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Oxidation Chemistry (oxidation + chemistry)
Selected AbstractsStudies on Nickel(II) Complexes with Amide-Based Ligands: Syntheses, Structures, Electrochemistry and Oxidation ChemistryEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2008Jyoti Singh Abstract The present work discusses the nickel chemistry in a set of amide-based open-chain ligands with subtle differences in the backbone or terminal amine substituents. The ligands coordinate to the Ni2+ ion through the Namide and Namine atoms maintaining a square-planar geometry. Absorption spectra and NMR studies reveal that the solid-state square-planar geometry is retained in solution. The electrochemical results suggest that the NiIII/NiII redox couple primarily depends on the N4 donors, which is composed of two Namide and twoNamine atoms and not on the peripheral substituents. All four ligands with variable backbone and substituents are equally competent in stabilizing the NiIII state. On the basis of electrochemical findings, chemical oxidations were carried out, and they reveal generation of the NiIII state in two cases, whereas decomposition was observed in others. Preliminary alkene epoxidation reactions suggest that the present nickel complexes transiently stabilize the higher oxidation state of the nickel ion that possibly participates in the oxidation of the substrates.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Oxidation chemistry of acid-volatile sulfide during analysisENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 5 2002Adrian M. Gonzalez Abstract The susceptibility of some components of sediment acid-volatile sulfide (AVS) to chemical oxidation is a critical factor impacting accurate measurement of AVS in sediment samples. This well-documented susceptibility to oxidation led to the requirement for oxygen-free conditions in the analytical method developed for AVS. In light of this acute potential to oxidize, the serendipitous finding that air can be used in the analysis of sediment AVS is counterintuitive and unexpected. To demonstrate and investigate this interesting observation, extraction experiments were performed using aqueous and solid-phase sulfide species. Experiments using air as the carrier gas showed a mean percentage recovery of sulfide matching that of traditional (nitrogen gas) analysis (i.e., >91%) and a time to completion of less than 30 min for aqueous sulfide and less than 60 min for sediment samples. These results are consistent with those of sulfide oxidation studies reported in the literature. Using air as the analytical carrier gas can provide an interesting alternative for developing an analytical method to determine AVS parameters in the field. [source] Evaluation of solution oxygenation requirements for azonitrile-based oxidative forced degradation studies of pharmaceutical compoundsJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 7 2006Eric D. Nelson Abstract AIBN and ACVA oxidative forced degradation models are examined for two drug molecules whose predominant oxidation chemistries arise from different reaction mechanisms (i.e., free radical vs. nucleophilic). Stress was conducted under a variety of initiator concentrations, and under ambient and pressurized oxygen atmospheres. In each case examined, the azonitrile initiator solutions served as a good predictive model of the major oxidative degradation products observed in pharmaceutical formulations. At low to moderate inititator concentrations, the degradation product distributions and degree of reactivity were similar for samples stored in ambient and pressurized oxygen environments. These results are rationalized with reference to the oxygen consumption kinetics of AIBN and ACVA solutions as a function of initiator concentration. The data suggests that ambient air provides sufficient oxygen to enable chain propagation of peroxy radicals in azonitrile solutions of concentrations appropriate to the forced degradation of pharmaceutical compounds. © 2006 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 95: 1527,1539, 2006 [source] Does Negative Hyperconjugation Assist Enzymatic Dehydrogenations?CHEMPHYSCHEM, Issue 9 2007Gloria Tabacchi Dr. Enzyme mechanisms: Using ab initio methods and natural bond orbital analysis, negative hyperconjugation is shown to govern L -lactate oxidation chemistry and may help to determine its enzymatic dehydrogenation mechanism. The picture shows the negative hyperconjugation interaction between the lone pair on the oxygen atom and the ,*(C,H,) orbital. [source] | ||||||||||