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Capillary affinity electrophoresis (CAE) has been employed to investigate quantitatively the interactions of valinomycin, macrocyclic depsipeptide antibiotic ionophore, with univalent cations, ammonium and alkali metal ions, K(+), Cs(+), Na(+), and Li(+), in methanol. The study involved measuring the change in effective electrophoretic mobility of valinomycin while the cation concentrations in the BGE were increased. The corresponding apparent stability (binding) constants of the valinomycin-univalent cation complexes were obtained from the dependence of valinomycin effective mobility on the cation concentration in BGE using a nonlinear regression analysis. The calculated apparent stability constants of the above-mentioned complexes show the substantially higher selectivity of valinomycin for K(+) and Cs(+) ions over Li(+), Na(+), and NH(4)(+) ions. CAE proved to be a suitable method for the investigation of both weak and strong interactions of valinomycin with small ions.

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The stability constants for the ML+ complex species, where M+ is an alkali metal cation and L is dibenzo-18-crown-6, in nitrobenzene saturated with water were calculated by employing published equilibrium data. The stability is found to increase in the cation order Li+ < Cs+ < Rb+ < K+ < Na+. For the NaL+, KL+, RbL+, and CsL+ complex cations the individual extraction constants in the water-nitrobenzene system were determined; their values increase in the series Na+ < K+ < Rb+ < Cs+.

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