Thermotropic properties of phospholipid analogues.

To understand the structural bases for the polymorphism of phospholipids, it is often essential to study the properties of "unnatural" phospholipid analogues with modified polar headgroups and or backbone structures. While the thermodynamic characteristics of the "classical" hydrated-gel-to-liquid-crystalline phase transition often appear surprisingly insensitive to these aspects of phospholipid structure, the rich and diverse solid-phase polymorphism of phospholipids is in fact exquisitely sensitive to the nature of both the polar headgroup and the backbone moieties. The tendencies of different phospholipids to form nonlamellar phases at higher temperatures also depend strongly (and in a sometimes surprising manner) on fine details of the headgroup and backbone structures. These points are illustrated by discussions of how the structures of headgroup- and backbone-modified phospholipid analogues influence their proclivities to form distinct types of hydrated solid phases, dehydrated "crystralline" phases and nonlamellar phases.