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Mechanism of lower oxidizability of eicosapentaenoate than linoleate in aqueous micelles

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Lipids

Abstract

The aerobic oxidation kinetics of methyl eicosapentaenoate (20:5n-3) and methyl linoleate (18:2n-6) were compared in homogeneous chlorobenzene solution and in Triton X-100 aqueous micelles at 37°C. The rate of disappearance of 20:5n-3 was two times faster than that of 18:2n-6 in chlorobenzene, while the former was five times slower than the latter in aqueous micelles. It was also observed that ΔO2=Δ18:2n-6 and ΔO2=2Δ20:5n-3 in aqueous micelles. In the oxidation of a 1∶1 mixture of 20:5n-3 and 18:2n-6 in micelles, the rate of disappearance of 20:5n-3 was 3.6 times faster than that of 18:2n-6, and the rate of total substrate disappearance was reduced by a factor of 5 as compared with 18:2n-6 oxidation. These data suggest that the peroxyl radical derived from 20:5n-3 is more polar than that from 18:2n-6, and the former is likely to diffuse from the core to the micelle surface. This lowers the oxidizability for 20:5n-3 in aqueous micelles by enhancing the termination reaction rate for peroxyl radicals and by reducing the rate of propagation since there may be more 20:5n-3 peroxyl radicals at the surface than in the micelle core.

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Abbreviations

AAPH:

2,2′-azobis(2-amidinopropane) dihydrochloride

AMVN:

2,2′-azobis(2,4-dimethylvaleronitrile)

16:0:

ethyl palmitate

GC:

gas chromatography

20:5n-3:

methyl eicosapentaenoate

18:2n-6:

methyl linoleate

PUFA:

polyunsaturated fatty acids

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Authors and Affiliations

  1. Department of Energy Resources, National Institute for Resources and Environment, 305, Ibaraki, Japan

    Kazumasa Yazu & Koji Ukegawa

  2. Research Center for Advanced Science and Technology, University of Tokyo, Komaba, Meguro-ku, 153, Tokyo, Japan

    Yorihiro Yamamoto & Etsuo Niki

Authors
  1. Kazumasa Yazu
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  2. Yorihiro Yamamoto
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  3. Koji Ukegawa
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  4. Etsuo Niki
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Yazu, K., Yamamoto, Y., Ukegawa, K. et al. Mechanism of lower oxidizability of eicosapentaenoate than linoleate in aqueous micelles. Lipids 31, 337–340 (1996). https://doi.org/10.1007/BF02529881

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  • DOI: https://doi.org/10.1007/BF02529881

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