High-valent iron-oxo species are thought to be intermediates in the catalytic cycles of oxygenases and peroxidases. An attractive route to these iron-oxo intermediates involves laser flash-quench oxidation of ferric hemes, as demonstrated by our work on the ferryl (compound II) and ferryl porphyrin radical cation (compound I) intermediates of horseradish peroxidase. Extension of this work to in...

Copper(II) complexes with N-oxyl reactants such as TEMPO can selectively oxidize alcohols to aldehydes or ketones. The proposed copper intermediates of the oxidation reaction were extensively theoretically studied, but they never experimentally detected. Here, we present an analysis “frozen” that contain without α-hydrogen atoms, thus preventing oxidation. copper(II)-TEMPO a bipyridine-type anc...

We compare the results from the oxidation of two unusual "enediamide" motifs (3,4-dihydropyrazin-2(1H)-ones), where a double bond is flanked by two amides. In one case the oxidation led to a ring-opened product arising from the cleavage of the double bond, and in the other a rare cis-dioxygenated compound was obtained. Both products have been characterized by X-ray crystallography. The outcomes...

The results of a mechanistic study using ab initio theoretical methods are used to outline plausible mechanistic sequences for alkane, alcohol, and alkene oxidation by chromyl and molybdyl chlorides. We suggest that the second oxo group is intimately involved in the reaction sequence. This spectator oxo group is suggested to play a central role in stabilizing critical intermediates in these rea...

In the present study, organophosphorus pesticides (OPs) (diazinon, methyl parathion, and parathion) were oxidized by bubbling ozone into a glass reactor. OP residues were detected using HPLC and ozonation intermediates were identified using GC-MS. The degradation of OPs followed pseudo-first-order kinetics through direct ozone oxidation and indirect hydroxyl radical oxidation. Diazinon, based o...

OBJECTIVE To understand relationships between exercise training-mediated improvements in insulin sensitivity (S(I)) and changes in circulating concentrations of metabolic intermediates, hormones, and inflammatory mediators. RESEARCH DESIGN AND METHODS Targeted mass spectrometry and enzyme-linked immunosorbent assays were used to quantify metabolic intermediates, hormones, and inflammatory mar...

Dps proteins are bacterial ferritins that protect DNA from oxidative stress and have been implicated in bacterial survival and virulence. In addition to direct oxidation of the Dps iron sites by diffusing oxidants, oxidation from a distance via DNA charge transport (CT), where electrons and electron holes are rapidly transported through the base-pair π-stack, could represent an efficient DNA pr...

Aryl hydrazides are oxidised to acyl radicals through a mechanism involving diimide intermediates that are prone to nucleophilic acyl substitution. This oxidation occurs regardless of the oxidant involved, however there is no evidence that the acyl radical formed undergoes further oxidation to the corresponding acylium ion, even in the presence of strong oxidants. This study may provide insight...