Superoxide dismutase enhances chain-breaking antioxidant capability of hydroquinones.
2-tert-butyl-(1), 2,6-dimethyl-(2), 2,5-dimethyl-(3), trimethyl-(4), and 2,3-dimethoxy-5-methyl-(5) substituted p-hydroquinones (QH2) were tested as a chain-breaking antioxidant during the oxidation of methyl linoleate (ML) in dodecyl sulfate micellar solution, pH 7.40, at 37 degrees C. In the absence of superoxide dismutase (SOD), all the studied QH2 displayed very moderate if any antioxidant capability. When 5-25 U/ml SOD was added, QH2 showed a pronounced ability to inhibit ML oxidation. The stoichiometric factor of inhibition was found to be about one for all the tested QH2 in the presence of SOD. The reactivities of QH2 to the ML peroxy radical increase in the order QH2 5 < QH2 3 < QH2 1 approximately QH2 2 < QH2 4; reactivity of QH2 4 exceeds that reported for the majority of phenolic antioxidants. The features of QH2 as an antioxidant in aqueous environment is likely associated with the reactivity of semiquinone (O.-) formed due to attack of the peroxy radical to QH2. O.- reacts readily with molecular oxygen with formation of superoxide (O2.-); in turn, O2.- attacks both to QH2 and ML (likely, as HO2.) that results in fast depleting QH2 and chain propagation, respectively. The addition of SOD results in purging a reaction mixture from O2.- and, as a corollary, in depressing undesirable reactions with the participation of O2.-. Under these conditions, QH2 displays the theoretically highest inhibitory activity which is determined solely by the reactivity of QH2 to the peroxy radical.
Roginsky
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N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygin St. 4, 117977 Moscow, Russia. rogin@postman.ru
D000975:Antioxidants / Q000494:pharmacology*; D006873:Hydroquinones / Q000494:pharmacology*; D007700:Kinetics; D008041:Linoleic Acids / Q000378:metabolism*; D015227:Lipid Peroxidation; D008081:Liposomes; D008823:Micelles; D010084:Oxidation-Reduction; D012967:Sodium Dodecyl Sulfate / Q000737:chemistry; D013482:Superoxide Dismutase / Q000378:metabolism*
D000975:Antioxidants; D006873:Hydroquinones; D008041:Linoleic Acids; D008081:Liposomes; D008823:Micelles; C005575:methyl linoleate; D012967:Sodium Dodecyl Sulfate; D013482:Superoxide Dismutase