The thiyl radical-mediated isomerization of cis-monounsaturated fatty acid residues in phospholipids: a novel path of membrane damage?

Abstract

Thiyl radicals, generated from biologically relevant thiols under biomimetic conditions, reversibly attack the double bonds of unsaturated phospholipids containing cis-fatty acid residues either in lipid solutions or lipid vesicles, thus producing phospholipids containing trans-fatty acid residues in high yield.

References

1. For reviews, see E. Niki, in Organic Peroxides, ed. W. Ando, Wiley, New York, 1992, pp. 764–787; L. C. R. Barclay, Can. J. Chem., 1993, 33, 1.
2. S. N. Muller, R. Batra, M. Senn, B. Giese, M. Kisel and O. Shadyro, J. Am. Chem. Soc., 1997, 119, 2795.
3. R. Holtwick, F. Meinhardt and H. Keweloh, Appl. Environ. Microbiol., 1997, 63, 4292; B. Loffeld and H. Keweloh, Lipids, 1996, 31, 811; H. Keweloh and H. J. Heipieper, Lipids, 1996, 31, 129.
4. R. L. Wolff and B. Entressangles, Biochim. Biophys. Acta, 1994, 1211, 198.
5. For a review, see P. E. Sonnet, Tetrahedron, 1980, 36, 557.
6. For catalytic hydrogenation of oils, see L. Ovesen, T. Leth and K. Hausen, Lipids, 1996, 31, 971 and references cited therein.
7. C. Chatgilialoglu, M. Ballestri, C. Ferreri and D. Vecchi, J. Org. Chem., 1995, 60, 3826.
8. For a review, see C. Chatgilialoglu and M. Guerra, in Supplement S: The Chemistry of Sulfur-containing Functional Groups, ed. S. Patai and Z. Rappoport, Wiley, London, 1993, pp. 363–394.
9. Liposomes a practical approach, ed. R. R. C. New, IRL Press, Oxford, 1990.
10. L. L. M. Van Deenen, in Progress in the Chemistry of Fats and Other Lipids. Vol. VIII, ed. R. T. T. Helman, Pergamon, Oxford, 1965, pp. 1–127.
11. C. Schöneich, U. Dillinger, F. von Bruchhausen and K.-D. Asmus, Arch. Biochem. Biophys., 1992, 292, 456.
12. L. R. C. Barclay, J. M. McNeil, J. J. VanKessel, B. Forrest, N. A. Porter, L. S. Lehman, K. J. Smith and J. C. Ellington Jr., J. Am. Chem. Soc., 1984, 106, 6740.
13. C. Schöneich, M. Bonifacic and K.-D. Asmus, Free Radical Res. Commun., 1989, 6, 393.
14. Transesterification in alkaline medium is preferable as reported by: J. F. K. Kramer, V. Fellner, M. E. R. Dugan, F. D. Sauer, M. M. Mossoba and M. P. Yurawecz, Lipids, 1997, 32, 12 19.
15. R. C. MacDonald, R. I. MacDonald, B. Ph. M. Menco, K. Takeshita, N. K. Subbarao and L. Hu, Biochim. Biophys. Acta, 1991, 1061, 297.
16. G. L. Newton, J. A. Aguilera, T. Kim, J. F. Ward and R. C. Fahey, Radiat. Res., 1996, 134, 215 and references cited therein.
17. For example, see R. Zhao, J. Lind, G. Merenyi and T. E. Eriksen, J. Am. Chem. Soc., 1994, 116, 12 010; M. S. Akhlaq and C. von Sonntag, J. Am. Chem. Soc., 1986, 108, 3542.
18. G. Stark, Biochim. Biophys. Acta, 1991, 1071, 103 and references cited therein.
19. After completion of this manuscript the following paper on thiyl-induced cis–trans isomerization of linoleate derivatives has appeared: J. Schwinn, H. Sprinz, K. Dröβler, S. Leistner and O. Brede, Int. J. Radiat. Biol., 1998, 74, 359.