Hydroperoxidation of Unsaturated Fatty Esters

  • Edwin N. Frankel
Part of the Basic Life Sciences book series (BLSC, volume 49)


Much work has been published on the hydroperoxides of unsaturated lipids. Only recently has significant progress been made, however, to clarify the mechanism and stereochemistry of lipid hydroperoxidation. Although there is considerable information available on the chemistry of lipid oxidation, the biological effects of lipid oxidation products are not well understood. Studies on the source of volatile oxidation products and on their physiological importance are still controversial and difficult to interpret.


Methyl Linolenate Lipid Oxidation Product Linolenate Hydroperoxide Photosensitize Oxidation Methyl Elaidate 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    A.J. Stirton, J. Turer, and R.W. Riemerischneider, Oxygen absorption of methyl esters of fatty acids, and the effect of antioxidants, Oil Soap 22:81 (1945).CrossRefGoogle Scholar
  2. 2.
    R.T. Holman, and O.C. Elmer, The rates of oxidation of unsaturated fatty acids and esters, J. Am. Oil Chem. Sec. 24:127 (1947).CrossRefGoogle Scholar
  3. 3.
    J.P. Cosgrove, D.F. Church, and W.A. Pryor, The kinetics of the autoxidation of polyunsaturated fatty acids, Lipids 22:299 (1987).PubMedCrossRefGoogle Scholar
  4. 4.
    G. Scott, Antioxidants in vitro and in vivo, Chemistry in Britain 7:648 (1985).Google Scholar
  5. 5.
    E.N. Frankel, Volatile lipid oxidation products, Prog. Lipid Res. 22:1 (1983).Google Scholar
  6. 6.
    E.N. Frankel, Recent advances in the chemistry of rancidity of fats, in: “Recent Advances in the Chemistry of Meat,” A.J. Bailey, ed., The Royal Society of Chemistry, London (1984).Google Scholar
  7. 7.
    H.R. Rawls and P.J. Van Santen, A possible source of the original hydroperoxides in fatty acids, Ann. N Y Acad. Sci. 171:135 (1970).CrossRefGoogle Scholar
  8. 8.
    H.R. Rawls and P.J. Van Santen, A possible role for singlet oxygen in the initiation of fatty acid autoxidation, J. Am. Oil Chem. Soc. 47:121 (1970).CrossRefGoogle Scholar
  9. 9.
    K. Warner and E.N. Frankel, Effects of ß-carotetene on light stability of soybean oil, J. Arc. Oil Chem. Soc. 64:213 (1987).CrossRefGoogle Scholar
  10. 10.
    E.N. Frankel, W.E. Neff, and T.R. Bessler, Analysis of autoxidized fats by gas chroiratography-mass spectrometry: V. Photosensitized oxidation, Lipids 14:961 (1979).CrossRefGoogle Scholar
  11. 11.
    E.N. Frankel, W.E. Neff, W.K. Rohwedder, B.P.S. Khaitibay, R.F. Garwood, and B.C.L. Weedon, Analysis of autoxidized fats by gas chramatography-inass spectrometry: I. Methyl oleate, Lipids 2:901 (1977).CrossRefGoogle Scholar
  12. 12.
    W.E. Neff and E.N. Frankel, Quantitative analysis of hydroxystearate isomers from hydroperoxides by high-pressure liquid chromatography of autoxidized and photosensitized oxidized fatty esters, Lipids 15:587 (1980).CrossRefGoogle Scholar
  13. 13.
    E.N. Frankel, R.F. Garwood, B.P.S. Khaitibay, G.P. Moss, and B.C.L. Weedon, Stereochemistry of olefin and fatty acid oxidation. III. The allylic hydroperoxides from the autoxidation of methyl oleate, J. Chem. Soc., Perkin Trans. I. 2233 (1984).CrossRefGoogle Scholar
  14. 14.
    E. Bascetta, F.D. Gunstone, and J.C. Walton, An electron spin resonance study of fatty acids and esters. Part 1. Hydrogen abstraction from olefinic and acetylenic long-chain esters, J. Chem. Soc., Perkin Trans. II. 603 (1983).Google Scholar
  15. 15.
    E.N. Frankel, W.E. Neff, W.K. Rohwedder, B.P.S. Khaitibay, R.F. Garwood, and B.C.L. Weedon, Analysis of autoxidized fats by gas chromatography-mass spectrometry: II. Methyl Linoleate, Lipids 12:908 (1977).PubMedCrossRefGoogle Scholar
  16. 16.
    H.W.-S. Chan, C.T. Costaras, F.A.A. Prescott, and P.A.T. Swoboda, Thermal isomerisations of linoleate hydroperoxides, a phenomenon affecting the determination of isomeric ratios, Biochim. Biobhvs. Acta 398:347 (1975).Google Scholar
  17. 17.
    H.W.-S. Chan, G. Levett, and J.A. Matthew, The mechanism of the rearrangement of linoleate hydroperoxides, Chem. Phys. Lipids 24:245 (1979).CrossRefGoogle Scholar
  18. 18.
    E.N. Frankel, Chemistry of free radical and singlet oxidation of lipids, Prog Lipid Res. 23:197 (1985).CrossRefGoogle Scholar
  19. 19.
    N.A. Porter, B.A. Weber, H. Weenen, and J.A. Khan, Autoxidation of polyunsaturated lipids. Factors controlling the stereochemistry of product hydroperoxides, J. Am. Chem. Soc. 102:5597 (1980).CrossRefGoogle Scholar
  20. 20.
    K.E. Peers, D.T. Coxon, and H.W.-S. Chan, Autoxidation of methyl linoleate: The effect of alpha-toœpherol, J. Sci. Food Agric. 32:898 (1981).CrossRefGoogle Scholar
  21. 21.
    P. Schieberle and W. Grosch, Detection of monohydroperoxides with unconjugated diene systems as minor products of the autoxidation of methyl linoleate, Z. lebensm. Unters. Forsch. 173:199 (1981).CrossRefGoogle Scholar
  22. 22.
    E.N. Frankel, C.D. Evans, D.G. McConnell, E. Selke, and H.J. Dutton, Autoxidation of methyl linolenate. Isolation and characterization of hydroperoxides, J. Org. Chem. 26:4663 (1961).CrossRefGoogle Scholar
  23. 23.
    E.N. Frankel, W.E. Neff, W.K. Rohwedder, B.P.S. Khaitibay, R.F. Garwood and B.C.L. Weedon, Analysis of autoxidized fats by gas chromatography-mass spectrometry: III. Methyl Linolenate, Lipids 12:1055 (1977).CrossRefGoogle Scholar
  24. 24.
    H.W.-S. Chan and G. Levett, Autoxidation of methyl linolenate. Analyses of methyl hydroxylinolenate isomers by high performance liquid diromatography, Lipids 12:837 (1977).CrossRefGoogle Scholar
  25. 25.
    W.E. Neff, E.N. Frankel and D. Weisleder, High-pressure liquid chrcmatography of autoxidized lipids: II. Hydroperoxy-cyclic peroxides and other secondary products from methyl linolenate, Lipids 16:439 (1981).CrossRefGoogle Scholar
  26. 26.
    D.T. Coxon, K.R. Price, and H.W.-S. Chan, Formation, isolation and structure determination of methyl linolenate diperoxides, Chem. Phys. Lipids 28:365 (1981).CrossRefGoogle Scholar
  27. 27.
    I. Toyoda, J. Terao, and S. Matsushita, Hydroperoxides formed by ferrous ion catalyzed oxidation of methyl linolenate, Lipids 17:84 (1982).CrossRefGoogle Scholar
  28. 28.
    J. Terao, and S. Matsushita, Analysis of hemoprotein catalyzed peroxidation products of arachidonic acid by gas dhromatography mass spectrometry, Agric. Biol. Chem. 45:595 (1981).Google Scholar
  29. 29.
    N.A. Porter, L.S. Lehman, B.A. Weber, and K.J. Smith, Unified mechanism for polyunsaturated fatty acid autoxidation. Competition of peroxy radical hydrogen atom abstraction, -scission, and cyclization, J. Am. Chem. Soc. 103:6447 (1981).CrossRefGoogle Scholar
  30. 30.
    H.W. Gardner, R. KLeiman, and D. Weisleder, Hemolytic decomposition of linoleic acid hydroperoxides: Identification of fatty acid esters, Lipids 9:696 (1984).CrossRefGoogle Scholar
  31. 31.
    W.A. Pryor, J.P. Stanley, and E. Blair, Autoxidation of polyunsaturated fatty acids: II. Suggested mechanism for the formation of TBA-reactive materials from prostaglandin-like endoperoxides, Lipids 11:370 (1979).CrossRefGoogle Scholar
  32. 32.
    D.E. O’Connor, E.D. Mihelich, and M.C. Coleman, Stereochemical course of the autoxidative cyclization of lipid hydroperoxides to prostaglandin-like bicycloendqperoxides, J. Am. Chem. Soc., 106:3577 (1984).CrossRefGoogle Scholar
  33. 33.
    W.E. Neff, E.N. Frankel, and D. Weisleder, Photosensitized oxidation of methyl linolenate. Secondary products, Lipids 17:780 (1982).CrossRefGoogle Scholar
  34. 34.
    J.A. Khan and N.A. Porter, Serial cyclization of an arachidonic acid hydroperoxide, Ancrew. Chem. Suppl. 513 (1982).Google Scholar
  35. 35.
    E.D. Mihelich, Structure and stereochemistry of novel endoperoxides isolated from the sensitized photoxidation of methyl linoleate. Implications for prostaglandin biosynthesis, J. Am. Chem. Soc. 102:7141 (1980).CrossRefGoogle Scholar
  36. 36.
    E.N. Frankel, W.E. Neff, E. Selke and D. Weisleder, Photosensitized oxidation of methyl linoleate. Secondary and volatile thermal decomposition products, Lipids 17:11 (1982).CrossRefGoogle Scholar
  37. 37.
    E.N. Frankel, W.E. Neff, and E. Selke, Analysis of autoxidized fats by gas chromatography-mass spectrometry: VII. Volatile thermal deconposition products of pure hydroperoxides from autoxidized and photosensitized oxidized methyl oleate, linoleate, and linolenate, Lipids 16:279 (1981).CrossRefGoogle Scholar
  38. 38.
    E.N. Frankel, W.E. Neff, E. Selke, and D.D. Brooks, Thermal and metal-catalyzed decomposition of methyl linolenate hydroperoxides, Lipids 22:322 (1987).CrossRefGoogle Scholar
  39. 39.
    K.S. Chio and A.L. Tappel, Synthesis and characterization of the fluorescent products derived from malonaldehyde and amino acids, Biochemistry 8:2821 (1969).PubMedCrossRefGoogle Scholar
  40. 40.
    C.J. Dillard and A.L. Tappel, Fluorescent products from reaction of peroxidizing polyunsaturated fatty acids with phosphatidyl ethanolamine and phenylalanine, Lipids 8:183 (1973).PubMedCrossRefGoogle Scholar
  41. 41.
    W.R. Bidlack and A.L. Tappel, Fluorescent products of phospholipids during lipid peroxidation, Lipids 8:203 (1973).PubMedCrossRefGoogle Scholar
  42. 42.
    R. Trombly and A. L. Tappel, Fractionation and analysis of fluorescent products of lipid peroxidation, Lipids 10:441 (1975).PubMedCrossRefGoogle Scholar
  43. 43.
    E.N. Frankel and W.E. Neff, Formation of malonaldéhyde from lipid oxidation products, Biochim. Biophvs. Acta 754:264 (1983).CrossRefGoogle Scholar
  44. 44.
    E.N. Frankel, W.E. Neff, and E. Selke, Analysis of autoxidized fats by gas chramatography-mass spectrometry. IX. Hemolytic vs. heterolytic cleavage of primary and secondary oxidation products, Lipids 19:790 (1984).CrossRefGoogle Scholar
  45. 45.
    P.A. Cerutti, Prooxidant states and tumor promotion, Science227:375 (1985).PubMedCrossRefGoogle Scholar
  46. 46.
    T.J. Slaga, A.J.P. Klein-Szanto, L.L. Triplett, L.P. Yotti, and J.E. Trosko, Skin tumor-prcraoting activity of benzoyl peroxide, a widely used free radical-generating compound, Science 213:1023 (1981).PubMedCrossRefGoogle Scholar
  47. 47.
    B.L. Van Duuren, N. Nelson, L. Orris, E.D. Palmes, and F.L. Schmitt, Carcinogenicity of epoxides, lactones, and peroxy compounds, J. Nat. Cancer Inst. 31:41 (1963).Google Scholar
  48. 48.
    E.N. Frankel, Hydroperoxides, in: “Syirposium on Foods: Lipids and Their Oxidation,” H.W. Schultz, E.A. Day, and R.O. Sinrihuber, eds., The Avi Publishing Co., Inc., Westport, C.T (1962).Google Scholar
  49. 49.
    K. Fujimoto, W.E. Neff, and E.N. Frankel, The reaction of DNA with lipid oxidation products, metals and reducing agents, Biochim. Biophys. Acta 795:100 (1984).PubMedCrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1988

Authors and Affiliations

  • Edwin N. Frankel
    • 1
  1. 1.Northern Regional Research CenterU. S. Department of AgriculturePeoriaUSA

Personalised recommendations