Trans fatty acids in membranes:: The free radical path

The double bond geometry of most of the naturally occurring unsaturated fatty acid residues is cis. Due to the relevance of fatty acids as structural components of cell membranes and as biologically active molecules, the change of the cis geometry means a change of the associated functions and activities. The finding that the cis to trans isomerization is effective in phospholipids by the intervention of radical species led to the discovery that there can indeed occur an endogenous formation of trans fatty acids, whose significance in biological systems started to be addressed with in vitro and in vivo studies. Studies of liposome models simulating the formation of isomerizing species and evaluating their ability to interact with the hydrophobic part of the membrane bilayer has contributed to the gain in knowledge of the fundamental features of the lipid isomerization in membranes. Further work is in progress for the identification of the real culprits of the in vivo lipid isomerization, and recent results are shown on oleic acid micelles, where (NO2)-N-center dot radicals are not able to induce double bond isomerization in comparison with amphiphilic thiol, such as 2-mercaptoethanol. H2S and sulfur-containing amino acid residues are two of the possible species involved in this process at a biological level. An update of the scenario of the geometrical isomerization in membranes by free radicals is provided, together with applications and perspectives in life sciences.