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251.
Electrochemical Monitoring of the Early Events of Hydrogen Peroxide Production by Mitochondria 下载免费PDF全文
Dr. Emmanuel Suraniti Salem Ben‐Amor Pauline Landry Prof. Michel Rigoulet Prof. Eric Fontaine Prof. Serge Bottari Dr. Anne Devin Prof. Neso Sojic Dr. Nicolas Mano Dr. Stéphane Arbault 《Angewandte Chemie (International ed. in English)》2014,53(26):6655-6658
Mitochondria consume oxygen in the respiratory chain and convert redox energy into ATP. As a side process, they produce reactive oxygen species (ROS), whose physiological activities are still not understood. However, current analytical methods cannot be used to monitor mitochondrial ROS quantitatively and unambiguously. We have developed electrochemical biosensors based on peroxidase‐redox polymer‐modified electrodes, providing selective detection of H2O2 with nanomolar sensitivity, linear response over five concentration decades, and fast response time. The release of H2O2 by mitochondria was then monitored under phosphorylating or inhibited respiration conditions. We report the detection of two concomitant regimes of H2O2 release: large fluxes (hundreds of nM ) under complex III inhibition, and bursts of a few nM immediately following mitochondria activation. These unprecedented bursts of H2O2 are assigned to the role of mitochondria as the hub of redox signaling in cells. 相似文献
252.
We have compared the reproducibility precisions provided by collaborative trials with precisions obtained from ruggedness tests specially designed to try to simulate between-laboratory variation. We found that the ruggedness tests underestimated the reproducibility variability consistently for those analytical methods requiring empirical calibration. The ruggedness tests provided on average a precision merely comparable with repeatability precision. This finding has implications for the estimation of uncertainty. 相似文献
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Pauline Souchal Thomas Roels Patrick Hémery Lucien Marx 《Journal of polymer science. Part A, Polymer chemistry》2012,50(19):4073-4084
The chloromagnesium exchange of 4‐chlorostyrene provides an easy access to a new versatile polymerizable 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide (TIPNO)‐based nitroxide. Indeed, first, its alkoxyamine based on the α‐methyl benzyl radical fragment efficiently mediates the polymerization of styrene (respectively n‐butyl acrylate) to yield branched polystyrene [respectively poly(n‐butyl acrylate)] with alkoxyamine function as branch point and well‐defined branches. Second, the self‐condensing of this polymerizable nitroxide by manganese coupling affords a mixture of oligomeric linear polyalkoxyamines. Polymerization of styrene mediated with these polyalkoxyamines gives multiblock polystyrenes with alkoxyamine group as linker between polystyrene blocks and exhibits the following features: the synthesis of the polystyrene blocks is controlled as their average molecular weight Mn(block) increases linearly with conversion and their average dispersity Mw/Mn(block) decreases with it. At a given temperature, the molecular weight and the dispersity of the polyalkoxyamines weakly impact Mn(block) and Mw/Mn(block). In contrast, the molecular weight of the multiblock polystyrene increases linearly with conversion until reaching a constant value. The number of block is independent of the molecular weight of the polyalkoxyamines. These unusual results can be explained by the fact that during polymerization, mediating TIPNO‐based polymeric nitroxides with different lengths are generated and are exchanged. Finally the dispersity of the multiblock polystyrene is quite broad and lies between 1.7 and 2.8. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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Dante M. Lepore Carl Barratt Pauline M. Schwartz 《Journal of mathematical chemistry》2011,49(2):356-370
Systems chemistry is a new discipline which investigates the interactions within a network of chemical reactions. We have studied several computational models of chemical systems inspired by mathematical paradoxes and have found that even simple systems may behave in a counterintuitive, non-linear manner depending upon various conditions. In the present study, we modeled a set of reactions inspired by one such paradox, Braess’ paradox, an interesting phenomenon whereby the introduction of additional capacity (e.g. pathways) in some simple network systems can lead to an unexpected reduction in the overall flow rate of “traffic” through the system. We devised several chemical systems that behaved in this counterintuitive manner; the overall rate of product formation was diminished when an additional pathway was introduced and, conversely, there was an enhancement of product formation when the same interconnecting pathway was removed. We found that, unlike a traffic model, the chemical model needed to include reversible pathways in order to mimic “congestion”—a condition necessary to produce Braess-like behavior. The model was investigated numerically, but a full analytical solution is also included. We propose that this intriguing situation may have interesting implications in chemistry, biochemistry and chemical engineering. 相似文献