Thermotropic and lyotropic phase properties of glycolipid diastereomers: role of headgroup and interfacial interactions in determining phase behaviour

Abstract

Recent advances in the area of glycobiology have been paralleled by progress in our understanding of the physical properties of glycoglycerolipids (GGLs). These advances have been accelerated by interest in the new found roles of these simple glycolipids in nature, by advances in synthetic procedures, and by an interest in the technological application of a group of amphiphiles with unique physical and chemical properties. Here, we consider the phase properties of some GGL/water systems containing either a single hexopyranoside or pentopyranoside headgroup. Recent calorimetric and X-ray diffraction measurements of some GGL diastereomers suggest that both headgroup and interfacial hydration play a major role in determining both lyotropism and mesomorphic phase properties as the chemical structure of the lipid headgroup, interface and hydrocarbon chains are systematically altered. For GGLs of a given chain length, interactions between the headgroup/interface and water determine whether or not a highly ordered, lamellar crystalline phase is formed, the number of such phases and their rate of formation and, in some cases, the nature of the molecular packing of those phases. In the liquid crystalline phases, the hydrocarbon chains determine the area per molecule in the lamellar liquid crystalline phase, but it is the cross-sectional area of the hydrated headgroup and the penetration of water into the interface which determines the nature of the non-lamellar phases, probably through small changes in interfacial geometry as the lateral stresses in the headgroup region increase.