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Chemical kinetics and reaction mechanisms
01 Jan 1981-
TL;DR: Reactions and reaction rates reactions with a simple kinetic form reversible and concurrent reactions consecutive reactions - the steady state and other approximations consecutive mechanisms - intermediates and numerical solutions deduction of reaction mechanisms transition state theory and microscopic reversibility chain reactions and oscillating reactions reactions in solution extrakinetic probes of mechanism reactions at extreme rates.
Abstract: Reactions and reaction rates reactions with a simple kinetic form reversible and concurrent reactions consecutive reactions - the steady state and other approximations consecutive mechanisms - intermediates and numerical solutions deduction of reaction mechanisms transition state theory and microscopic reversibility chain reactions and oscillating reactions reactions in solution extrakinetic probes of mechanism reactions at extreme rates.
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TL;DR: In this article, the authors provide a critical review of the methods for, and current rankings of, claimed transition-metal nanocluster stabilizers, with a focus on catalytically active nanoclusters.
406 citations
TL;DR: The results indicate that peroxynitrite is able to cross the erythrocyte membrane by two different mechanisms: in the anionic form through the DIDS-inhibitable anion channel, and in the protonated form by passive diffusion.
Abstract: Peroxynitrite anion (ONOO−) is a reactive species of increasingly recognized biological relevance that contributes to oxidative tissue damage At present, however, there is limited knowledge about the mechanisms of peroxynitrite diffusion through biological compartments In this work we have studied the diffusion of peroxynitrite across erythrocyte membranes In solution, peroxynitrite rapidly reacts with oxyhemoglobin to yield methemoglobin, with k2 = (104 ± 03) × 103 M−1⋅s−1 at pH 74 and 25°C Addition of peroxynitrite to intact erythrocytes caused oxidation of intracellular oxyhemoglobin to methemoglobin Oxidation yields in red blood cells at pH 70 were approximately 40% of those obtained in solution, which results mostly from competition of other cytosolic components for peroxynitrite Indeed, rather small differences were observed between oxidation yields in lysates compared with intact erythrocytes, in particular at acidic and neutral pH values, indicating that membrane was not precluding peroxynitrite diffusion Incubation of erythrocytes at pH 70 with 4,4′-diisothiocyanatostilbene-2,2′-disulfonic acid (DIDS), a specific inhibitor of anion exchange, resulted in up to 50% inhibition of oxyhemoglobin oxidation by peroxynitrite More protection by DIDS was achieved at alkaline pH, while no effect was observed at pH 55, where 95% of peroxynitrite is in the acidic form, ONOOH (pKa = 68) In addition, peroxynitrite caused nitration of intracellular hemoglobin, in a process that was enhanced in thiol-depleted erythrocytes Our results indicate that peroxynitrite is able to cross the erythrocyte membrane by two different mechanisms: in the anionic form through the DIDS-inhibitable anion channel, and in the protonated form by passive diffusion
392 citations
Cites methods from "Chemical kinetics and reaction mech..."
...The second-order rate constant for the reaction of oxyhemoglobin with peroxynitrite was determined by the method of initial velocities (34, 42) following the disappearance of oxyhemoglobin with time at 577 nm (« 5 11,000 M21zcm21; ref....
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353 citations
TL;DR: This work describes recent efforts to include the fluctuation effects caused by the structural organisation of the cytoplasm and the limited diffusion of molecules due to macromolecular crowding in stochastic modelling.
344 citations
Cites background from "Chemical kinetics and reaction mech..."
...Given knowledge of initial molecular concentrations, the law of mass action provides a complete picture of the component concentrations at all future time points(Espenson, 1995) ....
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...Given knowledge of initial molecular concentrations, the law of mass action provides a complete picture of the component concentrations at all future time points(Espenson, 1995)....
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TL;DR: In this article, the authors investigated the influence of various levels of chloride and carbonates on persulfate oxidation of trichloroethylene (TCE) at 20 degrees C under controlled conditions in a laboratory.
338 citations