Electrostatic interactions at charged lipid membranes. I. Effects of pH and univalent cations on membrane structure

Electrostatic interactions at charged lipid membranes make a significant contribution to the free energy of the system, and can be varied within a wide range by alteration either of the membrane's surface charge density or of the concentration of electrolytes in the surrounding medium. Changes in the charged membrane's structure, such as the ordered in equilibrium fluid phase transition, can thus be induced at constant temperature by variations in pH and salt concentration. An adequate quantitative description of these phenomena is obtained from the Gouy--Chapman theory. The good agreement between theory and experiment confirms that the expression derived for the electrostatic free energy especially in respect of its positive sign is correct. The classical expression derived for the electrostatic free energy, especially in respect of its positive sign, is correct. The classical expression for the "free energy of the double layer" derived by Verwey and Overbeek, which has a negative sign, is not applicable to lipid membranes with ionizable polar groups.