Autoxidation of synthetic isomers of triacylglycerol containing eicosapentaenoic acid

  • Yasushi Endo
  • Sanae Hoshizaki
  • Kenshiro Fujimoto


Several triacylglycerols (TAG) that contained eicosapentaenoic acid (EPA) were chemically synthesized and stored at 25°C to assess the influence of TAG structure on oxidative stability and formation of oxidation products. Oxidative stability was evaluated by oxygen consumption during storage of the TAG. Autoxidation products of TAG were analyzed by high-performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS). Results showed that a 2:1 (mole/mole) mixture of trieicosapentaenoylglycerol (EEE) and tripalmitoylglycerol (PPP) was most susceptible to autoxidation. The oxidative stability of TAG that contained EPA and palmitic acid was negatively correlated with the moles of EPA in a single TAG molecule. When TAG with one EPA and two other fatty acids were oxidized, chainlength of constituent fatty acids hardly affected the oxidative stability of EPA-containing TAG molecules, except for stearic acid. HPLC and LC-MS analyses showed that monohydroperoxides were major oxidation products regardless of type of TAG. Bis- and tris-hydroperoxides were formed during autoxidation of EEE and dieicos-apentaenoylpalmitoylglycerol. Monohydroperoxy epidioxides were found in all autoxidized TAG. These observations suggested that TAG structure affected the oxidation of TAG with highly unsaturated fatty acids.

Key Words

Autoxidation eicosapentaenoic acid hydroperoxide oxidative stability triacylglycerol triacylglycerol structure 


  1. 1.
    Raghuveer, K.G., and E.G. Hammond, The Influence of Glyceride Structure on the Rate of Autoxidation, J. Am. Oil Chem. Soc. 44:239–243 (1967).PubMedCrossRefGoogle Scholar
  2. 2.
    Lau, F.Y., E.G. Hammond, and P.F. Ross, Effect of Randomization on the Oxidation of Corn Oil, Ibid.:407–411 (1982).CrossRefGoogle Scholar
  3. 3.
    Wada, S., and C. Koizumi, Influence of the Position of Unsaturated Fatty Acid Esterified Glycerol on the Oxidation Rate of Triglyceride, Ibid.:1105–1109 (1983).Google Scholar
  4. 4.
    Tautorus, C.L., and A.R. McCurdy, Effect of Randomization on Oxidative Stability of Vegetable Oils at Two Different Temperatures, Ibid.:525–530 (1990).CrossRefGoogle Scholar
  5. 5.
    Neff, W.E., E. Selke, T.L. Mounts, W.W. Rinsch, E.N. Frankel, and M.A.M. Zeitoun, Effect of Triacylglycerol Composition and Structures on Oxidative Stability of Oils from Selected Soybean Germplasm,:111–118 (1992).CrossRefGoogle Scholar
  6. 6.
    Yoon, H.S., T. Ohshima, and C. Koizumi, Susceptibilities of Different Molecular Species of Soybean Oil Triglycerides to Non-Catalyzed and Fe2+-Catalyzed Oxidations, Nippon Shokuhin Kogyo Gakkaishi 40:123–132 (1993).Google Scholar
  7. 7.
    Neff, W.E., T.L. Mounts, W.M. Rinsch, H. Konishi, and M.A. El-Agaimy, Oxidative Stability of Purified Canola Oil Triacylglycerols with Altered Fatty Acid Compositions Affected by Triacylglycerol Composition and Structure, J. Am. Oil Chem. Soc. 71:1101–1109 (1994).CrossRefGoogle Scholar
  8. 8.
    Endo, Y., H. Kimoto, and K. Fujimoto, Retarded Autoxidation of Sardine Oil with Oleate, Biosci. Biotech. Biochem. 57:2202–2204 (1993).CrossRefGoogle Scholar
  9. 9.
    Kimoto, H., Y. Endo, and K. Fujimoto, Influence of Interesterification on the Oxidative Stability of Marine Oil Triacylglycerols, J. Am. Oil Chem. Soc. 71:469–473 (1994).CrossRefGoogle Scholar
  10. 10.
    Awl, R.A., E.N. Frankel, and D. Weisleder, Synthesis and Characterization of Triacylglycerols Containing Linoleate and Linolenate, Lipids 24:866–872 (1989).CrossRefGoogle Scholar
  11. 11.
    Frankel, E.N., E. Selke, W.E. Neff, and K. Miyashita, Autoxidation of Polyunsaturated Triacylglycerols. IV. Volatile Decomposition Products from Triacylglycerols Containing Linoleate and Linolenate, Ibid.:442–446 (1992).CrossRefGoogle Scholar
  12. 12.
    Miyashita, K., E.N. Frankel, W.E. Neff, and R.A. Awl, Autoxidation of Polyunsaturated Triacylglycerols. III. Synthetic Triacylglycerols Containing Linoleate and Linolenate, Ibid.:48–53 (1990).CrossRefGoogle Scholar
  13. 13.
    Park, D.K., J. Terao, and S. Matsushita, Influence of Interesterification on the Autoxidative Stability of Vegetable Oils, Agric. Biol. Chem. 47:121–123 (1983).Google Scholar
  14. 14.
    Park, D.K., J. Terao, and S. Matsushita, Influence of Triglyceride Molecular Species on Autoxidation, Ibid.:2243–2249 (1983).Google Scholar
  15. 15.
    Park, D.K., J. Terao, and S. Matsushita, Influence of the Positions of Unsaturated Acyl Groups in Glycerides on Autoxidation, Ibid.:2251–2255 (1983).Google Scholar
  16. 16.
    Yamauchi, R., T. Yamada, K. Kato, and Y. Ueno, Monohydroperoxides Formed by Autoxidation and Photosensitized Oxidation of Methyl Eicosapentaenoate, Ibid.:2897–2902 (1983).Google Scholar
  17. 17.
    Yamauchi, R., T. Yamada, K. Kato, and Y. Ueno, Autoxidation and Photosensitized Oxidation of Methyl Eicosapentaenoate: Secondary Oxidation Products, Ibid.:2077–2082 (1985).Google Scholar
  18. 18.
    Frankel, E.N., Review, Recent Advances in Lipid Oxidation, J. Sci. Food Agric. 54:495–511 (1991).CrossRefGoogle Scholar

Copyright information

© AOCS Press 1997

Authors and Affiliations

  • Yasushi Endo
    • 1
  • Sanae Hoshizaki
    • 1
  • Kenshiro Fujimoto
    • 1
  1. 1.Department of Applied Biological Chemistry, Faculty of AgricultureTohoku UniversitySendaiJapan

Personalised recommendations