Comparative study on dynamics of antioxidative action of alpha-tocopheryl hydroquinone, ubiquinol, and alpha-tocopherol against lipid peroxidation.
Alpha-tocopheryl quinone is a metabolite of alpha-tocopherol (TOH) in vivo. The antioxidant action of its reduced form, alpha-tocopheryl hydroquinone (TQH2), has received much attention recently. In the present study, the antioxidative activity of TQH2 was studied in various systems in vitro and compared with that of ubiquinol-10 (UQH2) or TOH to obtain the basic information on the dynamics of the antioxidant action of TQH2. First, their hydrogen-donating abilities were investigated in the reaction with galvinoxyl, a stable phenoxyl radical, and TQH2 was found to possess greater second-order rate constant (1.0 x 10(4) M(-1) s(-1)) than UQH2 (6.0 x 10(3) M(-1) s(-1)) and TOH (2.4 x 10(3) M(-1) s(-1)) at 25 degrees C in ethanol. The stoichiometric numbers were obtained as 1.9, 2.0, and 1.0 for TQH2, UQH2, and TOH, respectively, in reducing galvinoxyl. Second, their relative reactivities toward peroxyl radicals were assessed in competition with N,N'-diphenyl-p-phenylenediamine (DPPD) and found to be 6.0 (TQH2), 1.9 (UQH2), and 1.0 (TOH). Third, their antioxidant efficacies were evaluated in the oxidation of methyl linoleate in organic solvents and in aqueous dispersions. The antioxidant potency decreased in the order TOH > UQH2 > TQH2, as assessed by either the extent of the reduction in the rate of oxidation or the duration of inhibition period. The reverse order of their reactivities toward radicals and their antioxidant efficacies was interpreted by the rapid autoxidation of TQH2 and UQH2, carried out by hydroperoxyl radicals. Although neither TQH2 nor UQH2 acted as a potent antioxidant by itself, they acted as potent antioxidants in combination with TOH. TQH2 and UQH2 reduced alpha-tocopheroxyl radical to spare TOH, whereas TOH suppressed the autoxidation of TQH2 and UQH2. In the micelle oxidation, the antioxidant activities of TQH2, UQH2, and TOH were similar, whereas 2,2,5,7,8-pentamethyl-6-chromanol exerted much more potent efficacy than TQH2, UQH2, or TOH. These results clearly show that the antioxidant potencies against lipid peroxidation are determined not only by their chemical reactivities toward radicals, but also by the fate of an antioxidant-derived radical and the mobility of the antioxidant at the microenvironment.
Shi
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H
Research Center for Advanced Science and Technology, The University of Tokyo, Meguro, Japan.
Noguchi
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N
Niki
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E
D000975:Antioxidants / Q000494:pharmacology*; D001559:Benzhydryl Compounds / Q000378:metabolism; D016166:Free Radical Scavengers / Q000494:pharmacology; D005609:Free Radicals; D007700:Kinetics; D008041:Linoleic Acids / Q000378:metabolism; D015227:Lipid Peroxidation / Q000187:drug effects*; D008163:Luminescent Measurements; D008823:Micelles; D010084:Oxidation-Reduction; D014451:Ubiquinone / Q000031:analogs & derivatives / Q000494:pharmacology; D014810:Vitamin E / Q000031:analogs & derivatives / Q000494:pharmacology; D024502:alpha-Tocopherol / Q000031:analogs & derivatives*
D000975:Antioxidants; D001559:Benzhydryl Compounds; D016166:Free Radical Scavengers; D005609:Free Radicals; D008041:Linoleic Acids; D008823:Micelles; D014451:Ubiquinone; D014810:Vitamin E; C024838:alpha-tocopherol quinol; C005575:methyl linoleate; D024502:alpha-Tocopherol; C003741:ubiquinol; C020338:galvinoxyl