Skip to main content
SpringerLink
Log in

Mechanism of lower oxidizability of eicosapentaenoate than linoleate in aqueous micelles. II. Effect of antioxidants

  • Published:
Lipids

Abstract

We have reported that the peroxyl radicals derived from methyl eicosapentaenoate (20:5n-3) are more polar than those from methyl linoleate (18:2n-6) since the former peroxyl radicals have at least two molecules of oxygen in a molecule while the latter peroxyl radical has one. This lowers the oxidizability for 20:5n-3 in aqueous Triton X-100 micelles by enhancing the termination reaction rate for peroxyl radicals and by reducing the rate of propagation since there may be more polar peroxyl radicals derived from 20:5n-3 at the surface than within the micelle core. In this study, we measured the effect of three antioxidants, di-tert-butyl-4-methylphenol (BHT), 2,2,5,7,8-pentamethyl-6-chromanol (PMC) and 2-carboxy-2,5,7,8-tetramethyl-6-chromanol (Trolox), on the oxidation of lipids in aqueous micelle. Antioxidants give a clear induction period during oxidation of 18:2n-6 initiated with a water-soluble radical initiator, and its induction length decreases in the order of BHT>PMC>Trolox. This is consistent with the proposed location of three antioxidants: being in the core of micelle, at the surface, or in aqueous phase, respectively. However, BHT does not inhibit the oxidation of 20:5n-3 efficiently, and its rate of oxidation is slower than that observed in the oxidation of 18:2n-6, supporting the idea that polar peroxyl radicals derived from 20:5n-3 are preferentially located at the surface of the micelle. Similar results were obtained when oxidation was initiated with a lipid-soluble radical initiator except antioxidants had lesser effect on the oxidation rate of 20:5n-3.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Abbreviations

18:2n-6:

methyl linoleate

20:5n-3:

methyl eicosapentaenoate

AAPH:

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

AMVN:

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

BHT:

2,6-di-tert-butyl-4-methylphenol

PMC:

2,2,5,7,8-pentamethyl-6-chromanol

Trolox:

2-carboxy-2,5,7,8-tetramethyl-6-chromanol

References

  1. Howard, J.A., and Ingold, K.U. (1967) Absolute Rate Constants for Hydrocarbon Autoxidation. VI. Alkyl Aromatic and Olefinic Hydrocarbons, Can. J. Chem. 45, 793–802.

    Article  CAS  Google Scholar 

  2. Yamamoto, Y., Niki, E., and Kamiya, Y. (1982) Quantitative Determination of the Oxidation of Methyl Linoleate and Methyl Linolenate, Bull. Chem. Soc. Jpn. 55, 1548–1550.

    Article  CAS  Google Scholar 

  3. Yamamoto, Y., Niki, E., Kamiya, Y., and Shimasaki, H. (1984) Oxidation of Phosphatidylcholines in Homogeneous Solution and in Water Dispersion, Biochim. Biophys. Acta 795, 332–340.

    PubMed  CAS  Google Scholar 

  4. Cosgrove, J.P., Church, D.F., and Pryor, W.A. (1987) The Kinetics of the Autoxidation of Polyunsaturated Fatty Acids, Lipids 22, 299–304.

    PubMed  CAS  Google Scholar 

  5. Bruna, E., Petit, E., Beijean-Leymarie, M., Huynh S., and Nouvelot, A. (1989) Specific Susceptibility of Docosahexaenoic Acid and Eicosapentaenoic Acid to Peroxidation in Aqueous Solution, Lipids 24, 970–975.

    CAS  Google Scholar 

  6. Miyashita, K., Nara, E., and Ota, T. (1993) Oxidative Stability of Polyunsaturated Fatty Acids in an Aqueous Solution, Biosci. Biotech. Biochem. 57, 1638–1640.

    Article  CAS  Google Scholar 

  7. Yazu, K., Yamamoto, Y., Ukegawa, K., and Niki, E. (1996) Mechanism of Lower Oxidizability of Eicosapentaenoate Than Linoleate in Aqueous Micelles, Lipids 31, 337–340.

    PubMed  CAS  Google Scholar 

  8. Alauddin, M., and Verrall, R.E. (1984) Apparent Molal Volume studies of 2,6-Di-tert-butyl-4-methylphenol, 2-tert-Butyl-4-methoxyphenol, and 2,6-Di-tert-butyl-4-(hydroxymethyl)phenol in Aqueous Micelle Solutions of Sodium Dodecanoate as a Function of Micelle Concentration and Temperature, J. Phys. Chem. 88, 5725–5730.

    Article  CAS  Google Scholar 

  9. Alauddin, M., and Verrall, R.E. (1984) Apparent Molal Volume Studies of 2,6-Di-tert-butyl-4-methylphenol, 2-tert-Butyl-4-methoxyphenol, and 2,6-Di-tert-butyl-4-(hydroxymethyl)phenol in Aqueous Micelle Solutions of Cetyltrimethylammonium Bromide as a Function of Micelle Concentration and Temperature, J. Phys. Chem. 90, 1647–1655.

    Article  Google Scholar 

  10. Bidzilya, V.A., Golovkova, L.P., Vlasova, N.N., and Bogomaz, V.I. (1995) Solubilization of α-Tocopherol and Its Analogs in Aqueous Solutions of Nonionic Surfactant, Colloid J. 57, 157–159.

    CAS  Google Scholar 

  11. Castle, L., and Perkins, M.J. (1986) Inhibition Kinetics of Chain-Breaking Phenolic Antioxidants in SDS Micelles. Evidence That Intermicellar Diffusion Rates May Be Rate-limiting for Hydrophobic Inhibitors Such as α-Tocopherol, J. Am. Chem. Soc. 108, 6381–6382.

    Article  CAS  Google Scholar 

  12. Burton, G.W., and Ingold, K.U. (1981) The Antioxidant Activity of Vitamin E and Related Chain-breaking Phenolic Antioxidants in vitro, J. Am. Chem. Soc. 103, 6471–6477.

    Google Scholar 

  13. Burton, G.W., Doba, T., Gabe, E.J., Hughes, L., Lee, F.L., Prasad, L., and Ingold, K.U. (1985) Maximizing the Antioxidant Activity of Phenols, J. Am. Chem. Soc. 107, 7053–7065.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

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

    Kazumasa Yazu, Keiji Miki & 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
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yorihiro Yamamoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Etsuo Niki
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Keiji Miki
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Koji Ukegawa
    View author publications

    You can also search for this author in PubMed Google Scholar

About this article

Cite this article

Yazu, K., Yamamoto, Y., Niki, E. et al. Mechanism of lower oxidizability of eicosapentaenoate than linoleate in aqueous micelles. II. Effect of antioxidants. Lipids 33, 597–600 (1998). https://doi.org/10.1007/s11745-998-0245-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11745-998-0245-3

Keywords

Search

Navigation