2O2, superoxide free radical scavenging, iron chelating power, reducing power, β-carotene bleaching power, antioxidant capacity and total phenolics and flavonoids were evaluated. High Performance liquid Chromatography (HPLC) was also considered. Results Though all the fractions exhibited dose dependant activity. The samples with the highest activity were the butanol and methanol fractions in all the assays except hydrogen peroxide radical scavenging assay where chloroform fraction showed the highest scavenging aptitude. On the other hand, aquous fraction showed significant beta carotene linoleic acid, while n-hexane and ethyl acetate fractions exhibited a lesser antioxidant activity in all the assays. HPLC revealed the presence of rutin, luteolin-7-glucoside, vitexin and luteolin. Conclusion These results have to some extent substantiated the use of R. hastatus roots against different diseases, as an excellent basis of potential antioxidant due to the presence of sufficient amount of phenolics such as rutin and luteolin. PMID:24507200
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Comprehensive assessment of phenolics and antiradical potential of Rumex hastatus D. Don. roots.
Sahreen, Sumaira; Khan, Muhammad Rashid; Khan, Rahmat Ali
2014-02-08
Roots of Rumex hastatus (Polygonaceae) are traditionally used for the treatment of various ailments including liver and lung diseases. In this study, various solvent extracts of R. hastatus roots, like methanolic, n-hexane, ethyl acetate, chloroform, butanol and aqueous fractions were assessed through their antioxidant properties in vitro and determination of phenolic contents. Several parameters like DPPH˙, ABTS˙(+), ˙OH, H2O2, superoxide free radical scavenging, iron chelating power, reducing power, β-carotene bleaching power, antioxidant capacity and total phenolics and flavonoids were evaluated. High Performance liquid Chromatography (HPLC) was also considered. Though all the fractions exhibited dose dependant activity. The samples with the highest activity were the butanol and methanol fractions in all the assays except hydrogen peroxide radical scavenging assay where chloroform fraction showed the highest scavenging aptitude. On the other hand, aquous fraction showed significant beta carotene linoleic acid, while n-hexane and ethyl acetate fractions exhibited a lesser antioxidant activity in all the assays. HPLC revealed the presence of rutin, luteolin-7-glucoside, vitexin and luteolin. These results have to some extent substantiated the use of R. hastatus roots against different diseases, as an excellent basis of potential antioxidant due to the presence of sufficient amount of phenolics such as rutin and luteolin.
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Thorsen, Y; Stimec, B; Andersen, S N; Lindstrom, J C; Pfeffer, F; Oresland, T; Ignjatovic, D
2016-07-01
The aim of this study was to ascertain the impact of injury to the superior mesenteric nerve plexus caused by right colectomy with D3 extended mesenterectomy as performed in the prospective multicenter trial: "Safe Radical D3 Right Hemicolectomy for Cancer through Preoperative Biphasic Multi-detector Computed Tomography" in which all soft tissue surrounding the superior mesenteric vessels from the level of the middle colic artery to that of the ileocolic artery was removed. Bowel function and gastrointestinal quality of life in two consecutive cohorts that underwent right colectomy with and without D3 extended mesenterectomy were compared. Main outcome measures were the Diarrhea Assessment Scale (DAS) and Gastrointestinal Quality of Life Index (GIQLI). The data were collected prospectively through telephone interviews. Forty-nine patients per group, comparable for age, sex, length of bowel resected but with significantly shorter follow-up time in the experimental group, were included. There was no difference in total DAS scores, subscores or additional questions except for higher bowel frequency scores in the D3 group (p = 0.02). Comparison of total GIQLI scores and subscales showed no difference between groups. Regression analysis with correction for confounding factors showed 0.48 lower bowel frequency scores in the D2 group (p = 0.022). Within the D3 group presence of jejunal arteries cranial to the D3 dissection area showed 1.78 lower DAS scores and 0.7 lower bowel frequency scores. Small bowel denervation after right colectomy with D3 extended mesenterectomy leads to increased bowel frequency but does not impact gastrointestinal quality of life. Individual anatomical variants can affect postoperative bowel function differently despite standardized surgery.
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Involvement of the chloroplast plastoquinone pool in the Mehler reaction.
Vetoshkina, Daria V; Ivanov, Boris N; Khorobrykh, Sergey A; Proskuryakov, Ivan I; Borisova-Mubarakshina, Maria M
2017-09-01
Light-dependent oxygen reduction in the photosynthetic electron transfer chain, i.e. the Mehler reaction, has been studied using isolated pea thylakoids. The role of the plastoquinone pool in the Mehler reaction was investigated in the presence of dinitrophenyl ether of 2-iodo-4-nitrothymol (DNP-INT), the inhibitor of plastohydroquinone oxidation by cytochrome b6/f complex. Oxygen reduction rate in the presence of DNP-INT was higher than in the absence of the inhibitor in low light at pH 6.5 and 7.6, showing that the capacity of the plastoquinone pool to reduce molecular oxygen in this case exceeded that of the entire electron transfer chain. In the presence of DNP-INT, appearance of superoxide anion radicals outside thylakoid membrane represented approximately 60% of the total superoxide anion radicals produced. The remaining 40% of the produced superoxide anion radicals was suggested to be trapped by plastohydroquinone molecules within thylakoid membrane, leading to the formation of hydrogen peroxide (H 2 O 2 ). To validate the reaction of superoxide anion radical with plastohydroquinone, xanthine/xanthine oxidase system was integrated with thylakoid membrane in order to generate superoxide anion radical in close vicinity of plastohydroquinone. Addition of xanthine/xanthine oxidase to the thylakoid suspension resulted in a decrease in the reduction level of the plastoquinone pool in the light. The obtained data provide additional clarification of the aspects that the plastoquinone pool is involved in both reduction of oxygen to superoxide anion radicals and reduction of superoxide anion radicals to H 2 O 2 . Significance of the plastoquinone pool involvement in the Mehler reaction for the acclimation of plants to light conditions is discussed. © 2017 Scandinavian Plant Physiology Society.
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Point-of-Care Hemoglobin/Hematocrit Testing: Comparison of Methodology and Technology.
Maslow, Andrew; Bert, Arthur; Singh, Arun; Sweeney, Joseph
2016-04-01
Point-of-care (POC) testing allows rapid assessment of hemoglobin (Hgb) and hematocrit (Hct) values. This study compared 3 POC testing devices--the Radical-7 pulse oximeter (Radical-7, Neuchȃtel, Switzerland), the i-STAT (Abbott Point of Care, Princeton, NJ), and the GEM 4000 (Instrumentation Laboratory, Bedford, MA)--to the hospital reference device, the UniCel DxH 800 (Beckman Coulter, Brea, CA) in cardiac surgery patients. Prospective study. Tertiary care cardiovascular center. Twenty-four consecutive elective adult cardiac surgery patients. Hgb and Hct values were measured using 3 POC devices (the Radical-7, i-STAT, and GEM 4000) and a reference laboratory device (UniCel DxH 800). Data were collected simultaneously before surgery, after heparin administration, after heparin reversal with protamine, and after sternal closure. Data were analyzed using bias analyses. POC testing data were compared with that of the reference laboratory device. Hgb levels ranged from 6.8 to 15.1 g/dL, and Hct levels ranged from 20.1% to 43.8%. The overall mean bias was lowest with the i-STAT (Hct, 0.22%; Hgb 0.05 g/dL) compared with the GEM 4000 (Hct, 2.15%; Hgb, 0.63 g/dL) and the Radical-7 (Hgb 1.16 g/dL). The range of data for the i-STAT and Radical-7 was larger than that with the GEM 4000, and the pattern or slopes changed significantly with the i-STAT and Radical-7, whereas that of the GEM 4000 remained relatively stable. The GEM 4000 demonstrated a consistent overestimation of laboratory data, which tended to improve after bypass and at lower Hct/Hgb levels. The i-STAT bias changed from overestimation to underestimation, the latter in the post-cardiopulmonary bypass period and at lower Hct/Hgb levels. By contrast, the Radical-7 biases increased during the surgical procedure and in the lower ranges of Hgb. Important clinical differences and limitations were found among the 3 POC testing devices that should caution clinicians from relying on these data as sole determinants of when or when not to perform transfusion in patients. Even though a low bias might support the use of POC data, further analysis of the bias plots demonstrates pattern changes during the surgical procedure and across the range of Hct/Hgb data. Copyright © 2016 Elsevier Inc. All rights reserved.
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Cordova, Clarissa A S; Siqueira, Ionara R; Netto, Carlos A; Yunes, Rosendo A; Volpato, Ana M; Cechinel Filho, Valdir; Curi-Pedrosa, Rozangela; Creczynski-Pasa, Tânia B
2002-01-01
Calendula officinalis (marigold) has many pharmacological properties. It is used for the treatment of skin disorders, pain and also as a bactericide, antiseptic and anti-inflammatory. Reactive oxygen species (ROS) and reactive nitrogen species (RNS) are known to participate in the pathogenesis of various human diseases and may be involved in the conditions which C. officinalis is used to treat. The aim of this study was to investigate the relationship between the beneficial properties of this plant and its antioxidant action. The butanolic fraction (BF) was studied because it is non-cytotoxic and is rich in a variety of bioactive metabolites including flavonoids and terpenoids. Superoxide radicals (O(2)(*-)) and hydroxyl radicals (HO(*)) are observed in decreasing concentrations in the presence of increasing concentrations of BF with IC(50) values of 1.0 +/- 0.09 mg/ml and 0.5 +/- 0.02 mg/ml, respectively, suggesting a possible free radical scavenging effect. Lipid peroxidation in liver microsomes induced by Fe(2+)/ascorbate was 100% inhibited by 0.5 mg/ml of BF (IC(50) = 0.15 mg/ml). Its total reactive antioxidant potential (TRAP) (in microM Trolox equivalents) was 368.14 +/- 23.03 and its total antioxidant reactivity (TAR) was calculated to be 249.19 +/- 14.5 microM. The results obtained suggest that the butanolic fraction of C. officinalis possesses a significant free radical scavenging and antioxidant activity and that the proposed therapeutic efficacy of this plant could be due, in part, to these properties.
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Spikes, Geoffrey H; Sproules, Stephen; Bill, Eckhard; Weyhermüller, Thomas; Wieghardt, Karl
2008-12-01
The electronic structures of chromium and vanadium centers coordinated by three reduced 1,2-diketones have been elucidated by using density functional theory (DFT) calculations and a host of physical methods: X-ray crystallography; cyclic voltammetry; ultraviolet-visible (UV-vis), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) spectroscopy; and magnetic susceptibility measurements. The metal center in octahedral [CrIII(L*)3]0 (1), a CrIII (d3) ion is coupled antiferromagnetically to three monoanionic ligand pi-radicals affording an S ) 0 ground state. In contrast, Na2(Et2O)2[VIV(LRed)3] (2) (S ) 1/2), possesses a central VIV (d1) ion O,OE-coordinated to three closed-shell, doubly reduced ligands which in turn are coordinated by two Na cations enforcing a trigonal prismatic geometry at the vanadium center. 2 can be oxidized electrochemically by one and two electrons generating a monoanion, [V(L)3]1-, and a neutral species, [V(L)3]0, respectively. DFT calculations atthe B3LYP level show that the one-electron oxidized product contains an octahedral VIV ion coupled antiferromagnetically to one monoanionic ligand pi-radical [VIV(L*)(LRed)2]1- (S ) 0). In contrast, the two-electron oxidized product contains a VIII ion coupled antiferromagnetically to three ligand pi-radicals in an octahedral field[VIII(L*)3]0 (S ) 1/2).
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Mozziconacci, Olivier; Kerwin, Bruce A.; Schöneich, Christian
2013-01-01
The photodissociation of disulfide bonds in model peptides containing Ala and Ala-d3 generates a series of photoproducts following the generation of a CysS• thiyl radical pair. These photoproducts include transformations of Cys to dehydroalanine (Dha) and Ala, as well as Ala to Dha. Intramolecular Michael addition of an intact Cys with a photolytically generated Dha results in the formation of cyclic thioethers. The conversion of Cys into Dha likely involves a 1,3-H-shift from the Cys αC-H bond to the thiyl radical, followed by elimination of HS•. The conversion of Dha into Ala most likely involves hydrated electrons, which are generated through the photolysis of Cys, the photoproduct of disulfide photolysis. Prior to stable product formation, CysS• radicals engage in reversible hydrogen transfer reactions with αC-H and βC-H bonds of the surrounding amino acids. Especially for the βC-H bonds of Ala such hydrogen transfer reactions are unexpected based on thermodynamic grounds; however, the replacement of deuterons in Ala-d3 by hydrogens in H2O provides strong experimental evidence for such reactions. PMID:21895001
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Ciejka, Elżbieta; Kowalczyk, Agata; Gorąca, Anna
2014-01-01
Free radicals are atoms, molecules or their fragments, whose excess leads to the development of oxidative stress, the cause of many neoplastic, neurodegenerative and inflammatory diseases, as well as aging of organisms. Industrial pollution, tobacco smoke, ionizing radiation, ultrasound and magnetic fields are the major exogenous sources of free radicals. The low frequency mag- netic field is commonly applied in physiotherapy. The aim of the present study was to evaluate the effect of extremely low frequency magnetic field (1L.F-MF) on the concentration ofsullhydryl groups (-SH) and proteins in liver tissues of experimental animals de- pending on the time of exposure to the field. Twenty one Sprague-D)awley male rats, aged 3-4 months were randomly divided into 3 experimental groups (each containing 7 animals): controls (group I), the rats exposed to IEI.F-MF of 40 Hz, 7 mT (this kind of the ELF-MF is mostly used in magnetotherapy), 30 min/day for 2 weeks (group II) and the rats exposed to 40 Hz, 7 mT for 60 min/day for 2 weeks (group III). The concentrations of proteins and sulfhydryl groups in the liver tissues were determined after exposure to magnetic fields. Exposure to low magnetic field: 40 Hz, 7 mT for 30 min/day and 60 min/day for 2 weeks caused a significant increase in the concentration of-SH groups and total protein levels in the liver tissues. The study results suggest that exposure to magnetic fields leads to the development of adaptive mechanisms to maintain the balance in the body oxidation-reduction and in the case of the studied parameters does not depend on the time of exposure.
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Lin, Li-Yun; Peng, Chiung-Chi; Yang, Ya-Lu; Peng, Robert Y
2008-02-27
Nutrient levels in buckwheats that were maximized in day 8 sprouts (D8SP) included total phenolics, quercetin, and l-ascorbic acid, whereas those of oxalic, malic, tartaric, and citric acids, rutin, and gamma-aminobutyric acid (GABA) were found to reach maximum levels on day 10. Ethanolic extract of D8SP (2.5 mg/mL) revealed potent free-radical scavenging (FRS) and antioxidative (ANO) capabilities. However, its Fe2+-chelating capability was only moderate. To further study the hypolipidemic activity of D8SP, 36 Syrian hamsters were grouped into six groups and fed for 28 days, respectively, with (i) control meal, (ii) high fat plus high cholesterol meal, (iii) high fat plus high cholesterol plus 2.5% of buckwheat seeds, (iv) high fat plus high cholesterol plus 25% of buckwheat seeds, (v) high fat plus high cholesterol plus 2.5% of D8SP, and (vi) high fat plus high cholesterol plus 25% of D8SP. High seed meal prominently enhanced body weight gain, whereas high sprout meal exhibited the highest feed efficiency. Ratios of liver/body weight (L/B) were significantly lowered by all BS meals. Although low seed meal reduced serum total cholesterol (TC) levels (p<0.05), its effect was still inferior to the high seed and sprout meals (p<0.01). In contrast, serum triglyceride (TG) levels were lowered only by the high seed and sprout meals (p<0.05). Alternatively, levels of serum low-density lipoprotein cholesterol (LDL-C) were significantly suppressed by all buckwheat meals (p<0.01). Serum high-density lipoprotein cholesterol (HDL-C) levels were increased, however, insignificantly. Nutraceutically more meaningful is that both LDL-C/HDL-C and TC/HDL-C ratios were significantly lowered (p<0.01). Apparently, hepatic TC levels were significantly reduced, whereas hepatic TG levels were totally unaffected. Conclusively, sprouting triggers a variety of nutritional changes in buckwheats. Day 8 sprouts, consisting of high polyphenolic and moderate quercetin contents, are nutraceutically maximized when hypocholesterolemic, hypotriglyceridemic, and antioxidative activities are concerned.
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Vacuum ultraviolet photoionization cross section of the hydroxyl radical.
Dodson, Leah G; Savee, John D; Gozem, Samer; Shen, Linhan; Krylov, Anna I; Taatjes, Craig A; Osborn, David L; Okumura, Mitchio
2018-05-14
The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O( 1 D) + H 2 O in a flow reactor in He at 8 Torr. The initial O( 1 D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O( 3 P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O( 3 P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O( 3 P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra.
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Vacuum ultraviolet photoionization cross section of the hydroxyl radical
NASA Astrophysics Data System (ADS)
Dodson, Leah G.; Savee, John D.; Gozem, Samer; Shen, Linhan; Krylov, Anna I.; Taatjes, Craig A.; Osborn, David L.; Okumura, Mitchio
2018-05-01
The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O(1D) + H2O in a flow reactor in He at 8 Torr. The initial O(1D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O(3P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O(3P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O(3P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra.
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Li, Jian; Zhang, Baisheng; Zhang, Zhiqiang; Yan, Kefeng; Kang, Lixun
2014-12-01
The primary pyrolysis mechanisms of the sodium carboxylate group in sodium benzoate-used as a model compound of brown coal-were studied by performing quantum chemical computations using B3LYP and the CBS method. Various possible reaction pathways involving reactions such as unimolecular and bimolecular decarboxylation and decarbonylation, crosslinking, and radical attack in the brown coal matrix were explored. Without the participation of reactive radicals, unimolecular decarboxylation to release CO2 was calculated to be the most energetically favorable primary reaction pathway at the B3LYP/6-311+G (d, p) level of theory, and was also found to be more energetically favorable than decarboxylation of an carboxylic acid group. When CBS-QBS results were included, crosslinking between the sodium carboxylate group and the carboxylic acid and the decarboxylation of the sodium carboxylate group (catalyzed by the phenolic hydroxyl group) were found to be possible; this pathway competes with unimolecular decarboxylation of the sodium carboxylate group. Provided that H and CH3 radicals are present in the brown coal matrix and can access the sodium carboxylate group, accelerated pyrolysis of the sodium carboxylate group becomes feasible, leading to the release of an Na atom or an NaCO2 radical at the B3LYP/6-311+G (d, p) or CBS-QB3 level of theory, respectively.
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NASA Astrophysics Data System (ADS)
Willems, Gert; Benedikt, Jan; von Keudell, Achim
2016-09-01
A thorough understanding and good control of produced neutral and charged species by cold atmospheric plasmas is essential for potential environmental and/or bio-medical applications. In this study we use the COST reference micro plasma jet (µ-APPJ), which is a radio-frequency capacitive coupled plasma source with 1 mm electrode distance, which has been operated in helium-water vapour mixture and has been studied as a potential source of hydroxyl radicals and hydrogen peroxide molecules. The water vapour concentration was up to 1.2%. Molecular Beam mass spectrometry is used as diagnostic tool. An absolute calibration of hydrogen peroxide was conducted using a double bubbler concept, because the ionization cross section for hydrogen peroxide is not available. Additionally the effluent chemistry was investigated by use of a 0D and 2D model. Absolute densities of hydrogen peroxide and hydroxyl radicals from atmospheric plasma will be presented. Their dependency on water vapour concentration in the carrier gas as well as distance to target have been investigated. The measured density is between 5E-13 cm-3 (2.4ppm) and 1.5E-14 cm-3 (7.2ppm) for both hydrogen peroxide molecules and hydroxyl radicals. The achieved results are in good agreement with other experiments.
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Abuja, P M; Albertini, R; Esterbauer, H
1997-06-01
Kinetic simulation can help obtain deeper insight into the molecular mechanisms of complex processes, such as lipid peroxidation (LPO) in low-density lipoprotein (LDL). We have previously set up a single-compartment model of this process, initiating with radicals generated externally at a constant rate to show the interplay of radical scavenging and chain propagation. Here we focus on the initiating events, substituting constant rate of initiation (Ri) by redox cycling of Cu2+ and Cu+. Our simulation reveals that early events in copper-mediated LDL oxidation include (1) the reduction of Cu2+ by tocopherol (TocOH) which generates tocopheroxyl radical (TocO.), (2) the fate of TocO. which either is recycled or recombines with lipid peroxyl radical (LOO.), and (3) the reoxidation of Cu+ by lipid hydroperoxide which results in alkoxyl radical (LO.) formation. So TocO., LOO., and LO. can be regarded as primordial radicals, and the sum of their formation rates is the total rate of initiation, Ri. As experimental information of these initiating events cannot be obtained experimentally, the whole model was validated experimentally by comparison of LDL oxidation in the presence and absence of bathocuproine as predicted by simulation. Simulation predicts that Ri decreases by 2 orders of magnitude during lag time. This has important consequences for the estimation of oxidation resistance in copper-mediated LDL oxidation: after consumption of tocopherol, even small amounts of antioxidants may prolong the lag phase for a considerable time.
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UV + V UV double-resonance studies of autoionizing Rydberg states of the hydroxyl radical
DOE Office of Scientific and Technical Information (OSTI.GOV)
Green, Amy M.; Liu, Fang; Lester, Marsha I., E-mail: milester@sas.upenn.edu
2016-05-14
The hydroxyl radical (OH) is a key oxidant in atmospheric and combustion chemistry. Recently, a sensitive and state-selective ionization method has been developed for detection of the OH radical that utilizes UV excitation on the A{sup 2}Σ{sup +}–X{sup 2}Π transition followed by fixed 118 nm vacuum ultraviolet (VUV) radiation to access autoionizing Rydberg states [J. M. Beames et al., J. Chem. Phys. 134, 241102 (2011)]. The present study uses tunable VUV radiation generated by four-wave mixing to examine the origin of the enhanced ionization efficiency observed for OH radicals prepared in specific A{sup 2}Σ{sup +} intermediate levels. The enhancement ismore » shown to arise from resonant excitation to distinct rotational and fine structure levels of two newly identified {sup 2}Π Rydberg states with an A{sup 3}Π cationic core and a 3d electron followed by ionization. Spectroscopic constants are derived and effects due to uncoupling of the Rydberg electron are revealed for the OH {sup 2}Π Rydberg states. The linewidths indicate a Rydberg state lifetime due to autoionization on the order of a picosecond.« less
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Yang, Dan; Wang, Xiang-Yu; Gan, Lu-Jing; Zhang, Hua; Shin, Jung-Ah; Lee, Ki-Teak; Hong, Soon-Taek
2015-05-01
In this study, we have produced a structured lipid with a low ω6/ω3 ratio by lipase-catalysed interesterification with perilla and grape seed oils (1:3, wt/wt). A Ginkgo biloba leaf extract was fractionated in a column packed with HP-20 resin, producing a flavonoid glycoside fraction (FA) and a biflavone fraction (FB). FA exhibited higher antioxidant capacity than FB, showing 58.4 mmol gallic acid equivalent (GAE)/g-of-total-phenol-content, 58.8 mg quercetin equivalent (QUE)/g-of-total-flavonoid-content, 4.5 mmol trolox/g-of-trolox-equivalent antioxidant capacity, 0.14 mg extract/mL-of-free-radical-scavenging-activity (DPPH assay, IC50), and 2.3 mmol Fe2SO4 · 7H2O/g-of-ferric-reducing-antioxidant-power. The oil-in-water emulsion containing the stripped structured lipid as an oil phase with FA exhibited the highest stability and the lowest oil globule diameters (d43 and d32), where the aggregation was unnoticeable by Turbiscan and particle size analyses during 30 days of storage. Furthermore, FA was effective in retarding the oxidation of the emulsions. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Structural modifications of human beta 2 microglobulin treated with oxygen-derived radicals.
Capeillere-Blandin, C; Delaveau, T; Descamps-Latscha, B
1991-01-01
Treatment of human beta 2 microglobulin (beta 2m) with defined oxygen-derived species generated by treatment with gamma-radiation was studied. As assessed by SDS/PAGE, the hydroxyl radicals (.OH) caused the disappearance of the protein band at 12 kDa that represents beta 2m, and cross-linked the protein into protein bands stable to both SDS and reducing conditions. However, when .OH was generated under oxygen in equimolar combination with the superoxide anion radical (O2.-), the high-molecular-mass protein products were less represented, and fragmented derivatives were not obviously detectable. Exposure to .OH alone, or to .OH + O2.- in the presence of O2, induced the formation of beta 2m protein derivatives with a more acidic net electrical charge than the parent molecule. In contrast, O2.- alone had virtually no effect on molecular mass or pI. Changes in u.v. fluorescence during .OH attack indicated changes in conformation, as confirmed by c.d. spectrometry. A high concentration of radicals caused the disappearance of the beta-pleated sheet structure and the formation of a random coil structure. Loss of tryptophan and significant production of dityrosine (2,2'-biphenol type) were noted, exhibiting a clear dose-dependence with .OH alone or with .OH + O2.-. The combination of .OH + O2.- induced a pattern of changes similar to that with .OH alone, but more extensive for c.d. and tryptophan oxidation (2 Trp/beta 2m molecule), and more limited for dityrosine formation. Lower levels of these oxidative agents caused the reproducible formation of species at 18 and 25 kDa which were recognized by antibodies against native beta 2m. These findings provide a model for the protein pattern observed in beta 2m amyloidosis described in the literature. Images Fig. 4. Fig. 5. PMID:1649598
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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.
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Sun, Hongyan; Zhang, Peng; Law, Chung K
2012-05-31
The gas-phase kinetics of H-abstraction reactions of monomethylhydrazine (MMH) by OH radical was investigated by second-order multireference perturbation theory and two-transition-state kinetic model. It was found that the abstractions of the central and terminal amine H atoms by the OH radical proceed through the formation of two hydrogen bonded preactivated complexes with energies of 6.16 and 5.90 kcal mol(-1) lower than that of the reactants, whereas the abstraction of methyl H atom is direct. Due to the multireference characters of the transition states, the geometries and ro-vibrational frequencies of the reactant, transition states, reactant complexes, and product complexes were optimized by the multireference CASPT2/aug-cc-pVTZ method, and the energies of the stationary points of the potential energy surface were refined at the QCISD(T)/CBS level via extrapolation of the QCISD(T)/cc-pVTZ and QCISD(T)/cc-pVQZ energies. It was found that the abstraction reactions of the central and two terminal amine H atoms of MMH have the submerged energy barriers with energies of 2.95, 2.12, and 1.24 kcal mol(-1) lower than that that of the reactants respectively, and the abstraction of methyl H atom has a real energy barrier of 3.09 kcal mol(-1). Furthermore, four MMH radical-H(2)O complexes were found to connect with product channels and the corresponding transition states. Consequently, the rate coefficients of MMH + OH for the H-abstraction of the amine H atoms were determined on the basis of a two-transition-state model, with the total energy E and angular momentum J conserved between the two transition-state regions. In units of cm(3) molecule(-1) s(-1), the rate coefficient was found to be k(1) = 3.37 × 10(-16)T(1.295) exp(1126.17/T) for the abstraction of the central amine H to form the CH(3)N(•)NH(2) radical, k(2) = 2.34 × 10(-17)T(1.907) exp(1052.26/T) for the abstraction of the terminal amine H to form the trans-CH(3)NHN(•)H radical, k(3) = 7.41 × 10(-20)T(2.428) exp(1343.20/T) for the abstraction of the terminal amine H to form the cis-CH(3)NHN(•)H radical, and k(4) = 9.13 × 10(-21)T(2.964) exp(-114.09/T) for the abstraction of the methyl H atom to form the C(•)H(2)NHNH(2) radical, respectively. Assuming that the rate coefficients are additive, the total rate coefficient of these theoretical predictions quantitatively agrees with the measured rate constant at temperatures of 200-650 K, with no adjustable parameters.
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Lee, Shih-Huang; Chin, Chih-Hao; Chen, Wei-Kan; Huang, Wen-Jian; Hsieh, Chu-Chun
2011-05-14
We conducted the title reaction using a crossed molecular-beam apparatus, quantum-chemical calculations, and RRKM calculations. Synchrotron radiation from an undulator served to ionize selectively reaction products by advantage of negligibly small dissociative ionization. We observed two products with gross formula C(2)H(3)N and C(2)H(2)N associated with loss of one and two hydrogen atoms, respectively. Measurements of kinetic-energy distributions, angular distributions, low-resolution photoionization spectra, and branching ratios of the two products were carried out. Furthermore, we evaluated total branching ratios of various exit channels using RRKM calculations based on the potential-energy surface of reaction N((2)D)+C(2)H(4) established with the method CCSD(T)/6-311+G(3df,2p)//B3LYP/6-311G(d,p)+ZPE[B3LYP/6-311G(d,p)]. The combination of experimental and computational results allows us to reveal the reaction dynamics. The N((2)D) atom adds to the C=C π-bond of ethene (C(2)H(4)) to form a cyclic complex c-CH(2)(N)CH(2) that directly ejects a hydrogen atom or rearranges to other intermediates followed by elimination of a hydrogen atom to produce C(2)H(3)N; c-CH(2)(N)CH+H is the dominant product channel. Subsequently, most C(2)H(3)N radicals, notably c-CH(2)(N)CH, further decompose to CH(2)CN+H. This work provides results and explanations different from the previous work of Balucani et al. [J. Phys. Chem. A, 2000, 104, 5655], indicating that selective photoionization with synchrotron radiation as an ionization source is a good choice in chemical dynamics research.
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NASA Technical Reports Server (NTRS)
Simonaitis, R.; Heicklen, J.
1972-01-01
NO2 was photolyzed with 2288A radiation at 300 and 423 K in the presence of H2O, CO, and in some cases excess He. The photolysis produces O(1D) atoms which react with H2O to give HO radicals or are deactivated by CO to O(3P) atoms. The ratio k sub 5/k sub 3 is temperature dependent, being 0.33 at 300 K and 0.60 at 423 K. From these two points the Arrhenius expression is estimated to be k sub 5/k sub 3 = 2.6 exp(-1200/RT) where R is in calories/mole - K. The OH radical is either removed by NO2 or reacts with CO.
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Goel, Reema; Bitzer, Zachary T; Reilly, Samantha M; Foulds, Jonathan; Muscat, Joshua; Elias, Ryan J; Richie, John P
2018-05-07
Cigarette smoke is a major exogenous source of free radicals, and the resulting oxidative stress is one of the major causes of smoking-caused diseases. Yet, many of the factors that impact free radical delivery from cigarettes remain unclear. In this study, we machine-smoked cigarettes and measured the levels of gas- and particulate-phase radicals by electron paramagnetic resonance (EPR) spectroscopy using standardized smoking regimens (International Organization of Standardization (ISO) and Canadian Intense (CI)), puffing parameters, and tobacco blends. Radical delivery per cigarette was significantly greater in both gas (4-fold) and particulate (6-fold) phases when cigarettes were smoked under the CI protocol compared to the ISO protocol. Total puff volume per cigarette was the major factor with radical production being proportional to total volume, regardless of whether volume differences were achieved by changes in individual puff volume or puff frequency. Changing puff shape (bell vs sharp vs square) or puff duration (1-5 s), without changing volume, had no effect on radical yields. Tobacco variety did have a significant impact on free radical production, with gas-phase radicals highest in reconstituted > burley > oriental > bright tobacco and particulate-phase radicals highest in burley > bright > oriental > reconstituted tobacco. Our findings show that modifiable cigarette design features and measurable user smoking behaviors are key factors determining free radical exposure in smokers.
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Acylphenols and dimeric acylphenols from Myristica maxima Warb.
Othman, Muhamad Aqmal; Sivasothy, Yasodha; Looi, Chung Yeng; Ablat, Abdulwali; Mohamad, Jamaludin; Litaudon, Marc; Awang, Khalijah
2016-06-01
Giganteone E (1), a new dimeric acylphenol was isolated as a minor constituent from the bark of Myristica maxima Warb. The structure of 1 was established on the basis of 1D and 2D NMR techniques and LCMS-IT-TOF analysis. Malabaricones A-C (2-4), giganteones A and C (5 and 6), maingayones A and B (7 and 8), maingayic acid B (9) and β-sitosteryl oleate (10) were also characterized in this plant for the first time. Compound 10 was identified for the first time in the Myristicaceae. Compounds 2 and 5 were active against human prostate cancer cell-lines, thus making this the first report on the prostate cancer inhibiting potential of acylphenols and dimeric acylphenols. Compounds 1, 4, 5, 7 and 8 exhibited potent DPPH free radical scavenging activity. This is the first report on their free radical scavenging capacity. Copyright © 2016. Published by Elsevier B.V.
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The Infrared Spectrum of Isotopomers of the TeH Radical, Observed by CO Laser Magnetic Resonance
NASA Astrophysics Data System (ADS)
Gillett, D. A.; Towle, J. P.; Islam, M.; Brown, J. M.
1994-02-01
The infrared spectrum of the TeH radical in its X2Π state has been recorded using an intracavity CO laser magnetic resonance (LMR) spectrometer. Seven of the eight naturally occurring Te isotopomers were observed, with resonances originating from the first three vibrational levels; many were recorded as Lamb-dips. These observations have been combined with existing data for TeH and TeD in the X2Π state and used to determine the parameters of an N 2 Hamiltonian, including isotopic scaling and nonadiabatic corrections. The data are well described by the parameters. The different isotopic dependences of the effects of the parameters A D and γ has allowed their separation and the extent to which TeH shows Hund's case (c) coupling is discussed. Trends displayed by the chalcogen monohydrides are considered.
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Elmes, N J; Nasveld, P E; Kitchener, S J; Kocisko, D A; Edstein, M D
2008-11-01
Tafenoquine is being developed for radical cure and post-exposure prophylaxis of Plasmodium vivax malaria. In an open-label study, 1512 Australian Defence Force personnel received one of three tafenoquine 3 d regimens [400 mg once daily (od), 200 mg twice daily (bid), 200 mg od] or daily primaquine (22.5 mg) plus doxycycline (100 mg) over 14 d in Bougainville and in Timor-Leste for post-exposure prophylaxis. The relapse rate of subjects treated in Bougainville with tafenoquine (n=173) was 1.2% (200 mg bid x 3 d) and 2.3% (400 mg od x 3 d), while primaquine plus doxycycline (n=175) was 3.4%. For subjects treated in Timor-Leste with tafenoquine (n=636), the relapse rate was 4.9% (200 mg od x 3 d), 5.3% (200 mg bid x 3 d) and 11.0% (400 mg od x 3d), while primaquine plus doxycycline (n=289) was 10.0%. The most frequent adverse events reported across all groups were nausea, abdominal distress and diarrhoea. There was a dose-dependent reduction in adverse events with a reduced dose of tafenoquine, with the lowest dose (total 600 mg over 3 d) producing rates of adverse events equivalent to that of primaquine plus doxycycline. The much shorter dosing regimen of tafenoquine should increase compliance, which is often suboptimal with primaquine after leaving an endemic area. [Australian New Zealand Clinical Trials Registry Number 12607000588493].
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Antioxidant Activity and Total Phenolic and Flavonoid Contents of Hieracium pilosella L. Extracts
Stanojević, Ljiljana; Stanković, Mihajlo; Nikolić, Vesna; Nikolić, Ljubiša; Ristić, Dušica; Čanadanovic-Brunet, Jasna; Tumbas, Vesna
2009-01-01
The antioxidant activity of water, ethanol and methanol Hieracium pilosella L. extracts is reported. The antioxidative activity was tested by spectrophotometrically measuring their ability to scavenge a stable DPPH• free radical and a reactive hydroxyl radical trapped by DMPO during the Fenton reaction, using the ESR spectroscopy. Total phenolic content and total flavonoid content were evaluated according to the Folin-Ciocalteu procedure, and a colorimetric method, respectively. A HPLC method was used for identification of some phenolic compounds (chlorogenic acid, apigenin-7-O-glucoside and umbelliferone). The antioxidant activity of the investigated extracts slightly differs depending on the solvent used. The concentration of 0.30 mg/mL of water, ethanol and methanol extract is less effective in scavenging hydroxyl radicals (56.35, 58.73 and 54.35%, respectively) in comparison with the DPPH• radical scavenging activity (around 95% for all extracts). The high contents of total phenolic compounds (239.59–244.16 mg GAE/g of dry extract) and total flavonoids (79.13–82.18 mg RE/g of dry extract) indicated that these compounds contribute to the antioxidative activity. PMID:22346723
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Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical.
Parab, Prajakta Rajaram; Heufer, K Alexander; Fernandes, Ravi Xavier
2018-04-25
Isopentanol is a potential next-generation biofuel for future applications to Homogeneous Charge Compression Ignition (HCCI) engine concepts. To provide insights into the combustion behavior of isopentanol, especially to its auto-ignition behavior which is linked both to efficiency and pollutant formation in real combustion systems, detailed quantum chemical studies for crucial reactions are desired. H-Abstraction reaction rates from fuel molecules are key initiation steps for chain branching required for auto-ignition. In this study, rate constants are determined for the hydrogen atom abstraction reactions from isopentanol by the H atom and HO2˙ radical by implementing the CBS-QB3 composite method. For the treatment of the internal rotors, a Pitzer-Gwinn-like approximation is applied. On comparing the computed reaction energies, the highest exothermicity (ΔE = -46 kJ mol-1) is depicted for Hα abstraction by the H atom whereas the lowest endothermicity (ΔE = 29 kJ mol-1) is shown for the abstraction of Hα by the HO2˙ radical. The formation of hydrogen bonding is found to affect the kinetics of the H atom abstraction reactions by the HO2˙ radical. Further above 750 K, the calculated high pressure limit rate constants indicate that the total contribution from delta carbon sites (Cδ) is predominant for hydrogen atom abstraction by the H atom and HO2˙ radical.
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Chen, Hongjian; Wang, Yong; Cao, Peirang; Liu, Yuanfa
2017-11-01
Effect of temperatures on thermal oxidation of palmitic acid was studied by the combination of EPR and GC-MS/MS. DMPO was used as the spin trap. The experimental spectrum was simulated with alkyl and alkoxyl spin adducts. Total amount of spins, a parameter to indicate radical concentrations, detected at 180°C was nearly 10 times higher than that at 175°C. Besides, total amounts of spins detected at 180°C decreased rapidly because of the reaction between radical adducts and newly formed radicals. Signal intensities of alkyl radical adducts increased rapidly from 0.405 to 4.785 from 175°C to 180°C. Besides, more palmitic acid degraded to oxidized compounds from 175°C to 180°C than that of other temperature ranges. The C-C linkages between carbons 2 to 6 were easier to be oxidized at 180°C. The results all implied that oxidation rates of palmitic acid samples increased rapidly from 175°C to 180°C. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Murmu, Sanchita Biswas; Mishra, Hari Niwas
2018-04-15
The effect of five coating formulations viz.: (A) 5% Arabic gum (AG)+1% sodium caseinate (SC)+1% cinnamon oil (CE); (B) 5% AG + 1% SC + 2% CE; (C) 5% AG + 1% SC + 1% lemongrass oil (LG); (D) 5% AG + 1% SC + 2% LG; and (E) 5% AG + 1% SC + 2% CE + 2% LG on guava during 35 days storage at 4-7 °C was investigated. Thereafter samples were allowed to ripen for five days at 25 ± 2 °C. The quality of guava was analyzed at an interval of 7, 21, 35 and 40 days. The coating applications resulted in lower activity of PPO & POD, higher DPPH radical scavenging activity, higher retention of ascorbic acid, phenol & flavonoid content, exhibited slower rise of reducing and total sugar in guava pulp. Samples in treatment B and D were the best formulations for extending shelf-life of guava up to 40 days versus seven days of uncoated samples. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Antioxidant and antimicrobial activity of commercial propolis extract in beef patties.
Vargas-Sánchez, Rey D; Torrescano-Urrutia, Gastón R; Acedo-Félix, Evelia; Carvajal-Millán, Elizabeth; González-Córdova, Aarón F; Vallejo-Galland, Belinda; Torres-Llanez, María J; Sánchez-Escalante, Armida
2014-08-01
The objective of this study was to evaluate the efficacy of propolis extract (PE) to reduce lipid oxidation and microbial growth on beef patties during refrigerated storage. Beef patties were manufactured by incorporating PE in 4 different treatments: (1) Control (no PE addition); (2) commercial propolis 1 (2% w/w; CP1); (3) commercial propolis 2 (2% w/w; CP2); and (4) noncommercial propolis (2% w/w; NCP). Raw patties were wrapped with polyvinyl chloride and stored at 2 °C for 8 d. Total phenolic content (TPC), free-radical scavenging activity (FRS), and polyphenolic content of the PE were evaluated using high-performance liquid chromatography (HPLC). Lipid oxidation (thiobarbituric acid-reactive substances (TBARS), conjugated dienes (CnDs), metmyoglobin (MetMb%), pH variation, and color (L*, a*, b*, C*, and h*), and microbial growth (mesophilic and psychrotrophic bacteria) of patty samples were measured. NCP treatment demonstrated the highest FRS (64.8% at 100 μg/mL), which correlated with TPC and the presence of polyphenolic compounds. Lipid oxidation (78.54%, TBARS; 45.53%, CnD; 58.57%, MetMb) and microbial mesophilic and psychrotrophic growth (19.75 and 27.03%, respectively) values were reduced by NCP treatment in refrigerated samples after 8 d. These results indicate that PE has great potential as a natural antioxidant and antimicrobial additive to extend the shelf life of beef patties. © 2014 Institute of Food Technologists®
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Welz, Oliver; Burke, Michael P.; Antonov, Ivan O.
2015-07-16
We investigated the low-temperature oxidation of propane at 4 Torr and temperatures of 530, 600, and 670 K. The oxidation is initiated by pulsed laser photolysis of oxalyl chloride, (COCl)2, at 248 nm, which rapidly generates a ~1:1 mixture of 1-propyl (n-propyl) and 2-propyl (i-propyl) radicals via the fast Cl + propane reaction. Reactants, intermediates and products are probed with isomeric selectivity by time-resolved multiplexed photoionization mass spectrometry (MPIMS) with tunable synchrotron vacuum UV radiation as the ionization source. At all three temperatures, the major stable product species is propene, formed in the C3H7 + O2 reactions by direct HO2-eliminationmore » from both n- and i-propyl peroxy radicals. The experimentally derived propene yields relative to the initial concentration of Cl atoms are (20 ± 4)% at 530 K, (55 ± 11)% at 600 K, and (86 ± 17)% at 670 K at a reaction time of 20 ms. The lower yield of propene at low temperature reflects substantial formation of propyl peroxy radicals, which do not completely decompose on the experimental time scale. In addition, we detect the C3H6O isomers methyloxirane, oxetane, acetone and propanal as minor products. Our measured yields of oxetane and methyloxirane, which are co-products of OH radicals, suggest a revision of the OH formation pathways in models of low-temperature propane oxidation. The experimental results are modeled and interpreted using a multi-scale informatics approach that is presented in detail in a separate publication (Burke, M. P.; Goldsmith, C. F.; Klippenstein, S. J.; Welz, O.; Huang H.; Antonov I. O.; Savee J. D.; Osborn D. L.; Zádor, J.; Taatjes, C. A.; Sheps, L., Multi-Scale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Rections, submitted, 2015). The model predicts the time profiles and yields of the experimentally observed primary products well, and shows satisfactory agreement for products formed mostly via secondary radical-radical reactions.« less
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Charge transport kinetics in a robust radical-substituted polymer/nanocarbon composite electrode
NASA Astrophysics Data System (ADS)
Sato, Kan; Oyaizu, Kenichi; Nishide, Hiroyuki
We have reported a series of organic radical-substituted polymers as new-type charge storage and transport materials which could be used for energy related devices such as batteries and solar cells. Redox-active radical moieties introduced to the non-conjugated polymer backbones enable the rapid electron transfer among the adjacent radical sites, and thus large diffusive flux of electrical charge at a bulk scale. Here we present the elucidated charge transport kinetics in a radical polymer/single-walled carbon nanotube (SWNT) composite electrode. The synergetic effect of electrical conduction by a three-dimensional SWNT network and electron self-exchange reaction by radical polymers contributed to the 105-fold (per 1 g of added SWNT) boosting of electrochemical reactions and exceptionally large current density (greater than 1 A/cm2) as a rechargeable electrode. A totally organic-based secondary battery with a submicron thickness was fabricated to demonstrate the splendid electrochemical performances. Grants-in-Aid for Scientific Research (No. 24225003, 15J00888) and the Leading Graduate Program in Science and Engineering, from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT).
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Puganen, Anna; Kallio, Heikki P; Schaich, Karen M; Suomela, Jukka-Pekka; Yang, Baoru
2018-04-04
The potential for using extracts of press residues from black, green, red, and white currants and from sea buckthorn berries as sources of antioxidants for foods use was investigated. Press residues were extracted with ethanol in four consecutive extractions, and total Folin-Ciocalteu (F-C) reactive material and authentic phenolic compounds were determined. Radical quenching capability and mechanisms were determined from total peroxyl radical-trapping antioxidant capacity (TRAP) and oxygen radical absorbance capacity (ORAC) assays and from diphenylpicrylhydrazyl (DPPH) kinetics, respectively; specific activities were normalized to F-C reactive concentrations. Levels of total F-C reactive materials in press residue extracts were higher than in many fruits and showed significant radical quenching activity. Black currant had the highest authentic phenol content and ORAC, TRAP, and DPPH reactivity. Sea buckthorn grown in northern Finland showed extremely high total specific DPPH reactivity. These results suggest that berry press residues offer attractive value-added products that can provide antioxidants for use in stabilizing and fortifying foods.
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Is Nitrate radical a major oxidant of elemental mercury in the atmosphere?
NASA Astrophysics Data System (ADS)
Luria, M.; Obrist, D.; Peleg, M.; Matveev, V.; Tas, E.
2012-12-01
Nitrate radicals (NO3) play a major role in the nighttime atmospheric oxidation of VOC. The radicals are produced throughout the reaction between O3 and NO2 and are removed via a sequence of homogeneous and heterogeneous reactions. Nitrate radicals reach significant levels only at night and mostly under conditions of low humidity (Asaf et al, 2009, 2010 and references therein). Because of its very high photolysis rate, daytime levels are extremely low, and thus are insignificant in atmospheric oxidation processes. The reaction of Hg with NO3 has not been sufficiently investigated; a value of 4x10-15 cm3 molec-1 s-1 (Sommar et al 1997) is most commonly used. Its importance for the atmospheric mercury chemistry was discussed by Mao el al., (2008) who examined the potential oxidation of mercury by the most common atmospheric oxidants applying the best available rate coefficients. According to their report, the uncertainty in the oxidation capacity of O3 is very large (a factor of 20). If the lower limit is applied, as suggested by Calvert and Lindberg (2005), oxidation by O3 is nearly negligible and, NO3 radicals, at typical nighttime levels, are responsible for the bulk of the Hg oxidation. Obviously this is true in the absence of reactive halogen compounds (RHC, Peleg et al., 2008). The most common method of measuring nitrate radicals is the differential optical absorption system (DOAS) technique. In a recent study performed at an urban semi arid site (Jerusalem, Israel; Asaf et al., 2009, 2010) it was found that nitrate levels could reach levels of up to 800 ppt, significantly higher than ever reported in the past. They further demonstrated that under the conditions prevailed; nitrate radicals are at least as important as the hydroxyl radicals in the overall oxidation capacity of VOC in the atmosphere. Side by side measurements of Nitrate radicals using the DOAS technique and speciated mercury compounds (Total, Particulate and Reactive gaseous) were performed during the summer months of 2012. Measurements took place at the same site and the same period were the highest levels of NO3 were earlier observed. Preliminary data indicated that RGM levels up to 100 pg/m3 were observed during the dark hours concurrent with NO3 concentrations higher than 200 ppt . First round model simulations using a 1-d model, the same model used for the simulations of Hg oxidation at the Dead Sea (Obrist et al., 2010) were also performed. The results indicated that for a 10 hour nighttime average of 50 ppt of nitrate radicals, the concentrations of RGM increase by a factor of more than three.
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Videolaparoscopic Radical Hysterectomy Approach: a Ten-Year Experience
Limberger, Leo Francisco; Kalil, Antonio Nocchi; de Vargas, Gabriel Sebastião; Damiani, Paulo Agostinho; Haas, Fernanda Feltrin
2009-01-01
Background: Because of the advancements in surgical techniques and laparoscopic instruments, total laparoscopic radical hysterectomy can now be performed for the treatment of uterine cervical carcinoma. We assessed the feasibility, complications, and survival rates of patients who underwent total laparoscopic radical hysterectomy with pelvic lymphadenectomy. Methods: We retrospectively collected data from the medical charts of 29 patients who had undergone surgery between 1998 and 2008. The following data were assessed: age, staging, histological type, number of lymph nodes retrieved, parametrial measures, operative time, length of hospital stay, surgical complications, and disease-free time. Results: The mean patient age was 37.07±10.45 years. Forty percent of the patients had previously undergone abdominal or pelvic surgeries. Mean operative time was 228.96±60.41 minutes, and mean retrieved lymph nodes was 16.9±8.12. All patients had free margins. No conversions to laparotomy were necessary. Median time until hospital dismissal was 6.5 days (range 3–38 days). Four patients had intraoperative complications: 2 lacerations of the rectum, 1 laceration of the bladder, and 1 lesion of the ureter. Three patients developed bladder or ureteral fistulas postoperatively that were successfully corrected surgically. Conclusion: Laparoscopic radical hysterectomy is feasible and has acceptable complications. The radicalism of the surgery must be considered, bearing in mind the parametrial measures and the number of lymph nodes retrieved. PMID:20202391
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Peroxy Radical Measurements during PROPHET-AMOS 2016
NASA Astrophysics Data System (ADS)
Wood, E. C. D.; Deming, B.; Rollings, D.
2016-12-01
We present measurements of total peroxy radicals (HO2 + RO2) using the Ethane Chemical Amplifier (ECHAMP) technique during the PROPHET-AMOS project in Pellston, Michigan during July 2016. The C2H6/NO amplification chemistry occurred in FEP reaction chambers at the top of the PROPHET tower at a height of 34 m. The NO2 amplification product was transported through tubing to two cavity attenuated phase shift spectrometers (CAPS) housed inside the PROPHET laboratory. Two calibration sources were used: one based on water photolysis in the presence of isoprene and ozone actinometry, and another based on methyl iodide (CH3I) photolysis. The former was integrated into the inlet system, allowing for daily calibrations, whereas the latter was used twice during the campaign. Peak mixing ratios on warm, sunny days were approximately 40 ppt. Nighttime concentrations varied from below the instrumental detection limit to approximately 5 ppt. The measured peroxy radical concentrations will be compared to HO2 and HO2* mixing ratios measured by the Indiana University LIF-FAGE instrument.
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NASA Astrophysics Data System (ADS)
Araujo, M. T. De; Carneiro, J. W. De M.; Taranto, A. G.
The PCM/COSMO approach was employed to calculate the relative stability of radicals derived from the antimalarial artemisinin. The calculations were performed in polar (water) and apolar (THF) solvent at the density functional level [B3LYP/6-31g(d)]. Relative stabilities were calculated by means of isodesmic equations using artemisinin as reference. Replacement of oxygen atoms by CH2 unities was found to decrease the relative stability of the anionic radical intermediates. The degree of destabilization is reduced in the presence of solvent, being less in water than in THF. The dipole moment and the corresponding solvation free energies of these species modulate this effect. Derivatives with inverted stereochemistry are more stable than those with the artemisinin-like stereochemistry, although the solvent attenuates this stabilization effect. As was found in the in vacuo calculations, the radicals centered on carbon are always more stable than the corresponding radicals centered on oxygen.
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NASA Astrophysics Data System (ADS)
Qian, Muyang; Li, Gui; Kang, Jinsong; Liu, Sanqiu; Ren, Chunsheng; Zhang, Jialiang; Wang, Dezhen
2018-01-01
Atmospheric dielectric barrier discharge (DBD) was found to be promising in the context of plasma chemistry, plasma medicine, and plasma-assisted combustion. In this paper, we present a detailed fluid modeling study of abundant radical species produced by a positive streamer in atmospheric dense methane-air DBD. A two-dimensional axisymmetric fluid model is constructed, in which 82 plasma chemical reactions and 30 different species are considered. Spatial and temporal density distributions of dominant radicals and ions are presented. We lay our emphasis on the effect of varying relative permittivity (ɛr = 2, 4.5, and 9) on the streamer dynamics in the plasma column, such as electric field behavior, production, and destruction pathways of dominant radical species. We find that higher relative permittivity promotes propagation of electric field and formation of conduction channel in the plasma column. The streamer discharge is sustained by the direct electron-impact ionization of methane molecule. Furthermore, the electron-impact dissociation of methane (e + CH4 = >e + H+CH3) is found to be the dominant reaction pathway to produce CH3 and H radicals. Similarly, the electron-impact dissociations of oxygen (e + O2 = >e + O+O(1D), e + O2 = >e + O+O) are the major routes for O production.
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Reaction CH3 + OH studied over the 294-714 K temperature and 1-100 bar pressure ranges.
Sangwan, Manuvesh; Chesnokov, Evgeni N; Krasnoperov, Lev N
2012-08-30
Reaction of methyl radicals with hydroxyl radicals, CH(3) + OH → products (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 294-714 K temperature and 1-100 bar pressure ranges (bath gas He). Methyl radicals were produced by photolysis of acetone at 193.3 nm. Hydroxyl radicals were generated in reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N(2)O at 193.3 nm, with H(2)O. Temporal profiles of CH(3) were recorded via absorption at 216.4 nm using xenon arc lamp and a spectrograph; OH radicals were monitored via transient absorption of light from a dc discharge H(2)O/Ar low pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light inside the reactor was determined by an accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study indicate that the rate constant of reaction 1 is pressure independent within the studied pressure and temperature ranges and has slight negative temperature dependence, k(1) = (1.20 ± 0.20) × 10(-10)(T/300)(-0.49) cm(3) molecule(-1) s(-1).
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Entropic uncertainty relations and locking: Tight bounds for mutually unbiased bases
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ballester, Manuel A.; Wehner, Stephanie
We prove tight entropic uncertainty relations for a large number of mutually unbiased measurements. In particular, we show that a bound derived from the result by Maassen and Uffink [Phys. Rev. Lett. 60, 1103 (1988)] for two such measurements can in fact be tight for up to {radical}(d) measurements in mutually unbiased bases. We then show that using more mutually unbiased bases does not always lead to a better locking effect. We prove that the optimal bound for the accessible information using up to {radical}(d) specific mutually unbiased bases is log d/2, which is the same as can be achievedmore » by using only two bases. Our result indicates that merely using mutually unbiased bases is not sufficient to achieve a strong locking effect and we need to look for additional properties.« less
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Kim, Soodong; Sung, Gyung Tak
2018-03-27
Although nerve-sparing robot-assisted radical prostatectomy (NS-RALP) is performed, a large number of patients still experience erectile dysfunction (ED) after surgery. To evaluate the efficacy and safety of tadalafil 5 mg once daily (OaD) in ED treatment over 2 years and investigate the cause of vascular ED after NS-RARP. We retrospectively evaluated 95 men who underwent NS-RARP and had a penile rehabilitation treatment with tadalafil 5 mg OaD. They were classified into 3 groups: tadalafil 5 mg OaD for 2 years (group I), tadalafil 5 mg OaD for 1 year (group II), and no tadalafil (group III). All patients in group I underwent penile color duplex ultrasound to evaluate the cause of vascular ED. Patients were surveyed using the abridged 5-item International Index of Erectile Function (IIEF-5). Statistically significant improvements were observed in group I for all IIEF-5 domain scores (P = .000). There was no statistically significant difference in recovery of erectile function (EF) the 2-year follow-up between groups I and II. Sub-analysis based on NS status showed no difference in recovery of EF. However, group I showed better trends in EF improvement. Those with venogenic ED had poor responses compared with those with arteriogenic ED or unremarkable findings with tadalafil 5-mg OaD treatment (14.2% vs 55.0% vs 53.3%). The overall side effects included hot flushing in 9.5%, headache in 7.1%, and dizziness in 2.3% of patients. Long-term usage of tadalafil 5 mg OaD after RARP can be an effective option for penile rehabilitation. The present study is a retrospective study with a relatively small sample. Although the responses of patients with venogenic ED were limited compared with those with arteriogenic ED, tadalafil 5-mg OaD treatment was well tolerated and significantly improved EF up to 2 years after NS-RARP. Kim S, Sung GT. Efficacy and Safety of Tadalafil 5 mg Once Daily for the Treatment of Erectile Dysfunction After Robot-Assisted Laparoscopic Radical Prostatectomy: A 2-Year Follow-Up. Sex Med 2018;X:XXX-XXX. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.
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Pérez, Yohani; Oyárzabal, Ambar; Mas, Rosa; Molina, Vivian; Jiménez, Sonia
2013-01-01
D-002, a mixture of higher aliphatic beeswax alcohols, produces gastroprotective and antioxidant effects. To investigate the gastroprotective effect of D-002 against indomethacin-induced ulcers, oxidative variables and myeloperoxidase (MPO) activity in the rat gastric mucosa were examined. Rats were randomized into six groups: a negative vehicle control and five indomethacin (50 mg/kg) treated groups, comprising a positive control, three groups treated orally with D-002 (5, 25 and 100 mg/kg) and one group with omeprazole 20 mg/kg intraperitoneally (ip). The contents of malondialdehyde (MDA), protein carbonyl groups (PCG), hydroxyl radical generation and catalase (CAT), glutathione peroxidase (GSH-PX), superoxide dismutase (SOD) and MPO enzyme activities in the rat gastric mucosa were assessed. Indomethacin increased the content of MDA and PCG, the generation of *OH radical and MPO enzyme activity, while it decreased the CAT, GSH-PX and SOD activities as compared to the negative controls. D-002 (5-100 mg/kg) significantly and dose-dependently reduced indomethacin-induced ulceration to 75 %. Also, D-002 decreased the content of MDA and PCG, the generation of hydroxyl radicals and MPO activity as compared to the positive controls. The highest dose of D-002 (100 mg/kg) increased significantly GSH-PX and SOD activities, while all doses used increased CAT activities. Omeprazole 20 mg/kg, the reference drug, reduced significantly the ulcers (93 %), MDA and PCG, the generation of hydroxyl radicals and MPO activity, and increased the CAT, GSH-PX and SOD activities. D-002 treatment produced gastroprotective effects against indomethacin-induced gastric ulceration, which can be related to the reduction of hydroxyl radical generation, lipid peroxidation, protein oxidation and MPO activity, and to the increase of the antioxidant enzymes activities in the rat gastric mucosa.
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Silibinin phosphodiester glyco-conjugates: Synthesis, redox behaviour and biological investigations.
Romanucci, Valeria; Agarwal, Chapla; Agarwal, Rajesh; Pannecouque, Christophe; Iuliano, Mauro; De Tommaso, Gaetano; Caruso, Tonino; Di Fabio, Giovanni; Zarrelli, Armando
2018-04-01
New silibinin phosphodiester glyco-conjugates were synthesized by efficient phosphoramidite chemistry and were fully characterized by 2D-NMR. A wide-ranging study focused on the determination of their pKa and E° values as well as on their radical scavenging activities by different assays (DPPH, ABTS + and HRSA) was conducted. The new glyco-conjugates are more water-soluble than silibinin, and their radical scavenging activities are higher than those of silibinin. The conjugation therefore improves both the water solubilities and antioxidant activities of the flavonolignan moieties. The serum stability was evaluated under physiological conditions, and the glyco-conjugates degraded with half-lives of 40-70 h, making them useful in pro-drug approaches. We started by treating androgen-dependent prostate cancer (PCa) LNCaP cells and then expanded our studies to androgen-independent PCa PC3 and DU145 cells. In most cases, the new derivatives significantly reduced both total and live cell numbers, albeit at different levels. Anti-HIV activities were evaluated and the glucosamine-phosphate silibinin derivative showed higher activity (IC 50 = 73 μM) than silibinin. Copyright © 2018 Elsevier Inc. All rights reserved.
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Laboratory Studies Offer New Insights for Mesospheric Nightglow
NASA Astrophysics Data System (ADS)
Kalogerakis, K. S.; Matsiev, D.
2017-12-01
The hydroxyl radical has a key role in the chemistry and energetics of the Earth's middle atmosphere. A detailed knowledge of the rate constants and relevant pathways for OH(high v) vibrational relaxation by atomic and molecular oxygen and their temperature dependence is absolutely critical for understanding mesospheric OH and extracting reliable chemical heating rates from atmospheric observations. We have developed laser-based experimental approaches to study the complex collisional energy transfer processes involving the OH radical and other relevant atmospheric species. Work in our laboratory indicated that the total removal rate constant for OH(v = 9) + O at room temperature is more than one order of magnitude larger than that for removal by O2. Thus, O atoms are expected to significantly influence the intensity and vibrational distribution extracted from the Meinel OH(v) emissions. Our recent laboratory measurements corroborated the aforementioned result for OH(v = 9) + O and provided important new insights on the multi-quantum energy transfer pathways involved. We will discuss relevant atmospheric implications, including warranted revisions of mesospheric nightglow models. Research supported by SRI International Internal R&D and NSF Aeronomy Grant AGS-1441896. Previously funded by NASA Geospace Science Grant NNX12AD09G.
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Antioxidant Activities of Functional Beverage Concentrates Containing Herbal Medicine Extracts.
Park, Seon-Joo; Kim, Mi-Ok; Kim, Jung Hoan; Jeong, Sehyun; Kim, Min Hee; Yang, Su-Jin; Lee, Jongsung; Lee, Hae-Jeung
2017-03-01
This study investigated the antioxidant activity of functional beverage concentrates containing herbal medicine extracts (FBCH) using various antioxidant assays, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS) radical scavenging activity, and reducing power assay. The total polyphenolic content of FBCH (81.45 mg/100 g) was higher than Ssanghwa tea (SHT, 37.56 mg/100 g). The antioxidant activities of FBCH showed 52.92% DPPH and 55.18% ABTS radical scavenging activities at 100 mg/mL, respectively. FBCH showed significantly higher antioxidant activities compared to the SHT (DPPH, 23.43%; ABTS, 22.21%; reducing power optical density; 0.23, P <0.05). In addition, intracellular reactive oxygen species generation significantly decreased in a concentration-dependent manner following FBCH treatment. These results suggest that the addition of herbal medicine extract contributes to the improved functionality of beverage concentrates.
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Interactions of Oxygen and Hydrogen on Pd(111) surface
DOE Office of Scientific and Technical Information (OSTI.GOV)
Demchenko, D.O.; Sacha, G.M.; Salmeron, M.
2008-06-25
The coadsorption and interactions of oxygen and hydrogen on Pd(1 1 1) was studied by scanning tunneling microscopy and density functional theory calculations. In the absence of hydrogen oxygen forms a (2 x 2) ordered structure. Coadsorption of hydrogen leads to a structural transformation from (2 x 2) to a ({radical}3 x {radical}3)R30 degree structure. In addition to this transformation, hydrogen enhances the mobility of oxygen. To explain these observations, the interaction of oxygen and hydrogen on Pd(1 1 1) was studied within the density functional theory. In agreement with the experiment the calculations find a total energy minimum formore » the oxygen (2 x 2) structure. The interaction between H and O atoms was found to be repulsive and short ranged, leading to a compression of the O islands from (2 x 2) to ({radical}3 x {radical}3)R30 degree ordered structure at high H coverage. The computed energy barriers for the oxygen diffusion were found to be reduced due to the coadsorption of hydrogen, in agreement with the experimentally observed enhancement of oxygen mobility. The calculations also support the finding that at low temperatures the water formation reaction does not occur on Pd(1 1 1).« less
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Prostate brachytherapy - discharge
... chap 84. Read More Prostate brachytherapy Prostate cancer Prostate-specific antigen (PSA) blood test Radical prostatectomy Review Date 2/21/2017 Updated by: Jennifer Sobol, DO, Urologist with the Michigan ... Cancer Browse the Encyclopedia A.D.A.M., ...