Oxidation of tea extracts and tea catechins by molecular oxygen.
Tea polyphenols (PP) are known as potent antioxidants. At the same time, PP have been repeatedly reported to oxidize by molecular oxygen with the formation of active forms of oxygen. In this work, the Clark electrode technique was applied to study the kinetics of the autoxidation of tea extracts and individual tea PP as well as model PP, catechol, gallic acid, and pyrogallol. Aqueous extracts of both green and black teas were found to undergo extensive autoxidation under physiological conditions. The addition of superoxide dismutase (SOD) and milk resulted in a significant decrease in the rate of oxidation. Studied individually, PP were found to autoxidize at a rate, which increased with pH, proportional to PP concentration and nearly proportional to oxygen concentration. The collected data were used for the extrapolation/interpolation of the starting rates of oxidation to the standard conditions (at pH 7.40, 100 microM PP, 200 microM O2). PP oxidizability is basically determined by that of the key PP fragment (pyrogallol > gallate > catechol). Meta-OH groups do not contribute to the oxidation even at pH 13.0. Similar to tea brew, the oxidation of individual PP was inhibited by milk and SOD addition, with catechol being the only exception (the oxidation of catechol was accelerated when SOD was added). Comparison of the autoxidation of PP (o-hydroquinones) with that of p-hydroquinones (Roginsky, V.; Barsukova, T. K. J. Chem. Soc., Perkin Trans. 2 2000, 1575-1582) displays the dramatic difference both in the oxidizability and in the kinetic regularities. The difference in the kinetics has been suggested to be due to the difference in the initiation of the chain process. Whereas for p-hydroquinones the oxidation is initiated by the reaction between hydroquinone and a corresponding quinone, the oxidation of o-hydroquinones is likely started by direct interaction between substrate and molecular oxygen. As the second process is much slower, this may explain the relatively low oxidizability of PP as compared to p-hydroquinones.
Roginsky
Vitaly
V
N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygin Street 4, 117977 Moscow, Russian Federation. rogin@postman.ru
Alegria
Antonio E
AE
D002396:Catechols / Q000737:chemistry; D004566:Electrodes; D005419:Flavonoids / Q000737:chemistry*; D005707:Gallic Acid / Q000737:chemistry; D006873:Hydroquinones / Q000737:chemistry; D007700:Kinetics; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010636:Phenols / Q000737:chemistry*; D010936:Plant Extracts / Q000737:chemistry; D059808:Polyphenols; D011748:Pyrogallol / Q000737:chemistry; D013482:Superoxide Dismutase / Q000494:pharmacology; D013662:Tea / Q000737:chemistry*
D002396:Catechols; D005419:Flavonoids; D006873:Hydroquinones; D010636:Phenols; D010936:Plant Extracts; D059808:Polyphenols; D013662:Tea; D011748:Pyrogallol; D005707:Gallic Acid; D013482:Superoxide Dismutase; C034221:catechol; D010100:Oxygen