A statistical mechanical treatment of fatty acyl chain order in phospholipid bilayers and correlation with experimental data. A. Theory

A theoretical model has been developed in order to describe the organization of acyl chains in phospholipid bilayers. Since the model is intended to reproduce highly quantitative experimental results such as the deuterium magnetic resonance (NMR) data and to supplement the experimental information, all the rotameric degrees of freedom, the excluded volume interactions and the van der Waals interactions have been considered. The model is a direct extension of a generalized van der Waals theory of nematic liquid crystals to flexible molecules. In this picture, the anisotropy of the short-range repulsive forces which are treated by a hard core potential is introduced as the dominant factor governing intrinsic order among the chains. The anisotropy of the attractive forces, which are approximated by a molecular field, plays a somewhat secondary role. The dependence of the energy of interaction on the relative chain conformations is approximated by two order parameters reflecting respectively the ‘average shape’ of the molecules and the ‘average shape’ in a ‘mean orientation’. The influence of the interactions in the polar region on the lateral chain area is accounted for by an effective lateral pressure. In certain aspects the model has features in common with the Mar?elja theory.