Ordering of Saturated and Unsaturated Lipid Membranes near Their Phase Transitions Induced by an Amphiphilic Cyclodextrin and Cholesterol

When inserted in membranes of dimyristoyl phosphatidylcholine (DMPC), methylated beta-cyclodextrins with one (Trim beta MLC) or two (Trim beta DLC) lauryl acyl chains grafted onto the hydrophilic cavity exert a "cholesterol-like ordering effect", by straightening the acyl chains in the fluid phase at temperatures near the chain melting transition. This effect may be related to pretransitional events such as the "anomalous swelling" known to occur with saturated phosphatidylcholine membranes. To investigate this model, order profiles and bilayer thicknesses of DMPC and unsaturated 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC) membranes containing amphiphilic cyclodextrins or cholesterol were determined by deuterium NMR The pure lipid membranes display both a qualitatively similar chain ordering upon cooling in the fluid phase, more important at the chain extremity, which gets more pronounced near their fluid-to-gel transitions. Both membranes show a bilayer thickness increase by similar to 0.5 angstrom just above their transition, as observed previously with saturated phosphatidylcholines of various chain lengths. Membrane-insertion of 5% Trim beta MLC or cholesterol induces an important ordering of the DMPC acyl chains just above the transition, which is also more pronounced at the chain extremity. There is an additional increase of the bilayer thickness, most probably due to a deep insertion of these amphiphilic molecules, facilitated by increased bilayer softness in the anomalous swelling regime. These effects are more important with Trim beta MLC than with cholesterol. By contrast, no enhanced acyl chain ordering was observed when approaching the transition of Trim beta MLCcontaining POPC membranes, as a possible consequence of an eventual lack of anomalous swelling in unsaturated lipid membranes. Insertion of higher concentrations of Trim beta MLC was found to induce a magnetic orientation of the DMPC membranes in the fluid phase with 10% of this derivative, coupled with the appearance of a broad isotropic component when the concentration is raised to 20%. No membrane orientation or isotropic component was detected with Trim beta MLC-containing POPC membranes.