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Mechanisms of free radical oxidation of unsaturated lipids

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Lipids

Abstract

The primary producs formed from the autoxidation of lipids can be understood based upon a mechanism that involves five different reaction types. These reactions are: reaction of a carbon radical and molecular oxygen, atom transfer of a hydrogen from substrate to the chain carrying peroxyl, fragmentation of the chain carrying peroxyl to give oxygen and a carbon radical, rearrangement of the peroxyl, and cyclization of the peroxyl. The mechanisms of these primary reaction steps has been the focus of extensive research over the past fifty years, and the current level of understanding of these transformations is the subject of this review.

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Abbreviations

GC/MS:

gas chromatography/mass spectrometry

HPLC:

high-pressure liquid chromatography

NMR:

nuclear magnetic resonance

References

  1. Lavoisier, A.L. (1789)Elements of Chemistry (translasted by Robert Kerr) pp. 107–108, Dover Publications, 1965, New York.

  2. Mayo, F.R. (1986)J. Chem. Ed. 63, 97–98.

    CAS  Google Scholar 

  3. Walling, C. (1986)J. Chem. Ed. 63, 99–101.

    CAS  Google Scholar 

  4. Walling, C. (1987)Chem. Br., 23, 769–770.

    Google Scholar 

  5. Porter, N.A. (1986)Acc. Chem. Res. 19, 262–268.

    Article  CAS  Google Scholar 

  6. Porter, N.A. (1990)Membrane Lipid Oxidation (Vigo-Pelfrey, C., ed.) Vol. I, pp. 33–62, CRC Press, Boca Raton.

    Google Scholar 

  7. Marnett, L.J. (1987) inAnticarcinogenesis and Radiation Protection (Ceruti, P.A., Nygard, O.F., and Simic, M.G., eds.) pp. 71–80, Plenum Press, New York.

    Google Scholar 

  8. Gershon, D. (1988) inReactive Oxygen Species in Chemistry, Biology, and Medicine (Quintanilla, A., ed.) pp. 211–219, Plenum Press, New York.

    Google Scholar 

  9. Cheeseman, K.H., and Slater, T.F. (1993)British Med. Bull. 9, 481–493.

    Google Scholar 

  10. Gardner, H.W. (1983) inXenobiotics in Foods and Feeds, 234 (Finley, J.W., and Schwass, D.W., eds.) pp. 63–98, American Chemical Society Symposium Series, Washington, D.C.

  11. Porter, N.A. (1985) inChemical Changes in Food During Processing (Richardson, T., and Finley, J.W., eds.) pp. 73–78, AVI Publishing Co., Inc., Westport.

    Google Scholar 

  12. Hessler, J.R., Morel, D.W., Lewis, L.J., and Chisholm, G.M. (1983)Arteriosclerosis 3, 215–222.

    PubMed  CAS  Google Scholar 

  13. Steinbrecher, U.P., Parthasarathy, S., Leake, D.S., Witztum, J.L., and Steinberg, D. (1984)Proc. Natl. Acad. Sci. USA 81, 3883–3887.

    Article  PubMed  CAS  Google Scholar 

  14. Davies, A.G., Griller, D., Ingold, K.U., Lindsay, D.A., and Walton, J.C. (1981)J. Chem. Soc. Perkin Trans. II, 633–641.

    Google Scholar 

  15. Howard, J.A. (1973) inFree Radicals (Kochi, J.K., ed.) Vol. II, pp. 15–31, John Wiley and Sons, New York.

    Google Scholar 

  16. Nonhebel, D.C., and Walton, J.C. (1984) inFree Radical Chemistry, pp. 393–417, Cambridge University Press, London.

    Google Scholar 

  17. Howard, J.A. (1972) inAdvances in Free Radical Chemistry, Vol. IV, pp. 75–138, Academic Press, New York.

    Google Scholar 

  18. Farmer, E.H., and Sutton, D.A. (1943)J. Chem. Soc., 119–122.

  19. Farmer, E.H., Koch, H.P., and Sutton, D.A. (1943),J. Chem. Soc., 541–547.

  20. Bickford, W.G., Fisher, G.S., Kyame, L., and Swift, C.E. (1948)J. Am. Oil Chem. Soc. 24, 254–257.

    Google Scholar 

  21. Ross, J., Gebhart, A.I., and Gerecht, J.F. (1946)J. Am. Chem. Soc. 68, 1373–1376.

    Article  CAS  Google Scholar 

  22. Frankel, E.N. (1980) inAutoxidation in Food and Biological Systems (Simic, M., and Karel, M., eds.) pp. 141–183, Plenum Press, New York.

    Google Scholar 

  23. Frankel, E.N., Neff, W.E., and Rohwedder, W.K. (1977)Lipids 12, 901–907.

    Article  PubMed  CAS  Google Scholar 

  24. Frankel, E.N., Garwood, R.F., Khambay, B.P., Moss, G.P., and Weedon, B.C. (1984)J. Chem. Soc. Perkin Trans. I, 2233–2240.

    Article  Google Scholar 

  25. Pritzkow, W., Radeolia, R., and Schmidt-Renner, W. (1979)J. Prakt. Chem. 321, 813–826.

    Article  CAS  Google Scholar 

  26. Porter, N.A., Mills, K.A., and Carter, R.L. (1994)J. Am. Chem. Soc. 116, 6690–6696.

    Article  CAS  Google Scholar 

  27. Courtneidge, J.L., and Bush, M. (1992)J. Chem. Soc. Perkin Trans. I, 1531–1538.

    Article  Google Scholar 

  28. Courtneidge, J.L., Bush, M., and Loh, L.-S. (1992)J. Chem. Soc. Perkin Trans. I, 1539–1548.

    Article  Google Scholar 

  29. Courtneidge, J.L. (1992)J. Chem. Soc. Chem. Commun., 1270–1272.

  30. Howard, J.A., Schwalm, W.J., and Ingold, K.U. (1968)Adv. Chem. Ser. 75, 6–23.

    Google Scholar 

  31. Middleton, B.S., and Ingold, K.U. (1967)Can. J. Chem. 45, 191–194.

    Article  CAS  Google Scholar 

  32. Chenier, J.H., and Howard, J.A. (1975)Can. J. Chem. 53, 623–627.

    Article  CAS  Google Scholar 

  33. Howard, J.A. (1984)Israel J. Chem. 24, 33–37.

    CAS  Google Scholar 

  34. Thomas, J.R., and Tolman, C.A. (1962)J. Am. Chem. Soc. 84, 2079–2080.

    Article  CAS  Google Scholar 

  35. Thomas, J.R. (1967)J. Am. Chem. Soc. 84, 4872–4875.

    Article  Google Scholar 

  36. Saebo, S., Beckwith, A.L.J., and Radom, L. (1984)J. Am. Chem. Soc. 106, 5119–1522.

    Article  CAS  Google Scholar 

  37. Lindsay, D.A., Lusztyk, J., and Ingold, K.U. (1984)J. Am. Chem. Soc. 106, 7087–7093.

    Article  CAS  Google Scholar 

  38. Barclay, L.R.C., Lusztyk, J., and Ingold, K.U. (1984)J. Am. Chem. Soc. 106, 1793–1796.

    Article  CAS  Google Scholar 

  39. Crich, D., and Filzen, G.F. (1993)Tetrahedron Lett. 34, 3225–3229.

    Article  CAS  Google Scholar 

  40. Frimer, A.A. (1979)Chem. Rev. 79, 359–387.

    Article  CAS  Google Scholar 

  41. Brill, W.F. (1984)J. Chem. Soc. Perkin Trans. II, 621–627.

    Google Scholar 

  42. Schenck, G.O. (1957)Angew. Chem. 69, 579–599.

    CAS  Google Scholar 

  43. Schenck, G.O., Neumuller, O.A., and Eisfeld, K.C. (1958)Angew. Chem. 70, p. 595.

    CAS  Google Scholar 

  44. Smith, L.L. (1981)Cholesterol Autoxidation, Plenum Press, New York.

    Google Scholar 

  45. Beckwith, A.L., Davies, A.G., Davison, I.G., Macoll, A., and Mruzek, M.H. (1989)J. Chem. Soc. Perkin Trans. II, 815–824.

    Google Scholar 

  46. Davies, A.G., and Davison, I.G. (1989)J. Chem. Soc. Perkin Trans. II, 825–830.

    Google Scholar 

  47. Brill, W.F. (1965)J. Am. Chem. Soc. 87, 3286–3287.

    Article  CAS  Google Scholar 

  48. Brill, W.F. (1968)Adv. Chem. Ser. 75, 93–101.

    Article  Google Scholar 

  49. Porter, N.A., and Zuraw, P. (1985)J. Chem. Soc. Chem. Commun., 1472–1473.

  50. Boyd, S.L., Boyd, R.J., Shi, Z., Barclay, R.C., and Porter, N.A. (1993)J. Am. Chem. Soc. 115, 687–693.

    Article  CAS  Google Scholar 

  51. Porter, N.A., Kaplan, J.K., and Dussault, P.H. (1990)J. Am. Chem. Soc. 112, 1266–1267.

    Article  CAS  Google Scholar 

  52. Mills, K.A., Caldwell, S.E., Dubay, G.R., and Porter, N.A. (1992),J. Am. Chem. Soc. 114, 9689–9691.

    Article  CAS  Google Scholar 

  53. Porter, N.A., Mills, K.A., Caldwell, S.E., and Dubay, G.R. (1994)J. Am. Chem. Soc. 116, 6697–6705.

    Article  CAS  Google Scholar 

  54. Chan, H.W.S., Levett, G., and Matthew, J.A. (1979)Chem. Phys. Lipids 24, 245–256.

    Article  CAS  Google Scholar 

  55. Teng, J.I., and Smith, L.L. (1985)J. Chromatogr. 350, 445–451.

    Article  PubMed  CAS  Google Scholar 

  56. Porter, N.A., and Wujek, D.G. (1984)J. Am. Chem. Soc. 106, 2626–2629.

    Article  CAS  Google Scholar 

  57. Porter, N.A., Lehman, L.S., Weber, B.A., and Smith, K.J. (1981)J. Am. Chem. Soc. 103, 6447–6455.

    Article  CAS  Google Scholar 

  58. Iliou, J.P., Jourdheuil, D., Robin, F. Serkiz, B., Guivarch, P., Lolland, J.P., and Vilaine, J.P. (1992)Lipids 27, 959–967.

    PubMed  CAS  Google Scholar 

  59. Brash, A.R., Porter, J.D., and Maas, L.B. (1985)J. Biol. Chem. 260, 4210–4216.

    PubMed  CAS  Google Scholar 

  60. Beckwith, A.L.J., O'Shea, D.M., and Roberts, D.H. (1986)J. Am. Chem. Soc. 108, 6408–6409.

    Article  CAS  Google Scholar 

  61. Porter, N.A., Weber, B.A., Weenen, H., and Khan, J.A. (1980)J. Am. Chem. Soc. 102, 5597–5601.

    Article  CAS  Google Scholar 

  62. Dussault, P.H., and Hayden, M.R. (1992)Tetrahedron Lett. 33, 443–446.

    Article  CAS  Google Scholar 

  63. Bascetta, E., Gunstone, F.D., and Walton, J.C. (1983)J. Chem. Soc. Perkin Trans. II, 603–613.

    Google Scholar 

  64. Hoffmann, R.W. (1989)Chem. Rev. 89, 1841–1860.

    Article  CAS  Google Scholar 

  65. Haslbeck, F., Grosch, W., and Firl, J. (1983)Biochim. Biophys. Acta 705, 185–193.

    Google Scholar 

  66. Doba, T., Burton, G.W., and Ingold, K.U. (1983)J. Am. Chem. Soc. 105, 6505–6506.

    Article  CAS  Google Scholar 

  67. Burton, G.W., and Ingold, K.U. (1981)J. Am. Chem. Soc. 103, 6472–6477.

    Article  CAS  Google Scholar 

  68. Niki, E., Kawakami, A., Saito, M., Yamamoto, Y., Tsuchiya, J., and Kamiya, Y. (1985)J. Biol. Chem. 260, 2191–2196.

    PubMed  CAS  Google Scholar 

  69. Iwatsuki, M., Tsuchiya, J., Komuro, E., Yamamoto, Y., and Niki, E. (1994)Biochim. Biophys. Acta 1200 19–26.

    PubMed  CAS  Google Scholar 

  70. Barclay, L.R.C., Baskin, K.A., Dakin, K.A., Locke, S.J., and Vinqvist, M.R. (1990)Can. J. Chem. 68, 2258–2269.

    Article  CAS  Google Scholar 

  71. Burton, G.W., Doba, T., Gabe, E.J., Hughes, L., Lee, F.L., Prasad, L., and Ingold, K.U. (1985)J. Am. Chem. Soc. 107, 7053–7065.

    Article  CAS  Google Scholar 

  72. Liebler, D.C., Baker, P.F., and Kaysen, K.L. (1990)J. Am. Chem. Soc. 112, 6995–7000.

    Article  CAS  Google Scholar 

  73. Terao, J., and Matsushita, S. (1986)Lipids 21, 255–260.

    Article  CAS  Google Scholar 

  74. Koskas, J.P., Cillard, J., and Cillard, P. (1984)J. Am. Oil Chem. Soc. 61, 466–469.

    Google Scholar 

  75. Weenen, H., and Porter, N.A. (1982)J. Am. Chem. Soc. 104, 5216–5221.

    Article  CAS  Google Scholar 

  76. Peers, K.E., Coxon, D.T., and Chan, H.W.-S. (1981)J. Sci. Food Agric. 32, 898–904.

    Article  CAS  Google Scholar 

  77. Nagaoka, S., Okauchi, Y., Urano, S., Nagashima, U., and Maukai, K. (1990)J. Am. Chem. Soc. 112, 8921–8924.

    Article  CAS  Google Scholar 

  78. Bruna, E., Petit, E., Beljean-Leymarie, M., Huynh, S., and Nouvelot, A. (1990)Lipids 24, 970–975.

    Google Scholar 

  79. Khan, J.A., and Porter, N.A. (1982)Angew. Chem. Int. Ed. 21, 217–218.

    Article  Google Scholar 

  80. Porter, N.A., Wolf, R.A., Yarboro, E.M., and Weenen, H. (1979)Biochem. Biophys. Res. Commun. 89, 1058–1064.

    Article  PubMed  CAS  Google Scholar 

  81. Porter, N.A., Logan, J., and Kontoyiannidou, V. (1979)J. Org. Chem. 44, 3177–3181.

    Article  CAS  Google Scholar 

  82. O'Connor, D.E., Mihelich, E.D., and Coleman, M.C. (1984)J. Am. Chem. Soc. 106, 3577–3584.

    Article  Google Scholar 

  83. Porter, N.A., Funk, M.O., Gilmore, D., Isaac, R., and Nixon, J. (1976)J. Am. Chem. Soc. 98, 6000–6005.

    Article  PubMed  CAS  Google Scholar 

  84. Nugteren, D.H., Vonkeman, H., and Van Dorp, D.A. (1967)Recueil 86, 1237–1245.

    CAS  Google Scholar 

  85. Morrow, J.D., Harris, T.M., and Roberts, L.J. (1990)Anal. Biochem. 184, 1–10.

    Article  PubMed  CAS  Google Scholar 

  86. Morrow, J.D., Minton, T.A., Mukundan, C.R., Campbell, M.D., Zacker, W.E., Daniel, V.C., Badr, K.R., Blair, I.A., and Roberts, J.L. (1994)J. Biol. Chem. 269, 4317–4326.

    PubMed  CAS  Google Scholar 

  87. Parthasarathy, S., and Steinberg, D. (1992)Current Opinion in Lipidology 3, 313–317.

    Article  CAS  Google Scholar 

  88. Rosenfeld, M.E., and Lipton, B.A. (1992)Current Opinion in Lipidology 3, 318–323.

    Article  CAS  Google Scholar 

  89. Jialal, I., and Scaccini, C. (1992)Current Opinion in Lipidology 3, 324–328.

    Article  CAS  Google Scholar 

  90. Witzturn, J.L. (1990) inHypercholesterolemia Hypocholesterolemia, Hypertriglyceridemia, pp. 353–364, Plenum Press, New York.

    Google Scholar 

  91. Guyton, J.R., Black, B.L., and Seidel, C.L. (1990)Am. J. Pathol. 137, 425–434.

    PubMed  CAS  Google Scholar 

  92. Wagner, J.R., Motchnik, P.A., Stocker, R., Sies, H., and Ames, B.N. (1993)J. Biol. Chem. 278, 18502–18506.

    Google Scholar 

  93. Bowry, V.W., and Stocker, R. (1993)J. Am. Chem. Soc. 115, 6029–6044.

    Article  CAS  Google Scholar 

  94. Ingold, K.U., Bowry, V.W., Stocker, R., and Walling, C. (1993)Proc. Natl. Acad. Sci. USA 90, 45–49.

    Article  PubMed  CAS  Google Scholar 

  95. Stocker, R., Bowry, V.W., and Frei, B. (1991)Proc. Natl. Acad. Sci. USA 88, 1646–1650.

    Article  PubMed  CAS  Google Scholar 

  96. Sato, K., Niki, E., and Shimasaki, H. (1990)Arch. Biochem. and Biophys. 279, 402–405.

    Article  CAS  Google Scholar 

  97. Lenz, M.L., Hughes, H., Mitchell, J.R., Via, D.P., Guyton, J.R., Taylor, A.A., Gotto, A.M.J., and Smith, C.V. (1990)J. Lipid Res. 31, 1043–1050.

    PubMed  CAS  Google Scholar 

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Porter, N.A., Caldwell, S.E. & Mills, K.A. Mechanisms of free radical oxidation of unsaturated lipids. Lipids 30, 277–290 (1995). https://doi.org/10.1007/BF02536034

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