Betacyanins as phenol antioxidants. Chemistry and mechanistic aspects of the lipoperoxyl radical-scavenging activity in solution and liposomes.
Reaction kinetics of betanin and its aglycone betanidin towards peroxyl radicals generated from the azo-initiated oxidation of methyl linoleate in methanol and of a heterogeneous aqueous/soybean phosphatidylcholine liposomal system were studied by monitoring formation of linoleic acid hydroperoxides and consumption of the pigments. Betanin was a weak retarder in methanol and an effective chain breaking antioxidant in the liposomal model, indicating that kinetic solvent effects and partition in lipid bilayers may affect its activity. Betanidin behaved as a chain terminating antioxidant in both models. Kinetic parameters characterizing peroxyl radical-scavenging activity showed that betanidin was more effective than betanin, in terms of both radical-scavenging rate constant and stoichiometric factor, with effectiveness of the same order as vitamin E under comparable conditions. Products identified by spectrophotometric and HPLC techniques indicated reaction of the glucose-substituted monophenol and ortho-diphenol moieties of betanin and betanidin, respectively, and suggested mechanisms of the antioxidant activity. Either betanin or betanidin incorporated in liposomes with alpha-tocopherol had additive effects, supporting partition of the pigments in the bilayer and lipoperoxyl radical reduction.
Tesoriere
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Dipartimento Farmacochimico Tossicologico e Biologico, Università di Palermo, Via Michele Cipolla 74, 90128, Palermo, Italy.
Allegra
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Gentile
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Livrea
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MA
D050859:Betacyanins / Q000008:administration & dosage / Q000737:chemistry / Q000494:pharmacology*; D002851:Chromatography, High Pressure Liquid; D004357:Drug Synergism; D016166:Free Radical Scavengers / Q000008:administration & dosage / Q000737:chemistry / Q000494:pharmacology*; D019787:Linoleic Acid / Q000378:metabolism; D008041:Linoleic Acids / Q000378:metabolism; D008051:Lipid Bilayers; D015227:Lipid Peroxidation / Q000187:drug effects*; D008081:Liposomes / Q000008:administration & dosage; D000432:Methanol; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010713:Phosphatidylcholines / Q000737:chemistry; D012996:Solutions; D012997:Solvents; D013053:Spectrophotometry; D013329:Structure-Activity Relationship; D014867:Water; D024502:alpha-Tocopherol / Q000494:pharmacology
D050859:Betacyanins; D016166:Free Radical Scavengers; D008041:Linoleic Acids; D008051:Lipid Bilayers; D008081:Liposomes; D010713:Phosphatidylcholines; D012996:Solutions; D012997:Solvents; D014867:Water; C005575:methyl linoleate; C020228:betanin; D019787:Linoleic Acid; D024502:alpha-Tocopherol; D000432:Methanol