Opposing Effects of Cation Binding and Hydration on the Bending Rigidity of Anionic Lipid Bilayers

We correlate the molecularly realistic self-consistent field predictions for the mean bending modulus k(c) of charged lipid vesicles with experimental observations of the size R of corresponding vesicles that are produced by the freeze-thaw method. We elaborate on the Ansatz that the bending modulus is related to the membrane persistence length and that this length scale sets the radius of the vesicles. Alkali cations have a remarkable effect on the mean bending modulus and thus on the equilibrium radius of negatively charged entropically stabilized dioleoylphosphatidylglycerol (DOPG) vesicles. Where cation hydration typically results in thicker and thus stiffer membranes, specific adsorption to the bilayer surface results in a decrease of the surface charge density and the thickness of the membrane-associated electric double layer. As a result of these opposing effects on k(c) and R, the largest DOPG vesicles are found in the presence of K+, which combines an intermediate hydration enthalpy and PG-binding affinity.