Dipole potential of lipid membranes

Abstract

Of the individual potentials which comprise the potential profile of a membrane, the least well understood is the dipole potential. In general, the dipole potential is manifested between the hydrocarbon interior of the membrane and the first few water layers adjacent to the lipid head groups. Changes in dipole potential caused by spreading a lipid at an air- or oil-water interface can be measured directly and the dipole potential of bilayers can be estimated from the conductances of hydrophobic ions. For a typical phospholipid, like phosphatidylcholine, its measured value is ∼ 400 mV in monomolecular films and ∼ 280 mV in bilayer membranes, with the hydrocarbon region being positive relative to the aqueous phase. The difference between dipole potentials measured in monolayers and bilayer membranes appears to arise from the use of the lipid-free air- or oil-water interface as the reference point for monolayer measurements and can be corrected for. The species-specific correction term is a lipid concentration-independent potential, the existence of which suggests the ability of lipid headgroups to globally reorganize water structure at the interface. The dipole potential arises from the functional group dipoles of the terminal methyl groups of aliphatic chains, the glycerol-ester region of the lipids and the hydrated polar head groups. Classical methods for obtaining partial dipole moments for each of the three contributing regions are all based on questionable assumptions and give conflicting results. More sophisticated mean-field models of dipole potential origin recognize the important role of interfacial water in determining its value but still cannot adequately describe the microscopic nature of the interactions from which it arises. In part this is because the dipole potential develops in a region over which the dielectric constant of the medium is changing from 2 to 80. Despite of our limited understanding of the dipole potential, it is an important regulator of membrane structure and function. Membrane-membrane and membrane-ligand interactions are regulated by the hydration force, the value of which can be related to the dipole potential of the membrane. For thermotropically phase-separated or multicomponent membranes the size and shape of lipid domains is controlled by the balance between the line tension at the domain borders and the difference in dipole density between the domains. Line tension tends to make the domains compact and circular whereas dipole repulsion promotes transitions to complex domain shapes with larger perimeters. The role in enzyme regulation of mean interfacial dipole potential and differences in its lateral distribution is a promising area for future investigation and will contribute to our understanding of lipid-mediated cellular signaling in cells. An important tool in these investigations and in better understanding the origins of the dipole potential on a microscopic level will be the recently-developed Maxwell stress microscope.