Membrane Lipidomics and the Geometry of Unsaturated Fatty Acids From Biomimetic Models to Biological Consequences
In the last decades, free radical processes delineated an interdisciplinary field linking chemistry to biology and medicine. Free radical mechanisms became of importance as molecular basis of physiological and pathological conditions. Lipids, in particular, unsaturated fatty acids, are susceptible of free radical attack. The reactivity of the double bond toward free radicals is well known, in particular the reversible addition of radical species to this functionality determines the cis–trans double bond isomerization. Since the prevalent geometry displayed by unsaturated fatty acids in eukaryotes is cis, the occurrence of the cis–trans isomerization by free radicals corresponds to the loss of an important structural information linked to biological activity. The formation of trans isomers can have important meaning and consequences connected to radical stress.
Free radical isomerization of membrane fatty acids has been the subject of research coupling the top-down approach by model studies, such as biomimetic chemistry in liposomes, with the bottom-up approach dealing with the examination of cell membrane lipidome in living systems under several physiopathological conditions. Methodologies and molecular libraries have been settled, for both liposome experiments and the examination of the radical stress in biological membranes. This chapter will give an overview of the current procedures used for liposome models and the cis–trans isomerization experiments, in order to build-up a library of trans geometrical fatty acid isomers.
Key wordsMembrane lipidomics Geometrical trans fatty acid Radical stress Liposome Biomimetic chemistry Free radical isomerization
The authors wish to thank all collaborators that helped to develop methodologies in an interdisciplinary context. Support and sponsorship of the COST Action CM0603 “Free Radicals in Chemical Biology” is gratefully acknowledged.
- 4.Chatgilialoglu C, Ferreri C. 2005. Trans lipids: the free radical path. Chem Rev 31:441–448.Google Scholar
- 7.Vance DE, Vance JE, eds. 2002. Biochemistry of lipids, lipoproteins and membranes, 4th ed., Elsevier: Amsterdam.Google Scholar
- 8.Sébédio JL, Christie WW, eds. 1998. Trans fatty acids in human nutrition. The Oily Press: Dundee.Google Scholar
- 9.Chatgilialoglu C. 2007. Fats of life… explaining the villainous properties of trans fatty acids. Optimum Nutr 40–43.Google Scholar
- 16.Firestone D ed. 1998. Official Methods and Recommended Practices, Recommended Practice Cd 14d-96, 5th ed, American Oil Chemists’ Society: Champaign.Google Scholar
- 23.Cevc G, ed. 1993. Phospholipid Handbook, Marcel Dekker: New York.Google Scholar
- 24.New RRC. 1990. Liposomes: A Practical Approach. IRL Press: Oxford.Google Scholar
- 25.Lasic DD. 1993. Liposomes. From Physics to Applications. Elsevier: Amsterdam.Google Scholar
- 34.von Sonntag C. 1987. The Chemical Basis of Radiation Biology. Taylor & Francis: New York.Google Scholar
- 35.Alfassi ZB. 1999. S-Centered Radicals. Wiley: Chichester.Google Scholar
- 38.Ihara H, Hashizuma N, Hemmi H, Yoshida M. 2000. Antioxidant ability of bilirubin, vitamin E, vitamin C and albumin in the peroxyl-radical-induced hemolysis of human erythrocytes. J Anal Biosci 23:425–430.Google Scholar