Extension of the LOPLS-AA Force Field for Alcohols, Esters, and Monoolein Bilayers and its Validation by Neutron Scattering Experiments

• Published in: The journal of physical chemistry. B Vol. 119; no. 49; pp. 15287 - 15299
• Main Authors: Pluhackova, Kristyna, Morhenn, Humphrey, Lautner, Lisa, Lohstroh, Wiebke, Nemkovski, Kirill S, Unruh, Tobias, Böckmann, Rainer A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.12.2015
• Subjects: Alcohols - chemistry; Esters - chemistry; Glycerides - chemistry; Lipid Bilayers - chemistry; Neutrons; Scattering, Radiation
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.5b08569

The recently presented LOPLS-AA all-atom force field for long hydrocarbon chains, based on the OPLS-AA force field, was extended to alcohols, esters, and glyceryl monooleate (GMO) lipids as a model lipid. Dihedral angles were fitted against high level ab initio calculations, and ester charges were increased to improve their hydration properties. Additionally, the ester Lennard-Jones parameters were readjusted to reproduce experimental liquid bulk properties, densities, and heats of vaporization. This extension enabled the setup of LOPLS-AA parameters for GMO molecules. The properties of the lipid force field were tested for the liquid-crystalline phase of a GMO bilayer. The obtained area per lipid for GMO is in good agreement with experiment. Additionally, the lipid dynamics on the subpicosecond to the nanosecond time scale is in excellent agreement with results from time-of-flight (TOF) quasielastic neutron scattering (QENS) experiments on a multilamellar monoolein system, enabling here for the first time the critical evaluation of the short-time dynamics obtained from a molecular dynamics simulation of a membrane system.