Abstract
Ordered → fluid phase transitions in bilayers of charged lipids are accompanied by a decrease in electrostatic free energy mainly as a result of bilayer expansion. For uniform charge distribution the Gouy-Chapman theory of the electrical double layer predicts a decrease of the transition temperature with increasing charge density. We studied the effects of pH and mono- and divalent cations on the phase transition of lecithin, cephalin, phosphatidylserine, and phosphatidic acid bilayers. Phosphatidic acid with two ionizable protons was selected for a systematic investigation. A change in pH from 7 to 9 increases the charge per polar group from one to two elementary charges. This lowers the transition temperature by about 20°C in agreement with the theory. In this pH region rather small changes in pH suffice to induce the phase transition at constant temperature. Divalent cations (Mg++ and Ca++) increase the transition temperature by charge neutralization and thus can be used to induce the fluid → ordered transition at constant temperature. In contrast, monovalent cations (Li+, Na+, K+) lower the transition temperature, or fluidize the bilayer structure at a given temperature. Rather small changes in ionic environment can induce gross alterations in bilayer structure; divalent and monovalent cations have antagonistic effects. This result parallels current theories on nerve excitation and sensory transduction where cation-induced structural changes in biomembranes are invoked.
Keywords: triggering factors, cation binding, pH-dependence, ionic strength, double layer energy
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Selected References
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