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IJBB Vol.49(5) [October 2012] >


Title: Emergence of Oxyl Radicals as Selective Oxidants
Authors: Ramasarma, T
Keywords: Hydroxyl radicals
Metal oxyl radicals
Peroxo-vanadates
Lipid peroxidation
Issue Date: Oct-2012
Publisher: NISCAIR-CSIR, India
Abstract: Hydroxyl radicals (HO·) are derived in Fenton reaction with ferrous salt and H2O2 in acid medium, and at neutral pH, metal-oxyl radicals (M-O·) predominate. Evidence is accumulating that M-O· radicals are also active in oxidation reactions, in addition to metal-oxo (M=O) now shown in many publications. Reactivity of these radicals gives selective oxidized products useful in cellular activities, in contrast to purported indiscriminate cell damage by hydroxyl radicals. Reactions with vanadium compounds, such as diperoxovanadate, peroxo-bridged mixed valency divanadate, vanadium-oxyl radical, tetravalent vanadyl and decavanadate illustrates selective gain in oxidative capacity of oxo- and oxyl- species. Occurrence of ESR signals typical of hydroxyl radicals is demonstrated in cell homogenates and tissue perfusates treated with spin trap agents. It is known for a long time lipid peroxides are formed in tissue microsomal systems exclusively in presence of salts of iron, among many metals tested. Oxygen and a reducing agent, ascorbate (non-enzymic) or NADPH (enzymic) are required to produce 'ferryl', the chelated Fe=O active form (possibly Fe-O· and Fe-O-O-Fe ?) for the crucial step of H-atom abstraction. Yet literature is replete with unsupported affirmations that hydroxyl radicals initiate lipid peroxidation, an unexplained fixation of mindset. The best-known ·OH generator, a mixture of ferrous salt and H2O2, does not promote lipid peroxidation, nor do the many hydroxyl radical quenching agents stop it. The availability of oxo and oxyl-radical forms with transition metals, and also with non metals, P, S, N and V, calls for expansion of vision beyond superoxide and hydroxyl radicals and explore functions of multiple oxygen radicals for their biological relevance.
Page(s): 295-305
CC License:  CC Attribution-Noncommercial-No Derivative Works 2.5 India
ISSN: 0975-0959 (Online); 0301-1208 (Print)
Source:IJBB Vol.49(5) [October 2012]

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