Interactions between zwitterionic membranes in complex electrolytes

We investigate the electrostatic interactions of zwitterionic membranes immersed in mixed electrolytes composed of mono- and multivalent ions. We show that the presence of monovalent salt is a necessary condition for the existence of a finite electrostatic force on the membrane. As a result, the mean-field membrane pressure originating from the surface dipoles exhibits a nonuniform salt dependence, characterized by an enhancement for dilute salt conditions and a decrease at intermediate salt concentrations. On addition of multivalent cations to the submolar salt solution, the separate interactions of these cations with the opposite charges of the surface dipoles makes the intermembrane pressure more repulsive at low membrane separation distances and strongly attractive at intermediate distances, resulting in a discontinuous like-charge binding transition followed by the membrane binding transition. By extending our formalism to account for correlation corrections associated with large salt concentrations, we show that membranes of high surface dipole density immersed in molar salt solutions may undergo a membrane binding transition even without the multivalent cations. Hence, the tuning of the surface polarization forces by membrane engineering can be an efficient way to adjust the equilibrium configuration of dipolar membranes in concentrated salt solutions.