Abstract
Rates of α-tocopherol oxidation were measured for free-radical reactions produced by Fe(III)-catalyzed dissociations of hydroperoxides. The kinetics were treated as first-order in α-tocopherol. The hydroperoxides were preformed from methyl linoleate, methyl linolenate, ethyl arachidonate, methyl eicosapentaenoate, and a fraction of polyunsaturated fatty esters of menhaden oil. The degree of unsaturation of the lipid hydroperoxides had little effect on the rates of α-tocopherol oxidation. The rates of oxidation decrease with the concentration of water and increase with the acidity of the media. The pH data suggest a transition from one predominant mechanism to another, which may involve principally acid catalysis. A mechanism for α-tocopherol oxidation is suggested.
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References
Lea, C. H., in “Symposium on Foods: Lipids and Their Oxidation”, Edited by H. W. Schultz, E. A. Day and R. O. Sinnhuber, The Avi Publishing Co., Westport, 1962, p. 3–28.
Tappel, A. L., Federation Proc. 24(1):73–78 (1965).
Mellors, A., and A. L. Tappel, J. Biol. Chem. 241:4353–4356 (1966).
Desai, I. D., P. L. Sawant and A. L. Tappel, Biochim. Biophys. Acta 86:277–285 (1964).
Roubal, W. T., and A. L. Tappel, Arch. Biochem. Biophys. 113:150–155 (1966).
Wills, E. D., and A. E. Wilkinson, Biochem. J. 99: 657–666 (1966).
Pryor, W. S., “Free Radicals,” McGraw-Hill Book Co., New York, 1966, p. 57–60.
Barber, A. A., Lipids 1:146–151 (1966).
Kofler, M., P. F. Sommer, H. R. Bollinger, B. Schmidli and M. Vecchi, Vitamins Hormones 20:407–439 (1962).
Gruger, E. H., Jr., and A. L. Tappel, J. Chromatog. 40:177–181 (1969).
Frankel, E. N., in “Symposium on Foods: Lipids and Their Oxidation,” Edited by H. W. Schultz, E. A. Day and R. O. Sinnhuber, The Avi Publishing Co., Westport, 1962, p. 51–78.
Gruger, E. H., Jr., “Reactions of Biological Anti-oxidants With Aliphatic Hydroperoxides,” Ph. D. Dissertation, University of California, Davis, 1968.
Wise, W. S., and G. S. Twigg, J. Chem. Soc. (London) 1953:2168–2171.
Uri, N., in “Autoxidation and Antioxidants,” Vol. 1, Edited by W. O. Lundberg, Interscience Publishers, New York, 1961, p. 85–96.
Jaffe, H. H., and M. Orchin, “Theory and Application of Ultraviolet Spectroscopy,” John Wiley & Sons, Inc., New York, 1962, p. 558–563.
Knapp, F., and A. L. Tappel, JAOCS 38:151–156 (1961).
Goodhue, C. T., and H. A. Risley, Biochemistry 4:854–858 (1965).
Boyer, P. D., J. Am. Chem. Soc. 73:733–740 (1951).
Skinner, W. A., and P. Alaupovic, Science 140:803–805 (1963).
Inglett, G. E., and H. A. Mattill, J. Am. Chem. Soc. 77:6552–6554 (1955).
Folkers, K., J. L. Smith and H. W. Moore, Federation Proc. 24(1):79–84 (1965).
Scott, G., “Atmospheric Oxidation and Antioxidants,” Elsevier Publishing Co., New York, 1965, p. 52–54.
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Gruger, E.H., Tappel, A.L. Reactions of biological antioxidants: I. Fe(III)-catalyzed reactions of lipid hydroperoxides with α-tocopherol. Lipids 5, 326–331 (1970). https://doi.org/10.1007/BF02531464
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DOI: https://doi.org/10.1007/BF02531464