Atomic-scale structure and electrostatics of anionic POPG lipid bilayers with Na+ counterions

¹ Helsinki University of Technology, Finland
² University of Bradford, Bradford, UK
³ Tampere University of Technology, Finland
⁴ The University of Western Ontario, Canada

^* To whom correspondence should be addressed. E-mail: mkarttu{at}uwo.ca.

Submitted on March 31, 2006
Revised on May 3, 2006
Accepted on 5 September 2006

	Abstract

Anionic palmitoyloleoylphosphatidylglycerol, or POPG, is one of the most abundant lipids in nature, yet its atomic-scale properties have not received significant attention. Here we report extensive 150 ns molecular dynamics simulations of a pure POPG lipid membrane with sodium counterions. It turns out that the average area per lipid of the POPG bilayer under physiological conditions is about 19 % smaller than that of a bilayer built from its zwitterionic phosphatidylcholine analog POPC. This suggests that there are strong attractive interactions between anionic POPG lipids, which overcome the electrostatic repulsion between negative charges of PG head groups. We demonstrate that interlipid counterion bridges and strong intra- and intermolecular hydrogen bonding play a key role in this seemingly counterintuitive behavior. In particular, the substantial strength and stability of ion-mediated binding between anionic lipid head groups leads to complexation of PG molecules and ions, and formation of large PG-ion clusters that act in a concerted manner. The ion-mediated binding seems to provide a possible molecular-level explanation for the low permeability of PG-containing bacterial membranes to organic solvents: highly polar interactions at the water / membrane interface are able to create a high free energy barrier for hydrophobic molecules such as benzene.

Key Words: anionic, clusters, electrostatics, molecular dynamics, palmitoyloleoylphosphatidylglycerol

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