Spectroscopic characterization of the complex of vinyl radical and carbon dioxide : Matrix isolation and ab initio study

We report on the preparation and vibrational characterization of the C2H3 center dot center dot center dot CO2 complex, the first example of a stable intermolecular complex involving vinyl radicals. This complex was prepared in Ar and Kr matrices using UV photolysis of propiolic acid (HC3OOH) and subsequent thermal mobilization of H atoms. This preparation procedure provides vinyl radicals formed exclusively as a complex with CO2, without the presence of either CO2 or C2H3 monomers. The absorption bands corresponding to the nu(5)(C2H3), nu(7)(C2H3), nu(8)(C2H3), nu(2)(CO2), and nu(3)(CO2) modes of the C2H3 center dot center dot center dot CO2 complex were detected experimentally. The calculations at the UCCSD(T)/L2a level of theory predict two structures of the C2H3 center dot center dot center dot CO2 complex with C-s and C-1 symmetries and interaction energies of -1.92 and -5.19 kJ mol(-1). The harmonic vibrational frequencies of these structures were calculated at the same level of theory. The structural assignment of the experimental species is not straightforward because of rather small complexation-induced shifts and matrix-site splitting of the bands (for both complex and monomers). We conclude that the C-1 structure is the most probable candidate for the experimental C2H3 center dot center dot center dot O-2 complex based on the significant splitting of the bending vibration of CO2 and on the energetic and structural considerations. Published by AIP Publishing.Peer reviewe

Protective Effect of Meso-Tetrakis-(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin on the In Vivo Impact of Trimethyltin Chloride on the Antioxidative Defense System

The in vivo effect of trimethyltin chloride (Me(3)SnCl), free base meso-tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin (R′(4)PH(2)) and their equimolar mixture, on the enzymatic activity of catalase (CAT), superoxide dismutase (SOD), and on the total content of free sulfhydryl groups has been studied in rat liver and kidney. It was demonstrated that the simultaneous treatment of tested animals with the combination of Me(3)SnCl and R′(4)PH(2) reduced the toxic impact of Me(3)SnCl

Activation of Cytochrome C Peroxidase Function Through Coordinated Foldon Loop Dynamics upon Interaction with Anionic Lipids

Cardiolipin (CL) is a mitochondrial anionic lipid that plays important roles in the regulation and signaling of mitochondrial apoptosis. CL peroxidation catalyzed by the assembly of CL-cytochrome c (cyt c) complexes at the inner mitochondrial membrane is a critical checkpoint. The structural changes in the protein, associated with peroxidase activation by CL and different anionic lipids, are not known at a molecular level. To better understand these peripheral protein-lipid interactions, we compare how phosphatidylglycerol (PG) and CL lipids trigger cyt c peroxidase activation, and correlate functional differences to structural and motional changes in membrane-associated cyt c. Structural and motional studies of the bound protein are enabled by magic angle spinning solid state NMR spectroscopy, while lipid peroxidase activity is assayed by mass spectrometry. PG binding results in a surface-bound state that preserves a nativelike fold, which nonetheless allows for significant peroxidase activity, though at a lower level than binding its native substrate CL. Lipid-specific differences in peroxidase activation are found to correlate to corresponding differences in lipid-induced protein mobility, affecting specific protein segments. The dynamics of omega loops C and D are upregulated by CL binding, in a way that is remarkably controlled by the protein:lipid stoichiometry. In contrast to complete chemical denaturation, membrane-induced protein destabilization reflects a destabilization of select cyt c foldons, while the energetically most stable helices are preserved. Our studies illuminate the interplay of protein and lipid dynamics in the creation of lipid peroxidase-active proteolipid complexes implicated in early stages of mitochondrial apoptosis

Surface-Binding to Cardiolipin Nanodomains Triggers Cytochrome c Pro-apoptotic Peroxidase Activity via Localized Dynamics

The peroxidation of cardiolipins by reactive oxygen species, which is regulated and enhanced by cytochrome c (cyt c), is a critical signaling event in mitochondrial apoptosis. We probe the molecular underpinnings of this mitochondrial death signal through structural and functional studies of horse heart cyt c binding to mixed-lipid membranes containing cardiolipin with mono- and polyunsaturated acyl chains. Lipidomics reveal the selective oxidation of polyunsaturated fatty acid (PUFA) cardiolipin (CL), while multidimensional solid-state NMR probes the structure and dynamics of the membrane and the peripherally bound protein. The hydrophilic milieu at the membrane interface stabilizes a native-like fold, but also leads to localized flexibility at the membrane-interacting protein face. PUFA CL acts as both a preferred substrate and a dynamic regulator by affecting the dynamics of the cyt c N70-I85 Ω loop, which covers the heme cavity

Зависимость течения и исхода сепсиса от генетического варианта 3`-области гена аквапорина 4 (AQP4) и коморбидности

Aquaporins 4 and 5 are proteins that form water channels in the cell membrane, participate in the transfer and migration of immune cells, being expressed on many cell types including CNS astrocytes, kidney cells, lungs, and the immune system. We have previously shown that AQP5 genetic polymorphism is associated with different outcomes of abdominal sepsis. Since another common aquaporin protein, AQP4, is also expressed on the surface of immunocompetent cells, determining cell motility, it was suggested that AQP4 may also be important in the pathogenesis of sepsis, and that AQP4 polymorphism may predetermine sepsis severity and outcome. AQP4 rs1058427 genetic polymorphism has not been studied earlier.The aim of the study was to determine the effects of region 3` polymorphism in the AQP4 gene on the clinical course and outcome of sepsis.Materials and methods. The prospective study included 290 ICU patients from three clinical hospitals in Moscow aged 18-75 years with clinical signs of sepsis (SEPSIS-3, 2016).Results. It was found that the minor T allele of the AQP4 rs1058427 gene provides strong protection against septic shock, as among GG genotype carriers septic shock developed in 66%, but in presence of the minor T allele this number dropped two-fold (p=0.009, Fisher’s exact test, OR=1.99, 95% CI: 1.12-3.55, n=290). There was a significant association between AQP4 rs1058427 genetic polymorphism and 30-day hospital mortality in a subgroup of patients with more severe organ dysfunction and higher comorbidity burden (cardiovascular diseases, type II diabetes mellitus) requiring extracorporeal treatment modalities and ventilator support for 5 or more days (n=66). Carriers of the minor T allele showed better survival rates as compared AQP4 rs1058427 GG genotype carriers (5 deaths out of 10 and 47 deaths out of 56, respectively, p=0.003, Fisher’s exact test, n=66, OR=5.22, 95% CI: 1.25-21.82, P=0.009, log-rank criterion).Conclusion. The minor AQP4 rs1058427 T allele is associated with protection against septic shock and better survival in sepsis in a group of ICU patients with high comorbidity burden requiring extracorporeal life support interventions.Аквапорины 4 и 5 - белки, образующие водный канал в мембране клетки, участвующие в движении и миграции иммунных клеток и выявляющиеся на поверхности астроцитов ЦНС, клеток почек, легких, иммунной системы. Ранее мы показали, что генетический полиморфизм AQP5 ассоциируется с различными исходами абдоминального сепсиса. Поскольку другой распространенный аквапорин - белок AQP4 тоже экспрессируется на поверхности иммунокомпетентных клеток, определяя клеточную подвижность, предположили, что и он может иметь значение в патогенезе сепсиса, а полиморфизм AQP4 - определять тяжесть течения и исход сепсиса. Ранее генетический полиморфизм AQP4 rs1058427 при сепсисе не исследовали.Целью исследования явилось определение вклада полиморфизма 3`-области гена AQP4 в течение и исход сепсиса.Материалы и методы. В проспективное исследование включили 290 пациентов ОРИТ трех клинических больниц г. Москвы в возрасте 18-75 лет с клиническими признаками сепсиса (СЕПСИС-3, 2016).Результаты. Обнаружили, что минорный аллель T гена AQP4 rs1058427 защищает от развития септического шока при сепсисе. Среди пациентов-носителей генотипа GG септический шок развился у 66 %, у пациентов с минорной аллелью T – только в половине случаев (Р=0,009, ТМФ, ОШ=1,99, 95% ДИ: 1,12-3,55, n=290). В группе пациентов с более тяжелыми органными нарушениями и высокой частотой коморбидных состояний (сердечно-сосудистые заболевания, сахарный диабет второго типа), нуждающихся в экстракорпоральных методов лечения и находившихся на ИВЛ 5 и более суток (n=66), была обнаружена значимая ассоциация генетического полиморфизма AQP4 rs1058427 и 30-дневной госпитальной летальности. Носители минорного аллеля T выживали чаще по сравнению с пациентами генотипа AQP4 rs1058427 GG (5 летальных исходов из 10 и 47 летальных исходов из 56, соответственно, P=0,003, ТМФ, n=66, ОШ=5,22, 95% ДИ: 1,25- 21,82, P=0,009, лог-ранговый критерий). Заключение. Минорный аллель AQP4 rs1058427 T ассоциируется с защитой от развития септического шока и лучшей выживаемостью при сепсисе в группе пациентов ОРИТ с выраженной коморбидностью и нуждающихся в экстракорпоральных методах жизнеобеспечения

Alignment of the CMS tracker with LHC and cosmic ray data

© CERN 2014 for the benefit of the CMS collaboration, published under the terms of the Creative Commons Attribution 3.0 License by IOP Publishing Ltd and Sissa Medialab srl. Any further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation and DOI.The central component of the CMS detector is the largest silicon tracker ever built. The precise alignment of this complex device is a formidable challenge, and only achievable with a significant extension of the technologies routinely used for tracking detectors in the past. This article describes the full-scale alignment procedure as it is used during LHC operations. Among the specific features of the method are the simultaneous determination of up to 200 000 alignment parameters with tracks, the measurement of individual sensor curvature parameters, the control of systematic misalignment effects, and the implementation of the whole procedure in a multi-processor environment for high execution speed. Overall, the achieved statistical accuracy on the module alignment is found to be significantly better than 10μm

Penilaian Kinerja Keuangan Koperasi di Kabupaten Pelalawan

This paper describe development and financial performance of cooperative in District Pelalawan among 2007 - 2008. Studies on primary and secondary cooperative in 12 sub-districts. Method in this stady use performance measuring of productivity, efficiency, growth, liquidity, and solvability of cooperative. Productivity of cooperative in Pelalawan was highly but efficiency still low. Profit and income were highly, even liquidity of cooperative very high, and solvability was good

Differential cross section measurements for the production of a W boson in association with jets in proton–proton collisions at √s = 7 TeV

Measurements are reported of differential cross sections for the production of a W boson, which decays into a muon and a neutrino, in association with jets, as a function of several variables, including the transverse momenta (pT) and pseudorapidities of the four leading jets, the scalar sum of jet transverse momenta (HT), and the difference in azimuthal angle between the directions of each jet and the muon. The data sample of pp collisions at a centre-of-mass energy of 7 TeV was collected with the CMS detector at the LHC and corresponds to an integrated luminosity of 5.0 fb[superscript −1]. The measured cross sections are compared to predictions from Monte Carlo generators, MadGraph + pythia and sherpa, and to next-to-leading-order calculations from BlackHat + sherpa. The differential cross sections are found to be in agreement with the predictions, apart from the pT distributions of the leading jets at high pT values, the distributions of the HT at high-HT and low jet multiplicity, and the distribution of the difference in azimuthal angle between the leading jet and the muon at low values.United States. Dept. of EnergyNational Science Foundation (U.S.)Alfred P. Sloan Foundatio

Juxtaposing BTE and ATE – on the role of the European insurance industry in funding civil litigation

One of the ways in which legal services are financed, and indeed shaped, is through private insurance arrangement. Two contrasting types of legal expenses insurance contracts (LEI) seem to dominate in Europe: before the event (BTE) and after the event (ATE) legal expenses insurance. Notwithstanding institutional differences between different legal systems, BTE and ATE insurance arrangements may be instrumental if government policy is geared towards strengthening a market-oriented system of financing access to justice for individuals and business. At the same time, emphasizing the role of a private industry as a keeper of the gates to justice raises issues of accountability and transparency, not readily reconcilable with demands of competition. Moreover, multiple actors (clients, lawyers, courts, insurers) are involved, causing behavioural dynamics which are not easily predicted or influenced. Against this background, this paper looks into BTE and ATE arrangements by analysing the particularities of BTE and ATE arrangements currently available in some European jurisdictions and by painting a picture of their respective markets and legal contexts. This allows for some reflection on the performance of BTE and ATE providers as both financiers and keepers. Two issues emerge from the analysis that are worthy of some further reflection. Firstly, there is the problematic long-term sustainability of some ATE products. Secondly, the challenges faced by policymakers that would like to nudge consumers into voluntarily taking out BTE LEI

Optimasi Portofolio Resiko Menggunakan Model Markowitz MVO Dikaitkan dengan Keterbatasan Manusia dalam Memprediksi Masa Depan dalam Perspektif Al-Qur`an

Risk portfolio on modern finance has become increasingly technical, requiring the use of sophisticated mathematical tools in both research and practice. Since companies cannot insure themselves completely against risk, as human incompetence in predicting the future precisely that written in Al-Quran surah Luqman verse 34, they have to manage it to yield an optimal portfolio. The objective here is to minimize the variance among all portfolios, or alternatively, to maximize expected return among all portfolios that has at least a certain expected return. Furthermore, this study focuses on optimizing risk portfolio so called Markowitz MVO (Mean-Variance Optimization). Some theoretical frameworks for analysis are arithmetic mean, geometric mean, variance, covariance, linear programming, and quadratic programming. Moreover, finding a minimum variance portfolio produces a convex quadratic programming, that is minimizing the objective function ðð¥with constraintsð ð 𥠥 ðandð´ð¥ = ð. The outcome of this research is the solution of optimal risk portofolio in some investments that could be finished smoothly using MATLAB R2007b software together with its graphic analysis