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.
Similar content being viewed by others
Abbreviations
- GC/MS:
-
gas chromatography/mass spectrometry
- HPLC:
-
high-pressure liquid chromatography
- NMR:
-
nuclear magnetic resonance
References
Lavoisier, A.L. (1789)Elements of Chemistry (translasted by Robert Kerr) pp. 107–108, Dover Publications, 1965, New York.
Mayo, F.R. (1986)J. Chem. Ed. 63, 97–98.
Walling, C. (1986)J. Chem. Ed. 63, 99–101.
Walling, C. (1987)Chem. Br., 23, 769–770.
Porter, N.A. (1986)Acc. Chem. Res. 19, 262–268.
Porter, N.A. (1990)Membrane Lipid Oxidation (Vigo-Pelfrey, C., ed.) Vol. I, pp. 33–62, CRC Press, Boca Raton.
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.
Gershon, D. (1988) inReactive Oxygen Species in Chemistry, Biology, and Medicine (Quintanilla, A., ed.) pp. 211–219, Plenum Press, New York.
Cheeseman, K.H., and Slater, T.F. (1993)British Med. Bull. 9, 481–493.
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.
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.
Hessler, J.R., Morel, D.W., Lewis, L.J., and Chisholm, G.M. (1983)Arteriosclerosis 3, 215–222.
Steinbrecher, U.P., Parthasarathy, S., Leake, D.S., Witztum, J.L., and Steinberg, D. (1984)Proc. Natl. Acad. Sci. USA 81, 3883–3887.
Davies, A.G., Griller, D., Ingold, K.U., Lindsay, D.A., and Walton, J.C. (1981)J. Chem. Soc. Perkin Trans. II, 633–641.
Howard, J.A. (1973) inFree Radicals (Kochi, J.K., ed.) Vol. II, pp. 15–31, John Wiley and Sons, New York.
Nonhebel, D.C., and Walton, J.C. (1984) inFree Radical Chemistry, pp. 393–417, Cambridge University Press, London.
Howard, J.A. (1972) inAdvances in Free Radical Chemistry, Vol. IV, pp. 75–138, Academic Press, New York.
Farmer, E.H., and Sutton, D.A. (1943)J. Chem. Soc., 119–122.
Farmer, E.H., Koch, H.P., and Sutton, D.A. (1943),J. Chem. Soc., 541–547.
Bickford, W.G., Fisher, G.S., Kyame, L., and Swift, C.E. (1948)J. Am. Oil Chem. Soc. 24, 254–257.
Ross, J., Gebhart, A.I., and Gerecht, J.F. (1946)J. Am. Chem. Soc. 68, 1373–1376.
Frankel, E.N. (1980) inAutoxidation in Food and Biological Systems (Simic, M., and Karel, M., eds.) pp. 141–183, Plenum Press, New York.
Frankel, E.N., Neff, W.E., and Rohwedder, W.K. (1977)Lipids 12, 901–907.
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.
Pritzkow, W., Radeolia, R., and Schmidt-Renner, W. (1979)J. Prakt. Chem. 321, 813–826.
Porter, N.A., Mills, K.A., and Carter, R.L. (1994)J. Am. Chem. Soc. 116, 6690–6696.
Courtneidge, J.L., and Bush, M. (1992)J. Chem. Soc. Perkin Trans. I, 1531–1538.
Courtneidge, J.L., Bush, M., and Loh, L.-S. (1992)J. Chem. Soc. Perkin Trans. I, 1539–1548.
Courtneidge, J.L. (1992)J. Chem. Soc. Chem. Commun., 1270–1272.
Howard, J.A., Schwalm, W.J., and Ingold, K.U. (1968)Adv. Chem. Ser. 75, 6–23.
Middleton, B.S., and Ingold, K.U. (1967)Can. J. Chem. 45, 191–194.
Chenier, J.H., and Howard, J.A. (1975)Can. J. Chem. 53, 623–627.
Howard, J.A. (1984)Israel J. Chem. 24, 33–37.
Thomas, J.R., and Tolman, C.A. (1962)J. Am. Chem. Soc. 84, 2079–2080.
Thomas, J.R. (1967)J. Am. Chem. Soc. 84, 4872–4875.
Saebo, S., Beckwith, A.L.J., and Radom, L. (1984)J. Am. Chem. Soc. 106, 5119–1522.
Lindsay, D.A., Lusztyk, J., and Ingold, K.U. (1984)J. Am. Chem. Soc. 106, 7087–7093.
Barclay, L.R.C., Lusztyk, J., and Ingold, K.U. (1984)J. Am. Chem. Soc. 106, 1793–1796.
Crich, D., and Filzen, G.F. (1993)Tetrahedron Lett. 34, 3225–3229.
Frimer, A.A. (1979)Chem. Rev. 79, 359–387.
Brill, W.F. (1984)J. Chem. Soc. Perkin Trans. II, 621–627.
Schenck, G.O. (1957)Angew. Chem. 69, 579–599.
Schenck, G.O., Neumuller, O.A., and Eisfeld, K.C. (1958)Angew. Chem. 70, p. 595.
Smith, L.L. (1981)Cholesterol Autoxidation, Plenum Press, New York.
Beckwith, A.L., Davies, A.G., Davison, I.G., Macoll, A., and Mruzek, M.H. (1989)J. Chem. Soc. Perkin Trans. II, 815–824.
Davies, A.G., and Davison, I.G. (1989)J. Chem. Soc. Perkin Trans. II, 825–830.
Brill, W.F. (1965)J. Am. Chem. Soc. 87, 3286–3287.
Brill, W.F. (1968)Adv. Chem. Ser. 75, 93–101.
Porter, N.A., and Zuraw, P. (1985)J. Chem. Soc. Chem. Commun., 1472–1473.
Boyd, S.L., Boyd, R.J., Shi, Z., Barclay, R.C., and Porter, N.A. (1993)J. Am. Chem. Soc. 115, 687–693.
Porter, N.A., Kaplan, J.K., and Dussault, P.H. (1990)J. Am. Chem. Soc. 112, 1266–1267.
Mills, K.A., Caldwell, S.E., Dubay, G.R., and Porter, N.A. (1992),J. Am. Chem. Soc. 114, 9689–9691.
Porter, N.A., Mills, K.A., Caldwell, S.E., and Dubay, G.R. (1994)J. Am. Chem. Soc. 116, 6697–6705.
Chan, H.W.S., Levett, G., and Matthew, J.A. (1979)Chem. Phys. Lipids 24, 245–256.
Teng, J.I., and Smith, L.L. (1985)J. Chromatogr. 350, 445–451.
Porter, N.A., and Wujek, D.G. (1984)J. Am. Chem. Soc. 106, 2626–2629.
Porter, N.A., Lehman, L.S., Weber, B.A., and Smith, K.J. (1981)J. Am. Chem. Soc. 103, 6447–6455.
Iliou, J.P., Jourdheuil, D., Robin, F. Serkiz, B., Guivarch, P., Lolland, J.P., and Vilaine, J.P. (1992)Lipids 27, 959–967.
Brash, A.R., Porter, J.D., and Maas, L.B. (1985)J. Biol. Chem. 260, 4210–4216.
Beckwith, A.L.J., O'Shea, D.M., and Roberts, D.H. (1986)J. Am. Chem. Soc. 108, 6408–6409.
Porter, N.A., Weber, B.A., Weenen, H., and Khan, J.A. (1980)J. Am. Chem. Soc. 102, 5597–5601.
Dussault, P.H., and Hayden, M.R. (1992)Tetrahedron Lett. 33, 443–446.
Bascetta, E., Gunstone, F.D., and Walton, J.C. (1983)J. Chem. Soc. Perkin Trans. II, 603–613.
Hoffmann, R.W. (1989)Chem. Rev. 89, 1841–1860.
Haslbeck, F., Grosch, W., and Firl, J. (1983)Biochim. Biophys. Acta 705, 185–193.
Doba, T., Burton, G.W., and Ingold, K.U. (1983)J. Am. Chem. Soc. 105, 6505–6506.
Burton, G.W., and Ingold, K.U. (1981)J. Am. Chem. Soc. 103, 6472–6477.
Niki, E., Kawakami, A., Saito, M., Yamamoto, Y., Tsuchiya, J., and Kamiya, Y. (1985)J. Biol. Chem. 260, 2191–2196.
Iwatsuki, M., Tsuchiya, J., Komuro, E., Yamamoto, Y., and Niki, E. (1994)Biochim. Biophys. Acta 1200 19–26.
Barclay, L.R.C., Baskin, K.A., Dakin, K.A., Locke, S.J., and Vinqvist, M.R. (1990)Can. J. Chem. 68, 2258–2269.
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.
Liebler, D.C., Baker, P.F., and Kaysen, K.L. (1990)J. Am. Chem. Soc. 112, 6995–7000.
Terao, J., and Matsushita, S. (1986)Lipids 21, 255–260.
Koskas, J.P., Cillard, J., and Cillard, P. (1984)J. Am. Oil Chem. Soc. 61, 466–469.
Weenen, H., and Porter, N.A. (1982)J. Am. Chem. Soc. 104, 5216–5221.
Peers, K.E., Coxon, D.T., and Chan, H.W.-S. (1981)J. Sci. Food Agric. 32, 898–904.
Nagaoka, S., Okauchi, Y., Urano, S., Nagashima, U., and Maukai, K. (1990)J. Am. Chem. Soc. 112, 8921–8924.
Bruna, E., Petit, E., Beljean-Leymarie, M., Huynh, S., and Nouvelot, A. (1990)Lipids 24, 970–975.
Khan, J.A., and Porter, N.A. (1982)Angew. Chem. Int. Ed. 21, 217–218.
Porter, N.A., Wolf, R.A., Yarboro, E.M., and Weenen, H. (1979)Biochem. Biophys. Res. Commun. 89, 1058–1064.
Porter, N.A., Logan, J., and Kontoyiannidou, V. (1979)J. Org. Chem. 44, 3177–3181.
O'Connor, D.E., Mihelich, E.D., and Coleman, M.C. (1984)J. Am. Chem. Soc. 106, 3577–3584.
Porter, N.A., Funk, M.O., Gilmore, D., Isaac, R., and Nixon, J. (1976)J. Am. Chem. Soc. 98, 6000–6005.
Nugteren, D.H., Vonkeman, H., and Van Dorp, D.A. (1967)Recueil 86, 1237–1245.
Morrow, J.D., Harris, T.M., and Roberts, L.J. (1990)Anal. Biochem. 184, 1–10.
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.
Parthasarathy, S., and Steinberg, D. (1992)Current Opinion in Lipidology 3, 313–317.
Rosenfeld, M.E., and Lipton, B.A. (1992)Current Opinion in Lipidology 3, 318–323.
Jialal, I., and Scaccini, C. (1992)Current Opinion in Lipidology 3, 324–328.
Witzturn, J.L. (1990) inHypercholesterolemia Hypocholesterolemia, Hypertriglyceridemia, pp. 353–364, Plenum Press, New York.
Guyton, J.R., Black, B.L., and Seidel, C.L. (1990)Am. J. Pathol. 137, 425–434.
Wagner, J.R., Motchnik, P.A., Stocker, R., Sies, H., and Ames, B.N. (1993)J. Biol. Chem. 278, 18502–18506.
Bowry, V.W., and Stocker, R. (1993)J. Am. Chem. Soc. 115, 6029–6044.
Ingold, K.U., Bowry, V.W., Stocker, R., and Walling, C. (1993)Proc. Natl. Acad. Sci. USA 90, 45–49.
Stocker, R., Bowry, V.W., and Frei, B. (1991)Proc. Natl. Acad. Sci. USA 88, 1646–1650.
Sato, K., Niki, E., and Shimasaki, H. (1990)Arch. Biochem. and Biophys. 279, 402–405.
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.
Author information
Authors and Affiliations
About this article
Cite this article
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
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF02536034