Influence of humectants on the thermotropic behaviour and nanostructure of fully hydrated lecithin bilayers

Humectants are used widely in topical formulations as they provide cosmetic and health benefits to skin. Of particular interest to our laboratories is the interaction of humectants in phospholipid based topical skin care formulations. This study probed the effects of three exemplary humectants on a fully hydrated lecithin system (DPPC) by use of X-ray scattering and differential scanning calorimetry. While the three humectants affected the nanostructure of 1, 2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC, bilayers in a similar manner, leading to an increased membrane order, differences in the effect on the thermal behaviour of DPPC suggest that betaine and sarcosine interacted via a different mechanism compared to acetic monoethanolamide, AMEA. At concentrations above 0.4 M, betaine and sarcosine stabilised the gel phase by depletion of the interfacial water via the preferential exclusion mechanism. At the same time, a slight increase in the rigidity of the membrane was observed with an increase in the membrane thickness. Overall, the addition of betaine or sarcosine resulted in an increase in the pre- and main transition temperatures of DPPC. AMEA, on the other hand, decreases both transition temperatures, and although the interlamellar water layer was also decreased, there was evidence from the altered lipid chain packing, that AMEA molecules are present also at the bilayer interface, at least at high concentrations. Above the melting point in the fluid lamellar phase, none of the humectants induced significant structural changes, neither concerning the bilayer stacking order nor its overall membrane fluidity. An humectant-induced increase in the Hamaker constant is the most plausible explanation for the observed reduction of the inter-bilayer distances, both in the gel and fluid phase.