Complex formation analysis of water-soluble calixarenes by capillary zone electrophoresis

The equilibria of complex formation reactions between various kinds of cations and anionic calixarenes in an aqueous solution were analyzed by capillary zone electrophoresis on the basis of the change in electrophoretic mobility of the calixarenes. The apparent electrophoretic mobility of the calixarenes decreased with increasing concentrations of alkali metal ions and quaternary ammonium ions. Equilibrium constants were determined by a non-liner least-squares analysis using the changes in apparent electrophoretic mobility. The complex formation constants obtained with alkali metal ions were in the order of 10(2.3) - 10(3.0), and those with quaternary ammonium ions were 10(2.9) - 10(4.2), providing less selectivity among them. The selectivity of the calixarene toward alkali metal and quaternary ammonium ions in aqueous solution involves flexible structure, and compensative interactions of electrostatic and hydrophobic interactions. From the results obtained in this work, the electrophoretic method has proved to be useful for analyzing the reactivity of anionic calixarene in aqueous solution.