The dehydration dynamics of a model cell membrane induced by cholesterol analogue 6-ketocholestanol investigated using sum frequency generation vibrational spectroscopy

Dehydration of a surface is the first step for the interaction between biomolecules and the surface. In this study, we systematically investigated the influence of cholesterol analog 6-ketocholestanol (6-KC) on the dehydration of model cell membrane, using sum frequency generation vibrational spectroscopy. In pure DI water environment, two separate dehydration dynamic components were observed in neutrally charged and isotopically labeled 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and positively charged 1,2-dimyristoyl-sn-glycero-3-ethylphosphocholine(chloride salt) (DMEPC) bilayer: a large-amplitude fast component and a small-amplitude slow component, which originated from the water molecules with a weak and a strong water-membrane bound strengths, respectively. Dehydration of a negatively charged mixed DMPC/DMPG bilayer lead to the membrane-bound water being reorganized to ordered structures quickly. It is evident that the water-membrane bound strengths depend largely on the charge status of the lipid and has an order of neutrally charged membrane << positively charged membrane << negatively charged membrane. In an ionic environment, KCl solution can not only dehydrate DMPC bilayer, but also prevent the 6-KC from further dehydrating this model cell membrane. We observed that the dehydration dynamics behavior of DMPC bilayer in the presence of the chaotropic anions is similar to that of the negatively charged DMPG bilayer because of the penetration of chaotropic anions into the DMPC bilayer. The degree of dehydration difficulty in kosmotropic anions follows a Hofmeister series and linearly correlates with the hydration Gibbs free energy of the anions. Our results provide a molecular basis for the interpretation of the Hofmeister effect of kosmotropic anions on ion transport proteins.