Electrophoretic behavior and pKa determination of six quinolones with a piperazinyl substituent, together with two quinolones without a piperazinyl substituent and 1-phenylpiperazine, were investigated by capillary zone electrophoresis. The results indicate that quinolones with a piperazinyl substituent involve three protonation/deprotonation equilibria. The results also suggest that the contribution of the zwitterionic species of these quinolones to the effective mobility may not be neglected. This is probably due to a slightly incomplete protonation of the piperazinyl moiety in the pH range of 6.0-8.0, compared with the complete dissociation of the carboxylic group. Consequently, the zwitterionic species of ciprofloxacin, in particular, is slightly negatively charged. With the aid of computer simulation, three pKa values were determined for quinolones with a piperazinyl substituent, thus allowing us to rationalize precisely the influence of pH on the electrophoretic behavior of these compounds.

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The migration behavior of cationic solutes and influences of the interactions of cationic solutes with sodium dodecyl sulfate (SDS) on the formation of micelles and its critical micelle concentration (CMC) were investigated by capillary electrophoresis at neutral pH. Catecholamines and structurally related compounds, including epinephrine, norepinephrine, dopamine, norephedrine, and tyramine, which involve different extents of hydrophobic, ionic and hydrogen-bonding interactions with SDS surfactant, are selected as cationic solutes. The dependence of the effective electrophoretic mobility of cationic solutes on the concentration of surfactant monomers in the premicellar region provides direct evidence of the formation of ion-pairs between cationic solutes and anionic dodecyl sulfate monomers. Three different approaches, based on the variations of either the effective electrophoretic mobility or the retention factor as a function of surfactant concentration in the premicellar and micellar regions, and the linear relationship between the retention factor and the product of a distribution coefficient and the phase ratio, were considered to determine the CMC value of SDS micelles. The suitability of the methods used for the determination of the CMC of SDS with these cationic solutes was discussed. Depending on the structures of cationic solutes and electrophoretic conditions, the CMC value of SDS determined varies in a wide concentration range. The results indicate that, in addition to hydrophobic interaction, both ionic and hydrogen-bonding interactions have pronounced effects on the formation of SDS micelles. Ionic interaction between cationic solutes and SDS surfactant stabilizes the SDS micelles, whereas hydrogen-bonding interactions weakens the solubilization of the attractive ionic interaction. The elevation of the CMC of SDS depends heavily on hydrogen-bonding interactions between cationic solutes and SDS surfactant. Thus, the CMC value of SDS is remarkably elevated with catecholamines, such as epinephrine and norepinephrine, as compared with norephedrine. In addition, the effect of methanol content in the sample solution of these cationic solutes on the CMC of SDS was also examined.