Maximization of separation efficiency in capillary electrophoretic chiral separations by means of mobility-matching background electrolytes

It has been predicted, both theoretically and by computer simulation, that in capillary electrophoresis the electromigration-dispersion-induced peak broadening can be eliminated by matching the mobilities of the analyte and the background electrolyte co-ion. Though mobility matching can be achieved by invoking multiple secondary chemical equilibria in the background electrolyte — such as protonation or complexation - to change the mobility of the co-ion, this approach is not feasible when the composition of the background electrolyte is dictated by the need to achieve a certain separation selectivity. In this paper, a background electrolyte preparation principle is outlined which decouples the dual roles of the background electrolyte, namely the buffering function and the mobility matching function, by ascribing the buffering function solely to the counter-ion (a conjugate acid or conjugate base) and the mobility matching function solely to the co-ion (a strong electrolyte). The power of this approach is demonstrated by solving difficult enantiomer separations.