191 research outputs found

    Intramolecular hydrogen transfer reactions of thiyl radicals from glutathione: formation of carbon-centered radical at Glu, Cys and Gly

    Get PDF
    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemical Research in Toxicology, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/tx3000494Glutathione thiyl radicals (GS‱) were generated in H2O and D2O by either exposure of GSH to AAPH#, photoirradiation of GSH in the presence of acetone, or photoirradiation of GSSG. Detailed interpretation of the fragmentation pathways of deuterated GSH and GSH-derivatives during mass spectrometry analysis allowed us to demonstrate that reversible intramolecular H-atom transfer reactions between GS‱ and C-H bonds at Cys[αC], Cys[ÎČC], and Gly[αC] are possible

    The Interaction of Hypotaurine and Other Sulfinates with Reactive Oxygen and Nitrogen Species:A Survey of Reaction Mechanisms

    Get PDF
    Considerable strides have been made in understanding the oxidative mechanisms involved in the final steps of the cysteine pathway leading to taurine. The oxidation of sulfinates, hypotaurine and cysteine sulfinic acid, to the respective sulfonates, taurine and cysteic acid, has never been associated with any specific enzyme. Conversely, there is strong evidence that in vivo formation of taurine and cysteic acid is the result of sulfinate interaction with a variety of biologically relevant oxidants. In the last decade, many experiments have been performed to understand whether peroxynitrite, nitrogen dioxide and carbonate radical anion could be included in the biologically relevant reactive species capable of oxidizing sulfinates. Thanks to this work, it has been possible to highlight two possible reaction mechanisms (direct and indirect reaction) of sulfinates with reactive oxygen and nitrogen species.The sulfinates oxidation, mediated by peroxynitrite, is an example of both reaction mechanisms: through a two-electron-direct-reaction with peroxynitrite or through a one-electron-indirect-transfer reaction. In the indirect mechanism, the peroxynitrite homolysis releases hydroxyl and nitrogen dioxide radical and in addition the degradation of short-lived adduct formed by peroxynitrite and CO2 can generate carbonate radical anion. The reaction of hypotaurine and cysteine sulfinic acid with peroxynitrite-derived radicals is accompanied by extensive oxygen uptake with the generation of transient intermediates, which can begin a reaction by an oxygen-dependent mechanism with the sulfonates, taurine, and cysteic acid as final products. Due to pulse radiolysis studies, it has been shown that transient sulfonyl radicals (RSO2(‱)) have been produced during the oxidation of both sulfinates by one-electron transfer reaction.The purpose is to analyze all the aspects of the reactive mechanism in the sulfinic group oxidation of hypotaurine and cysteine sulfinic acid through the results obtained from our laboratory in recent years

    Đ’ĐœĐ”ĐŽŃ€Đ”ĐœĐžĐ” Đž ĐżŃ€ĐžĐœŃ†ĐžĐż Ń€Đ°Đ±ĐŸŃ‚Ń‹ ŃĐžŃŃ‚Đ”ĐŒŃ‹ сДĐčŃĐŒĐžŃ‡Đ”ŃĐșĐŸĐłĐŸ ĐŒĐŸĐœĐžŃ‚ĐŸŃ€ĐžĐœĐłĐ° ĐłĐŸŃ€ĐœĐŸĐłĐŸ ĐŒĐ°ŃŃĐžĐČĐ° ĐŽĐ»Ń Ń€Đ°Đ±ĐŸŃ‚Ń‹ ĐČ ŃƒŃĐ»ĐŸĐČоях ООО "йахта "УсĐșĐŸĐČсĐșая"

    Get PDF
    The status of the Silicon Microvertex Detector (SMD) and its installation into the LEP-L3 experiment are presented, highlighting novel features and sophisticated techniques. Preliminary results based on 1993 data are given and compared with Monte Carlo predictions, to understand the detector performances and its tracking capabilities

    Hyperacute Directional Hearing and Phonotactic Steering in the Cricket (Gryllus bimaculatus deGeer)

    Get PDF
    Background: Auditory mate or prey localisation is central to the lifestyle of many animals and requires precise directional hearing. However, when the incident angle of sound approaches 0u azimuth, interaural time and intensity differences gradually vanish. This poses a demanding challenge to animals especially when interaural distances are small. To cope with these limitations imposed by the laws of acoustics, crickets employ a frequency tuned peripheral hearing system. Although this enhances auditory directionality the actual precision of directional hearing and phonotactic steering has never been studied in the behaviourally important frontal range. Principal Findings: Here we analysed the directionality of phonotaxis in female crickets (Gryllus bimaculatus) walking on an open-loop trackball system by measuring their steering accuracy towards male calling song presented at frontal angles of incidence. Within the range of 630u, females reliably discriminated the side of acoustic stimulation, even when the sound source deviated by only 1u from the animal’s length axis. Moreover, for angles of sound incidence between 1u and 6u the females precisely walked towards the sound source. Measuring the tympanic membrane oscillations of the front leg ears with a laser vibrometer revealed between 0u and 30u a linear increasing function of interaural amplitude differences with a slope of 0.4 dB/u. Auditory nerve recordings closely reflected these bilateral differences in afferent response latency and intensity that provide the physiological basis for precise auditory steering

    Bioinorganic Chemistry of Alzheimer’s Disease

    Get PDF

    Search for neutral charmless B decays at LEP

    Get PDF
    A search for rare charmless decays of \Bd and \Bs mesons has been performed in the exclusive channels \Bd_{(\mathrm s)}\ra\eta\eta, \Bd_{(\mathrm s)}\ra\eta\pio and \Bd_{(\mathrm s)}\ra\pio\pio. The data sample consisted of three million hadronic \Zo decays collected by the L3 experiment at LEP from 1991 through 1994. No candidate event has been observed and the following upper limits at 90\% confidence level on the branching ratios have been set \begin{displaymath} \mathrm{Br}(\Bd\ra\eta\eta)<4.1\times 10^{-4},\,\, \mathrm{Br}(\Bs\ra\eta\eta)<1.5\times 10^{-3},\,\, \end{displaymath} \begin{displaymath} \mathrm{Br}(\Bd\ra\eta\pio)<2.5\times 10^{-4},\,\, \mathrm{Br}(\Bs\ra\eta\pio)<1.0\times 10^{-3},\,\, \end{displaymath} \begin{displaymath} \mathrm{Br}(\Bd\ra\pio\pio)<6.0\times 10^{-5},\,\, \mathrm{Br}(\Bs\ra\pio\pio)<2.1\times 10^{-4}. \end{displaymath} These are the first experimental limits on \Bd\ra\eta\eta and on the \Bs neutral charmless modes

    A search for flaring Very-High-Energy cosmic-ray sources with the L3+C muon spectrometer

    Get PDF
    The L3+C muon detector at the Cern electron-position collider, LEP, is used for the detection of very-high-energy cosmic \gamma-ray sources through the observation of muons of energies above 20, 30, 50 and 100 GeV. Daily or monthly excesses in the rate of single-muon events pointing to some particular direction in the sky are searched for. The periods from mid July to November 1999, and April to November 2000 are considered. Special attention is also given to a selection of known \gamma-ray sources. No statistically significant excess is observed for any direction or any particular source
    • 

    corecore