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Studies on the metal-ion and lipoxygenase-catalysed breakdown of hydroperoxides using electron-spin-resonance spectroscopy

M J Davies, T F Slater
Biochemical Journal Jul 01, 1987, 245 (1) 167-173; DOI: 10.1042/bj2450167
M J Davies
Department of Biochemistry, Brunel University, Uxbridge, Middx. U.K.
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T F Slater
Department of Biochemistry, Brunel University, Uxbridge, Middx. U.K.
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Abstract

The breakdown of cumene hydroperoxide and peroxidized fatty acids by iron is shown, by use of the spin trap 5,5-dimethyl-l-pyrroline-N-oxide, to be sensitive to (a) the oxidation state of the metal and (b) the nature of the chelating ligands. The initial step in the Fe2+-catalysed breakdown is the production of an alkoxyl radical by one-electron reduction, and this type of radical has been successfully trapped from each substrate. Subsequent reactions of this alkoxyl species produce both carbon-centred and peroxyl radicals, depending on the concentrations of the reagents present. The use of the same spin trap in microsomal systems undergoing either NADPH-supported or Fe2+-induced peroxidation led to the detection of low concentrations of radical adducts, among which are signals that are believed to be due to lipid alkoxyl radicals. Reaction of polyunsaturated fatty acid hydroperoxides with both Fe2+ and lipoxygenase under anaerobic conditions gives rise to signals not only from the alkoxy-radical adduct, but also from a further species which is tentatively identified as being due to an acyl [RC(O).]-radical adduct; chemical studies lend support to this assignment.

  • © 1987 London: The Biochemical Society
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July 1987

Volume: 245 Issue: 1

Biochemical Journal: 245 (1)
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Studies on the metal-ion and lipoxygenase-catalysed breakdown of hydroperoxides using electron-spin-resonance spectroscopy
M J Davies, T F Slater
Biochemical Journal Jul 1987, 245 (1) 167-173; DOI: 10.1042/bj2450167
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Studies on the metal-ion and lipoxygenase-catalysed breakdown of hydroperoxides using electron-spin-resonance spectroscopy
M J Davies, T F Slater
Biochemical Journal Jul 1987, 245 (1) 167-173; DOI: 10.1042/bj2450167

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