title: Superoxide and peroxyl radical generation from the reduction of polyunsaturated fatty acid hydroperoxides by soybean lipoxygenase.
abstract: Soybean lipoxygenase is shown to catalyze the breakdown of polyunsaturated fatty acid hydroperoxides to produce superoxide radical anion as detected by spin trapping with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). In addition to the DMPO/superoxide radical adduct, the adducts of peroxyl, acyl, carbon-centered, and hydroxyl radicals were identified in incubations containing linoleic acid and lipoxygenase. These DMPO radical adducts were observed just prior to the system becoming anaerobic. Only a carbon-centered radical adduct was observed under anaerobic conditions. The superoxide radical production required the presence of fatty acid substrates, fatty acid hydroperoxides, active lipoxygenase, and molecular oxygen. Superoxide radical production was inhibited when nordihydroguaiaretic acid, butylated hydroxytoluene, or butylated hydroxyanisole was added to the incubation mixtures. We propose that polyunsaturated fatty acid hydroperoxides are reduced to form alkoxyl radicals and that after an intramolecular rearrangement, the resulting hydroxyalkyl radical reacts with oxygen, forming a peroxyl radical which subsequently eliminates superoxide radical anion.
authors.affiliation: National Institute of Environmental Health Sciences, National Institutes of Health, Research Triangle Park, North Carolina 27709.
authors.forename: W
authors.initials: W
authors.lastname: Chamulitrat
authors.forename: M F
authors.initials: MF
authors.lastname: Hughes
authors.forename: T E
authors.initials: TE
authors.lastname: Eling
authors.forename: R P
authors.initials: RP
authors.lastname: Mason
mesh_terms: D003497:Cyclic N-Oxides; D004578:Electron Spin Resonance Spectroscopy; D005231:Fatty Acids, Unsaturated / Q000378:metabolism*; D005609:Free Radicals; D008054:Lipid Peroxides / Q000378:metabolism*; D008084:Lipoxygenase / Q000378:metabolism*; D010084:Oxidation-Reduction; D010545:Peroxides / Q000378:metabolism; D013025:Glycine max / Q000201:enzymology; D013113:Spin Labels; D013481:Superoxides / Q000378:metabolism
chemical_list: D003497:Cyclic N-Oxides; D005231:Fatty Acids, Unsaturated; D005609:Free Radicals; D008054:Lipid Peroxides; D010545:Peroxides; D013113:Spin Labels; D013481:Superoxides; C049375:perhydroxyl radical; C017245:5,5-dimethyl-1-pyrroline-1-oxide; D008084:Lipoxygenase