Thermodynamic and structural study of DMPC–alkanol systems

Abstract

The thermodynamic and structural behaviors of lamellar dimyristoylphosphatidylcholine-alkanol (abbreviation DMPC–CnOH, n = 8–18 is the even number of carbons in the alkyl chain) systems were studied by using DSC and SAXD/WAXD methods at a 0–0.8 CnOH : DMPC molar ratio range. Up to n ≤ 10 a significant biphasic effect depending on the main transition temperature t_m on the CnOH concentration was observed. Two breakpoints were revealed: turning point (TP), corresponding to the minimum, and threshold concentration (c_T), corresponding to the end of the biphasic tendency. These breakpoints were also observed in the alkanol concentration dependent change in the enthalpy of the main transition ΔH_m. In the case of CnOHs with n > 10 we propose a marked shift of TP and c_T to very low concentrations; consequently, only increase of t_m is observed. A partial phase diagram was constructed for a pseudo-binary DMPC–C12OH system. We suggest a fluid–fluid immiscibility of the DMPC–C12OH system above c_T with a consequent formation of domains with different C12OH contents. At a constant CnOH concentration, the effects of CnOHs on ΔH_m and bilayer repeat distance were found to depend predominantly on the mismatch between CnOH and lipid chain lengths. Observed effects are suggested to be underlined by a counterbalancing effect of interchain van der Waals interactions and headgroup repulsion.