Mass-action Formulations of Monovalent and Divalent Cation Adsorption by Phospholipid Membranes

An extension of a previous treatment (Cohen, J. A., and M. Cohen, 1981, Biophys. J., 36:623-651) is presented for the adsorption of monovalent and divalent cations by single-component phospholipid membranes, where monovalent cations adsorb with a cation/phospholipid stoichiometry of 1:1 and divalent cations adsorb with stoichiometries of 1:1 and 1:2. Previously the 1:1 and 1:2 binding of divalent cations were assumed to occur by independent, parallel pathways. Here a serial adsorption scheme is considered in which 1:2 binding occurs via reaction of 1:1-bound complexes with adjacent unoccupied phospholipids. This two-dimensional lattice reaction is shown to obey a law of mass action, and the mass-action equilibrium constant is used to parameterize the adsorption isotherm. This isotherm is shown to be mathematically equivalent to the previous isotherm, although the two formulations differ in the dependence of 1:2 binding on the 1:1 association constant.