Nitronate monooxygenase (NMO) catalyzes the flavin-dependent oxidation of propionate 3-nitronate (P3N) via the formation of an anionic flavosemiquinone. The oxidation of substrate includes the formation of a peroxy-nitro acid intermediate. P3N is activated to its radical form via a single electron transfer onto the FMN cofactor forming the anionic flavosemiquinone. Reoxidation of FMN cofactor f...

The sensitive Fluorescence Assay by Gas Expansion (FAGE) method has been used to detect methyl peroxy (CH3O2) and hydroperoxyl (HO2) radicals after their conversion titration with excess NO methoxy (CH3O) hydroxyl (OH) radicals, respectively, study the kinetics of reaction CH3O2 + HO2 radicals. rate coefficient was measured in Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) at 100...

UNLABELLED Selective cyclooxygenase (COX)-2 inhibitors have attracted much attention in relation to the design of non-steroidal anti-inflammatory agents (NSAIDs). The relationship between experimentally derived data on the antioxidant capacity, cytotoxicity and COX-2 inhibition for a range of 2-methoxyphenols and their calculated descriptors was investigated. MATERIALS AND METHODS Quantitativ...

Night-time chemistry in the Marine Boundary Layer has been modelled using a number of observationally constrained zero-dimensional box-models. The models were based upon the Master Chemical Mechanism (MCM) and the measurements were taken during the North Atlantic Marine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head, Ireland in July–September 2002. The model could reproduce, within t...

Kinetic studies on the AR (aldose reductase) protein have shown that it does not behave as a classical enzyme in relation to ring aldose sugars. As with non-enzymatic glycation reactions, there is probably a free-radical element involved derived from monosaccharide autoxidation. In the case of AR, there is free radical oxidation of NADPH by autoxidizing monosaccharides, which is enhanced in the...

The peroxy-asymmetric allylic alkylation of hydroperoxyalkanes with Morita-Baylis-Hillman carbonates was catalysed by modified cinchona alkaloids (up to 93% ee), from which chiral alpha-methylene-beta-hydroxy esters could be efficiently derived.

Abstract. We evaluate monoterpene-derived peroxy radical (MT-RO2) unimolecular autoxidation and self- cross-reactions with other RO2 species in the GEOS-Chem global chemical transport model. The formation of associated highly oxygenated organic molecules (HOMs) accretion products are tracked competition bimolecular reactions. Autoxidation is dominant fate up to 6–8 km for first-generation MT-RO...

Abstract. Based on the first measurements of gas-phase pyruvic acid (CH3C(O)C(O)OH) in boreal forest, we derive effective emission rates and compare them with monoterpene over diel cycle. Using a data-constrained box model, determine impact photolysis formation acetaldehyde (CH3CHO) peroxy radicals CH3C(O)O2 HO2 during an autumn campaign forest. The results are dependent quantum yield (φ) mecha...