Redox

About: Redox is a research topic. Over the lifetime, 26853 publications have been published within this topic receiving 862368 citations. The topic is also known as: reduction-oxidation & reduction-oxidation reaction.

Oxoammonium cation intermediate in the nitroxide-catalyzed dismutation of superoxide.

Abstract: Dismutation of superoxide has been shown previously to be catalyzed by stable nitroxide compounds. In the present study, the mechanism of superoxide (.O2-) dismutation by various five-membered ring and six-membered ring nitroxides was studied by electron paramagnetic resonance spectrometry, UV-visible spectrophotometry, cyclic voltammetry, and bulk electrolysis. Electron paramagnetic resonance signals from the carbocyclic nitroxide derivatives (piperidinyl, pyrrolidinyl, and pyrrolinyl) were unchanged when exposed to enzymatically generated .O2-, whereas, in the presence of .O2- and reducing agents such as NADH and NADPH, the nitroxides underwent reduction to their respective hydroxylamines. The reaction of 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine (Tempol-H) with .O2- was measured and, in agreement with earlier reports on related compounds, the rate was found to be too slow to be consistent with a mechanism of .O2- dismutation involving the hydroxylamine as an intermediate. Voltammetric analyses of the carbocyclic nitroxide derivatives revealed a reversible one-electron redox couple at positive potentials. In contrast, oxazolidine derivatives were irreversibly oxidized. At negative potentials, all of the nitroxides studied exhibited a broad, irreversible reductive wave. The rate of .O2- dismutation correlated with the reversible midpoint redox potential. Bulk electrolysis at positive potentials was found to generate a metastable oxidized form of the nitroxide. The results indicate that the dismutation of .O2- is catalyzed by the oxoammonium/nitroxide redox couple for carbocyclic nitroxide derivatives. In addition to the one-electron mitochondrial reduction pathway, the present results suggest the possibility that cellular bioreduction by a two-electron pathway may occur subsequent to oxidation of stable nitroxides. Furthermore, the cellular destruction of persistent spin adduct nitroxides might also be facilitated by a primary univalent oxidation.

Oxidation of sulfur dioxide to sulfur trioxide over supported vanadia catalysts

Abstract: The objectives of this research are to establish the fundamental kinetics and mechanism of sulfur dioxide oxidation over supported vanadia catalysts and use these insights to facilitate the design of SCR DeNOx catalysts with minimal sulfur dioxide oxidation activity. A series of supported vanadia catalysts were prepared on various metal-oxide supports: ceria, zirconia, titania, alumina and silica. Raman spectroscopy was used to determine the coordination of surface species. At low vanadia loadings, vanadia preferentially exists on oxide support surfaces as isolated tetrahedrally coordinated (M‐O)3V a5 aO species. At higher vanadia loadings, the isolated (M‐O)3V a5 aO species polymerize on the oxide support surface breaking two V‐O‐M bonds and forming two V‐O‐V bridging bonds. The turnover frequency for sulfur dioxide oxidation was very low, 10 ˇ4 to 10 ˇ6 s ˇ1 at 4008C, and was independent of vanadia coverage suggesting that only one vanadia site is required for the oxidation reaction. As the support was varied, sulfur dioxide oxidation activity of the supported vanadia catalysts varied by one order of magnitude (Ce>Zr, Ti>Al>Si). The basicity of the bridging V‐O‐M oxygen appears to be responsible for influencing the adsorption and subsequent oxidation of the acidic sulfur dioxide molecule. Over the range of conditions studied, the rate of sulfur dioxide oxidation is zero-order in oxygen, first-order in sulfur dioxide and inhibited by sulfur trioxide. The turnover frequency for sulfur dioxide oxidation over WO3/TiO2 was an order of magnitude lower than that found for V2O5/TiO2, and no redox synergism between the surface vanadia and tungsten oxide species was evident for a ternary V2O5/ WO3/TiO2 catalyst. This suggests that WO3 promoted catalysts may be suitable for low-temperature SCR where minimal sulfur dioxide oxidation activity is required. # 1998 Elsevier Science B.V. All rights reserved.

Redox- and Reactive Oxygen Species-Dependent Signaling into and out of the Photosynthesizing Chloroplast.

Abstract: Photosynthesis is a high-rate redox metabolic process that is subjected to rapid changes in input parameters, particularly light. Rapid transients of photon capture, electron fluxes, and redox potentials during photosynthesis cause reactive oxygen species (ROS) to be released, including singlet oxygen, superoxide anion radicals, and hydrogen peroxide. Thus, the photosynthesizing chloroplast functions as a conditional source of important redox and ROS information, which is exploited to tune processes both inside the chloroplast and, following retrograde release or processing, in the cytosol and nucleus. Analyses of mutants and comparative transcriptome profiling have led to the identification of these processes and associated players and have allowed the specificity and generality of response patterns to be defined. The release of ROS and oxidation products, envelope permeabilization (for larger molecules), and metabolic interference with mitochondria and peroxisomes produce an intricate ROS and redox signature, which controls acclimation processes. This photosynthesis-related ROS and redox information feeds into various pathways (e.g. the mitogen-activated protein kinase and OXI1 signaling pathways) and controls processes such as gene expression and translation.