Properties of Hydrated Excess Protons near Phospholipid Bilayers

The behavior of the hydrated excess proton near different lipid membranes is studied with the third generation of the multistate empirical valence bond (MS-EVB3) model [Wu, Y. J.; Chen, H. N.; Wang, F.; Paesani, F.; Voth, G. A. J. Phys. Chem. B 2008, 112, 467]. Dioleoylphosphatidylcholine (DOPC), dioleoylphosphatidylethanolamine (DOPE), and dioleoylphosphatidylglycerol (DOPG) are selected as example lipids. In spite of the differences of the head groups, the molecular dynamics simulations show that all the lipid membranes have a proton-collecting antenna effect with no free energy barrier between the bulk water and interface regions. By comparison with classical hydronium model simulations, it is found that an appropriate description of proton Grotthuss shuttling and associated charge defect delocalization are necessary to obtain the correct free energy profile for the hydrated excess proton. In addition, nanosecond time scale sampling is essential to evaluate the free energy profiles, because certain slo...