Effect of double-bonds on bimolecular films in membrane models.

The effect of unsaturation (especially by cis-bonds) is studied on bimolecular films of saturated and unsaturated alkylammonium ions and alkanols between silicate surfaces as model systems for lipid layers in membranes. Three types of structures are observed: all-trans-blocks, kink-blocks and gauche-blocks. The knowledge of the sequence of these phases and their thermal transitions provides detailed deductions about the role of double-bonds. cis-Unsaturated chains are taken up in bimolecular films as isomers with cis-trans-gauche conformation. This conformation makes the shape of the chain similar to that of kinked chains (chains with gauche-trans-gauche (--) conformation) and enables the incorporation into the film without greater sterical hindrance. The experimental results are in good agreement with X-ray measurements on biological membranes by Engelman (Engelman, D.M., J. Mol. Biol. 47, 115--117 (1970) and 58, 153--165 (1971)). Increasing the concentration of cis-chains decreases the transition temperature of the kink-blocks into gauche-blocks. The variation of the transition temperature with concentration of cis-unsaturated chains in the model system is similar to that observed for Escherichia coli membranes. It is suggested that phase changes in biomembranes are of the same nature: transition of kink-block analogues as ordered phases into gauche-block assemblies as less ordered phases.