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Drug-coated balloon angioplasty after directional atherectomy improves outcome in restenotic femoropopliteal arteries.

PubMed

Sixt, Sebastian; Carpio Cancino, Oscar Gerardo; Treszl, András; Beschorner, Ulrich; Macharzina, Roland; Rastan, Aljoscha; Krankenberg, Hans; Neumann, Franz-Josef; Zeller, Thomas

2013-09-01

Restenosis remains an unresolved problem despite different treatment modalities and new stent technology in femoropopliteal arteries. No standard therapy has proven to provide acceptable outcome data for this entity. Directional atherectomy alone did not result in satisfactory long-term patency rates. The outcome might be improved in conjunction with drug-coated balloon angioplasty. In this retrospective study, restenotic lesions of the femoropopliteal arteries were treated with directed atherectomy in 89 lesions of consecutive patients (58% male; mean age, 69 ± 11 years). All patients received adjunctive treatment with conventional balloon percutaneous angioplasty (PTA; n = 60) or drug-coated balloon angioplasty (DCB; n = 29). Lesion location was in the stent (DCB [n = 27] vs PTA [n = 36]) and in native restenotic vessels (DCB [n = 2] vs PTA [n = 25]). The 1-year Kaplan-Meier freedom from restenosis estimates (95% confidence intervals) in the DCB and PTA groups were 84.7% (70.9%-98.5%) and 43.8% (30.5%-57.1%), respectively. In a multivariable Cox model for restenosis, DCB treatment had a hazard ratio (95% confidence interval) of 0.28 (0.12-0.66; P = .0036) compared with the PTA group. In the multivariable model for procedural success, the effect of treatment did not differ between PTA and DCB (P = .134). The combination of directed atherectomy with adjunctive DCB is associated with a better event-free survival at 12 months of follow-up compared with PTA after directed atherectomy. Copyright © 2013 Society for Vascular Surgery. Published by Mosby, Inc. All rights reserved.

Treatment of femoro-popliteal lesions with scoring and drug-coated balloon angioplasty: 12-month results of the DCB-Trak registry.

PubMed

Baumhäkel, Magnus; Chkhetia, Shalva; Kindermann, Michael

2018-01-01

Debulking strategies prior to drug-coated balloon (DCB) angioplasty were suggested to improve clinical results in femoro-popliteal lesions. Currently, there are no data regarding plaque modification with a scoring balloon with subsequent DCB-angioplasty. Recently published 6-month results of the DCB-Trak registry in patients treated with scoring-balloon angioplasty and DCB-angioplasty were promising without any safety concerns. Herein, we report the 12-month follow-up data. In a single center registry, 29 consecutive patients with 32 femoro-popliteal lesions were treated with a scoring-balloon (VascuTrak®) and a DCB subsequently. The primary endpoint was the clinically driven target lesion revascularization (TLR). Secondary endpoints were clinically driven target vessel revascularization (TVR), binary restenosis (peak systolic velocity ratio > 2.4), change in Rutherford classification and ankle-brachial-index (ABI). Safety endpoints were major cardiovascular events (cardiovascular death, myocardial infarction, stroke, death) and need for amputation. The procedure was successful in 29 lesions. There were no clinically driven TLRs after 12 months. Two patients required clinically driven TVR and one patient had a binary restenosis. ABI significantly increased after the procedure (0.87±0.24 to 1.04±0.18, P < 0.01) without a relevant change after 6 months (1.01±0.15, P < 0.05) or 12 months (1.01±0.20, P < 0.05). Rutherford classification improved in more than 90% of patients after 6 and 12 months. There was one major cardiovascular event at 6-month follow-up, but no amputations at 6- or 12-month follow-up. Vessel preparation with a scoring-balloon and subsequent DCB-angioplasty was safe and effective in patients with femoro-popliteal lesions. Further multicenter trials have to validate these results.

Spectral and thermodynamic properties for the exciplexes of N-alkyl carbazoles with dicyanobenzenes in THF

NASA Astrophysics Data System (ADS)

Asim, Sadia; Mansha, Asim; Landgraf, Stephan; Grampp, Günter; Zahid, Muhammad; Bhatti, Haq Nawaz

2014-01-01

The exciplex emission spectra of N-ethylcarbazole with 1,2-dicyanobenzene (NEC/1,2-DCB), N-methylcarbazole with 1,2-dicyanobenzene (NMC/1,2-DCB), 1,3-dicyanobenzene (NMC/1,3-DCB), and 1,4-dicyanobenzene (NMC/1,4-DCB) are studied in tetrahydrofuran (THF) for the temperature range starting from 253 K to 334 K. Thermochromic shifts along with the spectral properties including change in peak intensities and the ratio of exciplex peak intensity to fluorophore peak intensity are studied. Effect of temperature on the energy of zero-zero transitions hνo‧, Huang-Rhys factor (S), Gauss broadening of vibronic level (σ) and the dominant high-frequency vibration (hνν) are also part of investigation. Enthalpy of exciplex formation (ΔHEX∗) calculated by the model proposed by A. Weller and the Gibb's energy of electron transfer (ΔGet∗) for all exciplex systems are also discussed in the present paper. All the exciplexes under study were observed to be dipolar in nature. The exciplex of the N-methylcarbazole/1,4-dicyanobenzene was found to be the most stable and the N-methylcarbazole/1,3-dicyanobenzene was the weakest exciplex system.

Streptomyces sp. is a powerful biotechnological tool for the biodegradation of HCH isomers: biochemical and molecular basis.

PubMed

Cuozzo, S A; Sineli, P E; Davila Costa, J; Tortella, G

2018-08-01

Actinobacteria are well-known degraders of toxic materials that have the ability to tolerate and remove organochloride pesticides; thus, they are used for bioremediation. The biodegradation of organochlorines by actinobacteria has been demonstrated in pure and mixed cultures with the concomitant production of metabolic intermediates including γ-pentachlorocyclohexene (γ-PCCH); 1,3,4,6-tetrachloro-1,4-cyclohexadiene (1,4-TCDN); 1,2-dichlorobenzene (1,2-DCB), 1,3-dichlorobenzene (1,3-DCB), or 1,4-dichlorobenzene (1,4-DCB); 1,2,3-trichlorobenzene (1,2,3-TCB), 1,2,4-trichlorobenzene (1,2,4-TCB), or 1,3,5-trichlorobenzene (1,3,5-TCB); 1,3-DCB; and 1,2-DCB. Chromatography coupled to mass spectrometric detection, especially GC-MS, is typically used to determine HCH-isomer metabolites. The important enzymes involved in HCH isomer degradation metabolic pathways include hexachlorocyclohexane dehydrochlorinase (LinA), haloalkane dehalogenase (LinB), and alcohol dehydrogenase (LinC). The metabolic versatility of these enzymes is known. Advances have been made in the identification of actinobacterial haloalkane dehydrogenase, which is encoded by linB. This knowledge will permit future improvements in biodegradation processes using Actinobacteria. The enzymatic and genetic characterizations of the molecular mechanisms involved in these processes have not been fully elucidated, necessitating further studies. New advances in this area suggest promising results. The scope of this paper encompasses the following: (i) the aerobic degradation pathways of hexachlorocyclohexane (HCH) isomers; (ii) the important genes and enzymes involved in the metabolic pathways of HCH isomer degradation; and (iii) the identification and quantification of intermediate metabolites through gas chromatography coupled to mass spectrometry (GC-MS).

Radical-Containing Ultrafine Particulate Matter Initiates Epithelial-to-Mesenchymal Transitions in Airway Epithelial Cells

PubMed Central

Thevenot, Paul T.; Saravia, Jordy; Jin, Nili; Giaimo, Joseph D.; Chustz, Regina E.; Mahne, Sarah; Kelley, Matthew A.; Hebert, Valeria Y.; Dellinger, Barry; Dugas, Tammy R.; DeMayo, Francesco J.

2013-01-01

Environmentally persistent free radicals (EPFRs) in combustion-generated particulate matter (PM) are capable of inducing pulmonary pathologies and contributing to the development of environmental asthma. In vivo exposure of infant rats to EPFRs demonstrates their ability to induce airway hyperresponsiveness to methacholine, a hallmark of asthma. However, the mechanisms by which combustion-derived EPFRs elicit in vivo responses remain elusive. In this study, we used a chemically defined EPFR consisting of approximately 0.2 μm amorphrous silica containing 3% cupric oxide with the organic pollutant 1,2-dichlorobenzene (DCB-230). DCB-230 possesses similar radical content to urban-collected EPFRs but offers several advantages, including lack of contaminants and chemical uniformity. DCB-230 was readily taken up by BEAS-2B and at high doses (200 μg/cm2) caused substantial necrosis. At low doses (20 μg/cm2), DCB-230 particles caused lysosomal membrane permeabilization, oxidative stress, and lipid peroxidation within 24 hours of exposure. During this period, BEAS-2B underwent epithelial-to-mesenchymal transition (EMT), including loss of epithelial cell morphology, decreased E-cadherin expression, and increased α–smooth muscle actin (α-SMA) and collagen I production. Similar results were observed in neonatal air–liquid interface culture (i.e., disruption of epithelial integrity and EMT). Acute exposure of infant mice to DCB-230 resulted in EMT, as confirmed by lineage tracing studies and evidenced by coexpression of epithelial E-cadherin and mesenchymal α-SMA proteins in airway cells and increased SNAI1 expression in the lungs. EMT in neonatal mouse lungs after EPFR exposure may provide an explanation for epidemiological evidence supporting PM exposure and increased risk of asthma. PMID:23087054

The Impact of Satellite Time Group Delay and Inter-Frequency Differential Code Bias Corrections on Multi-GNSS Combined Positioning

PubMed Central

Ge, Yulong; Zhou, Feng; Sun, Baoqi; Wang, Shengli; Shi, Bo

2017-01-01

We present quad-constellation (namely, GPS, GLONASS, BeiDou and Galileo) time group delay (TGD) and differential code bias (DCB) correction models to fully exploit the code observations of all the four global navigation satellite systems (GNSSs) for navigation and positioning. The relationship between TGDs and DCBs for multi-GNSS is clearly figured out, and the equivalence of TGD and DCB correction models combining theory with practice is demonstrated. Meanwhile, the TGD/DCB correction models have been extended to various standard point positioning (SPP) and precise point positioning (PPP) scenarios in a multi-GNSS and multi-frequency context. To evaluate the effectiveness and practicability of broadcast TGDs in the navigation message and DCBs provided by the Multi-GNSS Experiment (MGEX), both single-frequency GNSS ionosphere-corrected SPP and dual-frequency GNSS ionosphere-free SPP/PPP tests are carried out with quad-constellation signals. Furthermore, the author investigates the influence of differential code biases on GNSS positioning estimates. The experiments show that multi-constellation combination SPP performs better after DCB/TGD correction, for example, for GPS-only b1-based SPP, the positioning accuracies can be improved by 25.0%, 30.6% and 26.7%, respectively, in the N, E, and U components, after the differential code biases correction, while GPS/GLONASS/BDS b1-based SPP can be improved by 16.1%, 26.1% and 9.9%. For GPS/BDS/Galileo the 3rd frequency based SPP, the positioning accuracies are improved by 2.0%, 2.0% and 0.4%, respectively, in the N, E, and U components, after Galileo satellites DCB correction. The accuracy of Galileo-only b1-based SPP are improved about 48.6%, 34.7% and 40.6% with DCB correction, respectively, in the N, E, and U components. The estimates of multi-constellation PPP are subject to different degrees of influence. For multi-constellation combination SPP, the accuracy of single-frequency is slightly better than that of dual-frequency combinations. Dual-frequency combinations are more sensitive to the differential code biases, especially for the 2nd and 3rd frequency combination, such as for GPS/BDS SPP, accuracy improvements of 60.9%, 26.5% and 58.8% in the three coordinate components is achieved after DCB parameters correction. For multi-constellation PPP, the convergence time can be reduced significantly with differential code biases correction. And the accuracy of positioning is slightly better with TGD/DCB correction. PMID:28300787

The Impact of Satellite Time Group Delay and Inter-Frequency Differential Code Bias Corrections on Multi-GNSS Combined Positioning.

PubMed

Ge, Yulong; Zhou, Feng; Sun, Baoqi; Wang, Shengli; Shi, Bo

2017-03-16

We present quad-constellation (namely, GPS, GLONASS, BeiDou and Galileo) time group delay (TGD) and differential code bias (DCB) correction models to fully exploit the code observations of all the four global navigation satellite systems (GNSSs) for navigation and positioning. The relationship between TGDs and DCBs for multi-GNSS is clearly figured out, and the equivalence of TGD and DCB correction models combining theory with practice is demonstrated. Meanwhile, the TGD/DCB correction models have been extended to various standard point positioning (SPP) and precise point positioning (PPP) scenarios in a multi-GNSS and multi-frequency context. To evaluate the effectiveness and practicability of broadcast TGDs in the navigation message and DCBs provided by the Multi-GNSS Experiment (MGEX), both single-frequency GNSS ionosphere-corrected SPP and dual-frequency GNSS ionosphere-free SPP/PPP tests are carried out with quad-constellation signals. Furthermore, the author investigates the influence of differential code biases on GNSS positioning estimates. The experiments show that multi-constellation combination SPP performs better after DCB/TGD correction, for example, for GPS-only b1-based SPP, the positioning accuracies can be improved by 25.0%, 30.6% and 26.7%, respectively, in the N, E, and U components, after the differential code biases correction, while GPS/GLONASS/BDS b1-based SPP can be improved by 16.1%, 26.1% and 9.9%. For GPS/BDS/Galileo the 3rd frequency based SPP, the positioning accuracies are improved by 2.0%, 2.0% and 0.4%, respectively, in the N, E, and U components, after Galileo satellites DCB correction. The accuracy of Galileo-only b1-based SPP are improved about 48.6%, 34.7% and 40.6% with DCB correction, respectively, in the N, E, and U components. The estimates of multi-constellation PPP are subject to different degrees of influence. For multi-constellation combination SPP, the accuracy of single-frequency is slightly better than that of dual-frequency combinations. Dual-frequency combinations are more sensitive to the differential code biases, especially for the 2nd and 3rd frequency combination, such as for GPS/BDS SPP, accuracy improvements of 60.9%, 26.5% and 58.8% in the three coordinate components is achieved after DCB parameters correction. For multi-constellation PPP, the convergence time can be reduced significantly with differential code biases correction. And the accuracy of positioning is slightly better with TGD/DCB correction.

Correlating Coating Characteristics with the Performance of Drug-Coated Balloons – A Comparative In Vitro Investigation of Own Established Hydrogel- and Ionic Liquid-Based Coating Matrices

PubMed Central

Kaule, Sebastian; Minrath, Ingo; Stein, Florian; Kragl, Udo; Schmidt, Wolfram; Schmitz, Klaus-Peter; Sternberg, Katrin; Petersen, Svea

2015-01-01

Drug-coated balloons (DCB), which have emerged as a therapeutic alternative to drug-eluting stents in percutaneous cardiovascular intervention, are well described with regard to clinical efficacy and safety within a number of clinical studies. In vitro studies elucidating the correlation between coating additive and DCB performance are however rare but considered important for the understanding of DCB requirements and the improvement of established DCB. In this regard, we examined three different DCB-systems, which were developed in former studies based on the ionic liquid cetylpyridinium salicylate, the body-own hydrogel hyaluronic acid and the pharmaceutically well-established hydrogel polyvinylpyrrolidone, considering coating morphology, coating thickness, drug-loss, drug-transfer to the vessel wall, residual drug-concentration on the balloon surface and entire drug-load during simulated use in an in vitro vessel model. Moreover, we investigated particle release of the different DCB during simulated use and determined the influence of the three coatings on the mechanical behavior of the balloon catheter. We could show that coating characteristics can be indeed correlated with the performance of DCB. For instance, paclitaxel incorporation in the matrix can reduce the drug wash-off and benefit a high drug transfer. Additionally, a thin coating with a smooth surface and high but delayed solubility can reduce drug wash-off and decrease particle burden. As a result, we suggest that it is very important to characterize DCB in terms of mentioned properties in vitro in addition to their clinical efficacy in order to better understand their function and provide more data for the clinicians to improve the tool of DCB in coronary angioplasty. PMID:25734818

Drug‐coated balloons for de novo lesions in small coronary arteries: rationale and design of BASKET‐SMALL 2

PubMed Central

Gilgen, Nicole; Farah, Ahmed; Scheller, Bruno; Ohlow, Marc‐Alexander; Mangner, Norman; Weilenmann, Daniel; Wöhrle, Jochen; Jamshidi, Peiman; Leibundgut, Gregor; Möbius‐Winkler, Sven; Zweiker, Robert; Krackhardt, Florian; Butter, Christian; Bruch, Leonhard; Kaiser, Christoph; Hoffmann, Andreas; Rickenbacher, Peter; Mueller, Christian; Stephan, Frank‐Peter; Coslovsky, Michael

2018-01-01

The treatment of coronary small vessel disease (SVD) remains an unresolved issue. Drug‐eluting stents (DES) have limited efficacy due to increased rates of instent‐restenosis, mainly caused by late lumen loss. Drug‐coated balloons (DCB) are a promising technique because native vessels remain structurally unchanged. Basel Stent Kosten‐Effektivitäts Trial: Drug‐Coated Balloons vs. Drug‐Eluting Stents in Small Vessel Interventions (BASKET‐SMALL 2) is a multicenter, randomized, controlled, noninferiority trial of DCB vs DES in native SVD for clinical endpoints. Seven hundred fifty‐eight patients with de novo lesions in vessels <3 mm in diameter and an indication for percutaneous coronary intervention such as stable angina pectoris, silent ischemia, or acute coronary syndromes are randomized 1:1 to angioplasty with DCB vs implantation of a DES after successful initial balloon angioplasty. The primary endpoint is the combination of cardiac death, nonfatal myocardial infarction, and target‐vessel revascularization up to 1 year. Secondary endpoints include stent thrombosis, Bleeding Academic Research Consortium (BARC) type 3 to 5 bleeding, and long‐term outcome up to 3 years. Based on clinical endpoints after 1 year, we plan to assess the noninferiority of DCB compared to DES in patients undergoing primary percutaneous coronary intervention for SVD. Results will be available in the second half of 2018. This study will compare DCB and DES regarding long‐term safety and efficacy for the treatment of SVD in a large all‐comer population. PMID:29527709

A modified carrier-to-code leveling method for retrieving ionospheric observables and detecting short-term temporal variability of receiver differential code biases

NASA Astrophysics Data System (ADS)

Zhang, Baocheng; Teunissen, Peter J. G.; Yuan, Yunbin; Zhang, Xiao; Li, Min

2018-03-01

Sensing the ionosphere with the global positioning system involves two sequential tasks, namely the ionospheric observable retrieval and the ionospheric parameter estimation. A prominent source of error has long been identified as short-term variability in receiver differential code bias (rDCB). We modify the carrier-to-code leveling (CCL), a method commonly used to accomplish the first task, through assuming rDCB to be unlinked in time. Aside from the ionospheric observables, which are affected by, among others, the rDCB at one reference epoch, the Modified CCL (MCCL) can also provide the rDCB offsets with respect to the reference epoch as by-products. Two consequences arise. First, MCCL is capable of excluding the effects of time-varying rDCB from the ionospheric observables, which, in turn, improves the quality of ionospheric parameters of interest. Second, MCCL has significant potential as a means to detect between-epoch fluctuations experienced by rDCB of a single receiver.

Evidence for a pore-filling mechanism in the adsorption of aromatic hydrocarbons to a natural wood char.

PubMed

Nguyen, Thanh H; Cho, Hyun-Hee; Poster, Dianne L; Ball, William P

2007-02-15

Sorption isotherms for five aromatic hydrocarbons were obtained with a natural wood char (NC1) and its residue after solvent extraction (ENC1). Substantial isotherm nonlinearity was observed in all cases. ENC1 showed higher BET surface area, higher nitrogen-accessible micropore volume, and lower mass of extractable organic chemicals, including quantifiable polycyclic aromatic hydrocarbons (PAHs),while the two chars showed identical surface oxygen/ carbon (O/C) ratio. For two chlorinated benzenes that normally condense as liquids at the temperatures used, sorption isotherms with NC1 and ENC1 were found to be statistically identical. For the solid-phase compounds (1,4-dichlorobenzene (1,4-DCB) and two PAHs), sorption was statistically higher with ENC1, thus demonstrating sorption effects due to both (1) authigenic organic content in the sorbentand (2)the sorbate's condensed state. Polanyi-based isotherm modeling, pore size measurements, and comparisons with activated carbon showthe relative importance of adsorptive pore filling and help explain results. With both chars, maximum sorption increased in the order of decreasing molecular diameter: phenanthrene < naphthalene < 1,2-dichlorobenzene/1,2,4-trichlorobenzene < 1,4-DCB. Comparison of 1,4- and 1,2-DCB shows that the critical molecular diameter was apparently more important than the condensed state, suggesting that 1,4-DCB sorbed in the liquid state for ENC1.

Preparation and structural characterization of zwitterionic surfactant intercalated into NiZn-layered hydroxide salts

NASA Astrophysics Data System (ADS)

Liu, Jiexiang; Wang, Jianlong; Zhang, Xiaoguang; Fang, Binbin; Hu, Pan; Zhao, Xuyang

2015-10-01

Three zwitterionic surfactants, dodecyl dimethyl carboxylbetaine (DCB), dodecyl dimethyl sulfobetaine (DSB) and N-dodecyl-β-aminoprpionate (DAP), intercalated into NiZn-layered hydroxide salts (NZL-DCB, NZL-DSB and NZL-DAP) were synthesized by the coprecipitation method. The effect of surfactant content, pH, temperature and time of hydrothermal treatment on preparation was investigated and discussed. The NZL-DCB, NZL-DSB and NZL-DAP were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry analysis and differential thermal analysis (TGA/DTA). The results showed that basal spacings of NZL-DCB, NZL-DSB and NZL-DAP were around 3.45, 3.68 and 3.94 nm, respectively. DCB, DSB and DAP probably form an overlapped bilayer in the gallery. TGA/DTA data indicated that NZL-DCB, NZL-DSB and NZL-DAP displayed three loss weight stages: loss of adsorbed and structural water, dehydroxylation of matrix and decomposition of nitrate ions, decomposition and combustion of surfactants. Furthermore, chemical analysis data, BET surface area and scanning electron microscopic (SEM) were also measured and analyzed.

Drug-coated balloons for de novo lesions in small coronary arteries: rationale and design of BASKET-SMALL 2.

PubMed

Gilgen, Nicole; Farah, Ahmed; Scheller, Bruno; Ohlow, Marc-Alexander; Mangner, Norman; Weilenmann, Daniel; Wöhrle, Jochen; Jamshidi, Peiman; Leibundgut, Gregor; Möbius-Winkler, Sven; Zweiker, Robert; Krackhardt, Florian; Butter, Christian; Bruch, Leonhard; Kaiser, Christoph; Hoffmann, Andreas; Rickenbacher, Peter; Mueller, Christian; Stephan, Frank-Peter; Coslovsky, Michael; Jeger, Raban

2018-05-01

The treatment of coronary small vessel disease (SVD) remains an unresolved issue. Drug-eluting stents (DES) have limited efficacy due to increased rates of instent-restenosis, mainly caused by late lumen loss. Drug-coated balloons (DCB) are a promising technique because native vessels remain structurally unchanged. Basel Stent Kosten-Effektivitäts Trial: Drug-Coated Balloons vs. Drug-Eluting Stents in Small Vessel Interventions (BASKET-SMALL 2) is a multicenter, randomized, controlled, noninferiority trial of DCB vs DES in native SVD for clinical endpoints. Seven hundred fifty-eight patients with de novo lesions in vessels <3 mm in diameter and an indication for percutaneous coronary intervention such as stable angina pectoris, silent ischemia, or acute coronary syndromes are randomized 1:1 to angioplasty with DCB vs implantation of a DES after successful initial balloon angioplasty. The primary endpoint is the combination of cardiac death, nonfatal myocardial infarction, and target-vessel revascularization up to 1 year. Secondary endpoints include stent thrombosis, Bleeding Academic Research Consortium (BARC) type 3 to 5 bleeding, and long-term outcome up to 3 years. Based on clinical endpoints after 1 year, we plan to assess the noninferiority of DCB compared to DES in patients undergoing primary percutaneous coronary intervention for SVD. Results will be available in the second half of 2018. This study will compare DCB and DES regarding long-term safety and efficacy for the treatment of SVD in a large all-comer population. © 2018 The Authors. Clinical Cardiology published by Wiley Periodicals, Inc.

A Small Range Six-Axis Accelerometer Designed with High Sensitivity DCB Elastic Element

PubMed Central

Sun, Zhibo; Liu, Jinhao; Yu, Chunzhan; Zheng, Yili

2016-01-01

This paper describes a small range six-axis accelerometer (the measurement range of the sensor is ±g) with high sensitivity DCB (Double Cantilever Beam) elastic element. This sensor is developed based on a parallel mechanism because of the reliability. The accuracy of sensors is affected by its sensitivity characteristics. To improve the sensitivity, a DCB structure is applied as the elastic element. Through dynamic analysis, the dynamic model of the accelerometer is established using the Lagrange equation, and the mass matrix and stiffness matrix are obtained by a partial derivative calculation and a conservative congruence transformation, respectively. By simplifying the structure of the accelerometer, a model of the free vibration is achieved, and the parameters of the sensor are designed based on the model. Through stiffness analysis of the DCB structure, the deflection curve of the beam is calculated. Compared with the result obtained using a finite element analysis simulation in ANSYS Workbench, the coincidence rate of the maximum deflection is 89.0% along the x-axis, 88.3% along the y-axis and 87.5% along the z-axis. Through strain analysis of the DCB elastic element, the sensitivity of the beam is obtained. According to the experimental result, the accuracy of the theoretical analysis is found to be 90.4% along the x-axis, 74.9% along the y-axis and 78.9% along the z-axis. The measurement errors of linear accelerations ax, ay and az in the experiments are 2.6%, 0.6% and 1.31%, respectively. The experiments prove that accelerometer with DCB elastic element performs great sensitive and precision characteristics. PMID:27657089

Molybdenum(V) complexes with formate: Geometric isomerism of the [Mo2O4Cl2(Py)2(HCOO)]- ion

NASA Astrophysics Data System (ADS)

Modec, Barbara; Dolenc, Darko

2013-11-01

Reactions of (PyH)5[MoOCl4(H2O)]3Cl2 with formate resulted in trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1) and cis-(PyH)[Mo2O4Cl2(Py)2(HCOO)] (2), whereas the bromide starting material (PyH)[MoOBr4], yielded (PyH)3[Mo2O4Br4(HCOO)]·2CH3CN (3) and cis-(PyH)[Mo2O4Br2(Py)2(HCOO)] (4) (where Py stands for pyridine, PyH+ for pyridinium cation and (Py)2H+ for a hydrogen-bonded PyH+⋯Py ion). In all, the dinuclear metal-metal bonded { core may be recognized with its six coordination sites distributed among halides, pyridine ligands and formate. The latter is coordinated via both oxygen atoms, with each to a different metal ion. The [Mo2O4Cl2(Py)2(HCOO)]- ion exhibits geometric isomerism: the pyridine ligands, on each metal ion one, are either trans or cis to each other. The trans isomer crystallized with (Py)2H+ countercations, whereas the cis isomer as a PyH+ salt. In the crystal lattice of cis-(PyH)[Mo2O4Cl2(Py)2(HCOO)] (2), as confirmed by the X-ray structure analysis, pyridinium cation forms a hydrogen bond with the doubly-bridging oxide of the cis-[Mo2O4Cl2(Py)2(HCOO)]- ion. The countercations of trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1) cannot participate in hydrogen-bonding. The DFT calculations on the isomers of the [Mo2O4Cl2(Py)2(HCOO)]- ion show the trans isomer to be by ca. 15 kJ/mol more stable than the cis isomer. The calculations on the hydrogen-bonded PyH+⋯[Mo2O4Cl2(Py)2(HCOO)]- ion-pairs show a reversed order of stability. Hydrogen-bonding and weak Csbnd H⋯Cl interactions between PyH+ cations and the cis-[Mo2O4Cl2(Py)2(HCOO)]- ion increase the stability of the cis compound.

High-surface Thermally Stable Mesoporous Gallium Phosphates Constituted by Nanoparticles as Primary Building Blocks

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

V Parvulescu; V Parvulescu; D Ciuparu

In constant, search for micro/mesoporous materials, gallium phosphates, have attracted continued interest due to the large pore size reported for some of these solids in comparison with analogous aluminum phosphates. However up to now, the porosity of gallium phosphates collapsed upon template removal or exposure to the ambient moisture. In the present work, we describe high-surface thermally stable mesoporous gallium phosphates synthesized from gallium propoxide and PCl{sub 3} and different templating agents such as amines (dipropylamine, piperidine and aminopiperidine) and quaternary ammonium salts (C{sub 16}H{sub 33}(CH{sub 3})3NBr and C{sub 16}PyCl). These highly reactive precursors have so far not been usedmore » as gallium and phosphate sources for the synthesis of gallophosphates. Conceptually, our present synthetic procedure is based on the fast formation of gallium phosphate nanoparticles via the reaction of gallium propoxide with PCl{sub 3} and subsequent construction of the porous material with nanoparticles as building blocks. The organization of the gallophosphate nanoparticles in stable porous structures is effected by the templates. Different experimental procedures varying the molar composition of the sol-gel, pH and the pretreatment of gallium precursor were assayed, most of them leading to satisfactory materials in terms of thermal stability and porosity. In this way, a series of gallium phosphates with surface are above 200 m{sup 2} g{sup -1}, and narrow pore size from 3 to 6 nm and remarkable thermal stability (up to 550 C) have been prepared. In some cases, the structure tends to show some periodicity and regularity as determined by XRD. The remarkable stability has allowed us to test the catalytic activity of gallophosphates for the aerobic oxidation of alkylaromatics with notable good results. Our report reopens the interest for gallophosphates in heterogeneous catalysis.« less

Therapeutic potential of DCB-SLE1, an extract of a mixture of Chinese medicinal herbs, for severe lupus nephritis.

PubMed

Tsai, Pei-Yi; Ka, Shuk-Man; Chang, Jia-Ming; Chang, Wen-Liang; Huang, Yuan-Jen; Hung, Le-Mei; Jheng, Huei-Lin; Wu, Rey-Yuh; Chen, Ann

2011-10-01

The pathogenesis of lupus nephritis is mainly attributable to a complex interaction between the innate and adaptive immune systems, including T and B cell function abnormalities. In addition to autoantibody production and immune complex deposition, Th1 and Th17 cytokines may play key roles in the development and progression of lupus nephritis. Acute onset of severe lupus nephritis remains a challenge in terms of prevention and treatment. In the present study, we evaluated the therapeutic effects of DCB-SLE1, an extract of a mixture of four traditional Chinese medicinal herbs (Atractylodis macrocephalae Rhizoma, Eucommiae cortex, Lonicerae caulis, and Hedyotidis diffusae Herba), on an accelerated severe lupus nephritis model, characterized by acute onset of proteinuria, azotemia, autoantibody production, and development of severe nephritis, induced by twice weekly injection of New Zealand black/white F1 mice with Salmonella-type lipopolysaccharide. DCB-SLE1 was administered daily by gavage starting 2 days after the first dose of induction of lipopolysaccharide, and the mice were euthanized at week 1 or week 5. The results showed that DCB-SLE1 significantly ameliorated the hematuria, proteinuria, renal dysfunction, and severe renal lesions by 1) suppression of B cell activation and decreased autoantibody production; 2) negative regulation of T cell activation/proliferation and natural killer cell activity; 3) suppression of IL-18, IL-6, and IL-17 production and blocking of NF-κB activation in the kidney; and 4) prevention of lymphoid and renal apoptosis. These results show that DCB-SLE1 can protect the kidney from autoimmune response-mediated acute and severe damage through systemic immune modulation and anti-inflammation pathways.

Clinical Outcomes of Drug-Coated Balloons in Coronary Artery Disease Unsuitable for Drug-Eluting Stent Implantation.

PubMed

Iijima, Raisuke; Kougame, Norihiro; Hara, Hidehiko; Moroi, Masao; Nakamura, Masato

2018-06-12

The aim of this study was to investigate whether drug-coated balloon (DCB) treatment is effective for de novo coronary lesions that are unsuitable for drug-eluting stent (DES) implantation.Methods and Results:This retrospective study included 118 de novo lesions that were not suitable for DES implantation. Of the lesions, 40% was treated because of very small vessel disease. Patients with planned non-cardiac surgery and at high bleeding risk were 3% and 19%, respectively, and lesions that easily develop stent fracture comprised 26%. Clinically driven target lesion revascularization (TLR) was the primary endpoint. The rate of suboptimal lesion preparation before DCB treatment was set as the secondary endpoint. Optimal lesion preparation was defined as acquisition of Thrombolysis in Myocardial Infarction flow grade 3, minor coronary dissection, and residual stenosis ≤30%. The rate of suboptimal lesion preparation was 2.5% and 3 patients needed bail-out stenting. Accordingly, 115 patients were treated with a DCB. Clinically driven TLR had occurred in 8 patients (7.0%) at the 8-month follow-up. The presence of chronic total occlusion was identified as an independent predictor for TLR (odds 11.57; 95% confidence interval, 1.38-135.54; P=0.02). For lesions that are unsuitable for stent implantation, stent-less intervention using a DCB should be considered initially. The present study also highlighted that lesion preparation is key to a successful DCB strategy.

Environmentally persistent free radicals decrease cardiac function before and after ischemia/reperfusion injury in vivo

PubMed Central

Lord, Kevin; Moll, David; Lindsey, John K.; Mahne, Sarah; Raman, Girija; Dugas, Tammy; Cormier, Stephania; Troxlair, Dana; Lomnicki, Slawo; Dellinger, Barry; Varner, Kurt

2011-01-01

Exposure to airborne particles is associated with increased cardiovascular morbidity and mortality. During the combustion of chlorine-containing hazardous materials and fuels, chlorinated hydrocarbons chemisorb to the surface of transition metal-oxide-containing particles, reduce the metal, and form an organic free radical. These radical-particle systems can survive in the environment for days and are called environmentally persistent free radicals (EPFRs). This study determined whether EPFRs could decrease left ventricular function before and after ischemia and reperfusion (I/R) in vivo. Male Brown Norway rats were dosed (8 mg/kg, i.t.) 24 hr prior to testing with particles containing the EPFR of 1, 2-dichlorobenzene (DCB230). DCB230 treatment decreased systolic and diastolic function. DCB230 also produced pulmonary and cardiac inflammation. After ischemia, systolic, but not diastolic function was significantly decreased in DCB230-treated rats. Ventricular function was not affected by I/R in control rats. There was greater oxidative stress in the heart and increased 8-isoprostane (biomarker of oxidative stress) in the plasma of treated vs control rats after I/R. These data demonstrate for the first time that DCB230 can produce inflammation and significantly decrease cardiac function at baseline and after I/R in vivo. Furthermore, these data suggest that EPFRs may be a risk factor for cardiac toxicity in healthy individuals and individuals with ischemic heart disease. Potential mechanisms involving cytokines/chemokines and/or oxidative stress are discussed. PMID:21385100

Estimation and analysis of the short-term variations of multi-GNSS receiver differential code biases using global ionosphere maps

NASA Astrophysics Data System (ADS)

Li, Min; Yuan, Yunbin; Wang, Ningbo; Liu, Teng; Chen, Yongchang

2017-12-01

Care should be taken to minimize the adverse impact of differential code biases (DCBs) on global navigation satellite systems (GNSS)-derived ionospheric information determinations. For the sake of convenience, satellite and receiver DCB products provided by the International GNSS Service (IGS) are treated as constants over a period of 24 h (Li et al. (2014)). However, if DCB estimates show remarkable intra-day variability, the DCBs estimated as constants over 1-day period will partially account for ionospheric modeling error; in this case DCBs will be required to be estimated over shorter time period. Therefore, it is important to further gain insight into the short-term variation characteristics of receiver DCBs. In this contribution, the IGS combined global ionospheric maps and the German Aerospace Center (DLR)-provided satellite DCBs are used in the improved method to determine the multi-GNSS receiver DCBs with an hourly time resolution. The intra-day stability of the receiver DCBs is thereby analyzed in detail. Based on 1 month of data collected within the multi-GNSS experiment of the IGS, a good agreement within the receiver DCBs is found between the resulting receiver DCB estimates and multi-GNSS DCB products from the DLR at a level of 0.24 ns for GPS, 0.28 ns for GLONASS, 0.28 ns for BDS, and 0.30 ns for Galileo. Although most of the receiver DCBs are relatively stable over a 1-day period, large fluctuations (more than 9 ns between two consecutive hours) within the receiver DCBs can be found. We also demonstrate the impact of the significant short-term variations in receiver DCBs on the extraction of ionospheric total electron content (TEC), at a level of 12.96 TECu (TEC unit). Compared to daily receiver DCB estimates, the hourly DCB estimates obtained from this study can reflect the short-term variations of the DCB estimates more dedicatedly. The main conclusion is that preliminary analysis of characteristics of receiver DCB variations over short-term intervals should be finished prior to estimate daily multi-GNSS receiver DCB products.

Teratologic evaluation of p-dichlorobenzene in the rat

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

Giavini, E.; Broccia, M.L.; Prati, M.

1986-08-01

p-Dichlorobenzene (p-DCB) is a significant environmental chemical largely used as a moth repellent, space deodorant and fungicide. Long term rodents studies did not demonstrate carcinogenic potential after inhalation exposure levels up to 500 ppm. Teratogenic study in rats exposed to atmospheric concentrations of 75,200 or 500 ppm did not reveal embryotoxic, fetotoxic or teratogenic effects; furthermore p-DCB was not teratogenic or fetotoxic in rabbits are exposure levels up to 800 ppm by inhalation. The purpose of this study was to assess the teratogenic potential of p-DCB by a different route from that of inhalation, allowing higher levels of exposition. Pregnantmore » rats were exposed p-DCB by gavage.« less

Toxic effects of 1,4-dichlorobenzene on photosynthesis in Chlorella pyrenoidosa.

PubMed

Zhang, Jinhua; Wang, Jie; Feng, Jia; Lv, Junping; Cai, Jin; Liu, Qi; Xie, Shulian

2016-09-01

1,4-Dichlorobenzene (1,4-DCB) is a common organic contaminant in water. To determine the effects of this contaminant on photosynthesis in the freshwater alga Chlorella pyrenoidosa, algal cells were treated with 1,4-DCB at different concentrations for various times, and their photosynthetic pigment contents and chlorophyll fluorescence traits were analyzed. The results showed that 1,4-DCB exerted toxic effects on photosynthesis in C. pyrenoidosa, especially at concentrations exceeding 10 mg/L. The inhibitory effects of 1,4-DCB were time- and concentration-dependent. After treatment with 1,4-DCB (≥10 mg/L), the contents of photosynthetic pigments decreased significantly, the photosystem II reaction center was irreversibly damaged, and the quantum yield of photosystem II decreased significantly. Also, there were sharp decreases in the efficiency of photosynthetic electron transport and energy conversion. Photosystem II became overloaded as the amount of excitation energy distributed to it increased. All of these events weakened the photochemical reaction, and ultimately led to serious inhibition of photosynthesis.

Anaerobic bacteria that dechlorinate perchloroethene.

PubMed Central

Fathepure, B Z; Nengu, J P; Boyd, S A

1987-01-01

In this study, we identified specific cultures of anaerobic bacteria that dechlorinate perchlorethene (PCE). The bacteria that significantly dechlorinated PCE were strain DCB-1, an obligate anaerobe previously shown to dechlorinate chlorobenzoate, and two strains of Methanosarcina. The rate of PCE dechlorination by DCB-1 compared favorably with reported rates of trichloroethene bio-oxidation by methanotrophs. Even higher PCE dechlorination rates were achieved when DCB-1 was grown in a methanogenic consortium. PMID:3426224

A Novel Method for Characterizing Fatigue Delamination Growth Under Mode I Using the Double Cantilever Beam Specimen

NASA Technical Reports Server (NTRS)

Carvalho, Nelson; Murri, G.

2014-01-01

A novel method is proposed to obtain Mode I delamination growth rate from a Double Cantilever Beam (DCB) specimen. In the proposed method, Unidirectional (UD) DCB specimens are tested in fatigue at different initial maximum energy release rates levels. The growth rate data obtained in the first increments of crack growth at each maximum energy release rate level are used to generate a Paris Law equation, which characterizes delamination growth rate without fiber-bridging, and can also be used to determine a delamination onset curve. The remaining delamination growth rate data from each test are used to determine a modified Paris law, which characterizes the delamination growth rate in a DCB specimen, explicitly accounting for fiber-bridging. The proposed expression captures well the scatter in experimental data obtained using the DCB specimens, suggesting its adequacy. The Paris Law characterizing delamination growth rate without fiber-bridging predicts higher delamination growth rates for the same maximum energy release rate applied, leading to a conservative estimate for delamination growth. This is particularly relevant, since in generic ply interfaces, fiber-bridging is less predominant than in UD DCB specimens. Failing to account for fiber-bridging in UD DCB specimens may underestimate the delamination growth rate, yielding non-conservative predictions.

Treatment Effect of Drug-Coated Balloons Is Durable to 3 Years in the Femoropopliteal Arteries

PubMed Central

Laird, John R.; Tepe, Gunnar; Brodmann, Marianne; Zeller, Thomas; Scheinert, Dierk; Metzger, Christopher; Micari, Antonio; Sachar, Ravish; Jaff, Michael R.; Wang, Hong; Hasenbank, Melissa S.; Krishnan, Prakash

2018-01-01

Background— Randomized controlled trials have reported favorable 1-year outcomes with drug-coated balloons (DCBs) for the treatment of symptomatic peripheral arterial disease when compared with standard percutaneous transluminal angioplasty (PTA). Evidence remains limited on the durability of the treatment effect with DCBs in the longer term. Methods and Results— IN.PACT SFA is a single-blind, randomized trial (Randomized Trial of IN.PACT Admiral Paclitaxel-Coated Percutaneous Transluminal Angioplasty [PTA] Balloon Catheter vs Standard PTA for the Treatment of Atherosclerotic Lesions in the Superficial Femoral Artery [SFA] and/or Proximal Popliteal Artery [PPA]) that enrolled 331 patients with symptomatic (Rutherford 2–4) femoropopliteal lesions up to 18 cm in length. Patients were randomized 2:1 to receive treatment with DCB or PTA. The 36-month assessments included primary patency, freedom from clinically driven target lesion revascularization, major adverse events, and functional outcomes. At 36 months, primary patency remained significantly higher among patients treated with DCB compared with PTA (69.5% versus 45.1%; log rank P<0.001). The rates of clinically driven target lesion revascularization were 15.2% and 31.1% (P=0.002) for the DCB and PTA groups, respectively. Functional outcomes were similarly improved between treatment groups even though subjects in the DCB group required significantly fewer reinterventions versus those in the PTA group (P<0.001 for target lesion revascularization, P=0.001 for target vessel revascularization). There were no device- or procedure-related deaths as adjudicated by an independent Clinical Events Committee. Conclusions— Three-year results demonstrate a durable and superior treatment effect among patients treated with DCB versus standard PTA, with significantly higher primary patency and lower clinically driven target lesion revascularization, resulting in similar functional improvements with reduced need for repeat interventions. Clinical Trial Registration— URL: http://www.clinicaltrials.gov. Unique identifiers: NCT01175850 for IN.PACT SFA phase I in the European Union and NCT01566461 for IN.PACT SFA phase II in the United States. PMID:29326153

Drug-coated balloon angioplasty for de novo small vessel disease including chronic total occlusion and bifurcation in real-world clinical practice.

PubMed

Onishi, Takayuki; Onishi, Yuko; Kobayashi, Isshi; Umezawa, Shigeo; Niwa, Akihiro

2018-06-18

The aim of this study is to validate the efficacy of drug-coated balloons (DCBs) for real-world de novo small vessel diseases including chronic total occlusion and bifurcation. DCB angioplasty has been reported to be effective in the treatment of de novo small vessel disease. However, the number of reports that have focused on complex lesions is limited. This observational study comprised consecutive patients who underwent DCB angioplasty for de novo small vessel disease with a reference diameter of less than 2.5 mm by visual estimation. Outcome parameters included late lumen loss, restenosis rate, and major adverse cardiac events, such as cardiac death, non-fatal myocardial infarction, and target lesion revascularization (TLR). Fifty-two patients underwent DCB angioplasty for 59 lesions with a reference vessel diameter of 1.93 ± 0.63 mm. Thirty-eight of the lesions (69%) were classified as type B2/C, including chronic total occlusions (20%) and bifurcations (33%). At the 8-month follow-up, late lumen loss was - 0.01 ± 0.44 mm with a restenosis rate of 20%. No cardiac deaths or myocardial infarctions were reported and only 5 (9%) angiographically driven TLRs were reported. DCB angioplasty offered an acceptable 8-month lumen patency and a stable clinical outcome for real-world complex de novo coronary diseases.

Podocyte hypertrophy precedes apoptosis under experimental diabetic conditions.

PubMed

Lee, Sun Ha; Moon, Sung Jin; Paeng, Jisun; Kang, Hye-Young; Nam, Bo Young; Kim, Seonghun; Kim, Chan Ho; Lee, Mi Jung; Oh, Hyung Jung; Park, Jung Tak; Han, Seung Hyeok; Yoo, Tae-Hyun; Kang, Shin-Wook

2015-08-01

Podocyte hypertrophy and apoptosis are two hallmarks of diabetic glomeruli, but the sequence in which these processes occur remains a matter of debate. Here we investigated the effects of inhibiting hypertrophy on apoptosis, and vice versa, in both podocytes and glomeruli, under diabetic conditions. Hypertrophy and apoptosis were inhibited using an epidermal growth factor receptor inhibitor (PKI 166) and a pan-caspase inhibitor (zAsp-DCB), respectively. We observed significant increases in the protein expression of p27, p21, phospho-eukaryotic elongation factor 4E-binding protein 1, and phospho-p70 S6 ribosomal protein kinase, in both cultured podocytes exposed to high-glucose (HG) medium, and streptozotocin-induced diabetes mellitus (DM) rat glomeruli. These increases were significantly inhibited by PKI 166, but not by zAsp-DCB. In addition, the amount of protein per cell, the relative cell size, and the glomerular volume were all significantly increased under diabetic conditions, and these changes were also blocked by treatment with PKI 166, but not zAsp-DCB. Increased protein expression of cleaved caspase-3 and cleaved poly (ADP-ribose) polymerase, together with increased Bax/Bcl-2 ratios, were also observed in HG-stimulated podocytes and DM glomeruli. Treatment with either zAsp-DCB or PKI 166 resulted in a significant attenuation of these effects. Both PKI 166 and zAsp-DCB also inhibited the increase in number of apoptotic cells, as assessed by Hoechst 33342 staining and TUNEL assay. Under diabetic conditions, inhibition of podocyte hypertrophy results in attenuated apoptosis, whereas blocking apoptosis has no effect on podocyte hypertrophy, suggesting that podocyte hypertrophy precedes apoptosis.

Analysis of 2-alkylcyclobutanones in cashew nut, nutmeg, apricot kernel, and pine nut samples: re-evaluating the uniqueness of 2-alkylcyclobutanones for irradiated food identification.

PubMed

Leung, Elvis M K; Tang, Phyllis N Y; Ye, Yuran; Chan, Wan

2013-10-16

2-Alkylcyclobutanones (2-ACBs) have long been considered as unique radiolytic products that can be used as indicators for irradiated food identification. A recent report on the natural existence of 2-ACB in non-irradiated nutmeg and cashew nut samples aroused worldwide concern because it contradicts the general belief that 2-ACBs are specific to irradiated food. The goal of this study is to test the natural existence of 2-ACBs in nut samples using our newly developed liquid chromatography-tandem mass spectrometry (LC-MS/MS) method with enhanced analytical sensitivity and selectivity ( Ye , Y. ; Liu , H. ; Horvatovich , P. ; Chan , W. Liquid chromatography-electrospray ionization tandem mass spectrometric analysis of 2-alkylcyclobutanones in irradiated chicken by precolumn derivatization with hydroxylamine . J. Agric. Food Chem. 2013 , 61 , 5758 - 5763 ). The validated method was applied to identify 2-dodecylcyclobutanone (2-DCB) and 2-tetradecylcyclobutanone (2-TCB) in nutmeg, cashew nut, pine nut, and apricot kernel samples (n = 22) of different origins. Our study reveals that 2-DCB and 2-TCB either do not exist naturally or exist at concentrations below the detection limit of the existing method. Thus, 2-DCB and 2-TCB are still valid to be used as biomarkers for identifying irradiated food.

German Center Subanalysis of the LEVANT 2 Global Randomized Study of the Lutonix Drug-Coated Balloon in the Treatment of Femoropopliteal Occlusive Disease.

PubMed

Scheinert, Dierk; Schmidt, Andrej; Zeller, Thomas; Müller-Hülsbeck, Stefan; Sixt, Sebastian; Schröder, Henrik; Weiss, Norbert; Ketelsen, Dominik; Ricke, Jens; Steiner, Sabine; Rosenfield, Kenneth

2016-06-01

To report a subanalysis of the German centers enrolling patients in the prospective, global, multicenter, randomized LEVANT 2 pivotal trial (ClinicalTrials.gov identifier NCT01412541) of the Lutonix drug-coated balloon (DCB) for the treatment of femoropopliteal occlusive disease. Among the 476 patients in LEVANT 2, 126 patients (mean age 67.1±9.6 years; 79 men) were enrolled at the 8 participating German sites between August 2011 and July 2012 and were randomized 2:1 to treatment with the Lutonix DCB (n=83) vs an uncoated balloon during percutaneous transluminal angioplasty (PTA, n=43). All patients had intermittent claudication or rest pain (Rutherford categories 2-4). Average lesion length was 58 mm and average treated length was 100 mm. Severe calcification was present in 11% of lesions, and 23% were total occlusions. The efficacy outcome was primary patency at 12 months, and the safety outcome was 12-month freedom from a composite of perioperative death, index limb-related death, amputation (below or above the ankle), and index limb revascularization. Secondary endpoints included target lesion revascularization (TLR), major adverse events, and functional outcomes. Demographic, clinical, and lesion characteristics were matched between Lutonix DCB and PTA groups, as were the final percent diameter stenosis (19%) and procedure success (91%). By Kaplan-Meier analysis, the 12-month primary patency rate was 80% vs 58% (p=0.015) and the composite safety endpoint rate was 94% vs 72% (p=0.001), respectively. Freedom from TLR was higher for DCBs (96%) vs PTA (82%, p=0.012). Major adverse events were similar for both groups. The benefit favoring DCB over PTA was observed in German men and women. Compared to the non-German LEVANT 2 cohort, there was a shorter time between insertion and inflation of treatment balloons (21.8 vs 39.5 seconds, p<0.001) in the German cohort. Balloons were inflated to higher pressures (9.0 vs 7.7 atm, p<0.001) but for a shorter period of time (130 vs 167 seconds, p<0.001), and although treated lesions in the German cohort had a higher baseline stenosis, final postprocedure diameter stenosis was lower (19% vs 22%, p=0.04) than in the non-German patients. Superiority of DCB over PTA in the German cohort of LEVANT 2 was demonstrated for primary patency, composite safety, and freedom from TLR. The benefit of DCB was also consistent for both genders. Geographic or regional differences in procedural variables may account for the different outcomes between the German and non-German cohorts. © The Author(s) 2016.

Evidence for Cation-Controlled Excited-State Localization in a Ruthenium Polypyridyl Compound.

PubMed

Beauvilliers, Evan E; Meyer, Gerald J

2016-08-01

The visible absorption and photoluminescence (PL) properties of the four neutral ruthenium diimine compounds [Ru(bpy)2(dcb)] (B2B), [Ru(dtb)2(dcb)] (D2B), [Ru(bpy)2(dcbq)] (B2Q), and [Ru(dtb)2(dcbq)] (D2Q), where bpy is 2,2'-bipyridine, dcb is 4,4'-(CO2(-))2-bpy, dtb is 4,4'-(tert-butyl)2-bpy, and dcbq is 4,4'-(CO2(-))2-2,2'-biquinoline, are reported in the presence of Lewis acidic cations present in fluid solutions at room temperature. In methanol solutions, the measured spectra were insensitive to the presence of these cations, while in acetonitrile a significant red shift in the PL spectra (≤1400 cm(-1)) was observed consistent with stabilization of the metal-to-ligand charge transfer (MLCT) excited state through Lewis acid-base adduct formation. No significant spectral changes were observed in control experiments with the tetrabutylammonium cation. Titration data with Li(+), Na(+), Mg(2+), Ca(2+), Zn(2+), Al(3+), Y(3+), and La(3+) showed that the extent of stabilization saturated at high cation concentration with magnitudes that scaled roughly with the cation charge-to-size ratio. The visible absorption spectra of D2Q was particularly informative due to the presence of two well-resolved MLCT absorption bands: (1) Ru → bpy, λmax ≈ 450 nm; and (2) Ru → dcbq, λmax ≈ 540 nm. The higher-energy band blue-shifted and the lower-energy band red-shifted upon cation addition. The PL intensity and lifetime of the excited state of B2B first increased with cation addition without significant shifts in the measured spectra, behavior attributed to a cation-induced change in the localization of the emissive excited state from bpy to dcb. The importance of excited-state localization and stabilization for solar energy conversion is discussed.

Dichlorobenzene: an effective solvent for epoxy/graphene nanocomposites preparation

PubMed Central

Saharudin, Mohd Shahneel; Vo, Thuc; Inam, Fawad

2017-01-01

It is generally recognized that dimethylformamide (DMF) and ethanol are good media to uniformly disperse graphene, and therefore have been used widely in the preparation of epoxy/graphene nanocomposites. However, as a solvent to disperse graphene, dichlorobenzene (DCB) has not been fully realized by the polymer community. Owing to high values of the dispersion component (δd) of the Hildebrand solubility parameter, DCB is considered as a suitable solvent for homogeneous graphene dispersion. Therefore, epoxy/graphene nanocomposites have been prepared for the first time with DCB as a dispersant; DMF and ethanol have been chosen as the reference. The colloidal stability, mechanical properties, thermogravimetric analysis, dynamic mechanical analysis and scanning electron microscopic images of nanocomposites have been obtained. The results show that with the use of DCB, the tensile strength of graphene has been improved from 64.46 to 69.32 MPa, and its flexural strength has been increased from 97.17 to 104.77 MPa. DCB is found to be more effective than DMF and ethanol for making stable and homogeneous graphene dispersion and composites. PMID:29134080

Dichlorobenzene: an effective solvent for epoxy/graphene nanocomposites preparation.

PubMed

Wei, Jiacheng; Saharudin, Mohd Shahneel; Vo, Thuc; Inam, Fawad

2017-10-01

It is generally recognized that dimethylformamide (DMF) and ethanol are good media to uniformly disperse graphene, and therefore have been used widely in the preparation of epoxy/graphene nanocomposites. However, as a solvent to disperse graphene, dichlorobenzene (DCB) has not been fully realized by the polymer community. Owing to high values of the dispersion component ( δ d ) of the Hildebrand solubility parameter, DCB is considered as a suitable solvent for homogeneous graphene dispersion. Therefore, epoxy/graphene nanocomposites have been prepared for the first time with DCB as a dispersant; DMF and ethanol have been chosen as the reference. The colloidal stability, mechanical properties, thermogravimetric analysis, dynamic mechanical analysis and scanning electron microscopic images of nanocomposites have been obtained. The results show that with the use of DCB, the tensile strength of graphene has been improved from 64.46 to 69.32 MPa, and its flexural strength has been increased from 97.17 to 104.77 MPa. DCB is found to be more effective than DMF and ethanol for making stable and homogeneous graphene dispersion and composites.

Molecular level energy and electron transfer processes at nanocrystalline titanium dioxide interfaces

NASA Astrophysics Data System (ADS)

Farzad, Fereshteh

This thesis describes photo-induced molecular electron and energy transfer processes occurring at nanocrystalline semiconductor interfaces. The Introductory Chapter provides background and describes how these materials may be useful for solar energy conversion. In Chapter 2, results describing excitation of Ru(deeb)(bpy)2 2+, bis(2,2'-bipyridine)(2,2'-bipyridine-4,4 '-diethylester)ruthenium(II) hexafluorophosphate, bound to nanocrystalline TiO2 thin films, immersed in an acetonitrile bath are presented. The data indicates that light excitation forms predominately long-lived metal-to-ligand charge-transfer, MLCT, excited states under these conditions. Modeling of the data as a function of irradiance has been accomplished assuming parallel unimolecular and bimolecular excited state deactivation processes. The quantum yield for excited state formation depends on the excitation irradiance, consistent with triplet-triplet annihilation processes that occur with k > 1 x 108 s-1. Chapter 3 extends the work described in Chapter 2 to LiClO4 acetonitrile solutions. Li+ addition results in a red shift in the MLCT absorption and photoluminescence, PL, and a concentration dependent quenching of the PL intensity on TiO2. The Li+ induced spectroscopic changes were found to be reversible by varying the electrolyte composition. A second-order kinetic model quantified charge recombination transients. A model is proposed wherein Li+ ion adsorption stabilizes TiO2 acceptor states resulting in energetically more favorable interfacial electron transfer. The photophysical and photoelectrochemical properties of porous nanocrystalline anatase TiO2 electrodes modified with Ru(deeb)(bpy)2 2+, Os(deeb)(bpy)22+, and mixtures of both are described in Chapters 4 and 5. In regenerative solar cells with 0.5 M LiI/0.05 M I2 acetonitrile electrolyte, both compounds efficiently inject electrons into TiO2 producing monochromatic incident photon-to-current efficiencies (IPCE), IPCE (460 nm) = 0.70 + 0.05 for Ru(dcb)(bpy)2 2+/TiO2 and 0. 10 + 0.05 for Os(dcb)(bpy)2 2+/TiO2. Os(dcb)(bpy)22+ extends the spectral sensitivity of the TiO2 material beyond 700 rim. Application of a negative bias to the derivatized TiO2 surfaces results in inefficient interfacial electron transfer and no significant photocurrent. Instead, lateral energy transfer cross the nanocrystalline TiO2 surface from Ru(dcb)(bpy)22+* to Os(dcb)(bpy) 22+ is observed. The energy transfer process can be switched off with a positive applied bias ten times with no significant deterioration. The results demonstrate control of molecular excited states at nanostructured interfaces.

A two-step ionospheric modeling algorithm considering the impact of GLONASS pseudo-range inter-channel biases

NASA Astrophysics Data System (ADS)

Zhang, Rui; Yao, Yi-bin; Hu, Yue-ming; Song, Wei-wei

2017-12-01

The Global Navigation Satellite System presents a plausible and cost-effective way of computing the total electron content (TEC). But TEC estimated value could be seriously affected by the differential code biases (DCB) of frequency-dependent satellites and receivers. Unlike GPS and other satellite systems, GLONASS adopts a frequency-division multiplexing access mode to distinguish different satellites. This strategy leads to different wavelengths and inter-frequency biases (IFBs) for both pseudo-range and carrier phase observations, whose impacts are rarely considered in ionospheric modeling. We obtained observations from four groups of co-stations to analyze the characteristics of the GLONASS receiver P1P2 pseudo-range IFB with a double-difference method. The results showed that the GLONASS P1P2 pseudo-range IFB remained stable for a period of time and could catch up to several meters, which cannot be absorbed by the receiver DCB during ionospheric modeling. Given the characteristics of the GLONASS P1P2 pseudo-range IFB, we proposed a two-step ionosphere modeling method with the priori IFB information. The experimental analysis showed that the new algorithm can effectively eliminate the adverse effects on ionospheric model and hardware delay parameters estimation in different space environments. During high solar activity period, compared to the traditional GPS + GLONASS modeling algorithm, the absolute average deviation of TEC decreased from 2.17 to 2.07 TECu (TEC unit); simultaneously, the average RMS of GPS satellite DCB decreased from 0.225 to 0.219 ns, and the average deviation of GLONASS satellite DCB decreased from 0.253 to 0.113 ns with a great improvement in over 55%.

Incidence and Predictors of reCurrent Restenosis After Drug-coated Balloon Angioplasty for Restenosis of a drUg-eluting Stent: The ICARUS Cooperation.

PubMed

Cassese, Salvatore; Xu, Bo; Habara, Seiji; Rittger, Harald; Byrne, Robert A; Waliszewski, Matthias; Pérez-Vizcayno, María José; Gao, Runlin; Kastrati, Adnan; Alfonso, Fernando

2017-09-12

The incidence and predictors of recurrent restenosis after drug-coated balloon (DCB) angioplasty for drug-eluting stent (DES) restenosis remain poorly studied. We sought to evaluate the incidence and predictors of recurrent restenosis among participants in randomized controlled trials receiving DCB angioplasty for DES restenosis. The clinical and lesion data of individuals enrolled in 6 randomized controlled trials of DCB angioplasty for DES restenosis were pooled. All patients included in this report were assigned to receive paclitaxel-coated balloon angioplasty with the SeQuent Please DCB (B Braun, Melsungen, Germany). The current analysis focused on participants with available follow-up angiography at 6 to 9 months. The incidence of recurrent restenosis, defined as diameter restenosis ≥ 50% in the in-segment area at follow-up angiography, and its clinical and angiographic predictors were evaluated. A total of 546 patients were combined in a single dataset. Angiographic follow-up at 6 to 9 months was available for 484 patients (88.6%) with 518 treated lesions. Recurrent restenosis was detected in 101 (20.8%) patients. On multivariable analysis, lesion length (OR, 1.58; 95%CI, 1.10-2.26; P=.012 for 5mm increase) and vessel size (OR, 1.42; 95%, 1.12-1.79; P=.003 for 0.5mm reduction) were independently associated with recurrent restenosis. In the largest cohort to date of individuals with angiographic surveillance after DCB angioplasty for DES restenosis, we demonstrated that recurrent restenosis occurs in approximately 1 out of 5 patients. Predictors of recurrent restenosis are increased lesion length and small vessel size. Copyright © 2017 Sociedad Española de Cardiología. Published by Elsevier España, S.L.U. All rights reserved.

Novel paclitaxel-coated angioplasty balloon catheter based on cetylpyridinium salicylate: preparation, characterization and simulated use in an in vitro vessel model.

PubMed

Petersen, Svea; Kaule, Sebastian; Stein, Florian; Minrath, Ingo; Schmitz, Klaus-Peter; Kragl, Udo; Sternberg, Katrin

2013-10-01

Drug-coated balloons (DCB), which have emerged as therapeutic alternative to drug-eluting stents in percutaneous cardiovascular intervention, are well described with regard to clinical efficiency and safety within a number of clinical studies. In vitro studies elucidating the correlation of coating method and composition with DCB performance are however rare but considered important for the understanding of DCB requirements and the improvement of established DCB. In this context, we evaluated the applicability of a pipetting, dip-coating, and spray-coating process for the establishment of DCB based on paclitaxel (PTX) and the ionic liquid cetylpyridinium salicylate (Cetpyrsal) as novel innovative additive in three different compositions. Among tested methods and compositions, the pipetting process with 50 wt.% PTX resulted in most promising coatings as drug load was less controllable by the other processes and higher PTX contents led to considerable drug crystallization, as visualized by electron microscopy, accelerating PTX loss during short-term elution. Applying these conditions, homogeneous coatings could be applied on balloon catheter, whose simulated use in an in vitro vessel model revealed percental drug losses of 36 and 28% during transit and percental drug transfers of 12 and 40% under expansion for coatings applied in expanded and folded balloon condition, respectively. In comparison to literature values, these results support the high potential of Cetpyrsal as novel DCB matrix regarding low drug loss and efficient drug transfer. © 2013.

An update on the clinical use of drug-coated balloons in percutaneous coronary interventions.

PubMed

Cheng, Yanping; Leon, Martin B; Granada, Juan F

2016-06-01

Drug-coated balloons (DCB) promise to deliver anti-proliferative drugs and prevent restenosis leaving nothing behind. Although, randomized clinical trials have demonstrated their efficacy for the treatment of in-stent restenosis, clinical evidence supporting their use in other coronary applications is still lacking. This review summarizes the development status of clinically available DCB technologies and provides an update on the current data for their coronary use. Current generation DCB prevent restenosis by delivering paclitaxel particles on the surface of the vessel wall. Although clinically available technologies share a common mechanism of action, important differences in pharmacokinetic behavior and safety profiles do exist. Future technological improvements include the development of coatings displaying: high transfer efficiency; low particle embolization potential; and alternative drug formulations. Optimized balloon-based delivery systems and drug encapsulation technologies also promise to improve the technical limitations of current generation DCB. Although proving clinical superiority against DES may prove to be difficult in mainstream applications (i.e., de novo), new generation DCB technologies have the potential to achieve a strong position in the interventional field in clinical settings in which the efficacy of DES use is not proven or justified (i.e., bifurcations).

The gas chromatography/mass spectrometry can be used for dose estimation in irradiated pork

NASA Astrophysics Data System (ADS)

D'Oca, M. C.; Bartolotta, A.; Cammilleri, M. C.; Giuffrida, S. A.; Parlato, A.; Di Noto, A. M.; Caracappa, S.

2009-07-01

Food safety can be improved using ionizing radiation to reduce food spoilage and to extend its shelf life. The gas chromatography/mass spectrometry (GC/MS) has been validated by the European Community as a powerful method to identify irradiated food containing fat. The preliminary goals of our research were: (i) to set up this method, based on the detection of radiation induced 2-dodecylcyclobutanones (2-DCB) in pork muscle samples and (ii) to check the microbiological efficacy of the treatment. The main objective was to render the GC/MS a quantitative technique for dose estimation, through the measurement of the 2-DCB concentration in the irradiated sample. Our results show that the reduction of the microbial population is substantially reduced even at 2 kGy, and that a clear identification of irradiated samples can be achieved also one month after irradiation at 2 kGy in frozen-stored samples. The 2-DCB concentration showed a linear dependence on dose in the range 1-10 kGy, no matter the origin of the sample; a unique calibration function was obtained, that allowed dose estimation in irradiated pork samples. A retrospective evaluation on the quality of the treatment could be carried out this way.

The influence of grounding on GPS receiver differential code biases

NASA Astrophysics Data System (ADS)

Choi, Byung-Kyu; Lee, Sang Jeong

2018-07-01

The Global Positioning System (GPS) has become an effective tool for estimating ionospheric total electron content (TEC). One of the critical factors affecting ionospheric TEC estimation from GPS data is the differential code biases (DCBs) inherent in both GPS receivers and satellites. To investigate the factor that affects the receiver DCB, we consider the relationship between the receiver DCB and the grounding of an antenna. GPS data from 9 stations in South Korea from three periods (the years 2009, 2014, and 2017) were used in the analysis. It was found that a significant jump (∼8-13 ns, or ∼ 23-37 TECU) in hourly DCB time series occurred simultaneously at the two different sites when an antenna is changed from a grounded to the non-grounded state. Thus, our study clearly identifies that the grounding of GPS equipment is a factor of the receiver DCB changes.

Terrestrial pyrogenic carbon export to fluvial ecosystems: Lessons learned from the White Nile watershed of East Africa

NASA Astrophysics Data System (ADS)

Güereña, David T.; Lehmann, Johannes; Walter, Todd; Enders, Akio; Neufeldt, Henry; Odiwour, Holiance; Biwott, Henry; Recha, John; Shepherd, Keith; Barrios, Edmundo; Wurster, Chris

2015-11-01

Pyrogenic carbon (PyC) is important because of its role in the global organic C (OC) cycle and in modifying soil properties. However, our understanding of PyC movement from terrestrial to fluvial ecosystems is not robust. This study examined (i) whether erosion or subsurface transport was more important for PyC export from headwaters, (ii) whether PyC was exported preferentially to total OC (TOC), and (iii) whether the movement of PyC from terrestrial to aquatic ecosystems provides an explanation for the coupling of PyC and non-PyC observed in rivers at a global scale. In the Guineo-Congolian highland forest region of western Kenya, duplicate catchments with sizes of 1-12 ha were equipped with stream gauges in primary forest and adjacent mixed agricultural landscapes that were cleared by fire 10, 16, or 62 years before. Stream water samples were taken weekly throughout 1 year and compared with runoff to assess PyC movement. Additional stream samples were taken from all major tributaries of the White Nile watershed of Lake Victoria. PyC was not found to be preferentially eroded relative to TOC or non-PyC, as topsoil (0-0.15 m) PyC concentrations (6.3 ± 0.3% of TOC; means and standard errors) were greater than runoff sediment (1.9 ± 0.4%) and dissolved PyC concentrations (2.0 ± 0.4%, n = 252). In addition, PyC proportions in eroded sediment were lower than and uncorrelated (r2 = 0.04; P = 0.14) with topsoil PyC. An enrichment of PyC was found with depth in the soil, from 6.3 ± 0.3% of TOC in the topsoil (0-0.15 m) to 12.3 ± 0.3% of TOC at 1-2 m. Base flow PyC proportions of TOC correlated well with subsoil PyC (r2 = 0.57; P < 0.05) but not with topsoil PyC (r2 = 0.18; P > 0.05). Similar PyC proportions were found in the studied headwater streams (2.7 ± 0.2%), their downstream inflow into Lake Victoria (3.7%), the other nine major rivers into Lake Victoria (4.9 ± 0.8%), and its outflow into the White Nile (1.1%). A strong positive correlation between dissolved PyC and non-PyC (r2 = 0.91; P < 0.0001) in the headwater streams reflect relationships previously seen for a range of globally important rivers, and contrasts with a negative relationship for suspended sediments (r2 = -0.5; P < 0.0001). The estimated PyC export from the Lake Victoria watershed of 11 Gg yr-1 may therefore originate to a large extent from subsoil pathways in dissolved form that appeared to be an important source of PyC in aquatic environments and may explain the coupling of PyC and non-PyC at a global scale.

The coordination chemistry of the neutral tris-2-pyridyl silicon ligand [PhSi(6-Me-2-py)3].

PubMed

Plajer, Alex J; Colebatch, Annie L; Enders, Markus; García-Romero, Álvaro; Bond, Andrew D; García-Rodríguez, Raúl; Wright, Dominic S

2018-05-22

Difficulties in the preparation of neutral ligands of the type [RSi(2-py)3] (where 2-py is an unfunctionalised 2-pyridyl ring unit) have thwarted efforts to expand the coordination chemistry of ligands of this type. However, simply switching the pyridyl substituents to 6-methyl-pyridyl groups (6-Me-2-py) in the current paper has allowed smooth, high-yielding access to the [PhSi(6-Me-2-py)3] ligand (1), and the first exploration of its coordination chemistry with transition metals. The synthesis, single-crystal X-ray structures and solution dynamics of the new complexes [{PhSi(6-Me-2-py)3}CuCH3CN][PF6], [{PhSi(6-Me-2-py)3}CuCH3CN][CuCl2], [{PhSi(6-Me-2-py)3}FeCl2], [{PhSi(6-Me-2-py)3}Mo(CO)3] and [{PhSi(6-Me-2-py)3}CoCl2] are reported. The paramagnetic Fe2+ and Co2+ complexes show strongly shifted NMR resonances for the coordinated pyridyl units due to large Fermi-contact shifts. However, magnetic anisotropy also leads to considerable pseudo-contact shifts so that both contributions have to be included in the paramagnetic NMR analysis.

Endovascular Treatment of Haemodialysis Arteriovenous Fistula with Drug-Coated Balloon Angioplasty: A Single-Centre Study.

PubMed

Lučev, Jernej; Breznik, Silva; Dinevski, Dejan; Ekart, Robert; Rupreht, Mitja

2018-06-01

To evaluate the effect of percutaneous transluminal angioplasty (PTA) on haemodialysis fistulas utilising drug-coated balloons with plain balloon vessel preparation (DCB). In the study group, 31 patients (16 men; mean age 62.8 ± 17.2 years) with failing arteriovenous fistulas were treated, with DCB, and compared with a control group (31 patients; 15 men; mean age 67.0 ± 8.44 years), in which only plain balloon PTA was performed. All stenoses were dilated with regular PTA balloons. After achieving haemodynamic success (< 30% residual stenosis), drug-coated balloons were used for drug administration in the study group. The follow-up intervals were 6, 12 and 24 months. Target lesion primary patency, primary assisted patency and secondary patency were compared. The statistical significance was set at 0.05. Target lesion primary patency was compared in both groups and was significantly higher in the study group (DCB) at 6 months (90.3 vs. 61.3%; p = 0.016), 12 months (77.4 vs. 29%; p = 0.0004) as well as 24 months (45.2 vs. 16.1%; p = 0.026). Kaplan-Meier survival curves also showed a significant difference for target lesion primary patency (534.2 vs. 315.7 days; p = 0.0004). There were no significant differences in target lesion primary assisted patency and in secondary patency. However, only 38.7% of patients in the study group were treated twice or more versus 80.6% in the control group (p = 0.002). DCB increases target lesion primary patency during the first 24 months and decreases the rate of reinterventions.

Sequestration of maize crop straw C in different soils: role of oxyhydrates in chemical binding and stabilization as recalcitrance.

PubMed

Song, Xiangyun; Li, Lianqing; Zheng, Jufeng; Pan, Genxing; Zhang, Xuhui; Zheng, Jinwei; Hussain, Qaiser; Han, Xiaojun; Yu, Xinyan

2012-05-01

While biophysical controls on the sequestration capacity of soils have been well addressed with physical protection, chemical binding and stabilization processes as well as microbial community changes, the role of chemical binding and stabilization has not yet well characterized for soil organic carbon (SOC) sequestration in rice paddies. In this study, a 6-month laboratory incubation with and without maize straw amendment (MSA) was conducted using topsoil samples from soils with different clay mineralogy and free oxy-hydrate contents collected across Southern China. The increase in SOC under MSA was found coincident with that in Fe- and Al-bound OC (Fe/Al-OC) after incubation for 30 d (R(2)=0.90, P=0.05), and with sodium dithionate-citrate-bicarbonate (DCB) extractable Fe after incubation for 180 d (R(2)=0.99, P<0.01). The increase in SOC under MSA was found higher in soils rich in DCB extractable Fe than those poor in DCB extractable Fe. The greater SOC sequestration in soils rich in DCB extractable Fe was further supported by the higher abundance of (13)C which was a natural signature of MSA. Moreover, a weak positive correlation of the increased SOC under MSA with the increased humin (R(2)=0.87, P=0.06) observed after incubation for 180 d may indicate a chemical stabilization of sequestered SOC as humin in the long run. These results improved our understanding of SOC sequestration in China's rice paddies that involves an initial chemical binding of amended C and a final stabilization as recalcitrant C of humin. Copyright © 2012 Elsevier Ltd. All rights reserved.

A real-time ionospheric model based on GNSS Precise Point Positioning

NASA Astrophysics Data System (ADS)

Tu, Rui; Zhang, Hongping; Ge, Maorong; Huang, Guanwen

2013-09-01

This paper proposes a method of real-time monitoring and modeling the ionospheric Total Electron Content (TEC) by Precise Point Positioning (PPP). Firstly, the ionospheric TEC and receiver’s Differential Code Biases (DCB) are estimated with the undifferenced raw observation in real-time, then the ionospheric TEC model is established based on the Single Layer Model (SLM) assumption and the recovered ionospheric TEC. In this study, phase observations with high precision are directly used instead of phase smoothed code observations. In addition, the DCB estimation is separated from the establishment of the ionospheric model which will limit the impacts of the SLM assumption impacts. The ionospheric model is established at every epoch for real time application. The method is validated with three different GNSS networks on a local, regional, and global basis. The results show that the method is feasible and effective, the real-time ionosphere and DCB results are very consistent with the IGS final products, with a bias of 1-2 TECU and 0.4 ns respectively.

Measuring Core/Facesheet Bond Toughness in Honeycomb Sandwich Structures

NASA Technical Reports Server (NTRS)

Nettles, A. T.

2006-01-01

This study examines two test methods to evaluate the peel toughness of the skin to core debond of sandwich panels. The methods tested were the climbing drum (CD) peel test and the double cantilever beam (DCB) test. While the CD peel test is only intended for qualitative measurements, it is shown in this study that qualitative measurements can be performed and compare well with DCB test data. It is also shown that artificially stiffening the facesheets of a DCB specimen can cause the test to behave more like a flatwise tensile test than a peel test.

The NICE recommendation for drug-coated balloons and its global impact.

PubMed

Eccleshall, Simon; Waliszewski, M

2015-06-01

The clinical efficacy and safety of drug-coated balloon (DCB) angioplasty in patients with coronary in-stent restenosis (ISR) has been demonstrated. The objective of this article is to provide comparative cost efficacy data for DCB angioplasty in various countries based on the original methodology of the Medical Technologies Evaluation Programme (MTEP) at the National Institute for Health and Clinical Excellence (NICE) in 2010. Published and unpublished Health Technology Assessment (HTA) reports were evaluated for comparison in selected countries. Furthermore, a systematic review of economic evaluations of DCB angioplasty versus standard treatments (uncoated balloon angioplasty or drug-eluting stent implantations) was conducted. National cost efficacy data were evaluated using Markov state transition models which were adapted to fit each country's device and procedure related costs. The clinical input for adverse events was defined with two relevant trials for in-stent restenosis of bare metal stents (BMS-ISR) and of drug-eluting stents (DES-ISR). In the UK, Germany, Switzerland, South Africa, Japan and Brazil, DCB angioplasty is cost-effective when compared with drug-eluting stents to treat either BMS-ISR or DES-ISR. DCB angioplasty ought to be the preferred treatment option for patients with BMS-ISR and DES-ISR from the payers' point of view. © The Author(s), 2015.

Drug/Cell-line Browser: interactive canvas visualization of cancer drug/cell-line viability assay datasets.

PubMed

Duan, Qiaonan; Wang, Zichen; Fernandez, Nicolas F; Rouillard, Andrew D; Tan, Christopher M; Benes, Cyril H; Ma'ayan, Avi

2014-11-15

Recently, several high profile studies collected cell viability data from panels of cancer cell lines treated with many drugs applied at different concentrations. Such drug sensitivity data for cancer cell lines provide suggestive treatments for different types and subtypes of cancer. Visualization of these datasets can reveal patterns that may not be obvious by examining the data without such efforts. Here we introduce Drug/Cell-line Browser (DCB), an online interactive HTML5 data visualization tool for interacting with three of the recently published datasets of cancer cell lines/drug-viability studies. DCB uses clustering and canvas visualization of the drugs and the cell lines, as well as a bar graph that summarizes drug effectiveness for the tissue of origin or the cancer subtypes for single or multiple drugs. DCB can help in understanding drug response patterns and prioritizing drug/cancer cell line interactions by tissue of origin or cancer subtype. DCB is an open source Web-based tool that is freely available at: http://www.maayanlab.net/LINCS/DCB CONTACT: avi.maayan@mssm.edu Supplementary data are available at Bioinformatics online. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Probing the Watson-Crick, wobble, and sugar-edge hydrogen bond sites of uracil and thymine.

PubMed

Müller, Andreas; Frey, Jann A; Leutwyler, Samuel

2005-06-16

The nucleobases uracil (U) and thymine (T) offer three hydrogen-bonding sites for double H-bond formation via neighboring N-H and C=O groups, giving rise to the Watson-Crick, wobble and sugar-edge hydrogen bond isomers. We probe the hydrogen bond properties of all three sites by forming hydrogen bonded dimers of U, 1-methyluracil (1MU), 3-methyluracil (3MU), and T with 2-pyridone (2PY). The mass- and isomer-specific S1 <-- S0 vibronic spectra of 2PY.U, 2PY.3MU, 2PY.1MU, and 2PY.T were measured using UV laser resonant two-photon ionization (R2PI). The spectra of the Watson-Crick and wobble isomers of 2PY.1MU were separated using UV-UV spectral hole-burning. We identify the different isomers by combining three different diagnostic tools: (1) Selective methylation of the uracil N3-H group, which allows formation of the sugar-edge isomer only, and methylation of the N1-H group, which leads to formation of the Watson-Crick and wobble isomers. (2) The experimental S1 <-- S0 origins exhibit large spectral blue shifts relative to the 2PY monomer. Ab initio CIS calculations of the spectral shifts of the different hydrogen-bonded dimers show a linear correlation with experiment. This correlation allows us to identify the R2PI spectra of the weakly populated Watson-Crick and wobble isomers of both 2PY.U and 2PY.T. (3) PW91 density functional calculation of the ground-state binding and dissociation energies De and D0 are in agreement with the assignment of the dominant hydrogen bond isomers of 2PY.U, 2PY.3MU and 2PY.T as the sugar-edge form. For 2PY.U, 2PY.T and 2PY.1MU the measured wobble:Watson-Crick:sugar-edge isomer ratios are in good agreement with the calculated ratios, based on the ab initio dissociation energies and gas-phase statistical mechanics. The Watson-Crick and wobble isomers are thereby determined to be several kcal/mol less strongly bound than the sugar-edge isomers. The 36 observed intermolecular frequencies of the nine different H-bonded isomers give detailed insight into the intermolecular force field.

Effect of cooking on radiation-induced chemical markers in beef and pork during storage.

PubMed

Kwon, Joong-Ho; Kwon, Youngju; Kausar, Tusneem; Nam, Ki-Chang; Rok Min, Byong; Joo Lee, Eun; Ahn, Dong U

2012-02-01

Raw and cooked beef and pork loins were irradiated at 0 or 5 kGy. The radiation-induced marker compounds, such as hydrocarbons, 2-alkylcyclobutanones (2-ACBs), and sulfur volatiles, were determined after 0 and 6 mo of frozen storage. Two hydrocarbons (8-heptadecene [C(17:1)] and 6,9-heptadecadiene [C(17:2)]) and two 2-ACBs (2-dodecylcyclobutanone [2-DCB] and 2-tetradecylcyclobutanone [2-TCB]) were detected only in irradiated raw and cooked meats. Although precooked irradiated meats produced more hydrocarbons and 2-ACBs than the irradiated cooked ones, the amounts of individual hydrocarbons and 2-ACBs, such as 8-heptadecene, 6,9-heptadecadiene, 2-DCB, and 2-TCB, were sufficient enough to detect whether the meat was irradiated or not. Dimethyl disulfide and dimethyl trisulfide were also determined only in irradiated meats but dimethyl trisulfide disappeared after 6 mo of frozen storage under oxygen-permeable packaging conditions. The results indicated that 8-heptadecene, 6,9-heptadecadiene, 2-DCB, 2-TCB, and dimethyl disulfide, even though they were decreased with storage, could be used as marker compounds for the detection of irradiated beef and pork regardless of cooking under the frozen conditions for 6 mo. Radiation-induced chemical changes such as specific hydrocarbons, 2-ACBs, and sulfur volatiles may be used as potential identification markers by regulatory authorities to confirm irradiation history of frozen stored raw or cooked beef and pork. © 2012 Institute of Food Technologists®

A Mechanism for the induction of renal tumours in male Fischer 344 rats by short-chain chlorinated paraffins.

PubMed

Warnasuriya, Gayathri D; Elcombe, Barbara M; Foster, John R; Elcombe, Clifford R

2010-03-01

Short-chain chlorinated paraffins (SCCPs) cause kidney tumours in male rats, but not in female rats or mice of either sex. Male rat-specific tumours also occur in rats dosed with a range of compounds including 1,4- dichlorobenzene (DCB) and d-limonene (DL). These compounds bind to a male rat-specific hepatic protein, alpha-2-urinary globulin (α2u), and form degradationresistant complexes in the kidney. The resulting accumulation of α2u causes cell death and sustained regenerative cell proliferation, which in turn leads to the formation of renal tumours. To investigate whether the SCCP, Chlorowax 500C (C500C), causes tumours via the accumulation of α2u male rats were orally dosed with either C500C (625 mg/kg of body weight), DCB (300 mg/kg of body weight), or DL (150 mg/kg of body weight) for 28 consecutive days. An increase in renal α2u and cell proliferation was observed in DCB- and DL-treated rats but not in C500C-treated rats. C500C caused peroxisome proliferation and a down-regulation of α2u synthesis in male rat liver. This down-regulation occurred at the transcriptional level. Since less α2u was produced in C500C-treated rats, there was less available for accumulation in the kidney hence a typical α2u nephropathy did not appear. However, the administration of a radiolabelled SCCP, [14C]polychlorotridecane (PCTD), to male rats demonstrated its binding to renal α2u. Thus, it is possible that SCCPs bind to α2u and cause a slow accumulation of the protein in the kidney followed by delayed onset of α2u nephropathy. As a consequence of these findings in the current experiments, while evidence exists implicating α2u-globulin in the molecular mechanism of action of the C500C, the classic profile of a α2u-globulin nephropathy seen with other chemicals such as DCB and DL was not reproduced during this experimental protocol.

Receiver DCB estimation and GPS vTEC study at a low latitude station in the South Pacific

NASA Astrophysics Data System (ADS)

Prasad, Ramendra; Kumar, Sushil; Jayachandran, P. T.

2016-11-01

The statistical estimation of receiver differential code bias (DCB) of the GSV4004B receiver at a low latitude station, Suva (lat. 18.15°S, long. 178.45°E, Geomag. Lat. 21.07°S), Fiji, and the subsequent behaviour of vTEC, are presented. By means of least squares linear regression fitting technique, the receiver DCB was determined using the GPS vTEC data recorded during the year 2010, CODE TEC and IRI-2012 model for 2010. To substantiate the results, minimization of the standard deviation (SD) method was also used for GPS vTEC data. The overall monthly DCB was estimated to be in the range of 62.6 TECU. The vTEC after removing the resultant monthly DCB was consistent with other low latitude observations. The GPS vTEC 2010 data after eliminating the resultant DCB were lower in comparison to Faraday rotation vTEC measurements at Suva during 1984 primarily due to higher solar activity during 1984 as compared to 2010. Seasonally, vTEC was maximum during summer and minimum during winter. The winter showed least vTEC variability whereas equinox showed the largest daytime variability. The geomagnetic disturbances effect showed that both vTEC and its variability were higher on magnetically disturbed days as compared to quiet days with maximum variability in the daytime. Two geomagnetic storms of moderate strengths with main phases in the local daytime showed long duration (∼52 h) increase in vTEC by 33-67% which can be accounted by changes in E×B drifts due to prompt penetration of storm-time auroral electric field in the daytime and disturbance dynamo electric field in the nighttime to low latitudes.

On the convergence of ionospheric constrained precise point positioning (IC-PPP) based on undifferential uncombined raw GNSS observations.

PubMed

Zhang, Hongping; Gao, Zhouzheng; Ge, Maorong; Niu, Xiaoji; Huang, Ling; Tu, Rui; Li, Xingxing

2013-11-18

Precise Point Positioning (PPP) has become a very hot topic in GNSS research and applications. However, it usually takes about several tens of minutes in order to obtain positions with better than 10 cm accuracy. This prevents PPP from being widely used in real-time kinematic positioning services, therefore, a large effort has been made to tackle the convergence problem. One of the recent approaches is the ionospheric delay constrained precise point positioning (IC-PPP) that uses the spatial and temporal characteristics of ionospheric delays and also delays from an a priori model. In this paper, the impact of the quality of ionospheric models on the convergence of IC-PPP is evaluated using the IGS global ionospheric map (GIM) updated every two hours and a regional satellite-specific correction model. Furthermore, the effect of the receiver differential code bias (DCB) is investigated by comparing the convergence time for IC-PPP with and without estimation of the DCB parameter. From the result of processing a large amount of data, on the one hand, the quality of the a priori ionosphere delays plays a very important role in IC-PPP convergence. Generally, regional dense GNSS networks can provide more precise ionosphere delays than GIM and can consequently reduce the convergence time. On the other hand, ignoring the receiver DCB may considerably extend its convergence, and the larger the DCB, the longer the convergence time. Estimating receiver DCB in IC-PPP is a proper way to overcome this problem. Therefore, current IC-PPP should be enhanced by estimating receiver DCB and employing regional satellite-specific ionospheric correction models in order to speed up its convergence for more practical applications.

On the Convergence of Ionospheric Constrained Precise Point Positioning (IC-PPP) Based on Undifferential Uncombined Raw GNSS Observations

PubMed Central

Zhang, Hongping; Gao, Zhouzheng; Ge, Maorong; Niu, Xiaoji; Huang, Ling; Tu, Rui; Li, Xingxing

2013-01-01

Precise Point Positioning (PPP) has become a very hot topic in GNSS research and applications. However, it usually takes about several tens of minutes in order to obtain positions with better than 10 cm accuracy. This prevents PPP from being widely used in real-time kinematic positioning services, therefore, a large effort has been made to tackle the convergence problem. One of the recent approaches is the ionospheric delay constrained precise point positioning (IC-PPP) that uses the spatial and temporal characteristics of ionospheric delays and also delays from an a priori model. In this paper, the impact of the quality of ionospheric models on the convergence of IC-PPP is evaluated using the IGS global ionospheric map (GIM) updated every two hours and a regional satellite-specific correction model. Furthermore, the effect of the receiver differential code bias (DCB) is investigated by comparing the convergence time for IC-PPP with and without estimation of the DCB parameter. From the result of processing a large amount of data, on the one hand, the quality of the a priori ionosphere delays plays a very important role in IC-PPP convergence. Generally, regional dense GNSS networks can provide more precise ionosphere delays than GIM and can consequently reduce the convergence time. On the other hand, ignoring the receiver DCB may considerably extend its convergence, and the larger the DCB, the longer the convergence time. Estimating receiver DCB in IC-PPP is a proper way to overcome this problem. Therefore, current IC-PPP should be enhanced by estimating receiver DCB and employing regional satellite-specific ionospheric correction models in order to speed up its convergence for more practical applications. PMID:24253190

Crystal Structure of human Karyopherin β2 bound to the PY-NLS of Saccharomyces cerevisiae Nab2

PubMed Central

Soniat, Michael; Sampathkumar, Parthasarathy; Collett, Garen; Gizzi, Anthony S.; Banu, Radhika N.; Bhosle, Rahul C.; Chamala, Swetha; Chowdhury, Sukanya; Fiser, Andras; Glenn, Alan S.; Hammonds, James; Hillerich, Brandan; Khafizov, Kamil; Love, James D.; Matikainen, Bridget; Seidel, Ronald D.; Toro, Rafael; Kumar, P. Rajesh; Bonanno, Jeffery B.; Chook, Yuh Min; Almo, Steven C.

2013-01-01

Import-Karyopherin or Importin proteins bind nuclear localization signals (NLSs) to mediate the import of proteins into the cell nucleus. Karyopherin β2 or Kapβ2, also known as Transportin, is a member of this transporter family responsible for the import of numerous RNA binding proteins. Kapβ2 recognizes a targeting signal termed the PY-NLS that lies within its cargos to target them through the nuclear pore complex. The recognition of PY-NLS by Kapβ2 is conserved throughout eukaryotes. Kap104, the Kapβ2 homolog in Saccharomyces cerevisiae, recognizes PY-NLSs in cargos Nab2, Hrp1, and Tfg2. We have determined the crystal structure of Kapβ2 bound to the PY-NLS of the mRNA processing protein Nab2 at 3.05-Å resolution. A seven-residue segment of the PY-NLS of Nab2 is observed to bind Kapβ2 in an extended conformation and occupies the same PY-NLS binding site observed in other Kapβ2•PY-NLS structures. PMID:23535894

DNA Adduct Formation from Metabolic 5'-Hydroxylation of the Tobacco-Specific Carcinogen N'-Nitrosonornicotine in Human Enzyme Systems and in Rats.

PubMed

Zarth, Adam T; Upadhyaya, Pramod; Yang, Jing; Hecht, Stephen S

2016-03-21

N'-Nitrosonornicotine (NNN) is carcinogenic in multiple animal models and has been evaluated as a human carcinogen. NNN can be metabolized by cytochrome P450s through two activation pathways: 2'-hydroxylation and 5'-hydroxylation. While most previous studies have focused on 2'-hydroxylation in target tissues of rats, available evidence suggests that 5'-hydroxylation is a major activation pathway in human enzyme systems, in nonhuman primates, and in target tissues of some other rodent carcinogenicity models. In the study reported here, we investigated DNA damage resulting from NNN 5'-hydroxylation by quantifying the adduct 2-(2-(3-pyridyl)-N-pyrrolidinyl)-2'-deoxyinosine (py-py-dI). In rats treated with NNN in the drinking water (7-500 ppm), py-py-dI was the major DNA adduct resulting from 5'-hydroxylation of NNN in vivo. Levels of py-py-dI in the lung and nasal cavity were the highest, consistent with the tissue distribution of CYP2A3. In rats treated with (S)-NNN or (R)-NNN, the ratios of formation of (R)-py-py-dI to (S)-py-py-dI were not the expected mirror image, suggesting that there may be a carrier for one of the unstable intermediates formed upon 5'-hydroxylation of NNN. Rat hepatocytes treated with (S)- or (R)-NNN or (2'S)- or (2'R)-5'-acetoxyNNN exhibited a pattern of adduct formation similar to that of live rats. In vitro studies with human liver S9 fraction or human hepatocytes incubated with NNN (2-500 μM) demonstrated that py-py-dI formation was greater than the formation of pyridyloxobutyl-DNA adducts resulting from 2'-hydroxylation of NNN. (S)-NNN formed more total py-py-dI adducts than (R)-NNN in human liver enzyme systems, which is consistent with the critical role of CYP2A6 in the 5'-hydroxylation of NNN in human liver. The results of this study demonstrate that the major DNA adduct resulting from NNN metabolism by human enzymes is py-py-dI and provide potentially important new insights into the metabolic activation of NNN in rodents and humans.

Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange.

PubMed

Iali, Wissam; Green, Gary G R; Hart, Sam J; Whitwood, Adrian C; Duckett, Simon B

2016-11-21

[IrCl(COE) 2 ] 2 (1) reacts with pyridine (py) and H 2 to form crystallographically characterized IrCl(H) 2 (COE)(py) 2 (2). 2 undergoes py loss to form 16-electron IrCl(H) 2 (COE)(py) (3), with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves hyperpolarization of free py (and nicotinamide, nicotine, 5-aminopyrimidine, and 3,5-lutudine) via signal amplification by reversible exchange (SABRE) and hence reflects a simple and readily available precatayst for this process. 2 reacts further over 48 h at 298 K to form crystallographically characterized (Cl)(H)(py)(μ-Cl)(μ-H)(κ-μ-NC 5 H 4 )Ir(H)(py) 2 (4). This dimer is active in the hydrogen isotope exchange process that is used in radiopharmaceutical preparations. Furthermore, while [Ir(H) 2 (COE)(py) 3 ]PF 6 (6) forms upon the addition of AgPF 6 to 2, its stability precludes its efficient involvement in SABRE.

White-rot fungal response to fresh and photolytically-weathered pyrogenic organic matter

NASA Astrophysics Data System (ADS)

Gibson, C. D.; Berry, T. D.; Wang, R.; Bird, J. A.; Filley, T. R.

2013-12-01

Pyrogenic organic matter (PyOM or biochar) is the product of the incomplete combustion of biomass. A better understanding of the microbial-mediated degradation of PyOM is critical to assess its role in soil C sequestration and to serve as an agricultural amendment. Recent studies have shown that PyOM additions can prime native soil C but results have been inconsistent, with studies reporting no effect, an increase, or decrease in C mineralization. This study investigated the ability of saprotrophic white-rot fungus, Trametes versicolor, to decompose an unaltered 'fresh' PyOM and a photo-oxidized PyOM. In addition, we measured PyOM-induced priming effects on the mineralization of malt extract agar media (MEA). Enriched (13C) Pinus banksiana-derived PyOM, produced at 450oC under N2, was added fresh and after 4 weeks exposure to 254 nm light to MEA. Vials containing the various types of media were then monitored for CO2 evolution and oxidative enzyme activity. We found that MEA C respired was stimulated (positive priming) by photolyzed PyOM and was inhibited with fresh PyOM addition (negative priming) relative to controls. Vetryl alcohol addition, a laccase production stimulant, resulted in less activity in the presence of PyOM compared with a control, indicating PyOM may disrupt enzyme induction processes. Loss of PyOM-13CO2 was 0.2% (× 0.001) for fresh PyOM and 1.2% (×0.001) for photolyzed PyOM C during 10 weeks averaged across media treatments. While MEA C mineralization decreased after fresh PyOM addition, both oxidative (laccase and manganese peroxidase) and hydrolytic (β glucosidase) enzyme production increased with fresh PyOM in the absence of veratryl alcohol. However, there was a decrease in its presence. These results suggest that the physiological response of this common wood decay fungus to PyOM is complex and responsive to enzymatic triggers but that PyOM itself can act to promote or suppress overall litter or soil decay by fungi.

The global pyrogenic carbon cycle and its impact on the level of atmospheric CO2 over past and future centuries.

PubMed

Landry, Jean-Sébastien; Matthews, H Damon

2017-08-01

The incomplete combustion of vegetation and dead organic matter by landscape fires creates recalcitrant pyrogenic carbon (PyC), which could be consequential for the global carbon budget if changes in fire regime, climate, and atmospheric CO 2 were to substantially affect gains and losses of PyC on land and in oceans. Here, we included global PyC cycling in a coupled climate-carbon model to assess the role of PyC in historical and future simulations, accounting for uncertainties through five sets of parameter estimates. We obtained year-2000 global stocks of (Central estimate, likely uncertainty range in parentheses) 86 (11-154), 47 (2-64), and 1129 (90-5892) Pg C for terrestrial residual PyC (RPyC), marine dissolved PyC, and marine particulate PyC, respectively. PyC cycling decreased atmospheric CO 2 only slightly between 1751 and 2000 (by 0.8 Pg C for the Central estimate) as PyC-related fluxes changed little over the period. For 2000 to 2300, we combined Representative Concentration Pathways (RCPs) 4.5 and 8.5 with stable or continuously increasing future fire frequencies. For the increasing future fire regime, the production of new RPyC generally outpaced the warming-induced accelerated loss of existing RPyC, so that PyC cycling decreased atmospheric CO 2 between 2000 and 2300 for most estimates (by 4-8 Pg C for Central). For the stable fire regime, however, PyC cycling usually increased atmospheric CO 2 (by 1-9 Pg C for Central), and only the most extreme choice of parameters maximizing PyC production and minimizing PyC decomposition led to atmospheric CO 2 decreases under RCPs 4.5 and 8.5 (by 5-8 Pg C). Our results suggest that PyC cycling will likely reduce the future increase in atmospheric CO 2 if landscape fires become much more frequent; however, in the absence of a substantial increase in fire frequency, PyC cycling might contribute to, rather than mitigate, the future increase in atmospheric CO 2 . © 2016 John Wiley & Sons Ltd.

Quantification of a potent mutagenic 4-amino-3,3'-dichloro-5,4'-dinitrobiphenyl (ADDB) and the related chemicals in water from the Waka River in Wakayama, Japan.

PubMed

Mizuno, Tomoko; Takamura-Enya, Takeji; Watanabe, Tetsushi; Hasei, Tomohiro; Wakabayashi, Keiji; Ohe, Takeshi

2007-06-15

4-Amino-3,3'-dichloro-5,4'-dinitrobiphenyl (ADDB) is a novel chemical exerting strong mutagenicity, especially in the absence of metabolic activation. In addition to mutagenicity, ADDB may also disrupt the endocrine system in vitro. ADDB may be discharged from chemical plants near the Waka River and could be unintentionally formed via post-emission modification of drainage water containing 3,3'-dichlorobenzidine (DCB), which is a precursor in the manufacture of polymers and dye intermediates in chemical plants. The main purpose of this study was to make a comprehensive survey of the behaviour and levels of ADDB and suspected starting material or intermediates of ADDB, i.e., DCB, 3,3'-dichloro-4,4'-dinitrobiphenyl (DDB), and 4-amino-3,3'-dichloro-4'-nitrobipheny (ADNB) in Waka River water samples. We also postulated the formation pathway of ADDB. Water samples were collected at five sampling sites from the Waka River four times between March 2003 and December 2004. Samples were passed through Supelpak2 columns, and adsorbed materials were then extracted with methanol. Extracts were used for quantification of ADDB and the related chemicals by HPLC on reverse-phase columns; mutagenicity was evaluated in the Salmonella assay using the O-acetyltransferase-overexpressing strain YG1024. High levels of ADDB, DCB, DDB, and ADNB (12.0, 20,400, 134.8, and 149.4ng/L-equivalent) were detected in the samples collected at the site where wastewater was discharged from chemical plants into the river. These water samples also showed stronger mutagenicity in YG1024 both with and without S9 mix than the other water samples collected from upstream and downstream sites. The results suggest that ADDB is unintentionally formed from DCB via ADNB in the process of wastewater treatment of drainage water containing DCB from chemical plants.

Anaerobic Dehalogenation of Chloroanilines by Dehalococcoides mccartyi Strain CBDB1 and Dehalobacter Strain 14DCB1 via Different Pathways as Related to Molecular Electronic Structure.

PubMed

Zhang, Shangwei; Wondrousch, Dominik; Cooper, Myriel; Zinder, Stephen H; Schüürmann, Gerrit; Adrian, Lorenz

2017-04-04

Dehalococcoides mccartyi strain CBDB1 and Dehalobacter strain 14DCB1 are organohalide-respiring microbes of the phyla Chloroflexi and Firmicutes, respectively. Here, we report the transformation of chloroanilines by these two bacterial strains via dissimilar dehalogenation pathways and discuss the underlying mechanism with quantum chemically calculated net atomic charges of the substrate Cl, H, and C atoms. Strain CBDB1 preferentially removed Cl doubly flanked by two Cl or by one Cl and NH 2 , whereas strain 14DCB1 preferentially dechlorinated Cl that has an ortho H. For the CBDB1-mediated dechlorination, comparative analysis with Hirshfeld charges shows that the least-negative Cl discriminates active from nonactive substrates in 14 out of 15 cases and may represent the preferred site of primary attack through cob(I)alamin. For the latter trend, three of seven active substrates provide strong evidence, with partial support from three of the remaining four substrates. Regarding strain 14DCB1, the most positive carbon-attached H atom discriminates active from nonactive chloroanilines in again 14 out of 15 cases. Here, regioselectivity is governed for 10 of the 11 active substrates by the most positive H attached to the highest-charge (most positive or least negative) aromatic C carrying the Cl to be removed. These findings suggest the aromatic ring H as primary site of attack through the supernucleophile Co(I), converting an initial H bond to a full electron transfer as start of the reductive dehalogenation. For both mechanisms, one- and two-electron transfer to Cl (strain CBDB1) or H (strain 14DCB1) are compatible with the presently available data. Computational chemistry research into reaction intermediates and pathways may further aid in understanding the bacterial reductive dehalogenation at the molecular level.

Homogeneous reduction of CO2 by photogenerated pyridinyl radicals.

PubMed

Riboni, Francesca; Selli, Elena; Hoffmann, M R; Colussi, A J

2015-05-14

We report that 1-hydropyridinyl radicals (1-PyH(•)) photogenerated in solution react with dissolved CO2 en route to its 2e(-) reduction into carboxylic acids. The 254 nm excitation of pyridine (Py) in deaerated 2-PrOH/H2O mixtures saturated with 1 atm of CO2 yields a suite of products, among which we identified Na(HCOO)2(-) (m/z(-) = 113), C5H6NCOO(-) (m/z(-) = 124), and C5H10O2NCOO(-) (m/z(-) = 160) species by electrospray ionization mass spectrometry. These products demonstrably contain carboxylate functionalities that split CO2 neutrals via collisionally induced dissociation. We infer that 1-PyH(•) [from (1) (3)Py* + 2-PrOH → 1-PyH(•) + (•)PrOH] adds to CO2, in competition with radical-radical reactions, leading to intermediates that are in turn reduced by (•)PrOH into the observed species. The formation of carboxylates in this system, which is shown to require CO2, Py, 2-PrOH, and actinic radiation, amounts to the homogeneous 2e(-) reduction of CO2 by 2-PrOH initiated by Py*. We evaluate a rate constant (2) k2(1-PyH(•) + CO2 → (•)Py-1-COOH) ≈ O (10) M(-1) s(-1) and an activation energy E2 ≥ 9 kcal mol(-1) that are compatible with thermochemical estimates for this reaction.

The molecular characteristics of pyrogenic organic materials and their aqueous leachates

NASA Astrophysics Data System (ADS)

Wozniak, A. S.; Hatcher, P.; Mitra, S.; Bostick, K. W.; Zimmerman, A. R.

2016-12-01

Pyrogenic organic matter (Py-OM), or black carbon, is known to impact soil chemistry, pollutant transport, regional and global carbon cycling, and climate. Py-OM is incorporated into soils via atmospheric deposition (e.g., from biomass, fossil fuel combustion) or direct applications by humans (e.g., biochars applied for agricultural production). Due to its presumed refractory and immobile nature, soil Py-OM is thought to be efficiently buried, sequestering atmospheric CO2. However, tracers of dissolved Py-OM (Py-DOM) have been detected in appreciable quantities in riverine, estuarine, and oceanic waters suggesting that Py-OM is more mobile in the environment than expected. The molecular characteristics of Py-OM are likely to be a controlling factor in the quantities and impacts of Py-DOM released to aqueous systems. Yet, little is known about the detailed molecular composition of these materials, let alone how those molecular characteristics vary with combustion conditions or are altered by environmental processes. Here, we examine oak and grass Py-OM (combusted over a range of temperatures), natural Py-OM (chars aged in the environment for variable lengths of time), and their Py-DOM leachates via nuclear magnetic resonance spectroscopy (NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Multi-CP 13C NMR analyses of Py-OM materials and 1H NMR analyses of corresponding Py-DOM leachates reveal that Py-OM combustion temperature, environmental exposure, and molecular characteristics are reflected in Py-DOM quantities and characteristics. The relative amounts of aromatic C in Py-OM 1) decreases with environmental exposure, the relative oxygen-content in both Py-OM and Py-DOM, and the amount of Py-DOC released per g of Py-OC but 2) is positively correlated with combustion temperature and the relative contributions of acetate and aliphatic hydrogens (CH2) in Py-DOM. Preliminary FTICR-MS analyses show Py-DOM produced from oak at 400 °C to have lost carbohydrate-like compounds found in 250 °C Py-DOM and to contain an abundance of oxygenated aromatic compounds. Oak combusted at 650 °C produces Py-DOM characterized by high H/C, low O/C compounds. The results from this work will improve our understanding of Py-OM transport within and between terrestrial and aqueous systems.

Microsolvation of the pyrrole cation (Py+) with nonpolar and polar ligands: infrared spectra of Py+-Ln with L = Ar, N2, and H2O (n ≤ 3).

PubMed

Schütz, Markus; Matsumoto, Yoshiteru; Bouchet, Aude; Öztürk, Murat; Dopfer, Otto

2017-02-01

The solvation of aromatic (bio-)molecular building blocks has a strong impact on the intermolecular interactions and function of supramolecular assemblies, proteins, and DNA. Herein we characterize the initial microsolvation process of the heterocyclic aromatic pyrrole cation (Py + ) in its 2 A 2 ground electronic state with nonpolar, quadrupolar, and dipolar ligands (L = Ar, N 2 , and H 2 O) by infrared photodissociation (IRPD) spectroscopy of cold mass-selected Py + -L n (n ≤ 3) clusters in a molecular beam and dispersion-corrected density functional theory calculations at the B3LYP-D3/aug-cc-pVTZ level. Size- and isomer-specific shifts in the NH stretch frequency (Δν NH ) unravel the competition between various ligand binding sites, the strength of the respective intermolecular bonds, and the cluster growth. In Py + -Ar, linear H-bonding of Ar to the acidic NH group (NHAr) is competitive with π-stacking to the aromatic ring, and both Py + -Ar(H) and Py + -Ar(π) are observed. For L = N 2 and H 2 O, the linear NHL H-bond is much more stable than any other binding site and the only observed binding motif. For the Py + -Ar 2 and Py + -(N 2 ) 2 trimers, the H/π isomer with one H-bonded and one π-bonded ligand strongly competes with a 2H isomer with two bifurcated nonlinear NHL bonds. The latter are equivalent for Ar but nonequivalent for N 2 . Py + -H 2 O exhibits a strong and linear NHO H-bond with charge-dipole configuration and C 2v symmetry. IRPD spectra of cold Py + -H 2 O-L clusters with L = Ar and N 2 reveal that Ar prefers π-stacking to the Py + ring, while N 2 forms an OHN 2 H-bond to the H 2 O ligand. The Δν NH frequency shifts in Py + -L n are correlated with the strength of the NHL H-bond and the proton affinity (PA) of L, and a monotonic correlation between Δν NH of the Py + -L(H) dimers and PA is established. Comparison with neutral Py-L dimers reveals the strong impact of the positive charge on the acidity of the NH group, the strength of the NHL H-bond, and the preferred ligand binding motif.

12-Month Results From the First-in-Human Randomized Study of the Ranger Paclitaxel-Coated Balloon for Femoropopliteal Treatment.

PubMed

Steiner, Sabine; Willfort-Ehringer, Andrea; Sievert, Horst; Geist, Volker; Lichtenberg, Michael; Del Giudice, Costantino; Sauguet, Antoine; Diaz-Cartelle, Juan; Marx, Claudia; Ströbel, Armin; Schult, Ingolf; Scheinert, Dierk

2018-05-28

The authors sought to evaluate the performance of the Ranger paclitaxel-coated balloon versus uncoated balloon angioplasty for femoropopliteal lesions at 12 months. Drug-coated balloons (DCBs) are a promising endovascular treatment option for peripheral artery disease of the femoropopliteal segment, and each unique device requires dedicated clinical study. The prospective, randomized RANGER SFA (Comparison of the Ranger™ Paclitaxel-Coated PTA Balloon Catheter and Uncoated PTA Balloons in Femoropopliteal Arteries) study (NCT02013193) enrolled 105 patients with symptomatic lower limb ischemia (Rutherford category 2 to 4) and stenotic lesions in the nonstented femoropopliteal segment at 10 European centers. Seventy-one patients (mean age 68 ± 8 years, n = 53 men) were enrolled in the Ranger DCB arm, and 34 patients (mean age 67 ± 9 years, n = 23 men) were assigned to the control group. Twelve-month analysis included patency, safety, and clinical outcomes and quality-of-life assessments. The DCB group had a greater primary patency rate at 12 months (Kaplan-Meier estimate 86.4% vs. 56.5%), with a significantly longer time to patency failure (log-rank p < 0.001). The estimated freedom from target lesion revascularization rate was 91.2% in the DCB group and 69.9% in the control group at 12 months, with a significantly longer time to reintervention (p = 0.010). No target limb amputations or device-related deaths occurred in either group. Twelve-month results show that patency was maintained longer after Ranger DCB treatment than after conventional balloon angioplasty, and this result was associated with a low revascularization rate and good clinical outcomes. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

A Single-Center Experience with Dynamic Compression Bracing for Children with Pectus Carinatum.

PubMed

Poola, Ashwini Suresh; Pierce, Amy L; Orrick, Beth A; Peter, Shawn David St; Snyder, Charles L; Juang, David; Aguayo, Pablo; Fraser, Jason D; Holcomb, George W

2018-02-01

 Bracing for pectus carinatum (PC) has emerged as an alternative to surgical correction. However, predictive factors for bracing remain poorly understood, as much of the data have been reported from small series.  We reviewed a prospective dataset in patients with PC who underwent dynamic compression bracing (DCB) from July 2011 to July 2016. Bracing was initiated in patients > 10 years of age with a significant PC and desire for bracing. Data were analyzed for those observed two or more times after the brace was fitted to the patient.  A total of 503 patients were evaluated for PC and 340 (68%) underwent DCB. Eighty-five percent were males with an average age of 14 ± 2 years. There was a positive correlation of age with pressure of initial correction (PIC, r  = 0.2). One patient underwent operative correction as the initial therapy. Two hundred seventeen patients had two or more visits after the patient was fitted for the brace. The mean PIC in this cohort was 4 psi (range: 1.5-7.8), and the median duration of bracing in this group was 16 months (IQR: 7-23 months). One hundred three patients (47%) achieved complete correction after an average bracing time of 7.5 months and were then placed in the retainer mode. Thirty patients successfully completed bracing therapy and required an average of 23 months of therapy (2 months-4 years). No patient recurred after bracing was completed, but one failed bracing and required operative correction. Complications included mechanical problems (8%), skin complications (10%), complaints of tightness (3%), and pain (2%).  DCB has both early and lasting effects in the correction of PC with minimal complications. Predictive factors for successful resolution of the PC include increased duration of DCB and lower initial PIC. Georg Thieme Verlag KG Stuttgart · New York.

Spectroscopic, Electrochemical and Computational Characterisation of Ru Species Involved in Catalytic Water Oxidation: Evidence for a [Ru(V) (O)(Py2 (Me) tacn)] Intermediate.

PubMed

Casadevall, Carla; Codolà, Zoel; Costas, Miquel; Lloret-Fillol, Julio

2016-07-11

A new family of ruthenium complexes based on the N-pentadentate ligand Py2 (Me) tacn (N-methyl-N',N''-bis(2-picolyl)-1,4,7-triazacyclononane) has been synthesised and its catalytic activity has been studied in the water-oxidation (WO) reaction. We have used chemical oxidants (ceric ammonium nitrate and NaIO4 ) to generate the WO intermediates [Ru(II) (OH2 )(Py2 (Me) tacn)](2+) , [Ru(III) (OH2 )(Py2 (Me) tacn)](3+) , [Ru(III) (OH)(Py2 (Me) tacn)](2+) and [Ru(IV) (O)(Py2 (Me) tacn)](2+) , which have been characterised spectroscopically. Their relative redox and pH stability in water has been studied by using UV/Vis and NMR spectroscopies, HRMS and spectroelectrochemistry. [Ru(IV) (O)(Py2 (Me) tacn)](2+) has a long half-life (>48 h) in water. The catalytic cycle of WO has been elucidated by using kinetic, spectroscopic, (18) O-labelling and theoretical studies, and the conclusion is that the rate-determining step is a single-site water nucleophilic attack on a metal-oxo species. Moreover, [Ru(IV) (O)(Py2 (Me) tacn)](2+) is proposed to be the resting state under catalytic conditions. By monitoring Ce(IV) consumption, we found that the O2 evolution rate is redox-controlled and independent of the initial concentration of Ce(IV) . Based on these facts, we propose herein that [Ru(IV) (O)(Py2 (Me) tacn)](2+) is oxidised to [Ru(V) (O)(Py2 (Me) tacn)](2+) prior to attack by a water molecule to give [Ru(III) (OOH)(Py2 (Me) tacn)](2+) . Finally, it is shown that the difference in WO reactivity between the homologous iron and ruthenium [M(OH2 )(Py2 (Me) tacn)](2+) (M=Ru, Fe) complexes is due to the difference in the redox stability of the key M(V) (O) intermediate. These results contribute to a better understanding of the WO mechanism and the differences between iron and ruthenium complexes in WO reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relativistic effects in iron-, ruthenium-, and osmium porphyrins

NASA Astrophysics Data System (ADS)

Liao, Meng-Sheng; Scheiner, Steve

2002-12-01

Nonrelativistic and relativistic DFT calculations are performed on four-coordinate metal porphyrins MP and their six-coordinate adducts MP(py) 2 and MP(py)(CO) (py=pyridine) with M=Fe, Ru, and Os. The electronic structures of the MPs are investigated by considering all possible low-lying states with different configurations of nd-electrons. FeP and OsP have a 3A2 g ground state, while this state is nearly degenerate with 3Eg for RuP. Without relativistic corrections, the ground states of both RuP and OsP would be 3Eg. For the six-coordinate adducts with py and CO, the strong-field axial ligands raise the energy of the M d z2-orbital, thereby making the M II ion diamagnetic. The calculated redox properties of MP(py) 2 and MP(py)(CO) are in agreement with experiment. The difference between RuP(py)(CO) and OsP(py)(CO), in terms of site of oxidation, is due to relativistic effects.

Structural and energetic basis of ALS-causing mutations in the atypical proline-tyrosine nuclear localization signal of the Fused in Sarcoma protein (FUS)

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

Zhang, Zi Chao; Chook, Yuh Min

Mutations in the proline/tyrosine–nuclear localization signal (PY-NLS) of the Fused in Sarcoma protein (FUS) cause amyotrophic lateral sclerosis (ALS). Here we report the crystal structure of the FUS PY-NLS bound to its nuclear import receptor Karyopherinβ2 (Kapβ2; also known as Transportin). The FUS PY-NLS occupies the structurally invariant C-terminal arch of Kapβ2, tracing a path similar to that of other characterized PY-NLSs. Unlike other PY-NLSs, which generally bind Kapβ2 in fully extended conformations, the FUS peptide is atypical as its central portion forms a 2.5-turn α-helix. The Kapβ2-binding epitopes of the FUS PY-NLS consist of an N-terminal PGKM hydrophobic motif,more » a central arginine-rich α-helix, and a C-terminal PY motif. ALS mutations are found almost exclusively within these epitopes. Each ALS mutation site makes multiple contacts with Kapβ2 and mutations of these residues decrease binding affinities for Kapβ2 (K D for wild-type FUS PY-NLS is 9.5 nM) up to ninefold. Thermodynamic analyses of ALS mutations in the FUS PY-NLS show that the weakening of FUS-Kapβ2 binding affinity, the degree of cytoplasmic mislocalization, and ALS disease severity are correlated.« less

Spirolactone and spirothiolactone rhodamine-pyrene probes for detection of Hg2 + with different sensing properties and its application in living cells

NASA Astrophysics Data System (ADS)

Rui, Qing-Qing; Zhou, Yi; Fang, Yuan; Yao, Cheng

2016-04-01

Two new rhodamine B-based fluorescent probes PyRbS and PyRbO containing pyrene moiety were designed and synthesized. Both of the probes showed colorimetric and fluorometric sensing abilities for Hg2 + with high selectivity over other metal ions. The binding analysis using Job's plot suggested 1:1 stoichiometry for the complexes formed for Hg2 +. Compared with PyRbO, the PyRbS showed higher selectivity and sensitivity due to the thiophilic property of Hg2 + ion. The PyRbS exhibited the linear fluorescence quenching to Hg2 + in the range of 0.3 to 4.8 μM (λex = 365 nm) and 0.3 to 5.4 μM (λex = 515 nm), and the detection limit was 0.72 μM. Moreover, ratiometric changes of PyRbS with Hg2 + in absorption spectrum were observed, which could not be obtained in the combination of PyRbO with Hg2 +. In addition, the methyl thiazolyl tetrazolium (MTT) assay demonstrated that RbPyS had low cytotoxicity and was successfully used to monitor intracellular Hg2 + levels in living cells.

Comparison of Intralaminar and Interlaminar Mode-I Fracture Toughness of Unidirectional IM7/8552 Graphite/Epoxy Composite

NASA Technical Reports Server (NTRS)

Czabaj, Michael W.; Ratcliffe, James

2012-01-01

The intralaminar and interlaminar mode-I fracture-toughness of a unidirectional IM7/8552 graphite/epoxy composite were measured using compact tension (CT) and double cantilever beam (DCB) test specimens, respectively. Two starter crack geometries were considered for both the CT and DCB specimen configurations. In the first case, starter cracks were produced by 12.5 micron thick, Teflon film inserts. In the second case, considerably sharper starter cracks were produced by fatigue precracking. For each specimen configuration, use of the Teflon film starter cracks resulted in initially unstable crack growth and artificially high initiation fracture-toughness values. Conversely, specimens with fatigue precracks exhibited stable growth onset and lower initiation fracture toughness. For CT and DCB specimens with fatigue precracks, the intralaminar and interlaminar initiation fracture toughnesses were approximately equal. However, during propagation, the CT specimens exhibited more extensive fiber bridging, and rapidly increasing R-curve behavior as compared to the DCB specimens. Observations of initiation and propagation of intralaminar and interlaminar fracture, and the measurements of fracture toughness, were supported by fractographic analysis using scanning electron microscopy.

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

DiMarco, Brian N.; Troian-Gautier, Ludovic; Sampaio, Renato N.

Two sensitizers, [Ru(bpy) 2 (dcb)] 2+ ( RuC ) and [Ru(bpy) 2 (dpb)] 2+ ( RuP ), were anchored to mesoporous TiO 2 thin films and utilized to sensitize the reaction of TiO 2 electrons with oxidized triphenylamines to visible light in CH 3 CN electrolytes.

[Drug-coated Balloon Angioplasty in Femoropopliteal Arteries - Is There a Class Effect?

PubMed

Teichgräber, Ulf Karl-Martin; Klumb, Christof

2017-10-01

Aim Percutaneous transluminal angioplasty (PTA) is a well-accepted method to re-establish patency in stenotic and reoccluded vessels. One tool to improve results may be to use paclitaxel drug-coated balloon (DCB) catheters. This systematic review investigates whether there is a class effect among different DCBs. Methods The primary endpoint was "Freedom from Target Lesion Revascularisation" (FfTLR) after 12 months. A systematic literature search was performed in PubMed and risk of bias was assessed of the included trials. Efficacy of DCB vs. POBA (plain old balloon angioplasty) in binary outcomes was investigated with relative risks and number needed to treat (NNT). Results Ten trials including 1835 patients and investigating six different DCB were identified. A high risk of bias was found in these studies. There was a lower Late Lumen Loss at six months and a higher FfTLR and primary patency at one year after DCB-treatment. However, results varied greatly with NNTs ranging from three to thirty-three. Overall, there were no differences in ABI- and Rutherford-Outcome as well as incidence of adverse events. Conclusion Tested DCBs were able to improve PTA results at one year. There were large differences in efficacy between different DCB. A class effect cannot be confirmed yet. There is a risk of overestimating the effect of DCBs due to the high risk of bias in the included trials. Georg Thieme Verlag KG Stuttgart · New York.

Characterization of Thermally Activated Metalloenediyne Cytotoxicity in Human Melanoma Cells.

PubMed

Keller, Eric J; Porter, Meghan; Garrett, Joy E; Varie, Meredith; Wang, Haiyan; Pollok, Karen E; Turchi, John J; Zaleski, Jeffrey M; Dynlacht, Joseph R

2018-05-15

Enediynes are a highly cytotoxic class of compounds. However, metallation of these compounds may modulate their activation, and thus their cytotoxicity. We previously demonstrated that cytotoxicity of two different metalloenediynes, including (Z)-N,N'-bis[1-pyridyl-2-yl-meth-(E)-ylidene]octa-4-ene-2,6-diyne-1,8-diamine] (PyED), is potentiated when the compounds are administered to HeLa cells during hyperthermia treatment at concentrations that are minimally or not cytotoxic at 37°C. In this study, we further characterized the concentration, time and temperature dependence of cytotoxicity of PyED on human U-1 melanoma cells. We also investigated the potential mechanisms by which PyED cytotoxicity is enhanced during hyperthermia treatment. Cell killing with PyED was dependent on concentration, temperature during treatment and time of exposure. Potentiation of cytotoxicity was observed when cells were treated with PyED at temperatures ≥39.5°C, and enhancement of cell killing increased with temperature and with increasing time at a given temperature. All cells treated with PyED were shown to have DNA damage, but substantially more damage was observed in cells treated with PyED during heating. DNA repair was also inhibited in cells treated with the drug during hyperthermia. Thus, potentiation of PyED cytotoxicity by hyperthermia may be due to enhancement of drug-induced DNA lesions, and/or the inhibition of repair of sublethal DNA damage. While the selective thermal activation of PyED supports the potential clinical utility of metalloenediynes as cancer thermochemotherapeutic agents, therapeutic gain could be optimized by identifying compounds that produce minimal toxicity at 37°C but which become activated and show enhancement of cytotoxicity within a tumor subjected to localized hyperthermic or thermal ablative treatment, or which might act as bifunctional agents. We thus also describe the development and initial characterization of a novel cofactor complex of PyED, platinated PyED (Pt-PyED). Pt-PyED binds to DNA-like cisplatin, and much like PyED, cytotoxicity is greatly enhanced after treatment with the drug at elevated temperatures. However, in contrast to PyED, Pt-PyED is only minimally cytotoxic at 37°C, at concentrations at which cytotoxicity is enhanced by hyperthermia. Further development of cisplatin-based enediynes may result in compounds which, when activated, will possess multiple DNA binding modalities similar to cisplatin, but produce less side effects in tissues at normothermic temperatures.

Solvent extraction of thorium(IV), uranium(VI), and europium(III) with lipophilic alkyl-substituted pyridinium salts. Final report for subcontract 9-XZ2-1123E-1, June 1, 1992--December 1, 1995

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

Ensor, D.D.

1997-01-01

In the treatment of high level nuclear wastes, aromatic pyridinium salts which are radiation-resistant are desired for the extraction of actinides and lanthanides. The solvent extraction of Th{sup +4}, UO{sub 2}{sup +2}, and Eu{sup +3} by three aromatic extractants, 3,5-didodecylpyridinium nitrate (35PY), 2,6-didodecylpyridinium nitrate (26PY), and 1-methyl-3,5-didodecyl-pyridinium iodide (1M35PY) has been studied in nitric acid media. The general order of extractability of the three extractants in toluene was 1M35PY>> 26PY > 35PY. The overall extraction efficiency of the metal ions was Th{sup +4} >UO{sub 2}{sup +2} > Eu{sup +3}. The extraction of HNO{sub 3}, which was competitive with the extractionmore » of metal ions, was quantitatively investigated by NaOH titration and UV spectrometry. The loading capacity suggested that the extracted species in the organic phase for thorium was (R{sub 4}N{sup +}){sub 2}Th(NO{sub 3}{sup -}){sub 6}, where R{sub 4}N{sup +} denotes 1M35PY. A comparison of 1M35PY to the well-characterized extractant, Aliquat-336, an aliphatic ammonium salt was made. At the same extractant concentration, 1M35PY extracted thorium more efficiently than Aliquat-336 at high acidity. Thorium could be readily stripped with dilute nitric acid from 1M35PY. After irradiation of 0.1M 1M35PY with {sup 60}Co at 40R/min for 48 hours, no change in the extraction efficiency of thorium was observed.« less

Manganese Porphyrin, MnTE-2-PyP5+, Acts as a Pro-Oxidant to Potentiate Glucocorticoid-Induced Apoptosis in Lymphoma Cells

PubMed Central

Jaramillo, Melba C.; Briehl, Margaret M.; Crapo, James D.; Haberle, Ines Batinic; Tome, Margaret E.

2012-01-01

Using current chemotherapy protocols, over 55% of lymphoma patients fail treatment. Novel agents are needed to improve lymphoma survival. The manganese porphyrin, MnTE-2-PyP5+, augments glucocorticoid-induced apoptosis in WEHI7.2 murine thymic lymphoma cells, suggesting that it may have potential as a lymphoma therapeutic. However, the mechanism by which MnTE-2-PyP5+ potentiates glucocorticoid-induced apoptosis is unknown. Previously, we showed that glucocorticoid treatment increases the steady state levels of hydrogen peroxide ([H2O2]ss) and oxidizes the redox environment in WEHI7.2 cells. In the current study, we found that when MnTE-2-PyP5+ is combined with glucocorticoids, it augments dexamethasone-induced oxidative stress however, it does not augment the [H2O2]ss levels. The combined treatment depletes GSH, oxidizes the 2GSH:GSSG ratio, and causes protein glutathionylation to a greater extent than glucocorticoid treatment alone. Removal of the glucocorticoid-generated H2O2 or depletion of glutathione by BSO prevents MnTE-2-PyP5+ from augmenting glucocorticoid-induced apoptosis. In combination with glucocorticoids, MnTE-2-PyP5+ glutathionylates p65 NF-κB and inhibits NF-κB activity. Inhibition of NF-κB with SN50, an NF-κB inhibitor, enhances glucocorticoid-induced apoptosis to the same extent as MnTE-2-PyP5+. Taken together, these findings indicate that: 1) H2O2 is important for MnTE-2-PyP5+ activity; 2) Mn-TE-2-PyP5+ cycles with GSH; and 3) MnTE-2-PyP5+ potentiates glucocorticoid-induced apoptosis by glutathionylating and inhibiting critical survival proteins, including NF-κB. In the clinic, over-expression of NF-κB is associated with a poor prognosis in lymphoma. MnTE-2-PyP5+ may therefore, synergize with glucocorticoids to inhibit NF-κB and improve current treatment. PMID:22330065

UV-LIGA Microfabrication of 220 GHz Sheet Beam Amplifier Gratings with SU-8 Photoresists

DTIC Science & Technology

2010-01-01

4 4 4a Diethyl ether 3d, RT 0 Tetrahydrofuran (THF) 3d, RT 1 2 4 3 3 Py + pyridinium (Pym) HBr crystals 2d, RT 1 2 3 2 Py + Pym HCl crystals 2d, RT 1...1 1 Acetone + Pym HBr crystals 2d, RT 1 0 Pym dichromate in Py 2d, RT 1 2 1 Pym chlorochromate in Py 2d, RT 4 1 2 1a Propylamine (PA) 2d, RT 1 2 3 2

Spirolactone and spirothiolactone rhodamine-pyrene probes for detection of Hg²⁺ with different sensing properties and its application in living cells.

PubMed

Rui, Qing-Qing; Zhou, Yi; Fang, Yuan; Yao, Cheng

2016-04-15

Two new rhodamine B-based fluorescent probes PyRbS and PyRbO containing pyrene moiety were designed and synthesized. Both of the probes showed colorimetric and fluorometric sensing abilities for Hg(2+) with high selectivity over other metal ions. The binding analysis using Job's plot suggested 1:1 stoichiometry for the complexes formed for Hg(2+). Compared with PyRbO, the PyRbS showed higher selectivity and sensitivity due to the thiophilic property of Hg(2+) ion. The PyRbS exhibited the linear fluorescence quenching to Hg(2+) in the range of 0.3 to 4.8 μM (λ(ex)=365 nm) and 0.3 to 5.4 μM (λ(ex)=515 nm), and the detection limit was 0.72 μM. Moreover, ratiometric changes of PyRbS with Hg(2+) in absorption spectrum were observed, which could not be obtained in the combination of PyRbO with Hg(2+). In addition, the methyl thiazolyl tetrazolium (MTT) assay demonstrated that RbPyS had low cytotoxicity and was successfully used to monitor intracellular Hg(2+) levels in living cells. Copyright © 2016 Elsevier B.V. All rights reserved.

Epidermal growth factor-induced phosphatidylinositol 3-kinase activation and DNA synthesis. Identification of Grb2-associated binder 2 as the major mediator in rat hepatocytes.

PubMed

Kong, M; Mounier, C; Wu, J; Posner, B I

2000-11-17

In previous work we showed that the phosphatidylinositol 3-kinase (PI3-kinase), not the mitogen-activated protein kinase, pathway is necessary and sufficient to account for insulin- and epidermal growth factor (EGF)-induced DNA synthesis in rat hepatocytes. Here, using a dominant-negative p85, we confirmed the key role of EGF-induced PI3-kinase activation and sought to identify the mechanism by which this is effected. Our results show that EGF activates PI3-kinase with a time course similar to that of the association of p85 with three principal phosphotyrosine proteins (i. e. PY180, PY105, and PY52). We demonstrated that each formed a distinct p85-associated complex. PY180 and PY52 each constituted about 10% of EGF-activated PI3-kinase, whereas PY105 was responsible for 80%. PY105 associated with Grb2 and SHP-2, and although it behaved like Gab1, none of the latter was detected in rat liver. We therefore cloned a cDNA from rat liver, which was found to be 95% homologous to the mouse Grb2-associated binder 2 (Gab2) cDNA sequence. Using a specific Gab2 antibody, we demonstrated its expression in and association with p85, SHP-2, and Grb2 upon EGF treatment of rat hepatocytes. Gab2 accounted for most if not all of the PY105 species, since immunoprecipitation of Gab2 with specific antibodies demonstrated parallel immunodepletion of Gab2 and PY105 from the residual supernatants. We also found that the PI3-kinase activity associated with Gab2 was totally abolished by dominant negative p85. Thus, Gab2 appears to be the principal EGF-induced PY protein recruiting and activating PI3-kinase and mitogenesis.

Fracture toughness in Mode I (GIC) for ductile adhesives

NASA Astrophysics Data System (ADS)

Gálvez, P.; Carbas, RJC; Campilho, RDSG; Abenojar, J.; Martínez, MA; Silva LFM, da

2017-05-01

Works carried out in this publication belong to a project that seeks the replacement of welded joints by adhesive joints at stress concentration nodes in bus structures. Fracture toughness in Mode I (GIC) has been measured for two different ductile adhesives, SikaTack Drive and SikaForce 7720. SikaTack Drive is a single-component polyurethane adhesive with high viscoelasticity (more than 100%), whose main use is the car-glass joining and SikaForce 7720 is double-component structural polyurethane adhesive. Experimental works have been carried out from the test called Double Cantilever Beam (DCB), using two steel beams as adherents and an adhesive thickness according to the problem posed in the Project, of 2 and 3 mm for SikaForce 7720 and SikaTack Drive, respectively. Three different methods have been used for measuring the fracture toughness in mode I (GIC) from the values obtained in the experimental DCB procedure for each adhesive: Corrected Beam Theory (CBT), Compliance Calibration Method (CCM) and Compliance Based Beam Method (CBBM). Four DCB specimens have been tested for each adhesive. Dispersion of each GIC calculation method for each adhesive has been studied. Likewise variations between the three different methods have been also studied for each adhesive.

Enhanced dechlorination of m-DCB using iron@graphite/palladium (Fe@C/Pd) nanoparticles produced by pulsed laser ablation in liquid.

PubMed

Yu, Yiseul; Jung, Hyeon Jin; Je, Mingyu; Choi, Hyun Chul; Choi, Myong Yong

2016-07-01

In this work, the zero valent Fe (ZVI) and graphite-encapsulated Fe (Fe@C) nanoparticles (NPs) were easily and selectively prepared by a pulsed laser ablation (PLA) method in an aqueous sodium borohydride solution and ascorbic acid dissolved in methanol, respectively. Here, the Fe@C NPs were uniquely synthesized by PLA in methanol, where the solvent is used as both a carbon source for the graphitic layers and solvent, which is very unique. Furthermore, Pd NPs were loaded onto the surface of the Fe@C NPs to prepare bimetallic (Fe@C/Pd) NPs for the enhancement of the degradation efficiency of m-dichlorobenzene (m-DCB). The morphology, crystallinity, and surface composition of the prepared NPs were carefully characterized by high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray spectrometer (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The degradation rate of m-DCB using single (Fe and Pd) or bimetallic (Fe/Pd and Fe@C/Pd) NPs were compared by using gas chromatography. Among these NPs produced in this work, the Fe@C/Pd NPs with 1.71 wt % of Pd showed an excellent dechlorination efficiency for m-DCB with 100% degradation within 75 min. The graphitic layer on the Fe NPs played as not only an oxidation resistant for the Fe NPs to surroundings, but also a supporter of the Pd NPs for the enhanced degradation efficiency of m-DCB. Copyright © 2016 Elsevier Ltd. All rights reserved.

Periaqueductal grey stimulation induced panic-like behaviour is accompanied by deactivation of the deep cerebellar nuclei.

PubMed

Moers-Hornikx, Véronique M P; Vles, Johan S H; Lim, Lee Wei; Ayyildiz, Mustafa; Kaplan, Suleyman; Gavilanes, Antonio W D; Hoogland, Govert; Steinbusch, Harry W M; Temel, Yasin

2011-03-01

Until recently, the cerebellum was primarily considered to be a structure involved in motor behaviour. New anatomical and clinical evidence has shown that the cerebellum is also involved in higher cognitive functions and non-motor behavioural changes. Functional imaging in patients with anxiety disorders and in cholecystokinin tetrapeptide-induced panic-attacks shows activation changes in the cerebellum. Deep brain stimulation of the dorsolateral periaqueductal grey (dlPAG) and the ventromedial hypothalamus (VMH) in rats has been shown to induce escape behaviour, which mimics a panic attack in humans. We used this animal model to study the neuronal activation in the deep cerebellar nuclei (DCbN) using c-Fos immunohistochemistry. c-Fos expression in the DCbN decreased significantly after inducing escape behaviour by stimulation of the dlPAG and the VMH, indicating that the DCbN were deactivated. This study demonstrates that the DCbN are directly or indirectly involved in panic attacks. We suggest that the cerebellum plays a role in the selection of relevant information, and that deactivation of the cerebellar nuclei is required to allow inappropriate behaviour to occur, such as panic attacks.

Kinetic research on dechlorinating dichlorobenzene in aqueous system by nano-scale nickel/iron loaded with CMC/NFC hydrogel.

PubMed

Wan, Xiao-Fang; Guo, Congbao; Liu, Yu; Chai, Xin-Sheng; Li, Youming; Chen, Guangxue

2018-03-01

In this study, we reported on the nano-scale nickel/iron particles loaded in carboxymethyl/nanofibrillated cellulose (CMC/NFC) hydrogel for the dechlorination of o-dichlorobenzene (DCB) in aqueous solution. The biodegradable hydrogel may provide an ideal supporting material for fastening the bimetallic nano-scale particles, which was examined and characterized by TEM, SEM-EDX, FT-IR and BET. The performance of the selected bimetallic particles was evaluated by conducting the dechlorination of DCB in the solution under different reaction conditions (e.g., pH, dosage of nickel/iron nanoparticles and temperature). The results showed that about 70% of DCB could be dechlorinated at 20 °C in 8 h, which indicated that the immobilized reactive material had a high reduction activity when Ni/Fe loading dosage in the hydrogel (18 wt%) was considered. Moreover, the reduction behavior agreed to the pseudo-first order reaction, in which the dechlorination rate was irrelative to the pH aqueous solution. A kinetic model for predicting the concentration of DCB during the reduction reaction was established based on the experimental data. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pyrogenic carbon from tropical savanna burning: production and stable isotope composition

NASA Astrophysics Data System (ADS)

Saiz, G.; Wynn, J. G.; Wurster, C. M.; Goodrick, I.; Nelson, P. N.; Bird, M. I.

2014-10-01

Widespread burning of mixed tree-grass ecosystems represents the major natural locus of pyrogenic carbon (PyC) production. PyC is a significant, pervasive, and yet poorly understood "slow-cycling" form of carbon present in the atmosphere, hydrosphere, soils and sediments. We conducted sixteen experimental burns on a rainfall transect in northern Australian savannas with C4 grasses ranging from 35 to 99% of total biomass. Residues from each fire were partitioned into PyC and further into recalcitrant (HyPyC) components, with each of these also partitioned into proximal (> 125 μm) and distal (< 125 μm) fluxes. The median [range] PyC production across all burns was 16.0 [11.5]% of total carbon exposed (TCE), with HyPyC accounting for 2.5 [4.9]% of TCE. Both PyC and HyPyC were dominantly partitioned into the proximal flux, likely to remain (initially) close to the site of production. Production of HyPyC was strongly related to fire residence time, with shorter duration fires resulting in higher HyPyC yields. The carbon isotope (δ13C) compositions of PyC and HyPyC were generally lower by 1-3‰ relative to the original biomass, with marked depletion up to 7 ‰ for grasslands dominated by C4 biomass. δ13C values of CO2 produced by combustion was computed by mass balance and ranged from ~0.4 to 1.3‰. The depletion of 13C in PyC and HyPyC relative to the original biomass has significant implications for the interpretation of δ13C values of savanna soil organic carbon and of ancient PyC preserved in the geologic record, and for global 13C isotopic disequilibria calculations.

Consistent Estimates of Very Low HIV Incidence Among People Who Inject Drugs: New York City, 2005–2014

PubMed Central

Arasteh, Kamyar; McKnight, Courtney; Feelemyer, Jonathan; Campbell, Aimée N. C.; Tross, Susan; Smith, Lou; Cooper, Hannah L. F.; Hagan, Holly; Perlman, David

2016-01-01

Objectives. To compare methods for estimating low HIV incidence among persons who inject drugs. Methods. We examined 4 methods in New York City, 2005 to 2014: (1) HIV seroconversions among repeat participants, (2) increase of HIV prevalence by additional years of injection among new injectors, (3) the New York State and Centers for Disease Control and Prevention stratified extrapolation algorithm, and (4) newly diagnosed HIV cases reported to the New York City Department of Health and Mental Hygiene. Results. The 4 estimates were consistent: (1) repeat participants: 0.37 per 100 person-years (PY; 95% confidence interval [CI] = 0.05/100 PY, 1.33/100 PY); (2) regression of prevalence by years injecting: 0.61 per 100 PY (95% CI = 0.36/100 PY, 0.87/100 PY); (3) stratified extrapolation algorithm: 0.32 per 100 PY (95% CI = 0.18/100 PY, 0.46/100 PY); and (4) newly diagnosed cases of HIV: 0.14 per 100 PY (95% CI = 0.11/100 PY, 0.16/100 PY). Conclusions. All methods appear to capture the same phenomenon of very low and decreasing HIV transmission among persons who inject drugs. Public Health Implications. If resources are available, the use of multiple methods would provide better information for public health purposes. PMID:26794160

Donor/Acceptor Molecular Orientation-Dependent Photovoltaic Performance in All-Polymer Solar Cells.

PubMed

Zhou, Ke; Zhang, Rui; Liu, Jiangang; Li, Mingguang; Yu, Xinhong; Xing, Rubo; Han, Yanchun

2015-11-18

The correlated donor/acceptor (D/A) molecular orientation plays a crucial role in solution-processed all-polymer solar cells in term of photovoltaic performance. For the conjugated polymers PTB7-th and P(NDI2OD-T2), the preferential molecular orientation of neat PTB7-th films kept face-on regardless of the properties of processing solvents. However, an increasing content of face-on molecular orientation in the neat P(NDI2OD-T2) films could be found by changing processing solvents from chloronaphthalene (CN) and o-dichlorobenzene (oDCB) to chlorobenzene (CB). Besides, the neat P(NDI2OD-T2) films also exhibited a transformation of preferential molecular orientation from face-on to edge-on when extending film drying time by casting in the same solution. Consequently, a distribution diagram of molecular orientation for P(NDI2OD-T2) films was depicted and the same trend could be observed for the PTB7-th/P(NDI2OD-T2) blend films. By manufacture of photovoltaic devices with blend films, the relationship between the correlated D/A molecular orientation and device performance was established. The short-circuit current (Jsc) of devices processed by CN, oDCB, and CB enhanced gradually from 1.24 to 8.86 mA/cm(2) with the correlated D/A molecular orientation changing from face-on/edge-on to face-on/face-on, which could be attributed to facile exciton dissociation at D/A interface with the same molecular orientation. Therefore, the power conversion efficiency (PCE) of devices processed by CN, oDCB, and CB improved from 0.53% to 3.52% ultimately.

A Cu2+-selective fluorescent chemosensor based on BODIPY with two pyridine ligands and logic gate

NASA Astrophysics Data System (ADS)

Huang, Liuqian; Zhang, Jing; Yu, Xiaoxiu; Ma, Yifan; Huang, Tianjiao; Shen, Xi; Qiu, Huayu; He, Xingxing; Yin, Shouchun

2015-06-01

A novel near-infrared fluorescent chemosensor based on BODIPY (Py-1) has been synthesized and characterized. Py-1 displays high selectivity and sensitivity for sensing Cu2+ over other metal ions in acetonitrile. Upon addition of Cu2+ ions, the maximum absorption band of Py-1 in CH3CN displays a red shift from 603 to 608 nm, which results in a visual color change from pink to blue. When Py-1 is excited at 600 nm in the presence of Cu2+, the fluorescent emission intensity of Py-1 at 617 nm is quenched over 86%. Notably, the complex of Py-1-Cu2+ can be restored with the introduction of EDTA or S2-. Consequently, an IMPLICATION logic gate at molecular level operating in fluorescence mode with Cu2+ and S2- as chemical inputs can be constructed. Finally, based on the reversible and reproducible system, a nanoscale sequential memory unit displaying "Writing-Reading-Erasing-Reading" functions can be integrated.

Synthesis and DNA binding properties of 1-(3-aminopropyl)-imidazole-containing triamide f-Im*PyIm: a novel diamino polyamide designed to target 5'-ACGCGT-3'.

PubMed

Satam, Vijay; Babu, Balaji; Porte, Alexander; Savagian, Mia; Lee, Megan; Smeltzer, Thomas; Liu, Yang; Ramos, Joseph; Wilson, W David; Lin, Shicai; Kiakos, Kostantinos; Hartley, John A; Lee, Moses

2012-09-15

A novel diamino/dicationic polyamide f-Im(*)PyIm (5) that contains an orthogonally positioned aminopropyl chain on an imidazole (Im(*)) moiety was designed to target 5'-ACGCGT-3'. The DNA binding properties of the diamino polyamide 5, determined by CD, ΔT(M), DNase I footprinting, SPR, and ITC studies, were compared with those of its monoamino/monocationic counterpart f-ImPyIm (1) and its diamino/dicationic isomer f-ImPy(*)Im (2), which has the aminopropyl group attached to the central pyrrole unit (Py(*)). The results gave evidence for the minor groove binding and selectivity of polyamide 5 for the cognate sequence 5'-ACGCGT-3', and with strong affinity (K(eq)=2.3×10(7) M(-1)). However, the binding affinities varied according to the order: f-ImPy(*)Im (2)>f-ImPyIm (1)≥f-Im(*)PyIm (5) confirming that the second amino group can improve affinity, but its position within the polyamide can affect affinity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Changes in biogeochemistry of pyrogenic carbon in soil after one year

NASA Astrophysics Data System (ADS)

Singh, N.; Abiven, S.; Maestrini, B.; Bird, J. A.; Eoin, E. L.; Torn, M. S.; Schmidt, M. W. I.

2012-04-01

Pyrogenic carbon (PyC), incomplete combustion product of biomass and fossil fuel, is ubiquitous in the environment and widely assumed to remain stable in soil (1). The stability of PyC has been challenged by a series of recent laboratory and field experiments (2-4), which show that it is mineralized slowly to CO2 in soil. We are carrying out a long-term PyC degradation study within an experimental field setup located at Laegeren forest (Wettingen, Switzerland). We have installed cylindrical mesocosms (20 cm long and 10 cm diameter) in a randomized block design with 3 plots, 3 treatments (wood, PyC, and control) and 2 levels of nitrogen (N) input (+N = +60 kg ha-1 y-1 and -N = ambient N deposition). Wood (Pinus ponderosa) and PyC were highly labelled (13C 800‰ and 15N 4.2 atom%) and were added at a rate of 1.5 g-C kg-1 soil and 2.8 g-C kg-1 soil, respectively. We observed that PyC decomposed at a rate of 0.64 % year-1. We extracted the mesocosms after ca. 10 months in situ and sampled soil at different column depths (0-5, 5-10, 10-15 cm). We carried out δ13C and δ15N analysis to estimate the total recovery of the added substrate and its transport within the soil profile inside the mesocosms. The benzenepolycarboxylic acid (BPCA) molecular marker method was employed to quantify and characterize the PyC before and after its addition into the soil. Density fractionation was applied to identify organo-mineral interactions and understand the dynamics of PyC degradation in soil. We analysed soil sub-samples for microbial biomass using fumigation -extraction. We further study the effect of PyC on soil enzyme to determine if PyC could modify soil biological properties. We observed that after 10 months in the soil, 1) the quality of PyC, estimated by relative contribution of individual BPCA molecular markers, remained unchanged; 2) PyC showed negligible vertical movement within the soil profile; 3) most PyC was in free and occluded particulate fractions (22% PyC in occluded fraction); 4) Enzyme activity increased significantly (p <0.05) with increased nitrogen input and showed no significant difference in activity due to different substrate. We conclude that some degree of physical stabilization, for example in aggregates, might occur in the initial stages of PyC decomposition.

Critical appraisal of paclitaxel balloon angioplasty for femoral–popliteal arterial disease

PubMed Central

Herten, Monika; Torsello, Giovanni B; Schönefeld, Eva; Stahlhoff, Stefan

2016-01-01

Peripheral arterial disease, particularly critical limb ischemia, is an area with urgent need for optimized therapies because, to date, vascular interventions often have limited life spans. In spite of initial encouraging technical success after femoropopliteal percutaneous transluminal angioplasty or stenting, postprocedural restenosis remains the major problem. The challenging idea behind the drug-coated balloon (DCB) concept is the biological modification of the injury response after balloon dilatation. Antiproliferative drugs administered via DCBs or drug-eluting stents are able to suppress neointimal hyperplasia, the main cause of restenosis. This article reviews the results of DCB treatments of femoropopliteal and infrapopliteal lesions in comparison to standard angioplasty with uncoated balloons. A systematic literature search was performed in 1) medical journals (ie, MEDLINE), 2) international registers for clinical studies (ie, www.clinicaltrials.gov), and 3) abstracts of scientific sessions. Several controlled randomized trials with follow-up periods of up to 5 years demonstrated the efficacy of paclitaxel –DCB technology. However, calcified lesions seem to affect the efficacy of DCB. Combinations of preconditioning methods with DCBs showed promising results. Although the mechanical abrasion of calcium via atherectomy or laser ablation showed favorable periprocedural results, the long-term impact on restenosis and clinical outcome has to be demonstrated. Major advantages of the DCBs are the rapid delivery of drug at uniform concentrations with a single dose, their efficacy in areas wherein stents have been contraindicated until now (ie, bifurcation, ostial lesions), and in leaving no stent scaffold behind. Reinterventions are easier to perform because DCBs leave no metal behind. Various combinations of DCBs with other treatment modalities may prove to be viable options in future. The follow-up results of clinical studies will evaluate the long-term impact of DCBs. PMID:27621646

Class III peroxidases in cellulose deficient cultured maize cells during cell wall remodelling.

PubMed

Martínez-Rubio, Romina; Acebes, José Luis; Encina, Antonio; Kärkönen, Anna

2018-02-21

Maize (Zea mays L.) suspension-cultured cells habituated to a cellulose biosynthesis inhibitor 2,6-dichlorobenzonitrile (DCB) have a modified cell wall, in which the reduction in the cellulose content is compensated by a network of highly cross-linked feruloylated arabinoxylans and the deposition of lignin-like polymers. For both arabinoxylan cross-linking and lignin polymerization, class III peroxidases (POXs) have been demonstrated to have a prominent role. For the first time, a comparative study of POX activity and isoforms in control and cellulose-impaired cells has been addressed, also taking into account their cellular distribution in different compartments. Proteins from the spent medium (SM), soluble cellular (SC), ionically (ICW) and covalently bound cell wall protein fractions were assayed for total and specific peroxidase activity by using coniferyl and sinapyl alcohol and ferulic acid as substrates. The isoPOX profile was obtained by isoelectric focusing. POX activity was higher in DCB-habituated than in non-habituated cells in all protein fractions at all cell culture stages. For all substrates assayed, SC and ICW fractions showed higher activity at the early-log growth phase than at the late-log phase. However, the highest POX activity in the spent medium was found at the late-log phase. According to the isoPOX profiles, the highest diversity of isoPOXs was detected in the ICW and SM protein fractions. The latter fraction contained isoPOXs with higher activity in DCB-habituated cells. Some of the isoPOXs detected could be involved in cross-linking of arabinoxylans and in the lignin-like polymer formation in DCB-habituated cells. This article is protected by copyright. All rights reserved.

Critical appraisal of paclitaxel balloon angioplasty for femoral-popliteal arterial disease.

PubMed

Herten, Monika; Torsello, Giovanni B; Schönefeld, Eva; Stahlhoff, Stefan

2016-01-01

Peripheral arterial disease, particularly critical limb ischemia, is an area with urgent need for optimized therapies because, to date, vascular interventions often have limited life spans. In spite of initial encouraging technical success after femoropopliteal percutaneous transluminal angioplasty or stenting, postprocedural restenosis remains the major problem. The challenging idea behind the drug-coated balloon (DCB) concept is the biological modification of the injury response after balloon dilatation. Antiproliferative drugs administered via DCBs or drug-eluting stents are able to suppress neointimal hyperplasia, the main cause of restenosis. This article reviews the results of DCB treatments of femoropopliteal and infrapopliteal lesions in comparison to standard angioplasty with uncoated balloons. A systematic literature search was performed in 1) medical journals (ie, MEDLINE), 2) international registers for clinical studies (ie, www.clinicaltrials.gov), and 3) abstracts of scientific sessions. Several controlled randomized trials with follow-up periods of up to 5 years demonstrated the efficacy of paclitaxel -DCB technology. However, calcified lesions seem to affect the efficacy of DCB. Combinations of preconditioning methods with DCBs showed promising results. Although the mechanical abrasion of calcium via atherectomy or laser ablation showed favorable periprocedural results, the long-term impact on restenosis and clinical outcome has to be demonstrated. Major advantages of the DCBs are the rapid delivery of drug at uniform concentrations with a single dose, their efficacy in areas wherein stents have been contraindicated until now (ie, bifurcation, ostial lesions), and in leaving no stent scaffold behind. Reinterventions are easier to perform because DCBs leave no metal behind. Various combinations of DCBs with other treatment modalities may prove to be viable options in future. The follow-up results of clinical studies will evaluate the long-term impact of DCBs.

Capping Layer (CL) Induced Antidamping in CL/Py/β-W System (CL: Al, β-Ta, Cu, β-W).

PubMed

Behera, Nilamani; Guha, Puspendu; Pandya, Dinesh K; Chaudhary, Sujeet

2017-09-13

For achieving ultrafast switching speed and minimizing dissipation losses, the spin-based data storage device requires a control on effective damping (α eff ) of nanomagnetic bits. Incorporation of interfacial antidamping spin orbit torque (SOT) in spintronic devices therefore has high prospects for enhancing their performance efficiency. Clear evidence of such an interfacial antidamping is found in Al capped Py(15 nm)/β-W(t W )/Si (Py = Ni 81 Fe 19 and t W = thickness of β-W), which is in contrast to the increase of α eff (i.e., damping) usually associated with spin pumping as seen in Py(15 nm)/β-W(t W )/Si system. Because of spin pumping, the interfacial spin mixing conductance (g ↑↓ ) at Py/β-W interface and spin diffusion length (λ SD ) of β-W are found to be 1.63(±0.02) × 10 18 m -2 (1.44(±0.02) × 10 18 m -2 ) and 1.42(±0.19) nm (1.00(±0.10) nm) for Py(15 nm)/β-W(t W )/Si (β-W(t W )/Py(15 nm)/Si) bilayer systems. Other different nonmagnetic capping layers (CL), namely, β-W(2 nm), Cu(2 nm), and β-Ta(2,3,4 nm) were also grown over the same Py(15 nm)/β-W(t W ). However, antidamping is seen only in β-Ta(2,3 nm)/Py(15 nm)/β-W(t W )/Si. This decrease in α eff is attributed to the interfacial Rashba like SOT generated by nonequilibrium spin accumulation subsequent to the spin pumping. Contrary to this, when interlayer positions of Py(15 nm) and β-W(t W ) is interchanged irrespective of the fixed top nonmagnetic layer, an increase of α eff is observed, which is ascribed to spin pumping from Py to β-W layer.

4-Pyridone-3-carboxamide-1-β-D-ribonucleoside triphosphate (4PyTP), a novel NAD metabolite accumulating in erythrocytes of uremic children: a biomarker for a toxic NAD analogue in other tissues?

PubMed

Synesiou, Elena; Fairbanks, Lynnette D; Simmonds, H Anne; Slominska, Ewa M; Smolenski, Ryszard T; Carrey, Elizabeth A

2011-06-01

We have identified a novel nucleotide, 4-pyridone 3/5-carboxamide ribonucleoside triphosphate (4PyTP), which accumulates in human erythrocytes during renal failure. Using plasma and erythrocyte extracts obtained from children with chronic renal failure we show that the concentration of 4PyTP is increased, as well as other soluble NAD(+) metabolites (nicotinamide, N(1)-methylnicotinamide and 4Py-riboside) and the major nicotinamide metabolite N(1)-methyl-2-pyridone-5-carboxamide (2PY), with increasing degrees of renal failure. We noted that 2PY concentration was highest in the plasma of haemodialysis patients, while 4PyTP was highest in erythrocytes of children undergoing peritoneal dialysis: its concentration correlated closely with 4Py-riboside, an authentic precursor of 4PyTP, in the plasma. In the dialysis patients, GTP concentration was elevated: similar accumulation was noted previously, as a paradoxical effect in erythrocytes during treatment with immunosuppressants such as ribavirin and mycophenolate mofetil, which deplete GTP through inhibition of IMP dehydrogenase in nucleated cells such as lymphocytes. We predict that 4Py-riboside and 4Py-nucleotides bind to this enzyme and alter its activity. The enzymes that regenerate NAD(+) from nicotinamide riboside also convert the drugs tiazofurin and benzamide riboside into NAD(+) analogues that inhibit IMP dehydrogenase more effectively than the related ribosides: we therefore propose that the accumulation of 4PyTP in erythrocytes during renal failure is a marker for the accumulation of a related toxic NAD(+) analogue that inhibits IMP dehydrogenase in other cells.

Fire severity alters the distribution of pyrogenic carbon stocks across ecosystem pools in a Californian mixed-conifer forest

NASA Astrophysics Data System (ADS)

Maestrini, Bernardo; Alvey, Erin C.; Hurteau, Matthew D.; Safford, Hugh; Miesel, Jessica R.

2017-09-01

Pyrogenic carbon (PyC) is hypothesized to play an important role in the carbon (C) cycle due to its resistance to decomposition; however, much uncertainty still exists regarding the stocks of PyC that persist on-site after the initial erosion in postfire forests. Therefore, understanding how fire characteristics influence PyC stocks is vital, particularly in the context of California forests for which an increase of high-severity fires is predicted over the next decades. We measured forest C and persistent PyC stocks in areas burned by low-to-moderate and high-severity fire, as well as in adjacent unburned areas in a California mixed-conifer forest, 2 to 3 years after wildfire. We measured C and PyC stocks in the following compartments: standing trees, downed wood, forest floor, and mineral soil (0-5 cm), and we identified PyC using the weak nitric acid digestion method. We found that the total stock of PyC did not differ among fire severity classes (overall mean 248 ± 30 g C m-2); however, fire severity influenced the distribution of PyC in the individual compartments. Areas burned by high-severity fire had 2.5 times more PyC stocked in the coarse woody debris (p < 0.05), 3.3 times more PyC stocked in standing trees (p < 0.05), and a lower PyC stock in the forest floor (-22%, p < 0.05) compared to low-to-moderate fire severity areas. These results have important implications for the permanence time of PyC, which is putatively higher in standing trees and coarse woody debris compared to the forest floor, where it is susceptible to rapid losses through erosion.

A new SOD mimic, Mn(III) ortho N-butoxyethylpyridylporphyrin combines superb potency and lipophilicity with low toxicity

PubMed Central

Rajic, Zrinka; Tovmasyan, Artak; Spasojevic, Ivan; Sheng, Huaxin; Lu, Miaomiao; Li, Alice M.; Gralla, Edith B.; Warner, David S.; Benov, Ludmil; Batinic-Haberle, Ines

2012-01-01

The Mn porphyrins of kcat(O2˙−) as high as that of a superoxide dismutase enzyme, and of optimized lipophilicity have already been synthesized. Their exceptional in vivo potency is at least in part due to their ability to mimic site and location of mitochondrial superoxide dismutase, MnSOD. MnTnHex-2-PyP5+ is the most studied among lipophilic Mn porphyrins. It is of remarkable efficacy in animal models of oxidative stress injuries and particularly in central nervous system diseases. However, when used at high single and multiple doses it becomes toxic. The toxicity of MnTnHex-2-PyP5+ has been in part attributed to its micellar properties, i.e. the presence of polar cationic nitrogens and hydrophobic alkyl chains. The replacement of a CH2 group by oxygen atom in each of the four alkyl chains was meant to disrupt the porphyrin micellar character. When such modification occurs at the end of long alkyl chains, the oxygens become heavily solvated, which leads to a significant drop in the lipophilicity of porphyrin. However, when the oxygen atoms are buried deeper within the long heptyl chains, their excessive solvation is precluded and the lipophilicity preserved. The presence of oxygens and the high lipophilicity bestow the exceptional chemical and physical properties to Mn(III) meso-tetrakis(N-n-butoxyethylpyridinium-2-yl)porphyrin, MnTnBuOE-2-PyP5+. The high SOD-like activity is fully preserved and somewhat enhanced: log kcat(O2˙−) = 7.83 vs 7.48 and 7.65 for MnTnHex-2-PyP5+ and MnTnHep-2-PyP5+, respectively. MnTnBuOE-2-PyP5+ was tested in an O2˙− - specific in vivo assay – aerobic growth of SOD-deficient yeast, Saccharomyces cerevisiae, where it was fully protective in the range of 5 – 30 µM. MnTnHep-2-PyP5+ was already toxic at 5 µM, and MnTnHex-2-PyP5+ became toxic at 30 µM. In a mouse toxicity study, MnTnBuOE-2-PyP5+ was several-fold less toxic than either MnTnHex-2-PyP5+ or MnTnHep-2-PyP5+. PMID:22336516

Effectiveness of Sunscreen at Preventing Solar UV-Induced Alterations of Human Stratum Corneum

NASA Astrophysics Data System (ADS)

Martinez, O.; Dauskardt, R.; Biniek, K.; Novoa, F.

2012-12-01

The outermost layer of the epidermis, the stratum corneum, protects the body from harmful environmental conditions by serving as a selective barrier. Solar ultraviolet (UV) radiation is one of the most common conditions the body encounters and is responsible for many negative skin responses, including compromised barrier function. UV exposure has dramatic effects on stratum corneum cell cohesion and mechanical integrity that are related to its effects on the stratum corneum's intercellular lipids. Hypothesis Sunscreen contains chemicals that absorb UV radiation to prevent the radiation from penetrating the skin. Thus, it is expected that the application of sunscreen on human stratum corneum will reduce UV-induced alterations of human stratum corneum. Procedures/Equipment Human tissue was processed in order to isolate the stratum corneum, the top layer of the epidermis. Double cantilever beam (DCB) testing was used to study the effect of UV radiation on human stratum corneum. Two different types of DCB samples were created: control DCB samples with the application of carrier and UV light to the stratum corneum and DCB samples with the application of sunscreen and UV light to the stratum corneum. For the control sample, one side of the stratum corneum was glued to a polycarbonate beam and carrier was applied. Then, the sample was placed 10 cm away from the UV lamp inside of the environmental chamber and were exposed to UV dosages of about 800 J/cm2. Once this step was complete, a second polycarbonate beam was glued to the other side of the stratum corneum. The steps were similar for the DCB sample that had sunscreen applied and that was exposed to UV light. After gluing one side of the stratum corneum to a polycarbonate beam, Octinoxate sunscreen was applied. The next steps were similar to those of the control sample. All DCB samples were then let out to dry for two hours in a dry box in order for the moisture from the lab to be extracted. Each DCB sample was tested with a Delaminator test system (DTS Company). The Delaminator was used to measure the force required to break the bonds between the Stratum Corneum lipid layers. Delamination energies, Gc, were presented as mean values ± 1.96 x the standard error of the mean (STDEM) in which the mean values reported are expected to fall within these bounds with 95% confidence. Results The samples for the UV exposed carrier and Octinoxate samples were tested. Various samples were used to compare the average delamination energy in order to fulfill the 95% confidence level. The delamination energy was lower for the carrier samples than for the Octinoxate samples. The average Gc value for the carrier samples was 5, and the average Gc value for the Octinoxate samples was 7. Conclusion In response to the averaging lower Gc value for the carrier, it is evident that sunscreen does protect the stratum corneum's mechanical properties. It took higher delamination energy to break apart the lipids in the sunscreen sample than it did for the carrier sample. Therefore, the sunscreen helps the stratum corneum contain its intercellular cohesion.

Designed topology and site-selective metal composition in tetranuclear [MM'...M'M] linear complexes.

PubMed

Barrios, Leoní A; Aguilà, David; Roubeau, Olivier; Gamez, Patrick; Ribas-Ariño, Jordi; Teat, Simon J; Aromí, Guillem

2009-10-26

The ligand 1,3-bis[3-oxo-3-(2-hydroxyphenyl)propionyl]benzene (H(4)L), designed to align transition metals into tetranuclear linear molecules, reacts with M(II) salts (M=Ni, Co, Cu) to yield complexes with the expected [MMMM] topology. The novel complexes [Co(4)L(2)(py)(6)] (2; py=pyridine) and [Na(py)(2)][Cu(4)L(2)(py)(4)](ClO(4)) (3) have been crystallographically characterised. The metal sites in complexes 2 and 3, together with previously characterised [Ni(4)L(2)(py)(6)] (1), favour different coordination geometries. These have been exploited for the deliberate synthesis of the heterometallic complex [Cu(2)Ni(2)L(2)(py)(6)] (4). Complexes 1, 2, 3 and 4 exhibit antiferromagnetic interactions between pairs of metals within each cluster, leading to S=0 spin ground states, except for the latter cluster, which features two quasi-independent S=1/2 moieties within the molecule. Complex 4 gathers the structural and physical conditions, thus allowing it to be considered as prototype of a two-qbit quantum gate.

Solvothermal synthesis of stable nanoporous polymeric bases-crystalline TiO2 nanocomposites: visible light active and efficient photocatalysts for water treatment

NASA Astrophysics Data System (ADS)

Liu, Fujian; Kong, Weiping; Wang, Liang; Noshadi, Iman; Zhang, Zhonghua; Qi, Chenze

2015-02-01

Visible light active and stable nanoporous polymeric base-crystalline TiO2 nanocomposites were solvothermally synthesized from in situ copolymerization of divinylbenzene (DVB) with 1-vinylimidazolate (VI) or 4-vinylpyridine (Py) in the presence of tetrabutyl titanate without the use of any other additives (PDVB-VI-TiO2-x, PDVB-Py-TiO2-x, where x stands for the molar ratio of TiO2 to VI or Py), which showed excellent activity with respect to catalyzing the degradation of organic pollutants of p-nitrophenol (PNP) and rhodamine-B (RhB). TEM and SEM images show that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x have abundant nanopores, and TiO2 nanocrystals with a high degree of crystallinity were homogeneously embedded in the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x, forming a stable ‘brick-and-mortar’ nanostructure. PDVB-VI and PDVB-Py supports act as the glue linking TiO2 nanocrystals to form nanopores and constraining the agglomeration of TiO2 nanocrystals. XPS spectra show evidence of unique interactions between TiO2 and basic sites in these samples. UV diffuse reflectance shows that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x exhibit a unique response to visible light. Catalytic tests show that the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were active in catalyzing the degradation of PNP and RhB organic pollutants under visible light irradiation. The enhanced activities of the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were ascribed to synergistic effects between abundant nanopores and the unique optical adsorption of visible light in the samples.

Solvothermal synthesis of stable nanoporous polymeric bases-crystalline TiO2 nanocomposites: visible light active and efficient photocatalysts for water treatment.

PubMed

Liu, Fujian; Kong, Weiping; Wang, Liang; Noshadi, Iman; Zhang, Zhonghua; Qi, Chenze

2015-02-27

Visible light active and stable nanoporous polymeric base-crystalline TiO2 nanocomposites were solvothermally synthesized from in situ copolymerization of divinylbenzene (DVB) with 1-vinylimidazolate (VI) or 4-vinylpyridine (Py) in the presence of tetrabutyl titanate without the use of any other additives (PDVB-VI-TiO2-x, PDVB-Py-TiO2-x, where x stands for the molar ratio of TiO2 to VI or Py), which showed excellent activity with respect to catalyzing the degradation of organic pollutants of p-nitrophenol (PNP) and rhodamine-B (RhB). TEM and SEM images show that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x have abundant nanopores, and TiO2 nanocrystals with a high degree of crystallinity were homogeneously embedded in the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x, forming a stable 'brick-and-mortar' nanostructure. PDVB-VI and PDVB-Py supports act as the glue linking TiO2 nanocrystals to form nanopores and constraining the agglomeration of TiO2 nanocrystals. XPS spectra show evidence of unique interactions between TiO2 and basic sites in these samples. UV diffuse reflectance shows that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x exhibit a unique response to visible light. Catalytic tests show that the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were active in catalyzing the degradation of PNP and RhB organic pollutants under visible light irradiation. The enhanced activities of the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were ascribed to synergistic effects between abundant nanopores and the unique optical adsorption of visible light in the samples.

76 FR 33367 - Employment and Training Administration Program Year (PY) 2011 Allotments for the Workforce...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-08

... PY 2010 PY 2011 Difference % Diff Total ....... $52,230,420 $52,125,959 ($104,461) -0.2% AL Inter... State Grantee Name Type PY 2010 PY 2011 Difference % Diff Total ....... $13,861,035 $12,388,708 ($1,472,327) -10.60% AL Inter-Tribal Council of Alabama. ....... $5,098.00 $4,556.00 ($542) -10.60% AK...

Comparison of 3D-Printed Poly-ɛ-Caprolactone Scaffolds Functionalized with Tricalcium Phosphate, Hydroxyapatite, Bio-Oss, or Decellularized Bone Matrix^.

PubMed

Nyberg, Ethan; Rindone, Alexandra; Dorafshar, Amir; Grayson, Warren L

2017-06-01

Three-dimensional (3D)-printing facilitates rapid, custom manufacturing of bone scaffolds with a wide range of material choices. Recent studies have demonstrated the potential for 3D-printing bioactive (i.e., osteo-inductive) scaffolds for use in bone regeneration applications. In this study, we 3D-printed porous poly-ɛ-caprolactone (PCL) scaffolds using a fused deposition modeling (FDM) process and functionalized them with mineral additives that have been widely used commercially and clinically: tricalcium phosphate (TCP), hydroxyapatite (HA), Bio-Oss (BO), or decellularized bone matrix (DCB). We assessed the "print quality" of the composite scaffolds and found that the print quality of PCL-TCP, PCL-BO, and PCL-DCB measured ∼0.7 and was statistically lower than PCL and PCL-HA scaffolds (∼0.8). We found that the incorporation of mineral particles did not significantly decrease the compressive modulus of the graft, which was on the order of 260 MPa for solid blocks and ranged from 32 to 83 MPa for porous scaffolds. Raman spectroscopy revealed the surfaces of the scaffolds maintained the chemical profile of their dopants following the printing process. We evaluated the osteo-inductive properties of each scaffold composite by culturing adipose-derived stromal/stem cells in vitro and assessing their differentiation into osteoblasts. The calcium content (normalized to DNA) increased significantly in PCL-TCP (p < 0.05), PCL-BO (p < 0.001), and PCL-DCB (p < 0.0001) groups relative to PCL only. The calcium content also increased in PCL-HA but was not statistically significant (p > 0.05). Collagen 1 expression was 10-fold greater than PCL in PCL-BO and PCL-DCB (p < 0.05) and osteocalcin expression was 10-fold greater in PCL-BO and PCL-DCB (p < 0.05) as measured by quantitative-real time-polymerase chain reaction. This study suggests that PCL-BO and PCL-DCB hybrid material may be advantageous for bone healing applications over PCL-HA or PCL-TCP blends.

Photochemistry of fac-[Re(CO)3(dcbH2)( trans-stpy)]+: New Insights on the Isomerization Mechanism of Coordinated Stilbene-like Ligands.

PubMed

Faustino, Leandro A; Hora Machado, Antonio Eduardo; Patrocinio, Antonio Otavio T

2018-03-05

In this work, a novel complex fac-[Re(CO) 3 (dcbH 2 )( trans-stpy)] + , (dcbH 2 = 4,4'-dicarboxylic acid-2,2'-bipyridine; trans-stpy = trans-4-styrylpyridine) was synthesized and characterized toward its spectroscopic, photochemical, and photophysical properties. The experimental data provide new insights on the mechanism of photochemical trans-to- cis isomerization of the stilbene-like ligand coordinated to Re(I) polypyridyl complexes. The new complex exhibits an unusual and strong dependence of the isomerization quantum yield (Φ t →c ) on the irradiation wavelength. Φ t →c was 0.81 ± 0.08 for irradiation at 365 nm and continuously decreased as the irradiation wavelength is shifted to the visible. At 405 nm irradiation Φ t →c is almost 2 orders of magnitude lower (0.010 ± 0.005) than that observed at 365 nm excitation. This behavior can be explained by the low-lying triplet metal-to-ligand charge-transfer excited state ( 3 MLCT) that hinders the triplet photoreaction mechanism under visible light absorption. Under UV irradiation, direct population of styrylpyridine-centered excited state ( 1 IL) leads to the occurrence of the photoisomerization via a singlet mechanism. Further experiments were performed with the complex immobilized on the surface of TiO 2 and Al 2 O 3 films. The nonoccurrence of isomerization at the oxide surfaces even under UV excitation evidences the role of energy gap between the 1 IL/ 1 MLCT states on the photochemical/photophysical processes. The results establish important relationships between the molecular structure and the photoelectrochemical behavior, which can further contribute to the development of solid-state molecular switches based on Re(I) polypyridyl complexes.

In vitro effects of polychlorinated biphenyls on human platelets.

PubMed Central

Raulf, M; König, W

1991-01-01

Incubation of human platelets with polychlorinated biphenyls (PCB) induced and modulated cellular responses to a different degree. 3,3',4,4'-tetrachlorobiphenyl (TCB) was a more potent inducer of platelet aggregation, serotonin release and 12-HETE generation compared to the other PCB [2,2',3,3'-TCB,3,3'-dichlorobiphenyl (DCB),2,2',4,5,5'-pentachlorobiphenyl (PCB)]. 3,3',4,4'-TCB showed synergistic effects, in combination with other PCB, such as an enhanced formation of 12-HETE, when 3,3'-DCB and 2,2',3,3'-TCB were applied simultaneously. The combined incubation of platelets with PCB and sodium fluoride (NaF), an activator of G-proteins, resulted in synergistic 12-HETE generation compared to stimulation with NaF or PCB alone. Furthermore, when platelets were incubated with the PCB the enzymatic steps controlling the metabolism of the platelet-activating factor (PAF) were modulated. A direct relationship between the extent of platelet activation and the chloro-substitution pattern of PCB exists. PMID:1901832

Ferrocenes as potential chemotherapeutic drugs: Synthesis, cytotoxic activity, reactive oxygen species production and micronucleus assay

PubMed Central

Pérez, Wanda I.; Soto, Yarelys; Ortíz, Carmen; Matta, Jaime; Meléndez, Enrique

2014-01-01

Three new ferrocene complexes were synthesized with 4-(1H-pyrrol-1-yl)phenol group appended to one of the Cp ring. These are: 1,1′-4-(1H-pyrrol-1-yl)phenyl ferrocenedicarboxylate, (“Fc-(CO2-Ph-4-Py)2”), 1,4-(1H-pyrrol-1-yl)phenyl, 1′-carboxyl ferrocenecarboxylate (“Fc-(CO2-Ph-4-Py)CO2H”) and 4-(1H-pyrrol-1-yl)phenyl ferroceneacetylate (“Fc-CH2CO2-Ph-4-Py”). The new species were characterized by standard analytical methods. Cyclic voltammetry experiments showed that Fc-CH2CO2-Ph-4-Py has redox potential very similar to the Fc/Fc+ redox couple whereas Fc-(CO2-Ph-4-Py)2 and Fc-(CO2-Ph-4-Py)CO2H have redox potentials of over 400 mV higher than Fc/Fc+ redox couple. The in vitro studies on Fc-(CO2-Ph-4-Py)2 and Fc-(CO2-Ph-4-Py)CO2H revealed that these two compounds have moderate anti-proliferative activity on MCF-7 breast cancer cell line. In contrast Fc-CH2CO2-Ph-4-Py which displayed low anti-proliferative activity. In the HT-29 colon cancer cell line, the new species showed low anti-proliferaive activity. Cytokinesis-block micronucleus assay (CBMN) was performed on these ferrocenes and it was determined they induce micronucleus formation on binucleated cells and moderate genotoxic effects on the MCF-7 breast cancer cell line. There is a correlation between the IC50 values of the ferrocenes and the amount of micronucleus formation activity on binucleated cells and the reactive oxygen species (ROS) production on MCF-7 cell line. PMID:25555734

Dynamics of microbial community composition and soil organic carbon mineralization in soil following addition of pyrogenic and fresh organic matter.

PubMed

Whitman, Thea; Pepe-Ranney, Charles; Enders, Akio; Koechli, Chantal; Campbell, Ashley; Buckley, Daniel H; Lehmann, Johannes

2016-12-01

Pyrogenic organic matter (PyOM) additions to soils can have large impacts on soil organic carbon (SOC) cycling. As the soil microbial community drives SOC fluxes, understanding how PyOM additions affect soil microbes is essential to understanding how PyOM affects SOC. We studied SOC dynamics and surveyed soil bacterial communities after OM additions in a field experiment. We produced and mixed in either 350 °C corn stover PyOM or an equivalent initial amount of dried corn stover to a Typic Fragiudept soil. Stover increased SOC-derived and total CO 2 fluxes (up to 6x), and caused rapid and persistent changes in bacterial community composition over 82 days. In contrast, PyOM only temporarily increased total soil CO 2 fluxes (up to 2x) and caused fewer changes in bacterial community composition. Of the operational taxonomic units (OTUs) that increased in response to PyOM additions, 70% also responded to stover additions. These OTUs likely thrive on easily mineralizable carbon (C) that is found both in stover and, to a lesser extent, in PyOM. In contrast, we also identified unique PyOM responders, which may respond to substrates such as polyaromatic C. In particular, members of Gemmatimonadetes tended to increase in relative abundance in response to PyOM but not to fresh organic matter. We identify taxa to target for future investigations of the mechanistic underpinnings of ecological phenomena associated with PyOM additions to soil.

Twistacene contained molecule for optical nonlinearity: Excited-state based negative refraction and optical limiting

NASA Astrophysics Data System (ADS)

Wu, Xingzhi; Xiao, Jinchong; Sun, Ru; Jia, Jidong; Yang, Junyi; Ao, Guanghong; Shi, Guang; Wang, Yuxiao; Zhang, Xueru; Song, Yinglin

2018-06-01

Spindle-type molecules containing twisted acenes (PyBTA-1 &PyBTA-2) are designed, synthesized characterized. Picosecond Z-scan experiments under 532 nm show reverse saturable absorption and negative nonlinear refraction, indicating large third-order optical nonlinearity in PyBTA-1. The mechanism of the optical nonlinearity is investigated and the results show that the nonlinear absorption and refraction in PyBTA-1 originates from a charge transfer (CT) state. Furthermore, relatively long lifetime and absorptive cross section of the CT state are measured. Based on the excited state absorption in PyBTA-1, strong optical limiting with ∼0.3 J/cm2 thresholds are obtained when excited by picoseconds and nanoseconds pulses. The findings on nonlinear optics suggest PyBTA-1 a promising material of all optical modulation and laser protection, which enrich the potential applications of these spindle-type molecules. Comparing to the previously reported spindle-type molecules with analogous structures, the introduction of ICT in PyBTA-1 &PyBTA-2 dramatically decreases the two-photon absorption while enhances the nonlinear refraction. The results could be used to selectively tailor the optical nonlinearity in such kind of compounds.

Pyrogenic carbon from tropical savanna burning: production and stable isotope composition

NASA Astrophysics Data System (ADS)

Saiz, G.; Wynn, J. G.; Wurster, C. M.; Goodrick, I.; Nelson, P. N.; Bird, M. I.

2015-03-01

Widespread burning of mixed tree-grass ecosystems represents the major natural locus of pyrogenic carbon (PyC) production. PyC is a significant, pervasive and yet poorly understood "slow-cycling" form of carbon present in the atmosphere, hydrosphere, soils and sediments. We conducted 16 experimental burns on a rainfall transect through northern Australian savannas with C4 grasses ranging from 35 to 99% of total biomass. Residues from each fire were partitioned into PyC and further into recalcitrant (HyPyC) components, with each of these fluxes also partitioned into proximal components (>125 μm), likely to remain close to the site of burning, and distal components (<125 μm), likely to be transported from the site of burning. The median (range) PyC production across all burns was 16.0 (11.5) % of total carbon exposed (TCE), with HyPyC accounting for 2.5 (4.9) % of TCE. Both PyC and HyPyC were dominantly partitioned into the proximal flux. Production of HyPyC was strongly related to fire residence time, with shorter duration fires resulting in higher HyPyC yields. The carbon isotope (δ13C) compositions of PyC and HyPyC were generally lower by 1-3‰ relative to the original biomass, with marked depletion up to 7‰ for grasslands dominated by C4 biomass. δ13C values of CO2 produced by combustion were computed by mass balance and ranged from ~0.4 to 1.3‰. The depletion of 13C in PyC and HyPyC relative to the original biomass has significant implications for the interpretation of δ13C values of savanna soil organic carbon and of ancient PyC preserved in the geologic record, as well as for global 13C isotopic disequilibria calculations.

Weathering of pyrogenic organic matter induces fungal oxidative enzyme response in single culture inoculation experiments.

PubMed

Gibson, Christy; Berry, Timothy D; Wang, Ruzhen; Spencer, Julie A; Johnston, Cliff T; Jiang, Yong; Bird, Jeffrey A; Filley, Timothy R

2016-02-01

The addition of pyrogenic organic matter (PyOM), the aromatic carbon-rich product of the incomplete combustion of plant biomass or fossil fuels, to soil can influence the rate of microbial metabolism of native soil carbon. The interaction of soil heterotrophs with PyOM may be governed by the surficial chemical and physical properties of PyOM that evolve with environmental exposure. We present results of a 36-day laboratory incubation investigating the interaction of a common white-rot fungus, Trametes versicolor, with three forms of 13 C-enriched (2.08 atom% 13 C) PyOM derived from Pinus ponderosa (450 °C): one freshly produced, and two artificially weathered (254 nm, UV light-water treatment and water-leaching alone). Analysis (FTIR, XPS) of the UV-weathered PyOM showed increased aliphatic C-H content and oxidation of aromatic carbon relative to both the original and water-leached PyOM. The addition of both weathered forms of PyOM stimulated (positively primed) fungal respiration of the growth media, while the unaltered PyOM mildly inhibited (negatively primed) respiration. Artificial weathering resulted in higher oxidative (laccase and peroxidase) enzyme activity than unaltered PyOM, possibly the result of a diminished capacity to bind reactive substrates and extracellular enzymes after weathering. However, and contrary to expectations, simple water-leached weathering resulted in a relatively higher enzyme activity and respiration than that of UV-weathering. The 13 C content of respired CO 2 indicated negligible fungal oxidation of PyOM for all treatments, demonstrating the overall low microbial reactivity of this high temperature PyOM. The increased enzymatic and positive priming response of T. versicolor to weathered PyOM highlights the importance of weathering-induced chemistry in controlling PyOM-microbe-soil carbon interactions.

Discovery of African bat polyomaviruses and infrequent recombination in the large T antigen in the Polyomaviridae.

PubMed

Carr, Michael; Gonzalez, Gabriel; Sasaki, Michihito; Ito, Kimihito; Ishii, Akihiro; Hang'ombe, Bernard M; Mweene, Aaron S; Orba, Yasuko; Sawa, Hirofumi

2017-04-01

Bat species represent natural reservoirs for a number of high-consequence human pathogens. The present study investigated the diversity of polyomaviruses (PyVs) in Zambian insectivorous and fruit bat species. We describe the complete genomes from four newly proposed African bat PyV species employing the recently recommended criteria provided by the Polyomaviridae Study Group of the International Committee on Taxonomy of Viruses. A comprehensive phylogenetic and recombination analysis was performed to determine genetic relationships and the distribution of recombination events in PyV from mammalian and avian species. The novel species of PyV from Zambian bats segregated with members of the genera Alphapolyomavirus and Betapolyomavirus, forming monophyletic clades with bat and non-human primate PyVs. Miniopterus schreibersii polyomavirus 1 and 2 segregated in a clade with South American bat PyV species, Old World monkey and chimpanzee PyVs and Human polyomavirus 13 (New Jersey PyV). Interestingly, the newly described Egyptian fruit bat PyV, tentatively named Rousettus aegyptiacus polyomavirus 1, had the highest nucleotide sequence identity to species of PyV from Indonesian fruit bats, and Rhinolophus hildebrandtii polyomavirus 1 was most closely related to New World monkey PyVs. The distribution of recombination events in PyV genomes was non-random: recombination boundaries existed in the intergene region between VP1 and LTAg and also at the 3' end of VP2/3 in the structural genes, whereas infrequent recombination was present within the LTAg gene. These findings indicate that recombination within the LTAg gene has been negatively selected against during polyomaviral evolution and support the recent proposal for taxonomic classification based on LTAg to define novel PyV species.

Towards a global assessment of pyrogenic carbon from vegetation fires.

PubMed

Santín, Cristina; Doerr, Stefan H; Kane, Evan S; Masiello, Caroline A; Ohlson, Mikael; de la Rosa, Jose Maria; Preston, Caroline M; Dittmar, Thorsten

2016-01-01

The production of pyrogenic carbon (PyC; a continuum of organic carbon (C) ranging from partially charred biomass and charcoal to soot) is a widely acknowledged C sink, with the latest estimates indicating that ~50% of the PyC produced by vegetation fires potentially sequesters C over centuries. Nevertheless, the quantitative importance of PyC in the global C balance remains contentious, and therefore, PyC is rarely considered in global C cycle and climate studies. Here we examine the robustness of existing evidence and identify the main research gaps in the production, fluxes and fate of PyC from vegetation fires. Much of the previous work on PyC production has focused on selected components of total PyC generated in vegetation fires, likely leading to underestimates. We suggest that global PyC production could be in the range of 116-385 Tg C yr(-1) , that is ~0.2-0.6% of the annual terrestrial net primary production. According to our estimations, atmospheric emissions of soot/black C might be a smaller fraction of total PyC (<2%) than previously reported. Research on the fate of PyC in the environment has mainly focused on its degradation pathways, and its accumulation and resilience either in situ (surface soils) or in ultimate sinks (marine sediments). Off-site transport, transformation and PyC storage in intermediate pools are often overlooked, which could explain the fate of a substantial fraction of the PyC mobilized annually. We propose new research directions addressing gaps in the global PyC cycle to fully understand the importance of the products of burning in global C cycle dynamics. © 2015 The Authors. Global Change Biology Published by John Wiley & Sons Ltd.

Radioprotection of the Brain White Matter by Mn(III) N-Butoxyethylpyridylporphyrin-Based Superoxide Dismutase Mimic MnTnBuOE-2-PyP5+

PubMed Central

Weitzel, Douglas H.; Tovmasyan, Artak; Ashcraft, Kathleen A.; Rajic, Zrinka; Weitner, Tin; Liu, Chunlei; Li, Wei; Buckley, Anne F.; Prasad, Mark R.; Young, Kenneth H.; Rodriguiz, Ramona M.; Wetsel, William C.; Peters, Katherine B.; Spasojevic, Ivan; Herndon, James E.; Batinic-Haberle, Ines; Dewhirst, Mark W.

2015-01-01

Cranial irradiation is a standard therapy for primary and metastatic brain tumors. A major drawback of radiotherapy (RT), however, is long-term cognitive loss that affects quality of life. Radiation-induced oxidative stress in normal brain tissue is thought to contribute to cognitive decline. We evaluated the effectiveness of a novel mimic of superoxide dismutase enzyme (SOD), MnTnBuOE-2-PyP5+ (Mn(III) meso-tetrakis(N-n-butoxyethylpyridinium-2-yl)porphyrin), to provide long-term neuroprotection following 8 Gy of whole brain irradiation. Long-term RT damage can only be assessed by brain imaging and neurocognitive studies. C57BL/6J mice were treated with MnTnBuOE-2-PyP5+ before and after RT and evaluated three months later. At this time point, drug concentration in the brain was 25 nmol/L. Mice treated with MnTnBuOE-2-PyP5+/RT exhibited MRI evidence for myelin preservation in the corpus callosum compared with saline/RT treatment. Corpus callosum histology demonstrated a significant loss of axons in the saline/RT group that was rescued in the MnTnBuOE-2-PyP5+/RT group. In addition, the saline/RT groups exhibited deficits in motor proficiency as assessed by the rotorod test and running wheel tests. These deficits were ameliorated in groups treated with MnTnBuOE-2-PyP5+/RT. Our data demonstrate that MnTnBuOE-2-PyP5+ is neuroprotective for oxidative stress damage caused by radiation exposure. In addition, glioblastoma cells were not protected by MnTnBuOE-2-PyP5+ combination with radiation in vitro. Likewise, the combination of MnTnBuOE-2-PyP5+ with radiation inhibited tumor growth more than RT alone in flank tumors. In summary, MnTnBuOE-2-PyP5+ has dual activity as a neuroprotector and a tumor radiosensitizer. Thus, it is an attractive candidate for adjuvant therapy with RT in future studies with patients with brain cancer. PMID:25319393

Comparison of GPS receiver DCB estimation methods using a GPS network

NASA Astrophysics Data System (ADS)

Choi, Byung-Kyu; Park, Jong-Uk; Min Roh, Kyoung; Lee, Sang-Jeong

2013-07-01

Two approaches for receiver differential code biases (DCB) estimation using the GPS data obtained from the Korean GPS network (KGN) in South Korea are suggested: the relative and single (absolute) methods. The relative method uses a GPS network, while the single method determines DCBs from a single station only. Their performance was assessed by comparing the receiver DCB values obtained from the relative method with those estimated by the single method. The daily averaged receiver DCBs obtained from the two different approaches showed good agreement for 7 days. The root mean square (RMS) value of those differences is 0.83 nanoseconds (ns). The standard deviation of the receiver DCBs estimated by the relative method was smaller than that of the single method. From these results, it is clear that the relative method can obtain more stable receiver DCBs compared with the single method over a short-term period. Additionally, the comparison between the receiver DCBs obtained by the Korea Astronomy and Space Science Institute (KASI) and those of the IGS Global Ionosphere Maps (GIM) showed a good agreement at 0.3 ns. As the accuracy of DCB values significantly affects the accuracy of ionospheric total electron content (TEC), more studies are needed to ensure the reliability and stability of the estimated receiver DCBs.

A Cu²⁺-selective fluorescent chemosensor based on BODIPY with two pyridine ligands and logic gate.

PubMed

Huang, Liuqian; Zhang, Jing; Yu, Xiaoxiu; Ma, Yifan; Huang, Tianjiao; Shen, Xi; Qiu, Huayu; He, Xingxing; Yin, Shouchun

2015-06-15

A novel near-infrared fluorescent chemosensor based on BODIPY (Py-1) has been synthesized and characterized. Py-1 displays high selectivity and sensitivity for sensing Cu(2+) over other metal ions in acetonitrile. Upon addition of Cu(2+) ions, the maximum absorption band of Py-1 in CH3CN displays a red shift from 603 to 608 nm, which results in a visual color change from pink to blue. When Py-1 is excited at 600 nm in the presence of Cu(2+), the fluorescent emission intensity of Py-1 at 617 nm is quenched over 86%. Notably, the complex of Py-1-Cu(2+) can be restored with the introduction of EDTA or S(2-). Consequently, an IMPLICATION logic gate at molecular level operating in fluorescence mode with Cu(2+) and S(2-) as chemical inputs can be constructed. Finally, based on the reversible and reproducible system, a nanoscale sequential memory unit displaying "Writing-Reading-Erasing-Reading" functions can be integrated. Copyright © 2015 Elsevier B.V. All rights reserved.

PyKE3: data analysis tools for NASA's Kepler, K2, and TESS missions

NASA Astrophysics Data System (ADS)

Hedges, Christina L.; Cardoso, Jose Vinicius De Miranda; Barentsen, Geert; Gully-Santiago, Michael A.; Cody, Ann Marie; Barclay, Thomas; Still, Martin; BAY AREA ENVIRONMENTAL RESEARCH IN

2018-01-01

The PyKE package is a set of easy to use tools for working with Kepler/K2 data. This includes tools to correct light curves for cotrending basis vectors, turn the raw Target Pixel File data into motion corrected light curves, check for exoplanet false positives and run new PSF photometry. We are now releasing PyKE 3, which is compatible with Python 3, is pip installable and no longer depends on PyRAF. Tools are available both as Python routines and from the command line. New tutorials are available and under construction for users to learn about Kepler and K2 data and how to best use it for their science goals. PyKE is open source and welcomes contributions from the community. Routines and more information are available on the PyKE repository on GitHub.

Asymmetric and symmetric triazenido cyclopalladated complexes: Synthesis, structural analysis and DFT calculations

NASA Astrophysics Data System (ADS)

Härter Vaniel, Ana Paula; Mauro, Antonio Eduardo; de Godoy Netto, Adelino Vieira; de Almeida, Eduardo Tonon; Piquini, Paulo Cesar; Zambiazi, Priscilla; Back, Davi Fernando; Hörner, Manfredo

2015-03-01

The reaction of [Pd{dmba}(μ-N3)]2 (dmba = N,N-dimethylbenzylamine) with 1-(2-fluorophenyl)-3-(4-nitrophenyl)triazenido (L1) or 1,3-bis(4-nitrophenyl)triazenido (L2) anions, in methanol, and subsequent treatment with pyridine (py) allows the preparation of the corresponding cyclopalladated compounds [Pd(dmba)(L1)(py)] (1) and [Pd(dmba)(L2)(py)]ṡpy (2). The acentric mononuclear entities of (1) and (2) are connected by weak intermolecular non-classical Csbnd H⋯C hydrogen bonds, which results in 2-D arrangements by translation, along the [1 0 0] and [0 0 1] crystallographic directions, respectively.

Towards a global assessment of pyrogenic carbon from vegetation fires

NASA Astrophysics Data System (ADS)

Dittmar, Thorsten; Santín, Cristina; Doerr, Stefan; Kane, Evan; Masiello, Caroline; Ohlson, Mikael; De La Rosa, Jose Maria; Preston, Caroline

2016-04-01

The production of pyrogenic carbon (PyC; a continuum of organic carbon (C) ranging from partially charred biomass and charcoal to soot) is a widely acknowledged C sink, with the latest estimates indicating that ~50% of the PyC produced by vegetation fires potentially sequesters C over centuries. Nevertheless, the quantitative importance of PyC in the global C balance remains contentious, and therefore, PyC is rarely considered in global C cycle and climate studies. Here we examine the robustness of existing evidence and identify the main research gaps in the production, fluxes and fate of PyC from vegetation fires. Much of the previous work on PyC production has focused on selected components of total PyC generated in vegetation fires, likely leading to underestimates. We suggest that global PyC production could be in the range of 116-385 Tg C per year, that is ~0.2-0.6% of the annual terrestrial net primary production. According to our estimations, atmospheric emissions of soot/black C might be a smaller fraction of total PyC (<2%) than previously reported. Research on the fate of PyC in the environment has mainly focused on its degradation pathways, and its accumulation and resilience either in situ (surface soils) or in ultimate sinks (marine sediments). Off-site transport, transformation and PyC storage in intermediate pools are often overlooked, which could explain the fate of a substantial fraction of the PyC mobilized annually. Rivers carry about 25-28 Tg dissolved PyC per year into the ocean where it accumulates in dissolved form over ten-thousands of year to one of the largest PyC pool on Earth. The riverine flux of suspended (particulate) PyC is largely unconstrained to date. We propose new research directions addressing gaps in the global PyC cycle to fully understand the importance of the products of burning in global C cycle dynamics. This presentation is based largely on a recent review by the same group of authors (Santín et al., 2016, Global Change Biology 22, 76-91, doi: 10.1111/gcb.12985).

MnTnBuOE-2-PyP protects normal colorectal fibroblasts from radiation damage and simultaneously enhances radio/chemotherapeutic killing of colorectal cancer cells

PubMed Central

Kosmacek, Elizabeth A.; Chatterjee, Arpita; Tong, Qiang; Lin, Chi; Oberley, Rebecca E.

2016-01-01

Manganese porphyrins have been shown to be potent radioprotectors in a variety of cancer models. However, the mechanism as to how these porphyrins protect normal tissues from radiation damage still remains largely unknown. In the current study, we determine the effects of the manganese porphyrin, MnTnBuOE-2-PyP, on primary colorectal fibroblasts exposed to irradiation. We found that 2 Gy of radiation enhances the fibroblasts' ability to contract a collagen matrix, increases cell size and promotes cellular senesence. Treating fibroblasts with MnTnBuOE-2-PyP significantly inhibited radiation-induced collagen contraction, preserved cell morphology and also inhibited cellular senescence. We further showed that MnTnBuOE-2-PyP enhanced the overall viability of the fibroblasts following exposure to radiation but did not protect colorectal cancer cell viability. Specifically, MnTnBuOE-2-PyP in combination with irradiation, caused a significant decrease in tumor clonogenicity. Since locally advanced rectal cancers are treated with chemoradiation therapy followed by surgery and non-metastatic anal cancers are treated with chemoradiation therapy, we also investigated the effects of MnTnBuOE-2-PyP in combination with radiation, 5-fluorouracil with and without Mitomycin C. We found that MnTnBuOE-2-PyP in combination with Mitomycin C or 5-fluorouracil further enhances those compounds' ability to suppress tumor cell growth. When MnTnBuOE-2-PyP was combined with the two chemotherapeutics and radiation, we observed the greatest reduction in tumor cell growth. Therefore, these studies indicate that MnTnBuOE-2-PyP could be used as a potent radioprotector for normal tissue, while at the same time enhancing radiation and chemotherapy treatment for rectal and anal cancers. PMID:27119354

MnTnBuOE-2-PyP protects normal colorectal fibroblasts from radiation damage and simultaneously enhances radio/chemotherapeutic killing of colorectal cancer cells.

PubMed

Kosmacek, Elizabeth A; Chatterjee, Arpita; Tong, Qiang; Lin, Chi; Oberley-Deegan, Rebecca E

2016-06-07

Manganese porphyrins have been shown to be potent radioprotectors in a variety of cancer models. However, the mechanism as to how these porphyrins protect normal tissues from radiation damage still remains largely unknown. In the current study, we determine the effects of the manganese porphyrin, MnTnBuOE-2-PyP, on primary colorectal fibroblasts exposed to irradiation. We found that 2 Gy of radiation enhances the fibroblasts' ability to contract a collagen matrix, increases cell size and promotes cellular senesence. Treating fibroblasts with MnTnBuOE-2-PyP significantly inhibited radiation-induced collagen contraction, preserved cell morphology and also inhibited cellular senescence. We further showed that MnTnBuOE-2-PyP enhanced the overall viability of the fibroblasts following exposure to radiation but did not protect colorectal cancer cell viability. Specifically, MnTnBuOE-2-PyP in combination with irradiation, caused a significant decrease in tumor clonogenicity. Since locally advanced rectal cancers are treated with chemoradiation therapy followed by surgery and non-metastatic anal cancers are treated with chemoradiation therapy, we also investigated the effects of MnTnBuOE-2-PyP in combination with radiation, 5-fluorouracil with and without Mitomycin C. We found that MnTnBuOE-2-PyP in combination with Mitomycin C or 5-fluorouracil further enhances those compounds' ability to suppress tumor cell growth. When MnTnBuOE-2-PyP was combined with the two chemotherapeutics and radiation, we observed the greatest reduction in tumor cell growth. Therefore, these studies indicate that MnTnBuOE-2-PyP could be used as a potent radioprotector for normal tissue, while at the same time enhancing radiation and chemotherapy treatment for rectal and anal cancers.

Dynamics of microbial community composition and soil organic carbon mineralization in soil following addition of pyrogenic and fresh organic matter

DOE PAGES

Whitman, Thea; Pepe-Ranney, Charles; Enders, Akio; ...

2016-04-29

Pyrogenic organic matter (PyOM) additions to soils can have large impacts on soil organic carbon (SOC) cycling. As the soil microbial community drives SOC fluxes, understanding how PyOM additions affect soil microbes is essential to understanding how PyOM affects SOC. We studied SOC dynamics and surveyed soil bacterial communities after OM additions in a field experiment. We produced and mixed in either 350 °C corn stover PyOM or an equivalent initial amount of dried corn stover to a Typic Fragiudept soil. Stover increased SOC-derived and total CO 2 fluxes (up to 6x), and caused rapid and persistent changes in bacterialmore » community composition over 82 days. In contrast, PyOM only temporarily increased total soil CO 2 fluxes (up to 2x) and caused fewer changes in bacterial community composition. Of the operational taxonomic units (OTUs) that increased in response to PyOM additions, 70% also responded to stover additions. These OTUs likely thrive on easily mineralizable carbon (C) that is found both in stover and, to a lesser extent, in PyOM. In contrast, we also identified unique PyOM responders, which may respond to substrates such as polyaromatic C. In particular, members of Gemmatimonadetes tended to increase in relative abundance in response to PyOM but not to fresh organic matter. As a result, we identify taxa to target for future investigations of the mechanistic underpinnings of ecological phenomena associated with PyOM additions to soil.« less

Dynamics of microbial community composition and soil organic carbon mineralization in soil following addition of pyrogenic and fresh organic matter

PubMed Central

Whitman, Thea; Pepe-Ranney, Charles; Enders, Akio; Koechli, Chantal; Campbell, Ashley; Buckley, Daniel H; Lehmann, Johannes

2016-01-01

Pyrogenic organic matter (PyOM) additions to soils can have large impacts on soil organic carbon (SOC) cycling. As the soil microbial community drives SOC fluxes, understanding how PyOM additions affect soil microbes is essential to understanding how PyOM affects SOC. We studied SOC dynamics and surveyed soil bacterial communities after OM additions in a field experiment. We produced and mixed in either 350 °C corn stover PyOM or an equivalent initial amount of dried corn stover to a Typic Fragiudept soil. Stover increased SOC-derived and total CO2 fluxes (up to 6x), and caused rapid and persistent changes in bacterial community composition over 82 days. In contrast, PyOM only temporarily increased total soil CO2 fluxes (up to 2x) and caused fewer changes in bacterial community composition. Of the operational taxonomic units (OTUs) that increased in response to PyOM additions, 70% also responded to stover additions. These OTUs likely thrive on easily mineralizable carbon (C) that is found both in stover and, to a lesser extent, in PyOM. In contrast, we also identified unique PyOM responders, which may respond to substrates such as polyaromatic C. In particular, members of Gemmatimonadetes tended to increase in relative abundance in response to PyOM but not to fresh organic matter. We identify taxa to target for future investigations of the mechanistic underpinnings of ecological phenomena associated with PyOM additions to soil. PMID:27128990

Dynamics of microbial community composition and soil organic carbon mineralization in soil following addition of pyrogenic and fresh organic matter

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

Whitman, Thea; Pepe-Ranney, Charles; Enders, Akio

Pyrogenic organic matter (PyOM) additions to soils can have large impacts on soil organic carbon (SOC) cycling. As the soil microbial community drives SOC fluxes, understanding how PyOM additions affect soil microbes is essential to understanding how PyOM affects SOC. We studied SOC dynamics and surveyed soil bacterial communities after OM additions in a field experiment. We produced and mixed in either 350 °C corn stover PyOM or an equivalent initial amount of dried corn stover to a Typic Fragiudept soil. Stover increased SOC-derived and total CO 2 fluxes (up to 6x), and caused rapid and persistent changes in bacterialmore » community composition over 82 days. In contrast, PyOM only temporarily increased total soil CO 2 fluxes (up to 2x) and caused fewer changes in bacterial community composition. Of the operational taxonomic units (OTUs) that increased in response to PyOM additions, 70% also responded to stover additions. These OTUs likely thrive on easily mineralizable carbon (C) that is found both in stover and, to a lesser extent, in PyOM. In contrast, we also identified unique PyOM responders, which may respond to substrates such as polyaromatic C. In particular, members of Gemmatimonadetes tended to increase in relative abundance in response to PyOM but not to fresh organic matter. As a result, we identify taxa to target for future investigations of the mechanistic underpinnings of ecological phenomena associated with PyOM additions to soil.« less

Adhesion of Antireflective Coatings in Multijunction Photovoltaics

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

Brock, Ryan; Miller, David C.; Dauskardt, Reinhold H.

2016-11-21

The development of a new composite dual cantilever beam (cDCB) thin-film adhesion testing method is reported, which allows the measurement of adhesion on the fragile thin substrates used in multijunction photovoltaics. We address the adhesion of several antireflective coating systems on multijunction cells. By varying interface chemistry and morphology, we demonstrate the ensuing effects on adhesion and help to develop an understanding of how high adhesion can be achieved, as adhesion values ranging from 0.5 J/m2 to 10 J/m2 were measured. Damp Heat (85 degrees C/85% RH) was used to invoke degradation of interfacial adhesion. We show that even withmore » germanium substrates that fracture easily, quantitative measurements of adhesion can still be made at high test yield. The cDCB test is discussed as an important new methodology, which can be broadly applied to any system that makes use of thin, brittle, or otherwise fragile substrates.« less

Adhesion of Antireflective Coatings in Multijunction Photovoltaics: Preprint

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

Brock, Ryan; Dauskardt, Reinhold H.; Miller, David C.

2016-06-16

The development of a new composite dual cantilever beam (cDCB) thin-film adhesion testing method is reported, which allows the measurement of adhesion on the fragile thin substrates used in multijunction photovoltaics. We address the adhesion of several antireflective coating systems on multijunction cells. By varying interface chemistry and morphology, we demonstrate the ensuing effects on adhesion and help to develop an understanding of how high adhesion can be achieved, as adhesion values ranging from 0.5 J/m2 to 10 J/m2 were measured. Damp Heat (85 degrees C/85% RH) was used to invoke degradation of interfacial adhesion. We show that even withmore » germanium substrates that fracture easily, quantitative measurements of adhesion can still be made at high test yield. The cDCB test is discussed as an important new methodology, which can be broadly applied to any system that makes use of thin, brittle, or otherwise fragile substrates.« less

Enhanced expression of rat hepatic CYP2B1/2B2 and 2E1 by pyridine: differential induction kinetics and molecular basis of expression.

PubMed

Kim, H; Putt, D; Reddy, S; Hollenberg, P F; Novak, R F

1993-11-01

Expression of the cytochrome P450 (CYP) 2B subfamily in rat and rabbit hepatic tissues after pyridine (PY) treatment has been examined, and the molecular basis for enhanced 2B1/2B2 expression has been determined. P450 expression was monitored using metabolic activity, sodium dodecyl sulfate-polyacrylamide gel electrophoresis and immunoblot analyses, and the identity of the proteins was confirmed through N-terminus microsequence analysis. PY caused a dose-dependent elevation of hepatic CYP2B1/B2B levels in rats, which ranged from 4- to 22-fold over the dosing regimen of 100 to 400 mg PY/kg/day, for 3 days, respectively. PY at low dose failed to induce CYP2B in rabbit hepatic tissue, suggesting a species-dependent response in 2B expression. Anti-2B1 IgG addition to PY-induced microsomes inhibited benzphetamine N-demethylase activity by only approximately 15%, in sharp contrast to the approximately 73% inhibition observed for phenobarbital-induced microsomes, suggesting the induction of other form(s) of P450 having benzphetamine N-demethylase activity. Northern blot analysis revealed that PY treatment increased 2B1 and 2B2 poly(A)+ RNA levels approximately 69- and approximately 34-fold, respectively, whereas the 2E1 poly(A)+ RNA levels failed to increase. The results of this study show that PY induces CYP2B1/2B2 and that induction is species-dependent and kinetically distinguishable from 2E1 induction. Moreover, 2B1/2B2 induction occurs as a result of elevated mRNA levels associated with either transcriptional activation or mRNA stabilization, and it differs from the mechanism of hepatic 2E1 induction by PY.

Pyrogenic carbon erosion: implications for stock and persistence of pyrogenic carbon in soil

NASA Astrophysics Data System (ADS)

Abney, Rebecca B.; Berhe, Asmeret Asefaw

2018-03-01

Pyrogenic carbon (PyC) constitutes an important pool of soil organic matter, particularly for its reactivity and because of its assumed long residence times in soil. In the past, research on the dynamics of PyC in the soil system has focused on quantifying stock and mean residence time of PyC in soil, as well as determining both PyC stabilization mechanisms and loss pathways. Much of this research has focused on decomposition as the most important loss pathway for PyC from soil. However, the low density of PyC and its high concentration on the soil surface after fire indicates that a significant proportion of PyC formed or deposited on the soil surface is likely laterally transported away from the site of production by wind and water erosion. Here, we present a synthesis of available data and literature to compare the magnitude of the water-driven erosional PyC flux with other important loss pathways, including leaching and decomposition, of PyC from soil. Furthermore, we use a simple first-order kinetic model of soil PyC dynamics to assess the effect of erosion and deposition on residence time of PyC in eroding landscapes. Current reports of PyC mean residence time (MRT) range from 250 to 660 years. Using a specific example-based model system, we find that ignoring the role of erosion may lead to the under- or over-estimation of PyC MRT on the centennial time scale. Furthermore, we find that, depending on the specific landform positions, timescales considered, and initial concentrations of PyC in soil, ignoring the role of erosion in distributing PyC across a landscape can lead to discrepancies in PyC concentrations on the order of several hundred g PyC m-2. Erosion is an important PyC flux that can act as a significant control on the stock and residence time of PyC in the soil system.

Results of ASTM round robin testing for mode 1 interlaminar fracture toughness of composite materials

NASA Technical Reports Server (NTRS)

Obrien, T. Kevin; Martin, Roderick H.

1992-01-01

The results are summarized of several interlaboratory 'round robin' test programs for measuring the mode 1 interlaminar fracture toughness of advanced fiber reinforced composite materials. Double Cantilever Beam (DCB) tests were conducted by participants in ASTM committee D30 on High Modulus Fibers and their Composites and by representatives of the European Group on Fracture (EGF) and the Japanese Industrial Standards Group (JIS). DCB tests were performed on three AS4 carbon fiber reinforced composite materials: AS4/3501-6 with a brittle epoxy matrix; AS4/BP907 with a tough epoxy matrix; and AS4/PEEK with a tough thermoplastic matrix. Difficulties encountered in manufacturing panels, as well as conducting the tests are discussed. Critical issues that developed during the course of the testing are highlighted. Results of the round robin testing used to determine the precision of the ASTM DCB test standard are summarized.

Performance enhanced miniaturized and electrically tunable patch antenna with patterned permalloy based magneto-dielectric substrate

NASA Astrophysics Data System (ADS)

Peng, Yujia; Farid Rahman, B. M.; Wang, Xuehe; Wang, Guoan

2014-05-01

Perspective magneto-dielectric materials with high permeability are potential substrates to miniaturize the patch antenna without deteriorating its performance. Besides its high permeability at high frequency, patterned Permalloy (Py) also presents tunable permeability by applying DC current. A performance enhanced miniaturized and electrically tunable patch antenna with patterned Py thin film is first presented and developed in this paper. To suppress the magnetic loss, the Py thin film layer is consisted of an array of 2 μm × 2 μm square Py patterns between the copper patch antenna and dielectric substrate. The DC current could be applied directly on Py patterns through the copper strip lines beneath the Py patterns along the length of patch antenna. The copper strip lines are specially designed with the same width of Py patterns and the thickness much less than the skin depth at the operating frequency, which can reduce their deteriorating effects to the performance of antenna. The structure of the antenna is presented and simulated with high frequency structure simulator. The results show that compared with non-magnetic antenna, the performance of Py thin film based antenna is improved with 50% bandwidth increase from 4 MHz to 8 MHz and 1.2 dB gain enhancement from 1.16 dB to 2.36 dB. The resonant frequency of the antenna could be continuously tuned from 937 MHz to 911 MHz with the permeability of Py thin film changing from 1750 to 1 900 by applying the DC current.

Magnetic headspace adsorptive extraction of chlorobenzenes prior to thermal desorption gas chromatography-mass spectrometry.

PubMed

Vidal, Lorena; Ahmadi, Mazaher; Fernández, Elena; Madrakian, Tayyebeh; Canals, Antonio

2017-06-08

This study presents a new, user-friendly, cost-effective and portable headspace solid-phase extraction technique based on graphene oxide decorated with iron oxide magnetic nanoparticles as sorbent, located on one end of a small neodymium magnet. Hence, the new headspace solid-phase extraction technique has been called Magnetic Headspace Adsorptive Extraction (Mag-HSAE). In order to assess Mag-HSAE technique applicability to model analytes, some chlorobenzenes were extracted from water samples prior to gas chromatography-mass spectrometry determination. A multivariate approach was employed to optimize the experimental parameters affecting Mag-HSAE. The method was evaluated under optimized extraction conditions (i.e., sample volume, 20 mL; extraction time, 30 min; sorbent amount, 10 mg; stirring speed, 1500 rpm, and ionic strength, non-significant), obtaining a linear response from 0.5 to 100 ng L -1 for 1,3-DCB, 1,4-DCB, 1,2-DCB, 1,3,5-TCB, 1,2,4-TCB and 1,2,3-TCB; from 0.5 to 75 ng L -1 for 1,2,4,5-TeCB, and PeCB; and from 1 to 75 ng L -1 for 1,2,3,4-TeCB. The repeatability of the proposed method was evaluated at 10 ng L -1 and 50 ng L -1 spiking levels, and coefficients of variation ranged between 1.5 and 9.5% (n = 5). Limits of detection values were found between 93 and 301 pg L -1 . Finally, tap, mineral and effluent water were selected as real water samples to assess method applicability. Relative recoveries varied between 86 and 110% showing negligible matrix effects. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of initial delamination on Mode 1 and Mode 2 interlaminar fracture toughness and fatigue fracture threshold

NASA Technical Reports Server (NTRS)

Murri, Gretchen Bostaph; Martin, Roderick H.

1991-01-01

Static and fatigue double-cantilever beam (DCB) and end-notch flexure (ENF) tests were conducted to determine the effect of the simulated initial delamination in interlaminar fracture toughness, G(sub c), and fatigue fracture threshold, G(sub th). Unidirectional, 24-ply specimens of S2/SP250 glass/epoxy were tested using Kapton inserts of four different thickness - 13, 25, 75, and 130 microns, at the midplane at one end, or with tension or shear precracks, to simulate an initial delamination. To determine G(sub c), the fatigue fracture threshold below which no delamination growth would occur in less than 1 x 10(exp 6) cycles, fatigue tests were conducted by cyclically loading specimens until delamination growth was detected. Consistent values of model 1 fracture toughness, G(sub Ic), were measured from DCB specimens with inserts of thickness 75 microns or thinner, or with shear precracks. The fatigue DCB tests gave similar values of G(sub Ith) for the 13, 25, and 75 microns specimens. Results for the shear precracked specimens were significantly lower that for specimens without precracks. Results for both the static and fatigue ENF tests showed that measured G(IIc) and G(IIth) values decreased with decreasing insert thickness, so that no limiting thickness could be determined. Results for specimens with inserts of 75 microns or thicker were significantly higher than the results for precracked specimens or specimens with 13 or 25 microns inserts.

Redox interplay of oxo-thio-tungsten centers with sulfur-donor co-ligands.

PubMed

Thomas, Simon; Eagle, Aston A; Sproules, Stephen A; Hill, Jason P; White, Jonathan M; Tiekink, Edward R T; George, Graham N; Young, Charles G

2003-09-22

The oxo-thio-W(VI) complexes TpWOS(S(2)PR(2)-S) and TpWOS(pyS-S) (Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate, R = OEt, Ph; pyS = pyridine-2-thiolate) have been prepared and characterized by microanalytical, spectroscopic, and structural techniques. Crystals of the 1,2-dichloroethane hemisolvate of TpWOS(S(2)PPh(2)-S) belong to the triclinic space group Ponemacr; with a = 10.732(6) A, b = 16.91(1) A, c = 10.021(4) A, alpha = 104.40(4) degrees, beta = 107.52(3) degrees, gamma = 96.09(5) degrees, V = 1647(1) A(3) for Z = 2. The complex exhibits a distorted octahedral structure featuring a facial tridentate Tp ligand and mutually cis terminal oxo (W-O(1) = 1.712(7) A), terminal thio (W-S(1) = 2.162(3) A), and monodentate dithiophosphinate ligands. X-ray absorption and extended X-ray absorption fine structure results support a related oxo-thio formulation for TpWOS(pyS-S). The complexes are reduced to the corresponding oxo-thio-W(V) anions, [TpWOS(S(2)PR(2)-S)](-) and [TpWOS(pyS-S)](-), which exhibit highly anisotropic EPR spectra. They are oxidized to form the EPR-active (dithio)oxo-W(V) cations, [TpWO(S(3)PR(2)-S,S')](+) and [TpWO(pyS(2)-N,S)](+) (pyS(2) = pyridine-2-dithio). Green [TpWO(pyS(2)-N,S)]BF(4), formed in the reaction of TpWOS(pyS) and NOBF(4), has been isolated and spectroscopically and structurally characterized. Crystals of [TpWO(pyS(2)-N,S)]BF(4) belong to the monoclinic space group Cc with a = 16.007(5) A, b = 14.091(4) A, c = 13.608(4) A, beta = 124.525(4) degrees, V = 2528.8(13) A(3) for Z = 4. The cation exhibits a distorted octahedral structure featuring facial tridentate Tp, terminal oxo (W-O(1) = 1.632(12) A), and bidentate pyridine-2-dithio-N,S (W-S(1) = 2.317(7) A, S(1)-S(2) = 2.037(9) A) ligands. The structures and redox behavior of the complexes are compared and contrasted with those of the related molybdenum complexes, TpMo(VI)OS(S(2)PR(2)-S) and TpMo(IV)O(pyS(2)-N,S) (Hill, J. P.; Laughlin, L. J.; Gable, R. W.; Young, C. G. Inorg. Chem. 1996, 35, 3447).

Pyrogenic carbon distribution in mineral topsoils of the northeastern United States

USGS Publications Warehouse

Jauss, Verena; Sullivan, Patrick J.; Sanderman, Jonathan; Smith, David; Lehmann, Johannes

2017-01-01

Due to its slow turnover rates in soil, pyrogenic carbon (PyC) is considered an important C pool and relevant to climate change processes. Therefore, the amounts of soil PyC were compared to environmental covariates over an area of 327,757 km2 in the northeastern United States in order to understand the controls on PyC distribution over large areas. Topsoil (defined as the soil A horizon, after removal of any organic horizons) samples were collected at 165 field sites in a generalised random tessellation stratified design that corresponded to approximately 1 site per 1600 km2 and PyC was estimated from diffuse reflectance mid-infrared spectroscopy measurements using a partial least-squares regression analysis in conjunction with a large database of PyC measurements based on a solid-state 13C nuclear magnetic resonance spectroscopy technique. Three spatial models were applied to the data in order to relate critical environmental covariates to the changes in spatial density of PyC over the landscape. Regional mean density estimates of PyC were 11.0 g kg− 1 (0.84 Gg km− 2) for Ordinary Kriging, 25.8 g kg− 1(12.2 Gg km− 2) for Multivariate Linear Regression, and 26.1 g kg− 1 (12.4 Gg km− 2) for Bayesian Regression Kriging. Akaike Information Criterion (AIC) indicated that the Multivariate Linear Regression model performed best (AIC = 842.6; n = 165) compared to Ordinary Kriging (AIC = 982.4) and Bayesian Regression Kriging (AIC = 979.2). Soil PyC concentrations correlated well with total soil sulphur (P < 0.001; n = 165), plant tissue lignin (P = 0.003), and drainage class (P = 0.008). This suggests the opportunity of including related environmental parameters in the spatial assessment of PyC in soils. Better estimates of the contribution of PyC to the global carbon cycle will thus also require more accurate assessments of these covariates.

Dye-sensitized electron transfer from TiO 2 to oxidized triphenylamines that follows first-order kinetics

DOE PAGES

DiMarco, Brian N.; Troian-Gautier, Ludovic; Sampaio, Renato N.; ...

2018-01-01

Two sensitizers, [Ru(bpy) 2 (dcb)] 2+ ( RuC ) and [Ru(bpy) 2 (dpb)] 2+ ( RuP ), were anchored to mesoporous TiO 2 thin films and utilized to sensitize the reaction of TiO 2 electrons with oxidized triphenylamines to visible light in CH 3 CN electrolytes.

Tetra-2,3-pyrazinoporphyrazines with externally appended pyridine rings. 15. Effects of the pyridyl substituents and fused exocyclic rings on the UV-visible spectroscopic properties of Mg(II)-porphyrazines: a combined experimental and DFT/TDDFT study.

PubMed

Donzello, Maria Pia; De Mori, Giorgia; Viola, Elisa; Ercolani, Claudio; Ricciardi, Giampaolo; Rosa, Angela

2014-08-04

Two new Mg(II) porphyrazine macrocycles, the octakis(2-pyridyl)porphyrazinato-magnesium(II), [Py8PzMg(H2O)], and the tetrakis-[6,7-di(2-pyridyl)quinoxalino]porphyrazinato-magnesium(II), [Py8QxPzMg(H2O)], were prepared by Mg-template macrocyclization processes, and their general physicochemical properties were examined. The previously reported porphyrazine analog, the tetrakis-2,3-[5,6-di(2-pyridyl)-pyrazino]porphyrazinato-magnesium(II), [Py8PyzPzMg(H2O)], has been also considered in the present work. The UV-visible solution spectra in nonaqueous solvents of this triad of externally octapyridinated Mg(II) complexes exhibit the usual profile observed for phthalocyanine and porphyrazine macrocycles, with intense absorptions in the Soret (300-450 nm) and Q band (600-800 nm) regions. It is observed that the Q band maximum sensibly shifts toward the red with peak values at 635 → 658 → 759 nm along the series [Py8PzMg(H2O)], [Py8PyzPzMg(H2O)], and [Py8QxPzMg(H2O)], as the extension of the macrocycle π-system increases. TDDFT calculations of the electronic absorption spectra were performed for the related water-free model compounds [Py8PzMg], [Py8PyzPzMg], and [Py8QxPzMg] to provide an interpretation of the UV-visible spectral changes occurring upon introduction of the pyrazine and quinoxaline rings at the periphery of the Pz macrocycle. To discriminate the electronic effects of the fused exocyclic rings from those of the appended 2-pyridyl rings, the UV-visible spectra of [PzMg] and [PyzPzMg] were also theoretically investigated. The theoretical results prove to agree very well with the experimental data, providing an accurate description of the UV-visible spectra. The observed spectral changes are interpreted on the basis of the electronic structure changes occurring along the series.

Food wastes derived adsorbents for carbon dioxide and benzene gas sorption.

PubMed

Opatokun, Suraj Adebayo; Prabhu, Azhagapillai; Al Shoaibi, Ahmed; Srinivasakannan, C; Strezov, Vladimir

2017-02-01

Food wastes are produced worldwide in large quantities that could have potential to produce higher value products, including industrial adsorbents. The present work attempts valorization of food waste by CO 2 activation and functionalization through nitric acid and melamine treatment. The prepared porous materials were subjected to gas phase adsorption of CO 2 and benzene gases. The resultant highly porous carbon materials with surface area range from 797 to 1025 m 2 /g were synthesized showing uptake capacities of 4.41, 4.07, 4.18 and 4.36 mmol/g of CO 2 and 345, 305, 242.5 and 380.7 mg/g of C 6 H 6 respectively for PyF515, PyF520, PyF715 and PyF720 in the absence of doped carbon matrix. Differential thermogravimetric (DTG) analysis showed the thermostability of the precursors to validate selected initial pyrolysis temperatures (500 and 700 °C). C 6 H 6 sorption lies mainly in the physisorption region for all adsorbents ensuring re-generation potential. PyF720 and PyF520 recorded the highest isosteric enthalpy of 64.4 kJ/mol and 48.7 kJ/mol respectively, despite the low degree of coverage of the latter. Thus, PyF515 and PyF720 demonstrated the potential for use as sustainable and cost effective adsorbents for benzene gas containment suitable for swing adsorption system. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantitative adhesion characterization of antireflective coatings in multijunction photovoltaics

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

Brock, Ryan; Rewari, Raunaq; Novoa, Fernando D.

We discuss the development of a new composite dual cantilever beam (cDCB) thin-film adhesion testing method, which enables the quantitative measurement of adhesion on the thin and fragile substrates used in multijunction photovoltaics. In particular, we address the adhesion of several 2- and 3-layer antireflective coating systems on multijunction cells. By varying interface chemistry and morphology through processing, we demonstrate the marked effects on adhesion and help to develop an understanding of how high adhesion can be achieved, as adhesion values ranging from 0.5 J/m2 to 10 J/m2 were measured. Damp heat (85 degrees C/85% RH) was used to invokemore » degradation of interfacial adhesion. We demonstrate that even with germanium substrates that fracture relatively easily, quantitative measurements of adhesion can be made at high test yield. The cDCB test is discussed as an important new methodology, which can be broadly applied to any system that makes use of thin, brittle, or otherwise fragile substrates.« less

TEN- AND NINETY-DAY TOXICITY STUDIES OF 1,2-DICHLOROBENZENE ADMINISTERED BY ORAL GAVAGE TO SPRAGUE-DAWLEY RATS

EPA Science Inventory

Subacute (10-day) and subchronic (90-day) toxicity studies of 1,2-dichlorobenzene (DCB) were conducted in male and female Sprague-Dawley rats. ,2-Dichlorobenzene was administered in corn oil by oral gavage; control animals received corn oil. t time of sacrifice, gross necropsies ...

G protein-coupled estrogen receptor (GPER) regulates mammary tumorigenesis and metastasis

PubMed Central

Marjon, Nicole A.; Hu, Chelin

2014-01-01

The role of 17β-estradiol (E2) in breast cancer development and tumor growth has traditionally been attributed exclusively to the activation of ERα. Although targeted inhibition of ERα is a successful approach for patients with ERα+ breast cancer, many patients fail to respond or become resistant to anti-estrogen therapy. The discovery of the G protein-coupled estrogen receptor (GPER1) suggested an additional mechanism through which E2 could exert its effects in breast cancer. Studies have demonstrated clinical correlations between GPER expression in human breast tumor specimens and increased tumor size, distant metastasis, and recurrence, as well as established a proliferative role for GPER in vitro; however, direct in vivo evidence has been lacking. To this end, a GPER null mutation [GPER knockout (KO)] was introduced, through interbreeding, into a widely used transgenic mouse model of mammary tumorigenesis [MMTV-PyMT (PyMT)]. Early tumor development, assessed by the extent of hyperplasia and proliferation, was not different between GPER wild-type/PyMT (WT/PyMT) and those mice harboring the GPER null mutation (KO/PyMT). However, by 12-13 weeks of age, tumors from KO/PyMT mice were smaller with decreased proliferation compared to those from WT/PyMT mice. Furthermore, tumors from the KO/PyMT mice were of histologically lower grade compared to tumors from their WT counterparts, suggesting less aggressive tumors in the KO/PyMT mice. Finally, KO/PyMT mice displayed dramatically fewer lung metastases compared to WT/PyMT mice. Combined, these data provide the first in vivo evidence that GPER plays a critical role in breast tumor growth and distant metastasis. PMID:25030371

Ionospheric and receiver DCB-constrained multi-GNSS single-frequency PPP integrated with MEMS inertial measurements

NASA Astrophysics Data System (ADS)

Gao, Zhouzheng; Ge, Maorong; Shen, Wenbin; Zhang, Hongping; Niu, Xiaoji

2017-11-01

Single-frequency precise point positioning (SF-PPP) is a potential precise positioning technique due to the advantages of the high accuracy in positioning after convergence and the low cost in operation. However, there are still challenges limiting its applications at present, such as the long convergence time, the low reliability, and the poor satellite availability and continuity in kinematic applications. In recent years, the achievements in the dual-frequency PPP have confirmed that its performance can be significantly enhanced by employing the slant ionospheric delay and receiver differential code bias (DCB) constraint model, and the multi-constellation Global Navigation Satellite Systems (GNSS) data. Accordingly, we introduce the slant ionospheric delay and receiver DCB constraint model, and the multi-GNSS data in SF-PPP modular together. In order to further overcome the drawbacks of SF-PPP in terms of reliability, continuity, and accuracy in the signal easily blocking environments, the inertial measurements are also adopted in this paper. Finally, we form a new approach to tightly integrate the multi-GNSS single-frequency observations and inertial measurements together to ameliorate the performance of the ionospheric delay and receiver DCB-constrained SF-PPP. In such model, the inter-system bias between each two GNSS systems, the inter-frequency bias between each two GLONASS frequencies, the hardware errors of the inertial sensors, the slant ionospheric delays of each user-satellite pair, and the receiver DCB are estimated together with other parameters in a unique Kalman filter. To demonstrate its performance, the multi-GNSS and low-cost inertial data from a land-borne experiment are analyzed. The results indicate that visible positioning improvements in terms of accuracy, continuity, and reliability can be achieved in both open-sky and complex conditions while using the proposed model in this study compared to the conventional GPS SF-PPP.

Reaction landscape of a pentadentate N5-ligated Mn(II) complex with O2˙- and H2O2 includes conversion of a peroxomanganese(III) adduct to a bis(μ-oxo)dimanganese(III,IV) species.

PubMed

Leto, Domenick F; Chattopadhyay, Swarup; Day, Victor W; Jackson, Timothy A

2013-09-28

Herein we describe the chemical reactivity of the mononuclear [Mn(II)(N4py)(OTf)](OTf) (1) complex with hydrogen peroxide and superoxide. Treatment of 1 with one equivalent superoxide at -40 °C in MeCN formed the peroxomanganese(III) adduct, [Mn(III)(O2)(N4py)](+) (2) in ~30% yield. Complex 2 decayed over time and the formation of the bis(μ-oxo)dimanganese(III,IV) complex, [Mn(III)Mn(IV)(μ-O)2(N4py)2](3+) (3) was observed. When 2 was formed in higher yields (~60%) using excess superoxide, the [Mn(III)(O2)(N4py)](+) species thermally decayed to Mn(II) species and 3 was formed in no greater than 10% yield. Treatment of [Mn(III)(O2)(N4py)](+) with 1 resulted in the formation of 3 in ~90% yield, relative to the concentration of [Mn(III)(O2)(N4py)](+). This reaction mimics the observed chemistry of Mn-ribonucleotide reductase, as it features the conversion of two Mn(II) species to an oxo-bridged Mn(III)Mn(IV) compound using O2(-) as oxidant. Complex 3 was independently prepared through treatment of 1 with H2O2 and base at -40 °C. The geometric and electronic structures of 3 were probed using electronic absorption, electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), variable-temperature, variable-field MCD (VTVH-MCD), and X-ray absorption (XAS) spectroscopies. Complex 3 was structurally characterized by X-ray diffraction (XRD), which revealed the N4py ligand bound in an unusual tetradentate fashion.

Preparation of anticoagulant PyC biomaterials with super-hydrophobic surface.

PubMed

Ze, Wang; Wen-Sheng, Tan; Ye-Xia; Ming, Zhang; Xiao-Ping, Li; Jian-Guo, Qiu; Xiao-Hong, Yang

2018-01-01

Pyrolytic carbon (PyC) is a kind of biomaterial which is chemically inert and has excellent biocompatibility. In order to obtain a super-hydrophobic PyC surface to improve anticoagulation and inhibit thrombus, this study prepares grating pair structure, microhole array structure, helix structure on PyC surface by nanoseconds laser etching. Rod-like ZnO film and ball-like ZnO film are prepared on the PyC surface by the hydrothermal method; polyvinyl pyrrolidone (PVP) nanofiber film and PVP/TiO 2 complex nanofiber film are prepared on the PyC surface by the electrospinning method; the PyC surface is silanized. Finally, surface microstructure and surface energy are characterized by scanning electron microscopy and contact angle meter (OCA20, German DataPhysics Co.). The periodical microstructures are formed respectively by nanoseconds laser etching. The surface roughness is increased by the hydrothermal and electrospinning method. Through infiltration experiment on rough and smooth PyC surfaces, rough PyC surface with microstructure is super-hydrophobic and has greater than 150° contact angle, which decreases blood flow resistance and inhibits thrombus.

A Manganese Alternative to Gadolinium for MRI Contrast

PubMed Central

Gale, Eric M.; Atanasova, Iliyana P.; Blasi, Francesco; Ay, Ilknur; Caravan, Peter

2016-01-01

Contrast-enhanced computed tomography (CT) and magnetic resonance imaging (MRI) are routinely used to diagnose soft tissue and vascular abnormalities. However safety concerns limit the use of iodinated and gadolinium- (Gd) based CT and MRI contrast media in renally compromised patients. With an estimated 14% of the US population suffering from chronic kidney disease (CKD), contrast media compatible with renal impairment is sorely needed. We present the new manganese(II) complex [Mn(PyC3A)(H2O)]- as a Gd alternative. [Mn(PyC3A)(H2O)]- is amongst the most stable Mn(II) complexes at pH 7.4 (log KML = 11.40). In the presence of 25 mol equiv. Zn at pH 6.0, 37 °C, [Mn(PyC3A)(H2O)]- is 20-fold more resistant to dissociation than [Gd(DTPA)(H2O)]2-. Relaxivity of [Mn(PyC3A)(H2O)]- in blood plasma is comparable to commercial Gd contrast agents. Biodistribution analysis confirms that [Mn(PyC3A)(H2O)]- clears via a mixed renal/ hepatobiliary pathway with >99% elimination by 24h. [Mn(PyC3A)(H2O)]- was modified to form a bifunctional chelator and 4 chelates were conjugated to a fibrin-specific peptide to give Mn-FBP. Mn-FBP binds the soluble fibrin fragment DD(E) with Kd = 110 nM. Per Mn relaxivity of Mn-FBP is 4-fold greater than [Mn(PyC3A)(H2O)]- and increases 60% in the presence of fibrin, consistent with binding. Mn-FBP provided equivalent thrombus enhancement to the state of the art Gd analog, EP-2104R, in a rat model of arterial thrombosis. Mn metabolite analysis reveals no evidence of dechelation and the probe was >99% eliminated after 24 hr. [Mn(PyC3A)(H2O)]- is a lead development candidate for an imaging probe that is compatible with renally compromised patients. PMID:26588204

Synthesis, photophysical properties, and computational studies of four-coordinate copper(I) complexes based on benzimidazolylidene N-heterocyclic carbene (NHC) ligands bearing aryl substituents

NASA Astrophysics Data System (ADS)

Xu, Shengxian; Wang, Jinglan; Liu, Shaobo; Zhao, Feng; Xia, Hongying; Wang, Yibo

2018-02-01

Three four-coordinate N-heterocyclic carbene (NHC) copper(I) complexes, [Cu(Ph-BenIm-Py)(POP)]PF6 (1), [Cu(Naph-BenIm-Py)(POP)]PF6 (2), and [Cu(Anthr-BenIm-Py)(POP)]PF6 (3) (Ph-BenIm-Py = 3-benzyl-1-(pyridin-2-yl)-1H-benzimidazolylidene, Naph-BenIm-Py = 3-(naphthalen-2-yl-1-(pyridin-2-yl)-1H- benzimidazolylidene, Anthr-BenIm-Py = 3-(anthracen-9-yl)-1-(pyridin-2-yl)-1H-benzimidazolylidene, and POP = bis[2-diphenylphosphino]-phenyl)ether) have been synthesized and characterized. The different aryl substituents (phenyl, naphthyl, and anthracyl groups) were introduced into NHC ligands and the corresponding photophysical properties of the complexes were systematically investigated. The absorption spectra of all NHCsbnd Cu(I) complexes show a characteristic feature of metal-to-ligand charge transfer (MLCT) in the lower-energy region. Complex 1 exhibited good photoluminescence (PL) properties companying with the high quantum yields and long excited-state lifetimes, whereas 2 and 3 with naphthyl and anthracyl groups show the low PL efficiency caused by the strong π-π stacking interactions. Density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations were employed to rationalize the photophysical properties of the NHCsbnd Cu(I) complexes.

Temperature & wood source control PyOM turnover in a Northern American forest

NASA Astrophysics Data System (ADS)

Hatton, Pierre-Joseph; Le Moine, James; Auclerc, Apolline; Gormley, Mark; Filley, Tim R.; Nadelhoffer, Knute J.; Bird, Jeff. A.

2016-04-01

Surprisingly little is known about how pyrolysis temperature and wood source affect the stability of forest-fire derived pyrogenic organic matter (PyOM). Here, we show that wood source and temperature affect in situ mineralization rates of PyOM in soils for two co-occurring gymnosperm (jack pine; JP [Pinus banksiana]) and angiosperm (red maple; RM [Acer rubrum])¬ species from North American boreal-temperate ecotones. We assess the effect of pyrolysis temperature on PyOM fates by following the decay of 13C/15N-enriched JP wood (JPwood) and PyOM produced at 300 °C (JP300) and 450 °C (JP450); and assess the effect of PyOM wood source by comparing fates of JP450 and RM450. JPwood mineralized 18× faster than JP300 and 44× faster than JP450 after 2.8y. RM450 mineralized initially faster than JP450 during the first ~2y, but became equivalent afterwards (1.1±0.2% of CO¬2 losses after 2.8y). Modeled turnover times suggest that this can be attributed to ~1% of fast-cycling PyOM (<3y). Slower-cycling pools are 12× faster for JPwood (13±5y) than for JP300 (157±28y) and 55× faster than for JP450 (700±229y). Modeled turnover times of the slow-cycling pools were equivalent for JP450 and RM450. The priming effect was positive for JPwood (0.10±0.05), neutral for JP300 (-0.02±0.04), and negative for JP450 (-0.15±0.03) and RM50 (-0.59±0.03). DOC losses were minimal compared with CO2 losses (DOC:CO2 ratio ≤0.005), but followed the same patterns: JPwood 6× greater than that of JP300 and 39× greater compared with JP450. After 1y, C recoveries were lower for JPwood than for PyOM, with no influence of pyrolysis temperature or wood source (yet); N recoveries did not differ. PLFA-(13)C data reveal that (i) treatments have similar microbial communities after 1y, (ii) JPwood is preferentially utilized by fungi, and (iii) bacteria increasingly utilize PyOM as pyrolysis temperature increases. Estimated carbon use efficiency decreased with increasing pyrolysis temperature (JPwood~JP300>JP450~RM450). Although insignificant, potential phenol oxidase and peroxidase activities decrease with increasing pyrolysis temperature. Neither PyOM nor wood additions (~11% of soil C stock 0-20 cm depth) affected pH or Ec after 1y. We provide the first, field experimental evidence that pyrolysis temperature and wood source affect the turnover of PyOM in soil. We show faster, initial decay for PyOM produced at lesser temperature and RM (angiosperm) compared with JP (gymnosperm). This study offers realistic insights on (i) the controls underlying in situ PyOM turnover, and on (ii) how ongoing/projected changes in tree species composition and fire frequency/intensity/distribution may affect PyOM in soil of North America temperate-boreal ecotones.

Research Update: Spin transfer torques in permalloy on monolayer MoS 2

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

Zhang, Wei; Sklenar, Joseph; Hsu, Bo

2016-03-01

We observe current induced spin transfer torque resonance in permalloy (Py) grown on monolayer MoS2. By passing rf current through the Py/MoS2 bilayer, field-like and damping-like torques are induced which excite the ferromagnetic resonance of Py. The signals are detected via a homodyne voltage from anisotropic magnetoresistance of Py. In comparison to other bilayer systems with strong spin-orbit torques, the monolayer MoS2 cannot provide bulk spin Hall effects and thus indicates the purely interfacial nature of the spin transfer torques. Therefore our results indicate the potential of two-dimensional transition-metal dichalcogenide for the use of interfacial spin-orbitronics applications.

Research update: Spin transfer torques in permalloy on monolayer MoS 2

DOE PAGES

Zhang, Wei; Sklenar, Joseph; Hsu, Bo; ...

2016-03-03

We observe current induced spin transfertorque resonance in permalloy (Py) grown on monolayer MoS 2. By passing rf current through the Py/MoS 2 bilayer, field-like and damping-like torques are induced which excite the ferromagnetic resonance of Py. The signals are detected via a homodyne voltage from anisotropic magnetoresistance of Py. In comparison to other bilayer systems with strong spin-orbit torques, the monolayer MoS 2 cannot provide bulk spin Hall effects and thus indicates the purely interfacial nature of the spin transfer torques. Furthermore, our results indicate the potential of two-dimensional transition-metal dichalcogenide for the use of interfacial spin-orbitronics applications.

A comparative study of magnetization dynamics in dinuclear dysprosium complexes featuring bridging chloride or trifluoromethanesulfonate ligands.

PubMed

Burns, Corey P; Wilkins, Branford O; Dickie, Courtney M; Latendresse, Trevor P; Vernier, Larry; Vignesh, Kuduva R; Bhuvanesh, Nattamai S; Nippe, Michael

2017-07-25

We utilized a rigid ligand platform PyCp 2 2- (PyCp 2 2- = [2,6-(CH 2 C 5 H 3 ) 2 C 5 H 3 N] 2- ) to isolate dinuclear Dy 3+ complexes [(PyCp 2 )Dy-(μ-O 2 SOCF 3 )] 2 (1) and [(PyCp 2 )Dy-(μ-Cl)] 2 (3) as well as the mononuclear complex (PyCp 2 )Dy(OSO 2 CF 3 )(thf) (2). Compounds 1 and 2 are the first examples of organometallic Dy 3+ complexes featuring triflate binding. The isolation of compounds 1 and 3 allows us to comparatively evaluate the effects of the bridging anions on the magnetization dynamics of the dinuclear systems. Our investigations show that although the exchange coupling interactions differ for 1 and 3, the dynamic magnetic properties are dominated by relaxation via the first excited state Kramers doublet of the individual Dy sites. Compounds 1 and 3 exhibit barriers to magnetization reversal (U eff = 49 cm -1 ) that can be favorably compared to those of the previously reported examples of [Cp 2 Dy(μ-Cl)] 2 (U eff = 26 cm -1 ) and [Cp 2 Dy(thf)(μ-Cl)] 2 (U eff = 34 cm -1 ).

Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes

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

Erickson, Karla A.; Lichtscheidl, Alejandro G.; Monreal, Marisa Jennifer

The terminal actinide fluoride bonds in (C 5Me 5) 2ThF 2(py) (py = pyridine) and (C 5Me 5) 2UF 2(O=PR 3) (R = Me, Ph) react with two equivalents of Me 3SiN 3 in toluene to form the polymeric thorium bis(azide), [(C 5Me 5) 2Th(N 3)2] ∞, and a new class of monometallic uranium bis(azide) complexes, (C 5Me 5) 2U(N 3)2(O=PR 3), respectively. Full characterization of the novel complexes (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2UF 2(O=PR 3) are reported, including the solid-state structures of (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2U(N 3) 2(O=PPhmore » 3). Lastly, electronic absorption spectral data are also reported for (C 5Me 5) 2AnF 2(py) (An = Th, U) and (C 5Me 5) 2U(N 3) 2(O=PR 3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.« less

Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes

DOE PAGES

Erickson, Karla A.; Lichtscheidl, Alejandro G.; Monreal, Marisa Jennifer; ...

2017-11-04

The terminal actinide fluoride bonds in (C 5Me 5) 2ThF 2(py) (py = pyridine) and (C 5Me 5) 2UF 2(O=PR 3) (R = Me, Ph) react with two equivalents of Me 3SiN 3 in toluene to form the polymeric thorium bis(azide), [(C 5Me 5) 2Th(N 3)2] ∞, and a new class of monometallic uranium bis(azide) complexes, (C 5Me 5) 2U(N 3)2(O=PR 3), respectively. Full characterization of the novel complexes (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2UF 2(O=PR 3) are reported, including the solid-state structures of (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2U(N 3) 2(O=PPhmore » 3). Lastly, electronic absorption spectral data are also reported for (C 5Me 5) 2AnF 2(py) (An = Th, U) and (C 5Me 5) 2U(N 3) 2(O=PR 3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.« less

Polyoma small T antigen triggers cell death via mitotic catastrophe

PubMed Central

Fernando, Arun T Pores; Andrabi, Shaida; Cizmecioglu, Onur; Zhu, Cailei; Livingston, David M.; Higgins, Jonathan M.G; Schaffhausen, Brian S; Roberts, Thomas M

2014-01-01

Polyoma small T antigen (PyST), an early gene product of the polyoma virus, has been shown to cause cell death in a number of mammalian cells in a protein phosphatase 2A (PP2A)-dependent manner. In the current study, using a cell line featuring regulated expression of PyST, we found that PyST arrests cells in mitosis. Live-cell and immunofluorescence studies showed that the majority of the PyST-expressing cells were arrested in prometaphase with almost no cells progressing beyond metaphase. These cells exhibited defects in chromosomal congression, sister chromatid cohesion and spindle positioning, resulting in the activation of the Spindle Assembly Checkpoint (SAC). Prolonged mitotic arrest then led to cell death via mitotic catastrophe. Cell cycle inhibitors that block cells in G1/S prevented PyST-induced death. PyST-induced cell death that occurs during M is not dependent on p53 status. These data suggested, and our results confirmed that, PP2A inhibition could be used to preferentially kill cancer cells with p53 mutations that proliferate normally in the presence of cell cycle inhibitors. PMID:24998850

Homogeneous coating of ionomer on electrocatalyst assisted by polybenzimidazole as an adhesive layer and its effect on fuel cell performance

NASA Astrophysics Data System (ADS)

Yang, Zehui; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-12-01

The fabrication of homogeneous ionomer distribution in fuel cell catalyst layers is necessary and important to improve the platinum utilization as well as the power density. Here, we focus on the effect of poly[2,2‧-(2,6-pyridine)-5,5‧-bibenzimidazole] (PyPBI) wrapped on multi-walled carbon nanotubes (MWNTs) for anchoring Nafion ionomer to the electrocatalyst, in which PyPBI functions as the binding sites for platinum nanoparticles (Pt-NPs) used as a catalyst. Based on the result using a control composite without having PyPBI, a strong interaction of the Nafion onto the PyPBI layer is recognized. Importantly, we find that the membrane-electrode assembly (MEA) shows a much higher maximum power density than that of the MEA without PyPBI. A homogeneous coating of Nafion on the electrocatalyst using the PyPBI forms a long-range network of the ionomer, leading to an improved Pt-NP utilization efficiency as well as an enhanced power density of the MEA.

Versatile ruthenium(II) dye towards blue-light emitter and dye-sensitizer for solar cells

NASA Astrophysics Data System (ADS)

Zanoni, Kassio P. S.; Amaral, Ronaldo C.; Murakami Iha, Neyde Y.; Abreu, Felipe D.; de Carvalho, Idalina M. M.

2018-06-01

A versatile Ru(II) complex bearing an anthracene moiety was synthesized in our search for suitable compounds towards efficient molecular devices. The new engineered dye, cis‑[Ru(dcbH2)(NCS)2(mbpy‑anth)] (dcbH2 = 2,2‧‑bipyridyl‑4,4‧‑dicarboxylic acid, mbpy‑anth = 4‑[N‑(2‑anthryl)carbamoyl]‑4‧‑methyl‑2,2‧‑bipyridine), exhibits a blueish emission in a vibronically structured spectrum ascribed to the fluorescence of a 1LCAnth (ligand centered) excited state in the anthracene and has a potential to be exploited in the fields of smart lighting and displays. This complex was also employed in dye-sensitized solar cells with fairly efficient solar energy conversion with the use of self-assembled TiO2 compact layers beneath the TiO2 mesoporous film to prevent meso‑TiO2/dye back reactions. Further photoelectrochemical investigations through incident photon-to-current efficiency and electrochemical impedance spectra showed that the all-nano-TiO2 compact layer acts as contact layers that increase the electron harvesting in the external circuit, enhancing efficiencies up to 50%.

Versatile ruthenium(II) dye towards blue-light emitter and dye-sensitizer for solar cells.

PubMed

Zanoni, Kassio P S; Amaral, Ronaldo C; Murakami Iha, Neyde Y; Abreu, Felipe D; de Carvalho, Idalina M M

2018-06-05

A versatile Ru(II) complex bearing an anthracene moiety was synthesized in our search for suitable compounds towards efficient molecular devices. The new engineered dye, cis‑[Ru(dcbH 2 )(NCS) 2 (mbpy‑anth)] (dcbH 2 =2,2'‑bipyridyl‑4,4'‑dicarboxylic acid, mbpy‑anth=4‑[N‑(2‑anthryl)carbamoyl]‑4'‑methyl‑2,2'‑bipyridine), exhibits a blueish emission in a vibronically structured spectrum ascribed to the fluorescence of a 1 LC Anth (ligand centered) excited state in the anthracene and has a potential to be exploited in the fields of smart lighting and displays. This complex was also employed in dye-sensitized solar cells with fairly efficient solar energy conversion with the use of self-assembled TiO 2 compact layers beneath the TiO 2 mesoporous film to prevent meso‑TiO 2 /dye back reactions. Further photoelectrochemical investigations through incident photon-to-current efficiency and electrochemical impedance spectra showed that the all-nano-TiO 2 compact layer acts as contact layers that increase the electron harvesting in the external circuit, enhancing efficiencies up to 50%. Copyright © 2018 Elsevier B.V. All rights reserved.

Can you score with balloons to enhance outcomes after drug coated balloon angioplasty? Insights from the Paris DCB Registry for in-stent restenosis.

PubMed

Merat, Benoît; Waliszewski, Matthias; Dillinger, Guillaume; Henry, Patrick; Sideris, Georgios

2018-06-01

The objective of this study was to assess the 12-month clinical outcomes in patients with drug-eluting stent in-stent restenosis (DES-ISR) who were either pre-dilated with non-compliant balloons (NCBA) and with additional scoring balloons (NCBA + SBA) prior to drug coated balloon (DCB) angioplasty. This monocentric, retrospective study included patients with DES-ISR who were routinely treated over a 2-year time span. Patients with stable angina and documented ischemia or selected forms of unstable angina due to a culprit DES-ISR lesion were analyzed. The primary endpoint was the clinically driven target-lesion revascularization (TLR) rate at 12 months. Secondary endpoints included post-interventional lumen gain and late lumen loss (LLL) at 6 months. The 12-month TLR rates in 124 patients who underwent either NCBA + SBA or NCBA only group were not different (17.3%, 9/52 vs 11.6%, 8/69, P = 0.371) and low as compared to other comparable studies. The use of SBA led to equally high post minimal lumen diameters (MLD) in both treatment arms (NCBA 2.21 ± 0.33 vs NCBA + SBA 2.18 ± 0.41, P = 0.868). We did not find a significant difference in late lumen loss (LLL) between both groups (0.50 ± 0.62 mm vs 0.40 ± 0.46 mm, P = 0.468). Scoring Balloon Angioplasty can safely and effectively prepare DES-ISR lesions to render them suitable for DCB angioplasty with acceptable TLR and MACE rates. © 2018, Wiley Periodicals, Inc.

Pyrogenic Carbon in soils: a literature-based inventory and a global estimation of its content in soil organic carbon and stocks

NASA Astrophysics Data System (ADS)

Reisser, Moritz; Purves, Ross; Schmidt, Michael W. I.; Abiven, Samuel

2016-08-01

Pyrogenic carbon (PyC) is considered one of the most stable components in soil and can represent more than 30% of total soil organic carbon (SOC). However, few estimates of global PyC stock or distribution exist and thus PyC is not included in any global carbon cycle models, despite its potential major relevance for the soil pool. To obtain a global picture, we reviewed the literature for published PyC content in SOC data. We generated the first PyC database including more than 560 measurements from 55 studies. Despite limitations due to heterogeneous distribution of the studied locations and gaps in the database, we were able to produce a worldwide PyC inventory. We found that global PyC represent on average 13.7% of the SOC and can be even up to 60%, making it one of the largest groups of identifiable compounds in soil, together with polysaccharides. We observed a consistent range of PyC content in SOC, despite the diverse methods of quantification. We tested the PyC content against different environmental explanatory variables: fire and land use (fire characteristics, land use, net primary productivity), climate (temperature, precipitation, climatic zones, altitude) and pedogenic properties (clay content, pH, SOC content). Surprisingly, soil properties explain PyC content the most. Soils with clay content higher than 50% contain significantly more PyC (> 30% of the SOC) than with clay content lower than 5% (< 6% of the SOC). Alkaline soils contain at least 50% more PyC than acidic soils. Furthermore, climatic conditions, represented by climatic zone or mean temperature or precipitation, correlate significantly with the PyC content. By contrast, fire characteristics could only explain PyC content, if site-specific information was available. Datasets derived from remote sensing did not explain the PyC content. To show the potential of this database, we used it in combination with other global datasets to create a global worldwide PyC content and a stock estimation, which resulted in around 200Pg PyC for the uppermost 2 meters. These modelled estimates indicated a clear mismatch between the location of the current PyC studies and the geographical zones where we expect high PyC stocks.

Photo-reduction of CO2 Using a Rhenium Complex Covalently Supported on a Graphene/TiO2 Composite.

PubMed

Cui, Shi-Cong; Sun, Xue-Zhong; Liu, Jin-Gang

2016-07-07

One of the promising solutions for decreasing atmospheric CO2 is artificial photosynthesis, in which CO2 can be photoconverted into solar fuels. In this study, a rhenium complex Re(PyBn)(CO)3 Cl (PyBn=1-(2-picolyl)-4-phenyl-1H-1,2,3-triazole) was covalently grafted onto the surface of reduced graphene oxide (rGO). This was further combined with TiO2 to fabricate a novel catalyst composite TiO2 -rGO-Re(PyBn)(CO)3 Cl for CO2 photo-reduction. This hybrid composite demonstrated high selectivity conversion of CO2 into CO under xenon-lamp irradiation. Compared with the unsupported homogeneous catalyst Re(PyBn)(CO)3 Cl, the covalent immobilized catalyst composite TiO2 -rGO-Re(PyBn)(CO)3 Cl enhanced the turnover number six times and significantly improved catalyst stability. During the process of CO2 photo-reduction, intermediate species with lifetimes longer than hundreds of microseconds were observed and the formation of CO products was revealed using timeresolved infrared spectroscopy. A plausible mechanism for CO2 photo-reduction by the TiO2 -rGO-Re(PyBn)(CO)3 Cl catalyst composite has been suggested. The obtained results have implications for the future design of efficient catalyst composites for CO2 photo-conversion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alternative modelling approaches for estimating pyrogenic carbon, soil organic carbon and total nitrogen in contrasting ecoregions within the United States

NASA Astrophysics Data System (ADS)

Jauss, Verena; Sullivan, Patrick; Lehmann, Johannes; Sanderman, Jonathan; Daub, Markus

2017-04-01

Given that turnover rates of pyrogenic carbon (PyC) in soil are substantially slower than those of other organic carbon input, it is considered an important carbon pool and its function and fate are relevant to global environmental change processes. Research on PyC has expanded greatly over recent years, but the analytical challenges of determining environmental core factors influencing its production, accumulation and dispersion still require elucidation across different scales. Mid-infrared spectroscopy and partial least-squares analysis were used in conjunction with ultraviolet photo-oxidation followed by nuclear magnetic resonance spectroscopy techniques, to quantify PyC, soil organic carbon (SOC) and total nitrogen (total N) amounts for samples we collected of surface and subsurface soils across the United States at National Science Foundation supported Long Term Ecological Research (LTER) sites as well as samples from a national soil sampling effort by the U.S. Geological Survey. In our study, we illustrate the impact of the aforementioned natural factors by examining their correlation with PyC content in soils under contrasting environmental conditions thus identifying the factors affecting PyC accumulation. Our central findings revealed a statistically significant relationship of PyC with environmental variables soil drainage, lignin content of the vegetation, mean annual temperature and mean annual precipitation as well as for the USGS sites total soil sulphur. During our investigations we evaluated PyC on different spatial scales. On a geographically smaller scale we examined samples from New England and New York. We developed a new and innovative Bayesian framework and applied three spatial models to the data in order to relate critical environmental covariates to changes in spatial density of PyC over the landscape. Akaike Information Criterion demonstrated that the Bayesian Multivariate Linear Regression model performed best (r2=0.6; p<<0.0001) in our analysis, giving global mean density estimates for PyC of 25.8 g kg-1 (12.2 Gg km-2) as opposed to the Ordinary Kriging model, which performed worst (r2=0.0; p>>0.05) with estimates of 11.0 g kg-1 (0.84 Gg km-2). On a larger scale, we looked at selected profiles at five diverse LTER sites as well as sites along a vegetation gradient in Oregon. At the LTER sites PyC content ranged from 9.8 mg g-1 (Coweeta, NC) to 56.4 mg g-1 (Bonanza, AK). Furthermore, we examined the multivariate relationships between environmental factors and our measurements of PyC, SOC and total N at the LTER sites through the application of a canonical correspondence analysis. Using our Oregon samples, we expanded on a previously established method to predict soil properties vertically in the soil profile using equal-area quadratic splines in order to calculate PyC stocks as well as to infer and visualize PyC contents, which were most prevalent in the first 0.2 m with 7-24% of SOC, and could be found in the subsoil of all locations. However, PyC contents did not change consistently with soil depth.

Copper-containing ceramic precursor synthesis: Solid-state transformations and materials technology

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Eckles, William E.; Duraj, Stan A.; Andras, Maria T.; Fanwick, Phillip E.; Richman, Robert M.; Sabat, Michael L.; Power, Michael B.; Gordon, Edward M.; Barron, Andrew

1994-01-01

Three copper systems with relevance to materials technology are discussed. In the first, a CuS precursor, Cu4S1O (4-methylpyridine)(sub 4)- (4-MePy), was prepared by three routes: reaction of Cu2S, reaction of CuBr-SMe2, and oxidation of copper powder with excess sulfur in 4-methylpyridine by sulfur. In the second, copper powder was found to react with excess thiourea (H2NC(S)NH2) in 4-methylpyridine to produce thiocyanate (NCS(-)) complexes. Three isolated and characterized compounds are: Cu(NCS)(4-MePy)(sub 2), a polymer, (4-MePy-H)(Cu(NCS)(sub 3)(4-MePy)(sub 2)), a salt, and t-Cu(NCS)(sub 2)(4-MePy)(sub 4). Finally, an attempt to produce a mixed-metal sulfide precursor of Cu and Ga in N-methylimidazole (N-MeIm) resulted in the synthesis of a Cu-containing polymer, Cu(SO4)(N-MeIm). The structures are presented; the chemistry will be briefly discussed in the context of preparation and processing of copper-containing materials for aerospace applications.

Highly Efficient and Robust Nickel Phosphides as Bifunctional Electrocatalysts for Overall Water-Splitting.

PubMed

Li, Jiayuan; Li, Jing; Zhou, Xuemei; Xia, Zhaoming; Gao, Wei; Ma, Yuanyuan; Qu, Yongquan

2016-05-04

To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h.

Impact of pyrogenic organic matter decomposition and induced priming effect on soil C budget.

NASA Astrophysics Data System (ADS)

Maestrini, Bernardo; Abiven, Samuel

2014-05-01

Pyrogenic organic matter (PyOM) results from the incomplete combustion of biomass and may contribute to constitute an important fraction of soil C in forest and agricultural soils, in the form of charcoal (produced by wildfires) or biochar (anthropogenic). Although many evidences exist on the long mean residence time of PyOM there is still a large uncertainty on PyOM loss processes and rate and on possible induced priming effect on non-PyOM. Therefore determining PyOM mineralization rate, loss processes and possible induced priming effect on soil organic matter decomposition are key issues to understand the impact of PyOM on the carbon (C) cycle. We investigated the impact of PyOM on soil C budget by combining results from three independent studies: (i) a field study to investigate PyOM mineralization rate and the relative importance of PyOM loss processes, (ii) a PyOM and soil incubation experiment to correlate C and N mineralization rates, (iii) a review of the priming effect induced by PyOM on soil organic C. We employed 13C labelled pinewood-derived PyOM for the field experiment and 13C labelled ryegrass-derived PyOM in the incubation experiment to trace PyOM losses. In the field experiment it was observed that: (i) Pyrolysis process reduced pinewood decomposition by a factor of 60, (ii) leaching and translocation of fresh PyOM along the soil profile were negligible compared to losses as CO2. In the incubation experiment we found that ryegrass induced a two phase priming effect on native soil organic matter, with a positive priming effect followed by a negative priming effect phase, we also found that ryegrass-derived PyOM decomposition was much slower than pinewood one. The different decomposition rate results probably from the different aromaticity of the two PyOM together with the different set-up of the two experiments. Both the incubation experiment and the meta-analysis revealed that PyOM may induce a two-phase priming effect on native soil organic matter decomposition: positive on the short term and negative on the long term. The meta-analysis showed that that positive priming effect is induced mostly on the native soil organic matter on the short term and by PyOM characterised by a low C content. This result was not confirmed on the freshly added organic matter. We believe that the presence of a labile fraction in PyOM may induce positive priming effect on the short term by mean of co-metabolism. We conclude that PyOM chemical composition and feedstock play an important role in predicting PyOM mineralization rate, and that on the short term PyOM may induce a positive priming effect therefore decreasing the abatement potential of PyOM as a C-sink.

Evidence for Dual Binding Sites for 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) in Insect Sodium Channels*

PubMed Central

Du, Yuzhe; Nomura, Yoshiko; Zhorov, Boris S.; Dong, Ke

2016-01-01

1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), the first organochlorine insecticide, and pyrethroid insecticides are sodium channel agonists. Although the use of DDT is banned in most of the world due to its detrimental impact on the ecosystem, indoor residual spraying of DDT is still recommended for malaria control in Africa. Development of resistance to DDT and pyrethroids is a serious global obstacle for managing disease vectors. Mapping DDT binding sites is necessary for understanding mechanisms of resistance and modulation of sodium channels by structurally different ligands. The pioneering model of the housefly sodium channel visualized the first receptor for pyrethroids, PyR1, in the II/III domain interface and suggested that DDT binds within PyR1. Previously, we proposed the second pyrethroid receptor, PyR2, at the I/II domain interface. However, whether DDT binds to both pyrethroid receptor sites remains unknown. Here, using computational docking of DDT into the Kv1.2-based mosquito sodium channel model, we predict that two DDT molecules can bind simultaneously within PyR1 and PyR2. The bulky trichloromethyl group of each DDT molecule fits snugly between four helices in the bent domain interface, whereas two p-chlorophenyl rings extend into two wings of the interface. Model-driven mutagenesis and electrophysiological analysis confirmed these propositions and revealed 10 previously unknown DDT-sensing residues within PyR1 and PyR2. Our study proposes a dual DDT-receptor model and provides a structural background for rational development of new insecticides. PMID:26637352

Evidence for Dual Binding Sites for 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) in Insect Sodium Channels.

PubMed

Du, Yuzhe; Nomura, Yoshiko; Zhorov, Boris S; Dong, Ke

2016-02-26

1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), the first organochlorine insecticide, and pyrethroid insecticides are sodium channel agonists. Although the use of DDT is banned in most of the world due to its detrimental impact on the ecosystem, indoor residual spraying of DDT is still recommended for malaria control in Africa. Development of resistance to DDT and pyrethroids is a serious global obstacle for managing disease vectors. Mapping DDT binding sites is necessary for understanding mechanisms of resistance and modulation of sodium channels by structurally different ligands. The pioneering model of the housefly sodium channel visualized the first receptor for pyrethroids, PyR1, in the II/III domain interface and suggested that DDT binds within PyR1. Previously, we proposed the second pyrethroid receptor, PyR2, at the I/II domain interface. However, whether DDT binds to both pyrethroid receptor sites remains unknown. Here, using computational docking of DDT into the Kv1.2-based mosquito sodium channel model, we predict that two DDT molecules can bind simultaneously within PyR1 and PyR2. The bulky trichloromethyl group of each DDT molecule fits snugly between four helices in the bent domain interface, whereas two p-chlorophenyl rings extend into two wings of the interface. Model-driven mutagenesis and electrophysiological analysis confirmed these propositions and revealed 10 previously unknown DDT-sensing residues within PyR1 and PyR2. Our study proposes a dual DDT-receptor model and provides a structural background for rational development of new insecticides. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Trends in HIV testing, prevalence among first-time testers, and incidence in most-at-risk populations in Spain: the EPI-VIH Study, 2000 to 2009.

PubMed

Diez, M; Bleda, M J; Varela, J R; Ordonana, J; Azpiri, M A; Vall, M; Santos, C; Viloria, L; de Armas, C; Urena, J M; Trullen, J; Pueyo, I; Martinez, B; Puerta, T; Vera, M; Sanz, I; Junquera, M L; Landa, M C; Martinez, E; Camara, M M; Belda, J; Bru, F J; Diaz, A

2014-11-27

During 2000 to 2009, data on people undergoing HIV testing and on those newly diagnosed with HIV were collected in a network of 20 Spanish clinics specialising in sexually transmitted infections and/or HIV testing and counselling. The number of tests performed, overall and disaggregated by different variables, was obtained. HIV prevalence among first-time testers and HIV incidence among repeat testers were calculated. To evaluate trends, joinpoint regression models were fitted. In total, 236,939 HIV tests were performed for 165,745 individuals. Overall HIV prevalence among persons seeking HIV testing was 2.5% (95% CI: 2.4 to 2.6). Prevalence was highest in male sex workers who had sex with other men (19.0% (95% CI: 16.7 to 21.4)) and was lowest in female sex workers (0.8% (95% CI: 0.7 to 0.9)). Significant trends in prevalence were observed in men who have sex with men (MSM) (increasing) and heterosexual individuals (decreasing). The incidence analysis included 30,679 persons, 64,104 person-years (py) of follow-up and 642 seroconversions. The overall incidence rate (IR) was 1.0/100 py (95% CI: 0.9/100 to 1.1/100). Incidence was significantly higher in men and transgender females than in women (1.8/100 py (95% CI: 1.6 to 1.9), 1.2/100 py (95% CI: 0.5 to 2.8) and 0.1/100 py (95% CI: 0.09 to 0.2) respectively) and increased with age until 35–39 years. IRs in MSM and people who inject drugs were significantly greater than in heterosexual individuals (2.5/100 py (95% CI: 2.3 to 2.7), 1.6/100 py (95% CI: 1.1 to 2.2) and 0.1/100 py (95% CI: 0.09 to 0.2) respectively), and an upward trend was observed in MSM. Our results call for HIV prevention to be reinforced in MSM and transgender women in Spain.

Recognition of the 3′ splice site RNA by the U2AF heterodimer involves a dynamic population shift

PubMed Central

Voith von Voithenberg, Lena; Sánchez-Rico, Carolina; Kang, Hyun-Seo; Madl, Tobias; Zanier, Katia; Barth, Anders; Warner, Lisa R.; Sattler, Michael; Lamb, Don C.

2016-01-01

An essential early step in the assembly of human spliceosomes onto pre-mRNA involves the recognition of regulatory RNA cis elements in the 3′ splice site by the U2 auxiliary factor (U2AF). The large (U2AF65) and small (U2AF35) subunits of the U2AF heterodimer contact the polypyrimidine tract (Py-tract) and the AG-dinucleotide, respectively. The tandem RNA recognition motif domains (RRM1,2) of U2AF65 adopt closed/inactive and open/active conformations in the free form and when bound to bona fide Py-tract RNA ligands. To investigate the molecular mechanism and dynamics of 3′ splice site recognition by U2AF65 and the role of U2AF35 in the U2AF heterodimer, we have combined single-pair FRET and NMR experiments. In the absence of RNA, the RRM1,2 domain arrangement is highly dynamic on a submillisecond time scale, switching between closed and open conformations. The addition of Py-tract RNA ligands with increasing binding affinity (strength) gradually shifts the equilibrium toward an open conformation. Notably, the protein–RNA complex is rigid in the presence of a strong Py-tract but exhibits internal motion with weak Py-tracts. Surprisingly, the presence of U2AF35, whose UHM domain interacts with U2AF65 RRM1, increases the population of the open arrangement of U2AF65 RRM1,2 in the absence and presence of a weak Py-tract. These data indicate that the U2AF heterodimer promotes spliceosome assembly by a dynamic population shift toward the open conformation of U2AF65 to facilitate the recognition of weak Py-tracts at the 3′ splice site. The structure and RNA binding of the heterodimer was unaffected by cancer-linked myelodysplastic syndrome mutants. PMID:27799531

Synthesis, physical properties and self-assembly behavior of azole-fused pyrene derivatives

NASA Astrophysics Data System (ADS)

Xiao, Jinchong; Xiao, Xuyu; Zhao, Yanlei; Wu, Bo; Liu, Zhenying; Zhang, Xuemin; Wang, Sujuan; Zhao, Xiaohui; Liu, Lei; Jiang, Li

2013-05-01

A novel selenadiazole-fused pyrene derivative PySe was successfully synthesized and characterized. Its single structure is almost planar and adopts a sandwich-herringbone packing model. The self-assembly behaviors based on compound PySe and its analogue thiadiazole-fused pyrene derivative PyS were studied in detail and the as-formed nanostructures were fully characterized by means of UV-vis absorption, emission spectra, X-ray diffraction, field emission SEM and TEM. We attribute the bathochromic shift absorption and emission spectra of PyS and PySe in aqueous solution to the formation of J-type aggregation. In addition, our investigation demonstrated that the shape and size of the as-prepared nanostructures could be tuned by different chalcogen analogues and the volume ratio of water to organic solvent.A novel selenadiazole-fused pyrene derivative PySe was successfully synthesized and characterized. Its single structure is almost planar and adopts a sandwich-herringbone packing model. The self-assembly behaviors based on compound PySe and its analogue thiadiazole-fused pyrene derivative PyS were studied in detail and the as-formed nanostructures were fully characterized by means of UV-vis absorption, emission spectra, X-ray diffraction, field emission SEM and TEM. We attribute the bathochromic shift absorption and emission spectra of PyS and PySe in aqueous solution to the formation of J-type aggregation. In addition, our investigation demonstrated that the shape and size of the as-prepared nanostructures could be tuned by different chalcogen analogues and the volume ratio of water to organic solvent. Electronic supplementary information (ESI) available: TGA analysis, spectra characterization data for compound 1, 2, 3 and X-ray crystallographic data for compound PySe (2, CIF). CCDC 917821. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3nr00523b

Net clinical benefit of warfarin in individuals with atrial fibrillation across stroke risk and across primary and secondary care.

PubMed

Allan, Victoria; Banerjee, Amitava; Shah, Anoop Dinesh; Patel, Riyaz; Denaxas, Spiros; Casas, Juan-Pablo; Hemingway, Harry

2017-02-01

To investigate net clinical benefit (NCB) of warfarin in individuals with atrial fibrillation (AF) across stroke risk and across primary and secondary care. We conducted a linked electronic health record cohort study of 70 206 individuals with initial record of diagnosis of AF in primary (n=29 568) or secondary care (n=40 638) in England (1998-2010). We defined stroke risk according to the CHA 2 DS 2 -VASc score, and followed individuals over a median 2.2 years for 7005 ischaemic strokes (IS) and for 906 haemorrhagic strokes (HS). We calculated incidence rates (IRs) and 95% CIs per 100 person-years (PYs) (IR (95% CI)/100 PY) of IS and HS, with and without use of warfarin, and the NCB (ie, number of IS avoided) per 100 PYs of warfarin use (NCB (95% CI)/100 PY). Compared with individuals with initial record of diagnosis in secondary care, those in primary care had lower scores of IS risk (CHA 2 DS 2 -VASc≤2: 30.8% vs 20.6%), and lower overall incidence of IS (IR (95% CI)/100 PY: 2.3 (2.2 to 2.4) vs 4.3 (4.2 to 4.4), p value=0.00); however among individuals with CHA 2 DS 2 -VASc=0, 1 or 2 there were no differences in IS rate between those with initial record of diagnosis in primary care or secondary care (IR (95% CI)/100 PY: 0.2 (0.1 to 0.3) vs 0.3 (0.2 to 0.5), p value=0.16), (IR (95% CI)/100 PY: 0.6 (0.4 to 0.7) vs 0.7 (0.6 to 0.9), p value=0.08) and (IR (95% CI)/100 PY: 1.1 (1.00 to 1.3) vs 1.4 (1.2 to 1.6), p value=0.05), respectively. For CHA 2 DS 2 -VASc=0, 1 and 2, IRs of IS with versus without warfarin were (IR (95% CI)/100 PY: 0.4 (0.2 to 0.8) vs 0.2 (0.1 to 0.3), p value=0.16), (IR (95% CI)/100 PY: 0.4 (0.3 to 0.7) vs 0.7 (0.6 to 0.8), p value=0.03) and (IR (95% CI)/100 PY: 0.8 (0.7 to 1.0) vs 1.4 (1.3 to 1.6), p value=0.00), respectively. We found a significant positive NCB of warfarin from CHA 2 DS 2 -VASc≥2 in men (NCB (95% CI)/100 PY: 0.5 (0.1 to 0.9)) and from CHA 2 DS 2 -VASc≥3 in women (NCB (95% CI)/100 PY: 1.5 (1.1 to 1.9)). CHA 2 DS 2 -VASc accurately stratifies IS risk in individuals with AF across both primary and secondary care. However, the incidence rate of ischaemic stroke at CHA 2 DS 2 -VASc=1 are lower than previously reported, which may change the decision to start anticoagulation with warfarin in these individuals. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Net clinical benefit of warfarin in individuals with atrial fibrillation across stroke risk and across primary and secondary care

PubMed Central

Banerjee, Amitava; Shah, Anoop Dinesh; Patel, Riyaz; Denaxas, Spiros; Casas, Juan-Pablo; Hemingway, Harry

2017-01-01

Objective To investigate net clinical benefit (NCB) of warfarin in individuals with atrial fibrillation (AF) across stroke risk and across primary and secondary care. Methods We conducted a linked electronic health record cohort study of 70 206 individuals with initial record of diagnosis of AF in primary (n=29 568) or secondary care (n=40 638) in England (1998–2010). We defined stroke risk according to the CHA2DS2-VASc score, and followed individuals over a median 2.2 years for 7005 ischaemic strokes (IS) and for 906 haemorrhagic strokes (HS). We calculated incidence rates (IRs) and 95% CIs per 100 person-years (PYs) (IR (95% CI)/100 PY) of IS and HS, with and without use of warfarin, and the NCB (ie, number of IS avoided) per 100 PYs of warfarin use (NCB (95% CI)/100 PY). Results Compared with individuals with initial record of diagnosis in secondary care, those in primary care had lower scores of IS risk (CHA2DS2-VASc≤2: 30.8% vs 20.6%), and lower overall incidence of IS (IR (95% CI)/100 PY: 2.3 (2.2 to 2.4) vs 4.3 (4.2 to 4.4), p value=0.00); however among individuals with CHA2DS2-VASc=0, 1 or 2 there were no differences in IS rate between those with initial record of diagnosis in primary care or secondary care (IR (95% CI)/100 PY: 0.2 (0.1 to 0.3) vs 0.3 (0.2 to 0.5), p value=0.16), (IR (95% CI)/100 PY: 0.6 (0.4 to 0.7) vs 0.7 (0.6 to 0.9), p value=0.08) and (IR (95% CI)/100 PY: 1.1 (1.00 to 1.3) vs 1.4 (1.2 to 1.6), p value=0.05), respectively. For CHA2DS2-VASc=0, 1 and 2, IRs of IS with versus without warfarin were (IR (95% CI)/100 PY: 0.4 (0.2 to 0.8) vs 0.2 (0.1 to 0.3), p value=0.16), (IR (95% CI)/100 PY: 0.4 (0.3 to 0.7) vs 0.7 (0.6 to 0.8), p value=0.03) and (IR (95% CI)/100 PY: 0.8 (0.7 to 1.0) vs 1.4 (1.3 to 1.6), p value=0.00), respectively. We found a significant positive NCB of warfarin from CHA2DS2-VASc≥2 in men (NCB (95% CI)/100 PY: 0.5 (0.1 to 0.9)) and from CHA2DS2-VASc≥3 in women (NCB (95% CI)/100 PY: 1.5 (1.1 to 1.9)). Conclusions CHA2DS2-VASc accurately stratifies IS risk in individuals with AF across both primary and secondary care. However, the incidence rate of ischaemic stroke at CHA2DS2-VASc=1 are lower than previously reported, which may change the decision to start anticoagulation with warfarin in these individuals. PMID:27580623

Effect of deuteration on hydrogen bonding: A comparative concentration dependent Raman and DFT study of pyridine in CH3OH and CD3OD and pyrimidine in H2O and D2O

NASA Astrophysics Data System (ADS)

Singh, Anurag; Gangopadhyay, Debraj; Popp, Jürgen; Singh, Ranjan K.

2012-12-01

The relative effect of hydrogen bonding of pyrimidine (Pyr) in H2O/D2O and pyridine (Py) in CH3OH/CD3OD has been analyzed using Raman Difference Spectroscopic (RDS) technique and DFT calculations. This study is focused on analyzing the concentration dependent variation of linewidth, peak position and intensity of ring breathing mode of Py and Pyr. The ring breathing mode of Pyr in H2O and D2O has three components; due to free Pyr, lighter complexes of mPyr + nH2O/D2O and heavier complexes of mPyr + nH2O/D2O. The pyridine molecules, however, show only two components in CH3OH and CD3OD. Of these two components, one corresponds to free Py and the other inhomogeneously broadened profile corresponds to all mPy + nCH3OH/CD3OD complexes. The variation of peak position and linewidth establishes the role of dipole moment of complexes and the diffusion in the mixture. In case of CD3OD solution splitting was observed in ˜1030 cm-1 band of Py, where an additional band at ˜1034 cm-1 appears at x(Py) ⩽ 0.4. However, this band remains single at all concentrations in case of CH3OH solvent.

Synthesis and structural analysis of tungsten-carbonyl dimers bridged with oligo(2,5-dialkoxy-1,4-phenylene vinylene)s through pyridine coordination.

PubMed

Yorsaeng, Sakkawet; Tsutsumi, Ken; Kitiyanan, Boonyarach; Nomura, Kotohiro

2015-10-14

Tungsten carbonyl dimers bridged with oligo(2,5-dialkoxy-1,4-phenylene vinylene)s through coordination with pyridine as the end groups, expressed as [W(CO)5]2-(nPV-Py2) [n = 1, 3; alkoxy = O(CH2)2OSi(i)Pr3], have been prepared from W(CO)5(THF) with nPV-Py2 in THF, and their structures were determined by X-ray crystallography. Both increase in absorbance and redshift in the λmax values in [W(CO)5]2-(nPV-Py2) from their nPV-Py2 were observed in the UV-vis spectra, due to increase in the conjugation length through tungsten by coordination of the pyridine moiety; an extension of the conjugation was also confirmed by the crystallographic analysis as well as fluorescence spectra.

SpiceyPy, a Python Wrapper for SPICE

NASA Astrophysics Data System (ADS)

Annex, A.

2017-06-01

SpiceyPy is an open source Python wrapper for the NAIF SPICE toolkit. It is available for macOS, Linux, and Windows platforms and for Python versions 2.7.x and 3.x as well as Anaconda. SpiceyPy can be installed by running: “pip install spiceypy.”

Reductive dehalogenation of chlorophenols by Desulfomonile tiedjei DCB-1.

PubMed Central

Mohn, W W; Kennedy, K J

1992-01-01

Reductive dehalogenation of chlorophenols has been reported in undefined anaerobic cultures but never before in an anaerobic pure culture. We found that the sulfate-reducing bacterium Desulfomonile tiedjei DCB-1 reductively dehalogenates pentachlorophenol (PCP) and other chlorophenols. The maximum rate of PCP dechlorination observed was 54 mu mol of Cl- h-1 g of protein-1. 3-Chlorobenzoate appeared to serve as a required inducer for PCP dehalogenation; however, neither PCP nor 3-chlorophenol induced dehalogenation. Dehalogenation was catalyzed by living cells, and formate served as a required electron donor. D. tiedjei dehalogenated meta-chlorine substituents of chlorophenols (i.e., PCP was degraded to 2,4,6-trichlorophenol). Generally, more highly chlorinated phenol congeners were more readily dechlorinated, and 3-chlorophenol was not dehalogenated. Growing cultures dehalogenated PCP, but greater than 10 microM PCP (approximately 1.7 mmol g of protein-1) reversibly inhibited growth. PMID:1599254

Structure-Property Study on Two New D-A Type Materials Comprising Pyridazine Moiety and the OLED Application as Host.

PubMed

Liu, Shaojie; Zhang, Xunlu; Ou, Changjin; Wang, Shulei; Yang, Xinli; Zhou, Xinhui; Mi, Baoxiu; Cao, Dapeng; Gao, Zhiqiang

2017-08-09

In this paper, two new pyridazine based donor-acceptor type materials, i.e., 3CzPyaPy: 9,9'-(3-(6-(9H-carbazol-9-yl)pyridazin-3-yl)pyridine-2,6-diyl)bis(9H-carbazole) and 4CzPyPyaPy: 3,6-bis(2,6-di(9H-carbazol-9-yl)pyridin-3-yl)pyridazine, were synthesized with high yields. These two materials exhibited strong absorption/emission with high molar extinction coefficients and moderate photoluminescence quantum yield. The glass transition temperature of 3CzPyaPy was detected to be as high as 131 °C, showing its high thermal stability. Although the absorption energies and oxidation/reduction behaviors of the two materials were similar, the emission from 4CzPyPyaPy with longer effective-conjugation length presented hypsochromic shift both in films and in dilute solutions, contradicting to the common sense. The single crystal structure study disclosed their different space stretching and packing: 3CzPyaPy was twisted in larger angles and adopted dimerlike packing, while 4CzPyPyaPy showed smaller torsion angles and exhibited slipped herringbone packing. The dimerlike packing in 3CzPyaPy is responsible for its bathochromic shift of emission in solid state, while its unsymmetrical molecular structure accounts for that in solution. We believe that the unsymmetrical molecular structure of 3CzPyaPy is partially responsible for its high thermal-stability and also responsible for its HOMO dispersion which renders it slightly more difficult to oxidize. 3CzPyaPy was proved to be a bipolar-transport material and when served as a phosphor host, a green phosphorescent device achieved maximum efficiencies of 54.0 cd A -1 , 42.4 lm W -1 , and 17.7%, which are among the best with nonoptimized device structure, demonstrating its great potential for optoelectronic application. Furthermore, the new synthesized pyridazine derivatives and the corresponding structural and molecular-packing influences on material properties give a new insight into molecule tailoring.

General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides.

PubMed

Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Xiang, Jing; Wong, Tsz-Wing; Lam, Wing-Hong; Wong, Wing-Tak; Peng, Shie-Ming; Lau, Tai-Chu

2008-07-07

Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.

NMR spectroscopic study of the carbon and nitrogen dynamics of grass-derived pyrogenic organic material during 2.3 years of incubation in soil

NASA Astrophysics Data System (ADS)

Hilscher, André; Knicker, Heike

2010-05-01

Incomplete combustion of vegetation results in pyrogenic organic material (PyOM) which occurs ubiquitously in soils and sediments. To understand the C sequestration potential of PyOM in environmental systems knowledge is required about the respective degradation and humification mechanisms and the stability of the different chemical PyOM structures. The present study focuses on the microbial recalcitrance of PyOM on molecular scale. Therefore, microcosms incubation experiments were performed using PyOM produced from highly isotopically enriched 13C and 15N rye grass (Lolium perenne) at 350°C under oxic conditions for one (1M) and four minutes (4M). Solid-state CPMAS 13C and 15N NMR studies were accomplished to obtain insights into the involved humification mechanisms at different stages the PyOM degradation. In total up to 38% of the bulk PyOM C was mineralised during the 28 months of incubation. The O/N-alkyl C and alkyl C residues which survived the charring process were effectively decomposed. At the end of the incubation up to 73% and 57% of the initial O/N-alkyl C and alkyl C amount were mineralised or converted to other C groups, respectively. The total aryl C group recovery of the PyOM decreased significantly during the 28 months of incubation (P ≤ 0.001). After 20 months of incubation between 26% and 40% of the initial aryl C amount was lost. For this group, relative short half time periods in the range of 3.0 and 3.8 years were obtained. The observed loss of aromatic C structures may be attributed to two simultaneous processes, the mineralisation to CO2 and the conversion to other C groups by partial oxidation. The presence of a readily decomposable co-substrate showed no significant changes in the degradation pattern of the different PyOM, possibly because decomposable sources were already available in the starting PyOM. Most of the organic bound N of the fresh PyOM was assignable to heterocyclic aromatic compounds such as pyrrole and indole-like structures with contributions of 62% and 72% for PyOM 1M and PyOM 4M, respectively. The other part of the 15N NMR signal intensity was assignable to amide-like structures. No major alteration of the amide and heterocyclic N contribution was detected for the PyOM 1M incubates. For the more charred PyOM 4M, the relative heterocyclic N contribution decreased. After the 28 months of incubation no significant difference in the chemical N composition of PyOM 4M related to the PyOM 1M treatments could be observed (P=0.472). Further, we detect a continuous degrease of the total amounts for the amide and heterocyclic N compounds. After 20 months, only 49% to 59% of the heterocyclic N compounds were recovered. The respective amide N recoveries were larger with 59% to 87%. It can be concluded, that PyOM may not be as highly refractory as it is commonly assumed. During the efficient degradation not only a considerable PyOM amount is mineralised, but also the chemical structure of the remaining PyOM is strongly modified. This includes the formation of O-containing functional groups and the loss of aromatic C and N containing heterocyclic domains by mineralisation and conversion to other C and N groups.

Radioprotective effect of a metalloporphyrin compound in rat eye model.

PubMed

Mao, X W; Crapo, J D; Mekonnen, T; Lindsey, N; Martinez, P; Gridley, D S; Slater, J M

2009-01-01

The purpose of this study was to evaluate the efficacy of the antioxidant Mn (III) tetrakis (N-ethylpyridinium-2-yl) porphyrin (MnTE-2-PyP) in protecting ocular tissue and retinal microvasculature from radiation damage. 75 rats were treated with Mn TE-2-PyP at 2.5 micro g/injection into one eye an hour before proton irradiation. The radiation was delivered in a single fraction to total doses of 8 Gray (Gy) or 28 Gy; Rats were sacrificed 3 days and 3, 6, 9, and 12 months thereafter for histology and quantification of photoreceptor cell populations and retinal capillary changes. By 6 months following radiation, there was significant loss of retinal outer and inner nuclear layers in eyes receiving radiation only (8 and 28 Gy) (p < 0.05) compared to their controls and to the eyes of rats treated with radiation plus metalloporphyrin. Retinal microvessel length density decreased significantly 6 months following 28 Gy (p < 0.05) compared to their controls and to MnTE-2-PyP treated rats. By 12 months following irradiation, irradiated eyes showed extensive damage to the photoreceptor layer, whereas the eyes of animals receiving radiation plus MnTE-2-PyP showed almost no morphological damage. MnTE-2-PyP treatment also suppressed radiation-induced apoptosis in our study. These results demonstrated that MnTE-2-PyP protected both photoreceptors and retinal capillaries from radiation damage, suggesting that this metalloporphyrin antioxidant is effective in regulating the damage induced by proton radiation.

Effect of lipophilicity of Mn (III) ortho N-alkylpyridyl- and diortho N, N'-diethylimidazolylporphyrins in two in-vitro models of oxygen and glucose deprivation-induced neuronal death.

PubMed

Wise-Faberowski, Lisa; Warner, David S; Spasojevic, Ivan; Batinic-Haberle, Ines

2009-04-01

In vivo investigations have confirmed the beneficial effects of hydrophilic, cationic Mn(III) porphyrin-based catalytic antioxidants in different models of oxidative stress. Using a cell culture model of rat mixed neuronal/glial cells, this study investigated the effect of MnTnOct-2-PyP5+ on oxygen and glucose deprivation (OGD)-induced cell death as compared to the effects of widely studied hydrophilic analogues MnTE-2-PyP5+ and MnTDE-2-ImP5+ and a standard compound, dizocilpine (MK-801). It was hypothesized that the octylpyridylporphyrin, MnTnOct-2-PyP5+, a lipophilic but equally potent antioxidant as the other two porphyrins, would be more efficacious in reducing OGD-induced cell death due to its higher bioavailability. Cell death was evaluated at 24 h using lactate dehydrogenase (LDH) release and propidium iodide staining. At concentrations from 3-100 microM, all three porphyrins reduced cell death as compared to cultures exposed to OGD alone, the effects depending upon the concentrations and type of treatment. To assess the effect of lipophilicity the additional experiments were performed using submicromolar concentrations of MnTnOct-2-PyP5+ in an organotypic hippocampal slice model of OGD with propidium iodide and Sytox staining. When compared to oxygen and glucose deprivation alone, concentrations of MnTnOct-2-PyP5+ as low as 0.01 microM significantly (p<0.001; power 1.0) reduced neuronal cells similar to control. This is the first in vitro study on the mammalian cells which indicates that MnTnOct-2-PyP5+ is up to 3000-fold more efficacious than equally potent hydrophilic analogues, due entirely to its increased bioavailability. Such remarkable increase in efficacy parallels 5.7-orders of magnitude increase in lipophilicity of MnTnOct-2-PyP5+ (log P=-0.77) when compared to MnTE-2-PyP5+ (log POW=-6.43), POW being partition coefficient between n-octanol and water.

Mechanistic Investigation of Catalyst-Transfer Suzuki-Miyaura Condensation Polymerization of Thiophene-Pyridine Biaryl Monomers with the Aid of Model Reactions.

PubMed

Tokita, Yu; Katoh, Masaru; Ohta, Yoshihiro; Yokozawa, Tsutomu

2016-11-21

We have investigated the requirements for efficient Pd-catalyzed Suzuki-Miyaura catalyst-transfer condensation polymerization (Pd-CTCP) reactions of 2-alkoxypropyl-6-(5-bromothiophen-2-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (12) as a donor-acceptor (D-A) biaryl monomer. As model reactions, we first carried out the Suzuki-Miyaura coupling reaction of X-Py-Th-X' (Th=thiophene, Py=pyridine, X, X'=Br or I) 1 with phenylboronic acid ester 2 by using tBu 3 PPd 0 as the catalyst. Monosubstitution with a phenyl group at Th-I mainly took place in the reaction of Br-Py-Th-I (1 b) with 2, whereas disubstitution selectively occurred in the reaction of I-Py-Th-Br (1 c) with 2, indicating that the Pd catalyst is intramolecularly transferred from acceptor Py to donor Th. Therefore, we synthesized monomer 12 by introduction of a boronate moiety and bromine into Py and Th, respectively. However, examination of the relationship between monomer conversion and the M n of the obtained polymer, as well as the matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectra, indicated that Suzuki-Miyaura coupling polymerization of 12 with (o-tolyl)tBu 3 PPdBr initiator 13 proceeded in a step-growth polymerization manner through intermolecular transfer of the Pd catalyst. To understand the discrepancy between the model reactions and polymerization reaction, Suzuki-Miyaura coupling reactions of 1 c with thiopheneboronic acid ester instead of 2 were carried out. This resulted in a decrease of the disubstitution product. Therefore, step-growth polymerization appears to be due to intermolecular transfer of the Pd catalyst from Th after reductive elimination of the Th-Pd-Py complex formed by transmetalation of polymer Th-Br with (Pin)B-Py-Th-Br monomer 12 (Pin=pinacol). Catalysts with similar stabilization energies of metal-arene η 2 -coordination for D and A monomers may be needed for CTCP reactions of biaryl D-A monomers. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular recognition of DNA base pairs by the formamido/pyrrole and formamido/imidazole pairings in stacked polyamides.

PubMed

Buchmueller, Karen L; Staples, Andrew M; Uthe, Peter B; Howard, Cameron M; Pacheco, Kimberly A O; Cox, Kari K; Henry, James A; Bailey, Suzanna L; Horick, Sarah M; Nguyen, Binh; Wilson, W David; Lee, Moses

2005-01-01

Polyamides containing an N-terminal formamido (f) group bind to the minor groove of DNA as staggered, antiparallel dimers in a sequence-specific manner. The formamido group increases the affinity and binding site size, and it promotes the molecules to stack in a staggered fashion thereby pairing itself with either a pyrrole (Py) or an imidazole (Im). There has not been a systematic study on the DNA recognition properties of the f/Py and f/Im terminal pairings. These pairings were analyzed here in the context of f-ImPyPy, f-ImPyIm, f-PyPyPy and f-PyPyIm, which contain the central pairing modes, -ImPy- and -PyPy-. The specificity of these triamides towards symmetrical recognition sites allowed for the f/Py and f/Im terminal pairings to be directly compared by SPR, CD and DeltaT (M) experiments. The f/Py pairing, when placed next to the -ImPy- or -PyPy- central pairings, prefers A/T and T/A base pairs to G/C base pairs, suggesting that f/Py has similar DNA recognition specificity to Py/Py. With -ImPy- central pairings, f/Im prefers C/G base pairs (>10 times) to the other Watson-Crick base pairs; therefore, f/Im behaves like the Py/Im pair. However, the f/Im pairing is not selective for the C/G base pair when placed next to the -PyPy- central pairings.

Ionic liquid-in-oil microemulsions composed of double chain surface active ionic liquid as a surfactant: temperature dependent solvent and rotational relaxation dynamics of coumarin-153 in [Py][TF2N]/[C4mim][AOT]/benzene microemulsions.

PubMed

Rao, Vishal Govind; Mandal, Sarthak; Ghosh, Surajit; Banerjee, Chiranjib; Sarkar, Nilmoni

2012-07-19

In the recent past, nonaqueous microemulsions containing ionic liquids (ILs) have been utilized for performing chemical reactions, preparation of nanomaterials, and synthesis of nanostructured polymers and in drug delivery systems. The most promising fact about IL-in-oil microemulsions is their high thermal stability compared to that of aqueous microemulsions. In our earlier publication (Rao, V. G.; Ghosh, S.; Ghatak, C.; Mandal, S.; Brahmachari, U.; Sarkar, N. J. Phys. Chem. B 2012, 116, 2850-2855), we presented for the first time the possibility of creating huge number of IL-in-oil microemulsions, just by replacing the inorganic cation, Na(+), of NaAOT by any organic cation and using different ionic liquids as the polar core. In this manuscript we are interested in exploring the effect of temperature on such systems. We have characterized the phase diagram of the [Py][TF2N]/[C4mim][AOT]/benzene ternary system at 298 K. We have shown that in the experimental temperature range employed in this study, the microemulsions remain stable and a slight decrease in the size of the microemulsions is observed with increasing temperature. We have reported the detailed study of solvent and rotational relaxation of coumarin 153 (C-153) in neat IL, N-methyl-N-propylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide ([Py][TF2N]), and in [Py][TF2N]/[C4mim][AOT]/benzene microemulsions using steady state and picosecond time-resolved spectroscopy. We have monitored the effect of (i) varying the [Py][TF2N]/[C4mim][AOT] molar ratio (R value) and (ii) temperature on solvent and rotational relaxation of C-153. The features observed in absorption and emission spectra clearly indicate that (i) the probe molecules reside at the polar interfacial region of the [Py][TF2N]/[C4mim][AOT]/benzene microemulsions and (ii) with increasing R value the probe molecules move toward the polar IL-pool of the microemulsion. We have shown that the increase in solvation time on going from neat [Py][TF2N] to [Py][TF2N]-containing microemulsions is very small compared to the increase in solvation time on going from pure water to water-containing microemulsions. The average solvation time decreases with increasing R values at 298 K, but it shows only a small R dependence compared to microemulsions containing solvents capable of forming hydrogen bonds. We have also shown that the temperature has substantial effect on the solvent and rotational relaxation of C-153 in neat [Py][TF2N] compared to that of [Py][TF2N]/[C4mim][AOT]/benzene microemulsions at R = 0.69.

Iridium N-Heterocyclic Carbene Complexes as Efficient Catalysts for Magnetization Transfer from para-Hydrogen

PubMed Central

2011-01-01

While the characterization of materials by NMR is hugely important in the physical and biological sciences, it also plays a vital role in medical imaging. This success is all the more impressive because of the inherently low sensitivity of the method. We establish here that [Ir(H)2(IMes)(py)3]Cl undergoes both pyridine (py) loss as well as the reductive elimination of H2. These reversible processes bring para-H2 and py into contact in a magnetically coupled environment, delivering an 8100-fold increase in 1H NMR signal strength relative to non-hyperpolarized py at 3 T. An apparatus that facilitates signal averaging has been built to demonstrate that the efficiency of this process is controlled by the strength of the magnetic field experienced by the complex during the magnetization transfer step. Thermodynamic and kinetic data combined with DFT calculations reveal the involvement of [Ir(H)2(η2-H2)(IMes)(py)2]+, an unlikely yet key intermediate in the reaction. Deuterium labeling yields an additional 60% improvement in signal, an observation that offers insight into strategies for optimizing this approach. PMID:21469642

Iridium N-heterocyclic carbene complexes as efficient catalysts for magnetization transfer from para-hydrogen.

PubMed

Cowley, Michael J; Adams, Ralph W; Atkinson, Kevin D; Cockett, Martin C R; Duckett, Simon B; Green, Gary G R; Lohman, Joost A B; Kerssebaum, Rainer; Kilgour, David; Mewis, Ryan E

2011-04-27

While the characterization of materials by NMR is hugely important in the physical and biological sciences, it also plays a vital role in medical imaging. This success is all the more impressive because of the inherently low sensitivity of the method. We establish here that [Ir(H)(2)(IMes)(py)(3)]Cl undergoes both pyridine (py) loss as well as the reductive elimination of H(2). These reversible processes bring para-H(2) and py into contact in a magnetically coupled environment, delivering an 8100-fold increase in (1)H NMR signal strength relative to non-hyperpolarized py at 3 T. An apparatus that facilitates signal averaging has been built to demonstrate that the efficiency of this process is controlled by the strength of the magnetic field experienced by the complex during the magnetization transfer step. Thermodynamic and kinetic data combined with DFT calculations reveal the involvement of [Ir(H)(2)(η(2)-H(2))(IMes)(py)(2)](+), an unlikely yet key intermediate in the reaction. Deuterium labeling yields an additional 60% improvement in signal, an observation that offers insight into strategies for optimizing this approach.

Identification of Two Novel Members of the Tentative Genus Wukipolyomavirus in Wild Rodents

PubMed Central

Nainys, Juozas; Timinskas, Albertas; Schneider, Julia; Ulrich, Rainer G.; Gedvilaite, Alma

2015-01-01

Two novel polyomaviruses (PyVs) were identified in kidney and chest-cavity fluid samples of wild bank voles (Myodes glareolus) and common voles (Microtus arvalis) collected in Germany. All cloned and sequenced genomes had the typical PyV genome organization, including putative open reading frames for early regulatory proteins large T antigen and small T antigen on one strand and for structural late proteins (VP1, VP2 and VP3) on the other strand. Virus-like particles (VLPs) were generated by yeast expression of the VP1 protein of both PyVs. VLP-based ELISA and large T-antigen sequence-targeted polymerase-chain reaction investigations demonstrated signs of infection of these novel PyVs in about 42% of bank voles and 18% of common voles. In most cases only viral DNA, but not VP1-specific antibodies were detected. In additional animals exclusively VP1-specific antibodies, but no viral DNA was detected, indicative for virus clearance. Phylogenetic and clustering analysis including all known PyV genomes placed novel bank vole and common vole PyVs amongst members of the tentative Wukipolymavirus genus. The other known four rodent PyVs, Murine PyV and Hamster PyV, and Murine pneumotropic virus and Mastomys PyV belong to different phylogenetic clades, tentatively named Orthopolyomavirus I and Orthopolyomavirus II, respectively. In conclusion, the finding of novel vole-borne PyVs may suggest an evolutionary origin of ancient wukipolyomaviruses in rodents and may offer the possibility to develop a vole-based animal model for human wukipolyomaviruses. PMID:26474048

Systematic review with meta-analysis: the declining risk of colorectal cancer in ulcerative colitis.

PubMed

Castaño-Milla, C; Chaparro, M; Gisbert, J P

2014-04-01

Patients with ulcerative colitis (UC) have an increased risk of developing colorectal cancer (CRC); however, the magnitude of this effect is open to debate. To assess the risk of CRC in UC patients by systematic review and meta-analysis. A systematic literature search was performed up to November 2013. We selected studies describing the incidence and prevalence of CRC in patients with UC. Articles were assessed for quality using the Newcastle-Ottawa Scale. Cumulative incidence and incidence rates of CRC were combined and analysed using the generic inverse variance method. Sub-analyses were performed to identify factors associated with an increased risk of developing CRC. A total of 81 studies (181 923 patients) met the inclusion criteria. The incidence rate of CRC in patients with UC was 1.58 per 1000 patient-years (py) [95% confidence interval (CI), 1.39–1.76]. Results were heterogeneous (I2 = 81–89%). The incidence rate was 4.02/1000 py (95%CI = 2.74–5.31) in studies that only included patients with extensive colitis, and 1.24/1000 py (95%CI = 1.01–1.47) in population-based studies. The incidence rate was 0.91/1000 py (95%CI = 0.61–1.2) in the first decade of disease, 4.07/1000 py (95%CI = 2.58–5.56) in the second, and 4.55/1000 py (95%CI = 2.64–6.46) in the third. The incidence rate decreased from 4.29/1000 py in the studies published in the 1950s to 1.21/1000 py in studies published in the last decade. The risk of patients with ulcerative colitis developing colorectal cancer has decreased steadily over the last six decades, but the extent and duration of the disease increase this risk.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Lipophilicity of potent porphyrin-based antioxidants. Comparison of ortho and meta isomers of Mn(III) N-alkylpyridylporphyrins

PubMed Central

Kos, Ivan; Rebouças, Júlio S.; DeFreitas-Silva, Gilson; Salvemini, Daniela; Vujaskovic, Zeljko; Dewhirst, Mark W.; Spasojevic, Ivan; Batinic-Haberle, Ines

2009-01-01

Mn(III) N-alkylpyridylporphyrins are among the most potent known SOD mimics and catalytic peroxynitrite scavengers, and modulators of redox-based cellular transcriptional activity. In addition to their intrinsic antioxidant capacity, bioavailability plays major role in their in vivo efficacy. While of identical antioxidant capacity, lipophilic MnTnHex-2-PyP is up to 120-fold more efficient in reducing oxidative stress injuries than hydrophilic MnTE-2-PyP. Due to limitations of analytical nature, porphyrin lipophilicity has been often estimated by thin-layer chromatographic Rf parameter, instead of the standard n-octanol/water partition coefficient, POW. Herein we used a new methodological approach to finally describe the MnP lipophilicity, by the conventional log POW means, for a series of biologically active ortho and meta isomers of Mn(III) N-alkylpyridylporphyrins. Three new porphyrins (MnTnBu-3-PyP, MnTnHex-3-PyP and MnTnHep-2-PyP) were synthesized to strengthen the conclusions. The log POW was linearly related to Rf and to the number of carbons in the alkyl chain (nC) for both isomer series; the meta isomers being 10-fold more lipophilic than the analogous ortho porphyrins. Increasing the length of the alkyl chain for 1 carbon atom increases the log POW value ~ 1 log unit with both isomers. Dramatic ~4 and ~5 orders of magnitude increase in lipophilicity of ortho isomers by extending pyridyl alkyl chains from 2 (MnTE-2-PyP, log POW = −6.25) to 6 (MnTnHex-2-PyP, log POW = −2.29) and 8 carbon atoms (MnTnOct-2-PyP, log POW = −0.77) parallels the increased efficacy in several oxidative-stress injury models, particularly those of the central nervous system where transport across the blood-brain barrier is critical. Although meta isomers are only slightly less potent SOD mimics and antioxidants than their ortho analogues, their higher lipophilicity and smaller bulkiness may lead to a higher cellular uptake and overall similar effectiveness in vivo. PMID:19361553

Molecules Designed to Contain Two Weakly Coupled Spins with a Photoswitchable Spacer.

PubMed

Uber, Jorge Salinas; Estrader, Marta; Garcia, Jordi; Lloyd-Williams, Paul; Sadurní, Anna; Dengler, Dominik; van Slageren, Joris; Chilton, Nicholas F; Roubeau, Olivier; Teat, Simon J; Ribas-Ariño, Jordi; Aromí, Guillem

2017-10-04

Controlling the charges and spins of molecules lies at the heart of spintronics. A photoswitchable molecule consisting of two independent spins separated by a photoswitchable moiety was designed in the form of new ligand H 4 L, which features a dithienylethene photochromic unit and two lateral coordinating moieties, and yields molecules with [MM⋅⋅⋅MM] topology. Compounds [M 4 L 2 (py) 6 ] (M=Cu, 1; Co, 2; Ni, 3; Zn, 4) were prepared and studied by single-crystal X-ray diffraction (SCXRD). Different metal centers can be selectively distributed among the two chemically distinct sites of the ligand, and this enables the preparation of many double-spin systems. Heterometallic [MM'⋅⋅⋅M'M] analogues with formulas [Cu 2 Ni 2 L 2 (py) 6 ] (5), [Co 2 Ni 2 L 2 (py) 6 ] (6), [Co 2 Cu 2 L 2 (py) 6 ] (7), [Cu 2 Zn 2 L 2 (py) 6 ] (8), and [Ni 2 Zn 2 L 2 (py) 6 ] (9) were prepared and analyzed by SCXRD. Their composition was established unambiguously. All complexes exhibit two weakly interacting [MM'] moieties, some of which embody two-level quantum systems. Compounds 5 and 8 each exhibit a pair of weakly coupled S=1/2 spins that show quantum coherence in pulsed Q-band EPR spectroscopy, as required for quantum computing, with good phase memory times (T M =3.59 and 6.03 μs at 7 K). Reversible photoswitching of all the molecules was confirmed in solution. DFT calculations on 5 indicate that the interaction between the two spins of the molecule can be switched on and off on photocyclization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Landform Position and Combustion Temperature as Controls of Decomposition of Pyrogenic Organic Matter

NASA Astrophysics Data System (ADS)

Abney, R.; Berhe, A. A.

2016-12-01

Pyrogenic organic matter (PyOM) is the material left behind after incomplete combustion, which includes a spectrum of materials ranging from ash to charred biomass. Early research on PyOM assumed that it served as an inert carbon (C) pool within the soil. However, recent research has demonstrated that the decomposition of PyOM occurs on much shorter time scales. Even so, PyOM can serve as a C sink within the soil, and it can alter many soil properties. This study investigates the roles of both combustion temperature and landform position on decomposition of PyOM. Bark from Pinus jeffreyi was charred at three temperatures (200ºC, 350ºC, and 500ºC) to create PyOM, and this PyOM was incorporated into soil from two landform positions (eroding hillslope and deposition). Many recent studies on the decomposition of PyOM have utilized wood or agricultural byproducts as source material for PyOM, however bark experiences much of the effects of combustion, and it has received little to no research attention. Decomposition was measured via CO2 production from the soil and bark PyOM mixtures over an incubation period of six months. Microbial biomass was also measured throughout the incubation. The soil and PyOM mixtures were analyzed for elemental C and nitrogen, along with their stable isotopes, immediately after each gas measurement. We expect that the bark charred at higher temperatures will decompose slower than the bark charred at lower temperatures. We also expect that the bark incorporated into the depositional soil will decompose faster than the bark incorporated into the eroding soil. Several studies have already illustrated that landform position plays a critical role in controlling C storage and organic matter breakdown, however this has yet to be investigated with PyOM. Understanding the controls on PyOM breakdown is critical for better managing soils and the global C cycle.

Metal-organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln4(OH)4] building units

NASA Astrophysics Data System (ADS)

Abdelbaky, Mohammed S. M.; Amghouz, Zakariae; Fernández-Zapico, Eva; García-Granda, Santiago; García, José R.

2015-09-01

Lanthanide-organic frameworks based on 2,5-pyridinedicaboxylate (25p) ligand, formulated as [Yb4(OH)4(25p)4(H2O)3]·H2O (25pYb), [Y4(OH)4(25p)4(H2O)3]·H2O (25pY-1) and [Y6(OH)8(25p)5(H2O)2] (25pY-2), have been obtained as single phases under hydrothermal conditions. 25pYb and 25pY-1 are isostructural, and crystallize in the triclinic space group, P-1, with a=8.6075(5) Å, b=14.8478(7) Å, c=15.9164(9) Å, α=86.277(4)°, β=80.196(5)°, γ=81.785(4)°, and a=8.7166(6) Å, b=14.966(1) Å, c=15.966(1) Å, α=86.260(6)°, β=80.036(6)°, γ=81.599(6)°, respectively. 25pY-2 crystallizes in the monoclinic space group, P21/c, with a=24.9117(17) Å, b=13.7340(8) Å, c=14.3385(10) Å, β=100.551(7)°. 25pYb and 25pY-2 have been structurally characterized by single-crystal X-ray diffraction. The 25pYb structure is based on tetranuclear cubane-like [Yb4(OH)4]8+ clusters, which are interconnected to eight neighbouring clusters through teen surrounding 25p ligands leading to neutral 3D framework, while the structure of 25pY-2 is based on two independent cuban-like [Y4(OH)4]8+ clusters, which are joined together through Y1 cation leading to the formation of hexanuclear [Y6(OH)8]10+ clusters, which in turn are joined via Y2 cation resulting in infinite inorganic chain extending along c-axis, and each chain is interconnected to six adjacent chains through 25p ligands leading finally to 3D framework. The luminescence properties of Eu3+ and Tb3+ doped 25pY-1 and 25pY-2 compounds have also been investigated. All materials has been characterized by powder X-ray diffraction, thermal analyses (TG-SDTA-MS), FTIR spectroscopy, C-H-N elemental analysis, scanning electron microscopy (SEM-EDX), and powder X-ray thermodiffraction.

Tocilizumab in patients with active rheumatoid arthritis and inadequate responses to DMARDs and/or TNF inhibitors: a large, open-label study close to clinical practice

PubMed Central

Bykerk, Vivian P; Östör, Andrew J K; Alvaro-Gracia, José; Pavelka, Karel; Ivorra, José Andrés Román; Graninger, Winfried; Bensen, William; Nurmohamed, Michael T; Krause, Andreas; Bernasconi, Corrado; Stancati, Andrea; Sibilia, Jean

2012-01-01

Objective To evaluate the safety and efficacy of tocilizumab in clinical practice in patients with rheumatoid arthritis (RA) with inadequate responses (IR) to disease-modifying antirheumatic drugs (DMARDs) or both DMARDs and tumour necrosis factor α inhibitors (TNFis). Methods Patients—categorised as TNFi-naive, TNFi-previous (washout) or TNFi-recent (no washout) —received open-label tocilizumab (8 mg/kg) every 4 weeks ± DMARDs for 24 weeks. Adverse events (AEs) and treatment discontinuations were monitored. Efficacy end points included American College of Rheumatology (ACR) responses, 28-joint disease activity score (DAS28) and European League Against Rheumatism responses. Results Overall, 1681 (976 TNF-naive, 298 TNFi-previous and 407 TNFi-recent) patients were treated; 5.1% discontinued treatment because of AEs. The AE rate was numerically higher in TNFi-recent (652.6/100 patient-years (PY)) and TNFi-previous (653.6/100PY) than in TNFi-naive (551.1/100PY) patients. Serious AE rates were 18.0/100PY, 28.0/100PY and 18.6/100PY; serious infection rates were 6.0/100PY, 6.8/100PY and 4.2/100PY, respectively. At week 4, 36.5% of patients achieved ACR20 response and 14.9% DAS28 remission (<2.6); at week 24, 66.9%, 46.6%, 26.4% and 56.8% achieved ACR20/ACR50/ACR70 responses and DAS28 remission, respectively. Overall, 61.6% (TNFi-naive), 48.5% (TNFi-previous) and 50.4% (TNFi-recent) patients achieved DAS28 remission. Conclusions In patients with RA who were DMARD-IR/TNFi-IR, tocilizumab ± DMARDs provided rapid and sustained efficacy without unexpected safety concerns. PMID:22615456

Physiological characterization of strain DCB-1, a unique dehalogenating sulfidogenic bacterium.

PubMed Central

Stevens, T O; Linkfield, T G; Tiedje, J M

1988-01-01

Strain DCB-1 is an obligately anaerobic bacterium which carries out the reductive dehalogenation of halobenzoates and was previously known to grow only on pyruvate plus 20% ruminal fluid. When various electron acceptors were supplied, thiosulfate and sulfite were found to stimulate growth. Sulfide was produced from thiosulfate. Cytochrome c and desulfoviridin were detected. The mol% G+C was 49 (at the thermal denaturation temperature). Of 55 carbon sources tested, only pyruvate supported growth as the sole carbon source in mineral medium. Lactate, acetate, L- and D-malate, glycerol, and L- and D-arabinose stimulated growth when supplemented with 10% ruminal fluid and 20 mM thiosulfate. In mineral medium, pyruvate was converted to acetate and lactate, with small amounts of succinate and fumarate accumulating transiently. During growth with thiosulfate, all of these products accumulated transiently. Addition of excess hydrogen to pyruvate-grown cultures resulted in diversion of carbon to formate, lactate, and butyrate, which caused a decrease in cell yield. We conclude that strain DCB-1 is a new type of sulfidogenic bacterium. PMID:3223760

Peripheral Applications of Drug-Coated Balloons: Past, Present and Future

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

Krokidis, Miltiadis, E-mail: mkrokidis@hotmail.com; Spiliopoulos, Stavros, E-mail: stavspiliop@upatras.gr; Katsanos, Konstantinos, E-mail: katsanos@med.upatras.gr

2013-04-15

Drug-coated balloon (DCB) technologies represent the latest and hottest development in the field of endovascular treatment of peripheral arterial disease. Initial experience with paclitaxel-coated balloon use in the femoral artery has demonstrated lower mid-term restenosis and superior mid-term clinical outcomes in terms of improved wound healing and reduced repeat angioplasty rates compared with standard balloon angioplasty. Many companies are presently developing and/or improving DCB catheters and therefore ongoing, technical improvements of the already existing platforms, new drugs, and innovative carriers are expected. The ongoing basic research studies and various multicenter randomized, controlled trials that are currently in progress will offermore » valuable scientific insights regarding the long-term effectiveness and other crucial issues, such as efficacy in various vascular beds, optimal balloon dosage, and post angioplasty antiplatelet therapy. Future applications of these devices also could include in-stent restenosis, anastomotic stenosis of surgical bypass, and benign stenoses of the central venous system. The authors envision that DCB angioplasty will evolve to a major paradigm shift in the endovascular treatment of occlusive vascular diseases.« less

Genome-wide identification and characterization of five MyD88 duplication genes in Yesso scallop (Patinopecten yessoensis) and expression changes in response to bacterial challenge.

PubMed

Ning, Xianhui; Wang, Ruijia; Li, Xue; Wang, Shuyue; Zhang, Mengran; Xing, Qiang; Sun, Yan; Wang, Shi; Zhang, Lingling; Hu, Xiaoli; Bao, Zhenmin

2015-10-01

Myeloid differentiation factor 88 (MyD88) is a pivotal adaptor in the TLR/IL-1R signaling pathway, which plays an important role in activating the innate immune system. Although MyD88 genes have been identified in a variety of species, they have not been systematically characterized in scallops. In this study, five MyD88 genes were identified in Yesso scallop (Patinopecten yessoensis), PyMyD88-1, PyMyD88-2a, PyMyD88-2b, PyMyD88-3 and PyMyD88-4, which consisted of two pairs of tandem duplications located on the same chromosome. To our knowledge, this is the largest number of MyD88 genes found in an invertebrate. Phylogenetic and protein structural analyses were carried out to determine the identities and evolutionary relationships of these genes. PyMyD88s have highly conserved structures compared to MyD88 genes from other invertebrate species, except for PyMyD88-4, which contains only a DD domain, suggesting the evolutionarily conserved form of this particular gene member. We investigated the expression profiles of PyMyD88 genes at different developmental stages and in healthy adult tissues and hemocytes after Micrococcus luteus and Vibrio anguillarum infection using quantitative real-time PCR (qRT-PCR). The expression of most PyMyD88s was significantly induced in the acute phase (3-6 h) after infection with both gram-positive (M. luteus) and gram-negative (V. anguillarum) bacteria, with much more dramatic changes in PyMyD88 expression being observed after V. anguillarum challenge. Collectively, the abundance of MyD88s and their specific expression patterns provide insight into their versatile roles in the response of the bivalve innate immune system to gram-negative bacterial pathogens. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ligand effects on the ferro- to antiferromagnetic exchange ratio in bis(o-semiquinonato)copper(II).

PubMed

Ovcharenko, Victor I; Gorelik, Elena V; Fokin, Sergey V; Romanenko, Galina V; Ikorskii, Vladimir N; Krashilina, Anna V; Cherkasov, Vladimir K; Abakumov, Gleb A

2007-08-29

Heterospin complexes [Cu(SQ)2Py].C7H8, Cu(SQ)2DABCO, and [Cu(SQ)2NIT-mPy].C6H6, where Cu(SQ)2 is bis(3,6-di-tert-butyl-o-benzosemiquinonato)copper(II), DABCO is 1,4-diazabicyclo(2,2,2)octane, and NIT-mPy is the nitronyl nitroxide 2-(pyridin-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl, have been synthesized. The molecules of these complexes have a specific combination of the intramolecular ferro- and antiferromagnetic exchange interactions between the odd electrons of Cu(II) and SQ ligands, characterized by large exchange coupling parameters |J| approximately 100-300 cm(-1). X-ray and magnetochemical studies of a series of mixed-ligand compounds revealed that an extra ligand (Py, NIT-mPy, or DABCO) coordinated to the metal atom produces a dramatic effect on the magnetic properties of the complex, changing the multiplicity of the ground state. Quantum chemical analysis of magnetostructural correlations showed that the energy of the antiferromagnetic exchange interaction between the odd electrons of the SQ ligands in the Cu(SQ)2 bischelate is extremely sensitive to both the nature of the extra ligand and structural distortions of the coordination unit, arising from extra ligand coordination.

Cell Wall Structure in Cells Adapted to Growth on the Cellulose-Synthesis Inhibitor 2,6-Dichlorobenzonitrile 1

PubMed Central

Shedletzky, Esther; Shmuel, Miri; Trainin, Tali; Kalman, Sara; Delmer, Deborah

1992-01-01

Our previous work (E. Shedletzky, M. Shmuel, D.P. Delmer, D.T.A. Lamport [1990] Plant Physiol 94:980-987) showed that suspension-cultured tomato cells adapted to growth on the cellulose synthesis inhibitor 2,6-dichlorobenzonitrile (DCB) have a markedly altered cell wall composition, most notably a markedly reduced level of the cellulose-xyloglucan network. This study compares the adaptation to DCB of two cell lines from dicots (tomato [Lycopersicon esculentum] and tobacco [Nicotiana tabacum]) and a Graminaceous monocot (barley [Hordeum bulbosum] endosperm). The difference in wall structures between the dicots and the monocot is reflected in the very different types of wall modifications induced by growth on DCB. The dicots, having reduced levels of cellulose and xyloglucan, possess walls the major integrity of which is provided by Ca2+-bridged pectates because protoplasts can be prepared from these cells simply by treatment with divalent cation chelator and a purified endopolygalacturonase. The tensile strength of these walls is considerably less than walls from nonadapted cells, but wall porosity is not altered. In contrast, walls from adapted barley cells contain very little pectic material and normal to elevated levels of noncellulosic polysaccharides compared with walls from nonadapted cells. Surprisingly, they have tensile strengths higher than their nonadapted counterpart, although cellulose levels are reduced by 70%. Evidence is presented that these walls obtain their additional strength by an altered pattern of cross-linking of polymers involving phenolic components. Such cross-linking may also explain the observation that the porosity of these walls is also considerably reduced. Cells of adapted lines of both the dicots and barley are resistant to plasmolysis, suggesting that they possess very strong connections between the wall and the plasma membrane. Images Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 PMID:16652933

Quantitative analysis of the thermal requirements for stepwise physical dormancy-break in seeds of the winter annual Geranium carolinianum (Geraniaceae)

PubMed Central

Gama-Arachchige, N. S.; Baskin, J. M.; Geneve, R. L.; Baskin, C. C.

2013-01-01

Background and Aims Physical dormancy (PY)-break in some annual plant species is a two-step process controlled by two different temperature and/or moisture regimes. The thermal time model has been used to quantify PY-break in several species of Fabaceae, but not to describe stepwise PY-break. The primary aims of this study were to quantify the thermal requirement for sensitivity induction by developing a thermal time model and to propose a mechanism for stepwise PY-breaking in the winter annual Geranium carolinianum. Methods Seeds of G. carolinianum were stored under dry conditions at different constant and alternating temperatures to induce sensitivity (step I). Sensitivity induction was analysed based on the thermal time approach using the Gompertz function. The effect of temperature on step II was studied by incubating sensitive seeds at low temperatures. Scanning electron microscopy, penetrometer techniques, and different humidity levels and temperatures were used to explain the mechanism of stepwise PY-break. Key Results The base temperature (Tb) for sensitivity induction was 17·2 °C and constant for all seed fractions of the population. Thermal time for sensitivity induction during step I in the PY-breaking process agreed with the three-parameter Gompertz model. Step II (PY-break) did not agree with the thermal time concept. Q10 values for the rate of sensitivity induction and PY-break were between 2·0 and 3·5 and between 0·02 and 0·1, respectively. The force required to separate the water gap palisade layer from the sub-palisade layer was significantly reduced after sensitivity induction. Conclusions Step I and step II in PY-breaking of G. carolinianum are controlled by chemical and physical processes, respectively. This study indicates the feasibility of applying the developed thermal time model to predict or manipulate sensitivity induction in seeds with two-step PY-breaking processes. The model is the first and most detailed one yet developed for sensitivity induction in PY-break. PMID:23456728

The Interacting controls of pyrolysis temperature and plant taxa on pyrogenic organic matter stability and decomposition in a Northern Michigan forest soil

NASA Astrophysics Data System (ADS)

Gibson, C. D.; Filley, T. R.; Bird, J. A.; Hatton, P. J.; Stark, R. E.; Nadelhoffer, K. J.

2017-12-01

Pyrogenic organic matter (PyOM) produced during forest fires is considered a large sink of stable soil organic matter (SOM) in boreal-temperate forest ecotones, where fire frequency and intensity is growing with changing climate. Understanding how changes in fire regime and predicted shifts in plant taxa will interact to affect PyOM dynamics in soil is imperative to assessing the impact of climate change on SOM maintenance. The stability of PyOM in soil may be co-determined by the physiochemical structure imparted on PyOM during pyrolysis and by its initial taxa-dependent wood chemistry and anatomy. To determine PyOM-C turnover rates in soil, we followed the fate of 13C-enriched wood or PyOM (200, 300, 450, or 600°C) derived from red maple (RM) or jack pine (JP) wood in soil from a recently burned forest in northern Michigan, USA. We found that pyrolysis temperature-controlled physiochemical changes influenced, with threshold dynamics, PyOM stability resulting in mean residence times of 2 (PyOM 200°C) to 450 years for both taxa, confirming that most PyOM (<600°C) turns over on the century, not millennial time scale. Water leachable C, carbohydrate and non-lignin phenol content correlated positively with early PyOM-C mineralization for both JP and RM, but the pyrolysis temperature at which this interaction was strongest differed with taxa reflecting the difference in thermal transition in which carbonization begins (300°C for JP and 450°C for RM). In contrast to previous studies, the addition of sucrose suggests that a co-metabolism mechanism of PyOM decomposition is minor in this soil. Our results show that while the first order control on PyOM stability in this soil is pyrolysis temperature, wood taxa did affect PyOM C MRT, in part due to differences in the amount of water soluble C released by PyOM during the initial decomposition dynamics in soil.

Temperature and pressure variations of d-d luminescence band maxima of bis(pyridylalkenolato)palladium(II) complexes with different ligand substituents: opposite-signed trends.

PubMed

Poirier, Stéphanie; Czympiel, Lisa; Bélanger-Desmarais, Nicolas; Mathur, Sanjay; Reber, Christian

2016-04-21

Luminescence spectra of two d(8)-configured bis(pyridylalkenolato)palladium(ii) complexes, [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], are presented at variable temperature and pressure. Bands are assigned as d-d transitions. The heptafluoropropyl and methyl substituents on the ligands have different steric demands, influencing luminescence spectra. Broad bands with maxima at approximately 12 700 cm(-1) (790 nm) for ligands with heptafluoropropyl substituents and 12,100 cm(-1) (830 nm) for ligands with methyl substituents and widths of approximately 2100 cm(-1) for both complexes are observed at 80 K. Quenching of the luminescence is observed as temperature increases. The maxima of [Pd{PyCHC(C3F7)O}2] show a shift of -0.9 ± 0.1 cm(-1) K(-1) due to broadening of the spectra to lower energy. The luminescence maxima of [Pd{PyCHC(CH3)O}2] shift in the opposite direction by +7.2 ± 0.7 cm(-1) K(-1). Shifts with different signs are also obtained from variable-pressure luminescence spectra, with values of +13 ± 2 cm(-1) kbar(-1) and -15 ± 7 cm(-1) kbar(-1) for [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], respectively. The pressure-induced decrease is unusual and likely caused by intermolecular interactions involving the palladium(ii) center and a vinylic proton of a neighboring complex.

Non-cytomegalovirus ocular opportunistic infections in patients with acquired immunodeficiency syndrome.

PubMed

Gangaputra, Sapna; Drye, Lea; Vaidya, Vijay; Thorne, Jennifer E; Jabs, Douglas A; Lyon, Alice T

2013-02-01

To report the incidence and clinical outcomes of non-cytomegalovirus (non-CMV) ocular opportunistic infections in patients with acquired immunodeficiency syndrome (AIDS) in the era of highly active antiretroviral therapy. Multicenter, prospective, observational study of patients with AIDS. Medical history, ophthalmologic examination, and laboratory tests were performed at enrollment and every 6 months subsequently. Once an ocular opportunistic infection was diagnosed, patients were seen every 3 months for outcomes. At enrollment, 37 non-CMV ocular opportunistic infections were diagnosed: 16 patients, herpetic retinitis; 11 patients, toxoplasmic retinitis; and 10 patients, choroiditis. During the follow-up period, the estimated incidences (and 95% confidence intervals [CI]) of these were: herpetic retinitis, 0.007/100 person-years (PY) (95% CI 0.0004, 0.039); toxoplasmic retinitis, 0.007/100 PY (95% CI 0.004, 0.039); and choroiditis, 0.014/ 100 PY (95% CI 0.0025, 0.050). The mortality rates appeared higher among those patients with newly diagnosed or incident herpetic retinitis and choroiditis (rates = 21.7 deaths/100 PY [P = .02] and 12.8 deaths/100 PY [P = .04]), respectively, than those for patients with AIDS without an ocular opportunistic infection (4.1 deaths/100 PY); toxoplasmic retinitis did not appear to be associated with greater mortality (6.4/100 PY, P = .47). Eyes with newly diagnosed herpetic retinitis appeared to have a poor visual prognosis, with high rates of visual impairment (37.9/100 PY) and blindness (17.5/100 PY), whereas those outcomes in eyes with choroiditis appeared to be lower (2.3/100 PY and 0/100 PY, respectively). Although uncommon, non-CMV ocular opportunistic infections may be associated with high rates of visual loss and/or mortality. Copyright © 2013 Elsevier Inc. All rights reserved.

Non-cytomegalovirus ocular opportunistic infections in patients with AIDS

PubMed Central

Gangaputra, Sapna; Drye, Lea; Vaidya, Vijay; Thorne, Jennifer E.; Jabs, Douglas A; Lyon, Alice T.

2014-01-01

Purpose To report the incidence and clinical outcomes of non-cytomegalovirus (non-CMV) ocular opportunistic infections in patients with AIDS in the era of highly active antiretroviral therapy (HAART). Design Multicenter, prospective, observational study of patients with AIDS Methods Medical history, ophthalmologic examination, and laboratory tests were performed at enrollment and every 6 months subsequently. Once an ocular opportunistic infection was diagnosed, patients were seen every 3 months for outcomes. Results At enrollment, 37 non-CMV ocular opportunistic infections were diagnosed: 16 patients, herpetic retinitis; 11 patients, toxoplasmic retinitis; and 10 patients, choroiditis. During the follow-up period, the estimated incidences (and 95% confidence intervals [CI]) of these were: herpetic retinitis, 0.007/100 person-years (PY) (95% CI 0.0004, 0.039); toxoplasmic retinitis, 0.007/100 PY (95% CI 0.004, 0.039); and choroiditis 0.014/100 PY (95% CI 0.0025, 0.050). The mortality rates appeared higher among those patients with newly diagnosed or incident herpetic retinitis and choroiditis (rates=21.7 deaths/100 PY [P=0.02] and 12.8 deaths/100 PY [P=0.04]) respectively, than that for patients with AIDS without an ocular opportunistic infection (4.1 deaths/100 PY); Toxoplasmic retinitis did not appear to be associated with greater mortality (6.4/100 PY, P=0.47). Eyes with newly-diagnosed herpetic retinitis appeared to have a poor visual prognosis with high rates of visual impairment (37.9/100 PY) and blindness (17.5/100 PY), whereas those outcomes in eyes with choroiditis appeared to be lower (2.3/100 PY and 0/100 PY, respectively). Conclusions Although uncommon, non-CMV ocular opportunistic infections may be associated with high rates of visual loss and/or mortality. PMID:23068916

Rootkit Detection Using a Cross-View Clean Boot Method

DTIC Science & Technology

2013-03-01

FindNextFile: [2] Kernel32.dll 4. SSDTHooks r -- ... CALL NtQueryDirectoryFile 5. Code Patch ing - 6. Layered Driver 4 NtQueryDirectoryFile : 7...NTFS Driver 0 Volume Manger Disk Driver [2] I. Disk Driver r ! J IAT hooks take advantage of function calls in applications [13]. When an...f36e923898161fa7be50810288e2f48a 61 Appendix D: Windows Source Code Windows Batch File @echo o f f py thon walk . py pause shutdown − r − t 0 Walk.py in

Identification of vascular patients at very high risk for recurrent cardiovascular events: validation of the current ACC/AHA very high risk criteria.

PubMed

van den Berg, M Johanneke; Bhatt, Deepak L; Kappelle, L Jaap; de Borst, Gert J; Cramer, Maarten J; van der Graaf, Yolanda; Steg, Ph Gabriel; Visseren, Frank L J

2017-11-14

To validate and assess performance of the current ACC/AHA very high risk criteria in patients with clinically manifest arterial disease. Data were used from the SMART study (n = 7216) and REACH Registry (n = 48 322), two prospective cohorts of patients with manifest atherosclerotic arterial disease. Prevalence and incidence rates of recurrent major adverse cardiovascular events (MACE) were calculated, according to the ACC/AHA VHR criteria (cardiovascular disease combined with diabetes, smoking, dyslipidaemia, and/or recent recurrent coronary events). Performance of the ACC/AHA criteria was compared with single very high risk factors in terms of C-statistics and Net Reclassification Index. All patients were at VHR according to the ESC guidelines (incidence of recurrent MACE in SMART was 2.4/100PY, with 95% CI 2.3-2.5/100PY and in REACH 5.1/100PY with 95% CI 5.0-5.3/100PY). In SMART 57% of the patients were at VHR according to the ACC/AHA criteria (incidence of recurrent MACE 2.7/100PY, 95% CI 2.5-2.9/100PY) and in REACH this was 64% (5.9/100PY, 95% CI 5.7-6.1/100PY). The C-statistic for the ACC/AHA VHR criteria was 0.53 in REACH and 0.54 in SMART. Very high risk factors with comparable or slightly better performance were eGFR < 45, polyvascular disease and age >70 years. Around two third of the patients meeting the ACC/AHA VHR criteria had a predicted 10-year risk of recurrent MACE <30%. The ACC/AHA VHR criteria have limited discriminative power. Identifying patients with clinically manifest arterial disease at VHR for recurrent vascular events using eGFR <45, polyvascular disease, or age >70 years performs as well as the ACC/AHA VHR criteria. Published on behalf of the European Society of Cardiology. All rights reserved. © The Author 2017. For permissions, please email: journals.permissions@oup.com.

Affinity and specificity of interactions between Nedd4 isoforms and the epithelial Na+ channel.

PubMed

Henry, Pauline C; Kanelis, Voula; O'Brien, M Christine; Kim, Brian; Gautschi, Ivan; Forman-Kay, Julie; Schild, Laurent; Rotin, Daniela

2003-05-30

The epithelial Na+ channel (alphabetagammaENaC) regulates salt and fluid homeostasis and blood pressure. Each ENaC subunit contains a PY motif (PPXY) that binds to the WW domains of Nedd4, a Hect family ubiquitin ligase containing 3-4 WW domains and usually a C2 domain. It has been proposed that Nedd4-2, but not Nedd4-1, isoforms can bind to and suppress ENaC activity. Here we challenge this notion and show that, instead, the presence of a unique WW domain (WW3*) in either Nedd4-2 or Nedd4-1 determines high affinity interactions and the ability to suppress ENaC. WW3* from either Nedd4-2 or Nedd4-1 binds ENaC-PY motifs equally well (e.g. Kd approximately 10 microm for alpha- or betaENaC, 3-6-fold higher affinity than WW4), as determined by intrinsic tryptophan fluorescence. Moreover, dNedd4-1, which naturally contains a WW3* instead of WW2, is able to suppress ENaC function equally well as Nedd4-2. Homology models of the WW3*.betaENaC-PY complex revealed that a Pro and Ala conserved in all WW3*, but not other Nedd4-WW domains, help form the binding pocket for PY motif prolines. Extensive contacts are formed between the betaENaC-PY motif and the Pro in WW3*, and the small Ala creates a large pocket to accommodate the peptide. Indeed, mutating the conserved Pro and Ala in WW3* reduces binding affinity 2-3-fold. Additionally, we demonstrate that mutations in PY motif residues that form contacts with the WW domain based on our previously solved structure either abolish or severely reduce binding affinity to the WW domain and that the extent of binding correlates with the level of ENaC suppression. Independently, we show that a peptide encompassing the PY motif of sgk1, previously proposed to bind to Nedd4-2 and alter its ability to regulate ENaC, does not bind (or binds poorly) the WW domains of Nedd4-2. Collectively, these results suggest that high affinity of WW domain-PY-motif interactions rather than affiliation with Nedd4-1/Nedd-2 is critical for ENaC suppression by Nedd4 proteins.

The murine polyomavirus microRNA locus is required to promote viruria during the acute phase of infection.

PubMed

Burke, James M; Bass, Clovis R; Kincaid, Rodney P; Ulug, Emin T; Sullivan, Christopher S

2018-06-06

Polyomaviruses (PyVs) can cause serious disease in immunosuppressed hosts. Several pathogenic PyVs encode microRNAs (miRNAs), small RNAs that regulate gene expression via RNA silencing. Despite recent advances in understanding the activities of PyV miRNAs, the biological functions of PyV miRNAs during in vivo infections are mostly unknown. Studies presented here use murine polyomavirus (MuPyV) as a model to assess the roles of the PyV miRNAs in a natural host. This analysis reveals that a MuPyV mutant that is unable to express miRNAs has enhanced viral DNA loads in select tissues at late times after infection. This is consistent with the PyV miRNAs functioning to reduce viral replication during the persistent phase of infection in a natural host. Additionally, the MuPyV miRNA locus promotes viruria during the acute phase of infection as evidenced by a defect in shedding during infection with the miRNA mutant virus. The viruria defect of the miRNA mutant virus could be rescued by infecting Rag2-/- mice. These findings implicate the miRNA locus as functioning in both the persistent and acute phases of infection and suggest a role for MuPyV miRNA in evading the adaptive immune response. IMPORTANCE MicroRNAs are expressed by diverse viruses, but for only a few is there any understanding of their in vivo function. PyVs can cause serious disease in immunocompromised hosts. Therefore, increased knowledge of how these viruses interact with the immune response is of clinical relevance. Here we show a novel activity for a viral miRNA locus in promoting virus shedding. This work indicates that in addition to any role for the PyV miRNA locus in long-term persistence, that it also has biological activity during the acute phase. As this mutant phenotype is alleviated by infection of mice lacking an adaptive immune response, our work also connects the in vivo activity of the PyV miRNA locus to the immune response. Given that PyV-associated disease is associated with alterations in the immune response, our findings help to better understand how the balance between PyVs and the immune response becomes altered in pathogenic states. Copyright © 2018 American Society for Microbiology.

A compact frequency tunable radio frequency phase shifter with patterned Py enabled transmission line

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

Rahman, B.M. Farid; Divan, Ralu; Rosenmann, Daniel

2015-01-01

A well designed frequency tunable phase shifter using patterned Py with different thickness has been demonstrated. Phase shifter is implemented with a slow wave coplanar wave guide (CPW)transmission line, where the signal line has alternate short narrow and wide sections. Py is patterned on the top of narrow section for high inductance density, and inter-digital capacitor is implemented in wide section for high capacitance density. Compared with phase shifter using regular CPW, the dimension of the developed phase shifter has been reduced from 14.86 mm to4.70 mm at 2 GHz. Phase shifter based on 100 nm and 200 nm thickmore » patterned Py with the same dimensions (14lm10lm) are implemented and investigated comprehensively. FMR frequency of 3.2 GHz and 3.6 GHz without any external magnetic field has been achieved for100 nm and 200 nm thick Py film, respectively. Thicker Py has increased inductance density from 1067.2 nH/m to 1193.2 nH/m while the center frequency of the phase shifter has been shifted to 1.80 GHz. Frequency tunability of the phase shifter has been also demonstrated withDC current. The phase shifter can provide 90phase shift continuously from 2 GHz to 1.80 GHz with DC current from 0 mA to 150 mA. The design concept has great potential in design arbitrary tunable RF components such as filters and couplers.« less

Mode 1 and Mode 2 Analysis of Graphite/Epoxy Composites Using Double Cantilever Beam and End-Notched Flexure Tests

NASA Technical Reports Server (NTRS)

Hufnagel, Kathleen P.

1995-01-01

The critical strain energy release rates associated with debonding of the adhesive bondlines in graphite/epoxy IM6/3501-6 interlaminar fracture specimens were investigated. Two panels were manufactured for this investigation; however, panel two was layed-up incorrectly. As a result, data collected from Panel Two serves no real purpose in this investigation. Double Cantilever Beam (DCB) specimens were used to determine the opening Mode I interlaminar fracture toughness, G1(sub c), of uni-directional fiber re-inforced composites. The five specimens tested from Panel One had an average value of 946.42J/sq m for G1(sub c) with an acceptable coefficient of variation. The critical strain energy release rate, G2(sub c), for initiation of delamination under inplane shear loading was investigated using the End-Notched Flexure (ENF) Test. Four specimens were tested from Panel One and an average value of 584.98J/sq m for G2(sub c) was calculated. Calculations from the DCB and ENF test results for Panel One represent typical values of G1(sub c) and G2(sub c) for the adhesive debonding in the material studied in this investigation.

PyHLA: tests for the association between HLA alleles and diseases.

PubMed

Fan, Yanhui; Song, You-Qiang

2017-02-06

Recently, several tools have been designed for human leukocyte antigen (HLA) typing using single nucleotide polymorphism (SNP) array and next-generation sequencing (NGS) data. These tools provide high-throughput and cost-effective approaches for identifying HLA types. Therefore, tools for downstream association analysis are highly desirable. Although several tools have been designed for multi-allelic marker association analysis, they were designed only for microsatellite markers and do not scale well with increasing data volumes, or they were designed for large-scale data but provided a limited number of tests. We have developed a Python package called PyHLA, which implements several methods for HLA association analysis, to fill the gap. PyHLA is a tailor-made, easy to use, and flexible tool designed specifically for the association analysis of the HLA types imputed from genome-wide genotyping and NGS data. PyHLA provides functions for association analysis, zygosity tests, and interaction tests between HLA alleles and diseases. Monte Carlo permutation and several methods for multiple testing corrections have also been implemented. PyHLA provides a convenient and powerful tool for HLA analysis. Existing methods have been integrated and desired methods have been added in PyHLA. Furthermore, PyHLA is applicable to small and large sample sizes and can finish the analysis in a timely manner on a personal computer with different platforms. PyHLA is implemented in Python. PyHLA is a free, open source software distributed under the GPLv2 license. The source code, tutorial, and examples are available at https://github.com/felixfan/PyHLA.

Responses of soil carbon turnover rates to pyrogenic carbon additions to a forest soil of Sierra Nevada, California: effects of pyrolysis temperature and soil depth

NASA Astrophysics Data System (ADS)

Santos, F.; Bird, J. A.; Berhe, A. A.

2017-12-01

Pyrogenic organic carbon (PyC) is a heterogenous mixture of thermally altered residues, ranging from slightly charred plant biomass to soot. Despite its apparent stability in soils, PyC has been reported to either increase or decrease (priming effect, PE), or have no effect on the mineralization rates of native soil organic matter (SOM), highlighting our limited knowledge on the mechanisms driving PyC-induced PE. Little is known about how PyC's pyrolysis temperature, and soil depth (surface versus subsurface) affect the direction of PE. To address this gap knowledge, we conducted from a 1-year laboratory incubation study aimed to investigate the interactive effects of pyrolysis temperature and soil depth on the mineralization rates of native SOM in fine-loamy, temperate forest soil that received additions of dual-labeled 13C and 15N jack pine pyrogenic organic matter produced at 300oC (PyC300) and 450oC (PyC450). Soil and PyC mixture were incubated in surface (0-10 cm) and subsurface (50-70 cm) forest soils in the dark at 55% soil field capacity and 25oC. Losses of native SOM as 13CO2 were measured periodically from the 13C-labeled PyC, and native (unlabeled) SOM during the incubation study using a Thermo Scientific GasBench interfaced to a Delta V Plus isotope ratio mass spectrometer. In surface soils, the addition of PyC300 decreased the turnover rates of native C relative to control treatments, whereas PyC400 had no effect on native C turnover rates. In subsurface soils, neither PyC300 nor PyC400 additions affected native C turnover rates. Our preliminary findings suggest that pyrolysis temperature is an important factor driving the persistence of soil C in Sierra Nevada forest soils.

Identification of a Second Raccoon-Associated Polyomavirus

PubMed Central

Geoghegan, Eileen M.; Welch, Nicole L.; Yabsley, Michael J.; Church, Molly E.; Pesavento, Patricia A.

2017-01-01

ABSTRACT Raccoon polyomavirus 1 (RacPyV1) is the suspected cause of an outbreak of fatal brain tumors among raccoons (Procyon lotor) in the western United States. Spleen samples from Georgia raccoons were screened for polyomaviruses. Although RacPyV1 was not detected, a previously unknown polyomavirus, which we designate RacPyV2, was identified and sequenced. PMID:28663292

Hepatitis C virus reinfection incidence and treatment outcome among HIV-positive MSM.

PubMed

Martin, Thomas C S; Martin, Natasha K; Hickman, Matthew; Vickerman, Peter; Page, Emma E; Everett, Rhiannon; Gazzard, Brian G; Nelson, Mark

2013-10-23

Liver disease secondary to hepatitis C virus (HCV) infection in the context of HIV infection is one of the leading non-AIDS causes of death. Sexual transmission of HCV infection among HIV-positive MSM appears to be leading to increased reports of acute HCV infection. Reinfection after successful treatment or spontaneous clearance is reported among HIV-positive MSM but the scale of reinfection is unknown. We calculate and compare HCV reinfection rates among HIV-positive MSM after spontaneous clearance and successful medical treatment of infection. Retrospective analysis of HIV-positive MSM with sexually acquired HCV who subsequently spontaneously cleared or underwent successful HCV treatment between 2004 and 2012. Among 191 individuals infected with HCV, 44 were reinfected over 562 person-years (py) of follow-up with an overall reinfection rate of 7.8/100 py [95% confidence interval (CI) 5.8-10.5]. Eight individuals were subsequently reinfected a second time at a rate of 15.5/100 py (95% CI 7.7-31.0). Combining all reinfections, 20% resulted in spontaneous clearance and treatment sustained viral response rates were 73% (16/22) for genotypes one and four and 100% (2/2) for genotypes two and three. Among 145 individuals with a documented primary infection, the reinfection rate was 8.0 per 100 py (95% CI 5.7-11.3) overall, 9.6/100 py (95% CI 6.6-14.1) among those successfully treated and 4.2/100 py (95% CI 1.7-10.0) among those who spontaneously cleared. The secondary reinfection rate was 23.2/100 py (95% CI 11.6-46.4). Despite efforts at reducing risk behaviour, HIV-positive MSM who clear HCV infection remain at high risk of reinfection. This emphasizes the need for increased sexual education, surveillance and preventive intervention work.

Fabrication and Structural Characterization of an Ultrathin Film of a Two-Dimensional-Layered Metal-Organic Framework, {Fe(py)2[Ni(CN)4]} (py = pyridine).

PubMed

Sakaida, Shun; Haraguchi, Tomoyuki; Otsubo, Kazuya; Sakata, Osami; Fujiwara, Akihiko; Kitagawa, Hiroshi

2017-07-17

We report the fabrication and characterization of the first example of a tetracyanonickelate-based two-dimensional-layered metal-organic framework, {Fe(py) 2 Ni(CN) 4 } (py = pyridine), thin film. To fabricate a nanometer-sized thin film, we utilized the layer-by-layer method, whereby a substrate was alternately soaked in solutions of the structural components. Surface X-ray studies revealed that the fabricated film was crystalline with well-controlled growth directions both parallel and perpendicular to the substrate. In addition, lattice parameter analysis indicated that the crystal system is found to be close to higher symmetry by being downsized to a thin film.

Molecular detection and in vitro antioxidant activity of S-allyl-L-cysteine (SAC) extracted from Allium sativum.

PubMed

Sun, Y-E; Wang, W-D

2016-06-30

It is well known that Allium sativum has potential applications to clinical treatment of various cancers due to its remarkable ability in eliminating free radicals and increasing metabolism. An allyl-substituted cysteine derivative - S-allyl-L-cysteine (SAC) was separated and identified from Allium sativum. The extracted SAC was reacted with 1-pyrenemethanol to obtain pyrene-labelled SAC (Py-SAC) to give SAC fluorescence properties. Molecular detection of Py-SAC was conducted by steady-state fluorescence spectroscopy and time-resolved fluorescence method to quantitatively measure concentrations of Py-SAC solutions. The ability of removing 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroxyl radical using Py-SAC was determined through oxygen radical absorbance capacity (ORAC). Results showed the activity of Py-SAC and Vitamin C (VC) with ORAC as index, the concentrations of Py-SAC and VC were 58.43 mg/L and 5.72 mg/L respectively to scavenge DPPH, and 8.16 mg/L and 1.67 mg/L to scavenge •OH respectively. Compared with VC, the clearance rates of Py-SAC to scavenge DPPH were much higher, Py-SAC could inhibit hydroxyl radical. The ability of removing radical showed a dose-dependent relationship within the scope of the drug concentration.

Continued Transmission of HIV Among Young Adults Who Inject Drugs in San Francisco: Still Room for Improvement.

PubMed

Mirzazadeh, Ali; Evans, Jennifer L; Hahn, Judith A; Jain, Jennifer; Briceno, Alya; Shiboski, Stephen; Lum, Paula J; Bentsen, Christopher; Davis, Geoff; Shriver, Kathy; Dimapasoc, Melanie; Stone, Mars; Busch, Michael P; Page, Kimberly

2018-04-01

We measured HIV incidence rate, trend and risk factors in 564 HIV-negative young people (< 30 years) who inject drugs (PWID) in San Francisco between 2000 and 2014. HIV incidence was 0.93/100 person-years (PY; 95% CI 0.50, 1.73). Incidence varied between 0.62/100 PY in 2000-2002 and 1.06/100 PY in 2012-2014 (P for trend = 1.0). HIV incidence varied significantly (P < 0.01) by race/ethnicity: among Hispanics it was 8.19/100 PY (95% CI 3.41, 19.68), African-Americans 4.59/100 PY (95% CI 1.15, 18.37), and Whites 0.26/100 PY (95% CI 0.06, 1.03). Male participants who reported sex with men (MSM) had higher HIV incidence (2.63/100 PY; 95% CI 1.31, 5.25) compared to males who did not report MSM (0.50/100 PY; 95% CI 0.12, 1.99) (P = 0.01). Despite an overall stable HIV incidence trend, incidence was elevated among African-American and Hispanic PWID, and men who have sex with men. Addressing prevention needs in these key populations is critical for the goal of eliminating HIV transmission.

Structure of the cobalamin-binding protein of a putative O-demethylase from Desulfitobacterium hafniense DCB-2

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

Sjuts, Hanno; Dunstan, Mark S.; Fisher, Karl

2013-08-01

The first crystal structure of the vitamin B12-binding protein from a three-component O-demethylase enzyme system is reported. During O-demethylation methyl groups are transferred from phenyl methyl ethers to tetrahydrofolate via methyl-B12 intermediates. This study describes the identification and the structural and spectroscopic analysis of a cobalamin-binding protein (termed CobDH) implicated in O-demethylation by the organohalide-respiring bacterium Desulfitobacterium hafniense DCB-2. The 1.5 Å resolution crystal structure of CobDH is presented in the cobalamin-bound state and reveals that the protein is composed of an N-terminal helix-bundle domain and a C-terminal Rossmann-fold domain, with the cobalamin coordinated in the base-off/His-on conformation similar tomore » other cobalamin-binding domains that catalyse methyl-transfer reactions. EPR spectroscopy of CobDH confirms cobalamin binding and reveals the presence of a cob(III)alamin superoxide, indicating binding of oxygen to the fully oxidized cofactor. These data provide the first structural insights into the methyltransferase reactions that occur during O-demethylation by D. hafniense.« less

Self-assembly of five 8-hydroxyquinolinate-based complexes: tunable core, supramolecular structure, and photoluminescence properties.

PubMed

Yuan, Guozan; Shan, Weilong; Qiao, Xuelong; Ma, Li; Huo, Yanping

2014-07-01

Five new Zn(II) complexes, namely [Zn(3)(L)(6)] (1), [Zn(2)(Cl)(2)(L)(2) (py)(2)] (2), [Zn(2)(Br)(2) (L)(2)(py)(2)] (3), [Zn(L)(2)(py)] (4), and [Zn(2)(OAc)(2)(L)(2)(py)(2)] (5), were prepared by the solvothermal reaction of ZnX(2) (X(-) =Cl(-), Br(-), F(-), and OAc(-)) salts with a 8-hydroxyquinolinate ligand (HL) that contained a trifluorophenyl group. All of the complexes were characterized by elemental analysis, IR spectroscopy, and powder and single-crystal X-ray crystallography. The building blocks exhibited unprecedented structural diversification and their self-assembly afforded one mononuclear, three binuclear, and one trinuclear Zn(II) structures in response to different anions and solvent systems. Complexes 1-5 featured four types of supramolecular network controlled by non-covalent interactions, such as π⋅⋅⋅π-stacking, C-H⋅⋅⋅π, hydrogen-bonding, and halogen-related interactions. Investigation of their photoluminescence properties exhibited disparate emission wavelengths, lifetimes, and quantum yields in the solid state. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of a family of structurally characterized dysprosium alkoxides for improved fatigue-resistance characteristics of PDyZT thin films.

PubMed

Boyle, Timothy J; Bunge, Scott D; Clem, Paul G; Richardson, Jacob; Dawley, Jeffrey T; Ottley, Leigh Anna M; Rodriguez, Mark A; Tuttle, Bruce A; Avilucea, Gabriel R; Tissot, Ralph G

2005-03-07

Using either an ammoniacal route, the reaction between DyCl3, Na0, and HOR in liquid ammonia, or preferentially reacting Dy(N(SiMe3)2)3 with HOR in a solvent, we isolated a family of dysprosium alkoxides as [Dy(mu-ONep)2(ONep)]4 (1), (ONep)2Dy[(mu3-ONep)(mu-ONep)Dy(ONep)(THF)]2(mu-ONep) (2), (ONep)2Dy[(mu3-ONep)(mu-ONep)Dy(ONep)(py)]2(mu-ONep) (3), [Dy3(mu3-OBut)2(mu-OBut3(OBut)4(HOBut)2] (4), [Dy3(mu3-OBut)2(mu-OBut)3(OBut)4(THF)2] (5), [Dy3(mu3-OBut)2(mu-OBut)3(OBut)4(py)2] (6), (DMP)Dy(mu-DMP)4[Dy(DMP)2(NH3)]2 (7), [Dy(eta6-DMP)(DMP)2]2 (8), Dy(DMP)3(THF)3 (9), Dy(DMP)3(py)3 (10), Dy(DIP)3(NH3)2 (11), [Dy(eta6-DIP)(DIP)2]2 (12), Dy(DIP)3(THF)2 (13), Dy(DIP)3(py)3 (14), Dy(DBP)3(NH3) (15), Dy(DBP)3 (16), Dy(DBP)3(THF) (17), Dy(DBP)3(py)2 (18), [Dy(mu-TPS)(TPS2]2 (19), Dy(TPS)3(THF)3 (20), and Dy(TPS)3(py)3 (21), where ONep = OCH2CMe3, OBut) = OCMe3, DMP = OC6H3(Me)(2)-2,6, DIP = OC6H3(CHMe2)(2)-2,6, DBP = OC6H3(CMe3)(2)-2,6, TPS = OSi(C6H5)3, tol = toluene, THF = tetrahydrofuran, and py = pyridine. We were not able to obtain X-ray quality crystals of compounds 2, 8, and 9. The structures observed and data collected for the Dy compounds are consistent with those reported for its other congeners. A number of these precursors were used as Dy dopants in Pb(Zr0.3Ti0.7)O3 (PZT 30/70) thin films, with compound 12 yielding the highest-quality films. The resulting Pb0.94Dy0.04(Zr0.3Ti0.7)O3 [PDyZT (4/30/70)] had similar properties to PZT (30/70), but showed substantial resistance to polarization reversal fatigue.

Magnetization reversal in Py/Gd heterostructures

DOE PAGES

Lapa, Pavel N.; Ding, Junjia; Pearson, John E.; ...

2017-07-13

Here, using a combination of magnetometry and magnetotransport techniques, we studied temperature and magnetic-field behavior of magnetization in Py/Gd heterostructures. It was shown quantitatively that proximity with Py enhances magnetic order of Gd. Micromagnetic simulations demonstrate that a spin-flop transition observed in a Py/Gd bilayer is due to exchange-spring rotation of magnetization in the Gd layer. Transport measurements show that the magnetoresistance of a [Py(2nm)/Gd(2nm)] 25 multilayer changes sign at the compensation temperature and below 20 K. The positive magnetoresistance above the compensation temperature can be attributed to an in-plane domain wall, which appears because of the structural inhomogeneity ofmore » the film over its thickness. By measuring the angular dependence of resistance, we are able to determine the angle between magnetizations in the multilayer and the magnetic field at different temperatures. The measurements reveal that, due to a change in the chemical thickness profile, a noncollinear magnetization configuration is only stable in magnetic fields above 10 kOe.« less

Magnetization reversal in Py/Gd heterostructures

NASA Astrophysics Data System (ADS)

Lapa, Pavel N.; Ding, Junjia; Pearson, John E.; Novosad, Valentine; Jiang, J. S.; Hoffmann, Axel

2017-07-01

Using a combination of magnetometry and magnetotransport techniques, we studied temperature and magnetic-field behavior of magnetization in Py/Gd heterostructures. It was shown quantitatively that proximity with Py enhances magnetic order of Gd. Micromagnetic simulations demonstrate that a spin-flop transition observed in a Py/Gd bilayer is due to exchange-spring rotation of magnetization in the Gd layer. Transport measurements show that the magnetoresistance of a [Py(2 nm ) /Gd (2 nm ) ] 25 multilayer changes sign at the compensation temperature and below 20 K. The positive magnetoresistance above the compensation temperature can be attributed to an in-plane domain wall, which appears because of the structural inhomogeneity of the film over its thickness. By measuring the angular dependence of resistance, we are able to determine the angle between magnetizations in the multilayer and the magnetic field at different temperatures. The measurements reveal that, due to a change in the chemical thickness profile, a noncollinear magnetization configuration is only stable in magnetic fields above 10 kOe.

Direct electron transfer of glucose oxidase and dual hydrogen peroxide and glucose detection based on water-dispersible carbon nanotubes derivative.

PubMed

Chen, Hsiao-Chien; Tu, Yi-Ming; Hou, Chung-Che; Lin, Yu-Chen; Chen, Ching-Hsiang; Yang, Kuang-Hsuan

2015-03-31

A water-dispersible multi-walled carbon nanotubes (MWCNTs) derivative, MWCNTs-1-one-dihydroxypyridine (MWCNTs-Py) was synthesis via Friedel-Crafts chemical acylation. Raman spectra demonstrated the conjugated level of MWCNTs-Py was retained after this chemical modification. MWCNTs-Py showed dual hydrogen peroxide (H2O2) and glucose detections without mutual interference by adjusting pH value. It was sensitive to H2O2 in acidic solution and displayed the high performances of sensitivity, linear range, response time and stability; meanwhile it did not respond to H2O2 in neutral solution. In addition, this positively charged MWCNTs-Py could adsorb glucose oxidase (GOD) by electrostatic attraction. MWCNTs-Py-GOD/GC electrode showed the direct electron transfer (DET) of GOD with a pair of well-defined redox peaks, attesting the bioactivity of GOD was retained due to the non-destroyed immobilization. The high surface coverage of active GOD (3.5×10(-9) mol cm(-2)) resulted in exhibiting a good electrocatalytic activity toward glucose. This glucose sensor showed high sensitivity (68.1 μA mM(-1) cm(-2)) in a linear range from 3 μM to 7 mM in neutral buffer solution. The proposed sensor could distinguish H2O2 and glucose, thus owning high selectivity and reliability. Copyright © 2015. Published by Elsevier B.V.

Synthesis, spectroscopic characterizations, crystal structures and DFT studies of nalidixic acid carbonyl hydrazones derivatives

NASA Astrophysics Data System (ADS)

Bergamini, F. R. G.; Ribeiro, M. A.; Lancellotti, M.; Machado, D.; Miranda, P. C. M. L.; Cuin, A.; Formiga, A. L. B.; Corbi, P. P.

2016-09-01

This article describes the synthesis and characterization of the 1-ethyl-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazide (hzd) and six carbonyl hydrazones derivatives of the nalidixic with 1H-pyrrol-2-ylmethylidene (hpyrr), 1H-imidazol-2-ylmethylidene (h2imi), pyridin-2-ylmethylidene (h2py), pyridin-3-ylmethylidene (h3py), pyridin-4-ylmethylidene(h4py) and (2-hydroxyphenyl)methylidene (hsali). The carbonyl hydrazones were characterized by elemental and ESI-QTOF-MS analyses, IR and detailed NMR spectroscopic measurements. The 2D NMR experiments allowed the unambiguous assignment of the hydrogen, carbon and nitrogen atoms, which have not been reported for nalidixic acid carbonyl hydrazone derivatives so far. Crystal structures of hzd and the new carbonyl hydrazones h2imi, hpyrr and h3py were determined by X-ray diffraction studies. Although the synthesis of hzd was reported decades ago, the hzd crystal structure have not been reported yet. Geometric optimizations of all the characterized structures were performed with the aid of DFT studies. Despite the fact that the hydrazones with 2-pyridine carboxylic acid (h2py) and salicyl aldehyde (hsali) were already reported by literature, a detailed spectroscopic study followed by DFT studies are also reported for such compounds in this manuscript. Antimicrobial studies of the compounds are also presented.

Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mössbauer spectra

NASA Astrophysics Data System (ADS)

Kitazawa, Takafumi; Kishida, Takanori; Kawasaki, Takeshi; Takahashi, Masashi

2017-11-01

We have prepared the 2D spin crossover complexes Fe(L)2Pd(CN)4 (L = py : 1a; py-D5 : 1b and py-15N : 1c). 1a has been characterised by 57Fe Mossbauer spectroscopic measurements, single crystal X-ray determination and SQUID measurements. The Mössbauer spectra for 1a indicate that the iron(II) spin states are in high spin states at 298 K and are in low spin states at 77 K. The crystal structures of 1a at 298 K and 90 K also show the high spin state and the low spin state respectively, associated with the Fe(II)-N distances. The spin transition temperature range of 1a is higher than that of Fe(py)2Ni(CN)4 since Pd(II) ions are larger and heavier than Ni(II) ions. SQUID data indicate isotope effects among 1a, 1b and 1c are observed in very small shifts of the transition temperatures probably due to larger and heavier Pd(II) ions. The delicate shifts would be associated with subtle balances between different vibrations around Fe(II) atoms and electronic factors.

Room-temperature ionic liquids as replacements for organic solvents in multiphase bioprocess operations.

PubMed

Cull, S G; Holbrey, J D; Vargas-Mora, V; Seddon, K R; Lye, G J

2000-07-20

Organic solvents are widely used in a range of multiphase bioprocess operations including the liquid-liquid extraction of antibiotics and two-phase biotransformation reactions. There are, however, considerable problems associated with the safe handling of these solvents which relate to their toxic and flammable nature. In this work we have shown for the first time that room-temperature ionic liquids, such as 1-butyl-3-methylimi- dazolium hexafluorophosphate, [bmim][PF(6)], can be successfully used in place of conventional solvents for the liquid-liquid extraction of erythromycin-A and for the Rhodococcus R312 catalyzed biotransformation of 1, 3-dicyanobenzene (1,3-DCB) in a liquid-liquid, two-phase system. Extraction of erythromycin with either butyl acetate or [bmim][PF(6)] showed that values of the equilibrium partition coefficient, K, up to 20-25 could be obtained for both extractants. The variation of K with the extraction pH was also similar in the pH range 5-9 though differed significantly at higher pH values. Biotransformation of 1,3-DCB in both water-toluene and water-[bmim][PF(6)] systems showed similar profiles for the conversion of 1,3-DCB initially to 3-cyanobenzamide and then 3-cyanobenzoic acid. The initial rate of 3-cyanobenzamide production in the water-[bmim][PF(6)] system was somewhat lower, however, due to the reduced rate of 1,3-DCB mass transfer from the more viscous [bmim] [PF(6)] phase. It was also shown that the specific activity of the biocatalyst in the water-[bmim] [PF(6)] system was almost an order of magnitude greater than in the water-toluene system which suggests that the rate of 3-cyanobenzamide production was limited by substrate mass transfer rather than the activity of the biocatalyst. Copyright 2000 John Wiley & Sons, Inc.

Adjunctive stent use during endovascular intervention to the femoropopliteal artery with drug coated balloons: Insights from the XLPAD registry.

PubMed

Kokkinidis, Damianos G; Jeon-Slaughter, Haekyung; Khalili, Houman; Brilakis, Emmanouil S; Shammas, Nicolas W; Banerjee, Subhash; Armstrong, Ehrin J

2018-06-01

With growing use of drug-coated balloons (DCB) for femoropopliteal (FP) artery interventions, there is limited information on rates of real-world adjunctive stent use and its association with short and long-term outcomes. We report on 225 DCB treated FP lesions in 224 patients from the Excellence in Peripheral Artery Disease (XLPAD) registry (NCT01904851) between 2014 and 2016. Cochran-Mantel-Haenszel and Wilcoxon rank sum statistics were used to compare stented (planned or 'bail-out') versus non-stented DCB treated lesions. Stents were implanted in 31% of FP DCB interventions. Among the 70 stents implanted, 46% were for 'bail-out' indications and 54% were planned. Lesions treated with stents were longer (mean 150 mm vs 100 mm; p < 0.001) and less likely to be in-stent restenosis lesions (10% vs 28%; p=0.003). Stenting was significantly more frequent in complex FP lesions, including chronic total occlusions (66% vs 34%; p < 0.001). For bail-out stenting, interwoven nitinol stents were the most common type (50%) followed by drug-eluting stents (34%) and bare-metal stents (22%). There were no differences in peri-procedural complication rates or 12-month target limb revascularization rates (18.6% vs 11.6%; p=0.162) or 12-month amputation rates (11.4% vs 11%; p=0.92) between lesions where adjunctive stenting was used versus lesions without adjunctive stenting, respectively. In conclusion, in a contemporary 'real-world' adjudicated multicenter US registry, adjunctive stenting was necessary in nearly a third of the lesions, primarily for the treatment of more complex FP lesions, with similar short and intermediate-term clinical outcomes compared with non-stented lesions.

Bacterial Community Composition Associated with Pyrogenic Organic Matter (Biochar) Varies with Pyrolysis Temperature and Colonization Environment

PubMed Central

Dai, Zhongmin; Barberán, Albert; Li, Yong; Brookes, Philip C.

2017-01-01

ABSTRACT Microbes that colonize pyrogenic organic matter (PyOM) (also called biochar) play an important role in PyOM mineralization and crucially affect soil biogeochemical cycling, while the microbial community composition associated with PyOM particles is poorly understood. We generated two manure-based PyOMs with different characteristics (PyOM pyrolyzed at the low temperature of 300°C [i.e., PyOM300] and at the high temperature of 700°C [i.e., PyOM700]) and added them to high-carbon (4.15%) and low-C (0.37%) soil for microbial colonization. 16S rRNA gene sequencing showed that Actinobacteria, particularly Actinomycetales, was the dominant taxon in PyOM, regardless of the PyOM pyrolysis temperature and soil type. Bacterial communities associated with PyOM particles from high-C soils were similar to those in non-PyOM-amended soils. PyOM300 had higher total microbial activity and more differential bacterial communities than PyOM700. More bacterial operational taxonomic units (OTUs) preferentially thrived on the low-pyrolysis-temperature PyOM, while some specific OTUs thrived on high-pyrolysis-temperature PyOM. In particular, Chloroflexi species tended to be more prevalent in high-pyrolysis-temperature PyOM in low-C soils. In conclusion, the differences in colonized bacterial community composition between the different PyOMs were strongly influenced by the pyrolysis temperatures of PyOM, i.e., under conditions of easily mineralizable C or fused aromatic C, and by other properties, e.g., pH, surface area, and nutrient content. IMPORTANCE Pyrogenic organic matter (PyOM) is widely distributed in soil and fluvial ecosystems and plays an important role in biogeochemical cycling. Many studies have reported changes in soil microbial communities stimulated by PyOM, but very little is known about the microbial communities associated with PyOM. The microbes that colonize PyOMs can participate in the mineralization of PyOM, so changing its structure affects the fate of PyOMs and contributes to soil biogeochemical cycling. This study identified the bacterial community composition associated with PyOMs on the basis of high-throughput sequencing and demonstrated that both PyOM pyrolysis temperature and the colonization environment determined the bacterial community composition. Our work increases our understanding of the dominant phylogenetic taxa associated with PyOMs, demonstrates mechanisms mediating microbial metabolism and growth in PyOMs, and expands a new research area for pyrogenic organic matter. This study identified the bacterial community composition associated with PyOM, which is widely distributed in the environment. Most bacterial OTUs preferentially thrived on PyOM pyrolyzed at low temperature, while some specific OTUs thrived on PyOM pyrolyzed at high temperature. PMID:28405627

Bacterial Community Composition Associated with Pyrogenic Organic Matter (Biochar) Varies with Pyrolysis Temperature and Colonization Environment.

PubMed

Dai, Zhongmin; Barberán, Albert; Li, Yong; Brookes, Philip C; Xu, Jianming

2017-01-01

Microbes that colonize pyrogenic organic matter (PyOM) (also called biochar) play an important role in PyOM mineralization and crucially affect soil biogeochemical cycling, while the microbial community composition associated with PyOM particles is poorly understood. We generated two manure-based PyOMs with different characteristics (PyOM pyrolyzed at the low temperature of 300°C [i.e., PyOM300] and at the high temperature of 700°C [i.e., PyOM700]) and added them to high-carbon (4.15%) and low-C (0.37%) soil for microbial colonization. 16S rRNA gene sequencing showed that Actinobacteria , particularly Actinomycetales , was the dominant taxon in PyOM, regardless of the PyOM pyrolysis temperature and soil type. Bacterial communities associated with PyOM particles from high-C soils were similar to those in non-PyOM-amended soils. PyOM300 had higher total microbial activity and more differential bacterial communities than PyOM700. More bacterial operational taxonomic units (OTUs) preferentially thrived on the low-pyrolysis-temperature PyOM, while some specific OTUs thrived on high-pyrolysis-temperature PyOM. In particular, Chloroflexi species tended to be more prevalent in high-pyrolysis-temperature PyOM in low-C soils. In conclusion, the differences in colonized bacterial community composition between the different PyOMs were strongly influenced by the pyrolysis temperatures of PyOM, i.e., under conditions of easily mineralizable C or fused aromatic C, and by other properties, e.g., pH, surface area, and nutrient content. IMPORTANCE Pyrogenic organic matter (PyOM) is widely distributed in soil and fluvial ecosystems and plays an important role in biogeochemical cycling. Many studies have reported changes in soil microbial communities stimulated by PyOM, but very little is known about the microbial communities associated with PyOM. The microbes that colonize PyOMs can participate in the mineralization of PyOM, so changing its structure affects the fate of PyOMs and contributes to soil biogeochemical cycling. This study identified the bacterial community composition associated with PyOMs on the basis of high-throughput sequencing and demonstrated that both PyOM pyrolysis temperature and the colonization environment determined the bacterial community composition. Our work increases our understanding of the dominant phylogenetic taxa associated with PyOMs, demonstrates mechanisms mediating microbial metabolism and growth in PyOMs, and expands a new research area for pyrogenic organic matter. This study identified the bacterial community composition associated with PyOM, which is widely distributed in the environment. Most bacterial OTUs preferentially thrived on PyOM pyrolyzed at low temperature, while some specific OTUs thrived on PyOM pyrolyzed at high temperature.

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

Temple, Brian Allen; Armstrong, Jerawan Chudoung

This document is a mid-year report on a deliverable for the PYTHON Radiography Analysis Tool (PyRAT) for project LANL12-RS-107J in FY15. The deliverable is deliverable number 2 in the work package and is titled “Add the ability to read in more types of image file formats in PyRAT”. Right now PyRAT can only read in uncompressed TIF files (tiff files). It is planned to expand the file formats that can be read by PyRAT, making it easier to use in more situations. A summary of the file formats added include jpeg, jpg, png and formatted ASCII files.

Nanoparticle formulation enhanced protective immunity provoked by PYGPI8p-transamidase related protein (PyTAM) DNA vaccine in Plasmodium yoelii malaria model.

PubMed

Cherif, Mahamoud Sama; Shuaibu, Mohammed Nasir; Kodama, Yukinobu; Kurosaki, Tomoaki; Helegbe, Gideon Kofi; Kikuchi, Mihoko; Ichinose, Akitoyo; Yanagi, Tetsuo; Sasaki, Hitoshi; Yui, Katsuyuki; Tien, Nguyen Huy; Karbwang, Juntra; Hirayama, Kenji

2014-04-07

We have previously reported the new formulation of polyethylimine (PEI) with gamma polyglutamic acid (γ-PGA) nanoparticle (NP) to have provided Plasmodium yoelii merozoite surface protein-1 (PyMSP-1) plasmid DNA vaccine with enhanced protective cellular and humoral immunity in the lethal mouse malaria model. PyGPI8p-transamidase-related protein (PyTAM) was selected as a possible candidate vaccine antigen by using DNA vaccination screening from 29 GPI anchor and signal sequence motif positive genes picked up using web-based bioinformatics tools; though the observed protection was not complete. Here, we observed augmented protective effect of PyTAM DNA vaccine by using PEI and γ-PGA complex as delivery system. NP-coated PyTAM plasmid DNA immunized mice showed a significant survival rate from lethal P. yoelii challenge infection compared with naked PyTAM plasmid or with NP-coated empty plasmid DNA group. Antigen-specific IgG1 and IgG2b subclass antibody levels, proportion of CD4 and CD8T cells producing IFN-γ in the splenocytes and IL-4, IFN-γ, IL-12 and TNF-α levels in the sera and in the supernatants from ex vivo splenocytes culture were all enhanced by the NP-coated PyTAM DNA vaccine. These data indicates that NP augments PyTAM protective immune response, and this enhancement was associated with increased DC activation and concomitant IL-12 production. Copyright © 2014 Elsevier Ltd. All rights reserved.

A luminescent organic radical with two pyridyl groups: high photostability and dual stimuli-responsive properties, with theoretical analyses of photophysical processes† †Electronic supplementary information (ESI) available: Crystal structure data, ESR spectral data, DFT and TD-DFT calculations data, spectroscopic data, quantum yield and photostability in various solvents, electrochemical data (PDF). CCDC 1559962. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04034b

PubMed Central

Kimura, Shun; Tanushi, Akira; Kochi, Shuntaro; Sato, Tohru

2018-01-01

Luminescent monoradicals are expected to show unique properties based on their doublet state, where establishing a method to improve their photostability is an important issue for expanding their photofunctionality. We synthesized a highly photostable luminescent organic radical, the bis(3,5-dichloro-4-pyridyl)(2,4,6-trichlorophenyl)methyl radical (bisPyTM), containing two pyridyl groups on a tris(2,4,6-trichlorophenyl)methyl radical (TTM) skeleton. bisPyTM in dichloromethane exhibited fluorescence with an emission peak wavelength, λem, of 650 nm. We visually detected an emission (λem = 712 nm) from crystalline bisPyTM at 77 K, which is the first example of definite solid-state emission in a radical. Introducing the two nitrogen atoms into the TTM skeleton was shown to lower the energies of the frontier orbitals. The oscillator strength, f, of the electronic transition between the lowest excited state and the ground state, and the off-diagonal vibronic coupling constants (VCCs) were calculated theoretically for bisPyTM and the (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM). The calculated PyBTM to bisPyTM ratios for f or VCC agreed well with experimental radiative and non-radiative rate constants (kr and knr) ratios, respectively. This study shows that scaled kr and knr can be estimated and compared in this class of radicals using theoretical calculations, greatly advancing the prediction and design of their photofunctionality. The half-life of bisPyTM upon continuous UV light irradiation in dichloromethane was 47 or 3000 times longer those that of PyBTM (which contains one pyridyl group) and TTM (which has no pyridyl rings), respectively. The electrochemical and luminescent properties of bisPyTM were modulated in two stages using protons or B(C6F5)3. PMID:29675247

Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies

DOE PAGES

Gonzalez-Fabra, Joan; Bandeira, Nuno A. G.; Velasco, Veronica; ...

2017-03-27

The solid-state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL) 3(NO 3)(py)(H 2O)] (1), (Hpy)[CeEr(HL) 3(NO 3)(py)(H 2O)] (2), (Hpy)[CeGd(HL) 3(NO 3)(py)(H 2O)] (3), (Hpy)[PrSm(HL) 3(NO 3)(py)(H 2O)] (4), and (Hpy) 2[LaYb(HL) 3(NO 3)(H 2O)](NO 3) (5), in which H 3L is 6-(3-oxo-3-(2-hydroxyphenyl)propionyl)pyridine-2-carboxylic acid and py is pyridine, were analyzed experimentally and by using DFT calculations. Complexes 3, 4, and 5 are described here for the first time, and were analyzed by using single-crystal X-ray diffraction and mass spectrometry. The theoretical study was also extended to the [LaCe] and [LaLu] analogues. The results are consistent with a remarkable selectivity ofmore » the metal distribution within the molecule in the solid state, enhanced by the size difference between the different ions. This selectivity was reduced in solution, particularly for ions with the most similar radii. This unique entry into 4f–4f" heterometallic chemistry establishes for the first time the difference between the selectivity in solution and that in the solid state, as a result of changes to the coordination that follow the dissociation of terminal ligands upon dissolution of the complexes.« less

Non-local Second Order Closure Scheme for Boundary Layer Turbulence and Convection

NASA Astrophysics Data System (ADS)

Meyer, Bettina; Schneider, Tapio

2017-04-01

There has been scientific consensus that the uncertainty in the cloud feedback remains the largest source of uncertainty in the prediction of climate parameters like climate sensitivity. To narrow down this uncertainty, not only a better physical understanding of cloud and boundary layer processes is required, but specifically the representation of boundary layer processes in models has to be improved. General climate models use separate parameterisation schemes to model the different boundary layer processes like small-scale turbulence, shallow and deep convection. Small scale turbulence is usually modelled by local diffusive parameterisation schemes, which truncate the hierarchy of moment equations at first order and use second-order equations only to estimate closure parameters. In contrast, the representation of convection requires higher order statistical moments to capture their more complex structure, such as narrow updrafts in a quasi-steady environment. Truncations of moment equations at second order may lead to more accurate parameterizations. At the same time, they offer an opportunity to take spatially correlated structures (e.g., plumes) into account, which are known to be important for convective dynamics. In this project, we study the potential and limits of local and non-local second order closure schemes. A truncation of the momentum equations at second order represents the same dynamics as a quasi-linear version of the equations of motion. We study the three-dimensional quasi-linear dynamics in dry and moist convection by implementing it in a LES model (PyCLES) and compare it to a fully non-linear LES. In the quasi-linear LES, interactions among turbulent eddies are suppressed but nonlinear eddy—mean flow interactions are retained, as they are in the second order closure. In physical terms, suppressing eddy—eddy interactions amounts to suppressing, e.g., interactions among convective plumes, while retaining interactions between plumes and the environment (e.g., entrainment and detrainment). In a second part, we employ the possibility to include non-local statistical correlations in a second-order closure scheme. Such non-local correlations allow to directly incorporate the spatially coherent structures that occur in the form of convective updrafts penetrating the boundary layer. This allows us to extend the work that has been done using assumed-PDF schemes for parameterising boundary layer turbulence and shallow convection in a non-local sense.

Heterobimetallic Nitrido Complexes of Group 8 Metalloporphyrins.

PubMed

Cheung, Wai-Man; Chiu, Wai-Hang; de Vere-Tucker, Matthew; Sung, Herman H-Y; Williams, Ian D; Leung, Wa-Hung

2017-05-15

Heterobimetallic nitrido porphyrin complexes with the [(L)(por)M-N-M'(L OEt )Cl 2 ] formula {por 2- = 5,10,15,20-tetraphenylporphyrin (TPP 2- ) or 5,10,15,20-tetra(p-tolyl)porphyrin (TTP 2- ) dianion; L OEt - = [Co(η 5 -C 5 H 5 ){P(O)(OEt) 2 } 3 ] - ; M = Fe, Ru, or Os; M' = Ru or Os; L = H 2 O or pyridine} have been synthesized, and their electrochemistry has been studied. Treatment of trans-[Fe(TPP)(py) 2 ] (py = pyridine) with Ru(VI) nitride [Ru(L OEt )(N)Cl 2 ] (1) afforded Fe/Ru μ-nitrido complex [(py)(TPP)Fe(μ-N)Ru(L OEt )Cl 2 ] (2). Similarly, Fe/Os analogue [(py)(TPP)Fe(μ-N)Os(L OEt )Cl 2 ] (3) was obtained from trans-[Fe(TPP)(py) 2 ] and [Os(L OEt )(N)Cl 2 ]. However, no reaction was found between trans-[Fe(TPP)(py) 2 ] and [Re(L OEt )(N)Cl(PPh 3 )]. Treatment of trans-[M(TPP)(CO)(EtOH)] with 1 afforded μ-nitrido complexes [(H 2 O)(TPP)M(μ-N)Ru(L OEt )Cl 2 ] [M = Ru (4a) or Os (5)]. TTP analogue [(H 2 O)(TTP)Ru(μ-N)Ru(L OEt )Cl 2 ] (4b) was prepared similarly from trans-[Ru(TTP)(CO)(EtOH)] and 1. Reaction of [(H 2 O)(por)M(μ-N)M(L OEt )Cl 2 ] with pyridine gave adducts [(py)(por)M(μ-N)Ru(L OEt )Cl 2 ] [por = TTP, and M = Ru (6); por = TPP, and M = Os (7)]. The diamagnetism and short (por)M-N(nitride) distances in 2 [Fe-N, 1.683(3) Å] and 4b [Ru-N, 1.743(3) Å] are indicative of the M IV ═N═M' IV bonding description. The cyclic voltammograms of the Fe/Ru (2) and Ru/Ru (4b) complexes in CH 2 Cl 2 displayed oxidation couples at approximately +0.29 and +0.35 V versus Fc +/0 (Fc = ferrocene) that are tentatively ascribed to the oxidation of the {L OEt Ru} and {Ru(TTP)} moieties, respectively, whereas the Fe/Os (3) and Os/Ru (5) complexes exhibited Os-centered oxidation at approximately -0.06 and +0.05 V versus Fc +/0 , respectively. The crystal structures of 2 and 4b have been determined.

New RuII Complex for Dual Activity: Photoinduced Ligand Release and 1O2 Production

PubMed Central

Loftus, Lauren M.; White, Jessica K.; Albani, Bryan A.; Kohler, Lars; Kodanko, Jeremy J.; Thummel, Randolph P.

2016-01-01

The new complex [Ru(pydppn)(biq)(py)]2+ (1) undergoes both py photodissociation in CH3CN with Φ500=0.0070(4) and 1O2 production with ΦΔ=0.75(7) in CH3OH from a long-lived 3ππ* state centered on the pydppn ligand (pydppn=3-(pyrid-2-yl)benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine; biq = 2,2′-biquinoline; py= pyridine). This represents an order of magnitude decrease in the Φ500 compared to the previously reported model compound [Ru(tpy)(biq)(py)]2+ (3) (tpy=2,2′:6′,2″-terpyridine) that undergoes only ligand exchange. The effect on the quantum yields by the addition of a second deactivation pathway through the low-lying 3ππ* state necessary for dual reactivity was investigated using ultrafast and nanosecond transient absorption spectroscopy, revealing a significantly shorter 3MLCT lifetime in 1 relative to that of the model complex 3. Due to the structural similarities between the two compounds, the lower values of Φ500 and ΦΔ compared to that of [Ru(pydppn)(bpy)(py)]2+ (2) (bpy=2,2′-bipyridine) are attributed to a competitive excited state population between the 3LF states involved in ligand dissociation and the long-lived 3ππ* state in 1. Complex 1 represents a model compound for dual activity that may be applied to photochemotherapy. PMID:26715085

The coordination behaviour of ferrocene-based pyridylphosphine ligands towards Zn(II), Cd(II) and Hg(II).

PubMed

Siemeling, Ulrich; Klemann, Thorsten; Bruhn, Clemens; Schulz, Jiří; Štěpnička, Petr

2011-05-07

The reaction of Group 12 metal dihalides MX(2) with the P,N-ligands [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-2-py)] (1) (2-py = pyrid-2-yl), [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-CH(2)-2-py)] (2) and [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-3-py)] (3) (3-py = pyrid-3-yl) was investigated. For a 1 : 1 molar ratio of MX(2) and the respective ligand, three structure types were found in the solid state, viz. chelate, cyclic dimer and chain-like coordination polymer. The M(II) coordination environment is distorted pseudo-tetrahedral in each case. The P-M-N angle is much larger in the chelates (≥119°) than in the ligand-bridged structures (≤109°). 1 prefers the formation of chelates [MX(2)(1-κ(2)N,P)]. 3 forms coordination polymers [MX(2)(μ-3)](n). With the more flexible 2 all three structure types can occur. Dynamic coordination equilibria were observed in solution for the molecular complexes obtained with 1 and 2. NMR data indicate that the N- and P-donor sites interact most strongly with Zn(II) and Hg(II), respectively. While the formation of bis(phosphine)mercury complexes (soft-soft) was easily achieved, no bis(pyridine)zinc complex (borderline-borderline) could be obtained, which is surprising in view of the HSAB principle.

Identification of a Second Raccoon-Associated Polyomavirus.

PubMed

Geoghegan, Eileen M; Welch, Nicole L; Yabsley, Michael J; Church, Molly E; Pesavento, Patricia A; Buck, Christopher B

2017-06-29

Raccoon polyomavirus 1 (RacPyV1) is the suspected cause of an outbreak of fatal brain tumors among raccoons ( Procyon lotor ) in the western United States. Spleen samples from Georgia raccoons were screened for polyomaviruses. Although RacPyV1 was not detected, a previously unknown polyomavirus, which we designate RacPyV2, was identified and sequenced. Copyright © 2017 Geoghegan et al.

Effects of Dose and Route on the Disposition and Kinetics of 1-Butyl-1-methylpyrrolidinium Chloride in Male F-344 Rats

PubMed Central

Knudsen, G. A.; Cheng, Y.; Kuester, R. K.; Hooth, M. J.

2009-01-01

Studies were conducted to characterize the effects of dose and route of administration on the disposition of 1-butyl-1-methylpyrrolidinium (BmPy-Cl) in male Fischer-344 rats. After a single oral administration of [14C]BmPy-Cl (50 mg/kg), BmPy-Cl in the blood decreased rapidly after Cmax of 89.1 min with a distribution half-life (t1/2α) of 21 min, an elimination half-life (t1/2β) of 5.6 h, and a total body clearance of 7.6 ml/min. After oral administration (50, 5, and 0.5 mg/kg), 50 to 70% of the administered radioactivity was recovered in the feces, with the remainder recovered in the urine. Serial daily oral administrations of [14C]BmPy-Cl (50 mg/kg/day for 5 days) did not result in a notable alteration in disposition or elimination. After each administration, 88 to 94% of the dose was eliminated in a 24-h period, with 63 to 76% of dose recovered in the feces. Intravenous administration of [14C]BmPy-Cl (5 mg/kg) resulted in biphasic elimination. Oral systemic bioavailability was 43.4%, approximately equal to the dose recovered in urine after oral administration (29–38%). Total dermal absorption of [14C]BmPy-Cl (5 mg/kg) was moderate when it was applied in dimethylformamide-water (34 ± 13%), variable in water (22 ± 8%), or minimal in ethanol-water (13 ± 1%) vehicles. Urine was the predominant route of elimination regardless of vehicle. Only parent [14C]BmPy-Cl was detected in the urine after all doses and routes of administration. BmPy-Cl was found to be a substrate for (Kt = 37 μM) and inhibitor of (IC50/tetraethylammonium = 0.5 μM) human organic cation transporter 2. In summary, BmPy-Cl is moderately absorbed, extracted by the kidney, and eliminated in the urine as parent compound, independent of dose, number, or route of administration. PMID:19704025

Influence of extractable soil manganese on oxidation capacity of different soils in Korea

NASA Astrophysics Data System (ADS)

Chon, Chul-Min; Kim, Jae Gon; Lee, Gyoo Ho; Kim, Tack Hyun

2008-08-01

We examined the relationship between soil oxidation capacity and extractable soil manganese, iron oxides, and other soil properties. The Korean soils examined in this study exhibited low to medium Cr oxidation capacities, oxidizing 0.00-0.47 mmol/kg, except for TG-4 soils, which had the highest capacity for oxidizing added Cr(III) [>1.01 mmol/kg of oxidized Cr(VI)]. TG and US soils, with high Mn contents, had relatively high oxidation capacities. The Mn amounts extracted by dithionite-citrate-bicarbonate (DCB) (Mnd), NH2OH·HCl (Mnh), and hydroquinone (Mnr) were generally very similar, except for the YS1 soils, and were well correlated. Only small proportions of either total Mn or DCB-extractable Mn were extracted by NH2OH·HCl and hydroquinone in the YS1 soils, suggesting inclusion of NH2OH·HCl and hydroquinone-resistant Mn oxides, because these extractants are weaker reductants than DCB. No Cr oxidation test results were closely related to total Mn concentrations, but Mnd, Mnh, and Mnr showed a relatively high correlation with the Cr tests ( r = 0.655-0.851; P < 0.01). The concentrations of Mnd and Mnh were better correlated with the Cr oxidation tests than was the Mnr concentration, suggesting that the oxidation capacity of our soil samples can be better explained by Mnd and Mnh than by Mnr. The first component in principal components analysis indicated that extractable soil Mn was a main factor controlling net Cr oxidation in the soils. Total soil Mn, Fe oxides, and the clay fraction are crucial for predicting the mobility of pollutants and heavy metals in soils. The second principal component indicated that the presence of Fe oxides in soils had a significant relationship with the clay fraction and total Mn oxide, and was also related to heavy-metal concentrations (Zn, Cd, and Cu, but not Pb).

Molecular recognition of DNA base pairs by the formamido/pyrrole and formamido/imidazole pairings in stacked polyamides

PubMed Central

Buchmueller, Karen L.; Staples, Andrew M.; Uthe, Peter B.; Howard, Cameron M.; Pacheco, Kimberly A. O.; Cox, Kari K.; Henry, James A.; Bailey, Suzanna L.; Horick, Sarah M.; Nguyen, Binh; Wilson, W. David; Lee, Moses

2005-01-01

Polyamides containing an N-terminal formamido (f) group bind to the minor groove of DNA as staggered, antiparallel dimers in a sequence-specific manner. The formamido group increases the affinity and binding site size, and it promotes the molecules to stack in a staggered fashion thereby pairing itself with either a pyrrole (Py) or an imidazole (Im). There has not been a systematic study on the DNA recognition properties of the f/Py and f/Im terminal pairings. These pairings were analyzed here in the context of f-ImPyPy, f-ImPyIm, f-PyPyPy and f-PyPyIm, which contain the central pairing modes, –ImPy– and –PyPy–. The specificity of these triamides towards symmetrical recognition sites allowed for the f/Py and f/Im terminal pairings to be directly compared by SPR, CD and ΔTM experiments. The f/Py pairing, when placed next to the –ImPy– or –PyPy– central pairings, prefers A/T and T/A base pairs to G/C base pairs, suggesting that f/Py has similar DNA recognition specificity to Py/Py. With –ImPy– central pairings, f/Im prefers C/G base pairs (>10 times) to the other Watson–Crick base pairs; therefore, f/Im behaves like the Py/Im pair. However, the f/Im pairing is not selective for the C/G base pair when placed next to the –PyPy– central pairings. PMID:15703305

Annual burning of a tallgrass prairie inhibits C and N cycling in soil, increasing recalcitrant pyrogenic organic matter storage while reducing N availability.

PubMed

Soong, Jennifer L; Cotrufo, M Francesca

2015-06-01

Grassland ecosystems store an estimated 30% of the world's total soil C and are frequently disturbed by wildfires or fire management. Aboveground litter decomposition is one of the main processes that form soil organic matter (SOM). However, during a fire biomass is removed or partially combusted and litter inputs to the soil are substituted with inputs of pyrogenic organic matter (py-OM). Py-OM accounts for a more recalcitrant plant input to SOM than fresh litter, and the historical frequency of burning may alter C and N retention of both fresh litter and py-OM inputs to the soil. We compared the fate of these two forms of plant material by incubating (13) C- and (15) N-labeled Andropogon gerardii litter and py-OM at both an annually burned and an infrequently burned tallgrass prairie site for 11 months. We traced litter and py-OM C and N into uncomplexed and organo-mineral SOM fractions and CO2 fluxes and determined how fire history affects the fate of these two forms of aboveground biomass. Evidence from CO2 fluxes and SOM C:N ratios indicates that the litter was microbially transformed during decomposition while, besides an initial labile fraction, py-OM added to SOM largely untransformed by soil microbes. Additionally, at the N-limited annually burned site, litter N was tightly conserved. Together, these results demonstrate how, although py-OM may contribute to C and N sequestration in the soil due to its resistance to microbial degradation, a long history of annual removal of fresh litter and input of py-OM infers N limitation due to the inhibition of microbial decomposition of aboveground plant inputs to the soil. These results provide new insight into how fire may impact plant inputs to the soil, and the effects of py-OM on SOM formation and ecosystem C and N cycling. © 2014 John Wiley & Sons Ltd.

Dye-sensitized electron transfer from TiO2 to oxidized triphenylamines that follows first-order kinetics

PubMed Central

DiMarco, Brian N.; Troian-Gautier, Ludovic; Sampaio, Renato N.

2017-01-01

Two sensitizers, [Ru(bpy)2(dcb)]2+ (RuC) and [Ru(bpy)2(dpb)]2+ (RuP), where bpy is 2,2′-bipyridine, dcb is 4,4′-dicarboxylic acid-2,2′-bipyridine and dpb is 4,4′-diphosphonic acid-2,2′-bipyridine, were anchored to mesoporous TiO2 thin films and utilized to sensitize the reaction of TiO2 electrons with oxidized triphenylamines, TiO2(e–) + TPA+ → TiO2 + TPA, to visible light in CH3CN electrolytes. A family of four symmetrically substituted triphenylamines (TPAs) with formal Eo(TPA+/0) reduction potentials that spanned a 0.5 eV range was investigated. Surprisingly, the reaction followed first-order kinetics for two TPAs that provided the largest thermodynamic driving force. Such first-order reactivity indicates a strong Coulombic interaction between TPA+ and TiO2 that enables the injected electron to tunnel back in one concerted step. The kinetics for the other TPA derivatives were non-exponential and were modelled with the Kohlrausch–William–Watts (KWW) function. A Perrin-like reaction sphere model is proposed to rationalize the kinetic data. The activation energies were the same for all of the TPAs, within experimental error. The average rate constants were found to increase with the thermodynamic driving force, consistent with electron transfer in the Marcus normal region. PMID:29629161

Mössbauer studies on some Argentinian soil: Mollisols from Bahia Blanca

NASA Astrophysics Data System (ADS)

Saragovi, C.; Labenski, F.; Duhalde, S. M.; Acebal, S.; Venegas, R.

1994-12-01

Clay fractions of a Mollisol sample as is, treated with ammonium oxalate (AO), with dithionite-citrate-bicarbonate (DCB) and with dithionite-ethilene-diamine-tetraacetic acid (D-EDTA) methods, were studied. Illite-montmorillonites together with hematites, goethites and maghemites, all of the AI-substituted and with a wide range of sizes, were identified. It is found that the AO attack extracts little iron, whereas the other two attacks extract the magnetic signal. Furthermore, the DCB attack facilitates the reduction of the Fe3+ ions, while the D-EDTA method does not. Instead, this attack extracts more clay mineral Fe ions. A comparison with large grain soil samples is made.

Experimental Study of the Mode I Interlaminar Fracture Toughness Improvement on Stitched CFRP Laminates

NASA Astrophysics Data System (ADS)

Iwahori, Yutaka; Ishikawa, Takashi; Watanabe, Naoyuki; Hayashi, Yoichi; Ito, Akira

Experimental investigations have been made on the mode I interlaminar fracture toughness (GIC) of stitched CFRP (carbon fiber reinforced plastic) laminates. The GIC of stitched CFRP laminates fabricated by resin transfer molding (RTM) and stitching with five kinds of stitch thread thicknesses, 400d (denier), 600d, 800d, 1000d, and 1200d were experimentally obtained by double cantilever beam (DCB) tests. Interlaminar tension tests for stitched CFRP laminates for a specimen containing only one stitch thread were also carried out. The consumption energy of the single stitched CFRP laminates (Wt) and stitch threads broken modes were obtained by such interlaminar tension tests. DCB test results show that the GIC of stitched CFRP laminates of several stitch thread thicknesses are governed by stitch density (SD). It is found that the relationship between ΔGIC/ΔSD and Wt are linear function. In other words, the GIC of Kevlar® stitched CFRP laminates is not only governed by SD but also Wt obtained from the interlaminar tension tests. It is also suggested that the interlaminar tension test results exhibit the potential for GIC estimation on the Kevlar® stitched CFRP laminates instead of conducting the DCB tests.

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

Borden, R.C.; Bedient, P.B.

A three well injection-production test was performed at the United Creosoting Company (UCC) site in Conroe, Texas, to estimate the effective in situ retardation factors for adsorption and to evaluate the significance of biotransformation in limiting the transport of polycyclic aromatics present in the shallow aquifer. The field test was also used as a model to determine if this type of testing would be feasible at other hazardous waste sites. During the test, chloride, a non-reactive tracer and two organic compounds, naphthalene and paradichlorobenzene (pDCB), were injected into a center well for 24 hours followed by clean ground water formore » six days. Ground water was continuously produced from two adjoining wells and monitored to observe the breakthrough of these compounds. Data from the test were analyzed by comparing the statistical moments of the chloride and organics distributions. Retardation factors for naphthalene and pDCB were estimated to be 0.03 and 0.97 by comparison of the statistical moments. A significant loss of naphthalene and pDCB was also observed during the three well test, apparently due to biotransformation. These results suggest that biotransformation is the major process limiting the transport of naphthalene and similar compounds at the UCC site.« less

A method of estimating GPS instrumental biases with a convolution algorithm

NASA Astrophysics Data System (ADS)

Li, Qi; Ma, Guanyi; Lu, Weijun; Wan, Qingtao; Fan, Jiangtao; Wang, Xiaolan; Li, Jinghua; Li, Changhua

2018-03-01

This paper presents a method of deriving the instrumental differential code biases (DCBs) of GPS satellites and dual frequency receivers. Considering that the total electron content (TEC) varies smoothly over a small area, one ionospheric pierce point (IPP) and four more nearby IPPs were selected to build an equation with a convolution algorithm. In addition, unknown DCB parameters were arranged into a set of equations with GPS observations in a day unit by assuming that DCBs do not vary within a day. Then, the DCBs of satellites and receivers were determined by solving the equation set with the least-squares fitting technique. The performance of this method is examined by applying it to 361 days in 2014 using the observation data from 1311 GPS Earth Observation Network (GEONET) receivers. The result was crosswise-compared with the DCB estimated by the mesh method and the IONEX products from the Center for Orbit Determination in Europe (CODE). The DCB values derived by this method agree with those of the mesh method and the CODE products, with biases of 0.091 ns and 0.321 ns, respectively. The convolution method's accuracy and stability were quite good and showed improvements over the mesh method.

GfaPy: a flexible and extensible software library for handling sequence graphs in Python.

PubMed

Gonnella, Giorgio; Kurtz, Stefan

2017-10-01

GFA 1 and GFA 2 are recently defined formats for representing sequence graphs, such as assembly, variation or splicing graphs. The formats are adopted by several software tools. Here, we present GfaPy, a software package for creating, parsing and editing GFA graphs using the programming language Python. GfaPy supports GFA 1 and GFA 2, using the same interface and allows for interconversion between both formats. The software package provides a simple interface for custom record types, which is an important new feature of GFA 2 (compared to GFA 1). This enables new applications of the format. GfaPy is available open source at https://github.com/ggonnella/gfapy and installable via pip. gonnella@zbh.uni-hamburg.de. Supplementary data are available at Bioinformatics online. © The Author (2017). Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com

The Bayesian Approach to Association

NASA Astrophysics Data System (ADS)

Arora, N. S.

2017-12-01

The Bayesian approach to Association focuses mainly on quantifying the physics of the domain. In the case of seismic association for instance let X be the set of all significant events (above some threshold) and their attributes, such as location, time, and magnitude, Y1 be the set of detections that are caused by significant events and their attributes such as seismic phase, arrival time, amplitude etc., Y2 be the set of detections that are not caused by significant events, and finally Y be the set of observed detections We would now define the joint distribution P(X, Y1, Y2, Y) = P(X) P(Y1 | X) P(Y2) I(Y = Y1 + Y2) ; where the last term simply states that Y1 and Y2 are a partitioning of Y. Given the above joint distribution the inference problem is simply to find the X, Y1, and Y2 that maximizes posterior probability P(X, Y1, Y2| Y) which reduces to maximizing P(X) P(Y1 | X) P(Y2) I(Y = Y1 + Y2). In this expression P(X) captures our prior belief about event locations. P(Y1 | X) captures notions of travel time, residual error distributions as well as detection and mis-detection probabilities. While P(Y2) captures the false detection rate of our seismic network. The elegance of this approach is that all of the assumptions are stated clearly in the model for P(X), P(Y1|X) and P(Y2). The implementation of the inference is merely a by-product of this model. In contrast some of the other methods such as GA hide a number of assumptions in the implementation details of the inference - such as the so called "driver cells." The other important aspect of this approach is that all seismic knowledge including knowledge from other domains such as infrasound and hydroacoustic can be included in the same model. So, we don't need to separately account for misdetections or merge seismic and infrasound events as a separate step. Finally, it should be noted that the objective of automatic association is to simplify the job of humans who are publishing seismic bulletins based on this output. The error metric for association should accordingly count errors such as missed events much higher than spurious events because the former require more work from humans. Furthermore, the error rate needs to be weighted higher during periods of high seismicity such as an aftershock sequence when the human effort tends to increase.

Role of overexpressed CFA/I fimbriae in bacterial swimming

NASA Astrophysics Data System (ADS)

Cao, Ling; Suo, Zhiyong; Lim, Timothy; Jun, SangMu; Deliorman, Muhammedin; Riccardi, Carol; Kellerman, Laura; Avci, Recep; Yang, Xinghong

2012-06-01

Enterotoxigenic Escherichia coli CFA/I is a protective antigen and has been overexpressed in bacterial vectors, such as Salmonella Typhimurium H683, to generate vaccines. Effects that overexpressed CFA/I may engender on the bacterial host remain largely unexplored. To investigate, we constructed a high CFA/I expression strain, H683-pC2, and compared it to a low CFA/I expression strain, H683-pC, and to a non-CFA/I expression strain, H683-pY. The results showed that H683-pC2 was less able to migrate into semisolid agar (0.35%) than either H683-pC or H683-pY. Bacteria that migrated showed motility halo sizes of H683-pC2 < H683-pC < H683-pY. In the liquid culture media, H683-pC2 cells precipitated to the bottom of the tube, while those of H683-pY did not. In situ imaging revealed that H683-pC2 bacilli tended to auto-agglutinate within the semisolid agar, while H683-pY bacilli did not. When the cfaBE fimbrial fiber encoding genes were deleted from pC2, the new plasmid, pC2(-), significantly recovered bacterial swimming capability. Our study highlights the negative impact of overexpressed CFA/I fimbriae on bacterial swimming motility.

Role of overexpressed CFA/I fimbriae in bacterial swimming.

PubMed

Cao, Ling; Suo, Zhiyong; Lim, Timothy; Jun, Sangmu; Deliorman, Muhammedin; Riccardi, Carol; Kellerman, Laura; Avci, Recep; Yang, Xinghong

2012-06-01

Enterotoxigenic Escherichia coli CFA/I is a protective antigen and has been overexpressed in bacterial vectors, such as Salmonella Typhimurium H683, to generate vaccines. Effects that overexpressed CFA/I may engender on the bacterial host remain largely unexplored. To investigate, we constructed a high CFA/I expression strain, H683-pC2, and compared it to a low CFA/I expression strain, H683-pC, and to a non-CFA/I expression strain, H683-pY. The results showed that H683-pC2 was less able to migrate into semisolid agar (0.35%) than either H683-pC or H683-pY. Bacteria that migrated showed motility halo sizes of H683-pC2 < H683-pC < H683-pY. In the liquid culture media, H683-pC2 cells precipitated to the bottom of the tube, while those of H683-pY did not. In situ imaging revealed that H683-pC2 bacilli tended to auto-agglutinate within the semisolid agar, while H683-pY bacilli did not. When the cfaBE fimbrial fiber encoding genes were deleted from pC2, the new plasmid, pC2(-), significantly recovered bacterial swimming capability. Our study highlights the negative impact of overexpressed CFA/I fimbriae on bacterial swimming motility.

A Naturally Transmitted Epitheliotropic Polyomavirus Pathogenic in Immunodeficient Rats: Characterization, Transmission, and Preliminary Epidemiologic Studies.

PubMed

Besch-Williford, Cynthia; Pesavento, Patricia; Hamilton, Shari; Bauer, Beth; Kapusinszky, Beatrix; Phan, Tung; Delwart, Eric; Livingston, Robert; Cushing, Susan; Watanabe, Rie; Levin, Stephen; Berger, Diana; Myles, Matthew

2017-07-01

We report the identification, pathogenesis, and transmission of a novel polyomavirus in severe combined immunodeficient F344 rats with null Prkdc and interleukin 2 receptor gamma genes. Infected rats experienced weight loss, decreased fecundity, and mortality. Large basophilic intranuclear inclusions were observed in epithelium of the respiratory tract, salivary and lacrimal glands, uterus, and prostate gland. Unbiased viral metagenomic sequencing of lesioned tissues identified a novel polyomavirus, provisionally named Rattus norvegicus polyomavirus 2 (RatPyV2), which clustered with Washington University (WU) polyomavirus in the Wuki clade of the Betapolyomavirus genus. In situ hybridization analyses and quantitative polymerase chain reaction (PCR) results demonstrated viral nucleic acids in epithelium of respiratory, glandular, and reproductive tissues. Polyomaviral disease was reproduced in Foxn1 rnu nude rats cohoused with infected rats or experimentally inoculated with virus. After development of RatPyV2-specific diagnostic assays, a survey of immune-competent rats from North American research institutions revealed detection of RatPyV2 in 7 of 1,000 fecal samples by PCR and anti-RatPyV2 antibodies in 480 of 1,500 serum samples. These findings suggest widespread infection in laboratory rat populations, which may have profound implications for established models of respiratory injury. Additionally, RatPyV2 infection studies may provide an important system to investigate the pathogenesis of WU polyomavirus diseases of man.

Autocatalytic Pyrolysis of Wastewater Biosolids for Product Upgrading.

PubMed

Liu, Zhongzhe; McNamara, Patrick; Zitomer, Daniel

2017-09-05

The main goals for sustainable water resource recovery include maximizing energy generation, minimizing adverse environmental impacts, and recovering beneficial resources. Wastewater biosolids pyrolysis is a promising technology that could help facilities reach these goals because it produces biochar that is a valuable soil amendment as well as bio-oil and pyrolysis gas (py-gas) that can be used for energy. The raw bio-oil, however, is corrosive; therefore, employing it as fuel is challenging using standard equipment. A novel pyrolysis process using wastewater biosolids-derived biochar (WB-biochar) as a catalyst was investigated to decrease bio-oil and increase py-gas yield for easier energy recovery. WB-biochar catalyst increased the py-gas yield nearly 2-fold, while decreasing bio-oil production. The catalyzed bio-oil also contained fewer constituents based on GC-MS and GC-FID analyses. The energy shifted from bio-oil to py-gas, indicating the potential for easier on-site energy recovery using the relatively clean py-gas. The metals contained in wastewater biosolids played an important role in upgrading pyrolysis products. The Ca and Fe in WB-biochar reduced bio-oil yield and increased py-gas yield. The py-gas energy increase may be especially useful at water resource recovery facilities that already combust anaerobic digester biogas for energy since it may be possible to blend biogas and py-gas for combined use.

Coupling Graphene Sheets with Iron Oxide Nanoparticles for Energy Storage and Microelectronics

DTIC Science & Technology

2015-08-13

of highly oriented pyrolytic graphite ( HOPG ) flake. Two electrode system containing platinum as counter electrode and HOPG as working electrode is... XRD ) patterns of the HOPG , exfoliated graphene, PyDop1-ɤ-Fe2O3 and PyDop1-ɤ-Fe2O3-graphene are given in Figure 1e. HOPG show a very sharp diffraction...atoms arranged in hexagonal pattern in honey comb crystal lattice, (c) TEM (d) HRTEM image of graphene- PyDop1-MNP hybrid, (e) XRD pattern of the HOPG

Identification of the WW domain-interaction sites in the unstructured N-terminal domain of EBV LMP 2A.

PubMed

Seo, Min-Duk; Park, Sung Jean; Kim, Hyun-Jung; Lee, Bong Jin

2007-01-09

Epstein-Barr virus latency is maintained by the latent membrane protein (LMP) 2A, which mimics the B-cell receptor (BCR) and perturbs BCR signaling. The cytoplasmic N-terminal domain of LMP2A is composed of 119 amino acids. The N-terminal domain of LMP2A (LMP2A NTD) contains two PY motifs (PPPPY) that interact with the WW domains of Nedd4 family ubiquitin-protein ligases. Based on our analysis of NMR data, we found that the LMP2A NTD adopts an overall random-coil structure in its native state. However, the region between residues 60 and 90 was relatively ordered, and seemed to form the hydrophobic core of the LMP2A NTD. This region resides between two PY motifs and is important for WW domain binding. Mapping of the residues involved in the interaction between the LMP2A NTD and WW domains was achieved by chemical shift perturbation, by the addition of WW2 and WW3 peptides. Interestingly, the binding of the WW domains mainly occurred in the hydrophobic core of the LMP2A NTD. In addition, we detected a difference in the binding modes of the two PY motifs against the two WW peptides. The binding of the WW3 peptide caused the resonances of five residues (Tyr(60), Glu(61), Asp(62), Trp(65), and Gly(66)) just behind the N-terminal PY motif of the LMP2A NTD to disappear. A similar result was obtained with WW2 binding. However, near the C-terminal PY motif, the chemical shift perturbation caused by WW2 binding was different from that due to WW3 binding, indicating that the residues near the PY motifs are involved in selective binding of WW domains. The present work represents the first structural study of the LMP2A NTD and provides fundamental structural information about its interaction with ubiquitin-protein ligase.

Characterization of short interspersed elements (SINEs) in a red alga, Porphyra yezoensis.

PubMed

Zhang, Wenbo; Lin, Xiaofei; Peddigari, Suresh; Takechi, Katsuaki; Takano, Hiroyoshi; Takio, Susumu

2007-02-01

Short interspersed element (SINE)-like sequences referred to as PySN1 and PySN2 were identified in a red alga, Porphyra yezoensis. Both elements contained an internal promoter with motifs (A box and B box) recognized by RNA polymerase III, and target site duplications at both ends. Genomic Southern blot analysis revealed that both elements were widely and abundantly distributed on the genome. 3' and 5' RACE suggested that PySN1 was expressed as a chimera transcript with flanking SINE-unrelated sequences and possessed the poly-A tail at the same position near the 3' end of PySN1.

Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent.

PubMed

Postils, Verònica; Company, Anna; Solà, Miquel; Costas, Miquel; Luis, Josep M

2015-09-08

The reaction mechanisms for alkane hydroxylation catalyzed by non-heme Fe(V)O complexes presented in the literature vary from rebound stepwise to concerted highly asynchronous processes. The origin of these important differences is still not completely understood. Herein, in order to clarify this apparent inconsistency, the hydroxylation of a series of alkanes (methane and substrates bearing primary, secondary, and tertiary C-H bonds) through a Fe(V)O species, [Fe(V)(O)(OH)(PyTACN)](2+) (PyTACN = 1-(2'-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane), has been computationally examined at the gas phase and in acetonitrile solution. The initial breaking of the C-H bond can occur via hydrogen atom transfer (HAT), leading to an intermediate where there is an interaction between the radical substrate and [Fe(IV)(OH)2(PyTACN)](2+), or through hydride transfer to form a cationic substrate interacting with the [Fe(III)(OH)2(PyTACN)](+) species. Our calculations show the following: (i) except for methane in the rest of the alkanes studied, the intermediate formed by R(+) and [Fe(III)(OH)2(PyTACN)](+) is more stable than that involving the alkyl radical and the [Fe(IV)(OH)2(PyTACN)](2+) complex; (ii) in spite of (i), the first step of the reaction mechanism for all substrates is a HAT instead of hydride abstraction; (iii) the HAT is the rate-determining step for all analyzed cases; and (iv) the barrier for the HAT decreases along methane → primary → secondary → tertiary carbon. The second part of the reaction mechanism corresponds to the rebound process. Therefore, the stereospecific hydroxylation of alkane C-H bonds by non-heme Fe(V)(O) species occurs through a rebound stepwise mechanism that resembles that taking place at heme analogues. Finally, our study also shows that, to properly describe alkane hydroxylation processes mediated by Fe(V)O species, it is essential to consider the solvent effects during geometry optimizations. The use of gas-phase geometries explains the variety of mechanisms for the hydroxylation of alkanes reported in the literature.

Recurrence of intestinal metaplasia and early neoplasia after endoscopic eradication therapy for Barrett’s esophagus: a systematic review and meta-analysis *

PubMed Central

Fujii-Lau, Larissa L.; Cinnor, Birtukan; Shaheen, Nicholas; Gaddam, Srinivas; Komanduri, Srinadh; Muthusamy, V. Raman; Das, Ananya; Wilson, Robert; Simon, Violette C.; Kushnir, Vladimir; Mullady, Daniel; Edmundowicz, Steven A.; Early, Dayna S.; Wani, Sachin

2017-01-01

Background  Conflicting data exist with regard to recurrence rates of intestinal metaplasia (IM) and dysplasia after achieving complete eradication of intestinal metaplasia (CE-IM) in Barrett’s esophagus (BE) patients. Aim  (i) To determine the incidence of recurrent IM and dysplasia achieving CE-IM and (ii) to compare recurrence rates between treatment modalities [radiofrequency ablation (RFA) with or without endoscopic mucosal resection (EMR) vs stepwise complete EMR (SRER)]. Methods  A systematic search was performed for studies reporting on outcomes and estimates of recurrence rates after achieving CE-IM. Pooled incidence [per 100-patient-years (PY)] and risk ratios with 95 %CI were obtained. Heterogeneity was measured using the I 2 statistic. Subgroup analyses, decided a priori, were performed to explore heterogeneity in results. Results  A total of 39 studies were identified (25-RFA, 13-SRER, and 2 combined). The pooled incidence of any recurrence was 7.5 (95 %CI 6.1 – 9.0)/100 PY with a pooled incidence of IM recurrence rate of 4.8 (95 %CI 3.8 – 5.9)/100 PY, and dysplasia recurrence rate of 2.0 (95 %CI 1.5 – 2.5)/100 PY. Compared to the SRER group, the RFA group had significantly higher overall [8.6 (6.7 – 10.5)/100 PY vs. 5.1 (3.1 – 7)/100 PY, P  = 0.01] and IM recurrence rates [5.8 (4.3 – 7.3)/100 PY vs. 3.1 (1.7 – 4)/100 PY, P  < 0.01] with no difference in recurrence rates of dysplasia. Significant heterogeneity between studies was identified. The majority of recurrences were amenable to repeat endoscopic eradication therapy (EET). Conclusion  The results of this study demonstrate that the incidence rates of overall, IM, and dysplasia recurrence rates post-EET are not inconsiderable and reinforce the importance of close surveillance after achieving CE-IM. PMID:28573176

Recurrence of intestinal metaplasia and early neoplasia after endoscopic eradication therapy for Barrett's esophagus: a systematic review and meta-analysis.

PubMed

Fujii-Lau, Larissa L; Cinnor, Birtukan; Shaheen, Nicholas; Gaddam, Srinivas; Komanduri, Srinadh; Muthusamy, V Raman; Das, Ananya; Wilson, Robert; Simon, Violette C; Kushnir, Vladimir; Mullady, Daniel; Edmundowicz, Steven A; Early, Dayna S; Wani, Sachin

2017-06-01

 Conflicting data exist with regard to recurrence rates of intestinal metaplasia (IM) and dysplasia after achieving complete eradication of intestinal metaplasia (CE-IM) in Barrett's esophagus (BE) patients.  (i) To determine the incidence of recurrent IM and dysplasia achieving CE-IM and (ii) to compare recurrence rates between treatment modalities [radiofrequency ablation (RFA) with or without endoscopic mucosal resection (EMR) vs stepwise complete EMR (SRER)].  A systematic search was performed for studies reporting on outcomes and estimates of recurrence rates after achieving CE-IM. Pooled incidence [per 100-patient-years (PY)] and risk ratios with 95 %CI were obtained. Heterogeneity was measured using the I 2 statistic. Subgroup analyses, decided a priori, were performed to explore heterogeneity in results.  A total of 39 studies were identified (25-RFA, 13-SRER, and 2 combined). The pooled incidence of any recurrence was 7.5 (95 %CI 6.1 - 9.0)/100 PY with a pooled incidence of IM recurrence rate of 4.8 (95 %CI 3.8 - 5.9)/100 PY, and dysplasia recurrence rate of 2.0 (95 %CI 1.5 - 2.5)/100 PY. Compared to the SRER group, the RFA group had significantly higher overall [8.6 (6.7 - 10.5)/100 PY vs. 5.1 (3.1 - 7)/100 PY, P  = 0.01] and IM recurrence rates [5.8 (4.3 - 7.3)/100 PY vs. 3.1 (1.7 - 4)/100 PY, P  < 0.01] with no difference in recurrence rates of dysplasia. Significant heterogeneity between studies was identified. The majority of recurrences were amenable to repeat endoscopic eradication therapy (EET).  The results of this study demonstrate that the incidence rates of overall, IM, and dysplasia recurrence rates post-EET are not inconsiderable and reinforce the importance of close surveillance after achieving CE-IM.

Airland Battle Doctrine

DTIC Science & Technology

1988-09-01

Professional Paper 463 / September 1988 OTIC - EL cOPY V 0- 00 00 N Airland Battle Doctrine DTIC S ELECTE DEC 2 81988D Douglas W. Skinner Dcb A...missiles to ground targets. Initial deployment will be on the Army’s OV-i Bronco and the Air Force’s TR-l and C-18. This is another outgrowth of the

Coupling of tandem Smad ubiquitination regulatory factor (Smurf) WW domains modulates target specificity.

PubMed

Chong, P Andrew; Lin, Hong; Wrana, Jeffrey L; Forman-Kay, Julie D

2010-10-26

Smad ubiquitination regulatory factor 2 (Smurf2) is an E3 ubiquitin ligase that participates in degradation of TGF-β receptors and other targets. Smurf2 WW domains recognize PPXY (PY) motifs on ubiquitin ligase target proteins or on adapters, such as Smad7, that bind to E3 target proteins. We previously demonstrated that the isolated WW3 domain of Smurf2, but not the WW2 domain, can directly bind to a Smad7 PY motif. We show here that the WW2 augments this interaction by binding to the WW3 and making auxiliary contacts with the PY motif and a novel E/D-S/T-P motif, which is N-terminal to all Smad PY motifs. The WW2 likely enhances the selectivity of Smurf2 for the Smad proteins. NMR titrations confirm that Smad1 and Smad2 are bound by Smurf2 with the same coupled WW domain arrangement used to bind Smad7. The analogous WW domains in the short isoform of Smurf1 recognize the Smad7 PY peptide using the same coupled mechanism. However, a longer Smurf1 isoform, which has an additional 26 residues in the inter-WW domain linker, is only partially able to use the coupled WW domain binding mechanism. The longer linker results in a decrease in affinity for the Smad7 peptide. Interdomain coupling of WW domains enhances selectivity and enables the tuning of interactions by isoform switching.

Coupling of tandem Smad ubiquitination regulatory factor (Smurf) WW domains modulates target specificity

PubMed Central

Chong, P. Andrew; Lin, Hong; Wrana, Jeffrey L.; Forman-Kay, Julie D.

2010-01-01

Smad ubiquitination regulatory factor 2 (Smurf2) is an E3 ubiquitin ligase that participates in degradation of TGF-β receptors and other targets. Smurf2 WW domains recognize PPXY (PY) motifs on ubiquitin ligase target proteins or on adapters, such as Smad7, that bind to E3 target proteins. We previously demonstrated that the isolated WW3 domain of Smurf2, but not the WW2 domain, can directly bind to a Smad7 PY motif. We show here that the WW2 augments this interaction by binding to the WW3 and making auxiliary contacts with the PY motif and a novel E/D-S/T-P motif, which is N-terminal to all Smad PY motifs. The WW2 likely enhances the selectivity of Smurf2 for the Smad proteins. NMR titrations confirm that Smad1 and Smad2 are bound by Smurf2 with the same coupled WW domain arrangement used to bind Smad7. The analogous WW domains in the short isoform of Smurf1 recognize the Smad7 PY peptide using the same coupled mechanism. However, a longer Smurf1 isoform, which has an additional 26 residues in the inter-WW domain linker, is only partially able to use the coupled WW domain binding mechanism. The longer linker results in a decrease in affinity for the Smad7 peptide. Interdomain coupling of WW domains enhances selectivity and enables the tuning of interactions by isoform switching. PMID:20937913

Multiple interactions drive adaptor-mediated recruitment of the ubiquitin ligase rsp5 to membrane proteins in vivo and in vitro.

PubMed

Sullivan, James A; Lewis, Michael J; Nikko, Elina; Pelham, Hugh R B

2007-07-01

Recognition of membrane proteins by the Nedd4/Rsp5 ubiquitin ligase family is a critical step in their targeting to the multivesicular body pathway. Some substrates contain "PY" motifs (PPxY), which bind to WW domains in the ligase. Others lack PY motifs and instead rely on adaptors that recruit the ligase to them. To investigate the mechanism of adaptor-mediated ubiquitination, we have characterized the interactions between the adaptor Bsd2, the ubiquitin ligase Rsp5, and the membrane proteins Cps1, Tre1, and Smf1 from Saccharomyces cerevisiae. We have reconstituted adaptor-mediated modification of Cps1 and Tre1 in vitro, and we show that two PY motifs in Bsd2 and two WW domains (WW2 and WW3) in Rsp5 are crucial for this. The binding of a weak noncanonical DMAPSY motif in Bsd2 to WW3 is an absolute requirement for Bsd2 adaptor function. We show that sorting of the manganese transporter Smf1, which requires both Bsd2 and Tre1, depends upon two PY motifs in Bsd2 and one motif in Tre1 but only two WW domains in Rsp5. We suggest that sequential assembly of first a Bsd2/Rsp5 complex, then a Tre1/Bsd2/Rsp5 complex followed by a rearrangement of PY-WW interactions is required for the ubiquitination of Smf1.

Spintronics with metals: Current perpendicular-to-the-plane magneto-transport studies

NASA Astrophysics Data System (ADS)

Sharma, Amit

In this thesis, we present studies to produce new information about three topics: current perpendicular to the plane magnetoresistance (CPP-MR), spin transfer torque (STT), and antiferromagnetic spintronics. Large values of CPP-MR interface parameters---specific interface resistance (Area times resistance), 2AR*, and scattering asymmetry, gamma---are desirable for the use of CPP-MR in devices. Stimulated by a nanopillar study by the Cornell Group, we first discovered that Py/Al had an unusually large 2AR*, but a small gamma. In the hope of finding metal pairs with large values of both the interface parameters, the Py/Al studies led us to study the following interfaces: (a) F/Al with F: Py (= Ni84Fe16). Co, Fe, Co91Fe9, and (b) F/N: Py/Pd, Fe/V, Fe/Nb and Co/Pt. None of the metal pairs looks better for CPP-MR devices. The Cornell group also found that bracketing Al with thin Cu in Py/Al/Py nanopillars, gave an MR similar to Py/Al/Py rather than to Py/Cu/Py. To try to understand this result, we studied the effect of Cu/Al/Cu spacers on ADeltaR = AR(AP) - AR(P) of Py exchange biased spin valves (EBSVs). Here AR(AP) and AR(P) are the specific resistances in the anti-parallel (AP) and parallel (P) configurations of the F layers. Intriguingly, fixing the Al thickness tAl = 10 nm and varying tCu has no effect on ADeltaR, but fixing tCu = 10 nm and varying t Al significantly affected ADeltaR. These unusual behaviors are probably due to strong Al and Cu intermixing, with probable formation of some fraction of ordered alloys. Recent calculations predicted that 2AR of Al/Ag interfaces would vary substantially with orientation and with alloying. The latter is a special potential problem, because Al and Ag interdiffuse at room temperature. To compare with the calculations, we determined 2AR of sputtered Al/Ag interfaces with (111) orientation. Our estimate agrees with calculations that assume 4 monolayers of interfacial disorder, consistent with modest intermixing. To aid in understanding the physics underlying spin transfer torque in F/N/F trilayers, we devised a simple test, where we change the transport properties of only the N-spacer from ballistic to diffusive. To try to minimize effects of systematic errors, we compare ratios of results for diffusive and ballistic transport with calculations. The ratios disagree with predictions of those models that were expected to be most, reliable. Recently, it was predicted that spintronics effects: magnetoresistance, and spin transfer torque induced magnetization switching, should be observable in systems where ferromagnets are replaced by antiferromagnets. We have done the first experiments to search for those predicted antiferromagnetic spintronics effects. We find effects of large current densities on exchange bias, but no clear evidence for antiferromagnetic giant magnetoresistance.

Comparison of the effect of daily consumption of probiotic compared with low-fat conventional yogurt on weight loss in healthy obese women following an energy-restricted diet: a randomized controlled trial.

PubMed

Madjd, Ameneh; Taylor, Moira A; Mousavi, Neda; Delavari, Alireza; Malekzadeh, Reza; Macdonald, Ian A; Farshchi, Hamid R

2016-02-01

Despite evidence for the beneficial effects of probiotics and low-fat dairy products, to our knowledge, no study has compared the beneficial effect on weight loss of consuming a probiotic yogurt (PY) compared with a standard low-fat yogurt (LF) during a hypoenergetic program. We compared the effect of the PY with LF yogurt consumption on body weight and cardiometabolic risk factors in women during a weight-loss program. Overweight and obese women [body mass index (in kg/m(2)): 27-40; age: 18-50 y) who usually consumed standard LFs were asked to consume either PY or LF every day with their main meals for 12 wk while following a weight-loss program. A total of 89 participants were randomly assigned to one of the 2 intervention groups. Baseline variables were not significantly different between groups. A statistically significant reduction in anthropometric measurements and significant improvements in cardiometabolic risk characteristics were observed over the 12 wk in both groups. However, no significant differences in weight loss and anthropometric measurements were seen between groups after the intervention. Compared with the LF group, the PY group had a greater (mean ± SD) decrease in total cholesterol (PY = -0.36 ± 0.10 mmol/L, LF = -0.31 ± 0.10 mmol/L; P = 0.024), low-density lipoprotein cholesterol (PY = -0.35 ± 0.10 mmol/L, LF = -0.31 ± 0.11 mmol/L; P = 0.018), homeostasis model assessment of insulin resistance (PY = -0.55 ± 0.32, LF = -0.42 ± 0.20; P = 0.002), 2-h postprandial glucose (PY = -0.61 ± 0.24 mmol/L, LF = -0.44 ± 0.19 mmol/L; P < 0.001), and fasting insulin concentration (PY = -1.76 ± 1.01 mU/mL, LF = -1.32 ± 0.62 mU/mL; P = 0.002), as secondary endpoints after the study. No significant differences were found for fasting plasma glucose, high-density lipoprotein cholesterol, or triglycerides within both groups after the 12 wk. Consumption of PY compared with LF with main meals showed no significant effects on weight loss. However, it may have positive effects on lipid profiles and insulin sensitivity during a weight-loss program. This trial was registered at http://www.irct.ir/ as IRCT201402177754N8. © 2016 American Society for Nutrition.

The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation

DOE PAGES

Matheu, Roc; Ertem, Mehmed Z.; Pipelier, Muriel; ...

2018-01-19

A family of Ru complexes based on the pentadentate ligand t5a 3– ((2,5-bis(6-carboxylatopyridin-2-yl)pyrrol-1-ide) and pyridine (py) that includes {Ru II(Ht5a-κ-N 2O)(py) 3} (1H II(κ-N 2O)), {Ru III(t5a-κ-N 3O 1.5)(py) 2} (2 III(κ-N 3O 1.5)), and {Ru IV(t5a-κ-N 3O 2)(py) 2}+ ({2 IV(κ-N3O 2)}+) has been prepared and thoroughly characterized. Complexes 1HII(κ-N 2O), 2 III(κ-N 3O 1.5), and {2 IV(κ-N 3O 2)}+ have been investigated in solution by spectroscopic methods (NMR, UV–vis) and in the solid state by single-crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2 III(κ-N 3O 1.5) have beenmore » studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a 3– ligand. Under neutral to basic conditions complex {2 IV(κ-N3O 2)}+ undergoes aquation, generating {Ru IV(OH)(t5a-κ-N 2O)(py) 2} (2 IV(OH)(κ-N 2O)). Further oxidation of the complex forms {Ru V(O)(t5a-κ-N 2O)(py) 2} (2 V(O)(κ-N 2O)), which is a very efficient water oxidation catalyst, reaching a TOF MAX value of 9400 s –1 at pH 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2 V(O)(κ-N 2O) is due not only to the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the noncoordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.« less

The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation

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

Matheu, Roc; Ertem, Mehmed Z.; Pipelier, Muriel

A family of Ru complexes based on the pentadentate ligand t5a 3– ((2,5-bis(6-carboxylatopyridin-2-yl)pyrrol-1-ide) and pyridine (py) that includes {Ru II(Ht5a-κ-N 2O)(py) 3} (1H II(κ-N 2O)), {Ru III(t5a-κ-N 3O 1.5)(py) 2} (2 III(κ-N 3O 1.5)), and {Ru IV(t5a-κ-N 3O 2)(py) 2}+ ({2 IV(κ-N3O 2)}+) has been prepared and thoroughly characterized. Complexes 1HII(κ-N 2O), 2 III(κ-N 3O 1.5), and {2 IV(κ-N 3O 2)}+ have been investigated in solution by spectroscopic methods (NMR, UV–vis) and in the solid state by single-crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2 III(κ-N 3O 1.5) have beenmore » studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a 3– ligand. Under neutral to basic conditions complex {2 IV(κ-N3O 2)}+ undergoes aquation, generating {Ru IV(OH)(t5a-κ-N 2O)(py) 2} (2 IV(OH)(κ-N 2O)). Further oxidation of the complex forms {Ru V(O)(t5a-κ-N 2O)(py) 2} (2 V(O)(κ-N 2O)), which is a very efficient water oxidation catalyst, reaching a TOF MAX value of 9400 s –1 at pH 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2 V(O)(κ-N 2O) is due not only to the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the noncoordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.« less

Pyrazole derived ultra-short antimicrobial peptidomimetics with potent anti-biofilm activity.

PubMed

Ahn, Mija; Gunasekaran, Pethaiah; Rajasekaran, Ganesan; Kim, Eun Young; Lee, Soo-Jae; Bang, Geul; Cho, Kun; Hyun, Jae-Kyung; Lee, Hyun-Ju; Jeon, Young Ho; Kim, Nam-Hyung; Ryu, Eun Kyoung; Shin, Song Yub; Bang, Jeong Kyu

2017-01-05

In this study, we report on the first chemical synthesis of ultra-short pyrazole-arginine based antimicrobial peptidomimetics derived from the newly synthesized N-alkyl/aryl pyrazole amino acids. Through the systematic tuning of hydrophobicity, charge, and peptide length, we identified the shortest peptide Py11 with the most potent antimicrobial activity. Py11 displayed greater antimicrobial activity against antibiotic-resistant bacteria, including MRSA, MDRPA, and VREF, which was approximately 2-4 times higher than that of melittin. Besides its higher selectivity (therapeutic index) toward bacterial cells than LL-37, Py11 showed highly increased proteolytic stability against trypsin digestion and maintained its antimicrobial activity in the presence of physiological salts. Interestingly, Py11 exhibited higher anti-biofilm activity against MDRPA compared to LL-37. The results from fluorescence spectroscopy and transmission electron microscopy (TEM) suggested that Py11 kills bacterial cells possibly by integrity disruption damaging the cell membrane, leading to the cytosol leakage and eventual cell lysis. Furthermore, Py11 displayed significant anti-inflammatory (endotoxin-neutralizing) activity by inhibiting LPS-induced production of nitric oxide (NO) and TNF-α. Collectively, our results suggest that Py11 may serve as a model compound for the design of antimicrobial and antisepsis agents. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Gas-phase lifetimes of nucleobase analogues by picosecond pumpionization and streak techniques.

PubMed

Blaser, Susan; Frey, Hans-Martin; Heid, Cornelia G; Leutwyler, Samuel

2014-01-01

The picosecond (ps) timescale is relevant for the investigation of many molecular dynamical processes such as fluorescence, nonradiative relaxation, intramolecular vibrational relaxation, molecular rotation and intermolecular energy transfer, to name a few. While investigations of ultrafast (femtosecond) processes of biological molecules, e.g. nucleobases and their analogues in the gas phase are available, there are few investigations on the ps time scale. We have constructed a ps pump-ionization setup and a ps streak camera fluorescence apparatus for the determination of lifetimes of supersonic jet-cooled and isolated molecules and clusters. The ps pump-ionization setup was used to determine the lifetimes of the nucleobase analogue 2-aminopurine (2AP) and of two 2AP˙(H2O)n water cluster isomers with n=1 and 2. Their lifetimes lie between 150 ps and 3 ns and are strongly cluster-size dependent. The ps streak camera setup was used to determine accurate fluorescence lifetimes of the uracil analogue 2-pyridone (2PY), its self-dimer (2PY)2, two isomers of its trimer (2PY)3 and its tetramer (2PY)4, which lie in the 7-12 ns range.

Global Distribution of Pyrogenic Carbon

NASA Astrophysics Data System (ADS)

Reisser, Moritz; Abiven, Samuel; Schmidt, Michael W. I.

2016-04-01

Pyrogenic Carbon (PyC) is ubiquitous in the environment and represents presumably one of the most stable compounds of the total organic carbon. Due to its persistence in the soil, it might play an important role in the global carbon cycle. In order to model future CO2 emissions from soils it is thus crucial to know where and how much of PyC exists on a global scale. Yet, only rough estimates for global PyC stocks in soils could be made, and even less is known about the distribution across ecosystems. Therefore we propose here literature analysis of data on PyC concentrations and stocks worldwide. We extracted PyC values in soils from the literature (n = 600) and analysed the percentage of PyC in the soil organic carbon (SOC) as a function of climate (temperature, precipitation), soil parameters (pH, clay content), fire characteristics (fire frequency and fire regime) and land use. Overall, the average contribution of PyC to SOC was 13 %, ranging from 0.1 % up to 60 %. We observed that the PyC content was significantly higher with high clay content, higher pH, and in cultivated land as compared to forest and grassland. We did not observe any relationships between fire activity, frequency or intensity and PyC % at a global scale. When the fire regime was monitored on site (only 12 % of the data we collected), we observed higher PyC concentrations with higher fire frequencies. We hypothesise that the resolution of global fire datasets is neither temporally nor spatially high enough to explain the very local fire history of the soil samples. Data points were not homogeneously distributed on the globe, but rather aggregated in places like Central Europe, the Russian Steppe or North America. Therefore, a global interpolation is not directly possible. We modelled PyC concentrations, based on the five most significant parameters, which were clay content, pH, mean annual temperature and precipitation as well as land use. We then predicted worldwide PyC using global datasets existing for these five variables. We present a global map of PyC concentrations as well as it stocks. In arid ecosystems, where SOC is generally low, stocks of PyC are also low, even though concentrations can be very high. On the other hand, stocks are mostly very large in temperate and boreal ecosystems, even if concentrations are rather low, because total SOC stocks are very high there. Integrating our modelled data, we result in a total global stock of about 230 Pg PyC, corresponding to about 10 % of the total soil organic carbon stock. This value lies well in range with current rule-of-thump estimates of previous studies.

REUSABLE ADSORBENTS FOR DILUTE SOLUTIONS SEPARATION. 6. BATCH AND CONTINUOUS REACTORS FOR ADSORPTION AND DEGRADATION OF 1,2-DICHLOROBENZENE FROM DILUTE WASTEWATER STREAMS USING TITANIA AS A PHOTOCATALYST. (R828598C753)

EPA Science Inventory

Two types of external lamp reactors were investigated for the titania catalyzed photodegradation of 1,2-dichlorobenzene (DCB) from a dilute water stream. The first one was a batch mixed slurry reactor and the second one was a semi-batch reactor with continuous feed recycle wit...

Physical Processes Dictate Early Biogeochemical Dynamics of Soil Pyrogenic Organic Matter in a Subtropical Forest Ecosystem

NASA Astrophysics Data System (ADS)

Stuart, Jason M.; Anderson, Russell; Lazzarino, Patrick; Kuehn, Kevin A.; Harvey, Omar R.

2018-05-01

Quantifying links between pyOM dynamics, environmental factors and processes is central to predicting ecosystem function and response to future perturbations. In this study, changes in carbon (TC), nitrogen (TN) , pH and relative recalcitrance (R50) for pine- and cordgrass-derived pyOM were measured at 3-6 weeks intervals throughout the first year of burial in the soil. Objectives were to 1) identify key environmental factors and processes driving early-stage pyOM dynamics, and 2) develop quantitative relationships between environmental factors and changes in pyOM properties. The study was conducted in sandy soils of a forested ecosystem in the Longleaf pine range, US with a focus on links between changes in pyOM properties, fire history (FH), cumulative precipitation (Pcum), average temperature (Tavg) and soil residence time (SRT). Pcum, SRT and Tavg were the main factors controlling TC and TN accounting for 77-91% and 64-96% of their respective variability. Fire history, along with Pcum, SRT and Tavg, exhibited significant controlling effects on pyOM, pH and R50 - accounting for 48-91% and 88-93% of respective variability. Volatilization of volatiles and leaching of water-soluble components (in summer) and the sorption of exogenous organic matter (fall through spring) were most plausibly controlling pyOM dynamics in this study. Overall, our results point to climatic and land management factors and physicochemical process as the main drivers of pyOM dynamics in the pine ecosystems of the Southeastern US.

Development of p-y curves of laterally loaded piles in cohesionless soil.

PubMed

Khari, Mahdy; Kassim, Khairul Anuar; Adnan, Azlan

2014-01-01

The research on damages of structures that are supported by deep foundations has been quite intensive in the past decade. Kinematic interaction in soil-pile interaction is evaluated based on the p-y curve approach. Existing p-y curves have considered the effects of relative density on soil-pile interaction in sandy soil. The roughness influence of the surface wall pile on p-y curves has not been emphasized sufficiently. The presented study was performed to develop a series of p-y curves for single piles through comprehensive experimental investigations. Modification factors were studied, namely, the effects of relative density and roughness of the wall surface of pile. The model tests were subjected to lateral load in Johor Bahru sand. The new p-y curves were evaluated based on the experimental data and were compared to the existing p-y curves. The soil-pile reaction for various relative density (from 30% to 75%) was increased in the range of 40-95% for a smooth pile at a small displacement and 90% at a large displacement. For rough pile, the ratio of dense to loose relative density soil-pile reaction was from 2.0 to 3.0 at a small to large displacement. Direct comparison of the developed p-y curve shows significant differences in the magnitude and shapes with the existing load-transfer curves. Good comparison with the experimental and design studies demonstrates the multidisciplinary applications of the present method.

Development of p-y Curves of Laterally Loaded Piles in Cohesionless Soil

PubMed Central

Khari, Mahdy; Kassim, Khairul Anuar; Adnan, Azlan

2014-01-01

The research on damages of structures that are supported by deep foundations has been quite intensive in the past decade. Kinematic interaction in soil-pile interaction is evaluated based on the p-y curve approach. Existing p-y curves have considered the effects of relative density on soil-pile interaction in sandy soil. The roughness influence of the surface wall pile on p-y curves has not been emphasized sufficiently. The presented study was performed to develop a series of p-y curves for single piles through comprehensive experimental investigations. Modification factors were studied, namely, the effects of relative density and roughness of the wall surface of pile. The model tests were subjected to lateral load in Johor Bahru sand. The new p-y curves were evaluated based on the experimental data and were compared to the existing p-y curves. The soil-pile reaction for various relative density (from 30% to 75%) was increased in the range of 40–95% for a smooth pile at a small displacement and 90% at a large displacement. For rough pile, the ratio of dense to loose relative density soil-pile reaction was from 2.0 to 3.0 at a small to large displacement. Direct comparison of the developed p-y curve shows significant differences in the magnitude and shapes with the existing load-transfer curves. Good comparison with the experimental and design studies demonstrates the multidisciplinary applications of the present method. PMID:24574932

Mortality in youth-onset type 1 and type 2 diabetes: The SEARCH for Diabetes in Youth study.

PubMed

Reynolds, Kristi; Saydah, Sharon H; Isom, Scott; Divers, Jasmin; Lawrence, Jean M; Dabelea, Dana; Mayer-Davis, Elizabeth J; Imperatore, Giuseppina; Bell, Ronny A; Hamman, Richard F

2018-06-01

To estimate short-term mortality rates for individuals with type 1 or type 2 diabetes diagnosed before age 20 years from the SEARCH for Diabetes in Youth study. We included 8358 individuals newly-diagnosed with type 1 (n = 6840) or type 2 (n = 1518) diabetes from 1/1/2002-12/31/2008. We searched the National Death Index through 12/31/2010. We calculated standardized mortality ratios (SMRs) based on age, sex, and race for the comparable US population in the geographic areas of the SEARCH study. During 44,893 person-years (PY) of observation (median follow-up = 5.3 years), 41 individuals died (91.3 deaths/100,000 PY); 26 with type 1 (70.6 deaths/100,000 PY) and 15 with type 2 (185.6 deaths/100,000 PY) diabetes. The expected mortality rate was 70.9 deaths/100,000 PY. The overall SMR (95% CI) was 1.3 (1.0, 1.8) and was high among individuals with type 2 diabetes 2.4 (1.3, 3.9), females 2.2 (1.3, 3.3), 15-19 year olds 2.7 (1.7,4.0), and non-Hispanic blacks 2.1 (1.2, 3.4). Compared to the state populations of similar age, sex, and race, our results show excess mortality in individuals with type 2 diabetes, females, older youth, and non-Hispanic blacks. We did not observe excess short-term mortality in individuals with type 1 diabetes. Copyright © 2018 Elsevier Inc. All rights reserved.

Analysis of gamma-irradiated melon, pumpkin, and sunflower seeds by electron paramagnetic resonance spectroscopy and gas chromatography-mass spectrometry.

PubMed

Sin, Della W M; Wong, Yiu Chung; Yao, Wai Yin

2006-09-20

Seeds of melon (Citrullus lanatus var. sp.), pumpkin (Cucurbita moschata), and sunflower (Heliantus annus) were gamma-irradiated at 1, 3, 5, and 10 kGy and analyzed by electron paramagnetic resonance (EPR) and gas chromatography-mass spectrometry (GC-MS) according to EN1787:2000 and EN1785:2003, respectively. Distinguishable triplet signals due to the presence of induced cellulose radicals were found at 2.0010-2.0047 g in the EPR spectra. The gamma-irradiated radiolytic markers of 2-dodecylcyclobutanone (2-DCB) and 2-tetradecylcyclobutanone (2-TCB) were identified in all irradiated seed samples. Both the free radicals and the alkylcyclobutanones were found to increase with irradiation dose. In general, linear relationships between the amount of radicals and irradiation dosage could be established. Studies at an ambient temperature (20-25 degrees C) in a humidity-controlled environment showed a complete disappearance of the cellulosic peaks for irradiated samples upon 60 days of storage. Such instability behavior was considered to render the usefulness of using EPR alone in the determination of irradiated seed samples. On the other hand, 2-DCB and 2-TCB were also found to decompose rapidly (>85% loss after 120 days of storage), but the radiolytic markers remained quantifiable after 120 days of postirradiation storage. These results suggest that GC-MS is a versatile and complimentary technique for the confirmation of irradiation treatment to seeds.

Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism.

PubMed

Puri, Mayank; Company, Anna; Sabenya, Gerard; Costas, Miquel; Que, Lawrence

2016-06-20

Detailed studies of oxygen atom exchange (OAE) between H2(18)O and synthetic non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands provide evidence that they proceed by a common mechanism but within two different kinetic regimes, with OAE rates that span 2 orders of magnitude. The first kinetic regime involves initial reversible water association to the Fe(IV) complex, which is evidenced by OAE rates that are linearly dependent on [H2(18)O] and H2O/D2O KIEs of 1.6, while the second kinetic regime involves a subsequent rate determining proton-transfer step between the bound aqua and oxo ligands that is associated with saturation behavior with [H2(18)O] and much larger H2O/D2O KIEs of 5-6. [Fe(IV)(O)(TMC)(MeCN)](2+) (1) and [Fe(IV)(O)(MePy2TACN)](2+) (9) are examples of complexes that exhibit kinetic behavior in the first regime, while [Fe(IV)(O)(N4Py)](2+) (3), [Fe(IV)(O)(BnTPEN)](2+) (4), [Fe(IV)(O)(1Py-BnTPEN)](2+) (5), [Fe(IV)(O)(3Py-BnTPEN)](2+) (6), and [Fe(IV)(O)(Me2Py2TACN)](2+) (8) represent complexes that fall in the second kinetic regime. Interestingly, [Fe(IV)(O)(PyTACN)(MeCN)](2+) (7) exhibits a linear [H2(18)O] dependence below 0.6 M and saturation above 0.6 M. Analysis of the temperature dependence of the OAE rates shows that most of these complexes exhibit large and negative activation entropies, consistent with the proposed mechanism. One exception is complex 9, which has a near-zero activation entropy and is proposed to undergo ligand-arm dissociation during the RDS to accommodate H2(18)O binding. These results show that the observed OAE kinetic behavior is highly dependent on the nature of the supporting ligand and are of relevance to studies of non-heme oxoiron(IV) complexes in water or acetonitrile/water mixtures for applications in photocatalysis and water oxidation chemistry.

Timing group delay and differential code bias corrections for BeiDou positioning

NASA Astrophysics Data System (ADS)

Guo, Fei; Zhang, Xiaohong; Wang, Jinling

2015-05-01

This article first clearly figures out the relationship between parameters of timing group delay (TGD) and differential code bias (DCB) for BDS, and demonstrates the equivalence of TGD and DCB correction models combining theory with practice. The TGD/DCB correction models have been extended to various occasions for BDS positioning, and such models have been evaluated by real triple-frequency datasets. To test the effectiveness of broadcast TGDs in the navigation message and DCBs provided by the Multi-GNSS Experiment (MGEX), both standard point positioning (SPP) and precise point positioning (PPP) tests are carried out for BDS signals with different schemes. Furthermore, the influence of differential code biases on BDS positioning estimates such as coordinates, receiver clock biases, tropospheric delays and carrier phase ambiguities is investigated comprehensively. Comparative analysis show that the unmodeled differential code biases degrade the performance of BDS SPP by a factor of two or more, whereas the estimates of PPP are subject to varying degrees of influences. For SPP, the accuracy of dual-frequency combinations is slightly worse than that of single-frequency, and they are much more sensitive to the differential code biases, particularly for the B2B3 combination. For PPP, the uncorrected differential code biases are mostly absorbed into the receiver clock bias and carrier phase ambiguities and thus resulting in a much longer convergence time. Even though the influence of the differential code biases could be mitigated over time and comparable positioning accuracy could be achieved after convergence, it is suggested to properly handle with the differential code biases since it is vital for PPP convergence and integer ambiguity resolution.

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

Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.

Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf andmore » 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.« less

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

Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.

Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py 3tren)CoCuCl (1-Cl) and (py 3tren)CoCu(CH 3CN) (2-CH 3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH 3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH 3CN with AgOTf generated (py 3tren)CoCuOTf (1-OTf).more » The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH 3CN is reversible at -0.56 and -0.33 V vs Fc +/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu) +4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu) +3 analogue, and the d-electrons are fully localized at individual metals.« less

Cytotoxic effects of Mn(III) N-alkylpyridylporphyrins in the presence of cellular reductant, ascorbate

PubMed Central

Ye, Xiaodong; Fels, Diane; Tovmasyan, Artak; Aird, Katherine M.; Dedeugd, Casey; Allensworth, Jennifer L.; Kos, Ivan; Park, Won; Spasojevic, Ivan; Devi, Gayathri R.; Dewhirst, Mark W.; Leong, Kam W.; Batinic-Haberle, Ines

2012-01-01

Due to the ability to easily accept and donate electrons Mn(III) N-alkylpyridylporphyrins (MnPs) can dismute O2˙−, reduce peroxynitrite, but also generate reactive species and behave as pro-oxidants if conditions favour such action. Herein two ortho isomers, MnTE-2-PyP5+, MnTnHex-2-PyP5+, and a meta isomer MnTnHex-3-PyP5+, which differ greatly with regard to their metal-centered reduction potential, E1/2 (MnIIIP/MnIIP) and lipophilicity, were explored. Employing MnIIIP/MnIIP redox system for coupling with ascorbate, these MnPs catalyze ascorbate oxidation and thus peroxide production. Consequently, cancer oxidative burden may be enhanced, which in turn would suppress its growth. Cytotoxic effects on Caco-2, Hela, 4T1, HCT116 and SUM149 were studied. When combined with ascorbate, MnPs killed cancer cells via peroxide produced outside of the cell. MnTE-2-PyP5+ was the most efficacious catalyst for peroxide production, while MnTnHex-3-PyP5+ is most prone to oxidative degradation with H2, and thus the least efficacious. A 4T1 breast cancer mouse study of limited scope and success was conducted. The tumour oxidative stress was enhanced and its microvessel density reduced when mice were treated either with ascorbate or MnP/ascorbate; the trend towards tumour growth suppression was detected. PMID:21859376

Identification of the same polyomavirus species in different African horseshoe bat species is indicative of short-range host-switching events.

PubMed

Carr, Michael; Gonzalez, Gabriel; Sasaki, Michihito; Dool, Serena E; Ito, Kimihito; Ishii, Akihiro; Hang'ombe, Bernard M; Mweene, Aaron S; Teeling, Emma C; Hall, William W; Orba, Yasuko; Sawa, Hirofumi

2017-10-06

Polyomaviruses (PyVs) are considered to be highly host-specific in different mammalian species, with no well-supported evidence for host-switching events. We examined the species diversity and host specificity of PyVs in horseshoe bats (Rhinolophus spp.), a broadly distributed and highly speciose mammalian genus. We annotated six PyV genomes, comprising four new PyV species, based on pairwise identity within the large T antigen (LTAg) coding region. Phylogenetic comparisons revealed two instances of highly related PyV species, one in each of the Alphapolyomavirus and Betapolyomavirus genera, present in different horseshoe bat host species (Rhinolophus blasii and R. simulator), suggestive of short-range host-switching events. The two pairs of Rhinolophus PyVs in different horseshoe bat host species were 99.9 and 88.8 % identical with each other over their respective LTAg coding sequences and thus constitute the same virus species. To corroborate the species identification of the bat hosts, we analysed mitochondrial cytb and a large nuclear intron dataset derived from six independent and neutrally evolving loci for bat taxa of interest. Bayesian estimates of the ages of the most recent common ancestors suggested that the near-identical and more distantly related PyV species diverged approximately 9.1E4 (5E3-2.8E5) and 9.9E6 (4E6-18E6) years before the present, respectively, in contrast to the divergence times of the bat host species: 12.4E6 (10.4E6-15.4E6). Our findings provide evidence that short-range host-switching of PyVs is possible in horseshoe bats, suggesting that PyV transmission between closely related mammalian species can occur.

Assessing soil carbon vulnerability in the Western USA by geospatial modeling of pyrogenic and particulate carbon stocks

NASA Astrophysics Data System (ADS)

Ahmed, Zia U.; Woodbury, Peter B.; Sanderman, Jonathan; Hawke, Bruce; Jauss, Verena; Solomon, Dawit; Lehmann, Johannes

2017-02-01

To predict how land management practices and climate change will affect soil carbon cycling, improved understanding of factors controlling soil organic carbon fractions at large spatial scales is needed. We analyzed total soil organic (SOC) as well as pyrogenic (PyC), particulate (POC), and other soil organic carbon (OOC) fractions in surface layers from 650 stratified-sampling locations throughout Colorado, Kansas, New Mexico, and Wyoming. PyC varied from 0.29 to 18.0 mg C g-1 soil with a mean of 4.05 mg C g-1 soil. The mean PyC was 34.6% of the SOC and ranged from 11.8 to 96.6%. Both POC and PyC were highest in forests and canyon bottoms. In the best random forest regression model, normalized vegetation index (NDVI), mean annual precipitation (MAP), mean annual temperature (MAT), and elevation were ranked as the top four important variables determining PyC and POC variability. Random forests regression kriging (RFK) with environmental covariables improved predictions over ordinary kriging by 20 and 7% for PyC and POC, respectively. Based on RFK, 8% of the study area was dominated (≥50% of SOC) by PyC and less than 1% was dominated by POC. Furthermore, based on spatial analysis of the ratio of POC to PyC, we estimated that about 16% of the study area is medium to highly vulnerable to SOC mineralization in surface soil. These are the first results to characterize PyC and POC stocks geospatially using stratified sampling scheme at the scale of 1,000,000 km2, and the methods are scalable to other regions.

Priming of native soil organic matter by pyrogenic organic matter

NASA Astrophysics Data System (ADS)

DeCiucies, Silene; Dharmakeerthi, Saman; Whitman, Thea; Woolf, Dominic; Lehmann, Johannes

2015-04-01

Priming, in relation to pyrogenic organic matter (PyOM), describes the change in mineralization rate of non-pyrogenic ("native") soil organic matter (nSOM) due to the addition of PyOM. Priming may be 'positive', in that the addition of pyC increases the mineralization rate of native SOM, or 'negative', in that the mineralization rate of nSOM is decreased. Reasons for increased mineralization may include: (i) co-metabolism: microbial decomposition of labile C-additions increases microbial activity, and facilitates additional decomposition of npSOC by active enzymes; (ii) stimulation: substrate additions result in lifted pH, nutrient, oxygen, or water constraints resulting in increased microbial activity. Decreased mineralization may be a result of: (i) inhibition: the opposite of stimulation whereby constraints are aggravated by substrate addition. Substrate addition may also cause inhibition by interfering with enzymes or signaling compounds; (ii) preferential substrate utilization: labile fraction of PyOM additions are preferentially used up by microbes thus causing a decrease in nSOC decomposition; (iii) sorption: organic compounds are adsorbed onto PyOM surfaces, decreasing their rate of mineralization; (iv) stabilization: formation of organo-mineral associations forms stable SOC pools. We have conducted a suite of experiments to investigate these potential interactions. In a seven year long incubation study, PyOM additions increased total OM mineralization for the first 2.5 years, was equal to control after 6.2 years, and was 3% lower after 7.1 years. Cumulative nSOM mineralization was 23% less with the PyOM additions than without, and over 60% of the added PyOM was present in the labile soil fraction after the 7.1 year incubation. Two additional incubation studies, one with and without plants, showed greater nSOM mineralization in the short term and lower nSOM mineralization over the long term. Increased nSOC mineralization due to the presence of plants was counteracted by PyOM additions. However, repeated additions of crop residues over seven years did not result in lower mineralization of the residue and nSOM. We have also determined that, although there is no optimal duration for pre-incubation of soil before SOC studies, the type of carbon available is crucial in determining the effects of PyOM additions. We will continue to examine the contribution of the different mechanisms by isolating variables such as nutrient addition, soil texture, and mineral availability. We anticipate that sorption on PyOM surfaces are important in nSOM stabilization and will continue to study these effects using highly labeled substrates and nano secondary ion mass spectrometry (nano-SIMS).

Mineralogy and trace element geochemistry of the Co- and Cu-bearing sulfides from the Shilu Fe-Co-Cu ore district in Hainan Province of South China

NASA Astrophysics Data System (ADS)

Wang, Zhilin; Xu, Deru; Zhang, Zhaochong; Zou, Fenghui; Wang, Li; Yu, Liangliang; Hu, Mingyue

2015-12-01

Hosted within the metamorphosed, neritic siliciclastic rocks and sedimentary carbonates of the Proterozoic Shilu Group, the Shilu Fe-Co-Cu ore district in Hainan Province of South China comprises the upper Fe- and the lower Co-Cu ore layers. Combined with the field observation, the mineralogical and geochemical studies of sulfides using electron microprobe and laser ablation ICP-MS analyses recognized three types of Co-Cu ores. Type I is represented by massive ores and mainly comprises the first generation of pyrite (PyI) which occurred either as recrystallized, subhedral to euhedral microcrystal aggregates (PyIa) or as elongated, fine-grained euhedral grains (PyIb) with an orientated alignment parallel to S1 foliation. Type II is banded, disseminated and brecciated ores, and composed of the second generation of pyrite (PyII) which displays internal rhythmic growth zoning, the first generations of chalcopyrite (CcpI) and pyrrhotite (PoI), and associated Co-(Ni)-(As)-sulfide minerals. Type III occurring as veins or veinlets mainly consists of the third generation of pyrite (PyIII) and the second generations of chalcopyrite (CcpII) and pyrrhotite (PoII), of which PyIII appears as subhedral to euhedrall grains or as rims of composite pyrite. The moderate Co and As, and high Ni contents as well as the low Co/Ni ratios (∼2-5) in PyI indicate a sedimentary-metamorphic origin for Type I ores. The higher Co, Ni and As concentrations in PyIb relative to PyIa likely was related to an inhomogeneous deformation-metamorphism. The highest Co (av. 51,195 ppm) in PyII and Ni (av. 3374 ppm) in PoI most likely were linked to the preferred incorporation of Co into pyrite and Ni into pyrrhotite. Combined with the high Ag concentrations in CcpI (av. 266 ppm) and PyII (av. 13.32 ppm), the high Co/Ni ratios in PyII (av. 1241) suggest the derivation of Type II ores from a Co-Cu-Ni-Ag-rich hydrothermal fluid. Further, up to 9 wt.% Co concentrations in PyII show a temperature condition of 310-400 °C. In contrast, the depletion of trace elements in CcpII and PyIII, and the lower Co/Ni ratios (av. 46) in PyIII suggest a Co-poor but Cu-bearing hydrothermal fluid for origin of Type III ores. The complex texture and chemical composition of sulfides combined with previous work confirm a four-stage metallogenesis for the Shilu Co-Cu ores. From early to late, these include: (1) the ca. 1075-880 Ma deposition of the primary Co-Cu ore source beds which most likely were derived from submarine, metalliferous hydrothermal fluids, (2) the syn-structural metamorphism which led to Type I ores due to the South China Caledonian Orogeny, (3) the first stage of hydrothermalism which produced Type II ores and most likely was associated with Indosinian magmatism, and (4) the second stage of hydrothermalism which yielded Type III ores and likely was related to Yanshanian magmatism. The first stage of hydrothermalism was considered to be significant for the Co-Cu enrichment. The Shilu Co-Cu ores thus are better attributed to a BIF origin, but greatly reworked and enriched by late structural deformation and hydrothermal activities.

Soil carbon content and character in an old-growth forest in northwestern Pennsylvania: a case study introducing pyrolysis molecular beam mass spectrometry (py-MBMS)

Treesearch

C.M. Hoover; K.A. Magrini; R.J. Evans

2002-01-01

This study was conducted to: (1) test the utility of a new and rapid analytical method, pyrolysis molecular beam mass spectrometry (py-MBMS), for the measurement and characterization of carbon in forest soils, and (2) examine the effects of natural disturbance on soil carbon dynamics. An additional objective was to test the ability of py-MBMS to distinguish recent from...

Effect of acute acid-base disturbances on ErbB1/2 tyrosine phosphorylation in rabbit renal proximal tubules.

PubMed

Skelton, Lara A; Boron, Walter F

2013-12-15

The renal proximal tubule (PT) is a major site for maintaining whole body pH homeostasis and is responsible for reabsorbing ∼80% of filtered HCO3(-), the major plasma buffer, into the blood. The PT adapts its rate of HCO3(-) reabsorption (JHCO3(-)) in response to acute acid-base disturbances. Our laboratory previously showed that single isolated perfused PTs adapt JHCO3(-) in response to isolated changes in basolateral (i.e., blood side) CO2 and HCO3(-) concentrations but, surprisingly, not to pH. The response to CO2 concentration can be blocked by the ErbB family tyrosine kinase inhibitor PD-168393. In the present study, we exposed enriched rabbit PT suspensions to five acute acid-base disturbances for 5 and 20 min using a panel of phosphotyrosine (pY)-specific antibodies to determine the influence of each disturbance on pan-pY, ErbB1-specific pY (four sites), and ErbB2-specific pY (two sites). We found that each acid-base treatment generated a distinct temporal pY pattern. For example, the summated responses of the individual ErbB1/2-pY sites to each disturbance showed that metabolic acidosis (normal CO2 concentration and reduced HCO3(-) concentration) produced a transient summated pY decrease (5 vs. 20 min), whereas metabolic alkalosis produced a transient increase. Respiratory acidosis (normal HCO3(-) concentration and elevated CO2 concentration) had little effect on summated pY at 5 min but produced an elevation at 20 min, whereas respiratory alkalosis produced a reduction at 20 min. Our data show that ErbB1 and ErbB2 in the PT respond to acute acid-base disturbances, consistent with the hypothesis that they are part of the signaling cascade.

Effect of acute acid-base disturbances on ErbB1/2 tyrosine phosphorylation in rabbit renal proximal tubules

PubMed Central

Skelton, Lara A.

2013-01-01

The renal proximal tubule (PT) is a major site for maintaining whole body pH homeostasis and is responsible for reabsorbing ∼80% of filtered HCO3−, the major plasma buffer, into the blood. The PT adapts its rate of HCO3− reabsorption (JHCO3−) in response to acute acid-base disturbances. Our laboratory previously showed that single isolated perfused PTs adapt JHCO3− in response to isolated changes in basolateral (i.e., blood side) CO2 and HCO3− concentrations but, surprisingly, not to pH. The response to CO2 concentration can be blocked by the ErbB family tyrosine kinase inhibitor PD-168393. In the present study, we exposed enriched rabbit PT suspensions to five acute acid-base disturbances for 5 and 20 min using a panel of phosphotyrosine (pY)-specific antibodies to determine the influence of each disturbance on pan-pY, ErbB1-specific pY (four sites), and ErbB2-specific pY (two sites). We found that each acid-base treatment generated a distinct temporal pY pattern. For example, the summated responses of the individual ErbB1/2-pY sites to each disturbance showed that metabolic acidosis (normal CO2 concentration and reduced HCO3− concentration) produced a transient summated pY decrease (5 vs. 20 min), whereas metabolic alkalosis produced a transient increase. Respiratory acidosis (normal HCO3− concentration and elevated CO2 concentration) had little effect on summated pY at 5 min but produced an elevation at 20 min, whereas respiratory alkalosis produced a reduction at 20 min. Our data show that ErbB1 and ErbB2 in the PT respond to acute acid-base disturbances, consistent with the hypothesis that they are part of the signaling cascade. PMID:24133121

Effects of vitamin D-fortified low fat yogurt on glycemic status, anthropometric indexes, inflammation, and bone turnover in diabetic postmenopausal women: A randomised controlled clinical trial.

PubMed

Jafari, Tina; Faghihimani, Elham; Feizi, Awat; Iraj, Bijan; Javanmard, Shaghayegh Haghjooy; Esmaillzadeh, Ahmad; Fallah, Aziz A; Askari, Gholamreza

2016-02-01

Low levels of serum 25-hydroxy vitamin D (25(OH)D) are common in type 2 diabetic patients and cause several complications particularly, in postmenopausal women due to their senile and physiological conditions. This study aimed to assess the effects of vitamin D-fortified low fat yogurt on glycemic status, anthropometric indexes, inflammation, and bone turnover in diabetic postmenopausal women. In a randomized, placebo-controlled, double-blind parallel-group clinical trial, 59 postmenopausal women with type 2 diabetes received fortified yogurt (FY; 2000 IU vitamin D in 100 g/day) or plain yogurt (PY) for 12 weeks. Glycemic markers, anthropometric indexes, inflammatory, and bone turnover markers were assessed at baseline and after 12 weeks. After intervention, in FY group (vs PY group), were observed: significant increase in serum 25(OH)D and decrease of PTH (stable values in PY); significant improvement in serum fasting insulin, HOMA-IR, HOMA-B, QUICKI, and no changes in serum fasting glucose and HbA1c (significant worsening of all indexes in PY); significant improvement in WC, WHR, FM, and no change in weight and BMI (stable values in PY); significant increase of omentin (stable in PY) and decrease of sNTX (significant increase in PY). Final values of glycemic markers (except HbA1c), omentin, and bone turnover markers significantly improved in FY group compared to PY group. Regarding final values of serum 25(OH)D in FY group, subjects were classified in insufficient and sufficient categories. Glycemic status improved more significantly in the insufficient rather than sufficient category; whereas the other parameters had more amelioration in the sufficient category. Daily consumption of 2000 IU vitamin D-fortified yogurt for 12 weeks improved glycemic markers (except HbA1c), anthropometric indexes, inflammation, and bone turnover markers in postmenopausal women with type 2 diabetes. www.irct.ir (IRCT2013110515294N1). Copyright © 2015 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

A turn-on supramolecular fluorescent probe for sensing benzimidazole fungicides and its application in living cell imaging

NASA Astrophysics Data System (ADS)

Tang, Qing; Zhang, Jing; Sun, Tao; Wang, Cheng-Hui; Huang, Ying; Zhou, Qingdi; Wei, Gang

2018-02-01

A cucurbit[8]uril-based turn-on supramolecular fluorescent probe between cucurbit[8]uril (Q[8]) and pyronine Y (PyY) (designated 2PyY@Q[8]) in acidic aqueous solution showed a remarkable fluorescence 'turn-on' response to benzimidazole fungicides such as thiabendazole, fuberidazole and carbendazim. The 2PyY@Q[8] fluorescent probe can be used to detect benzimidazole fungicides with high sensitivity and selectivity with a detection limit of 10- 8 mol/L. A good linear relationship of emission intensity at 580 nm for benzimidazole fungicides at concentrations of 0.4-5.0 μmol/L was observed. The proposed sensing mechanism was investigated using 1H NMR spectroscopy combined with density functional theory calculations at the B3LYP/6-31G(d) level. The cell imaging study showed that the 2PyY@Q[8] complex could be used to image benzimidazole fungicide in prostate cancer (PC3) cells, which may help to elucidate relevant biological processes at the molecular level.

Extracellular calcium regulates protein tyrosine phosphorylation through calcium-sensing receptor (CaSR) in stallion sperm.

PubMed

Macías-García, Beatriz; Rocha, Antonio; González-Fernández, Lauro

2016-03-01

Protein tyrosine phosphorylation (PY), a hallmark of sperm capacitation, is inhibited by extracellular calcium in stallion sperm. The objective of this study was to determine the presence and influence of the calcium-sensing receptor (CaSR) in this phenomenon. First, the presence of the CaSR was demonstrated in stallion sperm. We then tested its function in these gametes using its inhibitor NPS2143 or its agonist AC34356. Sperm were capacitated for 4 hr in modified Whitten's medium with 25 mM bicarbonate plus NPS2143 and 2.4 mM calcium or AC34356 alone, followed by analysis of PY. Inhibition of CaSR with NPS2143 prevented the calcium-dependent PY inhibition in a dose-dependent manner (5, 10, and 15 μM) whereas AC34356 (100 μM) inhibited PY similarly to calcium. Stallion sperm motility and viability significantly decreased in presence of 15 μM of NPS2143 whereas only sperm motility decreased with 100 μM of AC34356. CaSR function was also studied in the complete absence of calcium by including 2 mM ethylene glycol tetraacetic acid (EGTA); under these conditions, AC34356 again inhibited PY, but this time induced a significant increase in sperm motility. Inhibition of calmodulin by W-7 did not recover the AC34356-mediated PY inhibition. When stallion sperm were incubated under capacitating conditions (calcium, bicarbonate, plus bovine serum albumin) at elevated pH (7.9 or 8.5) AC34356 did not block PY. These results thus elucidate the effect of extracellular conditions on the regulation of CaSR, and point to its modulatory role on stallion sperm PY, motility, and viability. Mol. Reprod. Dev. 83: 236-245, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

N-(2-Hydroxypropyl)methacrylamide polymer conjugated pyropheophorbide-a, a promising tumor-targeted theranostic probe for photodynamic therapy and imaging.

PubMed

Fang, Jun; Šubr, Vladimír; Md Islam, Waliul; Hackbarth, Steffen; Md Islam, Rayhanul; Etrych, Tomáš; Ulbrich, Karel; Maeda, Hiroshi

2018-06-07

Tumor-targeted photodynamic therapy (PDT) using polymeric photosensitizers is a promising therapeutic strategy for cancer treatment. In this study, we synthesized a pHPMA conjugated pyropheophorbide-a (P-PyF) as a cancer theranostic agent for PDT and photodynamic diagnostics (PDD). Pyropheophorbide-a has one carboxyl group which was conjugated to pHPMA via amide bond yielding the intended product with high purity. In aqueous solutions, P-PyF showed a mean particle size of ∼200 nm as it forms micelle which exhibited fluorescence quenching and thus very little singlet oxygen ( 1 O 2 ) production. In contrast, upon disruption of micelle strong fluorescence and 1 O 2 production were observed. In vitro study clearly showed the PDT effect of P-PyF. More potent 1 O 2 production and PDT effect were observed during irradiation at ∼420 nm, the maximal absorbance of pyropheophorbide-a, than irradiation at longer wavelength (i.e., ∼ 680 nm), suggesting selection of proper absorption light is essential for successful PDT. In vivo study showed high tumor accumulation of P-PyF compared with most of normal tissues due to the enhanced permeability and retention (EPR) effect, which resulting in superior antitumor effect under irradiation using normal xenon light source of endoscope, and clear tumor imaging profiles even in the metastatic lung cancer at 28 days after administration of P-PyF. On the contrary irradiation using long wavelength (i.e., ∼ 680 nm), the lowest Q-Band, exhibited remarkable tumor imaging effect with little autofluorescence of background. These findings strongly suggested P-PyF may be a potential candidate-drug for PDT/PDD, particularly using two different wavelength for treatment and detection/imaging, respectively. Copyright © 2018. Published by Elsevier B.V.

Metal–organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln{sub 4}(OH){sub 4}] building units

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

Abdelbaky, Mohammed S.M.; Amghouz, Zakariae, E-mail: amghouz.uo@uniovi.es; Servicios Científico-Técnicos, University of Oviedo—CINN, Oviedo 33006

Lanthanide–organic frameworks based on 2,5-pyridinedicaboxylate (25p) ligand, formulated as [Yb{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pYb), [Y{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pY-1) and [Y{sub 6}(OH){sub 8}(25p){sub 5}(H{sub 2}O){sub 2}] (25pY-2), have been obtained as single phases under hydrothermal conditions. 25pYb and 25pY-1 are isostructural, and crystallize in the triclinic space group, P-1, with a=8.6075(5) Å, b=14.8478(7) Å, c=15.9164(9) Å, α=86.277(4)°, β=80.196(5)°, γ=81.785(4)°, and a=8.7166(6) Å, b=14.966(1) Å, c=15.966(1) Å, α=86.260(6)°, β=80.036(6)°, γ=81.599(6)°, respectively. 25pY-2 crystallizes in the monoclinic space group, P2{sub 1}/c, with a=24.9117(17) Å, b=13.7340(8) Å, c=14.3385(10) Å, β=100.551(7)°. 25pYb and 25pY-2 have been structurally characterizedmore » by single-crystal X-ray diffraction. The 25pYb structure is based on tetranuclear cubane-like [Yb{sub 4}(OH){sub 4}]{sup 8+} clusters, which are interconnected to eight neighbouring clusters through teen surrounding 25p ligands leading to neutral 3D framework, while the structure of 25pY-2 is based on two independent cuban-like [Y{sub 4}(OH){sub 4}]{sup 8+} clusters, which are joined together through Y1 cation leading to the formation of hexanuclear [Y{sub 6}(OH){sub 8}]{sup 10+} clusters, which in turn are joined via Y2 cation resulting in infinite inorganic chain extending along c-axis, and each chain is interconnected to six adjacent chains through 25p ligands leading finally to 3D framework. The luminescence properties of Eu{sup 3+} and Tb{sup 3+} doped 25pY-1 and 25pY-2 compounds have also been investigated. All materials has been characterized by powder X-ray diffraction, thermal analyses (TG–SDTA–MS), FTIR spectroscopy, C–H–N elemental analysis, scanning electron microscopy (SEM-EDX), and powder X-ray thermodiffraction. - Graphical abstract: Nowadays, lanthanide–organic frameworks (LOFs) attract tremendous attention due to the unique characteristic of lanthanide cations, such as variable coordination numbers and geometries which often lead to novel complex structures, and also to their magnetic and photoluminescence properties. Herein, three LOFs formulated as [Ln{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (Ln=Y, Yb) and [Y{sub 6}(OH){sub 8}(25p){sub 5}(H{sub 2}O){sub 2}] have been obtained by hydrothermal method and characterized, and the photoluminescence properties of the Eu and Tb doped compounds are discussed. - Highlights: • Three novel LnOFs has been synthesized and characterized. • Crystal structures are based on tetranuclear cuban-like [Ln{sub 4}(OH){sub 4}]{sup 8+} clusters. • 25pYb and 25pY-1 are based on isolated [Ln{sub 4}(OH){sub 4}]{sup 8+} clusters. • 25pY-2 is based on infinite inorganic chains built up from [Y{sub 4}(OH){sub 4}]{sup 8+} clusters. • Photoluminescence studies show strong red and green light emissions.« less

Wood source and pyrolysis temperature interact to control PyOM degradation rates

NASA Astrophysics Data System (ADS)

Bird, J. A.; Hatton, P. J.; Filley, T. R.; Chatterjee, S.; Auclerc, A.; Gormley, M.; Dastmalchi, K.; Stark, R. E.; Nadelhoffer, K. J.

2015-12-01

Surprisingly little is known about how shifts in tree species composition and increased forest fire frequency and intensity will affect one of the most stable pools of soil organic matter, i.e. the pyrogenic organic matter (PyOM or char). In a previous study, we showed that wood source and pyrolysis temperature interact to control PyOM structure and potential reactivity for two tree species common in high-latitude forests, jack pine (JP) and red maple (RM). Here, we investigate whether these differences affect PyOM turnover by examining the fates of 13C/15N-enriched JP wood and PyOM pyrolyzed at 300 (JP300) and 450 °C (JP450) and RM pyrolyzed at 450 °C (RM450). The substrates were applied 1-3 cm below the O/A interface of a well-drained Spodosol in a long-term forest fire study located at the University of Michigan Biological Station (Pellston, MI, USA). 13C-CO2effluxes from the first 996 days of decay showed a significant wood source by pyrolysis temperature interaction on PyOM field mineralisation rates, with RM450 mineralising twice faster than JP450 during the first 90 days. Increasing pyrolysis temperature substantially decreased field mineralization rates during the first 996 days, with mineralisation rates 24 and 80 times slower for JP300 and JP450 compared with JP wood. After 1 year, (i) bacterial groups were large sinks for PyOM-derived C as pyrolysis temperature increased and as substrate use efficiency decreased; (ii) potential phenol oxidase and net peroxidase activities were unaffected by the PyOM addition, although net peroxidase activities measured tended to lesser for soils amended with JP450 and RM450; and (iii) Collembola detritivores appeared less likely to be found for soils amended with JP450 and RM450. PyOM-derived C and N recoveries did not differ after 1 year; we will present 3-y recovery data. Our results suggest that the composition of angiosperms (e.g. RM) and gymnosperms (e.g. JP) in high-latitude forests is an underappreciated but essential determinant of soil PyOM stocks and reactivity, with angiosperms yielding more degradable PyOM. Considering the wood source by pyrolysis temperature interaction on PyOM will help providing more comprehensive large-scale assessments of PyOM stocks and reactivity potentials under current and future climate conditions.

Identification of a Polyomavirus microRNA Highly Expressed in Tumors

PubMed Central

Chen, Chun Jung; Cox, Jennifer E.; Azarm, Kristopher; Wylie, Karen N.; Woolard, Kevin D.; Pesavento, Patricia A.; Sullivan, Christopher S.

2014-01-01

Polyomaviruses (PyVs) are associated with tumors including Merkel cell carcinoma (MCC). Several PyVs encode microRNAs (miRNAs) but to date no abundant PyV miRNAs have been reported in tumors. To better understand the function of the Merkel cell PyV (MCPyV) miRNA, we examined phylogenetically-related viruses for miRNA expression. We show that two primate PyVs and the more distantly-related raccoon PyV (RacPyV) encode miRNAs that share genomic position and partial sequence identity with MCPyV miRNAs. Unlike MCPyV miRNA in MCC, RacPyV miRNA is highly abundant in raccoon tumors. RacPyV miRNA negatively regulates reporters of early viral (T antigen) transcripts, yet robust viral miRNA expression is tolerated in tumors. We also identify raccoon miRNAs expressed in RacPyV-associated neuroglial brain tumors, including several likely oncogenic miRNAs (oncomiRs). This work describes the first PyV miRNA abundantly expressed in tumors and is consistent with a possible role for both host and viral miRNAs in RacPyV-associated tumors. PMID:25514573

State-specific transport properties of electronically excited Ar and C

NASA Astrophysics Data System (ADS)

Istomin, V. A.; Kustova, E. V.

2018-05-01

In the present study, a theoretical model of state-resolved transport properties in electronically excited atomic species developed earlier is applied to argon and carbon atomic species. It is shown that for Ar and C, similarly to the case of atomic nitrogen and oxygen, the Slater-like models can be applied to calculate diameters of electronically excited atoms. Using the Slater-like model it is shown that for half-filled N (2 px1py1pz1) and full-filled Ar (3 px2py2pz2) electronic shells the growth of atomic radius goes slowly compared to C (2 px1py1) and O (2 px2py1pz1). The effect of collision diameters on the transport properties of Ar and C is evaluated. The influence of accounted number of electronic levels on the transport coefficients is examined for the case of Boltzmann distributions over electronic energy levels. It is emphasized that in the temperature range 1000-14000 K, for Boltzmann-like distributions over electronic states the number of accounted electronic levels do not influence the transport coefficients. Contrary to this, for higher temperatures T > 14000 K this effect becomes of importance, especially for argon.

T cell-independent and T cell-dependent immunoglobulin G responses to polyomavirus infection are impaired in complement receptor 2-deficient mice.

PubMed

Szomolanyi-Tsuda, Eva; Seedhom, Mina O; Carroll, Michael C; Garcea, Robert L

2006-08-15

Polyomavirus (PyV) infection induces protective T cell-independent (TI) IgM and IgG antibody responses in T cell-deficient mice, but these responses are not generated by immunization with viral proteins or virus like particles. We hypothesized that innate signals contribute to the generation of isotype-switched antiviral antibody responses. We studied the role of complement receptor (CR2) engagement in TI and T cell-dependent (TD) antibody responses to PyV using CR2-deficient mice. Antiviral IgG responses were reduced by 80-40% in CR2-/- mice compared to wild type. Adoptive transfer experiments demonstrated the need for CR2 not only in TD, but also in TI IgG responses to PyV. Transfer of CR2-/- B lymphocytes to SCID mice resulted in TI antiviral IgG responses that corresponded to 10% of that seen in wild-type B cell-reconstituted mice. Thus, our studies revealed a profound dependence of TI and TD antiviral antibody responses on CR2-mediated signals in PyV-infected mice, where the viral antigen is abundant and persistent.

Mitochondrial targeted catalase suppresses invasive breast cancer in mice.

PubMed

Goh, Jorming; Enns, Linda; Fatemie, Soroosh; Hopkins, Heather; Morton, John; Pettan-Brewer, Christina; Ladiges, Warren

2011-05-23

Treatment of invasive breast cancer has an alarmingly high rate of failure because effective targets have not been identified. One potential target is mitochondrial generated reactive oxygen species (ROS) because ROS production has been associated with changes in substrate metabolism and lower concentration of anti-oxidant enzymes in tumor and stromal cells and increased metastatic potential. Transgenic mice expressing a human catalase gene (mCAT) were crossed with MMTV-PyMT transgenic mice that develop metastatic breast cancer. All mice (33 mCAT positive and 23 mCAT negative) were terminated at 110 days of age, when tumors were well advanced. Tumors were histologically assessed for invasiveness, proliferation and metastatic foci in the lungs. ROS levels and activation status of p38 MAPK were determined. PyMT mice expressing mCAT had a 12.5 per cent incidence of high histological grade primary tumor invasiveness compared to a 62.5 per cent incidence in PyMT mice without mCAT. The histological grade correlated with incidence of metastasis with 56 per cent of PyMT mice positive for mCAT showing evidence of pulmonary metastasis compared to 85.4 per cent of PyMT mice negative for mCAT with pulmonary metastasis (p ≤ 0.05). PyMT tumor cells expressing mCAT had lower ROS levels and were more resistant to hydrogen peroxide-induced oxidative stress than wild type tumor cells, suggesting that mCAT has the potential of quenching intracellular ROS and subsequent invasive behavior. The metastatic tumor burden in PyMT mice expressing mCAT was 0.1 mm2/cm2 of lung tissue compared with 1.3 mm2/cm2 of lung tissue in PyMT mice expressing the wild type allele (p ≤ 0.01), indicating that mCAT could play a role in mitigating metastatic tumor progression at a distant organ site. Expression of mCAT in the lungs increased resistance to hydrogen peroxide-induced oxidative stress that was associated with decreased activation of p38MAPK suggesting ROS signaling is dependent on p38MAPK for at least some of its downstream effects. Targeting catalase within mitochondria of tumor cells and tumor stromal cells suppresses ROS-driven tumor progression and metastasis. Therefore, increasing the antioxidant capacity of the mitochondrial compartment could be a rational therapeutic approach for invasive breast cancer.

Discerning the biochemical stability of pyrogenic C in soils

NASA Astrophysics Data System (ADS)

De la Rosa, José M.; Paneque, Marina; Contreras-Bernal, Lidia; Miller, Ana Z.; Knicker, Heike

2016-04-01

The soil organic matter (SOM) constitutes approximately 2/3 of the global terrestrial C pool, which corresponds to estimated 4000 Pg to a depth of 3 m [1] and therefore, the dynamics of organic carbon (OC) in soils control a large part of the terrestrial C cycle. The term Pyrogenic Carbon (PyC) comprises the whole range of pyrogenic organic materials, from partly charred material through charcoal to soot produced during fire, as well as technical chars (biochars) produced by pyrolysis of biomass. The previously common assumption of PyC being inert has long been proven wrong [2]. In theory, the pyrogenic process confers these materials a longer mean residence time in the soils than their precursors, thus the application of PyC in general and particularly biochar to soil is proposed as a valid approach to establish a significant, long-term sink for atmospheric carbon dioxide in terrestrial ecosystems [3]. Nevertheless, the knowledge concerning the biochemical recalcitrance of PyOM in soils is still limited. This study combines the analysis by 13C solid state Nuclear Magnetic Resonance Spectroscopy (13C NMR), Field Emission Scanning Electron Microscopy (FESEM), analytical pyrolysis (Py-GC/MS) and CO2 emissions in incubated pots of burned and unburned soils as well as in biochar amended and un-amended soils. By using this integrated approach we achieved a more complete understanding of the stability of different forms of PyC in the soil and the chemical changes occurring during aging. Significant differences are found between the stability of PyC. They depend on the nature of the source material, surficial properties of PyC, the pyrolysis process and the soil conditions during aging. Acknowledgements: The Marie Skłodowska-Curie actions (PCIG12-GA-2012-333784-Biocharisma project and PIEF-GA-2012-328689-DECAVE project), and the Spanish Ministry of Economy and Competitiveness (MINECO) (project PCGL2012-37041) are thanked for the financial support of the present study. References: [1] Hernández-Soriano M.C., Peña A., Mingorance MD., 2013. Env. Toxicol. Chem. 32(5), 1027-1032. [2] De la Rosa J.M., Knicker H., 2011. Soil Biol. Biochem. 43, 2368-2373. [3] Sohi S., Lopez-Capel E., Krull E., Bol R., 2009. Rep. No. 05/09. CSIRO. 1834-6618.

Immunogenicity and Protective Efficacy of a Plasmodium yoelii Hsp60 DNA Vaccine in BALB/c Mice

PubMed Central

Sanchez, Gloria I.; Sedegah, Martha; Rogers, William O.; Jones, Trevor R.; Sacci, John; Witney, Adam; Carucci, Daniel J.; Kumar, Nirbhay; Hoffman, Stephen L.

2001-01-01

The gene encoding the 60-kDa heat shock protein of Plasmodium yoelii (PyHsp60) was cloned into the VR1012 and VR1020 mammalian expression vectors. Groups of 10 BALB/c mice were immunized intramuscularly at 0, 3, and 9 weeks with 100 μg of PyHsp60 DNA vaccine alone or in combination with 30 μg of pmurGMCSF. Sera from immunized mice but not from vector control groups recognized P. yoelii sporozoites, liver stages, and infected erythrocytes in an indirect fluorescent antibody test. Two weeks after the last immunization, mice were challenged with 50 P. yoelii sporozoites. In one experiment the vaccine pPyHsp60-VR1012 used in combination with pmurGMCSF gave 40% protection (Fisher's exact test; P = 0.03, vaccinated versus control groups). In a second experiment this vaccine did not protect any of the immunized mice but induced a delay in the onset of parasitemia. In neither experiment was there any evidence of a protective effect against the asexual erythrocytic stage of the life cycle. In a third experiment mice were primed with PyHsp60 DNA, were boosted 2 weeks later with 2 × 103 irradiated P. yoelii sporozoites, and were challenged several weeks later. The presence of PyHsp60 in the immunization regimen did not lead to reduced blood-stage infection or development of parasites in hepatocytes. PyHsp60 DNA vaccines were immunogenic in BALB/c mice but did not consistently, completely protect against sporozoite challenge. The observation that in some of the PyHsp60 DNA vaccine-immunized mice there was protection against infection or a delay in the onset of parasitemia after sporozoite challenge deserves further evaluation. PMID:11349057

Genome-wide identification, characterization and expression analyses of two TNFRs in Yesso scallop (Patinopecten yessoensis) provide insight into the disparity of responses to bacterial infections and heat stress in bivalves.

PubMed

Xing, Qiang; Yu, Qian; Dou, Huaiqian; Wang, Jing; Li, Ruojiao; Ning, Xianhui; Wang, Ruijia; Wang, Shi; Zhang, Lingling; Hu, Xiaoli; Bao, Zhenmin

2016-05-01

Tumor necrosis factors receptors (TNFRs) comprise a superfamily of proteins characterized by a unique cysteine-rich domain (CRD) and play important roles in diverse physiological and pathological processes in the innate immune system, including inflammation, apoptosis, autoimmunity and organogenesis. Although significant effects of TNFRs on immunity have been reported in most vertebrates as well as some invertebrates, the complete TNFR superfamily has not been systematically characterized in scallops. In this study, two different types of TNFR-like genes, including PyTNFR1 and PyTNFR2 genes were identified from Yesso scallop (Patinopecten yessoensis, Jay, 1857) through whole-genome scanning. Phylogenetic and protein structural analyses were carried out to determine the identities and evolutionary relationships of the two genes. The expression profiling of PyTNFRs was performed at different development stages, in healthy adult tissues and in hemocytes after bacterial infection and heat stress. Expression analysis revealed that both PyTNFRs were significantly induced during the acute phase (3 h) after infection with Gram-positive (Micrococcus luteus) and Gram-negative (Vibrio anguillarum) bacteria, though much more dramatic chronic-phase (24 h) changes were observed after V. anguillarum challenge. For heat stress, only PyTNFR2 displayed significant elevation at 12 h and 24 h, which suggests a functional difference in the two PyTNFRs. Collectively, this study provides novel insight into the PyTNFRs and the specific role and response of TNFR-involved pathways in host immune responses against different bacterial pathogens and heat stress in bivalves. Copyright © 2016 Elsevier Ltd. All rights reserved.

[Study on the prevalence of loss to follow-up and risk factors among human immunodeficiency virus (HIV)/acquired immunodeficiency syndrome (AIDS) patients in Baoshan city, Yunnan province].

PubMed

Huang, Dongsheng; Zheng, Weibin; Yang, Jiafang; Li, Yanping; Hu, Anyan; Xu, Zhengcui

2014-08-01

To determine the prevalence of loss to follow-up (PLF) and risk factors among human immunodeficiency virus (HIV)/acquired immunodeficiency syndrome (AIDS) patients from 1989 to 2012 in Baoshan city, Yunnan province. The epidemic and follow-up databases of HIV/AIDS patients by the end of 2012 were downloaded from "the history card downloading site" of HIV/AIDS database in China Information System for Disease Control and Prevention and obtained the related data of patients from 1989 to 2012 who had local residence in Baoshan city. These data included demographic characteristics (genders, age at the time of HIV testing positive, and occupation, marital status, and education levels, et al), transmission routes, and disease staging, antiretroviral therapy (ART), and sources of samples, the first CD4(+)T cell counts, and status of follow-up, et al. Descriptive epidemiological study was used to describe the general characteristics of loss to follow-up. Multivariable Cox regression was used for determining risk factors associated with loss to follow-up. A total of 3 295 eligible HIV/AIDS patients from 1989 to 2012 were included. The accumulative study person-year was 11 416.59 years, 222 HIV/AIDS patients were lost to follow-up, and the PLF was 0.019 4/ person years (py). The highest PLF was 0.052 8/py in 2008, the lowest was 0.006 2/py in 2012. The lost patients included 56.76% (126/222) males and 43.24% (96/222) females, the PLFs were 0.020 4/py, 0.018 3/py, respectively. Baoshan city, other cities in Yunnan province, and other provinces, foreign nationality as the family register reached 53.60% (119/222) , 28.83% (64/222) , and 5.86% (13/222) , 11.71% (26/222) , respectively, and their PLFs were 0.012 5/py, 0.046 3/py, and 0.053 6/py, 0.095 6/py, respectively. Receiving ART and not receiving ART occupied 6.76% (15/222) , 93.24% (207/222) , respectively, and the PLFs were 0.001 9/py, 0.0588/py. AIDS and HIV staging standed at 8.11% (18/222) , 91.89% (204/222) , respectively, and the PLFs were 0.003 3, 0.034 5/py. The first CD4(+)T cell counts < 200, 200-350, and > 350 cells /ml accounted for 4.95% (11/222) , 73.87% (164/222) , 21.17% (47/222) , respectively, and the PLFs were 0.004 8/py, 0.024 0/py, 0.020 3/py. The results of multivariable Cox regression showed the risks of loss to follow-up (RLFs) of family register as other cities in Yunnan province (HR = 3.11, 95%CI:2.28-4.25) , other provinces (HR = 2.55, 95%CI:1.42-4.56) , and foreign nationality (HR = 2.12, 95%CI:1.35-3.33) higher than that of Baoshan city, respectively. The RLFs of not receiving ART (HR = 20.83, 95%CI:11.74-36.96) and HIV staging (HR = 3.61, 95%CI:1.82-7.16) were higher than those of receiving ART and AIDS staging, respectively, moreover, the RFLs of the first CD4(+)T cell counts between 200-350 cells/ml (HR = 0.35, 95%CI:0.15-0.82) and the first CD4(+)T cell counts > 350 cells/ml (HR = 0.29, 95%CI:0.12-0.72) were less than that of first CD4(+)T cell counts < 200 cells /ml, respectively. The RLF of transmission route as injecting drug (HR = 0.60, 95%CI:0.41-0.88) was less than that of heterosexual contact. Overall, the prevalence of loss to follow-up among HIV/AIDS patients shows a downward trend, moreover, patients of outsiders, heterosexual contact, HIV staging, baseline CD4(+)T cell counts < 200 cells/ml are at higher risk of loss to follow-up.

PyPedia: using the wiki paradigm as crowd sourcing environment for bioinformatics protocols.

PubMed

Kanterakis, Alexandros; Kuiper, Joël; Potamias, George; Swertz, Morris A

2015-01-01

Today researchers can choose from many bioinformatics protocols for all types of life sciences research, computational environments and coding languages. Although the majority of these are open source, few of them possess all virtues to maximize reuse and promote reproducible science. Wikipedia has proven a great tool to disseminate information and enhance collaboration between users with varying expertise and background to author qualitative content via crowdsourcing. However, it remains an open question whether the wiki paradigm can be applied to bioinformatics protocols. We piloted PyPedia, a wiki where each article is both implementation and documentation of a bioinformatics computational protocol in the python language. Hyperlinks within the wiki can be used to compose complex workflows and induce reuse. A RESTful API enables code execution outside the wiki. Initial content of PyPedia contains articles for population statistics, bioinformatics format conversions and genotype imputation. Use of the easy to learn wiki syntax effectively lowers the barriers to bring expert programmers and less computer savvy researchers on the same page. PyPedia demonstrates how wiki can provide a collaborative development, sharing and even execution environment for biologists and bioinformaticians that complement existing resources, useful for local and multi-center research teams. PyPedia is available online at: http://www.pypedia.com. The source code and installation instructions are available at: https://github.com/kantale/PyPedia_server. The PyPedia python library is available at: https://github.com/kantale/pypedia. PyPedia is open-source, available under the BSD 2-Clause License.

pyBSM: A Python package for modeling imaging systems

NASA Astrophysics Data System (ADS)

LeMaster, Daniel A.; Eismann, Michael T.

2017-05-01

There are components that are common to all electro-optical and infrared imaging system performance models. The purpose of the Python Based Sensor Model (pyBSM) is to provide open source access to these functions for other researchers to build upon. Specifically, pyBSM implements much of the capability found in the ERIM Image Based Sensor Model (IBSM) V2.0 along with some improvements. The paper also includes two use-case examples. First, performance of an airborne imaging system is modeled using the General Image Quality Equation (GIQE). The results are then decomposed into factors affecting noise and resolution. Second, pyBSM is paired with openCV to evaluate performance of an algorithm used to detect objects in an image.

Is fire a long term sink or source of atmospheric carbon? A comprehensive evaluation of a boreal forest fire

NASA Astrophysics Data System (ADS)

Santin, C.; Doerr, S. H.; Preston, C.; Bryant, R.

2012-12-01

Fires lead to a rapid release of carbon (C) from forest and other fire-prone ecosystems, emitting important quantities of C to the atmosphere. Every year 300-600 Mill. ha burn around the globe, generating CO2 emissions equivalent to half of the current annual global from fossil fuel combustion. Over the longer-term vegetation fires are widely considered as 'net zero Carbon (C) emission events', because C emissions from fires, excluding those associated with deforestation, are balanced by C uptake by regenerating vegetation. This 'zero C emission' scenario, however, may be flawed, as it does not consider the role of pyrogenic C (PyC). During fire, some of the fuel is transformed into PyC (i.e. charcoal, black C, soot), which is characterized by an enhanced recalcitrance and a longer mean residence time in the environment than its 'fresh' precursors. Therefore, after complete regeneration of the vegetation, the PyC generated represents an additional longer-term C pool and, hence, recurring fire-regrowth cycles could be considered as a 'net sink of atmospheric C'. To test the validity of this hypothesis, and to estimate how quantitatively important this PyC pool might be, accurate data on PyC production with respect to the fuel combusted are needed. Unfortunately, detailed quantification of fuel prior to fire is normally only available for prescribed and experimental fires, which are usually of low-intensity and therefore not representative of higher-intensity wildfires. Furthermore, what little data is available is usually based on only a specific fraction of the PyC present following burning rather than the whole range of PyC products and stores (i.e. PyC in soil, ash, downed wood and standing vegetation). The FireSmart project (Ft. Providence, NWT, Canada, June 2012) provided the ideal framework to address this research gap. This experimental fire reproduced wildfire conditions in boreal forest, i.e. stand-replacing crown fire and, at the same time, allowed i) pre-fire fuel assessment, ii) fire behaviour monitoring and iii) immediate post-fire fuel and PyC inventory. Before the fire, fuel characteristics were established and the site was instrumented with auto-logging thermocouples to provide temperature-duration profiles during burning. Also, different types of PyC were placed on the ground to determine PyC loss during the fire. Immediately after fire, the various post-burn PyC products and stores were sampled. Total PyC was quantified and the chemical recalcitrance of the different PyC forms found was determined. The results obtained will be discussed in the context of PyC production, and its different forms and quantities, with respect to (i) fire characteristics and fuel consumed, and (ii) the long term carbon balance in this boreal forest environment for recurring fire-regrowth cycles under current and predicted future climatic conditions.

Contribution of systemic and somatic factors to clinical response and resistance to PD-L1 blockade in urothelial cancer: An exploratory multi-omic analysis

PubMed Central

Ahuja, Arun; Al-Ahmadie, Hikmat; Yusko, Erik; Benzeno, Sharon; Boyd, Mariel; Moran, Meredith; Iyer, Gopa; Mardis, Elaine R.

2017-01-01

Background Inhibition of programmed death-ligand 1 (PD-L1) with atezolizumab can induce durable clinical benefit (DCB) in patients with metastatic urothelial cancers, including complete remissions in patients with chemotherapy refractory disease. Although mutation load and PD-L1 immune cell (IC) staining have been associated with response, they lack sufficient sensitivity and specificity for clinical use. Thus, there is a need to evaluate the peripheral blood immune environment and to conduct detailed analyses of mutation load, predicted neoantigens, and immune cellular infiltration in tumors to enhance our understanding of the biologic underpinnings of response and resistance. Methods and findings The goals of this study were to (1) evaluate the association of mutation load and predicted neoantigen load with therapeutic benefit and (2) determine whether intratumoral and peripheral blood T cell receptor (TCR) clonality inform clinical outcomes in urothelial carcinoma treated with atezolizumab. We hypothesized that an elevated mutation load in combination with T cell clonal dominance among intratumoral lymphocytes prior to treatment or among peripheral T cells after treatment would be associated with effective tumor control upon treatment with anti-PD-L1 therapy. We performed whole exome sequencing (WES), RNA sequencing (RNA-seq), and T cell receptor sequencing (TCR-seq) of pretreatment tumor samples as well as TCR-seq of matched, serially collected peripheral blood, collected before and after treatment with atezolizumab. These parameters were assessed for correlation with DCB (defined as progression-free survival [PFS] >6 months), PFS, and overall survival (OS), both alone and in the context of clinical and intratumoral parameters known to be predictive of survival in this disease state. Patients with DCB displayed a higher proportion of tumor-infiltrating T lymphocytes (TIL) (n = 24, Mann-Whitney p = 0.047). Pretreatment peripheral blood TCR clonality below the median was associated with improved PFS (n = 29, log-rank p = 0.048) and OS (n = 29, log-rank p = 0.011). Patients with DCB also demonstrated more substantial expansion of tumor-associated TCR clones in the peripheral blood 3 weeks after starting treatment (n = 22, Mann-Whitney p = 0.022). The combination of high pretreatment peripheral blood TCR clonality with elevated PD-L1 IC staining in tumor tissue was strongly associated with poor clinical outcomes (n = 10, hazard ratio (HR) (mean) = 89.88, HR (median) = 23.41, 95% CI [2.43, 506.94], p(HR > 1) = 0.0014). Marked variations in mutation loads were seen with different somatic variant calling methodologies, which, in turn, impacted associations with clinical outcomes. Missense mutation load, predicted neoantigen load, and expressed neoantigen load did not demonstrate significant association with DCB (n = 25, Mann-Whitney p = 0.22, n = 25, Mann-Whitney p = 0.55, and n = 25, Mann-Whitney p = 0.29, respectively). Instead, we found evidence of time-varying effects of somatic mutation load on PFS in this cohort (n = 25, p = 0.044). A limitation of our study is its small sample size (n = 29), a subset of the patients treated on IMvigor 210 (NCT02108652). Given the number of exploratory analyses performed, we intend for these results to be hypothesis-generating. Conclusions These results demonstrate the complex nature of immune response to checkpoint blockade and the compelling need for greater interrogation and data integration of both host and tumor factors. Incorporating these variables in prospective studies will facilitate identification and treatment of resistant patients. PMID:28552987

Contribution of systemic and somatic factors to clinical response and resistance to PD-L1 blockade in urothelial cancer: An exploratory multi-omic analysis.

PubMed

Snyder, Alexandra; Nathanson, Tavi; Funt, Samuel A; Ahuja, Arun; Buros Novik, Jacqueline; Hellmann, Matthew D; Chang, Eliza; Aksoy, Bulent Arman; Al-Ahmadie, Hikmat; Yusko, Erik; Vignali, Marissa; Benzeno, Sharon; Boyd, Mariel; Moran, Meredith; Iyer, Gopa; Robins, Harlan S; Mardis, Elaine R; Merghoub, Taha; Hammerbacher, Jeff; Rosenberg, Jonathan E; Bajorin, Dean F

2017-05-01

Inhibition of programmed death-ligand 1 (PD-L1) with atezolizumab can induce durable clinical benefit (DCB) in patients with metastatic urothelial cancers, including complete remissions in patients with chemotherapy refractory disease. Although mutation load and PD-L1 immune cell (IC) staining have been associated with response, they lack sufficient sensitivity and specificity for clinical use. Thus, there is a need to evaluate the peripheral blood immune environment and to conduct detailed analyses of mutation load, predicted neoantigens, and immune cellular infiltration in tumors to enhance our understanding of the biologic underpinnings of response and resistance. The goals of this study were to (1) evaluate the association of mutation load and predicted neoantigen load with therapeutic benefit and (2) determine whether intratumoral and peripheral blood T cell receptor (TCR) clonality inform clinical outcomes in urothelial carcinoma treated with atezolizumab. We hypothesized that an elevated mutation load in combination with T cell clonal dominance among intratumoral lymphocytes prior to treatment or among peripheral T cells after treatment would be associated with effective tumor control upon treatment with anti-PD-L1 therapy. We performed whole exome sequencing (WES), RNA sequencing (RNA-seq), and T cell receptor sequencing (TCR-seq) of pretreatment tumor samples as well as TCR-seq of matched, serially collected peripheral blood, collected before and after treatment with atezolizumab. These parameters were assessed for correlation with DCB (defined as progression-free survival [PFS] >6 months), PFS, and overall survival (OS), both alone and in the context of clinical and intratumoral parameters known to be predictive of survival in this disease state. Patients with DCB displayed a higher proportion of tumor-infiltrating T lymphocytes (TIL) (n = 24, Mann-Whitney p = 0.047). Pretreatment peripheral blood TCR clonality below the median was associated with improved PFS (n = 29, log-rank p = 0.048) and OS (n = 29, log-rank p = 0.011). Patients with DCB also demonstrated more substantial expansion of tumor-associated TCR clones in the peripheral blood 3 weeks after starting treatment (n = 22, Mann-Whitney p = 0.022). The combination of high pretreatment peripheral blood TCR clonality with elevated PD-L1 IC staining in tumor tissue was strongly associated with poor clinical outcomes (n = 10, hazard ratio (HR) (mean) = 89.88, HR (median) = 23.41, 95% CI [2.43, 506.94], p(HR > 1) = 0.0014). Marked variations in mutation loads were seen with different somatic variant calling methodologies, which, in turn, impacted associations with clinical outcomes. Missense mutation load, predicted neoantigen load, and expressed neoantigen load did not demonstrate significant association with DCB (n = 25, Mann-Whitney p = 0.22, n = 25, Mann-Whitney p = 0.55, and n = 25, Mann-Whitney p = 0.29, respectively). Instead, we found evidence of time-varying effects of somatic mutation load on PFS in this cohort (n = 25, p = 0.044). A limitation of our study is its small sample size (n = 29), a subset of the patients treated on IMvigor 210 (NCT02108652). Given the number of exploratory analyses performed, we intend for these results to be hypothesis-generating. These results demonstrate the complex nature of immune response to checkpoint blockade and the compelling need for greater interrogation and data integration of both host and tumor factors. Incorporating these variables in prospective studies will facilitate identification and treatment of resistant patients.

Pure MnTBAP selectively scavenges peroxynitrite over superoxide: Comparison of pure and commercial MnTBAP samples to MnTE-2-PyP in two different models of oxidative stress injuries, SOD-specific E. coli model and carrageenan-induced pleurisy

PubMed Central

Batinić-Haberle, Ines; Cuzzocrea, Salvatore; Rebouças, Júlio S.; Ferrer-Sueta, Gerardo; Mazzon, Emanuela; Di Paola, Rosanna; Radi, Rafael; Spasojević, Ivan; Benov, Ludmil; Salvemini, Daniela

2009-01-01

MnTBAP is often referred to as an SOD mimic in numerous models of oxidative stress. We have recently reported that pure MnTBAP does not dismute superoxide, but commercial/ill-purified samples are able to perform O2•− dismutation with low-to-moderate efficacy via non-innocent Mn-containing impurities. Herein, we show that neither commercial nor pure MnTBAP could substitute for SOD enzyme in the SOD-deficient E. coli model, while MnTE-2-PyP-treated SOD-deficient E. coli grew as well as wild-type strain. This SOD-specific system indicates that MnTBAP does not act as an SOD mimic in vivo. In another model, carrageenan-induced pleurisy in mice, inflammation was evidenced by increased pleural fluid exudate, and neutrophil infiltration and activation: these events were blocked by 0.3 mg/kg of MnTE-2-PyP and to a slightly lesser extent with 10 mg/kg of MnTBAP. Also, 3-nitrotyrosine formation, an indication of the peroxynitrite existence in vivo, was blocked by both compounds; again MnTE-2-PyP was 33-fold more effective. Pleurisy model data indicate that MnTBAP exert some protective actions in common with MnTE-2-PyP, which are not O2•−-related, and can be fully rationalized if one considers that the common biological role shared by MnTBAP and MnTE-2-PyP is related to their reduction of peroxynitrite and carbonate radical, the latter arising from ONOO− adduct with CO2. The log kcat (O2•−) value for MnTBAP is estimated to be about 3.16, which is ~5 and ~7 orders of magnitude smaller than the SOD activity of the potent SOD mimic MnTE-2-PyP and Cu, Zn-SOD, respectively. This very low value indicates that MnTBAP is very inefficient in dismuting superoxide to be of any biological impact, which was confirmed in the SOD-deficient E. coli model. Peroxynitrite scavenging ability of MnTBAP, however, is only ~2.5 orders of magnitude smaller than that of MnTE-2-PyP and is not significantly affected by the presence of the SOD-active impurities in commercial MnTBAP sample (log kred(ONOO−) = 5.06 for pure and 4.97 for commercial sample). The reduction of carbonate radical is equally fast with MnTBAP and MnTE-2-PyP. The dose of MnTBAP required to yield oxidative stress protection and block nitrotyrosine formation in the pleurisy model is >1.5 orders of magnitude higher than that of MnTE-2-PyP, which could be related to the smaller ability of MnTBAP to scavenge peroxynitrite. The slightly better protection observed with the commercial MnTBAP sample (relative to the pure MnTBAP one) could arise from its impurities, which, by scavenging O2•−, reduce consequently the overall peroxynitrite, and secondary ROS/RNS levels. These observations have profound biological repercussions as they may suggest that the effect of MnTBAP observed in numerous studies may conceivably relate to peroxynitrite scavenging. Moreover, provided that pure MnTBAP is unable to dismute superoxide at any significant extent, but is able to partially scavenge peroxynitrite and carbonate radical, this compound may prove valuable to distinguish ONOO−/CO3•− from O2•− pathways. PMID:19007878

SH2 Binding Site Protection Assay: A Method for Identification of SH2 Domain Interaction Partners by Exploiting SH2 Mediated Phosphosite Protection.

PubMed

Jadwin, Joshua A

2017-01-01

Over the last two decades there has been a significant effort in the field to characterize the phosphosite binding specificities of SH2 domains with the goal of deciphering the pY signaling code. Although high throughput studies in various formats using most SH2 domains have collectively provided a rich resource of in vitro SH2-pTyr site specificity maps, this data can only be used approximate what is happening in the cell where protein concentrations and localization are not homogenous, as they are for in vitro experiments. Here we describe an in vivo approach, SH2 site protection assay, which can capture the pTyr binding specificity of SH2 domains in the cell. The basis of this approach is SH2-pY site protection, the ability of SH2 domains to prevent the PTP-dependent dephosphorylation of their pY site binding partners. We overexpress a tracer SH2 domain in cells and quantify the change in abundance of tyrosine phosphorylated sites using MS. Since the method is performed in vivo, it has the advantage of identifying SH2-pY interactions as they occur within in the cell.

Characterization of Mode 1 and Mode 2 delamination growth and thresholds in graphite/peek composites

NASA Technical Reports Server (NTRS)

Martin, Roderick H.; Murri, Gretchen B.

1988-01-01

Composite materials often fail by delamination. The onset and growth of delamination in AS4/PEEK, a tough thermoplastic matrix composite, was characterized for mode 1 and mode 2 loadings, using the Double Cantilever Beam (DCB) and the End Notched Flexure (ENF) test specimens. Delamination growth per fatigue cycle, da/dN, was related to strain energy release rate, G, by means of a power law. However, the exponents of these power laws were too large for them to be adequately used as a life prediction tool. A small error in the estimated applied loads could lead to large errors in the delamination growth rates. Hence strain energy release rate thresholds, G sub th, below which no delamination would occur were also measured. Mode 1 and 2 threshold G values for no delamination growth were found by monitoring the number of cycles to delamination onset in the DCB and ENF specimens. The maximum applied G for which no delamination growth had occurred until at least 1,000,000 cycles was considered the threshold strain energy release rate. Comments are given on how testing effects, facial interference or delamination front damage, may invalidate the experimental determination of the constants in the expression.

Laser synthesized super-hydrophobic conducting carbon with broccoli-type morphology as a counter-electrode for dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Gokhale, Rohan; Agarkar, Shruti; Debgupta, Joyashish; Shinde, Deodatta; Lefez, Benoit; Banerjee, Abhik; Jog, Jyoti; More, Mahendra; Hannoyer, Beatrice; Ogale, Satishchandra

2012-10-01

A laser photochemical process is introduced to realize superhydrophobic conducting carbon coatings with broccoli-type hierarchical morphology for use as a metal-free counter electrode in a dye sensitized solar cell. The process involves pulsed excimer laser irradiation of a thin layer of liquid haloaromatic organic solvent o-dichlorobenzene (DCB). The coating reflects a carbon nanoparticle-self assembled and process-controlled morphology that yields solar to electric power conversion efficiency of 5.1% as opposed to 6.2% obtained with the conventional Pt-based electrode.A laser photochemical process is introduced to realize superhydrophobic conducting carbon coatings with broccoli-type hierarchical morphology for use as a metal-free counter electrode in a dye sensitized solar cell. The process involves pulsed excimer laser irradiation of a thin layer of liquid haloaromatic organic solvent o-dichlorobenzene (DCB). The coating reflects a carbon nanoparticle-self assembled and process-controlled morphology that yields solar to electric power conversion efficiency of 5.1% as opposed to 6.2% obtained with the conventional Pt-based electrode. Electronic supplementary information (ESI) available: Materials and equipment details, solar cell fabrication protocol, electrolyte spreading time measurement details, XPS spectra, electronic study, film adhesion test detailed analysis and field emission results. See DOI: 10.1039/c2nr32082g

Raman gas sensing of modified Ag nanoparticle SERS

NASA Astrophysics Data System (ADS)

Myoung, NoSoung; Yoo, Hyung Keun; Hwang, In-Wook

2014-03-01

Recent progress in modified Surface Enhanced Raman Scattering (SERS) using Ag nanoparticles makes them promising optical technique for direct gas sensing of interest. However, SERS has been shown to provide sub ppb level detection of the compounds in the vapor phase. The major problem with the sensitivity scaling-up was in the development of fabrication technology for stability and reproducibility of SERS substrates. We report an optimization of 1-propanethiol coated multiple Ag nanoparticle layers on SiO2 substrate as well as new records of real-time, simultaneous vapor phase detection of toluene and 1-2 dichlorobenzene by the radiation of fiber optic coupled 785 nm diode laser and spectrograph. Multiple depositions of Ag NPs were loaded on SiO2 and soaked in 1-propanethiol solution for 24 hours to modify the surface into hydrophobic due to the characteristics of vapor phase of our interests. Raman bands at 1003 cm-1 and 1130 cm-1 for toluene and 12DCB, respectively were compared to 1089 cm-1 and each gas concentration in 1000 mL flask were calculated as a function of each vapor phase ratio. The saturation of toluene and 12DCB were limited only by 800 ppm and the detectable range was 0.6-800 ppm.

Extending the language of DNA molecular recognition by polyamides: unexpected influence of imidazole and pyrrole arrangement on binding affinity and specificity.

PubMed

Buchmueller, Karen L; Staples, Andrew M; Howard, Cameron M; Horick, Sarah M; Uthe, Peter B; Le, N Minh; Cox, Kari K; Nguyen, Binh; Pacheco, Kimberly A O; Wilson, W David; Lee, Moses

2005-01-19

Pyrrole (Py) and imidazole (Im) polyamides can be designed to target specific DNA sequences. The effect that the pyrrole and imidazole arrangement, plus DNA sequence, have on sequence specificity and binding affinity has been investigated using DNA melting (DeltaT(M)), circular dichroism (CD), and surface plasmon resonance (SPR) studies. SPR results obtained from a complete set of triheterocyclic polyamides show a dramatic difference in the affinity of f-ImPyIm for its cognate DNA (K(eq) = 1.9 x 10(8) M(-1)) and f-PyPyIm for its cognate DNA (K(eq) = 5.9 x 10(5) M(-1)), which could not have been anticipated prior to characterization of these compounds. Moreover, f-ImPyIm has a 10-fold greater affinity for CGCG than distamycin A has for its cognate, AATT. To understand this difference, the triamide dimers are divided into two structural groupings: central and terminal pairings. The four possible central pairings show decreasing selectivity and affinity for their respective cognate sequences: -ImPy > -PyPy- > -PyIm- approximately -ImIm-. These results extend the language of current design motifs for polyamide sequence recognition to include the use of "words" for recognizing two adjacent base pairs, rather than "letters" for binding to single base pairs. Thus, polyamides designed to target Watson-Crick base pairs should utilize the strength of -ImPy- and -PyPy- central pairings. The f/Im and f/Py terminal groups yielded no advantage for their respective C/G or T/A base pairs. The exception is with the -ImPy- central pairing, for which f/Im has a 10-fold greater affinity for C/G than f/Py has for T/A.

Platinum-group element concentrations in pyrite from the Main Sulfide Zone of the Great Dyke of Zimbabwe

NASA Astrophysics Data System (ADS)

Piña, R.; Gervilla, F.; Barnes, S.-J.; Oberthür, T.; Lunar, R.

2016-10-01

The Main Sulfide Zone (MSZ) of the Great Dyke of Zimbabwe hosts the world's second largest resource of platinum-group elements (PGE) after the Bushveld Complex in South Africa. The sulfide assemblage of the MSZ comprises pyrrhotite, pentlandite, chalcopyrite, and minor pyrite. Recently, several studies have observed in a number of Ni-Cu-PGE ore deposits that pyrite may host significant amounts of PGE, particularly Pt and Rh. In this study, we have determined PGE and other trace element contents in pyrite from the Hartley, Ngezi, Unki, and Mimosa mines of the Great Dyke by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Based on the textures and PGE contents, two types of pyrite can be differentiated. Py1 occurs as individual euhedral or subhedral grains or clusters of crystals mostly within chalcopyrite and pentlandite, in some cases in the form of symplectitic intergrowths, and is PGE rich (up to 99 ppm Pt and 61 ppm Rh; 1.7 to 47.1 ppm Ru, 0.1 to 7.8 ppm Os, and 1.2 to 20.2 ppm Ir). Py2 occurs as small individual euhedral or subhedral crystals within pyrrhotite, pentlandite, and less frequently within chalcopyrite and silicates and has low PGE contents (<0.11 ppm Pt, <0.34 ppm Rh, <2.5 ppm Ru, <0.37 ppm Ir, and <0.40 ppm Os). Py1 contains higher Os, Ir, Ru, Rh, and Pt contents than the associated pyrrhotite, pentlandite, and chalcopyrite, whereas Py2 has similar PGE contents as coexisting pyrrhotite and pentlandite. Based on the textural relationships, two different origins are attributed for each pyrite type. Py1 intergrowth with pentlandite and chalcopyrite is inferred to have formed by late, low temperature (<300 °C) decomposition of residual Ni-rich monosulfide solid solution, whereas Py2 is suggested to have formed by replacement of pyrrhotite and pentlandite caused by late magmatic/hydrothermal fluids.

Phytotoxicity, uptake and metabolism of 1,4-dichlorobenzene by plant cells

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

Wang, M.J.; Bokern, M.; Boehme, C.

1996-07-01

Phytotoxicity, uptake, and metabolism of 1,4-dichlorobenzene (1,4-DCB) by carrot (Daucus carota L.), soybean (Glycine max. L.), tomato (Lycopersicon esculentum Mill.), and red goosefoot (Chenopodiun rubrum L.) cell suspension cultures were studied. Sealed glass systems were utilized for the investigation because 1,4-DCB is volatile. The sealed systems affect the growth of plant cells, but do not provide different results when testing xenobiotic uptake and metabolism. 1,4-Dichlorobenzene (40 {micro}g in 40 ml medium) was taken up by carrot (49%), soybean (50%), and red goosefoot (62%) cells. Only the soybean cell cultures provided evidence of the existence of metabolites of this compound, probablymore » conjugates of chlorophenols. Conditions for phytotoxicity tests were modified because the growth of cell cultures was affected when sealed for longer than 2 d. 1,4-Dichlorobenzene is toxic to cell cultures of the three tested plant species (tomato, soybean, and carrot). Concentrations of 0.5 mM caused 50% growth inhibition in carrot and soybean cultures. The tomato cultures were more sensitive, with 0.05 mM causing 50% growth inhibition.« less

Synthetic Approaches to (smif)2Ti (smif = 1,3-di-(2-pyridyl)-2-azaallyl) Reveal Redox Non-Innocence and C-C Bond-Formation

PubMed Central

Frazier, Brenda A.; Wolczanski, Peter T.; Keresztes, Ivan; DeBeer, Serena; Lobkovsky, Emil B.; Pierpont, Aaron W.; Cundari, Thomas R.

2012-01-01

Attempted syntheses of (smif)2Ti (smif = 1,3-di-(2-pyridyl)-2-azaallyl) based on metatheses of TiClnLm (n = 2–4) with M(smif) (M = Li, Na), in the presence of a reducing agent (Na/Hg) when necessary, failed, but several apparent Ti(II) species were identified by X-ray crystallography and multidimensional NMR spectroscopy: (smif){Li(smif-smif)}Ti (1, X-ray), [(smif)Ti]2(μ-κ3,κ3-N,N(py)2-smif,smif) (2), (smif)Ti(κ3-N,N(py)2-smif,(smif)H) (3), and (smif)Ti(dpma) (4). NMR spectroscopy and K-edge XAS showed that each compound possesses ligands that are redox non-innnocent, such that d1 Ti(III) centers AF-couple to ligand radicals: (smif){Li(smif-smif)2−}TiIII (1), [(smif2−)TiIII]2(μ-κ3,κ3-N,N(py)2-smif,smif) (2), [(smif2−)TiIII](κ3-N,N(py)2-smif,(smif)H) (3), and (smif2−)TiIII(dpma) (4). The instability of the (smif)2Ti relative to its C-C coupled dimer, 2, is rationalized via the complementary nature of the amide and smif radical anion ligands, which are also common to 3 and 4. Calculations support this contention. PMID:22830452

Incidence of herpes simplex virus type 2 infection in 5 sexually transmitted disease (STD) clinics and the effect of HIV/STD risk-reduction counseling.

PubMed

Gottlieb, Sami L; Douglas, John M; Foster, Mark; Schmid, D Scott; Newman, Daniel R; Baron, Anna E; Bolan, Gail; Iatesta, Michael; Malotte, C Kevin; Zenilman, Jonathan; Fishbein, Martin; Peterman, Thomas A; Kamb, Mary L

2004-09-15

The seroincidence of herpes simplex virus type 2 (HSV-2) infection was determined among 1766 patients attending sexually transmitted disease (STD) clinics and enrolled in a randomized, controlled trial of human immunodeficiency virus (HIV)/STD risk-reduction counseling (RRC). Arm 1 received enhanced RRC (4 sessions); arm 2, brief RRC (2 sessions); and arm 3, the control arm, brief informational messages. The overall incidence rate was 11.7 cases/100 person-years (py). Independent predictors of incidence of HSV-2 infection included female sex; black race; residence in Newark, New Jersey; <50% condom use with an occasional partner; and, in females, incident trichomoniasis and bacterial vaginosis. Only 10.8% of new HSV-2 infections were diagnosed clinically. Incidence rates were 12.9 cases/100 py in the control arm, 11.8 cases/100 py in arm 2, and 10.3 cases/100 py in arm 1 (hazard ratio, 0.8 [95% confidence interval, 0.6-1.1], vs. controls). The possible benefit of RRC in preventing acquisition of HSV-2 infection offers encouragement that interventions more specifically tailored to genital herpes may be useful and should be an important focus of future studies.

U(IV) chalcogenolates synthesized via oxidation of uranium metal by dichalcogenides.

PubMed

Gaunt, Andrew J; Scott, Brian L; Neu, Mary P

2006-09-04

Treatment of uranium metal with dichalcogenides in the presence of a catalytic amount of iodine in pyridine affords molecular U(IV) chalcogenolates that do not require stabilizing ancillary ligands. Oxidation of U(0) by PhEEPh yields monomeric seven-coordinate U(EPh)4(py)3 (E = S(1), Se(2)). The dimeric eight-coordinate complexes [U(EPh)2(mu2-EPh)2(CH3CN)2]2 (E = S(3), Se(4)) are obtained by crystallization from solutions of 1 and 2 dissolved in acetonitrile. Oxidation of U(0) by pySSpy and crystallization from thf yields nine-coordinate U(Spy)4(thf) (5). Incorporation of elemental selenium into the oxidation of U(0) by PhSeSePh results in the isolation of [U(py)2(SePh)(mu3-Se)(mu2-SePh)]4.4py (6), a tetrameric cluster in which each U(IV) ion is eight-coordinate and the U4Se4 core forms a distorted cube. The compounds were analyzed spectroscopically and the single-crystal X-ray structures of 1 and 3-6 were determined. The isolation of 1-6 represents six new examples of actinide chalcogenolates and allows insight into the nature of "hard" actinide ion-"soft" chalcogen donor interactions.

Course of Cytomegalovirus Retinitis in the Era of Highly Active Antiretroviral Therapy: Five-year Outcomes

PubMed Central

Jabs, Douglas A.; Ahuja, Alka; Van Natta, Mark; Lyon, Alice; Srivastava, Sunil; Gangaputra, Sapna

2010-01-01

Purpose To describe the five-year outcomes of patients with cytomegalovirus (CMV) retinitis and AIDS in the era of highly active antiretroviral therapy (HAART). Design Prospective, multicenter, observational study Participants 503 patients with AIDS and CMV retinitis Methods Follow-up every 3 months with medical history, ophthalmologic examination, laboratory testing, and retinal photographs. Participants were classified as having previously-diagnosed CMV retinitis and immune recovery (CD4+ T cells >100 cells/µL), previously-diagnosed retinitis and immune compromise, and newly-diagnosed CMV retinitis (diagnosis < 45 days prior to enrollment). Main outcome measures Mortality, retinitis progression (movement of the border of a CMV lesion ≥ ½ disc diameter or occurrence of a new lesion), retinal detachment, immune recovery uveitis (IRU), and visual loss (to worse than 20/40 and to 20/200 or worse), Results Overall mortality was 9.8 deaths/100 person-years (PY). Rates varied by group at enrollment from 3.0/100 PY for those with previously-diagnosed retinitis and immune recovery to 26.1/100 PY for those with newly-diagnosed retinitis. The rate of retinitis progression was 7.0/100 PY and varied from 1.4/100 PY for those with previously-diagnosed retinitis and immune recovery to 28.0/100 PY for those with newly-diagnosed retinitis. The rate of retinal detachment was 2.3/100 eye-years (EY) and varied from 1.2/100 EY for those with previously-diagnosed retinitis and immune recovery to 4.9/100 EY for those with newly-diagnosed retinitis. The rate of IRU was 1.7/100 PY and varied from 1.3/100 PY for those with previously-diagnosed retinitis and immune recovery at enrollment to 3.6/100 PY for those with newly-diagnosed retinitis who subsequently experienced immune recovery. The rates of visual loss to worse than 20/40 and to 20/200 or worse were 7.9/100 EY and 3.4/100 EY, respectively; they varied from 6.1/100 EY and 2.7/100 EY for those with previously-diagnosed retinitis and immune recovery to 11.8/100 EY and 5.1/100 EY for those with newly-diagnosed retinitis. Although the event rates tended to decline with time, in general, at no time did they reach zero. Conclusions Despite the availability of HAART, patients with AIDS and CMV retinitis remain at increased risk for mortality, retinitis progression, complications of the retinitis, and visual loss over a 5-year period. PMID:20673591

Inkjet Assisted Creation of Self-Healing Layers Between Composite Plies

DTIC Science & Technology

2013-07-29

technology into a prepreg manufacturing process. The approach consisted of depositing novel thermoplastic low-viscosity microdroplets with chemically and...mechanically comparable properties to epoxy matrix in aerospace grade composites onto fiber-reinforced epoxy prepregs before curing using an ink-jet... prepreg Cycom977-2. Double cantilever beam (DCB) and short beam shear (SBS) tests were used to evaluate the self-healing efficiency. It was shown

PyGeoTess 0.2.0

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

Maccarthy, Jonathan K.

2016-07-28

PyGeoTess is a Python interface module to the GeoTess gridding and earth model library from Sandia National Laboratories. It provides simplified access to a subset of the GeoTess C++ library, and takes advantage of Python's interactive interpreter and inline documentation system.

Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C-H Bonds with Stereoretention.

PubMed

Serrano-Plana, Joan; Oloo, Williamson N; Acosta-Rueda, Laura; Meier, Katlyn K; Verdejo, Begoña; García-España, Enrique; Basallote, Manuel G; Münck, Eckard; Que, Lawrence; Company, Anna; Costas, Miquel

2015-12-23

An unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [Fe(II)(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol(-1)) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tandem with kinetic analysis show that the 490 nm chromophore of 2 is associated with two S = 1/2 species in rapid equilibrium. The minor component 2a (∼5% iron) has g-values at 2.20, 2.19, and 1.99 characteristic of a low-spin iron(III) center, and it is assigned as [Fe(III)(OOAc)(PyNMe3)](2+), also by comparison with the EPR parameters of the structurally characterized hydroxamate analogue [Fe(III)(tBuCON(H)O)(PyNMe3)](2+) (4). The major component 2b (∼40% iron, g-values = 2.07, 2.01, 1.95) has unusual EPR parameters, and it is proposed to be [Fe(V)(O)(OAc)(PyNMe3)](2+), where the O-O bond in 2a has been broken. Consistent with this assignment, 2b undergoes exchange of its acetate ligand with CD3CO2D and very rapidly reacts with olefins to produce the corresponding cis-1,2-hydroxoacetate product. Therefore, this work constitutes the first example where a synthetic nonheme iron species responsible for stereospecific and site selective C-H hydroxylation is spectroscopically trapped, and its catalytic reactivity against C-H bonds can be directly interrogated by kinetic methods. The accumulated evidence indicates that 2 consists mainly of an extraordinarily reactive [Fe(V)(O)(OAc)(PyNMe3)](2+) (2b) species capable of hydroxylating unactivated alkyl C-H bonds with stereoretention in a rapid and site-selective manner, and that exists in fast equilibrium with its [Fe(III)(OOAc)(PyNMe3)](2+) precursor.

Locomotory and physiological responses induced by clove and cinnamon essential oils in the maize weevil Sitophilus zeamais.

PubMed

Gonzales Correa, Yenis Del Carmen; Faroni, Lêda R A; Haddi, Khalid; Oliveira, Eugênio E; Pereira, Eliseu José G

2015-11-01

Plant essential oils have been suggested as a suitable alternative for controlling stored pests worldwide. However, very little is known about the physiological or behavioral responses induced by these compounds in insect populations that are resistant to traditional insecticides. Thus, this investigation evaluated the toxicity (including the impacts on population growth) as well as the locomotory and respiratory responses induced by clove, Syzygium aromaticum L., and cinnamon, Cinnamomum zeylanicum L., essential oils in Brazilian populations of the maize weevil Sitophilus zeamais. We used populations that are resistant to phosphine and pyrethroids (PyPhR), only resistant to pyrethroids (PyR1 and PyR2) or susceptible to both insecticide types (SUS). The PyPhR population was more tolerant to cinnamon essential oil, and its population growth rate was less affected by both oil types. Insects from this population reduced their respiratory rates (i.e., CO2 production) after being exposed to both oil types and avoided (in free choice-experiments) or reduced their mobility on essential oil-treated surfaces. The PyR1 and PyR2 populations reduced their respiratory rates, avoided (without changing their locomotory behavior in no-choice experiments) essential oil-treated surfaces and their population growth rates were severely affected by both oil types. Individuals from SUS population increased their mobility on surfaces that were treated with both oil types and showed the highest levels of susceptibility to these oils. Our findings indicate that S. zeamais populations that are resistant to traditional insecticides might have distinct but possibly overlapping mechanisms to mitigate the actions of essential oils and traditional insecticides. Copyright © 2015 Elsevier Inc. All rights reserved.

On the tradeoffs of programming language choice for numerical modelling in geoscience. A case study comparing modern Fortran, C++/Blitz++ and Python/NumPy.

NASA Astrophysics Data System (ADS)

Jarecka, D.; Arabas, S.; Fijalkowski, M.; Gaynor, A.

2012-04-01

The language of choice for numerical modelling in geoscience has long been Fortran. A choice of a particular language and coding paradigm comes with different set of tradeoffs such as that between performance, ease of use (and ease of abuse), code clarity, maintainability and reusability, availability of open source compilers, debugging tools, adequate external libraries and parallelisation mechanisms. The availability of trained personnel and the scale and activeness of the developer community is of importance as well. We present a short comparison study aimed at identification and quantification of these tradeoffs for a particular example of an object oriented implementation of a parallel 2D-advection-equation solver in Python/NumPy, C++/Blitz++ and modern Fortran. The main angles of comparison will be complexity of implementation, performance of various compilers or interpreters and characterisation of the "added value" gained by a particular choice of the language. The choice of the numerical problem is dictated by the aim to make the comparison useful and meaningful to geoscientists. Python is chosen as a language that traditionally is associated with ease of use, elegant syntax but limited performance. C++ is chosen for its traditional association with high performance but even higher complexity and syntax obscurity. Fortran is included in the comparison for its widespread use in geoscience often attributed to its performance. We confront the validity of these traditional views. We point out how the usability of a particular language in geoscience depends on the characteristics of the language itself and the availability of pre-existing software libraries (e.g. NumPy, SciPy, PyNGL, PyNIO, MPI4Py for Python and Blitz++, Boost.Units, Boost.MPI for C++). Having in mind the limited complexity of the considered numerical problem, we present a tentative comparison of performance of the three implementations with different open source compilers including CPython and PyPy, Clang++ and GNU g++, and GNU gfortran.

Mouse Polyomavirus Enters Early Endosomes, Requires Their Acidic pH for Productive Infection, and Meets Transferrin Cargo in Rab11-Positive Endosomes

PubMed Central

Liebl, David; Difato, Francesco; Horníková, Lenka; Mannová, Petra; Štokrová, Jitka; Forstová, Jitka

2006-01-01

Mouse polyomavirus (PyV) virions enter cells by internalization into smooth monopinocytic vesicles, which fuse under the cell membrane with larger endosomes. Caveolin-1 was detected on monopinocytic vesicles carrying PyV particles in mouse fibroblasts and epithelial cells (33). Here, we show that PyV can be efficiently internalized by Jurkat cells, which do not express caveolin-1 and lack caveolae, and that overexpression of a caveolin-1 dominant-negative mutant in mouse epithelial cells does not prevent their productive infection. Strong colocalization of VP1 with early endosome antigen 1 (EEA1) and of EEA1 with caveolin-1 in mouse fibroblasts and epithelial cells suggests that the monopinocytic vesicles carrying the virus (and vesicles containing caveolin-1) fuse with EEA1-positive early endosomes. In contrast to SV40, PyV infection is dependent on the acidic pH of endosomes. Bafilomycin A1 abolished PyV infection, and an increase in endosomal pH by NH4Cl markedly reduced its efficiency when drugs were applied during virion transport towards the cell nucleus. The block of acidification resulted in the retention of a fraction of virions in early endosomes. To monitor further trafficking of PyV, we used fluorescent resonance energy transfer (FRET) to determine mutual localization of PyV VP1 with transferrin and Rab11 GTPase at a 2- to 10-nm resolution. Positive FRET between PyV VP1 and transferrin cargo and between PyV VP1 and Rab11 suggests that during later times postinfection (1.5 to 3 h), the virus meets up with transferrin in the Rab11-positive recycling endosome. These results point to a convergence of the virus and the cargo internalized by different pathways in common transitional compartments. PMID:16611921

PyRETIS: A well-done, medium-sized python library for rare events.

PubMed

Lervik, Anders; Riccardi, Enrico; van Erp, Titus S

2017-10-30

Transition path sampling techniques are becoming common approaches in the study of rare events at the molecular scale. More efficient methods, such as transition interface sampling (TIS) and replica exchange transition interface sampling (RETIS), allow the investigation of rare events, for example, chemical reactions and structural/morphological transitions, in a reasonable computational time. Here, we present PyRETIS, a Python library for performing TIS and RETIS simulations. PyRETIS directs molecular dynamics (MD) simulations in order to sample rare events with unbiased dynamics. PyRETIS is designed to be easily interfaced with any molecular simulation package and in the present release, it has been interfaced with GROMACS and CP2K, for classical and ab initio MD simulations, respectively. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Graphene as a nanocarrier for tamoxifen induces apoptosis in transformed cancer cell lines of different origins.

PubMed

Misra, Santosh K; Kondaiah, Paturu; Bhattacharya, Santanu; Rao, C N R

2012-01-09

A cationic amphiphile, cholest-5en-3β-oxyethyl pyridinium bromide (PY(+) -Chol), is able to efficiently disperse exfoliated graphene (GR) in water by the physical adsorption of PY(+) -Chol on the surface of GR to form stable, dark aqueous suspensions at room temperature. The GR-PY(+) -Chol suspension can then be used to solubilize Tamoxifen Citrate (TmC), a breast cancer drug, in water. The resulting TmC-GR-PY(+) -Chol is stable for a long time without any precipitation. Fluorescence emission and UV absorption spectra indicate the existence of noncovalent interactions between TmC, GR, and PY(+) -Chol in these suspensions. Electron microscopy shows the existence of segregated GR sheets and TmC 'ribbons' in the composite suspensions. Atomic force microscopy indicates the presence of 'extended' structures of GR-PY(+) -Chol, which grows wider in the presence of TmC. The slow time-dependent release of TmC is noticed in a reconstituted cell culture medium, a property useful as a drug carrier. TmC-GR-PY(+) -Chol selectively enhanced the cell death (apoptosis) of the transformed cancer cells compared to normal cells. This potency is found to be true for a wide range of transformed cancer cells viz. HeLa, A549, ras oncogene-transformed NIH3T3, HepG2, MDA-MB231, MCF-7, and HEK293T compared to the normal cell HEK293 in vitro. Confocal microscopy confirmed the high efficiency of TmC-GR-PY(+) -Chol in delivering the drug to the cells, compared to the suspensions devoid of GR. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

GillesPy: A Python Package for Stochastic Model Building and Simulation.

PubMed

Abel, John H; Drawert, Brian; Hellander, Andreas; Petzold, Linda R

2016-09-01

GillesPy is an open-source Python package for model construction and simulation of stochastic biochemical systems. GillesPy consists of a Python framework for model building and an interface to the StochKit2 suite of efficient simulation algorithms based on the Gillespie stochastic simulation algorithms (SSA). To enable intuitive model construction and seamless integration into the scientific Python stack, we present an easy to understand, action-oriented programming interface. Here, we describe the components of this package and provide a detailed example relevant to the computational biology community.

Blocking FAK Signaling in the Tumor or Stroma and Effects on Metastasis

DTIC Science & Technology

2010-04-01

5% sucrose controls (Fig. 2E and F ). In addition to inhibiting ascites-associated ID8 spheroid growth, PND-1186-treated mice showed significantly...as determined by anti-FaK followed by phospho-specific anti-FaK pY397 immu- noblotting. ( F ) Ratio of pY397 phospho- rylated FaK to total FaK levels...FAK pY397 by 0.5 mg/ml PND-1186 administration compared to 5% sucrose controls (Fig. 8E and F ). In addition to inhibiting ascites-associated ID8

GillesPy: A Python Package for Stochastic Model Building and Simulation

PubMed Central

Abel, John H.; Drawert, Brian; Hellander, Andreas; Petzold, Linda R.

2017-01-01

GillesPy is an open-source Python package for model construction and simulation of stochastic biochemical systems. GillesPy consists of a Python framework for model building and an interface to the StochKit2 suite of efficient simulation algorithms based on the Gillespie stochastic simulation algorithms (SSA). To enable intuitive model construction and seamless integration into the scientific Python stack, we present an easy to understand, action-oriented programming interface. Here, we describe the components of this package and provide a detailed example relevant to the computational biology community. PMID:28630888

All-fiber pyroelectric nanogenerator

NASA Astrophysics Data System (ADS)

Ghosh, Sujoy Kumar; Xie, Mengying; Bowen, Christopher Rhys; Mandal, Dipankar

2018-04-01

An all-fiber pyroelectric nanogenerator (PyNG) is fabricated where both the active pyroelectric component and the electrodes were composed of fiber. The pyroelectric component was made with randomly organized electrospun PVDF nano-fibers possessing ferroelectric β- and γ-phases. The PyNG possess higher level of sensitivity which can detect very low level of temperature fluctuation, as, low as, 2 K. In addition, the thermal energy harvesting ability of the PyNG under several temperature variations and cycling frequencies paves the way for next generation thermal sensor and self-powered flexible micro-electronics.

PyGirl: Generating Whole-System VMs from High-Level Prototypes Using PyPy

NASA Astrophysics Data System (ADS)

Bruni, Camillo; Verwaest, Toon

Virtual machines (VMs) emulating hardware devices are generally implemented in low-level languages for performance reasons. This results in unmaintainable systems that are difficult to understand. In this paper we report on our experience using the PyPy toolchain to improve the portability and reduce the complexity of whole-system VM implementations. As a case study we implement a VM prototype for a Nintendo Game Boy, called PyGirl, in which the high-level model is separated from low-level VM implementation issues. We shed light on the process of refactoring from a low-level VM implementation in Java to a high-level model in RPython. We show that our whole-system VM written with PyPy is significantly less complex than standard implementations, without substantial loss in performance.

IRISpy: Analyzing IRIS Data in Python

NASA Astrophysics Data System (ADS)

Ryan, Daniel; Christe, Steven; Mumford, Stuart; Baruah, Ankit; Timothy, Shelbe; Pereira, Tiago; De Pontieu, Bart

2017-08-01

IRISpy is a new community-developed open-source software library for analysing IRIS level 2 data. It is written in Python, a free, cross-platform, general-purpose, high-level programming language. A wide array of scientific computing software packages have already been developed in Python, from numerical computation (NumPy, SciPy, etc.), to visualization and plotting (matplotlib), to solar-physics-specific data analysis (SunPy). IRISpy is currently under development as a SunPy-affiliated package which means it depends on the SunPy library, follows similar standards and conventions, and is developed with the support of of the SunPy development team. IRISpy’s has two primary data objects, one for analyzing slit-jaw imager data and another for analyzing spectrograph data. Both objects contain basic slicing, indexing, plotting, and animating functionality to allow users to easily inspect, reduce and analyze the data. As part of this functionality the objects can output SunPy Maps, TimeSeries, Spectra, etc. of relevant data slices for easier inspection and analysis. Work is also ongoing to provide additional data analysis functionality including derivation of systematic measurement errors (e.g. readout noise), exposure time correction, residual wavelength calibration, radiometric calibration, and fine scale pointing corrections. IRISpy’s code base is publicly available through github.com and can be contributed to by anyone. In this poster we demonstrate IRISpy’s functionality and future goals of the project. We also encourage interested users to become involved in further developing IRISpy.

Effects of gamma-sterilization on the physico-chemical properties of natural sediments

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

Bank, Tracy L.; Kukkadapu, Ravi K.; Madden, Andrew S.

2008-06-30

A series of experiments were completed to determine the effects of soil sterilization on various soil chemical properties including U(VI) sorption, soil pH, natural organic matter (NOM), cation exchange capacity (CEC), and iron oxidation state. Soils under investigation were a saprolitic sequence of interbedded weathered shale and limestone collected from the Oak Ridge Reservation (ORR). Sediments were sterilized by either steam sterilization at 121oC or by γ-irradiation using a cobalt-60 source. Subsamples of sediments were pretreated with dithionate-citrate-bicarbonate (DCB) and/or H2O2 to remove reducible Fe(III) oxides and NOM. Results from aerobic U(VI) sorption experiments indicated that γ-sterilized sediments sorbed moremore » U(VI) compared to non-sterile sediments. Results from sorption experiments completed using DCB and H2O2-treated samples indicated that the iron oxide and NOM fractions of the sediment accounted for the majority of U(VI) sorption and that γ-irradiation of these phases resulted in increased sorption of U(VI). Mössbauer spectra of γ-sterilized sedimentsdisplayed a decrease in the amount of ferric iron associated with goethite and a small increase in the amount of reduced iron in silicate minerals compared to spectra from non-sterile samples. Our results suggest that sterilization by γ-irradiation induced iron reduction that may have increased sorption of U(VI) on these sediments.« less

Rational Organization of Lanthanide-Based SMM Dimers into Three-Dimensional Networks.

PubMed

Yi, Xiaohui; Calvez, Guillaume; Daiguebonne, Carole; Guillou, Olivier; Bernot, Kevin

2015-06-01

Optimization of the reaction of [Ln(hfac)3]·2H2O and pyridine-N-oxide (PyNO), which is known to afford double-bridged dimers, leads to triple-bridged dimers of formula [(Ln(hfac)3)2(PyNO)3] (Ln = Gd (1), Dy (2)) from which the Dy derivative (2) behaves as a single-molecule magnet (SMM). The pseudo threefold axis symmetry of this zero-dimensional building block makes possible its extension into a tridimensional network. By changing PyNO for 4,4'-bipyridine N,N'-dioxide (4,4'BipyNO) a tridimensional compound of formula {[Ln(hfac)3]2(4,4'BipyNO)2]} (Ln = Eu (3), Gd (4), and Dy (5)) is then rationally obtained. This covalent three-dimensional (3D) network has a remarkably high cell volume (V = 24 419 A(3)) and is an arrangement of interpenetrated 3D subnetworks whose triple-bridged dimers still behave as SMMs.

Voltammetry and conductivity of a polyether-pyridinium room temperature molten salt electrolyte and of its polymer electrolyte solutions in polydimethylsiloxane

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

Pyati, R.; Murray, R.W.

1996-02-01

This report describes the synthesis, microelectrode voltammetry, and ionic conductivity of a new room temperature molten salt N-(methoxy(ethoxy){sub 2}ethyl)pyridinium p-toluene sulfonate (abbreviated as[Py(E{sub 3}M){sup +}][Tos{sup {minus}}]) and of its solution in a hydroxy-terminated polydimethylsiloxane. Both ionically conductive liquids (conductivity = 1 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1}) exhibit voltammetric potential windows of about 1.5 V. The negative potential limit is determined by the reduction of the [Py(E{sub 3}M){sup +}] pyridinium species, with subsequent radical coupling to form a voltammetrically observed viologen dimer. The estimated diffusivities of the [Py(E{sub 3}M){sup +}] species, of a diethyleneglycol-tailed ferrocene redox solute studied, andmore » by application of Nernst-Einstein relation to the ionic charge carriers, all lie in the 10{sup {minus}7} to 10{sup {minus}8} cm{sup 2}/s range. Viscosities and glass transition thermal observations are reported as is the fit of the temperature dependencies of ionic conductivity in [Py(E{sub 3}M){sup +}][Tos{sup {minus}}] and in [Py(E{sub 3}M){sup +}][TOS{sup {minus}}]/PDMS mixtures to Vogel-Tamman-Fulcher predictions.« less

BK polyomavirus-associated hemorrhagic cystitis among pediatric allogeneic bone marrow transplant recipients: treatment response and evidence for nosocomial transmission.

PubMed

Koskenvuo, Minna; Dumoulin, Alexis; Lautenschlager, Irmeli; Auvinen, Eeva; Mannonen, Laura; Anttila, Veli-Jukka; Jahnukainen, Kirsi; Saarinen-Pihkala, Ulla M; Hirsch, Hans H

2013-01-01

BK polyomavirus-associated hemorrhagic cystitis (BK-PyVHC) is a significant complication of allogenic hematopoietic stem cell transplantation (HSCT), but risk factors and treatment are currently unresolved. BK-PyVHC typically presents with clinical cystitis, macrohematuria, and increasing urine and blood BKV loads. Characterization of children undergoing allogeneic HSCT with BK-PyVHC and their clinical and antibody response to cidofovir treatment. By prospective screening of urine and plasma in 50 pediatric allogenic HSCT performed between 2008 and 2010, we identified 6 (12%) children with BK-PyVHC. Cidofovir was administered intravenously to 5 patients and intravesically to 4 patients (3 double treatments). Decreasing BKV viremia of>2log(10)copies/mL and clinical resolution was seen in 4 patients over 5-12 weeks. Responses occurred only in patients mounting BKV-specific IgM and IgG responses. Epidemic curve plots, BKV genotyping and contact tracing provided evidence of transmission between 2 BKV-seronegative patients, but ruled out transmission among the remaining four patients The data suggest that BK-PyVHC may be the result of nosocomial transmission in children with low/undetectable BKV antibodies and raises urgent questions about appropriate infection control measures and the role of cidofovir. Copyright © 2012 Elsevier B.V. All rights reserved.

Capillary zone electrophoresis determination of aniline and pyridine in sewage samples using transient isotachophoresis with a system-induced terminator.

PubMed

Hattori, Takanari; Okamura, Hideo; Asaoka, Satoshi; Fukushi, Keiichi

2017-08-18

Transient isotachophoresis (tITP) with a system-induced terminator (SIT) was developed for capillary zone electrophoresis (CZE) determination of aniline (An + ) and pyridine (Py + ) in sewage samples. After sample injection, a water vial was set at the sample-inlet side. Then voltage was applied to generate a system-induced terminator (H + ). Experiments and simulations revealed a concentration effect by tITP with an SIT: background electrolyte (BGE) - 100mM acetic acid (AcOH) and 50mM NaOH (pH 4.6); detection wavelength - 200nm for An + and 254nm for Py + ; vacuum injection period - 15s (190nL); SIT generation - 10kV applied for 80s with the sample inlet side anode; separation voltage - 20kV with the sample inlet side anode. The limits of detection (LODs, S/N=3) of An + and Py + respectively reached 10 and 42μg/L, with good repeatability (peak area RSDs≤6.9%) and calibration graph linearity (R 2 =0.9997). The proposed method was applied for determination of An + and Py + in sewage samples. Recoveries of An + (0.50mg/L) and Py + (2.0mg/L) in spiked sewage samples were 94-104%. Copyright © 2017 Elsevier B.V. All rights reserved.

PyMidas: Interface from Python to Midas

NASA Astrophysics Data System (ADS)

Maisala, Sami; Oittinen, Tero

2014-01-01

PyMidas is an interface between Python and MIDAS, the major ESO legacy general purpose data processing system. PyMidas allows a user to exploit both the rich legacy of MIDAS software and the power of Python scripting in a unified interactive environment. PyMidas also allows the usage of other Python-based astronomical analysis systems such as PyRAF.

Trial by Fire: On the terminology and methods used in pyrogenic organic carbon research

NASA Astrophysics Data System (ADS)

Zimmerman, Andrew R.; Mitra, Siddhartha

2017-11-01

Our understanding of the cycling of fire-derived, i.e. pyrogenic organic matter (pyOM), as well as the goals of the community of researchers who study it, may be inhibited by the many terms and methods currently used in its quantification and characterization. Terms currently used for pyOM have evolved by convention, but are often poorly defined. Further, each of the different methods now used to quantify solid and dissolved pyrogenic carbon (pyC) comes with its own biases and artifacts. That is, each detects only a fraction of the total pyrogenic products produced by fire, while, at the same time, include some fraction of non-pyrogenic OM. This may be evident in the commonly observed correlations between pyC and total organic C reported for both soils and dissolved OM in many different systems. We suggest that our research area can be placed on a stronger footing by: 1) agreement upon a common set of terms tied to the method used for detection (e.g. of the form pyCmethod), 2) implementation of another ‘ring trial’ study with a wider set of natural soil and water samples that cross-compare more recently developed methods, and 3) further investigation of the processes which preserve/degrade/transport pyOM in the environment.

Combined use of directional atherectomy and drug-coated balloon for the endovascular treatment of common femoral artery disease: immediate and one-year outcomes.

PubMed

Cioppa, Angelo; Stabile, Eugenio; Salemme, Luigi; Popusoi, Grigore; Pucciarelli, Armando; Iacovelli, Fortunato; Arcari, Antonella; Coscioni, Enrico; Trimarco, Bruno; Esposito, Giovanni; Tesorio, Tullio

2017-02-20

Surgical endarterectomy is the therapy of choice for atherosclerotic common femoral artery (CFA) obstruction. Recently, some large single-centre series have shown encouraging results for the percutaneous treatment of CFA obstructions. The purpose of this study was to evaluate the safety, feasibility, and one-year efficacy of the endovascular treatment of CFA obstructions with combined use of directional atherectomy (DA) and a paclitaxel-coated balloon (DCB). Between January 2012 and July 2014, 30 consecutive patients with severely calcified obstructions of the common femoral artery were treated in our centre using DA followed by DCB dilatation. Provisional stenting was allowed in the case of a suboptimal result. Twenty cases (66%) were isolated CFA interventions, whereas five (17%) and five (17%) also involved inflow and outflow vessels, respectively. Chronic total CFA occlusions (CTO) were recanalised in six cases (20%). Procedural success was achieved in all cases; stenting was needed in three cases (10%). At one year, restenosis and target lesion revascularisation were observed in two of 30 (6.6%) and one of 30 (3.3%) patients, respectively. The secondary patency rate was 96.7%. This single-centre prospective study suggests that the combined use of DA and DCB is a safe and effective alternative to surgery, a treatment option for common femoral artery lesions and provides encouraging results in this setting.

Preparation, spectroscopic and antibacterial studies on charge-transfer complexes of 2-hydroxypyridine with picric acid and 7,7‧,8,8‧-tetracyano-p-quinodimethane

NASA Astrophysics Data System (ADS)

Gaballa, Akmal S.; Amin, Alaa S.

2015-06-01

The reactions of electron acceptors such as picric acid (HPA) and 7,7‧,8,8‧-tetracyano-p-quinodimethane (TCNQ) with 2-hydroxypyridine (HPyO) have been investigated in EtOH at room temperature. Based on elemental analysis and IR spectra of the solid CT-complexes along with the photometric titration curves for the reactions, the data obtained indicate the formation of 1:1 charge transfer complexes [(H2PyO)(PA)] and [(PyO)(HTCNQ)], respectively. The infrared and 1H NMR spectroscopic data indicate a charge transfer interaction associated with a proton migration from the acceptor to the donor followed by intramolecular hydrogen bonding in [(H2PyO)(PA)] complex. Another charge transfer interaction was observed in [(PyO)(HTCNQ)] complex. The formation constants (KCT) for the CT-complexes are shown to be strongly dependent on the type and structure of the electron acceptors. Factors affecting the CT-processes and the kinetics of thermal decomposition of the complexes have been studied. The CT complexes were screened for their antibacterial activities against selected bacterial strains.

Preparation, spectroscopic and antibacterial studies on charge-transfer complexes of 2-hydroxypyridine with picric acid and 7,7',8,8'-tetracyano-p-quinodimethane.

PubMed

Gaballa, Akmal S; Amin, Alaa S

2015-06-15

The reactions of electron acceptors such as picric acid (HPA) and 7,7',8,8'-tetracyano-p-quinodimethane (TCNQ) with 2-hydroxypyridine (HPyO) have been investigated in EtOH at room temperature. Based on elemental analysis and IR spectra of the solid CT-complexes along with the photometric titration curves for the reactions, the data obtained indicate the formation of 1:1 charge transfer complexes [(H2PyO)(PA)] and [(PyO)(HTCNQ)], respectively. The infrared and (1)H NMR spectroscopic data indicate a charge transfer interaction associated with a proton migration from the acceptor to the donor followed by intramolecular hydrogen bonding in [(H2PyO)(PA)] complex. Another charge transfer interaction was observed in [(PyO)(HTCNQ)] complex. The formation constants (KCT) for the CT-complexes are shown to be strongly dependent on the type and structure of the electron acceptors. Factors affecting the CT-processes and the kinetics of thermal decomposition of the complexes have been studied. The CT complexes were screened for their antibacterial activities against selected bacterial strains. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

Mitochondrial targeted catalase suppresses invasive breast cancer in mice

PubMed Central

2011-01-01

Background Treatment of invasive breast cancer has an alarmingly high rate of failure because effective targets have not been identified. One potential target is mitochondrial generated reactive oxygen species (ROS) because ROS production has been associated with changes in substrate metabolism and lower concentration of anti-oxidant enzymes in tumor and stromal cells and increased metastatic potential. Methods Transgenic mice expressing a human catalase gene (mCAT) were crossed with MMTV-PyMT transgenic mice that develop metastatic breast cancer. All mice (33 mCAT positive and 23 mCAT negative) were terminated at 110 days of age, when tumors were well advanced. Tumors were histologically assessed for invasiveness, proliferation and metastatic foci in the lungs. ROS levels and activation status of p38 MAPK were determined. Results PyMT mice expressing mCAT had a 12.5 per cent incidence of high histological grade primary tumor invasiveness compared to a 62.5 per cent incidence in PyMT mice without mCAT. The histological grade correlated with incidence of metastasis with 56 per cent of PyMT mice positive for mCAT showing evidence of pulmonary metastasis compared to 85.4 per cent of PyMT mice negative for mCAT with pulmonary metastasis (p ≤ 0.05). PyMT tumor cells expressing mCAT had lower ROS levels and were more resistant to hydrogen peroxide-induced oxidative stress than wild type tumor cells, suggesting that mCAT has the potential of quenching intracellular ROS and subsequent invasive behavior. The metastatic tumor burden in PyMT mice expressing mCAT was 0.1 mm2/cm2 of lung tissue compared with 1.3 mm2/cm2 of lung tissue in PyMT mice expressing the wild type allele (p ≤ 0.01), indicating that mCAT could play a role in mitigating metastatic tumor progression at a distant organ site. Expression of mCAT in the lungs increased resistance to hydrogen peroxide-induced oxidative stress that was associated with decreased activation of p38MAPK suggesting ROS signaling is dependent on p38MAPK for at least some of its downstream effects. Conclusion Targeting catalase within mitochondria of tumor cells and tumor stromal cells suppresses ROS-driven tumor progression and metastasis. Therefore, increasing the antioxidant capacity of the mitochondrial compartment could be a rational therapeutic approach for invasive breast cancer. Please see related commentary article: http://www.biomedcentral.com/1741-7015/9/62 PMID:21605372

DCB - Cancer Immunology, Hematology, and Etiology Research

Cancer.gov

Part of NCI’s Division of Cancer Biology’s research portfolio, studies supported include the characterization of basic mechanisms relevant to anti-tumor immune responses and hematologic malignancies.

New Human Immunodeficiency Virus diagnoses among Men Who Have Sex with Men attending STD clinics, STD Surveillance Network, January 2010 to June 2013.

PubMed

Llata, Eloisa; Braxton, Jim; Asbel, Lenore; Kerani, Roxanne P; Murphy, Ryan; Pugsley, River; Pathela, Preeti; Schumacher, Christina; Tabidze, Irina; Weinstock, Hillard S

2018-02-07

To estimate new HIV diagnosis rates among HIV negative MSM who are repeatedly tested for HIV in sexually transmitted disease (STD) clinics, and assess the impact of demographic and disease-specific characteristics that are associated with higher HIV diagnosis rates. Retrospective analysis using 2010-2013 data from the STD Surveillance Network (SSuN), a sentinel surveillance system comprised of health departments in 12 cities conducting sentinel surveillance in 40 STD clinics. We analyzed data from all MSM repeatedly (≥2 times) tested for HIV, with an initial negative HIV test required for staggered cohort entry. Follow-up time was accrued from the date of the first negative HIV test to the most recent negative test or the first positive HIV test. STD diagnoses during the follow-up period were reviewed. We estimated HIV diagnoses rates (number of HIV diagnoses/total number of person-years at risk) by demographic and clinical characteristics with 95% confidence intervals (CI) using an inverse variance weighted random effects model, adjusting for heterogeneity between SSuN jurisdictions. Overall, 640 HIV diagnoses occurred among 14,824 individuals and 20,951.6 person-years (PY) of observation, for an adjusted incidence of HIV diagnosis of 3.0 per 100 PY (95% CI 2.6, 3.4). Rates varied across race/ethnicity groups with the highest rate among Blacks (4.7/100 PY; 95% CI 4.1-5.3) followed by Hispanics, Whites and persons of other races/ethnicities. MSM having a diagnosis of P&S syphilis on or after the first negative HIV test had a higher new HIV diagnosis rate (7.2/100 PY; 95% CI 5.8-9.0) compared to MSM who did not have a P&S syphilis diagnosis (2.8/100 PY; 95% CI 2.6-3.1). MSM who tested positive for rectal gonorrhea (6.3/100 PY; 95% CI 5.7-6.9) or rectal chlamydia (5.6/100 PY; 95% CI 4.6-6.6) had higher rates of new HIV diagnosis when compared to those with negative test results. MSM attending SSuN STD clinics have high rates of new HIV diagnoses, particularly those with a previous diagnosis of P&S syphilis, rectal chlamydia and/or gonorrhea. STD clinics continue to be important clinical setting for diagnosing HIV among MSM populations.

PySE: Software for extracting sources from radio images

NASA Astrophysics Data System (ADS)

Carbone, D.; Garsden, H.; Spreeuw, H.; Swinbank, J. D.; van der Horst, A. J.; Rowlinson, A.; Broderick, J. W.; Rol, E.; Law, C.; Molenaar, G.; Wijers, R. A. M. J.

2018-04-01

PySE is a Python software package for finding and measuring sources in radio telescope images. The software was designed to detect sources in the LOFAR telescope images, but can be used with images from other radio telescopes as well. We introduce the LOFAR Telescope, the context within which PySE was developed, the design of PySE, and describe how it is used. Detailed experiments on the validation and testing of PySE are then presented, along with results of performance testing. We discuss some of the current issues with the algorithms implemented in PySE and their interaction with LOFAR images, concluding with the current status of PySE and its future development.

Magnetostriction and complex permeability of [Fe62Co19Ga19/Py]5/glass multilayered films

NASA Astrophysics Data System (ADS)

Liu, Chi-Ching; Jen, Shien-Uang; Lin, Yu-Cha; Lai, Chih-Huang; Liao, Sheng-Chieh; Chien, Chia-Hua

2015-07-01

[Fe62Co19Ga19(x)/Py(40-x)]5/glass multilayered films, where x=0, 5, 10, 15, 20 nm, y=x(nm)/40(nm), and 0≤y≤1, were made by the magnetron sputtering method at room temperature. The total number of combined [Fe-Co-Ga/Py] unit-layers was five. The total film thickness (tf) was fixed at 200 nm. We have performed two kinds of experiments on these films: (i) the saturation magnetostriction (λS) measurement, and (ii) the complex permeability (μ=μR-jμI) experiment to find the resonance frequency (fR) as a function of external magnetic field (HE). By definition, the microwave power absorption Pabs at ferromagnetic resonance (FMR) for a metallic conductor is written as Pabs = [(μR2+ μI2)1/2 +μI ]1/2 . We define the half-width of the absorption peak Δf as Δf ≣ ΔfS+ΔfA, where ΔfS and ΔfA are the symmetric and asymmetric parts in Δf. The degree of asymmetry, ΔfA/Δf, of each absorption peak is associated with the structural and/or magnetic inhomogeneity in the film. The main findings from this study are summarized as follows: (A) maximum λS occurs in the y=1 film, and as y increases, λS increases; (B) biasing field for magnetostriction decreases greatly by adding Py layers; (C) the magnetostriction sensitivity remains almost constant in the range 0.4

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

Tomopy is a Python toolbox to perform x-ray data processing, image reconstruction and data exchange tasks at synchrotron facilities. The dependencies of the software are currently as follows: -Python related python standard library (http://docs.python.org/2/library/) numpy (http://www.numpy.org/) scipy (http://scipy.org/) matplotlib (http://matplotlip.org/) sphinx (http://sphinx-doc.org) pil (http://www.pythonware.com/products/pil/) pyhdf (http://pysclint.sourceforge.net/pyhdf/) h5py (http://www.h5py.org) pywt (http://www.pybytes.com/pywavelets/) file.py (https://pyspec.svn.sourceforge.net/svnroot/pyspec/trunk/pyspec/ccd/files.py) -C/C++ related: gridec (anonymous?? C-code written back in 1997 that uses standard C library) fftw (http://www.fftw.org/) tomoRecon (multi-threaded C++ verion of gridrec. Author: Mark Rivers from APS. http://cars9.uchicago.edu/software/epics/tomoRecon.html) epics (http://www.aps.anl.gov/epics/)

Characterization of Mode I and Mode II delamination growth and thresholds in AS4/PEEK composites

NASA Technical Reports Server (NTRS)

Martin, Roderick H.; Murri, Gretchen Bostaph

1990-01-01

Composite materials often fail by delamination. The onset and growth of delamination in AS4/PEEK, a tough thermoplastic matrix composite, was characterized for mode 1 and mode 2 loadings, using the Double Cantilever Beam (DCB) and the End Notched Flexure (ENF) test specimens. Delamination growth per fatigue cycle, da/dN, was related to strain energy release rate, G, by means of a power law. However, the exponents of these power laws were too large for them to be adequately used as a life prediction tool. A small error in the estimated applied loads could lead to large errors in the delamination growth rates. Hence strain energy release rate thresholds, G sub th, below which no delamination would occur were also measured. Mode 1 and 2 threshold G values for no delamination growth were found by monitoring the number of cycles to delamination onset in the DCB and ENF specimens. The maximum applied G for which no delamination growth had occurred until at least 1,000,000 cycles was considered the threshold strain energy release rate. Comments are given on how testing effects, facial interference or delamination front damage, may invalidate the experimental determination of the constants in the expression.

Massive processing of pyro-chromatogram mass spectra (py-GCMS) of soil samples using the PARAFAC2 algorithm

NASA Astrophysics Data System (ADS)

Cécillon, Lauric; Quénéa, Katell; Anquetil, Christelle; Barré, Pierre

2015-04-01

Due to its large heterogeneity at all scales (from soil core to the globe), several measurements are often mandatory to get a meaningful value of a measured soil property. A large number of measurements can therefore be needed to study a soil property whatever the scale of the study. Moreover, several soil investigation techniques produce large and complex datasets, such as pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) which produces complex 3-way data. In this context, straightforward methods designed to speed up data treatments are needed to deal with large datasets. GC-MS pyrolysis (py-GCMS) is a powerful and frequently used tool to characterize soil organic matter (SOM). However, the treatment of the results of a py-GCMS analysis of soil sample is time consuming (number of peaks, co-elution, etc.) and the treatment of large data set of py-GCMS results is rather laborious. Moreover, peak position shifts and baseline drifts between analyses make the automation of GCMS programs data treatment difficult. These problems can be fixed using the Parallel Factor Analysis 2 (PARAFAC 2, Kiers et al., 1999; Bro et al., 1999). This algorithm has been applied frequently on chromatography data but has never been applied to analyses of SOM. We developed a Matlab routine based on existing Matlab packages dedicated to the simultaneous treatment of dozens of pyro-chromatograms mass spectra. We applied this routine on 40 soil samples. The benefits and expected improvements of our method will be discussed in our poster. References Kiers et al. (1999) PARAFAC2 - PartI. A direct fitting algorithm for the PARAFAC2 model. Journal of Chemometrics, 13: 275-294. Bro et al. (1999) PARAFAC2 - PartII. Modeling chromatographic data with retention time shifts. Journal of Chemometrics, 13: 295-309.

Interfacial microstructure and mechanical properties of Cf/AZ91D composites with TiO2 and PyC fiber coatings.

PubMed

Li, Shaolin; Qi, Lehua; Zhang, Ting; Ju, Luyan; Li, Hejun

2017-10-01

In spite of the effectiveness of the fiber coatings on interface modification of carbon fiber reinforced magnesium matrix composites, the cost and exclusive equipment for the coatings preparation are usually ignored during research work. In this paper, pyrolytic carbon (PyC) and TiO 2 were coated on carbon fiber surface to study the effects of fiber coatings on interfacial microstructure and mechanical properties of carbon fiber reinforced AZ91D composites (C f /AZ91D composites). It was indicated that both the two coatings could modify the interface and improve the mechanical properties of the composites. The ultimate tensile strength of the TiO 2 -C f /AZ91D and the PyC-C f /AZ91D composite were 333MPa and 400MPa, which were improved by 41.7% and 70.2% respectively, compared with the untreated-C f /AZ91D composite. The microstructure observation revealed that the strengthening of the composites relied on fiber integrity and moderate interfacial bonding. MgO nano-particles were generated at the interface due to the reaction of TiO 2 with Mg in the TiO 2 -C f /AZ91D composite. The volume expansion resulting from the reaction let to disordered intergranular films and crystal defects at the interface. The fibers were protected and the interfacial reaction was restrained by PyC coating in the PyC-C f /AZ91D composite. The principle to select the coating of fiber was proposed by comparing the effectiveness and cost of the coatings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of a Heterocyclic Nitrogen-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by Aminopolycarboxylate Complexants

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

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa

Here, the novel metal chelator N-2-(pyridylmethyl)diethylenetriamine- N,N',N",N"-tetraacetic acid (DTTA-PyM) was designed to replace a single oxygen-donor acetate group of the well-known aminopolycarboxylate complexant diethylenetriamine- N,N,N',N",N"-pentaacetic acid (DTPA) with a nitrogen-donor 2-pyridylmethyl. Potentiometric, spectroscopic, computational, and radioisotope distribution methods show distinct differences for the 4f and 5f coordination environments and enhanced actinide binding due to the nitrogen-bearing heterocyclic moiety. The Am 3+, Cm 3+, and Ln 3+ complexation studies for DTTA-PyM reveal an enhanced preference, relative to DTPA, for trivalent actinide binding. Fluorescence studies indicate no changes to the octadentate coordination of trivalent curium, while evidence of heptadentate complexation of trivalentmore » europium is found in mixtures containing EuHL (aq) complexes at the same aqueous acidity. The denticity change observed for Eu 3+ suggests that complex protonation occurs on the pyridyl nitrogen. Formation of the CmHL (aq) complex is likely due to the protonation of an available carboxylate group because the carbonyl oxygen can maintain octadentate coordination through a rotation. The observed suppressed protonation of the pyridyl nitrogen in the curium complexes may be attributed to stronger trivalent actinide binding by DTTA-PyM. Density functional theory calculations indicate that added stabilization of the actinide complexes with DTTA-PyM may originate from π-back-bonding interactions between singly occupied 5f orbitals of Am 3+ and the pyridyl nitrogen. The differences between the stabilities of trivalent actinide chelates (Am 3+, Cm 3+) and trivalent lanthanide chelates (La 3+–Lu 3+) are observed in liquid–liquid extraction systems, yielding unprecedented 4f/5f differentiation when using DTTA-PyM as an aqueous holdback reagent. In addition, the enhanced nitrogen-donor softness of the new DTTA-PyM chelator was perturbed by adding a fluorine onto the pyridine group. The comparative characterization of N-(3-fluoro-2-pyridylmethyl)diethylenetriamine- N,N',N",N"-tetraacetic acid (DTTA-3-F-PyM) showed subdued 4 f/5 f differentiation due to the presence of this electron-withdrawing group.« less

Asterism: an integrated, complete, and open-source approach for running seismologist continuous data-intensive analysis on heterogeneous systems

NASA Astrophysics Data System (ADS)

Ferreira da Silva, R.; Filgueira, R.; Deelman, E.; Atkinson, M.

2016-12-01

We present Asterism, an open source data-intensive framework, which combines the Pegasus and dispel4py workflow systems. Asterism aims to simplify the effort required to develop data-intensive applications that run across multiple heterogeneous resources, without users having to: re-formulate their methods according to different enactment systems; manage the data distribution across systems; parallelize their methods; co-place and schedule their methods with computing resources; and store and transfer large/small volumes of data. Asterism's key element is to leverage the strengths of each workflow system: dispel4py allows developing scientific applications locally and then automatically parallelize and scale them on a wide range of HPC infrastructures with no changes to the application's code; Pegasus orchestrates the distributed execution of applications while providing portability, automated data management, recovery, debugging, and monitoring, without users needing to worry about the particulars of the target execution systems. Asterism leverages the level of abstractions provided by each workflow system to describe hybrid workflows where no information about the underlying infrastructure is required beforehand. The feasibility of Asterism has been evaluated using the seismic ambient noise cross-correlation application, a common data-intensive analysis pattern used by many seismologists. The application preprocesses (Phase1) and cross-correlates (Phase2) traces from several seismic stations. The Asterism workflow is implemented as a Pegasus workflow composed of two tasks (Phase1 and Phase2), where each phase represents a dispel4py workflow. Pegasus tasks describe the in/output data at a logical level, the data dependency between tasks, and the e-Infrastructures and the execution engine to run each dispel4py workflow. We have instantiated the workflow using data from 1000 stations from the IRIS services, and run it across two heterogeneous resources described as Docker containers: MPI (Container2) and Storm (Container3) clusters (Figure 1). Each dispel4py workflow is mapped to a particular execution engine, and data transfers between resources are automatically handled by Pegasus. Asterism is freely available online at http://github.com/dispel4py/pegasus_dispel4py.

A well-defined terminal vanadium(III) oxo complex.

PubMed

King, Amanda E; Nippe, Michael; Atanasov, Mihail; Chantarojsiri, Teera; Wray, Curtis A; Bill, Eckhard; Neese, Frank; Long, Jeffrey R; Chang, Christopher J

2014-11-03

The ubiquity of vanadium oxo complexes in the V+ and IV+ oxidation states has contributed to a comprehensive understanding of their electronic structure and reactivity. However, despite being predicted to be stable by ligand-field theory, the isolation and characterization of a well-defined terminal mononuclear vanadium(III) oxo complex has remained elusive. We present the synthesis and characterization of a unique terminal mononuclear vanadium(III) oxo species supported by the pentadentate polypyridyl ligand 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine (PY5Me2). Exposure of [V(II)(NCCH3)(PY5Me2)](2+) (1) to either dioxygen or selected O-atom-transfer reagents yields [V(IV)(O)(PY5Me2)](2+) (2). The metal-centered one-electron reduction of this vanadium(IV) oxo complex furnishes a stable, diamagnetic [V(III)(O)(PY5Me2)](+) (3) species. The vanadium(III) oxo species is unreactive toward H- and O-atom transfer but readily reacts with protons to form a putative vanadium hydroxo complex. Computational results predict that further one-electron reduction of the vanadium(III) oxo species will result in ligand-based reduction, even though pyridine is generally considered to be a poor π-accepting ligand. These results have implications for future efforts toward low-valent vanadyl chemistry, particularly with regard to the isolation and study of formal vanadium(II) oxo species.

Metal-polypyridyl catalysts for electro- and photochemical reduction of water to hydrogen.

PubMed

Zee, David Z; Chantarojsiri, Teera; Long, Jeffrey R; Chang, Christopher J

2015-07-21

Climate change, rising global energy demand, and energy security concerns motivate research into alternative, sustainable energy sources. In principle, solar energy can meet the world's energy needs, but the intermittent nature of solar illumination means that it is temporally and spatially separated from its consumption. Developing systems that promote solar-to-fuel conversion, such as via reduction of protons to hydrogen, could bridge this production-consumption gap, but this effort requires invention of catalysts that are cheap, robust, and efficient and that use earth-abundant elements. In this context, catalysts that utilize water as both an earth-abundant, environmentally benign substrate and a solvent for proton reduction are highly desirable. This Account summarizes our studies of molecular metal-polypyridyl catalysts for electrochemical and photochemical reduction of protons to hydrogen. Inspired by concept transfer from biological and materials catalysts, these scaffolds are remarkably resistant to decomposition in water, with fast and selective electrocatalytic and photocatalytic conversions that are sustainable for several days. Their modular nature offers a broad range of opportunities for tuning reactivity by molecular design, including altering ancillary ligand electronics, denticity, and/or incorporating redox-active elements. Our first-generation complex, [(PY4)Co(CH3CN)2](2+), catalyzes the reduction of protons from a strong organic acid to hydrogen in 50% water. Subsequent investigations with the pentapyridyl ligand PY5Me2 furnished molybdenum and cobalt complexes capable of catalyzing the reduction of water in fully aqueous electrolyte with 100% Faradaic efficiency. Of particular note, the complex [(PY5Me2)MoO](2+) possesses extremely high activity and durability in neutral water, with turnover frequencies at least 8500 mol of H2 per mole of catalyst per hour and turnover numbers over 600 000 mol of H2 per mole of catalyst over 3 days at an overpotential of 1.0 V, without apparent loss in activity. Replacing the oxo moiety with a disulfide affords [(PY5Me2)MoS2](2+), which bears a molecular MoS2 triangle that structurally and functionally mimics bulk molybdenum disulfide, improving the catalytic activity for water reduction. In water buffered to pH 3, catalysis by [(PY5Me2)MoS2](2+) onsets at 400 mV of overpotential, whereas [(PY5Me2)MoO](2+) requires an additional 300 mV of driving force to operate at the same current density. Metalation of the PY5Me2 ligand with an appropriate Co(ii) source also furnishes electrocatalysts that are active in water. Importantly, the onset of catalysis by the [(PY5Me2)Co(H2O)](2+) series is anodically shifted by introducing electron-withdrawing functional groups on the ligand. With the [(bpy2PYMe)Co(CF3SO3)](1+) system, we showed that introducing a redox-active moiety can facilitate the electro- and photochemical reduction of protons from weak acids such as acetic acid or water. Using a high-throughput photochemical reactor, we examined the structure-reactivity relationship of a series of cobalt(ii) complexes. Taken together, these findings set the stage for the broader application of polypyridyl systems to catalysis under environmentally benign aqueous conditions.

Antidamping spin-orbit torques in epitaxial-Py(100)/β-Ta

NASA Astrophysics Data System (ADS)

Tiwari, Dhananjay; Behera, Nilamani; Kumar, Akash; Dürrenfeld, Philipp; Chaudhary, Sujeet; Pandya, D. K.; Åkerman, Johan; Muduli, P. K.

2017-12-01

We perform spin torque ferromagnetic resonance measurements on the Si(100)/TiN(100)/epi-Py(100)/β-Ta system. We demonstrate current induced modulation of the Gilbert damping constant, which is about 30% for a current density of 6.25 × 109 A/m2. We show that the observed modulation of the Gilbert damping constant cannot be explained by spin transfer torques arising from the spin Hall effect of the β-Ta layer. An additional mechanism such as antidamping spin-orbit torque resulting from the interface or the crystalline structure of Py thin films needs to be considered.

High-Permeability Magnetic Polymer Additives for Lightweight Electromagnetic Shielding

DTIC Science & Technology

2015-08-01

organometallic complexes containing Fe2+ cations. [Cp] = cyclopentadiene; [Py] = pyrrole ; [Imid] = imidazole. ΔEmag values calculated with DFT using the...27 Table A-6 Energy difference between high- and low-spin magnetic states in transition metal ion- pyrrole (Py) complexes...2-],52 pyrrole (C4NH5),53 and other heterocyclic ligands.36,54 The cyclopentadienyl ligand, in particular, is ubiquitous in organometallic chemistry

DCB - DNA and Chromosome Aberrations Research

Cancer.gov

Part of NCI's Division of Cancer Biology's research portfolio, this research area is focused on making clear the genetic and epigenetic mechanisms of tumorigenesis and mechanisms of chemical and physical carcinogenesis.

Mortality, Causes of Death and Associated Factors Relate to a Large HIV Population-Based Cohort.

PubMed

Garriga, César; García de Olalla, Patricia; Miró, Josep M; Ocaña, Inma; Knobel, Hernando; Barberá, Maria Jesús; Humet, Victoria; Domingo, Pere; Gatell, Josep M; Ribera, Esteve; Gurguí, Mercè; Marco, Andrés; Caylà, Joan A

2015-01-01

Antiretroviral therapy has led to a decrease in HIV-related mortality and to the emergence of non-AIDS defining diseases as competing causes of death. This study estimates the HIV mortality rate and their risk factors with regard to different causes in a large city from January 2001 to June 2013. We followed-up 3137 newly diagnosed HIV non-AIDS cases. Causes of death were classified as HIV-related, non-HIV-related and external. We examined the effect of risk factors on survival using mortality rates, Kaplan-Meier plots and Cox models. Finally, we estimated survival for each main cause of death groups through Fine and Gray models. 182 deaths were found [14.0/1000 person-years of follow-up (py); 95% confidence interval (CI):12.0-16.1/1000 py], 81.3% of them had a known cause of death. Mortality rate by HIV-related causes and non-HIV-related causes was the same (4.9/1000 py; CI:3.7-6.1/1000 py), external was lower [1.7/1000 py; (1.0-2.4/1000 py)]. Kaplan-Meier estimate showed worse survival in intravenous drug user (IDU) and heterosexuals than in men having sex with men (MSM). Factors associated with HIV-related causes of death include: IDU male (subHazard Ratio (sHR):3.2; CI:1.5-7.0) and <200 CD4 at diagnosis (sHR:2.7; CI:1.3-5.7) versus ≥500 CD4. Factors associated with non-HIV-related causes of death include: ageing (sHR:1.5; CI:1.4-1.7) and heterosexual female (sHR:2.8; CI:1.1-7.3) versus MSM. Factors associated with external causes of death were IDU male (sHR:28.7; CI:6.7-123.2) and heterosexual male (sHR:11.8; CI:2.5-56.4) versus MSM. There are important differences in survival among transmission groups. Improved treatment is especially necessary in IDUs and heterosexual males.

Cumene oxidation by cis-[RuIV(bpy)2(py)(O)]2+, revisited.

PubMed

Bryant, Jasmine R; Matsuo, Takashi; Mayer, James M

2004-02-23

cis-[RuIV(bpy)2(py)(O)]2+ oxidizes cumene (2-phenylpropane) in acetonitrile solution primarily to cumyl alcohol (2-phenyl-2-propanol), alpha-methylstyrene, and acetophenone. Contrary to a prior report, the rate of the reaction is not accelerated by added nucleophiles. There is thus no evidence for the hydride transfer mechanism originally proposed. Instead, the results are consistent with a mechanism of initial hydrogen atom transfer from cumene to the ruthenium oxo group. This is indicated by the correlation of rate with C-H bond strength and by the various products observed. The formation of acetophenone, with one carbon less than cumene, is suggested to occur via a multistep pathway involving decarbonylation of the acyl radical from 2-phenylpropanal. An alternative mechanism involving beta-scission of cumyloxyl radical is deemed unlikely because of the difficulty of generating alkoxyl radicals under anaerobic conditions and the lack of rearranged products in the oxidation of triphenylmethane by cis-[RuIV(bpy)2(py)(O)]2+.

Guanidinium ionic liquid-based surfactants as low cytotoxic extractants: Analytical performance in an in-situ dispersive liquid-liquid microextraction method for determining personal care products.

PubMed

Pacheco-Fernández, Idaira; Pino, Verónica; Ayala, Juan H; Afonso, Ana M

2018-07-20

The IL-based surfactant octylguanidinium chloride (C 8 Gu-Cl) was designed and synthetized with the purpose of obtaining a less harmful surfactant: containing guanidinium as core cation and a relatively short alkyl chain. Its interfacial and aggregation behavior was evaluated through conductivity and fluorescence measurements, presenting a critical micelle concentration value of 42.5 and 44.6mmolL -1 , respectively. Cytotoxicity studies were carried out with C 8 Gu-Cl and other IL-based and conventional surfactants, specifically the analogue 1-octyl-3-methylimidazolium chloride (C 8 MIm-Cl), and other imidazolium- (C 16 MIm-Br) and pyridinium- (C 16 Py-Cl) based surfactants, together with the conventional cationic CTAB and the conventional anionic SDS. From these studies, C 8 Gu-Cl was the only one to achieve the classification of low cytotoxicity. An in situ dispersive liquid-liquid microextraction (DLLME) method based on transforming the water-soluble C 8 Gu-Cl IL-based surfactant into a water-insoluble IL microdroplet via a simple metathesis reaction was then selected as the extraction/preconcentration method for a group of 6 personal care products (PCPs) present in cosmetic samples. The method was carried out in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The method was properly optimized, requiring the use of only 30μL of C 8 Gu-Cl for 10mL of aqueous sample with a NaCl content of 8% (w/v) to adjust the ionic strength and pH value of 5. The metathesis reaction required the addition of the anion exchange reagent (bis[(trifluoromethyl)sulfonyl]imide - 1:1 molar ratio), followed by vortex and centrifugation, and dilution of the final microdroplet up to 60μL with acetonitrile before the injection in the HPLC-DAD system. The optimum in situ DLLME-HPLC-DAD method takes ∼10min for the extraction step and ∼22min for the chromatographic separation, with analytical features of low detection limits: down to 0.4μgL -1 ; high reproducibility: with RSD values lower than 10% (intra-day) and 16% (inter-day) for a spiked level of 15μgL -1 ; and an average enrichment factor of 89. The requirement of low volumes (30μL) of a low cytotoxic IL-based surfactant allows the method to be considered less harmful than other common analytical microextraction approaches. Copyright © 2017 Elsevier B.V. All rights reserved.

Unexpected formal insertion of CO 2 into the C-Si bonds of a zinc compound

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

Kemp, Richard A.; McGrew, Genette I.; Khatri, Pathik A.

Reaction of [κ 2-PR 2C(SiMe 3)Py] 2Zn (R = Ph, 2a; iPr, 2b) with CO 2 affords the products of formal insertion at the C–Si bond, [κ 2-PR 2CC(O)O(SiMe 3)Py] 2Zn (R = Ph, 3a; iPr, 3b). Insertion product 3b was structurally characterized. As a result, the reaction appears to be a stepwise insertion and rearrangement of CO 2 based on kinetic data.

Unexpected formal insertion of CO 2 into the C-Si bonds of a zinc compound

DOE PAGES

Kemp, Richard A.; McGrew, Genette I.; Khatri, Pathik A.; ...

2015-09-08

Reaction of [κ 2-PR 2C(SiMe 3)Py] 2Zn (R = Ph, 2a; iPr, 2b) with CO 2 affords the products of formal insertion at the C–Si bond, [κ 2-PR 2CC(O)O(SiMe 3)Py] 2Zn (R = Ph, 3a; iPr, 3b). Insertion product 3b was structurally characterized. As a result, the reaction appears to be a stepwise insertion and rearrangement of CO 2 based on kinetic data.

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

Jonathan Helmus, Scott Collis

The Python-ARM Radar Toolkit (Py-ART) is a collection of radar quality control and retrieval codes which all work on two unifying Python objects: the PyRadar and PyGrid objects. By building ingests to several popular radar formats and then abstracting the interface Py-ART greatly simplifies data processing over several other available utilities. In addition Py-ART makes use of Numpy arrays as its primary storage mechanism enabling use of existing and extensive community software tools.

An ab initio study of the potential energy surface in the S 1 state of 2-hydroxypyridine

NASA Astrophysics Data System (ADS)

Sobolewski, Andrzej L.; Adamowicz, Ludwik

1996-12-01

The potential energy (PE) surface of the lowest excited singlet state relevant to the photophysics of interconversion of the 2-hydroxypyridine/2 (1H)-pyridinone (2HP/2PY) system is characterized by ab initio calculations. The geometry optimizations in the S 1 state performed at the CIS/6-31G (d,p) level confirm the experimental findings that the 2HP form is planar in this state whereas the 2PY form is significantly out-of-plane distorted. The lowest-energy first-order saddle-points which are relevant to the photophysics of the "mobile" hydrogen atom on the S 1 PE surface lead toward its dissociation from the molecule. There is no saddle-point for a "direct" proton transfer reaction on the S 1 PE surface leading from the 2HP form to the 2PY form. The results confirm the hypothesis that the photo-induced dissociation-association (PIDA) mechanism is probably responsible for the excited-state tautomerization observed in this system.

An Atomically Precise Au10 Ag2 Nanocluster with Red-Near-IR Dual Emission.

PubMed

Lei, Zhen; Guan, Zong-Jie; Pei, Xiao-Li; Yuan, Shang-Fu; Wan, Xian-Kai; Zhang, Jin-Yuan; Wang, Quan-Ming

2016-08-01

A red-near-IR dual-emissive nanocluster with the composition [Au10 Ag2 (2-py-C≡C)3 (dppy)6 ](BF4 )5 (1; 2-py-C≡C is 2-pyridylethynyl, dppy=2-pyridyldiphenylphosphine) has been synthesized. Single-crystal X-ray structural analysis reveals that 1 has a trigonal bipyramidal Au10 Ag2 core that contains a planar Au4 (2-py-C≡C)3 unit sandwiched by two Au3 Ag(dppy)3 motifs. Cluster 1 shows intense red-NIR dual emission in solution. The visible emission originates from metal-to-ligand charge transfer (MLCT) from silver atoms to phosphine ligands in the Au3 Ag(dppy)3 motifs, and the intense NIR emission is associated with the participation of 2-pyridylethynyl in the frontier orbitals of the cluster, which is confirmed by a time-dependent density functional theory (TD-DFT) calculation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of iron plaque on uptake and accumulation of Cd by rice (Oryza sativa L.) seedlings grown in soil.

PubMed

Liu, Houjun; Zhang, Junling; Christie, Peter; Zhang, Fusuo

2008-05-15

Iron plaque is ubiquitously formed on the root surfaces of rice. However, little is known about the role of iron plaque in Cd movement from soil to the plant aboveground parts. A pot experiment was conducted to investigate the influence of iron plaque in Cd uptake and accumulation by rice seedlings in soil. Rice seedlings were pre-cultivated in solution culture for 16 days. Two seedlings were transplanted in a nylon bag containing no substrate but surrounded by soil amended with Fe and Cd combined at rates of 0, 1, or 2 g Fe kg(-1) and 0, 2.0, or 10 mg Cd kg(-1) soil. Fe was added to induce different amounts of iron plaque, and Cd to simulate Cd-polluted soils. Plants were grown for a further 43 days and then harvested. The length of the longest leaf and SPAD values of the newly mature leaves were measured during plant growth. Fe and Cd concentrations were determined in dithionite-citrate-bicarbonate (DCB) soil extracts and in plant roots and shoots. Shoot and root dry weights were significantly affected by Fe supply level but not by added Cd. Root dry weight declined with increasing Fe supply but shoot dry weight decreased at 2 g Fe kg(-1) and increased at 1 g Fe kg(-1) (except at 2 mg Cd kg(-1)). The length of the longest leaf and SPAD values of the newly mature leaves were significantly affected by plant growth stage and added Fe and Cd. Fe tended to diminish the negative effect of Cd on these two parameters. Cd concentrations in DCB extracts increased with increasing Cd and Fe supply. In contrast, external Fe supply markedly reduced shoot and root Cd concentrations and there was generally no significant difference between the two Fe supply levels. Shoot and root Cd concentrations increased with increasing Cd addition. Root Cd concentrations were negatively correlated with root Fe concentrations. The proportion of Cd in DCB extracts was significantly lower than in roots or shoots. The results indicate that enhanced Fe uptake by plants can diminish the negative effects of Cd to some extent and that iron plaque on root surfaces is of little significance in affecting uptake and accumulation of Cd by rice plants.

Agronomic assessment of pyrolysed food waste digestate for sandy soil management.

PubMed

Opatokun, Suraj Adebayo; Yousef, Lina F; Strezov, Vladimir

2017-02-01

The digestate (DFW) of an industrial food waste treatment plant was pyrolysed for production of biochar for its direct application as bio-fertilizer or soil enhancer. Nutrient dynamics and agronomic viability of the pyrolysed food waste digestate (PyD) produced at different temperatures were evaluated using germination index (GI), water retention/availability and mineral sorption as indicators when applied on arid soil. The pyrolysis was found to enrich P, K and other micronutrients in the biochar at an average enrichment factor of 0.87. All PyD produced at different temperatures indicated significantly low phytotoxicity with GI range of 106-168% and an average water retention capacity of 40.2%. Differential thermogravimetric (DTG) thermographs delineated the stability of the food waste digestate pyrolysed at 500 °C (PyD500) against the degradation of the digestate food waste despite the latter poor nutrient sorption potential. Plant available water in soil is 40% when treated with 100 g of digestate per kg soil, whereas PyD500 treated soil indicated minimal effect on plant available water, even with high application rates. However, the positive effects of PyD on GI and the observed enrichment in plant macro and micronutrients suggest potential agronomic benefits for PyD use, in addition to the benefits from energy production from DFW during the pyrolysis process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Edge Stenosis After Covered Stenting for Long Superficial Femoral Artery Occlusive Disease: Risk Factor Analysis and Prevention With Drug-Coated Balloon Angioplasty.

PubMed

Lin, Ting-Chao; Huang, Chun-Yang; Chen, Po-Lin; Lee, Chiu-Yang; Shih, Chun-Che; Chen, I-Ming

2018-06-01

To report a retrospective analysis of risk factors for edge restenosis after Viabahn stent-graft treatment of superficial femoral artery (SFA) occlusive disease and determine any protective effect of drug-coated balloons (DCBs) used at the time of stent-graft implantation. Between October 2011 and July 2016, 110 patients (mean age 73.3±7.6 years; 78 men) were treated with the Viabahn stent-graft for long SFA occlusions. Thirty-eight (34.5%) patients had DCB reinforcement at the distal edge of the stent-graft. For analysis, the population was divided into groups of no edge stenosis patients (n=88; mean lesion length 22.4±4.2 cm) and edge stenosis patients (n=22; mean lesion length 23.5±5.7 cm). The clinical outcomes, ankle-brachial indices, computed tomography angiography findings, and patency were compared at a minimum of 12 months. Logistic regression analysis was employed to determine risk factors for edge stenosis; the results are presented as the odds ratio (OR) and 95% confidence interval. No differences in clinical or procedural characteristics were identified except the higher incidence of diabetes (p=0.008) and greater need for retrograde access (p=0.033) in the edge stenosis group. DCB reinforcement reduced the incidence of edge stenosis (p=0.021) and target lesion revascularization (TLR; p=0.010) and resulted in a significantly higher 1-year primary patency rate (92.1% vs 76.4%, p=0.042). However, multivariate analysis revealed only poor distal runoff (OR 0.31, 95% CI 0.11 to 0.83, p=0.020) as a predictor of edge stenosis. The risk of edge stenosis after Viabahn implantation was higher in patients with poor distal runoff. DCB reinforcement over the distal edge reduced edge stenosis, decreased 1-year TLR, and improved 1-year primary patency.

Imidazopyridine/Pyrrole and hydroxybenzimidazole/pyrrole pairs for DNA minor groove recognition.

PubMed

Renneberg, Dorte; Dervan, Peter B

2003-05-14

The DNA binding properties of fused heterocycles imidazo[4,5-b]pyridine (Ip) and hydroxybenzimidazole (Hz) paired with pyrrole (Py) in eight-ring hairpin polyamides are reported. The recognition profile of Ip/Py and Hz/Py pairs were compared to the five-membered ring pairs Im/Py and Hp/Py on a DNA restriction fragment at four 6-base pair recognition sites which vary at a single position 5'-TGTNTA-3', where N = G, C, T, A. The Ip/Py pair distinguishes G.C from C.G, T.A, and A.T, and the Hz/Py pair distinguishes T.A from A.T, G.C, and C.G, affording a new set of heterocycle pairs to target the four Watson-Crick base pairs in the minor groove of DNA.

Assessment of global and gene-specific DNA methylation in rat liver and kidney in response to non-genotoxic carcinogen exposure

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

Ozden, Sibel, E-mail: stopuz@istanbul.edu.tr; Turgut Kara, Neslihan; Sezerman, Osman Ugur

Altered expression of tumor suppressor genes and oncogenes, which is regulated in part at the level of DNA methylation, is an important event involved in non-genotoxic carcinogenesis. This may serve as a marker for early detection of non-genotoxic carcinogens. Therefore, we evaluated the effects of non-genotoxic hepatocarcinogens, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), hexachlorobenzene (HCB), methapyrilene (MPY) and male rat kidney carcinogens, d-limonene, p-dichlorobenzene (DCB), chloroform and ochratoxin A (OTA) on global and CpG island promoter methylation in their respective target tissues in rats. No significant dose-related effects on global DNA hypomethylation were observed in tissues of rats compared to vehicle controls using LC–MS/MSmore » in response to short-term non-genotoxic carcinogen exposure. Initial experiments investigating gene-specific methylation using methylation-specific PCR and bisulfite sequencing, revealed partial methylation of p16 in the liver of rats treated with HCB and TCDD. However, no treatment related effects on the methylation status of Cx32, e-cadherin, VHL, c-myc, Igfbp2, and p15 were observed. We therefore applied genome-wide DNA methylation analysis using methylated DNA immunoprecipitation combined with microarrays to identify alterations in gene-specific methylation. Under the conditions of our study, some genes were differentially methylated in response to MPY and TCDD, whereas d-limonene, DCB and chloroform did not induce any methylation changes. 90-day OTA treatment revealed enrichment of several categories of genes important in protein kinase activity and mTOR cell signaling process which are related to OTA nephrocarcinogenicity. - Highlights: • Studied non-genotoxic carcinogens caused no change on global DNA hypomethylation. • d-Limonene, DCB and chloroform did not show any genome-wide methylation changes. • Some genes were differentially methylated in response to MPY, TCDD and OTA. • Protein kinase activity and mTOR cell signaling are involved in OTA carcinogenicity. • Our data highlight Cpne4 may be a potential biomarker for non-genotoxic carcinogens.« less

Recent advances in the structure elucidation of small organic molecules by the LSD software.

PubMed

Plainchont, Bertrand; de Paulo Emerenciano, Vicente; Nuzillard, Jean-Marc

2013-08-01

The LSD software proposes the structures of small organic molecules that fit with structural constraints from 1D and 2D NMR spectroscopy. Its initial design introduced limits that needed to be eliminated to extend its scope and help its users choose the most likely structure among those proposed. The LSD software code has been improved, so that it recognizes a wider set of atom types to build molecules. More flexibility has been given in the interpretation of 2D NMR data, including the automatic detection of very long-range correlations. A program named pyLSD was written to deal with problems in which atom types are ambiguously defined. It also provides a (13)C NMR chemical shift-based solution ranking algorithm. PyLSD was able to propose the correct structure of hexacyclinol, a natural product whose structure determination has been highly controversal. The solution was ranked first within a list of ten structures that were produced by pyLSD from the literature NMR data. The structure of an aporphin natural product was determined by pyLSD, taking advantage of the possibility of handling electrically charged atoms. The structure generation of the insect antifeedant azadirachtin by LSD was reinvestigated by pyLSD, considering that three (13)C resonances did not lead to univocal hybridization states. Copyright © 2013 John Wiley & Sons, Ltd.

TLR4 and TLR9 signals stimulate protective immunity against blood-stage Plasmodium yoelii infection in mice.

PubMed

Zhang, Yanjun; Zhu, Xiaotong; Feng, Yonghui; Pang, Wei; Qi, Zanmei; Cui, Liwang; Cao, Yaming

2016-11-01

The mechanisms regulating the induction of protective immunity against blood-stage malaria remain unclear. Resistant DBA/2 mouse develops a higher Th1 response compared with a susceptible BALB/c strain during Plasmodium yoelii (Py) infection. It is known that the T helper cell response is initiated and polarized by dendritic cells (DCs) of the innate immune system, during which TLR4 and TLR9 are important receptors for the innate recognition of the malaria parasite and its products. We hypothesized that TLR4/9 may play critical roles in the induction of protective immunity against Py infection. We used TLR4/9 antagonists and agonists to study their effects on mouse resistance to Py infection. We found that the administration of an antagonist prior to infection aggravated disease outcomes, impaired DC functions and suppressed the pro-inflammatory response to Py infection in resistant DBA/2 mice. Treatment with the TLR4 agonist lipopolysaccharide (LPS) but not TLR9 agonist significantly improved the survival rate of susceptible Py-infected BALB/c mice. LPS administration promoted the activation and expansion of DCs and drove a Th1-biased response. Our data demonstrate the important roles of TLR4/9 signals in inducing resistance to malaria parasites and provide evidence for the rational use of TLR agonists to potentiate protective immunity against Plasmodium infection. Copyright © 2016 Elsevier Inc. All rights reserved.

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

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

McSkimming, Alex; Su, Jing; Cheisson, Thibault

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

DOE PAGES

McSkimming, Alex; Su, Jing; Cheisson, Thibault; ...

2018-03-23

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

Impact of HMG-CoA reductase inhibitors on the incidence of polyomavirus-associated nephropathy in renal transplant recipients with human BK polyomavirus viremia.

PubMed

Gabardi, S; Ramasamy, S; Kim, M; Klasek, R; Carter, D; Mackenzie, M R; Chandraker, A; Tan, C S

2015-08-01

Up to 20% of renal transplant recipients (RTR) will develop human BK polyomavirus (BKPyV) viremia. BKPyV viremia is a pre-requisite of polyomavirus-associated nephropathy (PyVAN). Risk of BKPyV infections increases with immunosuppression. Currently, the only effective therapy against PyVAN is reductions in immunosuppression, but this may increase the risk of rejection. In vitro data have shown that pravastatin dramatically decreased caveolin-1 expression in human renal proximal tubular epithelial cells (HRPTEC) and suppressed BKPyV infection in these cells. Based on these data, we postulated that statin therapy may prevent the progression of BKPyV viremia to PyVAN. A multicenter, retrospective study was conducted in adult RTR transplanted between July 2005 and March 2012. All patients with documented BKPyV viremia (viral load >500 copies/mL on 2 consecutive tests) were included. Group I consisted of patients taking a statin before the BKPyV viremia diagnosis (n = 32), and Group II had no statin exposure before or after the BKPyV viremia diagnosis (n = 36). The primary endpoint was the incidence of PyVAN. Demographic data, transplant characteristics, and the degree of immunosuppression (i.e., induction/maintenance therapies, rejection treatment) were similar between the groups, with the exception of more diabetics in Group I. The incidence of PyVAN was comparable between the 2 groups (Group I = 28.1% vs. Group II = 41.7%; P = 0.312). Despite the proven in vitro effectiveness of pravastatin preventing BKPyV infection in HRPTEC, statins at doses maximized for cholesterol lowering, in RTR with BKPyV viremia, did not prevent progression to PyVAN. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Impact of HMG-CoA reductase inhibitors on the incidence of polyomavirus-associated nephropathy in renal transplant recipients with human BK polyomavirus viremia

PubMed Central

Gabardi, S.; Ramasamy, S.; Kim, M.; Klasek, R.; Carter, D.; Mackenzie, M.R.; Chandraker, A.; Tan, C.S.

2015-01-01

Introduction Up to 20% of renal transplant recipients (RTR) will develop human BK polyomavirus (BKPyV) viremia. BKPyV viremia is a pre-requisite of polyomavirus-associated nephropathy (PyVAN). Risk of BKPyV infections increases with immunosuppression. Currently, the only effective therapy against PyVAN is reductions in immunosuppression; but this may increase the risk of rejection. In vitro data have shown that pravastatin dramatically decreased caveolin-1 expression in human renal proximal tubular epithelial cells (HRPTEC) and suppressed BKPyV infection in these cells. Based on these data, we postulated that statin therapy may prevent the progression of BKPyV viremia to PyVAN. Patients and methods A multicenter, retrospective study was conducted in adult RTR transplanted between July 2005 and March 2012. All patients with documented BKPyV viremia (viral load >500 copies/mL on 2 consecutive tests) were included. Group I consisted of patients taking a statin before the BKPyV viremia diagnosis (n = 32), and Group II had no statin exposure before or after the BKPyV viremia diagnosis (n = 36). The primary endpoint was the incidence of PyVAN. Results Demographic data, transplant characteristics, and the degree of immunosuppression (i.e., induction/maintenance therapies, rejection treatment) were similar between the groups, with the exception of more diabetics in Group I. The incidence of PyVAN was comparable between the 2 groups (Group I = 28.1% vs. Group II = 41.7%; P = 0.312). Conclusions Despite the proven in vitro effectiveness of pravastatin preventing BKPyV infection in HRPTEC, statins at doses maximized for cholesterol lowering, in RTR with BKPyV viremia, did not prevent progression to PyVAN. PMID:25989423

Linking pyrolysis and anaerobic digestion (Py-AD) for the conversion of lignocellulosic biomass.

PubMed

Fabbri, Daniele; Torri, Cristian

2016-04-01

Biogas is a mixture of CO2 and CH4 produced by a consortia of Bacteria and Archeae operating in anaerobic digestion (AD) plants. Biogas can be burnt as such in engines to produce electricity and heat or upgraded into biomethane. Biomethane is a drop-in fuel that can be injected in the natural gas grid or utilised as a transport fuel. While a wide array of biomass feedstock can be degraded into biogas, unconverted lignin, hemicellulose and cellulose end up in the co-product digestate leaving a large portion of chemical energy unutilised. Pyrolysis (Py) transforms in a single step and without chemical reagents the lignocellulose matrix into gaseous (syngas), liquid (bio-oil, pyrolysis oil) and solid (biochar) fractions for the development of renewable fuels and materials. The Py route applied downstream to AD is actively investigated in order to valorise the solid digestate presently destined only for soil applications. Coupling Py upstream to AD is an emerging field of research aimed at expanding the feedstock towards biologically recalcitrant substrates (wood, paper, sludge). The biomethanation potential was demonstrated for gaseous (H2/CO) and water soluble pyrolysis products, while the influence of insoluble pyrolytic lignin remains fairly unexplored. Biochar can promote the production of biomethane by acting as a support for microorganism colonisation, conductor for direct interspecies electron transfer, sorbent for hydrophobic inhibitors, and reactant for in situ biogas upgrading. Enhancing the advantages (carbon source) over the side effects (toxicity) of Py fractions represents the main challenge of Py-AD. This can be addressed by increasing the selectivity of the thermochemical process or improving the ecological flexibility of mixed bacterial consortia towards chemically complex environments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Management of Varicose Veins and Chronic Venous Insufficiency in a Comparative Registry with Nine Venoactive Products in Comparison with Stockings.

PubMed

Belcaro, G; Dugall, M; Luzzi, R; Corsi, M; Ledda, A; Ricci, A; Pellegrini, L; Cesarone, M R; Hosoi, M; Errichi, B M; Cornelli, U; Cotellese, R; Agus, G; Feragalli, B

2017-09-01

The aim of this registry study was to compare products used to control symptoms of CVI. Endpoints of the study were microcirculation, effects on volume changes, and symptoms (analogue scale). Pycnogenol, venoruton, troxerutin, the complex diosmin-hesperidin, Antistax, Mirtoselect (bilberry), escin, and the combination Venoruton-Pycnogenol (VE-PY) were compared with compressions. No safety or tolerability problems were observed. At inclusion, measurements in the groups were comparable: 1,051 patients completed the registry. Best performers : Venoruton, Pycnogenol, and the combination VE-PY produced the best effects on skin flux. These products and the combination VE-PY better improved PO 2 and PCO 2 . The edema score was decreased more effectively with the combination and with Pycnogenol. Venoruton; Antistax also had good results. Considering volumetry, the best performers were the combination PY-VE and the two single products Venoruton and Pycnogenol. Antistax results for edema were also good. The best improvement in symptoms score were obtained with Pycnogenol and compression. A larger decrease in oxidative stress was observed with Pycnogenol, Venoruton, and with the VE-PY combination. Good effects of Antistax were also observed. Parestesias were lower with Pycnogenol and with Antistax. Considering the need for interventions, the best performers were Pycnogenol, VE-PY, and compression. The efficacy of Pycnogenol and the combination are competitive with stockings that do not have the same tolerability in warmer climates. A larger and more prolonged evaluation is suggested to evaluate cost-efficacy (and non-interference with drugs) of these products in the management of CVI. The registry is in progress; other products are in evaluation.

Microstructural control over soluble pentacene deposited by capillary pen printing for organic electronics.

PubMed

Lee, Wi Hyoung; Min, Honggi; Park, Namwoo; Lee, Junghwi; Seo, Eunsuk; Kang, Boseok; Cho, Kilwon; Lee, Hwa Sung

2013-08-28

Research into printing techniques has received special attention for the commercialization of cost-efficient organic electronics. Here, we have developed a capillary pen printing technique to realize a large-area pattern array of organic transistors and systematically investigated self-organization behavior of printed soluble organic semiconductor ink. The capillary pen-printed deposits of organic semiconductor, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS_PEN), was well-optimized in terms of morphological and microstructural properties by using ink with mixed solvents of chlorobenzene (CB) and 1,2-dichlorobenzene (DCB). Especially, a 1:1 solvent ratio results in the best transistor performances. This result is attributed to the unique evaporation characteristics of the TIPS_PEN deposits where fast evaporation of CB induces a morphological evolution at the initial printed position, and the remaining DCB with slow evaporation rate offers a favorable crystal evolution at the pinned position. Finally, a large-area transistor array was facilely fabricated by drawing organic electrodes and active layers with a versatile capillary pen. Our approach provides an efficient printing technique for fabricating large-area arrays of organic electronics and further suggests a methodology to enhance their performances by microstructural control of the printed organic semiconducting deposits.

Automatic Parallelization of Numerical Python Applications using the Global Arrays Toolkit

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

Daily, Jeffrey A.; Lewis, Robert R.

2011-11-30

Global Arrays is a software system from Pacific Northwest National Laboratory that enables an efficient, portable, and parallel shared-memory programming interface to manipulate distributed dense arrays. The NumPy module is the de facto standard for numerical calculation in the Python programming language, a language whose use is growing rapidly in the scientific and engineering communities. NumPy provides a powerful N-dimensional array class as well as other scientific computing capabilities. However, like the majority of the core Python modules, NumPy is inherently serial. Using a combination of Global Arrays and NumPy, we have reimplemented NumPy as a distributed drop-in replacement calledmore » Global Arrays in NumPy (GAiN). Serial NumPy applications can become parallel, scalable GAiN applications with only minor source code changes. Scalability studies of several different GAiN applications will be presented showing the utility of developing serial NumPy codes which can later run on more capable clusters or supercomputers.« less

A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

DOE PAGES

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

2016-05-23

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

Biochemical resistance of pyrogenic organic matter in fire-affected mineral soils of Southern Europe

NASA Astrophysics Data System (ADS)

Knicker, H.; González Vila, F. J.; Clemente Salas, L.

2012-04-01

Incorporated into the soil, naturally formed pyrogenic organic matter (PyOM) is considered as highly recalcitrant, but direct estimation of PyOM decomposition rates are scarce. With this aim in mind, we subjected organic matter (OM) of fire-affected and unaffected soils to biochemical degradation under laboratory conditions and monitored CO2 production over a period of seven months. The soils derived from fire affected and unaffected areas of the Sierra de Aznalcóllar and the Doñana National Park, Southern Spain. Virtual fractionation of the solid-state 13C nuclear magnetic resonance (NMR) spectra of the fire affected soils into fire-unaffected soil organic matter (SOM) and PyOM yielded charcoal C contributions of 30 to 50% to the total organic C (Corg) of the sample derived from the Aznalcóllar region. Fitting the respiration data with a double exponential decay model revealed a fast carbon flush during the first three weeks of the experiment. Solid-state 13C NMR spectroscopy evidenced the contribution of aromatic moieties of the PyOM to this initial carbon release and to the biosynthesis of new microbial biomass. The input of PyOM resulted in an increase of the mean residence time (MRT) of the slow OM pool of the soil by a factor of 3 to 4 to approximately 40 years which rises doubts rises doubts about the presumed big influence of PyOM as an additional C-sink in soils. On the other hand, although being small the difference in turnover rates is evident and has some major implication with respect to long-term alteration of the chemical composition of OM in fire-affected soils. Based on the obtained results and the analysis of PyOM in other soil systems, a conceptual model is presented which can explain the different behavior of PyOM under different soil conditions.

ScrumPy: metabolic modelling with Python.

PubMed

Poolman, M G

2006-09-01

ScrumPy is a software package used for the definition and analysis of metabolic models. It is written using the Python programming language that is also used as a user interface. ScrumPy has features for both kinetic and structural modelling, but the emphasis is on structural modelling and those features of most relevance to analysis of large (genome-scale) models. The aim is at describing ScrumPy's functionality to readers with some knowledge of metabolic modelling, but implementation, programming and other computational details are omitted. ScrumPy is released under the Gnu Public Licence, and available for download from http://mudshark.brookes.ac.uk/ ScrumPy.

Improved assessment of pyrogenic carbon quantity and quality in soils by liquid chromatography

NASA Astrophysics Data System (ADS)

Wiedemeier, Daniel B.; Hilf, Michael D.; Smittenberg, Rienk H.; Schmidt, Michael W. I.

2013-04-01

Fire-derived (pyrogenic) carbon (PyC) is produced by the incomplete combustion of biomass, for example during wildfires. It can persist in the environment for a long time due to its relative resistance against biological and chemical breakdown. Its accurate quantification in soils, sediments and other environmental media is of great interest because the slow turn-over of PyC has implications for the global carbon cycle. It is thus relevant for climate scenarios and mitigation. Moreover, PyC in pedological and sedimentological records can be used to reconstruct wildfire history, which is closely linked to climate history. PyC assessment is also a valuable tool for characterizing biochars and other pyrogenic products. A whole suite of PyC quantification methods exists because PyC is not a defined chemical structure but rather a continuum of thermally altered biomass. The benzene polycarboxylic acids (BPCA) analysis is a molecular marker method that was shown to yield conservative estimates of PyC quantity in soils and environmental samples. In addition, it yields unique qualitative information about the degree of aromaticity and condensation of PyC, which is indicative for the pyrolysis temperature of PyC and its resistance against degradation. The commonly used BPCA method consists in digesting samples with nitric acid that breaks down the PyC into a suite of BPCAs, which are cleaned, derivatized and finally analyzed by gas chromatography-flame ionization detection (GC-FID). Here, we present a modified BPCA quantification method for soils, sediments and other environmental samples that uses a high performance liquid chromatography system coupled to diode array detection (HPLC-DAD). We demonstrate that this method greatly enhances the reproducibility of PyC measurements while significantly reducing analysis time. Moreover, much less sample material is needed for precise PyC assessment and we show that the HPLC-DAD method yields more consistent PyC measurements than the GC-FID method. Additionally, the new method also facilitates δ13C and 14C measurements of the PyC fraction in these complex matrix samples. The isotopic information of PyC further supports the assessment of carbon budgets in soils, sediments or (bio-)chars and the reconstruction of past burning and climate events, as will be shown with examples.

Magnetic vortex nucleation/annihilation in artificial-ferrimagnet microdisks

DOE PAGES

Lapa, Pavel N.; Ding, Junjia; Phatak, Charudatta; ...

2017-08-28

The topological nature of magnetic-vortex state gives rise to peculiar magnetization reversal observed in magnetic microdisks. Interestingly, magnetostatic and exchange energies which drive this reversal can be effectively controlled in artificial ferrimagnet heterostructures composed of rare-earth and transition metals. [Py(t)/Gd(t)] 25 (t=1 or 2 nm) superlattices demonstrate a pronounced change of the magnetization and exchange stiffness in a 10–300 K temperature range as well as very small magnetic anisotropy. Due to these properties, the magnetization of cylindrical microdisks composed of these artificial ferrimagnets can be transformed from the vortex to uniformly-magnetized states in a permanent magnetic field by changing themore » temperature. We explored the behavior of magnetization in 1.5-µm [Py(t)/Gd(t)] 25 (t=1 or 2 nm) disks at different temperatures and magnetic fields and observed that due to the energy barrier separating vortex and uniformly-magnetized states, the vortex nucleation and annihilation occur at different temperatures. This causes the temperature dependences of the Py/Gd disks magnetization to demonstrate unique hysteretic behavior in a narrow temperature range. It was discovered that for the [Py(2 nm)/Gd(2 nm)] 25 microdisks the vortex can be metastable at a certain temperature range.« less

Magnetic vortex nucleation/annihilation in artificial-ferrimagnet microdisks

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

Lapa, Pavel N.; Ding, Junjia; Phatak, Charudatta

The topological nature of magnetic-vortex state gives rise to peculiar magnetization reversal observed in magnetic microdisks. Interestingly, magnetostatic and exchange energies which drive this reversal can be effectively controlled in artificial ferrimagnet heterostructures composed of rare-earth and transition metals. [Py(t)/Gd(t)] 25 (t=1 or 2 nm) superlattices demonstrate a pronounced change of the magnetization and exchange stiffness in a 10–300 K temperature range as well as very small magnetic anisotropy. Due to these properties, the magnetization of cylindrical microdisks composed of these artificial ferrimagnets can be transformed from the vortex to uniformly-magnetized states in a permanent magnetic field by changing themore » temperature. We explored the behavior of magnetization in 1.5-µm [Py(t)/Gd(t)] 25 (t=1 or 2 nm) disks at different temperatures and magnetic fields and observed that due to the energy barrier separating vortex and uniformly-magnetized states, the vortex nucleation and annihilation occur at different temperatures. This causes the temperature dependences of the Py/Gd disks magnetization to demonstrate unique hysteretic behavior in a narrow temperature range. It was discovered that for the [Py(2 nm)/Gd(2 nm)] 25 microdisks the vortex can be metastable at a certain temperature range.« less

Incidence of Hepatitis C Infection among Prisoners by Routine Laboratory Values during a 20-Year Period

PubMed Central

Marco, Andrés; Gallego, Carlos; Caylà, Joan A.

2014-01-01

Background To estimate the incidence of Hepatitis C virus (HCV) and the predictive factors through repeated routine laboratory analyses. Methods An observational cohort study was carried out in Quatre Camins Prison, Barcelona. The study included subjects with an initial negative HCV result and routine laboratory analyses containing HCV serology from 1992 to 2011. The incidence of infection was calculated for the study population and for sub-groups by 100 person-years of follow-up (100 py). The predictive factors were determined through Kaplan-Meier curves and a Cox regression. Hazard ratios (HR) and 95% confidence intervals (CI) were calculated. Results A total of 2,377 prisoners were included with a median follow-up time of 1,540.9 days per patient. Among the total population, 117 HCV seroconversions were detected (incidence of 1.17/100 py). The incidence was higher between 1992 and 1995 (2.57/100 py), among cases with HIV co-infection (8.34/100 py) and among intravenous drug users (IDU) without methadone treatment (MT) during follow-up (6.66/100 py). The incidence rate of HCV seroconversion among cases with a history of IDU and current MT was 1.35/100 py, which is close to that of the total study population. The following variables had a positive predictive value for HCV infection: IDU (p<0.001; HR = 7,30; CI: 4.83–11.04), Spanish ethnicity (p = 0.009; HR = 2,03; CI: 1.93–3.44) and HIV infection (p = 0.015; HR = 1.97; CI: 1.14–3.39). Conclusion The incidence of HCV infection among prisoners was higher during the first part of the study and among IDU during the entire study period. Preventative programs should be directed toward this sub-group of the prison population. PMID:24587394

DCB - Tumor Metastasis Research

Cancer.gov

Tumor metastasis research examines the mechanisms that allow cancer cells to leave the primary tumor and spread to another part of the body. Learn about recent tumor metastasis research studies supported by the Division of Cancer Biology.

Amazon soil charcoal: Pyrogenic carbon stock depends of ignition source distance and forest type in Roraima, Brazil.

PubMed

da Silva Carvalho, Lidiany C; Fearnside, Philip M; Nascimento, Marcelo T; Barbosa, Reinaldo I

2018-04-18

Pyrogenic carbon (PyC) derived from charcoal particles (paleo + modern) deposited in the soil column has been little studied in the Amazon, and our understanding of the factors that control the spatial and vertical distribution of these materials in the region's forest soils is still unclear. The objective of this study was to test the effect of forest type and distance from the ignition source on the PyC stocks contained in macroscopic particles of soil charcoal (≥2 mm; 1 m depth) dispersed in ecotone forests of the northern Brazilian Amazon. Thirty permanent plots were set up near a site that had been occupied by pre-Columbian and by modern populations until the late 1970s. The sampled plots represent seasonal and ombrophilous forests that occur under different hydro-edaphic restrictions. Our results indicate that the largest PyC stock was spatially dependent on distance to the ignition source (<3 km), occurring mainly in flood-free ombrophilous forests (3.46 ± 5.22 Mg PyC/ha). The vertical distribution of PyC in the deeper layers of the soil (> 50 cm) in seasonal forests was limited by hydro-edaphic impediments that restricted the occurrence of charcoal. These results suggest that PyC stocks derived from macroscopic charcoal particles in the soil of this Brazilian Amazon ecotone region are controlled by the distance from the ignition source of the fire, and that forest types with higher hydro-edaphic restrictions can inhibit formation and accumulation of charcoal. Making use of these distinctions reduces uncertainty and improves our ability to understand the variability of PyC stocks in forests with a history of fire in the Amazon. © 2018 John Wiley & Sons Ltd.

Transcriptome and key genes expression related to carbon fixation pathways in Chlorella PY-ZU1 cells and their growth under high concentrations of CO2.

PubMed

Huang, Yun; Cheng, Jun; Lu, Hongxiang; He, Yong; Zhou, Junhu; Cen, Kefa

2017-01-01

The biomass yield of Chlorella PY-ZU1 drastically increased when cultivated under high CO 2 condition compared with that cultivated under air condition. However, less attention has been given to the microalgae photosynthetic mechanisms response to different CO 2 concentrations. The genetic reasons for the higher growth rate, CO 2 fixation rate, and photosynthetic efficiency of microalgal cells under higher CO 2 concentration have not been clearly defined yet. In this study, the Illumina sequencing and de novo transcriptome assembly of Chlorella PY-ZU1 cells cultivated under 15% CO 2 were performed and compared with those of cells grown under air. It was found that carbonic anhydrase (CAs, enzyme for interconversion of bicarbonate to CO 2 ) dramatically decreased to near 0 in 15% CO 2 -grown cells, which indicated that CO 2 molecules directly permeated into cells under high CO 2 stress without CO 2 -concentrating mechanism. Extrapolating from the growth conditions and quantitative Real-Time PCR of CCM-related genes, the K m (CO 2 ) (the minimum intracellular CO 2 concentration that rubisco required) of Chlorella PY-ZU1 might be in the range of 80-192 μM. More adenosine triphosphates was saved for carbon fixation-related pathways. The transcript abundance of rubisco (the most important enzyme of CO 2 fixation reaction) was 16.3 times higher in 15% CO 2 -grown cells than that under air. Besides, the transcript abundances of most key genes involved in carbon fixation pathways were also enhanced in 15% CO 2 -grown cells. Carbon fixation and nitrogen metabolism are the two most important metabolisms in the photosynthetic cells. These genes related to the two most metabolisms with significantly differential expressions were beneficial for microalgal growth (2.85 g L -1 ) under 15% CO 2 concentration. Considering the micro and macro growth phenomena of Chlorella PY-ZU1 under different concentrations of CO 2 (0.04-60%), CO 2 transport pathways responses to different CO 2 (0.04-60%) concentrations was reconstructed.

Pyrolytic Carbon Coatings on Aligned Carbon Nanotube Assemblies and Fabrication of Advanced Carbon Nanotube/Carbon Composites

NASA Astrophysics Data System (ADS)

Faraji, Shaghayegh

Chemical vapor deposition (CVD) is a technique used to create a pyrolytic carbon (PyC) matrix around fibrous preforms in carbon/carbon (C/C) composites. Due to difficulties in producing three-dimensional carbon nanotube (CNT) assemblies, use of nanotubes in CVD fabricated CNT/C composites is limited. This dissertation describes efforts to: 1) Study the microstructure of PyC deposited on CNTs in order to understand the effect of microstructure and morphology of carbon coatings on graphitization behavior of CNT/PyC composites. This understanding helped to suggest a new approach for controlled radial growth of CNTs. 2) Evaluate the properties of CNT/PyC structures as a novel form of CNT assemblies with resilient, anisotropic and tunable properties. PyC was deposited on aligned sheets of nanotubes, drawn from spinnable CNT arras, using CVD of acetylene gas. At longer deposition times, the microstructure of PyC changed from laminar turbostratic carbon to a disordered carbon. For samples with short PyC deposition times (up to 30 minutes), deposited carbon layer rearranged during graphitization treatment and resulted in a crystalline structure where the coating and original tube walls could not be easily differentiated. In contrast, in samples with longer carbon deposition durations, carbon layers close to the surface of the coating remained disordered even after graphitization thermal treatment. Understanding the effect of PyC microstructure transition on graphitization behavior of CNT/PyC composites was used to develop a new method for controlled radial growth of CNTs. Carbon coated aligned CNT sheets were graphitized after each short (20 minutes) carbon deposition cycle. This prevented development of disorder carbon during subsequent PyC deposition cycles. Using cyclic-graphitization method, thick PyC coating layers were successfully graphitized into a crystalline structure that could not be differentiated from the original nanotube walls. This resulted into radial growth of CNTs, from 40 to 100 nm. Infiltration of PyC into stacked layered sheets of aligned CNTs produced resilient foam-like materials that exhibited complete recovery from 90% compressive strain. PyC coated the junctions between nanotubes and also increased their surface roughness. These changes were assumed to be responsible for the resiliency of the, once inelastic, assembly of nanotubes. While nanotubes' alignment resulted in anisotropic properties of the foams, variation in PyC infiltration duration was used to tune the foams' properties. Further investigation into properties of these foams showed promising results for their application as pressure/strain sensor and selective liquid absorbers for oil spill clean ups. Finally, CNT foams were used as novel substrates for growth of secondary nanotube assemblies. In order to achieve that, foams were first coated with alumina buffer layers using atomic layer deposition (ALD) method. New nanotubes were further grown inside the foams by CVD of acetylene over iron nano-particles. Super low density and highly porous structure of the foams allowed for diffusion of catalyst along with growth gasses into their bulk, which resulted in growth of secondary nanotubes throughout the thickness of the foams. The thickness of the alumina buffer layer was shown to influence CNT nucleation density and growth uniformity across the thickness of the foams. Compressive mechanical testing of the foams showed an order of magnitude increase in compression strength after secondary CNT growth.

Incidence of dementia in elderly Latin Americans: Results of the Maracaibo Aging Study.

PubMed

Maestre, Gladys E; Mena, Luis J; Melgarejo, Jesus D; Aguirre-Acevedo, Daniel C; Pino-Ramírez, Gloria; Urribarrí, Milady; Chacon, Inara J; Chávez, Carlos A; Falque-Madrid, Luis; Gaona, Ciro A; Terwilliger, Joseph D; Lee, Joseph H; Scarmeas, Nikolaos

2018-02-01

There are few longitudinal studies of dementia in developing countries. We used longitudinal data from the Maracaibo Aging Study to accurately determine the age- and sex-specific incidence of dementia in elderly Latin Americans. The Diagnostic and Statistical Manual of Mental Disorders (Fourth Edition, Text Revision) was used to diagnose dementia, which was classified as Alzheimer's disease, vascular dementia, or other. Age- and sex-specific incidence was estimated as the number of new cases of dementia divided by person-years (p-y) of follow-up. The incidence of all dementia diagnoses was 9.10 per 1000 p-y (95% confidence interval [CI] 7.13-11.44; 8026 total p-y), 5.18 for Alzheimer's disease (95% CI 3.72-7.03; 7916 total p-y), and 3.35 for vascular dementia (95% CI 2.19-4.91; 7757 total p-y). Among Maracaibo Aging Study participants younger than 65 years, the incidence of dementia was higher than that of US Whites. Among individuals older than 65 years, the incidence was comparable to the mean of previous incidence estimates for other populations worldwide. Copyright © 2017 the Alzheimer's Association. Published by Elsevier Inc. All rights reserved.

Synthesis, structural characterisation and magnetic studies of polymetallic iron phosphonate cages.

PubMed

Khanra, Sumit; Helliwell, Madeleine; Tuna, Floriana; McInnes, Eric J L; Winpenny, Richard E P

2009-08-21

Four new polymetallic iron(III) phosphonate cages have been made and structurally characterised. These are an octanuclear cage [Fe(8)O(3)(OH)(2)(O(2)C(t)Bu)(11)(PhCH(2)PO(3))(3)(py)(3)], a decanuclear cage [Fe(10)O(2)(OH)(8)(O(2)C(t)Bu)(10)(PhCH(2)PO(3))(4)(pip)(2)], a heterometallic cage [Fe(6)Li(5)(mu(3)-O)(2)((t)BuPO(3))(6)(O(2)C(t)Bu)(8)(MeOH)(2)(Py)(4)] and a tridecanuclear cage [Et(3)NH](2)[Fe(13)(mu(3)-O)(3)(mu(2)-OH)(7)((t)BuPO(3))(7)(Me(3)CCO(2))(14)(H(2)O)] (pip = piperidine, py = pyridine). Magnetic studies of the first three compounds show anti-ferromagnetic exchange between the iron(III) centers leading to diamagnetic ground states for the homometallic cages. For the heterometallic cage, the six Fe(III) centers are arranged in two triangles, and each triangle has an S = 1/2 spin ground state.

pyNBS: A Python implementation for network-based stratification of tumor mutations.

PubMed

Huang, Justin K; Jia, Tongqiu; Carlin, Daniel E; Ideker, Trey

2018-03-28

We present pyNBS: a modularized Python 2.7 implementation of the network-based stratification (NBS) algorithm for stratifying tumor somatic mutation profiles into molecularly and clinically relevant subtypes. In addition to release of the software, we benchmark its key parameters and provide a compact cancer reference network that increases the significance of tumor stratification using the NBS algorithm. The structure of the code exposes key steps of the algorithm to foster further collaborative development. The package, along with examples and data, can be downloaded and installed from the URL http://www.github.com/huangger/pyNBS/. jkh013@ucsd.edu.

A Subdominant CD8+ Cytotoxic T Lymphocyte (CTL) Epitope from the Plasmodium yoelii Circumsporozoite Protein Induces CTLs That Eliminate Infected Hepatocytes from Culture

PubMed Central

Franke, Eileen D.; Sette, Alessandro; Sacci, John; Southwood, Scott; Corradin, Giampietro; Hoffman, Stephen L.

2000-01-01

Previous studies indicated that the Plasmodium yoelii circumsporozoite protein (PyCSP) 57–70 region elicits T cells capable of eliminating infected hepatocytes in vitro. Herein, we report that the PyCSP58–67 sequence contains an H-2d binding motif, which binds purified Kd molecules in vitro with low affinity (3,267 nM) and encodes an H-2d-restricted cytotoxic T lymphocyte (CTL) epitope. Immunization of BALB/c mice with three doses of a multiple antigen peptide (MAP) construct containing four branches of amino acids 57 to 70 linked to a lysine-glycine core [MAP4(PyCSP57–70)] and Lipofectin as the adjuvant induced both T-cell proliferation and a peptide-specific CTL response that was PyCSP59–67 specific, H-2d restricted, and CD8+ T cell dependent. Immunization with either DNA encoding the PyCSP or irradiated sporozoites demonstrated that this CTL epitope is subdominant since it is not recognized in the context of whole CSP immunization. The biological relevance of this CTL response was underlined by the demonstration that it could mediate genetically restricted, CD8+- and nitric-oxide-dependent elimination of infected hepatocytes in vitro, as well as partial protection of BALB/c mice against sporozoite challenge. These findings indicate that subdominant epitopes with low major histocompatibility complex affinity can be used to engineer epitope-based vaccines and have implications for the selection of epitopes for subunit-based vaccines. PMID:10816491

Mouse breast cancer model-dependent changes in metabolic syndrome-associated phenotypes caused by maternal dioxin exposure and dietary fat

PubMed Central

La Merrill, Michele; Baston, David S.; Denison, Michael S.; Birnbaum, Linda S.; Pomp, Daniel; Threadgill, David W.

2009-01-01

Diets high in fat are associated with increased susceptibility to obesity and metabolic syndrome. Increased adipose tissue that is caused by high-fat diets (HFD) results in altered storage of lipophilic toxicants like 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), which may further increase susceptibility to metabolic syndrome. Because both TCDD and HFD are associated with increased breast cancer risk, we examined their effects on metabolic syndrome-associated phenotypes in three mouse models of breast cancer: 7,12-dimethylbenz[a]anthracene (DMBA), Tg(MMTV-Neu)202Mul/J (HER2), and TgN(MMTV-PyMT)634Mul/J (PyMT), all on an FVB/N genetic background. Pregnant mice dosed with 1 μg/kg of TCDD or vehicle on gestational day 12.5 were placed on a HFD or low-fat diet (LFD) at parturition. Body weights, percent body fat, and fasting blood glucose were measured longitudinally, and triglycerides were measured at study termination. On HFD, all cancer models reached the pubertal growth spurt ahead of FVB controls. Among mice fed HFD, the HER2 model had a greater increase in body weight and adipose tissue from puberty through adulthood compared with the PyMT and DMBA models. However, the DMBA model consistently had higher fasting blood glucose levels than the PyMT and HER2 models. TCDD only impacted serum triglycerides in the PyMT model maintained on HFD. Because the estrogenic activity of the HFD was three times lower than that of the LFD, differential dietary estrogenic activities did not drive the observed phenotypic differences. Rather, the HFD-dependent changes were cancer model dependent. These results show that cancer models can have differential effects on metabolic syndrome-associated phenotypes even before cancers arise. PMID:18840765

uPy: a ubiquitous computer graphics Python API with Biological Modeling Applications

PubMed Central

Autin, L.; Johnson, G.; Hake, J.; Olson, A.; Sanner, M.

2015-01-01

In this paper we describe uPy, an extension module for the Python programming language that provides a uniform abstraction of the APIs of several 3D computer graphics programs called hosts, including: Blender, Maya, Cinema4D, and DejaVu. A plugin written with uPy is a unique piece of code that will run in all uPy-supported hosts. We demonstrate the creation of complex plug-ins for molecular/cellular modeling and visualization and discuss how uPy can more generally simplify programming for many types of projects (not solely science applications) intended for multi-host distribution. uPy is available at http://upy.scripps.edu PMID:24806987

PlasmaPy: beginning a community developed Python package for plasma physics

NASA Astrophysics Data System (ADS)

Murphy, Nicholas A.; Huang, Yi-Min; PlasmaPy Collaboration

2016-10-01

In recent years, researchers in several disciplines have collaborated on community-developed open source Python packages such as Astropy, SunPy, and SpacePy. These packages provide core functionality, common frameworks for data analysis and visualization, and educational tools. We propose that our community begins the development of PlasmaPy: a new open source core Python package for plasma physics. PlasmaPy could include commonly used functions in plasma physics, easy-to-use plasma simulation codes, Grad-Shafranov solvers, eigenmode solvers, and tools to analyze both simulations and experiments. The development will include modern programming practices such as version control, embedding documentation in the code, unit tests, and avoiding premature optimization. We will describe early code development on PlasmaPy, and discuss plans moving forward. The success of PlasmaPy depends on active community involvement and a welcoming and inclusive environment, so anyone interested in joining this collaboration should contact the authors.

Sex Work as an Emerging Risk Factor for Human Immunodeficiency Virus Seroconversion Among People who Inject Drugs in the SurvUDI Network.

PubMed

Blouin, Karine; Leclerc, Pascale; Morissette, Carole; Roy, Élise; Blanchette, Caty; Parent, Raymond; Serhir, Bouchra; Alary, Michel

2016-10-01

Recent analyses have shown an emerging positive association between sex work and human immunodeficiency virus (HIV) incidence among people who inject drugs (PWIDs) in the SurvUDI network. Participants who had injected in the past 6 months were recruited across the Province of Quebec and in the city of Ottawa, mainly in harm reduction programs. They completed a questionnaire and provided gingival exudate for HIV antibody testing. The associations with HIV seroconversion were tested with a Cox proportional hazard model using time-dependent covariables including the main variable of interest, sexual activity (sex work; no sex work; sexually inactive). The final model included significant variables and confounders of the associations with sexual activity. Seventy-two HIV seroconversions were observed during 5239.2 person-years (py) of follow-up (incidence rates: total = 1.4/100 py; 95% confidence interval [CI], 1.1-1.7; sex work = 2.5/100 py; 95% CI, 1.5-3.6; no sex work = 0.8/100 py; 95% CI, 0.5-1.2; sexually inactive = 1.8/100 py; 95% CI, 1.1-2.5). In the final multivariate model, HIV incidence was significantly associated with sexual activity (sex work: adjusted hazard ratio [AHR], 2.19; 95% CI, 1.13-4.25; sexually inactive: AHR, 1.62; 95% CI, 0.92-2.88), and injection with a needle/syringe used by someone else (AHR, 2.84; 95% CI, 1.73-4.66). Sex work is independently associated with HIV incidence among PWIDs. At the other end of the spectrum of sexual activity, sexually inactive PWIDs have a higher HIV incidence rate, likely due to more profound dependence leading to increased vulnerabilities, which may include mental illness, poverty, and social exclusion. Further studies are needed to understand whether the association between sex work and HIV is related to sexual transmission or other vulnerability factors.

Structure of salts of lithium chloride and lithium hexafluorophosphate as solvates with pyridine and vinylpyridine and structural comparisons: (C5H5N)LiPF6, [p-(CH2=CH)C5H4N]LiPF6, [(C5H5N)LiCl]n, and [p-(CH2=CH)C5H4N]2Li(μ-Cl)2Li[p-(CH2=CH)C5H4N]2.

PubMed

Jalil, AbdelAziz; Clymer, Rebecca N; Hamilton, Clifton R; Vaddypally, Shivaiah; Gau, Michael R; Zdilla, Michael J

2017-03-01

Due to the flammability of liquid electrolytes used in lithium ion batteries, solid lithium ion conductors are of interest to reduce danger and increase safety. The two dominating general classes of electrolytes under exploration as alternatives are ceramic and polymer electrolytes. Our group has been exploring the preparation of molecular solvates of lithium salts as alternatives. Dissolution of LiCl or LiPF 6 in pyridine (py) or vinylpyridine (VnPy) and slow vapor diffusion with diethyl ether gives solvates of the lithium salts coordinated by pyridine ligands. For LiPF 6 , the solvates formed in pyridine and vinylpyridine, namely tetrakis(pyridine-κN)lithium(I) hexafluorophosphate, [Li(C 5 H 5 N) 4 ]PF 6 , and tetrakis(4-ethenylpyridine-κN)lithium(I) hexafluorophosphate, [Li(C 7 H 7 N) 4 ]PF 6 , exhibit analogous structures involving tetracoordinated lithium ions with neighboring PF 6 - anions in the I-4 and Aea2 space groups, respectively. For LiCl solvates, two very different structures form. catena-Poly[[(pyridine-κN)lithium]-μ 3 -chlorido], [LiCl(C 5 H 5 N)] n , crystalizes in the P2 1 2 1 2 1 space group and contains channels of edge-fused LiCl rhombs templated by rows of π-stacked pyridine ligands, while the structure of the LiCl-VnPy solvate, namely di-μ-chlorido-bis[bis(4-ethenylpyridine-κN)lithium], [Li 2 Cl 2 (C 7 H 7 N) 4 ], is described in the P2 1 /n space group as dinuclear (VnPy) 2 Li(μ-Cl) 2 Li(VnPy) 2 units packed with neighbors via a dense array of π-π interactions.

Discrimination in Degradability of Soil Pyrogenic Organic Matter Follows a Return-On-Energy-Investment Principle.

PubMed

Harvey, Omar R; Myers-Pigg, Allison N; Kuo, Li-Jung; Singh, Bhupinder Pal; Kuehn, Kevin A; Louchouarn, Patrick

2016-08-16

A fundamental understanding of biodegradability is central to elucidating the role(s) of pyrogenic organic matter (PyOM) in biogeochemical cycles. Since microbial community and ecosystem dynamics are driven by net energy flows, then a quantitative assessment of energy value versus energy requirement for oxidation of PyOM should yield important insights into their biodegradability. We used bomb calorimetry, stepwise isothermal thermogravimetric analysis (isoTGA), and 5-year in situ bidegradation data to develop energy-biodegradability relationships for a suite of plant- and manure-derived PyOM (n = 10). The net energy value (ΔE) for PyOM was between 4.0 and 175 kJ mol(-1); with manure-derived PyOM having the highest ΔE. Thermal-oxidation activation energy (Ea) requirements ranged from 51 to 125 kJ mol(-1), with wood-derived PyOM having the highest Ea requirements. We propose a return-on-investment (ROI) parameter (ΔE/Ea) for differentiating short-to-medium term biodegradability of PyOM and deciphering if biodegradation will most likely proceed via cometabolism (ROI < 1) or direct metabolism (ROI ≥ 1). The ROI-biodegradability relationship was sigmoidal with higher biodegradability associated with PyOM of higher ROI; indicating that microbes exhibit a higher preference for "high investment value" PyOM.

Polyomavirus and Naturally Occuring Neuroglial Tumors in Raccoons (Procyon Lotor).

PubMed

Pesavento, Patricia A; Brostoff, Terza; Church, Molly E; Dela Cruz, Florante N; Woolard, Kevin D

2016-01-01

Polyomavirus (PyV) infections are widespread in human populations and, although generally associated with silent persistence, rarely cause severe disease. Among diseases convincingly associated with natural PyV infections of humans, there are remarkably different tissue tropisms and outcomes, including progressive multifocal leukoencephalopathy, transient or progressive nephropathy, and cancer. The variable character and unpredictable outcomes of infection attest to large gaps in our basic understanding of PyV biology. In particular, the rich history of research demonstrating the oncogenic potential of PyVs in laboratory animals begs the question of why cancer is not more often associated with infection. Raccoon polyomavirus (RacPyV), discovered in 2010, is consistently identified in neuroglial tumors in free-ranging raccoons in the western United States. Exposure to RacPyV is widespread, and RacPyV is detected in tissues of raccoons without tumors. Studying the relationship of RacPyV with its natural host is a unique opportunity to uncover cogent cellular targets and protein interactions between the virus and its host. Our hypothesis is that RacPyV, as an intact episome, alters cellular pathways within neural progenitor cells and drives oncogenesis. © The Author 2016. Published by Oxford University Press on behalf of the Institute for Laboratory Animal Research. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Integral Equation Study of Molecular Fluids and Liquid Crystals in Two Dimensions

NASA Astrophysics Data System (ADS)

Ward, David Atlee

The Ornstein-Zernike (OZ) equation is solved with a Percus-Yevick (PY) closure for the hard ellipse and hard planar dumbell fluids in two dimensions. The correlation functions, including the orientation correlation function, are expanded in a set of orthogonal functions and the coefficients are solved for using an iterative algorithm developed by Lado. The pressure, compressibility, and orientation coefficients are computed for a variety of densities and molecular elongations. The hard planar dumbell fluid shows no orientational ordering. The PY values for the pressure differ from the corresponding Monte Carlo (MC) values by as much as 8% for the cases studied. The hard ellipse fluid exhibits some orientational ordering. Ordering is much more pronounced for ellipses with an axis ratio larger than 2.0. Pressure values computed for the hard ellipse fluid from the PY theory differ from the corresponding MC values by as much as 11% for the cases studied. As the PY solutions do exhibit a nematic character in the hard ellipse fluid, we find it to be a viable reference system for further studies of the nematic liquid crystal phase, though the isotropic-nematic (I-N) phase transition found by Vieillard-Baron was not observed in the PY solutions. The Maier-Saupe theory was reformulated based on the density functional formalism of Sluckin and Shukla. Using PY data of the hard ellipse as input for the direct correlation function in the isotropic phase, the orientational distribution was calculated. The values obtained showed only extremely weak nematic behavior.

Pyrrole-hyaluronic acid conjugates for decreasing cell binding to metals and conducting polymers

PubMed Central

Lee, Jae Young; Schmidt, Christine E.

2010-01-01

Surface modification of electrically conductive biomaterials has been studied to improve biocompatibility for a number of applications, such as implantable sensors and microelectrode arrays. In this study, we electrochemically coated electrodes with biocompatible and non-cell adhesive hyaluronic acid (HA) to reduce cellular adhesion for potential use in neural prostheses. To this end, pyrrole-conjugated hyaluronic acid (PyHA) was synthesized and employed for electrochemical coating of platinum, indium-tin-oxide, and polystyrene sulfonate-doped polypyrrole electrodes. This PyHA conjugate consists of (1) a pyrrole moiety that allows the compound to be electrochemically deposited onto a conductive substrate and (2) non-adhesive HA to minimize cell adhesion and to potentially decrease inflammatory tissue responses. Our characterization results showed the presence of a hydrophilic p(PyHA) layer on the modified electrode, and impedance measurements revealed impedance that was statistically the same as the unmodified electrode. We found that the p(PyHA)-coated electrodes minimized adhesion and migration of fibroblasts and astrocytes for a minimum of up to 3 months. Also, the coating was stable in physiological solution for 3 months and also stable against enzymatic degradation by hyaluronidase. These studies suggest that this p(PyHA)-coating has the potential to be used to mask conducting electrodes from adverse glial responses that occur upon implantation. In addition, electrochemical coating with PyHA can be potentially extended for the surface modification of other metallic and conducting substances such as stents and biosensors. PMID:20558330

The autumn effect: timing of physical dormancy break in seeds of two winter annual species of Geraniaceae by a stepwise process

PubMed Central

Gama-Arachchige, N. S.; Baskin, J. M.; Geneve, R. L.; Baskin, C. C.

2012-01-01

Background and Aims The involvement of two steps in the physical dormancy (PY)-breaking process previously has been demonstrated in seeds of Fabaceae and Convolvulaceae. Even though there is a claim for a moisture-controlled stepwise PY-breaking in some species of Geraniaceae, no study has evaluated the role of temperature in the PY-breaking process in this family. The aim of this study was to determine whether a temperature-controlled stepwise PY-breaking process occurs in seeds of the winter annuals Geranium carolinianum and G. dissectum. Methods Seeds of G. carolinianum and G. dissectum were stored under different temperature regimes to test the effect of storage temperature on PY-break. The role of temperature and moisture regimes in regulating PY-break was investigated by treatments simulating natural conditions. Greenhouse (non-heated) experiments on seed germination and burial experiments (outdoors) were carried out to determine the PY-breaking behaviour in the natural habitat. Key Results Irrespective of moisture conditions, sensitivity to the PY-breaking step in seeds of G. carolinianum was induced at temperatures ≥20 °C, and exposure to temperatures ≤20 °C made the sensitive seeds permeable. Sensitivity of seeds increased with time. In G. dissectum, PY-break occurred at temperatures ≥20 °C in a single step under constant wet or dry conditions and in two steps under alternate wet–dry conditions if seeds were initially kept wet. Conclusions Timing of seed germination with the onset of autumn can be explained by PY-breaking processes involving (a) two temperature-dependent steps in G. carolinianum and (b) one or two moisture-dependent step(s) along with the inability to germinate under high temperatures in G. dissectum. Geraniaceae is the third of 18 families with PY in which a two-step PY-breaking process has been demonstrated. PMID:22684684

Soil pyrogenic carbon lacks long-term persistence

NASA Astrophysics Data System (ADS)

Lutfalla, Suzanne; Abiven, Samuel; Barré, Pierre; Wiedemeier, Daniel; Christensen, Bent; Houot, Sabine; Kätterer, Thomas; Macdonald, Andy; van Oort, Fok; Chenu, Claire

2015-04-01

In the context of climate change, one mitigation technique currently investigated is the use of pyrogenic organic carbon (PyOC) -which is biomass turned into charcoal- to sequester carbon in soils with the hypothesis that PyOC is persistent and will not be biodegraded (or mineralized). In this study, we use the unique opportunity offered by five long term bare fallow (LTBF) experiments across Europe (Askov in Denmark, Grignon and Versailles in France, Ultuna in Sweden and Rothamsted in the United Kingdom) to compare the dynamics of PyOC and soil organic carbon (SOC) in the same plots at the decadal time scale (from 25 to 80 years of bare fallow depending on the site). Bare fallow plots were regularly sampled throughout the bare fallow duration and these samples were carefully archived. In bare fallow plots, with negligible external carbon input and with continuing biodegradation, SOC is depleting. Using the Benzene Polycarboxylic Acid (BPCA) technique to estimate the PyOC quantity and quality in the soils at different sampling dates, we investigated if PyOC content was also decreasing and compared the rates of depletion of PyOC and SOC. We found that PyOC contents decreased rapidly in soils at all sites. The loss of PyOC between the first and the last soil sampling ranged from 19.8 to 57.3% of the initial PyOC content. Furthermore, PyOC quality exhibited a similar evolution at all sites, becoming more enriched in condensed material with time. We applied a one pool model with mono-exponential decay to our data and found an average mean residence time of native PyOC of 116 years across the different sites, with a standard deviation of 15 years, just 1.6 times longer than that of SOC. Our results show that, though having a longer residence time than total SOC, PyOC content can decrease rapidly in soils suggesting that the potential for long-term C storage in soil by PyOC amendments is less than currently anticipated. Our results therefore question the concept of biochar production as a climate change mitigation strategy.

Charge Transfer Modulated Self-Assembly in Poly(aryl ether) Dendron Derivatives with Improved Stability and Transport Characteristics.

PubMed

Satapathy, Sitakanta; Prasad, Edamana

2016-10-05

Alteration of native gelation properties of anthracene and pyrene cored first generation poly(aryl ether) dendrons, G1-An and G1-Py, by introducing a common acceptor, 2,4,7-trinitro-9H-fluoren-9-one (TNF), results in forming charge transfer gels in long chain alcoholic solvents. This strategy leads to significant perturbation of optical and electronic properties within the gel matrix. Consequently, a noticeable increase of their electrical conductivities is observed, making these poly(aryl ether) dendron based gels potential candidates for organic electronics. While the dc-conductivity (σ) value for the native gel from G1-An is 2.8 × 10 -4 S m -1 , the value increased 3 times (σ = 8.7 × 10 -4 S m -1 ) for its corresponding charge transfer gel. Further, the dc-conductivity for the native gel self-assembled from G1-Py dramatically enhanced by approximately an order of magnitude from 4.9 × 10 -4 to 1.3 × 10 -3 S m -1 , under the influence of an acceptor. Apart from H-bonding and π···π interactions, charge transfer results in the formation of a robust 3D network of fibers, with improved aspect ratio, providing high thermo-mechanical stability to the gels compared to the native ones. The charge transfer gels self-assembled from G1-An/TNF (1:1) and G1-Py/TNF exhibit a 7.3- and 2.5-fold increase in their yield stress, respectively, compared to their native assemblies. A similar trend follows in the case of their thermal stabilities. This is attributed to the typical bilayer self-assembly of the former which is not present in the case of G1-Py/TNF charge transfer gel. Density functional calculations provide deeper insights accounting for the role of charge transfer interactions in the mode of self-assembly. The 1D potential energy surface for the G1-An/TNF dimer and G1-Py/TNF dimer is found to be 11.8 and 1.9 kcal mol -1 more stable than their corresponding native gel dimers, G1-An/G1-An and G1-Py/G1-Py, respectively.

The effect of subject measurement error on joint kinematics in the conventional gait model: Insights from the open-source pyCGM tool using high performance computing methods.

PubMed

Schwartz, Mathew; Dixon, Philippe C

2018-01-01

The conventional gait model (CGM) is a widely used biomechanical model which has been validated over many years. The CGM relies on retro-reflective markers placed along anatomical landmarks, a static calibration pose, and subject measurements as inputs for joint angle calculations. While past literature has shown the possible errors caused by improper marker placement, studies on the effects of inaccurate subject measurements are lacking. Moreover, as many laboratories rely on the commercial version of the CGM, released as the Plug-in Gait (Vicon Motion Systems Ltd, Oxford, UK), integrating improvements into the CGM code is not easily accomplished. This paper introduces a Python implementation for the CGM, referred to as pyCGM, which is an open-source, easily modifiable, cross platform, and high performance computational implementation. The aims of pyCGM are to (1) reproduce joint kinematic outputs from the Vicon CGM and (2) be implemented in a parallel approach to allow integration on a high performance computer. The aims of this paper are to (1) demonstrate that pyCGM can systematically and efficiently examine the effect of subject measurements on joint angles and (2) be updated to include new calculation methods suggested in the literature. The results show that the calculated joint angles from pyCGM agree with Vicon CGM outputs, with a maximum lower body joint angle difference of less than 10-5 degrees. Through the hierarchical system, the ankle joint is the most vulnerable to subject measurement error. Leg length has the greatest effect on all joints as a percentage of measurement error. When compared to the errors previously found through inter-laboratory measurements, the impact of subject measurements is minimal, and researchers should rather focus on marker placement. Finally, we showed that code modifications can be performed to include improved hip, knee, and ankle joint centre estimations suggested in the existing literature. The pyCGM code is provided in open source format and available at https://github.com/cadop/pyCGM.

The effect of subject measurement error on joint kinematics in the conventional gait model: Insights from the open-source pyCGM tool using high performance computing methods

PubMed Central

Dixon, Philippe C.

2018-01-01

The conventional gait model (CGM) is a widely used biomechanical model which has been validated over many years. The CGM relies on retro-reflective markers placed along anatomical landmarks, a static calibration pose, and subject measurements as inputs for joint angle calculations. While past literature has shown the possible errors caused by improper marker placement, studies on the effects of inaccurate subject measurements are lacking. Moreover, as many laboratories rely on the commercial version of the CGM, released as the Plug-in Gait (Vicon Motion Systems Ltd, Oxford, UK), integrating improvements into the CGM code is not easily accomplished. This paper introduces a Python implementation for the CGM, referred to as pyCGM, which is an open-source, easily modifiable, cross platform, and high performance computational implementation. The aims of pyCGM are to (1) reproduce joint kinematic outputs from the Vicon CGM and (2) be implemented in a parallel approach to allow integration on a high performance computer. The aims of this paper are to (1) demonstrate that pyCGM can systematically and efficiently examine the effect of subject measurements on joint angles and (2) be updated to include new calculation methods suggested in the literature. The results show that the calculated joint angles from pyCGM agree with Vicon CGM outputs, with a maximum lower body joint angle difference of less than 10-5 degrees. Through the hierarchical system, the ankle joint is the most vulnerable to subject measurement error. Leg length has the greatest effect on all joints as a percentage of measurement error. When compared to the errors previously found through inter-laboratory measurements, the impact of subject measurements is minimal, and researchers should rather focus on marker placement. Finally, we showed that code modifications can be performed to include improved hip, knee, and ankle joint centre estimations suggested in the existing literature. The pyCGM code is provided in open source format and available at https://github.com/cadop/pyCGM. PMID:29293565

The raccoon polyomavirus genome and tumor antigen transcription are stable and abundant in neuroglial tumors.

PubMed

Brostoff, Terza; Dela Cruz, Florante N; Church, Molly E; Woolard, Kevin D; Pesavento, Patricia A

2014-11-01

Raccoon polyomavirus (RacPyV) is associated with 100% of neuroglial tumors in free-ranging raccoons. Other tumor-associated polyomaviruses (PyVs), including simian virus 40 (SV40), murine PyV, and Merkel cell PyV, are found integrated in the host genome in neoplastic cells, where they constitutively express splice variants of the tumor antigen (TAg) gene. We have previously reported that RacPyV exists only as an episome (nonintegrated) in neuroglial tumors. Here, we have investigated TAg transcription in primary tumor tissue by transcriptome analysis, and we identified the alternatively spliced TAg transcripts for RacPyV. We also determined that TAg was highly transcribed relative to host cellular genes. We further colocalized TAg DNA and mRNA by in situ hybridization and found that the majority of tumor cells showed positive staining. Lastly, we examined the stability of the viral genome and TAg transcription by quantitative reverse transcriptase PCR in cultured tumor cells in vitro and in a mouse xenograft model. When tumor cells were cultured in vitro, TAg transcription increased nearly 2 log-fold over that of parental tumor tissue by passage 17. Both episomal viral genome and TAg transcription were faithfully maintained in culture and in tumors arising from xenotransplantation of cultured cells in mice. This study represents a minimal criterion for RacPyV's association with neuroglial tumors and a novel mechanism of stability for a polyomavirus in cancer. The natural cycle of polyomaviruses in mammals is to persist in the host without causing disease, but they can cause cancer in humans or in other animals. Because this is an unpredictable and rare event, the oncogenic potential of polyomavirus is primarily evaluated in laboratory animal models. Recently, raccoon polyomavirus (RacPyV) was identified in neuroglial tumors of free-ranging raccoons. Viral copy number was consistently high in these tumors but was low or undetectable in nontumor tissue or in unaffected raccoons. Unlike other oncogenic polyomaviruses, RacPyV was episomal, not integrated, in these tumors. To determine the stability of the viral genome and sustained transcription of the oncogenic tumor antigen genes, we cultured primary raccoon tumor cells and passaged them in mice, confirming the nonintegrated state of the virus and the maintenance of viral gene transcription throughout. RacPyV provides a naturally occurring and tractable model for a novel mechanism of polyomavirus-mediated oncogenesis. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

The Raccoon Polyomavirus Genome and Tumor Antigen Transcription Are Stable and Abundant in Neuroglial Tumors

PubMed Central

Brostoff, Terza; Dela Cruz, Florante N.; Church, Molly E.; Woolard, Kevin D.

2014-01-01

ABSTRACT Raccoon polyomavirus (RacPyV) is associated with 100% of neuroglial tumors in free-ranging raccoons. Other tumor-associated polyomaviruses (PyVs), including simian virus 40 (SV40), murine PyV, and Merkel cell PyV, are found integrated in the host genome in neoplastic cells, where they constitutively express splice variants of the tumor antigen (TAg) gene. We have previously reported that RacPyV exists only as an episome (nonintegrated) in neuroglial tumors. Here, we have investigated TAg transcription in primary tumor tissue by transcriptome analysis, and we identified the alternatively spliced TAg transcripts for RacPyV. We also determined that TAg was highly transcribed relative to host cellular genes. We further colocalized TAg DNA and mRNA by in situ hybridization and found that the majority of tumor cells showed positive staining. Lastly, we examined the stability of the viral genome and TAg transcription by quantitative reverse transcriptase PCR in cultured tumor cells in vitro and in a mouse xenograft model. When tumor cells were cultured in vitro, TAg transcription increased nearly 2 log-fold over that of parental tumor tissue by passage 17. Both episomal viral genome and TAg transcription were faithfully maintained in culture and in tumors arising from xenotransplantation of cultured cells in mice. This study represents a minimal criterion for RacPyV's association with neuroglial tumors and a novel mechanism of stability for a polyomavirus in cancer. IMPORTANCE The natural cycle of polyomaviruses in mammals is to persist in the host without causing disease, but they can cause cancer in humans or in other animals. Because this is an unpredictable and rare event, the oncogenic potential of polyomavirus is primarily evaluated in laboratory animal models. Recently, raccoon polyomavirus (RacPyV) was identified in neuroglial tumors of free-ranging raccoons. Viral copy number was consistently high in these tumors but was low or undetectable in nontumor tissue or in unaffected raccoons. Unlike other oncogenic polyomaviruses, RacPyV was episomal, not integrated, in these tumors. To determine the stability of the viral genome and sustained transcription of the oncogenic tumor antigen genes, we cultured primary raccoon tumor cells and passaged them in mice, confirming the nonintegrated state of the virus and the maintenance of viral gene transcription throughout. RacPyV provides a naturally occurring and tractable model for a novel mechanism of polyomavirus-mediated oncogenesis. PMID:25165109

Quantifying changes in total and pyrogenic carbon stocks across fire severity gradients using active wildfire incidents

NASA Astrophysics Data System (ADS)

Miesel, Jessica; Reiner, Alicia; Ewell, Carol; Maestrini, Bernardo; Dickinson, Matthew

2018-05-01

Positive feedbacks between wildfire emissions and climate are expected to increase in strength in the future; however, fires not only release carbon (C) from terrestrial to atmospheric pools, they also produce pyrogenic C (PyC) which contributes to longer-term C stability. Our objective was to quantify wildfire impacts on total C and PyC stocks in California mixed-conifer forest, and to investigate relationships between C and PyC stocks and changes across gradients of fire severity, using metrics derived from remote sensing and field observations. Our unique study accessed active wildfires to establish and measure plots within days before and after fire, prior to substantial erosion. We measured pre- and post-fire aboveground forest structure and woody fuels to calculate aboveground biomass, C and PyC, and collected forest floor and 0-5 cm mineral soil samples. Tree mortality increased with severity, but overstory C loss was minimal and limited primarily to foliage. Fire released 85% of understory and herbaceous C (comprising <1.0% of total ecosystem C). The greatest C losses occurred from downed wood and forest floor pools (19.3±5.1 Mg ha-1 and 25.9±3.2 Mg ha-1, respectively). Tree bark and downed wood contributed the greatest PyC gains (1.5±0.3 Mg ha-1 and 1.9±0.8 Mg ha-1, respectively), and PyC in tree bark showed non-significant positive trends with increasing severity. Overall PyC losses of 1.9±0.3 Mg ha-1 and 0.5±0.1 Mg ha-1 occurred from forest floor and 0-5 cm mineral soil, with no clear patterns across severity. Fire resulted in a net ecosystem PyC gain (0.96±0.98 Mg ha-1) across aboveground and belowground components of these forests, and there were no differences among severity levels. Carbon emissions represented only 21.6% of total forest C; however, extensive conversion of C from live to dead pools will contribute to large downed wood C pools susceptible to release in a subsequent fire, indicating that there may be a delayed relationship between fire severity and C emissions. This research advances understanding of forest C loss and stabilization as PyC in wildfires; however, poor relationships between C and PyC gains or losses and fire severity highlight the complexity of fire impacts on forest C.

Waterproof Anti-Explosive Powders for Coal Mines

NASA Astrophysics Data System (ADS)

Buczek, Bronisław; Vogt, Elżbieta

2014-03-01

Limestone powder characterized by hydrophobic properties is used as an anti-explosive agent in coal mining industry. Unfortunately, the standard method of producing such powder by milling limestone with stearic acid is practically unprofitable in many modernized quarries and plants, and sometimes literally impossible due to the introduction of technological changes and implementation of modern mills. Then new methods of hydrophobization of limestone surfaces ought be searched. In the work two methods hydrophobization: from the stearic acid vapour phase and from silicone solutions are proposed. Lime dust from the Czatkowice Quarry of Lime was used as a raw material during investigations. It is a good agent for research because it is possible to compare the properties of samples modified in this work to the properties of anti-explosive lime powder (Polish Standard, 1994) used in mining industry in Poland. The first technique of limestone powder hydrophobization was carried out in an apparatus of own design (Vogt, 2008, 2011), and it consisted in free sedimentation of the powder layer dispersed by stearic acid vapour in powder counter current flow. The second way of modification consisted in mixing in the evaporating dish substrates: limestone powder and dope - silicone solution - Sarsil® H-15 (Vogt & Opaliński, 2009; Vogt & Hołownia, 2010). Evaluation of properties so-obtained waterproof powders was carried out according to the Polish Standard, as well as using original powder determination ways, with the Powder Characteristic Tester (Index tables, Tablets & Capsules, 2005). Moreover water vapour adsorption isotherms were obtained and the thermal decomposition of powder was made. All modified samples acquired the hydrophobic character. Therefore we can state that the both proposed methods of hydrophobization of the limestone powder are useful. The parameters obtained with the use of Powder Characteristics Tester enable us to make a characterization of limestone properties not only as a water resistant material but also from the cohesion point of view. On the base of TG, DTG or DTA and EGA curves for all investigated materials was stated that the character of the thermal decomposition of modified samples is the same as this one for raw powder, what is profitable for application of hydrophobized powders as an anti-explosive agent. W górnictwie węgla kamiennego używany jest hydrofobowy pył wapienny jako substancja stosowana w systemie zabezpieczeń przeciwwybuchowych (Cybulski, 2004). Niestety, dotychczasowy sposób wy- twarzania takiego produktu polegający na współmieleniu kamienia wapiennego z kwasem stearynowym staje się praktycznie niemożliwy do stosowania w nowoczesnych zakładach np. kamieniołomy. Sytuacja taka jest wynikiem wprowadzania zmian technologicznych, głównie związanych z wymianą starych konstrukcji młynów na nowe urządzenia. Tym samym istnieje potrzeba poszukiwania nowych metod hydrofobizacji powierzchni pyłów wapiennych. W pracy omówiono dwie nowe metody hydrofobizacji pyłu wapiennego: za pomocą par kwasu stearynowego oraz roztworu silikonowego - Sarsil® H-15. Podczas badań używano surowego pyłu wapiennego pochodzącego z Kopalni Kamienia Wapiennego w Czatkowicach. Materiał ten jest dobrym materiałem do badań gdyż istnieje możliwość porównywania właściwości materiałów hydrofobowych otrzymanych w pracy z właściwościami handlowego pyłu przeciwwybuchowego (Polska Norma, 1994), używanego w polskich kopalniach. Pierwszy sposób hydrofobizacji pyłu wapiennego, polegający na swobodnym opadaniu pyłu wapiennego w oparach kwasu stearynowego przepływających w przeciwprądzie, przeprowadzono w aparacie własnej konstrukcji (Vogt, 2008, 2011). Aparat gwarantuje dobry kontakt modyfikatora z ziarnami pyłu. Pył opadając, nie napotyka żadnych przeszkód ulegał rozproszeniu, a wprowadzony w stanie parowym kwas stearynowy może swobodnie osiadać na jego powierzchni zewnętrznej oraz penetrować w głąb porów, blokując je dla wilgoci. Drugi sposób hydrofobizacji sprowadzał się w uproszczeniu do zmieszania substratów: pyłu wapiennego i domieszki silikonowej - Sarsil® H-15, w parownicy (Vogt i Opaliński, 2009; Vogt i Hołownia, 2010). We wstępnych badaniach określono objętość preparatu, jaką trzeba dodać do pyłu w celu uzyskania optymalnych warunków kontaktu preparatu z ciałem stałym. Otrzymany po modyfikacji materiał był zbrylony w niewielkim stopniu, a jego całkowite rozdrobnienie uzyskano poprzez przecieranie pyłu przez sito o odpowiednim wymiarze oczek. Badanie właściwości tak otrzymanych hydrofobowych materiałów przeprowadzono w oparciu o PN (Polska Norma, 1994), jak również w oparciu o standardowe metody badania materiałów proszkowych z użyciem aparatu Powder Characteristic Tester (Index tables, Tablets & Capsules, 2005) (Tablica 2,3). Oceny stopnia hydrofobizacji materiałów po modyfikacji dokonano, w przypadku proszku hydrofobizowanego parami kwasu stearynowego, w oparciu o procedurę opisaną w Polskiej Normie (1994), oznaczając procentową zawartość kwasu stearynowego. Otrzymany podczas badań pył hydrofobizowany kwasem stearynowym zawierał 0,18% modyfikatora, co jest ilością dopuszczalną przez Polską Normę (1994).W celu oceny właściwości hydrofobowych materiału modyfikowanego roztworem silikonowym do badań zaadaptowano technikę pomiaru zwilżalności ziaren węglowych "film flotation" (Fuerstenau i Williams, 1987) przyjmując, jako materiał odniesienia hydrofobizowaną mączkę wapienną z Kopalni Kamienia Wapiennego w Małogoszczy. Opracowano metodę wyznaczania współczynnika C określonego, jako stopień hydrofobizacji (Vogt i Opaliński, 2009). Średnia wartość C = 84% wskazuje, że materiał modyfikowany preparatem silikonowym uzyskał odpowiednie właściwości hydrofobowe. Tym samym oba materiały po modyfikacji uzyskały zadowalające właściwości wodoodporne. Ponadto, dla badanych pyłów wyznaczono izotermy adsorpcji pary wodnej (Rys. 1). Uzyskane niższe wartości adsorpcji dla materiałów po modyfikacji niż dla proszku surowego potwierdzają, że materiały posiadają charakter hydrofobowy, co pozwala stwierdzić, że obie proponowane metody hydrofobizacji są użyteczne do produkcji wodoodpornego pyłu wapiennego. Analizę termiczną pyłów wapiennych wykonano w celu porównania efektu cieplnego przemian zachodzących podczas ogrzewania pyłów modyfikowanych z efektem cieplnym zachodzącym podczas ogrzewania surowego pyłu wapiennego. W trakcie badań użyto termowagę firmy TA Instruments 2960 SDT ze sprzężonym spektrometrem masowym firmy Balzers TermoStar 300. Otrzymane wynikiprzedstawiono na Rys. 2. Linie ciągłe na Rys. 2a i 2b przedstawiają przebieg krzywych TG, DTG oraz DTA dla pyłu surowego. Linie przerywane zostały otrzymane dla pyłu modyfikowanego kwasem stearynowym (Rys. 2a) oraz preparatem SARSIL® H-15 (Rys. 2b). Na Rys. 3 zobrazowano wyniki analizy zawartości tlenku węgla IV w składzie gazów otrzymywanych podczas rozkładu termicznego pyłu wapiennego (EGA). Krzywa otrzymana dla pyłu modyfikowanego kwasem stearynowym w zasadzie pokrywa się z krzywą otrzymaną dla pyłu surowego. Parametry uzyskane z użyciem aparatu Powder Characteristics Tester umożliwiły scharakteryzowanie pyłów wapiennych nie tylko pod kątem ich właściwości hydrofobowych, ale także właściwości kohezyjnych i przepływowych.

Further Insight into the Lability of MeCN Ligands of Cytotoxic Cycloruthenated Compounds: Evidence for the Antisymbiotic Effect Trans to the Carbon Atom at the Ru Center.

PubMed

Barbosa, Ana Soraya Lima; Werlé, Christophe; Colunga, Claudia Olivia Oliva; Rodríguez, Cecilia Franco; Toscano, Ruben Alfredo; Le Lagadec, Ronan; Pfeffer, Michel

2015-08-03

The two MeCN ligands in [Ru(2-C6H4-2'-Py-κC,N)(Phen, trans-C)(MeCN)2]PF6 (1), both trans to a sp(2) hybridized N atom, cannot be substituted by any other ligand. In contrast, the isomerized derivative [Ru(2-C6H4-2'-Py-κC,N)(Phen, cis-C)(MeCN)2]PF6 (2), in which one MeCN ligand is now trans to the C atom of the phenyl ring orthometalated to Ru, leads to fast and quantitative substitution reactions with several monodentate ligands. With PPh3, 2 affords [Ru(2-C6H4-2'-Py-κC,N)(Phen, cis-C)(PPh3)(MeCN)]PF6 (3), in which PPh3 is trans to the C σ bound to Ru. Compound 3 is not kinetically stable, because, under thermodynamic control, it leads to 4, in which the PPh3 is trans to a N atom of the Phen ligand. Dimethylsulfoxide (DMSO) can also substitute a MeCN ligand in 2, leading to 5, in which DMSO is coordinated to Ru via its S atom trans to the N atom of the Phen ligand, the isomer under thermodynamic control being the only compound observed. We also found evidence for the fast to very fast substitution of MeCN in 2 by water or a chloride anion by studying the electronic spectra of 2 in the presence of water or NBu4Cl, respectively. An isomerization related to that observed between 3 and 4 is also found for the known monophosphine derivative [Ru(2-C6H4-2'-Py-κC,N)(PPh3, trans-C)(MeCN)3]PF6 (10), in which the PPh3 is located trans to the C of the cyclometalated 2-phenylpyridine, since, upon treatment by refluxing MeCN, it leads to its isomer 11, [Ru(2-C6H4-2'-Py-κC,N)(PPh3, cis-C)(MeCN)3]PF6. Further substitutions are also observed on 11, whereby N^N chelates (N^N = 2,2'-bipyridine and phenanthroline) substitute two MeCN ligands, affording [Ru(2-C6H4-2'-Py-κC,N)(PPh3, cis-C)(N^N)(MeCN)]PF6 (12a and 12b). Altogether, the behavior of the obtained complexes by ligand substitution reactions can be rationalized by an antisymbiotic effect on the Ru center, trans to the C atom of the cyclometalated unit, leading to compounds having the least nucleophilic ligand trans to C whenever an isomerization, involving either a monodentate or a bidentate ligand, is possible.

The Effect of Curing Temperature on the Fracture Toughness of Fiberglass Epoxy Composites

NASA Astrophysics Data System (ADS)

Ryan, Thomas J.

The curing reaction in a thermoset polymer matrix composite is often accelerated by the addition of heat in an oven or autoclave. The heat added increases the rate of the polymerization reaction and cross-linking in the material. The cure cycle used (temperature, pressure and time) can therefore alter the final material properties. This research focuses on how the curing temperature (250, 275, 300 °F) affects the yield strength and the mode I interlaminar fracture toughness, GI, of a unidirectional S-2 glass epoxy composite. The test method that was used for the tension test was ASTM D3039 and the test method for the mode I interlaminar fracture toughness, the double cantilever beam (DCB) test, was ASTM D5528. The DCB specimens were fabricated with a non-adhesive insert at the midplane of the composite that serves as the initiatior of the delamination. Opening forces were then applied to the specimen, causing the crack propagation. The results show that increasing the cure temperature by 50 °F increased the tensile strength by 10% (86.54 - 94.73 ksi) and decreased the fracture toughness 20% (506.23 - 381.31 J/m 2). Thus, the curing temperature can cause a trade-off between these two properties, which means that the curing cycle will need to be altered based on the intended use and the required material properties.

Recognition of Mg²⁺ by a new fluorescent "turn-on" chemosensor based on pyridyl-hydrazono-coumarin.

PubMed

Orrego-Hernández, Jessica; Nuñez-Dallos, Nelson; Portilla, Jaime

2016-05-15

A new fluoroionophore PyHC bearing 2-pyridylhydrazone and 7-hydroxycoumarin moieties for selective detection of Mg(2+) was synthesized and characterized. This chemosensor exhibited "turn-on" fluorescence behavior and was sensitive to Mg(2+) concentrations as low as 105 nmol L(-1) in ethanol-water solution. Detailed spectroscopic studies revealed the binding mode of a 1:1 complex between PyHC and Mg(2+) that leads to a fluorescence enhancement. Copyright © 2016 Elsevier B.V. All rights reserved.

Water-refined solution structure of the human Grb7-SH2 domain in complex with the erbB2 receptor peptide pY1139.

PubMed

Pias, Sally C; Johnson, Dennis L; Smith, David E; Lyons, Barbara A

2012-08-01

We report a refinement in implicit water of the previously published solution structure of the Grb7-SH2 domain bound to the erbB2 receptor peptide pY1139. Structure quality measures indicate substantial improvement, with residues in the most favored regions of the Ramachandran plot increasing by 14 % and with WHAT IF statistics (Vriend, G. J. Mol. Graph., 1990, 8(1), 52-56) falling closer to expected values for well-refined structures.

[Effect of preoperative oral 5'-DFUR on PyNPase level in gastrointestinal malignant tumor tissues].

PubMed

Wang, Wen-Jian; Shi, De; Wang, Shen-Ming

2003-06-01

Pyrimidine nucleoside phosphorylase (PyNPase) exists mainly in tumor tissues.5'-deoxy-5-fluorouridine(5'-DFUR) can decrease its level in tumor tissues. However, the effect of preoperative oral 5'-DFUR on PyNPase level in the different time after administration has not been reported. This study was designed to investigate the suitable duration of preoperative chemotherapy through observing the changes of PyNPase levels in gastrointestinal malignant tumors after preoperative oral administration of 5'- DFUR in different duration. Seventy-three patients with gastrointestinal malignant tumors were divided into four groups by the duration of preoperative oral 5'-DFUR (600-1,200 mg x d(-1)): group A, three days, 27 cases; group B, one week, 22 cases; group C, two weeks, 15 cases; group D, two months, 9 cases. Meanwhile, group E, control group, had 24 inpatients with gastrointestinal malignant tumors at the same term. All the above-mentioned patients did not receive the other chemotherapy or radiotherapy. The changes of PyNPase levels in tumor tissues of different groups were tested using reverse transcription polymerase chain reaction (RT-PCR) and immunohistochemistry (IHC), etc. (1)Under electron microscope, there were many irrecoverable, lethal changes in tumor cells of group C. The outlines of the tumor cells were normal under light microscope, and more fibroconnective tissues were seen only in the stroma of group D. (2)The expressing levels of PyNPase mRNA and protein production in tumor tissues reduced obviously in group A (0.79+/-0.08, 19.26+/-1.65), and decreased most obviously in group C (0.43+/-0.07,5.91+/-1.45) comparing with group E (0.95+/-0.09, 29.34+/-1.82). However, there was no significant difference between group C and group D (0.42+/-0.04, 5.36+/-1.19) for the levels of PyNPase mRNA and protein production. The correlation coefficient between the levels of PyNPase mRNA and protein in tumor tissues of different group was r=0.92(P< 0.0001). 5'-DFUR by oral administration before operation might destroy gastrointestinal malignant tumor cells. As the duration prolonged, the content of PyNPase in tumor tissues decreased progressively, being lowest level in two weeks after chemotherapy. So two-week duration might be suitable for the treatment.

Preparation and Biological Evaluation of 64Cu Labeled Tyr3-Octreotate Using a Phosphonic Acid-Based Cross-Bridged Macrocyclic Chelator

PubMed Central

Guo, Yunjun; Ferdani, Riccardo; Anderson, Carolyn J.

2014-01-01

Somatostatin receptors (SSTr) are overexpressed in a wide range of neuroendocrine tumors, making them excellent targets for nuclear imaging and therapy, and radiolabeled somatostatin analogues have been investigated for positron emission tomography imaging and radionuclide therapy of SSTr-positive tumors, especially of the subtype-2 (SSTr2). The aim of this study was to develop a somatostatin analogue, Tyr3-octreotate (Y3-TATE), conjugated to a novel cross-bridged macrocyclic chelator, 11-carboxymethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane-4-methanephosphonic acid (CB-TE1A1P). Unlike traditional cross-bridged macrocycles, such as 4, 11 - bis (carboxymethyl) - 1, 4, 8, 11 -etraazabicyclo[6.6.2]hexadecane (CB-TE2A), CB-TE1A1P-Y3-TATE was radiolabeled with 64Cu in high purity and high specific activity using mild conditions. Saturation binding assays revealed that 64Cu-CB-TE1A1P-Y3-TATE had comparable binding affinity but bound to more binding sites in AR42J rat pancreatic tumor cell membranes than 64Cu-CB-TE2A-Y3-TATE. Both radiopharmaceuticals showed comparable uptake in SSTr2 positive tissues in AR42J tumor-bearing rats. 64Cu-CB-TE1A1PY3- TATE demonstrated improved blood clearance compared to 64Cu-CB-TE2A-Y3-TATE, as the tumor/blood ratios of 64Cu-CB-TE1A1P-Y3-TATE were shown to be significantly higher than those of 64Cu-CB-TE2A-Y3-TATE at 4 and 24 h postinjection. 64Cu-CB-TE1A1P-Y3-TATE, in spite of a relatively high kidney uptake, accumulated less in nontarget organs such as liver, lung, and bone. Small animal PET/CT imaging of 64Cu-CB-TE1A1P-Y3-TATE in AR42J tumor bearing rats validated significant uptake and good contrast in the tumor. This study suggests that CB-TE1A1P is a promising bifunctional chelator for 64Cu-labeled for Y3-TATE, owing to high binding affinity and target tissue uptake, the ability to radiolabel the agent at lower temperatures, and improved tumor/nontarget organ ratios over 64Cu-CB-TE2A-Y3-TATE. PMID:22663248

Crystal structure of fac-tri-carbonyl-chlorido-bis-(4-hy-droxy-pyridine)-rhenium(I)-pyridin-4(1H)-one (1/1).

PubMed

Argibay-Otero, Saray; Carballo, Rosa; Vázquez-López, Ezequiel M

2017-10-01

The asymmetric unit of the title compound, [ReCl(C 5 H 5 NO) 2 (CO) 3 ]·C 5 H 5 NO, contains one mol-ecule of the complex fac -[ReCl(4-pyOH) 2 (CO) 3 ] (where 4-pyOH represents 4-hy-droxy-pyridine) and one mol-ecule of pyridin-4(1 H )-one (4-HpyO). In the mol-ecule of the complex, the Re atom is coordinated to two N atoms of the two 4-pyOH ligands, three carbonyl C atoms, in a facial configuration, and the Cl atom. The resulting geometry is slightly distorted octa-hedral. In the crystal structure, both fragments are associated by hydrogen bonds; two 4-HpyO mol-ecules bridge between two mol-ecules of the complex using the O=C group as acceptor for two different HO- groups of coordinated 4-pyOH from two neighbouring metal complexes. The resulting square arrangements are extented into infinite chains by hydrogen bonds involving the N-H groups of the 4-HpyO mol-ecule and the chloride ligands. The chains are further stabilized by π-stacking inter-actions.

Discrimination in Degradability of Soil Pyrogenic Organic Matter Follows a Return-On-Energy-Investment Principle

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

Harvey, Omar R.; Myers-Pigg, Allison N.; Kuo, Li-Jung

A fundamental understanding of biodegradability is central to elucidating the role(s) of pyrogenic organic matter (PyOM) in biogeochemical cycles. Since microbial community and ecosystem dynamics are driven by net energy flows, then a quantitative assessment of energy value versus energy requirement for oxidation of PyOM should yield important insights into their biodegradability. We used bomb calorimetry, step-wise isothermal thermogravimetric analysis (isoTGA) and 5-year in-situ bidegradation data, to develop energy-biodegradability relationships for a suite of plant- and manure-derived PyOM (n = 10). The net energy value (ΔE) for PyOM was between 4.0 and 175 kJ mol-1; with manure-derived PyOM having themore » highest ΔE. Thermal-oxidation activation energy (Ea) requirements ranged from 51 to 125 kJ mol-1, with wood-derived PyOM having the highest Ea requirements. We propose a return-on-investment (ROI) parameter (ΔE/Ea) for differentiating short-to-medium term biodegradability of PyOM and deciphering if biodegradation will most likely proceed via co-metabolism (ROI < 1) or direct metabolism (ROI ≥ 1). The ROI-biodegradability relationship was sigmoidal with higher biodegradability associated with PyOM of higher ROI; indicating that microbes exhibit a higher preference for “high investment value” PyOM.« less

Reducing persistent polyomavirus infection increases functionality of virus-specific memory CD8 T cells.

PubMed

Qin, Qingsong; Lauver, Matthew; Maru, Saumya; Lin, Eugene; Lukacher, Aron E

2017-02-01

Mouse polyomavirus (MuPyV) causes a smoldering persistent infection in immunocompetent mice. To lower MuPyV infection in acutely and persistently infected mice, and study the impact of a temporal reduction in viral loads on the memory CD8 T cell response, we created a recombinant MuPyV in which a loxP sequence was inserted into the A2 strain genome upstream of the early promoter and another loxP sequence was inserted in cis into the intron shared by all three T antigens. Using mice transgenic for tamoxifen-inducible Cre recombinase, we demonstrated that reduction in MuPyV load during persistent infection was associated with differentiation of virus-specific CD8 T cells having a superior recall response. Evidence presented here supports the concept that reduction in viral load during persistent infection can promote differentiation of protective virus-specific memory CD8 T cells in patients at risk for diseases caused by human polyomaviruses. Copyright © 2016 Elsevier Inc. All rights reserved.

Element migration of pyrites during ductile deformation of the Yuleken porphyry Cu deposit (NW-China)

USGS Publications Warehouse

Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen; Li, Jilei; Cao, Mingjian; Xiang, Peng; Wu, Chu; You, Jun

2017-01-01

The strongly deformed Yuleken porphyry Cu deposit (YPCD) occurs in the Kalaxiangar porphyry Cu belt (KPCB), which occupies the central area of the Central Asian Orogenic Belt (CAOB) between the Sawu’er island arc and the Altay Terrane in northern Xinjiang. The YPCD is one of several typical subduction-related deposits in the KPCB, which has undergone syn-collisional and post-collisional metallogenic overprinting. The YPCD is characterized by three pyrite-forming stages, namely a hydrothermal stage A (Py I), a syn-ductile deformation stage B (Py II) characterized by Cu-Au enrichment, and a fracture-filling stage C (Py III). In this study, we conducted systematic petrographic and geochemical studies of pyrites and coexist biotite, which formed during different stages, in order to constrain the physicochemical conditions of the ore formation. Euhedral, fragmented Py I has low Pb and high Te and Se concentration and Ni contents are low with Co/Ni ratios mostly between 1 and 10 (average 9.00). Py I is further characterized by enrichments of Bi, As, Ni, Cu, Te and Se in the core relative to the rim domains. Anhedral round Py II has moderate Co and Ni contents with high Co/Ni ratios >10 (average 95.2), and average contents of 46.5 ppm Pb and 5.80 ppm Te. Py II is further characterized by decreasing Bi, Cu, Pb, Zn, Ag, Te, Mo, Sb and Au contents from the rim to the core domains. Annealed Py III has the lowest Co content of all pyrite types with Co/Ni ratios mostly <0.1 (average 1.33). Furthermore, Py III has average contents of 3.31 ppm Pb, 1.33 ppm Te and 94.6 ppm Se. In addition, Fe does not correlate with Cu and S in the Py I and Py III, while Py II displays a negative correlation between Fe and Cu as well as a positive correlation between Fe and S. Therefore, pyrites which formed during different tectonic regimes also have different chemical compositions. Biotite geothermometer and oxygen fugacity estimates display increasing temperatures and oxygen fugacities from stage A to stage B, while temperature and oxygen fugacities decrease from stage B to stage C. The Co/Ni ratio of pyrite depends discriminates between the different mineralizing stages in the Yuleken porphyry copper deposit: Py II, associated with the deformation stage B and Cu-enrichment, shows higher Co/Ni ratios and enrichments of Pb, Zn, Mo, Te and Sb than the pyrites formed during the other two stages. The Co/Ni ratio of pyrite can not only apply to discriminate the submarine exhalative, magmatic or sedimentary origins for ore deposits but also can distinguish different ore-forming stages in a single porphyry Cu deposit. Thus, Co/Ni ratio of pyrites may act as an important exploration tool to distinguish pyrites from Cu-rich versus barren area. Furthermore, the distribution of Cu, Mo, Pb, Au, Bi, Sb and Zn in the variably deformed pyrite is proportional to the extent of deformation of the pyrites, indicating in accordance with variable physicochemical conditions different element migration behavior during the different stages of deformation and, thus, mineralisation.

Discrete Spring Model for Predicting Delamination Growth in Z-Fiber Reinforced DCB Specimens

NASA Technical Reports Server (NTRS)

Ratcliffe, James G.; OBrien, T. Kevin

2004-01-01

Beam theory analysis was applied to predict delamination growth in Double Cantilever Beam (DCB) specimens reinforced in the thickness direction with pultruded pins, known as Z-fibers. The specimen arms were modeled as cantilever beams supported by discrete springs, which were included to represent the pins. A bi-linear, irreversible damage law was used to represent Z-fiber damage, the parameters of which were obtained from previous experiments. Closed-form solutions were developed for specimen compliance and displacements corresponding to Z-fiber row locations. A solution strategy was formulated to predict delamination growth, in which the parent laminate mode I critical strain energy release rate was used as the criterion for delamination growth. The solution procedure was coded into FORTRAN 90, giving a dedicated software tool for performing the delamination prediction. Comparison of analysis results with previous analysis and experiment showed good agreement, yielding an initial verification for the analytical procedure.

Discrete Spring Model for Predicting Delamination Growth in Z-Fiber Reinforced DCB Specimens

NASA Technical Reports Server (NTRS)

Ratcliffe, James G.; O'Brien, T. Kevin

2004-01-01

Beam theory analysis was applied to predict delamination growth in DCB specimens reinforced in the thickness direction with pultruded pins, known as Z-fibers. The specimen arms were modeled as cantilever beams supported by discrete springs, which were included to represent the pins. A bi-linear, irreversible damage law was used to represent Z-fiber damage, the parameters of which were obtained from previous experiments. Closed-form solutions were developed for specimen compliance and displacements corresponding to Z-fiber row locations. A solution strategy was formulated to predict delamination growth, in which the parent laminate mode I fracture toughness was used as the criterion for delamination growth. The solution procedure was coded into FORTRAN 90, giving a dedicated software tool for performing the delamination prediction. Comparison of analysis results with previous analysis and experiment showed good agreement, yielding an initial verification for the analytical procedure.

Drug-Coated Balloon Angioplasty: A Novel Treatment for Pulmonary Artery In-Stent Stenosis in a Patient with Williams Syndrome.

PubMed

Cohen, Jennifer L; Glickstein, Julie S; Crystal, Matthew A

2017-12-01

A 20-month-old boy with Williams syndrome had undergone multiple surgical and catheter-based interventions for resistant peripheral pulmonary arterial stenoses with eventual bilateral stent placement and conventional balloon angioplasty. He persistently developed suprasystemic right ventricular (RV) pressure. Angioplasty with a drug-coated balloon (DCB) was performed for in-stent restenosis and to remodel his distal pulmonary vessels bilaterally. This resulted in immediate improvement in the in-stent stenosis and resultant decrease in RV pressure. Follow-up catheterization two months later continued to show long-lasting improvement in the in-stent stenosis. We hypothesize that the anti-proliferative effects of DCBs may be of benefit in the arteriopathy associated with Williams syndrome. We report this as a novel use of a DCB in the pulmonary arterial circulation in a patient with Williams syndrome.

Flaw growth of 7075, 7475, 7050 and 7049 aluminum alloy plate in stress corrosion environments: 4-year marine atmosphere results

NASA Technical Reports Server (NTRS)

Hasse, K. R.; Dorward, R. C.

1981-01-01

After nearly 53 months of exposure to marine atmosphere, crack growth in SL DCB specimens from 7075, 7475, 7050, and 7049-T7X plate has slowed to the arbitrary 10 to the -10 power m/sec used to define threshold stress intensity. Because some specimens appear to be approaching crack arrest, the importance of self-loading from corrosion product wedging as a significant driving force for crack propagation in overaged materials is questioned. Crack length-time data were analyzed using a computer curve fitting program which minimized the effects of normal data scatter, and provided a clearer picture of material performance. Precracked specimen data are supported by the results of smooth specimen tests. Transgranular stress corrosion cracking was observed in TL DCB specimens from all four alloys. This process is extremely slow and is characterized by a striated surface morphology.

Apex-4 for SpaceX CRS-10

NASA Image and Video Library

2017-02-16

APEX-04, or Advanced Plant EXperiments-04, is being prepared in a cold room in the Kennedy Space Center Processing Facility for SpaceX-10. Eric Morris from the cold stowage group places the APEX-04 science kits into the Double Cold Bag (DCB), which is a non-powered container that keeps the APEX petri plates at +4 degrees Celsius during launch and ascent. The cold bricks in the lower right of the photo are placed in the DCB prior to closure. Dr. Anna Lisa Paul of the University of Florida is the principal investigator for APEX-04. Apex-04 is an experiment involving Arabidopsis in petri plates inside the Veggie facility aboard the International Space Station. Since Arabidopsis is the genetic model of the plant world, it is a perfect sample organism for performing genetic studies in spaceflight. The experiment is the result of a grant from NASA’s Space Life and Physical Sciences division.

Coffee-Ring-Free Quantum Dot Thin Film Using Inkjet Printing from a Mixed-Solvent System on Modified ZnO Transport Layer for Light-Emitting Devices.

PubMed

Jiang, Congbiao; Zhong, Zhiming; Liu, Baiquan; He, Zhiwei; Zou, Jianhua; Wang, Lei; Wang, Jian; Peng, JunBiao; Cao, Yong

2016-10-05

Inkjet printing has been considered an available way to achieve large size full-color RGB quantum dots LED display, and the key point is to obtain printed film with uniform and flat surface profile. In this work, mixed solvent of 20 vol % 1,2-dichlorobenzene (oDCB) with cyclohexylbenzene (CHB) was used to dissolve green quantum dots (QDs) with CdSe@ZnS/ZnS core/shell structure. Then, by inkjet printing, a flat dotlike QDs film without the coffee ring was successfully obtained on polyetherimide (PEI)-modified ZnO layer, and the printed dots array exhibited great stability and repeatability. Here, adding oDCB into CHB solutions was used to reduce surface tension, and employing ZnO nanoparticle layer with PEI-modified was used to increase the surface free energy. As a result, a small contact angle is formed, which leads to the enhancement of evaporation rate, and then the coffee ring effect was suppressed. The printed dots with flat surface profile were eventually realized. Moreover, inverted green QD-LEDs with PEI-modified ZnO film as electron transport layer (ETL) and printed green QDs film as emission layer were successfully fabricated. The QD-LEDs exhibited the maximum luminance of 12 000 cd/m 2 and the peak current efficiency of 4.5 cd/A at luminance of 1500 cd/m 2 .

High Rates of Sexually transmitted infections in HIV-positive patients in the Australian HIV Observational Database - a prospective cohort study

PubMed Central

Mulhall, Brian P; Wright, Stephen; Allen, Debbie; Brown, Katherine; Dickson, Bridget; Grotowski, Miriam; Jackson, Eva; Petoumenos, Kathy; Read, Phillip; Read, Timothy; Russell, Darren; Smith, David J; Templeton, David J; Fairley, Christopher K; Law, Matthew G

2015-01-01

Background Sexually transmitted infections (STI) may directly increase the risk of HIV infection, or may indicate sexual practices that increase the risk of HIV infection. In persons with HIV they probably also increase the infectiousness of HIV, even in the context of treatment with antiretroviral drugs (ARV). Estimating STI in this group has proved problematic, and there are few longitudinal studies able to accurately measure incidence. Methods In 2010, we established a cohort of individuals from ten widely dispersed sexual health clinics that were already enrolled in the Australian HIV Observational Database (AHOD). We calculated retrospective diagnosis rates for four STI (chlamydia, gonorrhoea, infectious syphilis, anogenital warts) from 2005-2010, and prospective incidence rates from 2010-2011. Results At baseline (2010) , the patient characteristics (n=554) were similar to the rest of AHOD (n=1767), namely they were predominantly male, homosexual, middle-aged, and pre- treated with ARV. Overall, the incidence of any STI was 12.5/100 person years (py). There was a gradual increase in chlamydial infections , from 3.4/100 py (95% CI 1.9-5.7) in 2005 to 6.7/100py (95% CI 4.5-9.5) in 2011, with a substantial peak of 8.1/100py (95% CI 5.6-11.2) in 2010. The cases were distributed between rectal ( 61.9%), urethral (34%), and pharyngeal (6.3%) sites. Similarly, gonococcal infections increased, with a peak in 2010 of 4.7/100py (95% CI 5.6-11.2), (p value for trend=0.0099), distributed between rectal (63.9%), urethral (27.9%), and pharyngeal (14.8%) sites. Infectious syphilis showed several peaks, the largest in 2008 (5.3/100py , (95% CI 3.3-8.0), but the overall trend was not significant (p=0.113). Diagnoses of genital warts declined from 7.5/100py (95% CI 4.8-11.3) in 2005 (95% CI 4.8-11.3) to 2.4/100py (95% CI 1.1-4.5) in 2011 (p value for trend=0.0016). Conclusions The incidence of chlamydial and gonococcal infections in this cohort was higher than previous estimates in Australia among HIV-infected men who have sex with men (MSM), and increased during the 2005-2011 study period. Rectal infections greatly outnumbered infections at other sites. The incidence of infectious syphilis remained high, but did not increase, and the incidence of genital warts was lower, and decreased. These are the first measurements of STI incidence among persons being treated for HIV in Australia. They may underestimate the true incidence of these infections in the HIV-infected population. PMID:25109880

Electrochemical behavior of meso-substituted iron porphyrins in alkaline aqueous media

NASA Astrophysics Data System (ADS)

Berezina, N. M.; Bazanov, M. I.; Maksimova, A. A.; Semeikin, A. S.

2017-12-01

The effect meso-substitution in iron porphyrin complexes has on their redox behavior in alkaline aqueous solutions is studied via cyclic voltammetry. The voltammetric features of the reduction of iron pyridylporphyrins suggest that the sites of electron transfer lie at the ligand, the metal ion, and the pyridyl moieties. The electron transfer reactions between the different forms of these compounds, including the oxygen reduction reaction they mediate, are outlined to show the sequence and potential ranges in which they occur in alkaline aqueous media. Under our experimental conditions, the iron porphyrins exist as μ-oxo dimmers whose activity for the electrocatalytic reduction of oxygen displays a considerable dependence on the nature of the substitutents and nitrogen isomerization (for pyridylporphyrins) and grows in the order (Fe( ms-Ph)4P)2O, (Fe[ ms-(Py-3)Ph3]P)2O, (Fe[ ms-(Py-4)4]P)2O, and (Fe[ ms-(Py-3)4]P)2O.

Effect of oxygen and hydrogen on microstructure of pyrolytic carbon deposited from thermal decomposition of methane and ethanol

NASA Astrophysics Data System (ADS)

Ren, Biyun; Zhang, Shouyang; He, LiQun; Gu, Shengyue

2018-05-01

Chemical vapor infiltration (CVI) is the most extensive industrial preparation of carbon/carbon (C/C) composites. Precursor affects the CVI process considerably. In the present study, using carbon fiber bundles as preforms, methane and ethanol as precursors, the C/C composites were densified by decomposition of various gases in CVI. The thickness and texture of deposited pyrolytic carbon (PyC) were characterized by polarized light microscopy (PLM). The microstructure of PyC was analyzed by Raman spectroscopy. The morphologies of PyC were characterized by scanning electron microscopy (SEM). The composition of PyC was detected by X-ray photoelectron spectroscopy (XPS). Adding hydrogen in methane precursor resulted in a sharp decrease in the deposition rate and texture of PyC. Mixture of methane and ethanol as the precursor improved the deposition rate and texture remarkably. Besides, O element in ethanol was not remained as a constitution of PyC, and it was removed before the formation of PyC.

Spin-Valve Effect in NiFe/MoS2/NiFe Junctions.

PubMed

Wang, Weiyi; Narayan, Awadhesh; Tang, Lei; Dolui, Kapildeb; Liu, Yanwen; Yuan, Xiang; Jin, Yibo; Wu, Yizheng; Rungger, Ivan; Sanvito, Stefano; Xiu, Faxian

2015-08-12

Two-dimensional (2D) layered transition metal dichalcogenides (TMDs) have been recently proposed as appealing candidate materials for spintronic applications owing to their distinctive atomic crystal structure and exotic physical properties arising from the large bonding anisotropy. Here we introduce the first MoS2-based spin-valves that employ monolayer MoS2 as the nonmagnetic spacer. In contrast with what is expected from the semiconducting band-structure of MoS2, the vertically sandwiched-MoS2 layers exhibit metallic behavior. This originates from their strong hybridization with the Ni and Fe atoms of the Permalloy (Py) electrode. The spin-valve effect is observed up to 240 K, with the highest magnetoresistance (MR) up to 0.73% at low temperatures. The experimental work is accompanied by the first principle electron transport calculations, which reveal an MR of ∼9% for an ideal Py/MoS2/Py junction. Our results clearly identify TMDs as a promising spacer compound in magnetic tunnel junctions and may open a new avenue for the TMDs-based spintronic applications.

Reactivity of a series of isostructural cobalt pincer complexes with CO2, CO, and H(+).

PubMed

Shaffer, David W; Johnson, Samantha I; Rheingold, Arnold L; Ziller, Joseph W; Goddard, William A; Nielsen, Robert J; Yang, Jenny Y

2014-12-15

The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)2P(E)Py(E)P(t-Bu)2(CH3CN)2][BF4]2 (Py = pyridine, E = CH2, NH, O, and X = BF4 (1a-c)) and the corresponding one-electron reduced analogues [Co(t-Bu)2P(E)Py(E)P(t-Bu)2(CH3CN)2][BF4]2 (2a-c) are reported. The reactivity of the reduced cobalt complexes with CO2, CO, and H(+) to generate intermediates in a CO2 to CO and H2O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO2 was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H(+) versus CO2. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.

EdiPy: a resource to simulate the evolution of plant mitochondrial genes under the RNA editing.

PubMed

Picardi, Ernesto; Quagliariello, Carla

2006-02-01

EdiPy is an online resource appropriately designed to simulate the evolution of plant mitochondrial genes in a biologically realistic fashion. EdiPy takes into account the presence of sites subjected to RNA editing and provides multiple artificial alignments corresponding to both genomic and cDNA sequences. Each artificial data set can successively be submitted to main and widespread evolutionary and phylogenetic software packages such as PAUP, Phyml, PAML and Phylip. As an online bioinformatic resource, EdiPy is available at the following web page: http://biologia.unical.it/py_script/index.html.

Pyrolysis-gas chromatography-isotope ratio mass spectrometry for monitoring natural additives in polylactic acid active food packages.

PubMed

Llana-Ruíz-Cabello, M; Pichardo, S; Jiménez-Morillo, N T; González-Vila, F J; Guillamón, E; Bermúdez, J M; Aucejo, S; Camean, A M; González-Pérez, J A

2017-11-24

Compound-specific isotope analysis (CSIA) usually requires preparative steps (pretreatments, extraction, derivatization) to get amenable chromatographic analytes from bulk geological, biological or synthetic materials. Analytical pyrolysis (Py-GC/MS) can help to overcome such sample manipulation. This communication describe the results obtained by hyphenating analytical pyrolysis (Py-GC) with carbon isotope-ratio mass spectrometry (IRMS) for the analysis of a polylactic acid (PLA) a based bio-plastic extruded with variable quantities of a natural plant extract or oregano essential oil. The chemical structural information of pyrolysates was first determined by conventional analytical pyrolysis and the measure of δ 13 C in specific compounds was done by coupling a pyrolysis unit to a gas chromatograph connected to a continuous flow IRMS unit (Py-GC-C-IRMS). Using this Py-CSIA device it was possible to trace natural additives with depleted δ 13 C values produced by C3 photosystem vegetation (cymene: -26.7‰±2.52; terpinene: -27.1‰±0.13 and carvacrol: -27.5‰±1.80 from oregano and two unknown structures: -23.3‰±3.32 and -24.4‰±1.70 and butyl valerate: -24.1‰±3.55 from Allium spp.), within the naturally isotopically enriched bio-plastic backbone derived from corn (C4 vegetation) starch (cyclopentanones: -14.2‰±2.11; lactide enantiomers: -9.2‰±1.56 and larger polymeric units: -17.2‰±1.71). This is the first application of Py-CSIA to characterize a bio-plastic and is shown as a promising tool to study such materials, providing not only a fingerprinting, but also valuable information about the origin of the materials, allowing the traceability of additives and minimizing sample preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

PyClone: statistical inference of clonal population structure in cancer.

PubMed

Roth, Andrew; Khattra, Jaswinder; Yap, Damian; Wan, Adrian; Laks, Emma; Biele, Justina; Ha, Gavin; Aparicio, Samuel; Bouchard-Côté, Alexandre; Shah, Sohrab P

2014-04-01

We introduce PyClone, a statistical model for inference of clonal population structures in cancers. PyClone is a Bayesian clustering method for grouping sets of deeply sequenced somatic mutations into putative clonal clusters while estimating their cellular prevalences and accounting for allelic imbalances introduced by segmental copy-number changes and normal-cell contamination. Single-cell sequencing validation demonstrates PyClone's accuracy.

Redistribution of pyrogenic carbon from hillslopes to stream corridors following a large montane wildfire

Treesearch

M. Francesca Cotrufo; Claudia M. Boot; Stephanie Kampf; Peter A. Nelson; Daniel J. Brogan; Tim Covino; Michelle L. Haddix; Lee H. MacDonald; Sarah Rathburn; Sandra Ryan-Burkett; Sarah Schmeer; Ed Hall

2016-01-01

Pyrogenic carbon (PyC) constitutes a significant fraction of organic carbon in most soils. However, PyC soil stocks are generally smaller than what is expected from estimates of PyC produced from fire and decomposition losses, implying that other processes cause PyC loss from soils. Surface erosion has been previously suggested as one such process. To address this,...

Pyrogenic Carbon as a Nonlinear Driver in the Carbon and Nitrogen Cycles

NASA Astrophysics Data System (ADS)

Masiello, C. A.; Silberg, J. J.; Cheng, H. Y.; Gao, X.; Del Valle, I.

2016-12-01

Our first conceptual models of pyrogenic carbon's effects on the carbon cycle treated this material as a form of organic matter whose environmental residence time was long enough to render it inert, and PyC was modeled as an unreactive mass that moved through C cycle reservoirs essentially unmodified. This concept saw modifications with the recognition that some fractions of PyC were labile. For example, the reactive sugars and lignin monomers cleaved off the lignocellulose matrix by heating have lifetimes on the order of hours to weeks. However, the now-common multiple component model of PyC does not satisfactorily explain many nonlinearities that have been observed when it is added to soils. These nonlinearities include the positive and negative "priming" effects sometimes triggered, where the presence of PyC in some matrices can trigger shifts in the overall microbial community metabolism, as well as alteration of microbial community structure, shifts in the behavior of belowground and aboveground plant parasites, and shifted rates of greenhouse gas emissions that are not well-correlated to shifts in soil hydrologic processes. To understand the effects of PyC on the global C and N cycles, we will need a better understanding of the mechanisms behind PyC-driven C and N cycle nonlinearities. This talk will examine potential mechanisms driving the nonlinearities observed in soil systems following the introduction of PyC. Potential mechanisms discussed will include PyC effects on soil microbial communication and PyC effects on microbial electron transfer. Cell-cell communication through the secretion and detection of small molecules is used by soil microbes to manage many biogeochemically relevant processes including production of biofilms, production of extracellular enzymes, and management of methanogenesis and denitrification. PyC disrupts microbial cell-cell communication differentially, altering some species' ability to communicate more than others. Electron transfer between microbes is a central part of many environmental syntrophies, including those responsible for methanogenesis, and has been shown to be altered by the presence of PyC. Both these processes may underlie observed ecosystem-scale shifts following PyC amendment to soils.

Magnetic transport property of NiFe/WSe2/NiFe spin valve structure

NASA Astrophysics Data System (ADS)

Zhao, Kangkang; Xing, Yanhui; Han, Jun; Feng, Jiafeng; Shi, Wenhua; Zhang, Baoshun; Zeng, Zhongming

2017-06-01

Two-dimensional (2D) materials have been proposed as promising candidate for spintronic applications due to their atomic crystal structure and physical properties. Here, we introduce exfoliated few-layer tungsten diselenide (WSe2) as spacer in a Py/WSe2/Py vertical spin valve. In this junction, the WSe2 spacer exhibits metallic behavior. We observed negative magnetoresistance (MR) with a ratio of -1.1% at 4 K and -0.21% at 300 K. A general phenomenological analysis of the negative MR property is discussed. Our result is anticipated to be beneficial for future spintronic applications.

Risk of new or recurrent cancer under immunosuppressive therapy in patients with IBD and previous cancer.

PubMed

Beaugerie, Laurent; Carrat, Fabrice; Colombel, Jean-Frédéric; Bouvier, Anne-Marie; Sokol, Harry; Babouri, Abdenour; Carbonnel, Franck; Laharie, David; Faucheron, Jean-Luc; Simon, Tabassome; de Gramont, Aimery; Peyrin-Biroulet, Laurent

2014-09-01

To explore the risk of new or recurrent cancer among patients with IBD and previous cancer, exposed or not to immunosuppressants. Among the 17 047 patients of the CESAME prospective observational cohort who were enrolled from May 2004 to June 2005, and followed-up until December 2007, we identified 405 patients with cancer diagnosed previous to study entry. We calculated the rates of incident cancer in patients with or without previous cancer, and we assessed by survival analysis and nested case-control study the impact of immunosuppressants on the risk of incident new or recurrent cancer in patients with previous cancer. The rate of incident cancer was 21.1/1000 patient-years (PY) and 6.1/1000 PY in patients with and without previous cancer, respectively. The multivariate-adjusted HR of incident cancer between patients with and without previous cancer was 1.9 (95% CI 1.2 to 3.0, p=0.003). Among patients with previous cancer, the rates of new and recurrent cancers were, respectively, 13.2/1000 PY and 6.0/1000 PY in the 312 patients who were not taking immunosuppressant at the time of study entry, and 23.1/1000 PY and 3.9/1000 PY in the 93 patients treated with immunosuppressants at study entry. There was no significant association between the exposure to immunosuppressants and the risk of new or recurrent cancer. Patients with IBD with a history of cancer are at increased risk of developing any (new or recurrent) cancer, with a predominant incidence of new cancers. Treatment with immunosuppressants has no overall major impact per se on this risk. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Burden of Influenza in 4 Ecologically Distinct Regions of Peru: Household Active Surveillance of a Community Cohort, 2009-2015.

PubMed

Tinoco, Yeny O; Azziz-Baumgartner, Eduardo; Uyeki, Timothy M; Rázuri, Hugo R; Kasper, Matthew R; Romero, Candice; Silva, Maria E; Simons, Mark P; Soto, Giselle M; Widdowson, Marc-Alain; Gilman, Robert H; Bausch, Daniel G; Montgomery, Joel M

2017-10-16

There are limited data on the burden of disease posed by influenza in low- and middle-income countries. Furthermore, most estimates of influenza disease burden worldwide rely on passive sentinel surveillance at health clinics and hospitals that lack accurate population denominators. We documented influenza incidence, seasonality, health-system utilization with influenza illness, and vaccination coverage through active community-based surveillance in 4 ecologically distinct regions of Peru over 6 years. Approximately 7200 people in 1500 randomly selected households were visited 3 times per week. Naso- and oropharyngeal swabs were collected from persons with influenza-like illness and tested for influenza virus by real-time reverse-transcription polymerase chain reaction. We followed participants for 35353 person-years (PY). The overall incidence of influenza was 100 per 1000 PY (95% confidence interval [CI], 97-104) and was highest in children aged 2-4 years (256/1000 PY [95% CI, 236-277]). Seasonal incidence trends were similar across sites, with 61% of annual influenza cases occurring during the austral winter (May-September). Of all participants, 44 per 1000 PY (95% CI, 42-46) sought medical care, 0.7 per 1000 PY (95% CI, 0.4-1.0) were hospitalized, and 1 person died (2.8/100000 PY). Influenza vaccine coverage was 27% among children aged 6-23 months and 26% among persons aged ≥65 years. Our results indicate that 1 in 10 persons develops influenza each year in Peru, with the highest incidence in young children. Active community-based surveillance allows for a better understanding of the true burden and seasonality of disease that is essential to plan the optimal target groups, timing, and cost of national influenza vaccination programs. Published by Oxford University Press for the Infectious Diseases Society of America 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Interaction of In(I) and Tl(I) cations with 2,6-diaryl pyridine ligands: cation encapsulation within a very weakly interacting N/arene host environment.

PubMed

Mansaray, Hassanatu B; Tang, Christina Y; Vidovic, Dragoslav; Thompson, Amber L; Aldridge, Simon

2012-12-03

The interaction of 2,6-dimesitylpyridine with Tl(I) and In(I) cations has been investigated with a view to developing tractable molecular M(I) compounds which are soluble in organic media. In stark contrast to isosteric and isoelectronic terphenyl systems, complexes featuring the [(2,6-Mes(2)py)M](+) fragment feature very weak metal-ligand interactions in the solid state, as revealed by M-N distances of the order of 2.45 Å (M = In) and 2.64 Å (M = Tl). While additional weak π interactions are observed with arene solvate molecules in these systems, the related 2:1 complex [(2,6-Mes(2)py)(2)In][BAr(f)(4)] features an In(I) center wholly encapsulated by the bulky Mes(2)py donors, and even longer In-N distances [2.586(6) and 2.662(5) Å]. These contacts are about 0.5 Å greater than the sum of the respective covalent radii (2.13 Å) and provide evidence for an effectively "naked" In(I) cation stabilized to a minor extent by orbital interactions.

Exploring the chemodiversity and biological activities of the secondary metabolites from the marine fungus Neosartorya pseudofischeri.

PubMed

Liang, Wan-Ling; Le, Xiu; Li, Hou-Jin; Yang, Xiang-Ling; Chen, Jun-Xiong; Xu, Jun; Liu, Huan-Liang; Wang, Lai-You; Wang, Kun-Teng; Hu, Kun-Chao; Yang, De-Po; Lan, Wen-Jian

2014-11-24

The production of fungal metabolites can be remarkably influenced by various cultivation parameters. To explore the biosynthetic potentials of the marine fungus, Neosartorya pseudofischeri, which was isolated from the inner tissue of starfish Acanthaster planci, glycerol-peptone-yeast extract (GlyPY) and glucose-peptone-yeast extract (GluPY) media were used to culture this fungus. When cultured in GlyPY medium, this fungus produced two novel diketopiperazines, neosartins A and B (1 and 2), together with six biogenetically-related known diketopiperazines,1,2,3,4-tetrahydro-2, 3-dimethyl-1,4-dioxopyrazino[1,2-a]indole (3), 1,2,3,4-tetrahydro-2-methyl-3-methylen e-1,4-dioxopyrazino[1,2-a]indole (4), 1,2,3,4-tetrahydro-2-methyl-1,3,4-trioxopyrazino[1,2-a] indole (5), 6-acetylbis(methylthio)gliotoxin (10), bisdethiobis(methylthio)gliotoxin (11), didehydrobisdethiobis(methylthio)gliotoxin (12) and N-methyl-1H-indole-2-carboxamide (6). However, a novel tetracyclic-fused alkaloid, neosartin C (14), a meroterpenoid, pyripyropene A (15), gliotoxin (7) and five known gliotoxin analogues, acetylgliotoxin (8), reduced gliotoxin (9), 6-acetylbis(methylthio)gliotoxin (10), bisdethiobis(methylthio) gliotoxin (11) and bis-N-norgliovictin (13), were obtained when grown in glucose-containing medium (GluPY medium). This is the first report of compounds 3, 4, 6, 9, 10 and 12 as naturally occurring. Their structures were determined mainly by MS, 1D and 2D NMR data. The possible biosynthetic pathways of gliotoxin-related analogues and neosartin C were proposed. The antibacterial activity of compounds 2-14 and the cytotoxic activity of compounds 4, 5 and 7-13 were evaluated. Their structure-activity relationships are also preliminarily discussed.

Combined experimental and theoretical approach to understand the reactivity of a mononuclear Cu(II)-hydroperoxo complex in oxygenation reactions.

PubMed

Kamachi, Takashi; Lee, Yong-Min; Nishimi, Tomonori; Cho, Jaeheung; Yoshizawa, Kazunari; Nam, Wonwoo

2008-12-18

A copper(II) complex bearing a pentadentate ligand, [Cu(II)(N4Py)(CF(3)SO(3))(2)] (1) (N4Py = N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear Cu(II)-hydroperoxo complex, [Cu(II)(N4Py)(OOH)](+) (2), was then generated in the reaction of 1 and H(2)O(2) in the presence of base, and the reactivity of the intermediate was investigated in the oxidation of various substrates at -40 degrees C. In the reactivity studies, 2 showed a low oxidizing power such that 2 reacted only with triethylphosphine but not with other substrates such as thioanisole, benzyl alcohol, 1,4-cyclohexadiene, cyclohexene, and cyclohexane. In theoretical work, we have conducted density functional theory (DFT) calculations on the epoxidation of ethylene by 2 and a [Cu(III)(N4Py)(O)](+) intermediate (3) at the B3LYP level. The activation barrier is calculated to be 39.7 and 26.3 kcal/mol for distal and proximal oxygen attacks by 2, respectively. This result indicates that the direct ethylene epoxidation by 2 is not a plausible pathway, as we have observed in the experimental work. In contrast, the ethylene epoxidation by 3 is a downhill and low-barrier process. We also found that 2 cannot be a precursor to 3, since the homolytic cleavage of the O-O bond of 2 is very endothermic (i.e., 42 kcal/mol). On the basis of the experimental and theoretical results, we conclude that a mononuclear Cu(II)-hydroperoxo species bearing a pentadentate N5 ligand is a sluggish oxidant in oxygenation reactions.

RECURRENT STROKE IN THE WARFARIN VERSUS ASPIRIN IN REDUCED EJECTION FRACTION (WARCEF) TRIAL

PubMed Central

Pullicino, Patrick M.; Qian, Min; Sacco, Ralph L.; Freudenberger, Ron; Graham, Susan; Teerlink, John R.; Mann, Douglas; Di Tullio, Marco R.; Ponikowski, Piotr; Lok, Dirk J.; Anker, Stefan D.; Lip, Gregory Y.H.; Estol, Conrado J.; Levin, Bruce; Mohr, J.P.; Thompson, John L. P.; Homma, Shunichi

2014-01-01

Background and Purpose WARCEF randomized 2305 patients in sinus rhythm with ejection fraction (EF) ≤35% to warfarin (INR 2.0–3.5) or aspirin 325 mg. Warfarin reduced the incident ischemic stroke (IIS) hazard rate by 48% over aspirin in a secondary analysis. The IIS rate in heart failure (HF) is too low to warrant routine anticoagulation but epidemiologic studies show that prior stroke increases the stroke risk in HF. We here explore IIS rates in WARCEF patients with and without baseline stroke to look for risk factors for IIS and determine if a subgroup with an IIS rate high enough to give a clinically relevant stroke risk reduction can be identified. Methods We compared potential stroke risk factors between patients with baseline stroke and those without using the exact conditional score test for Poisson variables. We looked for risk factors for IIS, by comparing IIS rates between different risk factors. For EF we tried cutoff points of 10%, 15% and 20%. 15% was used as it was the highest EF that was associated with a significant increase in IIS rate. IIS and EF strata were balanced as to warfarin/aspirin assignment by the stratified randomized design. A multiple Poisson regression examined the simultaneous effects of all risk factors on IIS rate. IIS rates per hundred patient years (/100PY) were calculated in patient groups with significant risk factors. Missing values were assigned the modal value. Results Twenty of 248 (8.1%) patients with baseline stroke and 64 of 2048 (3.1%) without had IIS. IIS rate in patients with baseline stroke (2.37/100PY) was greater than patients without (0.89/100PY)(rate ratio 2.68, p<0.001). Fourteen of 219 (6.4%) patients with ejection fraction (EF)<15% and 70 of 2079 (3.4%) with EF ≥15% had IIS. In the multiple regression analysis stroke at baseline (p<0.001) and EF<15% vs. ≥15% (p=.005) remained significant predictors of IIS. IIS rate was 2.04/100PY in patients with EF<15% and 0.95/100PY in patients with EF ≥15% (p=0.009). IIS rate in patients with baseline stroke and reduced EF was 5.88/100PY with EF<15% decreasing to 2.62/100PY with EF<30%. Conclusions In a WARCEF exploratory analysis, prior stroke and EF<15% were risk factors for IIS. Further research is needed to determine if a clinically relevant stroke risk reduction is obtainable with warfarin in HF patients with prior stroke and reduced EF. PMID:25300706

Heterologous Expression of Bacterial Epoxyalkane:Coenzyme M Transferase and Inducible Coenzyme M Biosynthesis in Xanthobacter Strain Py2 and Rhodococcus rhodochrous B276

PubMed Central

Krum, Jonathan G.; Ensign, Scott A.

2000-01-01

Coenzyme M (CoM) (2-mercaptoethanesulfonic acid) biosynthesis is shown to be coordinately regulated with the expression of the enzymes of alkene and epoxide metabolism in the propylene-oxidizing bacteria Xanthobacter strain Py2 and Rhodococcus rhodochrous strain B276. These results provide the first evidence for the involvement of CoM in propylene metabolism by R. rhodochrous and demonstrate for the first time the inducible nature of eubacterial CoM biosynthesis. PMID:10762269

Electrooxidation of pyrrole-terminated self-assembled lipoic acid derivatives

NASA Astrophysics Data System (ADS)

Cabrita, Joana F.; Viana, Ana S.; Eberle, Christoph; Montforts, Franz-Peter; Mourato, Ana; Abrantes, Luisa M.

2009-08-01

New pyrrole derivatives, pyrrolyl lipoic acid (Py-LA 3) and dipyrrolyl lipoic acid (Py 2-LA 2) have been used for surface attachment and immobilisation on gold surfaces, by self-assembly. The electrooxidation of the surface-confined pyrroles was analysed by cyclic voltammetry and the modified electrodes morphological and thickness changes addressed by scanning probe microscopy and ellipsometry. The data support the formation of oligomers as a result of the pendant-pyrrolyl units ease oxidation but provide no evidence of an effective subsequent polymerisation.

Computational, electrochemical, and spectroscopic studies of two mononuclear cobaloximes: the influence of an axial pyridine and solvent on the redox behaviour and evidence for pyridine coordination to cobalt(I) and cobalt(II) metal centres†

PubMed Central

Lawrence, Mark A. W.; Celestine, Michael J.; Artis, Edward T.; Joseph, Lorne S.; Esquivel, Deisy L.; Ledbetter, Abram J.; Cropek, Donald M.; Jarrett, William L.; Bayse, Craig A.; Brewer, Matthew I.; Holder, Alvin A.

2018-01-01

[Co(dmgBF2)2(H2O)2] 1 (where dmgBF2 = difluoroboryldimethylglyoximato) was used to synthesize [Co(dmgBF2)2(H2O)(py)]·0.5(CH3)2CO 2 (where py = pyridine) in acetone. The formulation of complex 2 was confirmed by elemental analysis, high resolution MS, and various spectroscopic techniques. The complex [Co(dmgBF2)2(solv)(py)] (where solv = solvent) was readily formed in situ upon the addition of pyridine to complex 1. A spectrophotometric titration involving complex 1 and pyridine proved the formation of such a species, with formation constants, log K = 5.5, 5.1, 5.0, 4.4, and 3.1 in 2-butanone, dichloromethane, acetone, 1,2-difluorobenzene/acetone (4 : 1, v/v), and acetonitrile, respectively, at 20 °C. In strongly coordinating solvents, such as acetonitrile, the lower magnitude of K along with cyclic voltammetry, NMR, and UV-visible spectroscopic measurements indicated extensive dissociation of the axial pyridine. In strongly coordinating solvents, [Co(dmgBF2)2(solv)(py)] can only be distinguished from [Co(dmgBF2)2(solv)2] upon addition of an excess of pyridine, however, in weakly coordinating solvents the distinctions were apparent without the need for excess pyridine. The coordination of pyridine to the cobalt(II) centre diminished the peak current at the Epc value of the CoI/0 redox couple, which was indicative of the relative position of the reaction equilibrium. Herein we report the first experimental and theoretical 59Co NMR spectroscopic data for the formation of Co(I) species of reduced cobaloximes in the presence and absence of py (and its derivatives) in CD3CN. From spectroelectrochemical studies, it was found that pyridine coordination to a cobalt(I) metal centre is more favourable than coordination to a cobalt(II) metal centre as evident by the larger formation constant, log K = 4.6 versus 3.1, respectively, in acetonitrile at 20 °C. The electrosynthesis of hydrogen by complexes 1 and 2 in various solvents demonstrated the dramatic effects of the axial ligand and the solvent on the turnover number of the respective catalyst. PMID:27244471

Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes.

PubMed

Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako

2016-06-06

We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique.

Negative regulation of early polyomavirus expression in mouse embryonal carcinoma cells.

PubMed Central

Cremisi, C; Babinet, C

1986-01-01

Embryonal carcinoma cells are resistant to infection by polyomavirus (Py). We showed that this block was partially removed by inhibiting protein synthesis temporarily. The block was also partially removed when Py was coinfected with simian virus 40. Cycloheximide treatment of cells infected with Py mutants able to grow on PCC4 embryonal carcinoma cells led to 3- to 10-fold increases in the production of T-antigen-positive cells. At 31 degrees C, Py T-antigen expression was enhanced when the cells were treated with cycloheximide. We suggest that a negative labile regulatory protein(s) is synthesized in PCC4 cells, preventing the initiation of early Py transcription by binding to the noncoding sequence, especially the enhancer element B and perhaps also element A, and that the Py mutants retained a binding site(s). PMID:3016339

The Organic Matter Molecular Characteristics of Pyrogenic Solids and Their Aqueous Leachable Fractions

NASA Astrophysics Data System (ADS)

Wozniak, A. S.; Hatcher, P.; Mitra, S.; Bostick, K. W.; Zimmerman, A. R.

2016-02-01

Pyrogenic organic matter (Py-OM), or black carbon (BC), derives from the incomplete combustion of fossil fuels and biomass and is recognized for its impacts on soil chemistry, pollutant transport, climate, and regional and global carbon cycling. In fact, Py-OM is commonly applied to agricultural plots, in the form of "biochars," with the intention of enhancing agricultural production and the expectation of a carbon sequestration side benefit due to Py-OM's refractory and immobile nature. However, several studies of riverine, estuarine, and oceanic waters have detected tracers of dissolved Py-OM in appreciable quantities suggesting that it is more mobile in the environment than previously expected. The quantities and impacts of Py-OM released to aqueous systems are likely dependent on Py-OM molecular characteristics which in turn likely depend on initial combustion conditions and environmental processing. Yet, very little is known about the detailed molecular composition of these materials, let alone their relationships with combustion and environmental processing. Here, pyrophosphate extractable and water leachable components of a range of Py-OM materials (natural charcoals aged in the environment for variable lengths of time, oak and grass combusted over a range of temperatures) are examined by Fourier transform ion cyclotron resonance mass spectrometry. The molecular characteristics of the dissolved and pyrophosphate extractable Py-OM is then compared in the context of production conditions. Results of this study will greatly improve our understanding of Py-OM cycling between watersheds and the oceans.

PyCoTools: A Python Toolbox for COPASI.

PubMed

Welsh, Ciaran M; Fullard, Nicola; Proctor, Carole J; Martinez-Guimera, Alvaro; Isfort, Robert J; Bascom, Charles C; Tasseff, Ryan; Przyborski, Stefan A; Shanley, Daryl P

2018-05-22

COPASI is an open source software package for constructing, simulating and analysing dynamic models of biochemical networks. COPASI is primarily intended to be used with a graphical user interface but often it is desirable to be able to access COPASI features programmatically, with a high level interface. PyCoTools is a Python package aimed at providing a high level interface to COPASI tasks with an emphasis on model calibration. PyCoTools enables the construction of COPASI models and the execution of a subset of COPASI tasks including time courses, parameter scans and parameter estimations. Additional 'composite' tasks which use COPASI tasks as building blocks are available for increasing parameter estimation throughput, performing identifiability analysis and performing model selection. PyCoTools supports exploratory data analysis on parameter estimation data to assist with troubleshooting model calibrations. We demonstrate PyCoTools by posing a model selection problem designed to show case PyCoTools within a realistic scenario. The aim of the model selection problem is to test the feasibility of three alternative hypotheses in explaining experimental data derived from neonatal dermal fibroblasts in response to TGF-β over time. PyCoTools is used to critically analyse the parameter estimations and propose strategies for model improvement. PyCoTools can be downloaded from the Python Package Index (PyPI) using the command 'pip install pycotools' or directly from GitHub (https://github.com/CiaranWelsh/pycotools). Documentation at http://pycotools.readthedocs.io. Supplementary data are available at Bioinformatics.

Obtaining spheroplasts of armored dinoflagellates and first single-channel recordings of their ion channels using patch-clamping.

PubMed

Pozdnyakov, Ilya; Matantseva, Olga; Negulyaev, Yuri; Skarlato, Sergei

2014-09-05

Ion channels are tightly involved in various aspects of cell physiology, including cell signaling, proliferation, motility, endo- and exo-cytosis. They may be involved in toxin production and release by marine dinoflagellates, as well as harmful algal bloom proliferation. So far, the patch-clamp technique, which is the most powerful method to study the activity of ion channels, has not been applied to dinoflagellate cells, due to their complex cellulose-containing cell coverings. In this paper, we describe a new approach to overcome this problem, based on the preparation of spheroplasts from armored bloom-forming dinoflagellate Prorocentrum minimum. We treated the cells of P. minimum with a cellulose synthesis inhibitor, 2,6-dichlorobenzonitrile (DCB), and found out that it could also induce ecdysis and arrest cell shape maintenance in these microalgae. Treatment with 100-250 µM DCB led to an acceptable 10% yield of P. minimum spheroplasts and was independent of the incubation time in the range of 1-5 days. We show that such spheroplasts are suitable for patch-clamping in the cell-attached mode and can form 1-10 GOhm patch contact with a glass micropipette, allowing recording of ion channel activity. The first single-channel recordings of dinoflagellate ion channels are presented.

Obtaining Spheroplasts of Armored Dinoflagellates and First Single-Channel Recordings of Their Ion Channels Using Patch-Clamping

PubMed Central

Pozdnyakov, Ilya; Matantseva, Olga; Negulyaev, Yuri; Skarlato, Sergei

2014-01-01

Ion channels are tightly involved in various aspects of cell physiology, including cell signaling, proliferation, motility, endo- and exo-cytosis. They may be involved in toxin production and release by marine dinoflagellates, as well as harmful algal bloom proliferation. So far, the patch-clamp technique, which is the most powerful method to study the activity of ion channels, has not been applied to dinoflagellate cells, due to their complex cellulose-containing cell coverings. In this paper, we describe a new approach to overcome this problem, based on the preparation of spheroplasts from armored bloom-forming dinoflagellate Prorocentrum minimum. We treated the cells of P. minimum with a cellulose synthesis inhibitor, 2,6-dichlorobenzonitrile (DCB), and found out that it could also induce ecdysis and arrest cell shape maintenance in these microalgae. Treatment with 100–250 µM DCB led to an acceptable 10% yield of P. minimum spheroplasts and was independent of the incubation time in the range of 1–5 days. We show that such spheroplasts are suitable for patch-clamping in the cell-attached mode and can form 1–10 GOhm patch contact with a glass micropipette, allowing recording of ion channel activity. The first single-channel recordings of dinoflagellate ion channels are presented. PMID:25199048

Hypoglycemia and Medical Expenses in Patients with Type 2 Diabetes Mellitus: An Analysis Based on the Korea National Diabetes Program Cohort.

PubMed

Rhee, Sang Youl; Hong, Soo Min; Chon, Suk; Ahn, Kyu Jeung; Kim, Sung Hoon; Baik, Sei Hyun; Park, Yong Soo; Nam, Moon Suk; Lee, Kwan Woo; Woo, Jeong-Taek; Kim, Young Seol

2016-01-01

Hypoglycemia is one of the most important adverse events in individuals with type 2 diabetes mellitus (T2DM). However, hypoglycemia-related events are usually overlooked and have been documented less in clinical practice. We evaluated the incidence, clinical characteristics, and medical expenses of hypoglycemia related events in T2DM patients based on the Korea National Diabetes Program (KNDP), which is the largest multi-center, prospective cohort in Korea (n = 4,350). For accurate outcomes, the KNDP data were merged with claims data from the Health Insurance Review and Assessment Service (HIRA) of Korea. During a median follow-up period of 3.23 years (95% CI: 3.14, 3.19), 88 subjects (2.02%) were newly diagnosed with hypoglycemia, and the incidence of hypoglycemia was 6.44 cases per 1,000 person-years (PY). Individuals with hypoglycemia were significantly older (59.7±10.7 vs. 53.3±10.4 years, p < 0.001), had more hospital visits (121.94±126.88 days/PY, p < 0.001), had a longer hospital stays (16.13±29.21 days/PY, p < 0.001), and incurred greater medical costs ($2,447.56±4,056.38 vs. $1,336.37±3,403.39 /PY, p < 0.001) than subjects without hypoglycemia. Hypoglycemia-related events were infrequently identified among the medical records of T2DM subjects. However, they were associated significantly with poor clinical outcomes, and thus, hypoglycemia could have a substantial burden on the Korean national healthcare system.

Understanding the fate of black (pyrogenic) carbon in soil: Preliminary results from a long term field trial

NASA Astrophysics Data System (ADS)

Meredith, Will; Ascough, Philippa; Bird, Michael; Large, David; Shen, Licheng; Snape, Colin

2014-05-01

Black carbon (BC, also known as pyrogenic carbon) is an 'inert' form of carbon and has been proposed as a means of long-term carbon sequestration, particularly by amending soils and sediments with BC known as biochar. While there is abundant anecdotal evidence of biochar stability over extended timescales it is essential to gain a greater understanding of the degree and mechanisms of biochar degradation in the environment. This study aims to quantitatively assess the stability of biochar by investigating samples from field degradation trials first buried during 2009 in a tropical soil, and recovered after 12 and 36 month intervals. Catalytic hydropyrolysis (HyPy) is a novel analytical tool for the isolation of BC [1] in which high hydrogen pressure (150 bar) and a sulphided Mo catalyst reductively remove the non-BC fraction of the chars, and so isolate the most stable portion of the biochar, defined as BC(HyPy). This method also allows for the non-BC(HyPy) fraction of a sample, which from charcoal is known to include small ring PAHs (<7 rings) of pyrogenic origin to be recovered for molecular characterisation by GC-MS [2]. Biochars made from algae, sugarcane bagasse, and beech wood at 305, 414 and 512°C were emplaced under a variety of conditions allowing variables such as leaf cover, soil depth and pH to be investigated. Char stability (as measured by BC(HyPy) content) is dependent on both the feedstock and temperature of formation. HyPy is known to discriminate (in terms of BC isolation) against low temperature chars, composed of relatively small aromatic clusters [1], resulting in the low BC(HyPy) contents reported for the 305°C chars. Fresh charcoals, and those not subject to environmental degradation have display a similar distribution of aromatic clusters in the non-BC(HyPy) fraction, with 2 to 7 ring PAHs abundant [2]. However, environmentally degraded charcoals such as that from a Chinese river sediment, and an Australian river estuary [3] show a more restricted distribution with markedly fewer 2- and 3- ring PAH structures apparent. This may be evidence for the partial solubilisation of the charcoal as observed for a forest soil [4] and suggested as a mechanism for the transport of BC to the oceans [5], implying that BC cycling could be faster than previously thought [6]. Longer term field trials will be required (analysis of the 36 month samples) to observe systematic changes in the PAH distribution of the non-BCC(HyPy) fractions isolated form aged chars, although natural analogues with a better constrained environmental history may also be useful. [1] Meredith, W. et al., 2012. Geochimica et Cosmochimica Acta 97, 131-147. [2] Ascough, P.L. et al., 2010. Radiocarbon 52, 1336-1350. [3] Lockhart, R.S. et al., 2013. Journal of Analytical and Applied Pyrolysis 104, 640-652. [4] Hockaday, W.C. et al., 2007. Geochimica et Cosmochimica Acta 71, 3432-3445. [5] Jaffe, R. et al., 2013. Science 340, 345-347. [6] Zimmerman, M. et al., 2012. Global Change Biology 18, 3306-3316.

Water network-mediated, electron-induced proton transfer in [C5H5N ṡ (H2O)n]- clusters

NASA Astrophysics Data System (ADS)

DeBlase, Andrew F.; Wolke, Conrad T.; Weddle, Gary H.; Archer, Kaye A.; Jordan, Kenneth D.; Kelly, John T.; Tschumper, Gregory S.; Hammer, Nathan I.; Johnson, Mark A.

2015-10-01

The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ṡ (H2O)n=3-5]- clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH(0), occupying one of the primary solvation sites of the OH-. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the "solvent coordinate" at the heart of a prototypical proton-coupled electron transfer reaction.

Slow crack growth measurement using an electrical grid

NASA Technical Reports Server (NTRS)

Martin, D. J.; Davido, K. W.; Scott, W. D.

1986-01-01

Photolithography was used to produce a resistance grid on the surface of a DCB fracture specimen. The grid line spacings were 10 microns over a distance of 2 cm. Slow crack growth was measured on soda-lime-silica glass. At low values of K(I) (0.3 to 0.4 MPa.sq r + m, increased. Equations are given for the design of grids. The grid technique could be used to measure very slow crack growth at high temperature with appropriate compatible metal-ceramic materials.

Binuclear Phthalocyanines as Model Electrocatalysts for the Reduction of Oxygen.

DTIC Science & Technology

1985-05-01

solution, in which case the final product is Co(II)Pc. Aqueous acid addition (under nitrogen) to Co(I)Pc (in DCB/OH-) yields Co(II)Pc and presumably hydrogen ...little doubt, given the tendency for Co(I) to reduce aqueous acid to hydrogen [101, that hydrogen is produced in this reaction, though it was not proven...reduction occurs in water by a 2-electron process to hydrogen peroxide or a 4-electron process to water. This latter process must be catalysed on a

Pyrolysis-combustion 14C dating of soil organic matter

USGS Publications Warehouse

Wang, Hongfang; Hackley, Keith C.; Panno, S.V.; Coleman, D.D.; Liu, J.C.-L.; Brown, J.

2003-01-01

Radiocarbon (14C) dating of total soil organic matter (SOM) often yields results inconsistent with the stratigraphic sequence. The onerous chemical extractions for SOM fractions do not always produce satisfactory 14C dates. In an effort to develop an alternative method, the pyrolysis-combustion technique was investigated to partition SOM into pyrolysis volatile (Py-V) and pyrolysis residue (Py-R) fractions. The Py-V fractions obtained from a thick glacigenic loess succession in Illinois yielded 14C dates much younger but more reasonable than the counterpart Py-R fractions for the soil residence time. Carbon isotopic composition (??13C) was heavier in the Py-V fractions, suggesting a greater abundance of carbohydrate- and protein-related constituents, and ??13C was lighter in the Py-R fractions, suggesting more lignin- and lipid-related constituents. The combination of 14C dates and ??13C values indicates that the Py-V fractions are less biodegradation resistant and the Py-R fractions are more biodegradation resistant. The pyrolysis-combustion method provides a less cumbersome approach for 14C dating of SOM fractions. With further study, this method may become a useful tool for analyzing unlithified terrestrial sediments when macrofossils are absent. ?? 2003 University of Washington. Published by Elsevier Inc. All rights reserved.

Synthesis, crystal structure and cytotoxic activity of ruthenium(II) piano-stool complex with N,N-chelating ligand

NASA Astrophysics Data System (ADS)

Rogala, Patrycja; Jabłońska-Wawrzycka, Agnieszka; Kazimierczuk, Katarzyna; Borek, Agnieszka; Błażejczyk, Agnieszka; Wietrzyk, Joanna; Barszcz, Barbara

2016-12-01

A mononuclear compound of the general formula [(η6-p-cymene)RuIICl(2,2‧-PyBIm)]PF6 has been synthesized from a bidentate N,N-donor ligand, viz. 2,-(2‧-pyridyl)benzimidazole (2,2‧-PyBIm) and the corresponding chloro-complex [(η6-p-cymene)Ru(μ-Cl)Cl]2 (precursor). The isolated coordination compound was characterized by IR, UV-vis and 1H, 13C NMR spectroscopies. The single crystal X-ray analysis of the complex reveals that the asymmetric part of the unit cell consists of two symmetrically independent, [(η6-p-cymene)RuCl(2,2‧-PyBIm)]+ cationic complexes. Each cation exhibits a pseudo-octahedral three-legged piano-stool geometry, in which three "legs" are occupied by one chloride ion and two nitrogen donor atoms of the chelating ligand 2,2‧-PyBIm. The Hirshfeld surface analysis of obtained complex was determined, too. The ionic nature of the compound is identified by a strong band at around 830 cm-1 due to the νP-F stretching mode of the PF6- counter ion. The electronic spectrum of this monomeric complex displays high intensity bands in the ultraviolet region assignable to π→π*/n→π* transitions, as well as a band attributable to the metal-to-ligand charge transfer (MLCT) dπ(Ru)→π*(L) transition. Additionally, the complex has been screened for its cytotoxicity against three human cancer lines: non-small cell lung carcinoma (A549), colon adenocarcinoma (HT29) and breast adenocarcinoma (MCF-7) as well as normal mice fibroblast cells (BALB/3T3). The complex demonstrated a moderate antiproliferative activity against the cell lines tested.

Influence of long-term land use (arable and forest) and soil mineralogy on organic carbon stocks as well as composition and stability of soil organic matter

NASA Astrophysics Data System (ADS)

Kaiser, M.; Ellerbrock, R. H.; Wulf, M.; Dultz, S.; Hierath, C.; Sommer, M.

2009-04-01

The function of soils to sequester organic carbon (OC) and their related potential to mitigate the greenhouse effect is strongly affected by land use and soil mineralogy. This study is aimed to clarify long-term impacts of arable and forest land use as well as soil mineralogy on topsoil soil organic carbon (SOC) stocks as well as soil organic matter (SOM) composition and stability. Topsoil samples were taken from deciduous forest and adjacent arable sites (within Germany) that are continuously used for more than 100 years. The soils are different in genesis (Albic and Haplic Luvisol (AL, HL), Colluvic and Haplic Regosol (CR, HR), Haplic and Vertic Cambisol (HC, VC), Haplic Stagnosol (HSt)). First, particulate and water soluble organic matter were separated from the topsoil samples (Ap and Ah horizons). From the remaining solid extraction residues the Na-pyrophosphate soluble organic matter fractions (OM(PY)) were extracted, analysed for its OC content (OC(PY)) and characterized by FTIR spectroscopy and 14C analyses. The SOC stocks calculated for 0-40 cm depth are in general larger for the forest as compared to the adjacent arable soils (except VC). The largest difference between forest and arable topsoils was detected for the HR site (5.9 kg m-2) and seemed to be caused by a two times larger stock of exchangeable Ca of the forest topsoil. For the arable topsoils multiple regression analyses indicate a strong influence of clay, oxalate soluble Al and pyrophosphate soluble Mg on the content of OC(PY) weighted with its C=O content. Such relation is not found for the forest topsoils. Further, a positive relation between Δ14C values of OM(PY) and the following independent variables: (i) specific mineral surface area, (ii) relative C=O group content in OM(PY) and (iii) soil pH is found for the arable topsoils (pH 6.7 - 7.5) suggesting an increase in OM(PY) stability with increasing interactions between OM(PY) and soil mineral surfaces via cation bridging. A similar relation is found for the forest topsoils (pH < 5) if the specific mineral surface area is excluded from the multiple regression. This finding and the higher OC(PY) content of the forest topsoils suggest that in these soils the OM(PY) components are mainly cross-linked by cations and did not interact with mineral surfaces. We assume cross-linking to be less effective for OM stabilization as compared to cation bridging with mineral surfaces since Δ14C data indicate the OM(PY) from the forest topsoils to be less stable than that from arable topsoils.

Rush-hour aromatic and chlorinated hydrocarbons in selected subway stations of Shanghai, China.

PubMed

Zhang, Yanli; Li, Chunlei; Wang, Xinming; Guo, Hai; Feng, Yanli; Chen, Jianmin

2012-01-01

Air samples were collected simultaneously at platform, mezzanine and outdoor in five typical stations of subway system in Shanghai, China using stainless steel canisters and analyzed by gas chromatography-mass selective detector (GC-MSD) after cryogenic preconcentration. Benzene, toluene, ethylbenzene and xylenes (BTEX) at the platforms and mezzanines inside the stations averaged (10.3 +/- 2.1), (38.7 +/- 9.0), (19.4 +/- 10.1) and (30.0 +/- 11.1) microg/m3, respectively; while trichloroethylene (TrCE), tetrachloroethylene (TeCE) and para-dichlorobenzene (pDCB), vinyl chloride and carbon tetrachloride were the most abundant chlorinated hydrocarbons inside the stations with average levels of (3.6 +/- 1.3), (1.3 +/- 0.5), (4.1 +/- 1.1), (2.2 +/- 1.1) and (1.2 +/- 0.3) microg/m3, respectively. Mean levels of major aromatic and chlorinated hydrocarbons were higher indoor (platforms and mezzanines) than outdoor with average indoor/outdoor (I/O) ratios of 1.1-9.5, whereas no significant indoor/outdoor differences were found except for benzene and TrCE. The highly significant mutual correlations (p < 0.01) for BTEX between indoor and outdoor and their significant correlation (p < 0.05) with methyl tert-butyl ether (MTBE), a marker of traffic-related emission without other indoor and outdoor sources, indicated that BTEX were introduced into the subway stations from indoor/outdoor air exchange and traffic emission should be their dominant source. TrCE and pDCB were mainly from indoor emission and TeCE might have both indoor emission sources and contribution from outdoor air, especially in the mezzanines.

PlasmaPy: initial development of a Python package for plasma physics

NASA Astrophysics Data System (ADS)

Murphy, Nicholas; Leonard, Andrew J.; Stańczak, Dominik; Haggerty, Colby C.; Parashar, Tulasi N.; Huang, Yu-Min; PlasmaPy Community

2017-10-01

We report on initial development of PlasmaPy: an open source community-driven Python package for plasma physics. PlasmaPy seeks to provide core functionality that is needed for the formation of a fully open source Python ecosystem for plasma physics. PlasmaPy prioritizes code readability, consistency, and maintainability while using best practices for scientific computing such as version control, continuous integration testing, embedding documentation in code, and code review. We discuss our current and planned capabilities, including features presently under development. The development roadmap includes features such as fluid and particle simulation capabilities, a Grad-Shafranov solver, a dispersion relation solver, atomic data retrieval methods, and tools to analyze simulations and experiments. We describe several ways to contribute to PlasmaPy. PlasmaPy has a code of conduct and is being developed under a BSD license, with a version 0.1 release planned for 2018. The success of PlasmaPy depends on active community involvement, so anyone interested in contributing to this project should contact the authors. This work was partially supported by the U.S. Department of Energy.

Nonlocal electrical detection of spin accumulation generated by anomalous Hall effect in mesoscopic N i81F e19 films

NASA Astrophysics Data System (ADS)

Qin, Chuan; Chen, Shuhan; Cai, Yunjiao; Kandaz, Fatih; Ji, Yi

2017-10-01

Spin accumulation generated by the anomalous Hall effect (AHE) in mesoscopic ferromagnetic N i81F e19 (permalloy, Py) films is detected electrically by a nonlocal method. The reciprocal phenomenon, the inverse spin Hall effect (ISHE), can also be generated and detected all electrically in the same structure. For accurate quantitative analysis, a series of nonlocal AHE/ISHE structures and supplementary structures are fabricated on each sample substrate to account for statistical variations and to accurately determine all essential physical parameters in situ. By exploring Py thicknesses of 4, 8, and 12 nm, the Py spin diffusion length λPy is found to be much shorter than the film thicknesses. The product of λPy and the Py spin Hall angle αSH is determined to be independent of thickness and resistivity: αSHλPy=(0.066 ±0.009 ) nm at 5 K and (0.041 ±0.010 )nm at 295 K. These values are comparable to those obtained from mesoscopic Pt films.

Cyclopentadiene evolution during pyrolysis-gas chromatography of PMR polyimides

NASA Technical Reports Server (NTRS)

Alston, William B.; Gluyas, Richard E.; Snyder, William J.

1992-01-01

The effect of formulated molecular weight (FMW), extent of cure, and cumulative aging on the amount of cyclopentadiene (CPD) evolved from Polymerization of Monomeric Reactants (PMR) polyimides were investigated by pyrolysis-gas chromotography (PY-GC). The PMR polyimides are additional crosslinked resins formed from an aromatic diamine, a diester of an aromatic tetracarboxylic acid and a monoester of 5-norbornene-2, 3-dicarboxylic acid. The PY-GC results were related to the degree of crosslinking and to the thermo-oxidative stability (weight loss) of PMR polyimides. Thus, PY-GC has shown to be a valid technique for the characterization of PMR polyimide resins and composites via correlation of the CPD evolved versus the thermal history of the PMR sample.

Effect of ionic liquid treatment on the ultrastructural and topochemical features of compression wood in Japanese cedar (Cryptomeria japonica).

PubMed

Kanbayashi, Toru; Miyafuji, Hisashi

2016-07-18

The morphological and topochemical changes in wood tissues in compression wood of Japanese cedar (Cryptomeria japonica) upon treated with two types of ionic liquids, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and 1-ethylpyridinium bromide ([EtPy][Br]) were investigated. Compression wood tracheids were swollen by both ionic liquids but their swelling behaviors were different in the types of ionic liquids used. Under the polarized light, we confirmed that crystalline cellulose in compression wood is amorphized by [C2mim][Cl] treatment whereas it changes slightly by [EtPy][Br] treatment. Raman microscopic analyses revealed that [C2mim][Cl] can preferentially liquefy polysaccharides in compression wood whereas [EtPy][Br] liquefy lignin. In addition, the interaction of compression wood with ionic liquids is different for the morphological regions. These results will assist in the use of ionic liquid treatment of woody biomass to produce valuable chemicals, bio-fuels, bio-based composites and other products.

Effect of ionic liquid treatment on the ultrastructural and topochemical features of compression wood in Japanese cedar (Cryptomeria japonica)

PubMed Central

Kanbayashi, Toru; Miyafuji, Hisashi

2016-01-01

The morphological and topochemical changes in wood tissues in compression wood of Japanese cedar (Cryptomeria japonica) upon treated with two types of ionic liquids, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and 1-ethylpyridinium bromide ([EtPy][Br]) were investigated. Compression wood tracheids were swollen by both ionic liquids but their swelling behaviors were different in the types of ionic liquids used. Under the polarized light, we confirmed that crystalline cellulose in compression wood is amorphized by [C2mim][Cl] treatment whereas it changes slightly by [EtPy][Br] treatment. Raman microscopic analyses revealed that [C2mim][Cl] can preferentially liquefy polysaccharides in compression wood whereas [EtPy][Br] liquefy lignin. In addition, the interaction of compression wood with ionic liquids is different for the morphological regions. These results will assist in the use of ionic liquid treatment of woody biomass to produce valuable chemicals, bio-fuels, bio-based composites and other products. PMID:27426470

Study of the structure of PyHReO{sub 4} under high pressure

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

Kichanov, S. E., E-mail: ekich@nf.jinr.ru; Kozlenko, D. P.; Wasicki, J. W.

2007-05-15

The structure of deuterated pyridinium perrhenate (d{sub 5}PyH)ReO{sub 4} (C{sub 5}D{sub 5}NHReO{sub 4}) is studied by X-ray diffraction at room temperature and pressures up to 3.5 GPa and by neutron diffraction in the temperature range 10-293 K and at pressures up to 2.0 GPa. Under normal conditions, this compound belongs to the orthorhombic space group Cmc2{sub 1} (ferroelectric phase II). At room temperature and pressures above P > 0.7 GPa, a transition to an orthorhombic phase (paraelectric phase II) is observed. This paraelectric phase is described by the space group Cmcm. At a pressure as high as P = 2.0more » GPa, phase I remains stable at temperatures down to 10 K. This fact indicates that the high pressure suppresses the ferroelectric state in deuterated pyridinium perrhenate (d{sub 5}PyH)ReO{sub 4}.« less

A Mouse Polyomavirus-encoded microRNA Targets the Cellular Apoptosis Pathway through Smad2 Inhibition

PubMed Central

Sung, Chang Kyoo; Yim, Hyungshin; Andrews, Erik; Benjamin, Thomas L.

2014-01-01

Some viruses and most eukaryotic cells have microRNAs that regulate the expression of many genes. Although many viral miRNAs have been identified, only a few have been included in in vivo functional studies. Here we show that a Py-encoded miRNA downregulates the expression of the pro-apoptotic factor Smad2, resulting in the suppression of the apoptosis pathway. To study the Py miRNA in an in vivo context, a miRNA-deficient mutant virus was created on the background of the LID virus strain which establishes a rapid and lethal infection in newborn mice. Apoptosis analysis on kidney tissues indicates that the pro-apoptotic pathway is targeted in the infected host as well. Suppression of apoptosis through targeting of Smad2 by the Py miRNA is expected to synergize with anti-apoptotic effects previously attributed to the polyoma tumor antigens in support of virus replication in the natural host. PMID:25146733

Cupric Oxide (CuO) Oxidation Detects Pyrogenic Carbon in Burnt Organic Matter and Soils.

PubMed

Hatten, Jeff; Goñi, Miguel

2016-01-01

Wildfire greatly impacts the composition and quantity of organic carbon stocks within watersheds. Most methods used to measure the contributions of fire altered organic carbon-i.e. pyrogenic organic carbon (Py-OC) in natural samples are designed to quantify specific fractions such as black carbon or polyaromatic hydrocarbons. In contrast, the CuO oxidation procedure yields a variety of products derived from a variety of precursors, including both unaltered and thermally altered sources. Here, we test whether or not the benzene carboxylic acid and hydroxy benzoic acid (BCA) products obtained by CuO oxidation provide a robust indicator of Py-OC and compare them to non-Py-OC biomarkers of lignin. O and A horizons from microcosms were burned in the laboratory at varying levels of fire severity and subsequently incubated for 6 months. All soils were analyzed for total OC and N and were analyzed by CuO oxidation. All BCAs appeared to be preserved or created to some degree during burning while lignin phenols appeared to be altered or destroyed to varying extents dependent on fire severity. We found two specific CuO oxidation products, o-hydroxybenzoic acid (oBd) and 1,2,4-benzenetricarboxylic acid (BTC2) that responded strongly to burn severity and withstood degradation during post-burning microbial incubations. Interestingly, we found that benzene di- and tricarboxylic acids (BDC and BTC, respectively) were much more reactive than vanillyl phenols during the incubation as a possible result of physical protection of vanillyl phenols in the interior of char particles or CuO oxidation derived BCAs originating from biologically available classes of Py-OC. We found that the ability of these compounds to predict relative Py-OC content in burned samples improved when normalized by their respective BCA class (i.e. benzene monocarboxylic acids (BA) and BTC, respectively) and when BTC was normalized to total lignin yields (BTC:Lig). The major trends in BCAs imparted by burning persisted through a 6 month incubation suggesting that fire severity had first order control on BCA and lignin composition. Using original and published BCA data from soils, sediments, char, and interfering compounds we found that BTC:Lig and BTC2:BTC were able to distinguish Py-OC from compounds such as humic materials, tannins, etc. The BCAs released by the CuO oxidation procedure increase the functionality of this method in order to examine the relative contribution of Py-OC in geochemical samples.

Cupric Oxide (CuO) Oxidation Detects Pyrogenic Carbon in Burnt Organic Matter and Soils

PubMed Central

Hatten, Jeff; Goñi, Miguel

2016-01-01

Wildfire greatly impacts the composition and quantity of organic carbon stocks within watersheds. Most methods used to measure the contributions of fire altered organic carbon–i.e. pyrogenic organic carbon (Py-OC) in natural samples are designed to quantify specific fractions such as black carbon or polyaromatic hydrocarbons. In contrast, the CuO oxidation procedure yields a variety of products derived from a variety of precursors, including both unaltered and thermally altered sources. Here, we test whether or not the benzene carboxylic acid and hydroxy benzoic acid (BCA) products obtained by CuO oxidation provide a robust indicator of Py-OC and compare them to non-Py-OC biomarkers of lignin. O and A horizons from microcosms were burned in the laboratory at varying levels of fire severity and subsequently incubated for 6 months. All soils were analyzed for total OC and N and were analyzed by CuO oxidation. All BCAs appeared to be preserved or created to some degree during burning while lignin phenols appeared to be altered or destroyed to varying extents dependent on fire severity. We found two specific CuO oxidation products, o-hydroxybenzoic acid (oBd) and 1,2,4-benzenetricarboxylic acid (BTC2) that responded strongly to burn severity and withstood degradation during post-burning microbial incubations. Interestingly, we found that benzene di- and tricarboxylic acids (BDC and BTC, respectively) were much more reactive than vanillyl phenols during the incubation as a possible result of physical protection of vanillyl phenols in the interior of char particles or CuO oxidation derived BCAs originating from biologically available classes of Py-OC. We found that the ability of these compounds to predict relative Py-OC content in burned samples improved when normalized by their respective BCA class (i.e. benzene monocarboxylic acids (BA) and BTC, respectively) and when BTC was normalized to total lignin yields (BTC:Lig). The major trends in BCAs imparted by burning persisted through a 6 month incubation suggesting that fire severity had first order control on BCA and lignin composition. Using original and published BCA data from soils, sediments, char, and interfering compounds we found that BTC:Lig and BTC2:BTC were able to distinguish Py-OC from compounds such as humic materials, tannins, etc. The BCAs released by the CuO oxidation procedure increase the functionality of this method in order to examine the relative contribution of Py-OC in geochemical samples. PMID:27011012

DendroPy: a Python library for phylogenetic computing.

PubMed

Sukumaran, Jeet; Holder, Mark T

2010-06-15

DendroPy is a cross-platform library for the Python programming language that provides for object-oriented reading, writing, simulation and manipulation of phylogenetic data, with an emphasis on phylogenetic tree operations. DendroPy uses a splits-hash mapping to perform rapid calculations of tree distances, similarities and shape under various metrics. It contains rich simulation routines to generate trees under a number of different phylogenetic and coalescent models. DendroPy's data simulation and manipulation facilities, in conjunction with its support of a broad range of phylogenetic data formats (NEXUS, Newick, PHYLIP, FASTA, NeXML, etc.), allow it to serve a useful role in various phyloinformatics and phylogeographic pipelines. The stable release of the library is available for download and automated installation through the Python Package Index site (http://pypi.python.org/pypi/DendroPy), while the active development source code repository is available to the public from GitHub (http://github.com/jeetsukumaran/DendroPy).

uPy: a ubiquitous CG Python API with biological-modeling applications.

PubMed

Autin, Ludovic; Johnson, Graham; Hake, Johan; Olson, Arthur; Sanner, Michel

2012-01-01

The uPy Python extension module provides a uniform abstraction of the APIs of several 3D computer graphics programs (called hosts), including Blender, Maya, Cinema 4D, and DejaVu. A plug-in written with uPy can run in all uPy-supported hosts. Using uPy, researchers have created complex plug-ins for molecular and cellular modeling and visualization. uPy can simplify programming for many types of projects (not solely science applications) intended for multihost distribution. It's available at http://upy.scripps.edu. The first featured Web extra is a video that shows interactive analysis of a calcium dynamics simulation. YouTube URL: http://youtu.be/wvs-nWE6ypo. The second featured Web extra is a video that shows rotation of the HIV virus. YouTube URL: http://youtu.be/vEOybMaRoKc.

Reaction Kinetics of Phenolic Antioxidants toward Photoinduced Pyranine Free Radicals in Biological Models.

PubMed

Aspée, Alexis; Aliaga, Christian; Maretti, Luca; Zúñiga-Núñez, Daniel; Godoy, Jessica; Pino, Eduardo; Cárdenas-Jirón, Gloria; Lopez-Alarcon, Camilo; Scaiano, Juan C; Alarcon, Emilio I

2017-07-06

8-Hydroxy-1,3,6-pyrenetrisulfonic acid (pyranine, PyOH) free radicals were induced by laser excitation at visible wavelengths (470 nm). The photochemical process involves photoelectron ejection from PyO- to produce PyO• and PyO•- with maxima absorption at 450 and 510 nm, respectively. The kinetic rate constants for phenolic antioxidants with PyO•, determined by nanosecond time-resolved spectroscopy, were largely reliant on the ionic strength depending on the antioxidant phenol/phenolate dissociation constant. Further, the apparent rate constant measured in the presence of Triton X100 micelles was influenced by the antioxidant partition between the micelle and the dispersant aqueous media but limited by its exit rates from the micelle. Similarly, the rate reaction between ascorbic acid and PyO• was markedly affected by the presence of human serum albumin responding to the dynamic of the ascorbic acid binding to the protein.

Computational Workbench for Multibody Dynamics

NASA Technical Reports Server (NTRS)

Edmonds, Karina

2007-01-01

PyCraft is a computer program that provides an interactive, workbenchlike computing environment for developing and testing algorithms for multibody dynamics. Examples of multibody dynamic systems amenable to analysis with the help of PyCraft include land vehicles, spacecraft, robots, and molecular models. PyCraft is based on the Spatial-Operator- Algebra (SOA) formulation for multibody dynamics. The SOA operators enable construction of simple and compact representations of complex multibody dynamical equations. Within the Py-Craft computational workbench, users can, essentially, use the high-level SOA operator notation to represent the variety of dynamical quantities and algorithms and to perform computations interactively. PyCraft provides a Python-language interface to underlying C++ code. Working with SOA concepts, a user can create and manipulate Python-level operator classes in order to implement and evaluate new dynamical quantities and algorithms. During use of PyCraft, virtually all SOA-based algorithms are available for computational experiments.

Changes over time in risk factors for cardiovascular disease and use of lipid-lowering drugs in HIV-infected individuals and impact on myocardial infarction.

PubMed

Sabin, C A; d'Arminio Monforte, A; Friis-Moller, N; Weber, R; El-Sadr, W M; Reiss, P; Kirk, O; Mercie, P; Law, M G; De Wit, S; Pradier, C; Phillips, A N; Lundgren, J D

2008-04-01

Because of the known relationship between exposure to combination antiretroviral therapy and cardiovascular disease (CVD), it has become increasingly important to intervene against risk of CVD in human immunodeficiency virus (HIV)-infected patients. We evaluated changes in risk factors for CVD and the use of lipid-lowering therapy in HIV-infected individuals and assessed the impact of any changes on the incidence of myocardial infarction. The Data Collection on Adverse Events of Anti-HIV Drugs Study is a collaboration of 11 cohorts of HIV-infected patients that included follow-up for 33,389 HIV-infected patients from December 1999 through February 2006. The proportion of patients at high risk of CVD increased from 35.3% during 1999-2000 to 41.3% during 2005-2006. Of 28,985 patients, 2801 (9.7%) initiated lipid-lowering therapy; initiation of lipid-lowering therapy was more common for those with abnormal lipid values and those with traditional risk factors for CVD (male sex, older age, higher body mass index [calculated as the weight in kilograms divided by the square of the height in meters], family and personal history of CVD, and diabetes mellitus). After controlling for these, use of lipid-lowering drugs became relatively less common over time. The incidence of myocardial infarction (0.32 cases per 100 person-years [PY]; 95% confidence interval [CI], 0.29-0.35 cases per 100 PY) appeared to remain stable. However, after controlling for changes in risk factors for CVD, the rate decreased over time (relative rate in 2003 [compared with 1999-2000], 0.73 cases per 100 PY [95% CI, 0.50-1.05 cases per 100 PY]; in 2004, 0.64 cases per 100 PY [95% CI, 0.44-0.94 cases per 100 PY]; in 2005-2006, 0.36 cases per 100 PY [95% CI, 0.24-0.56 cases per 100 PY]). Further adjustment for lipid levels attenuated the relative rates towards unity (relative rate in 2003 [compared with 1999-2000], 1.06 cases per 100 PY [95% CI, 0.63-1.77 cases per 100 PY]; in 2004, 1.02 cases per 100 PY [95% CI, 0.61-1.71 cases per 100 PY]; in 2005-2006, 0.63 cases per 100 PY [95% CI, 0.36-1.09 cases per 100 PY]). Although the CVD risk profile among patients in the Data Collection on Adverse Events of Anti-HIV Drugs Study has decreased since 1999, rates have remained relatively stable, possibly as a result of a more aggressive approach towards managing the risk of CVD.

PyR@TE 2: A Python tool for computing RGEs at two-loop

NASA Astrophysics Data System (ADS)

Lyonnet, F.; Schienbein, I.

2017-04-01

Renormalization group equations are an essential tool for the description of theories across different energy scales. Even though their expressions at two-loop for an arbitrary gauge field theory have been known for more than thirty years, deriving the full set of equations for a given model by hand is very challenging and prone to errors. To tackle this issue, we have introduced in Lyonnet et al. (2014) a Python tool called PyR@TE; Python Renormalization group equations @ Two-loop for Everyone. With PyR@TE, it is easy to implement a given Lagrangian and derive the complete set of two-loop RGEs for all the parameters of the theory. In this paper, we present the new version of this code, PyR@TE 2, which brings many new features and in particular it incorporates kinetic mixing when several U(1) gauge groups are involved. In addition, the group theory part has been greatly improved as we introduced a new Python module dubbed PyLie that deals with all the group theoretical aspects required for the calculation of the RGEs as well as providing very useful model building capabilities. This allows the use of any irreducible representation of the SU(n) , SO(2 n) and SO(2n + 1) groups. Furthermore, it is now possible to implement terms in the Lagrangian involving fields which can be contracted into gauge singlets in more than one way. As a byproduct, results for a popular model (SM + complex triplet) for which, to our knowledge, the complete set of two-loop RGEs has not been calculated before are presented in this paper. Finally, the two-loop RGEs for the anomalous dimension of the scalar and fermion fields have been implemented as well. It is now possible to export the coupled system of beta functions into a numerical C++ function, leading to a consequent speed up in solving them.

Organic Electrolytes for Sodium Batteries

DTIC Science & Technology

1992-09-01

3 melts. 3.5.2.3.1.1 Standard potential of copper couples in AICI3 :BuPyCI melts versus aluminum in 3 . 5.3.4.1 acidic 2:1 (molar) A1CI3BuPyCI melt...19 cell. 3 . 5.4 . 2 . 5.2 V LT-i-t Qig~res.z Typical discharge/charge curves for the AI/MEICI:AICI 3 :FcCI 3 /RVC system inan acidic 1.3. 1 methyl...a 3.5.4. 1.2 acidic MEICh:AICI 3 (XAICI3 =0. 6 0) melt. vii List of Figures. Charge/discharge (2 mA) performance of cycle 10 for the Na/Nasi- 3 . 5

Cyanopyridine Based Bipolar Host Materials for Green Electrophosphorescence with Extremely Low Turn-On Voltages and High Power Efficiencies.

PubMed

Li, Wei; Li, Jiuyan; Liu, Di; Li, Deli; Wang, Fang

2016-08-24

Low driving voltage and high power efficiency are basic requirements when practical applications of organic light emitting diodes (OLEDs) in displays and lighting are considered. Two novel host materials m-PyCNmCP and 3-PyCNmCP incorporating cyanopyridine moiety as electron-transporting unit are developed for use in fac-tris(2-phenylpyridine)iridium(III) (Ir(ppy)3) based green phosphorescent OLEDs (PhOLEDs). Extremely low turn-on voltages of 2.01 and 2.27 V are realized, which are even lower than the theoretical limit of the emitted photon energy (hv)/electron charge (e) (2.37 V) of Ir(ppy)3. High power efficiency of 101.4 lm/W (corresponding to a maximum external quantum efficiency of 18.4%) and 119.3 lm/W (24.7%) are achieved for m-PyCNmCP and 3-PyCNmCP based green PhOLEDs. The excellent EL performance benefits from the ideal parameters of host materials by combining cyano and pyridine to enhance the n-type feature. The energetic favorable alignment of HOMO/LUMO levels of hosts with adjacent layers and the dopant for easy charge injections and direct charge trapping by dopant, their bipolar feature to balance charge transportations, sufficiently high triplet energy and small singlet/triplet energy difference (0.38 and 0.43 eV) combine to be responsible for the extremely low driving voltages and high power efficiencies of the green PhOLEDs.

Superoxide Dismutase Mimetic, MnTE-2-PyP, Attenuates Chronic Hypoxia-Induced Pulmonary Hypertension, Pulmonary Vascular Remodeling, and Activation of the NALP3 Inflammasome

PubMed Central

Villegas, Leah R.; Kluck, Dylan; Field, Carlie; Oberley-Deegan, Rebecca E.; Woods, Crystal; Yeager, Michael E.; El Kasmi, Karim C.; Savani, Rashmin C.; Bowler, Russell P.

2013-01-01

Abstract Aims: Pulmonary hypertension (PH) is characterized by an oxidant/antioxidant imbalance that promotes abnormal vascular responses. Reactive oxygen species, such as superoxide (O2•−), contribute to the pathogenesis of PH and vascular responses, including vascular remodeling and inflammation. This study sought to investigate the protective role of a pharmacological catalytic antioxidant, a superoxide dismutase (SOD) mimetic (MnTE-2-PyP), in hypoxia-induced PH, vascular remodeling, and NALP3 (NACHT, LRR, and PYD domain-containing protein 3)–mediated inflammation. Results: Mice (C57/BL6) were exposed to hypobaric hypoxic conditions, while subcutaneous injections of MnTE-2-PyP (5 mg/kg) or phosphate-buffered saline (PBS) were given 3× weekly for up to 35 days. SOD mimetic-treated groups demonstrated protection against increased right ventricular systolic pressure, indirect measurements of pulmonary artery pressure, and RV hypertrophy. Vascular remodeling was assessed by Ki67 staining to detect vascular cell proliferation, α-smooth muscle actin staining to analyze small vessel muscularization, and hyaluronan (HA) measurements to assess extracellular matrix modulation. Activation of the NALP3 inflammasome pathway was measured by NALP3 expression, caspase-1 activation, and interleukin 1-beta (IL-1β) and IL-18 production. Hypoxic exposure increased PH, vascular remodeling, and NALP3 inflammasome activation in PBS-treated mice, while mice treated with MnTE-2-PyP showed an attenuation in each of these endpoints. Innovation: This study is the first to demonstrate activation of the NALP3 inflammasome with cleavage of caspase-1 and release of active IL-1 β and IL-18 in chronic hypoxic PH, as well as its attenuation by the SOD mimetic, MnTE-2-PyP. Conclusion: The ability of the SOD mimetic to scavenge extracellular O2•− supports our previous observations in EC-SOD-overexpressing mice that implicate extracellular oxidant/antioxidant imbalance in hypoxic PH and implicates its role in hypoxia-induced inflammation. Antioxid. Redox Signal. 18, 1753–1764. PMID:23240585