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α-tocopherol oxidation mediated by superoxide anion (O −2 ) I. Reactions in aprotic and protic conditions

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Lipids

Abstract

The reaction of α-tocopherol (α-T) with superoxide anion (O −2 ) in both dry acetonitrile and in aqueous acetonitrile solution is described. The O −2 was generated by the electrochemical reduction of molecular oxygen in acetonitrile, using tetrabutylammonium bromide as an electrolyte. α-T was reacted with O −2 either in dry acetonitrile or in a 10% aqueous acetonitrile solution. In dry acetonitrile, α-T was oxidized to a very unstable primary intermediate, which was further oxidized to a secondary, more stable intermediate. The formation of the secondary intermediate depended upon the presence of molecular oxygen. This intermediate readily converted into two compounds in equimolar amounts (designated A and B). The primary, very unstable intermediate was readily reduced again to α-T by treatment with LiAlH4 or ascorbic acid. However, the secondary intermediate or the stable oxidation products could not be reduced to α-T. In the 10% aqueous acetonitrile, α-T was oxidized to α-tocopheryl quinone, α-tocopherol dimer and α-tocopherol dihydroxy dimer, and an unknown compound. In the aqueous medium, no intermediates were formed by the action of O −2 . The results of this study indicate that the reaction of α-T with O −2 under aprotic conditions is different from that observed under protic conditions.

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Abbreviations

α-T:

α-tocopherol

D:

α-T dimer

DHD:

α-T dihydroxy dimer

HPLC:

high-performance liquid chromatography

O −2 :

superoxide anion

O.D.:

optical density

TBAB:

tetrabutylammonium bromide

TQ:

α-tocopheryl quinone

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Author notes

  1. Yeong L. Ha

    Present address: Gyeongsang National University, 900 Gazwa-Dong, Chinju, Korea

Authors and Affiliations

  1. Department of Food Science and Nutrition, University of Minnesota, 55108, St. Paul, Minnesota

    A. Saari Csallany & Yeong L. Ha

Authors
  1. A. Saari Csallany
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  2. Yeong L. Ha
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Csallany, A.S., Ha, Y.L. α-tocopherol oxidation mediated by superoxide anion (O −2 ) I. Reactions in aprotic and protic conditions. Lipids 27, 195–200 (1992). https://doi.org/10.1007/BF02536178

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  • DOI: https://doi.org/10.1007/BF02536178

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