"Schizophrenic" behavior of zones in capillary zone electrophoresis: explanation of an old problem

Background electrolyte (BGE) systems with two coions are frequently used in capillary zone electrophoresis (CZE), especially in cases where indirect optical detection is employed. This study investigates the behavior of analytes, which possess mobilities intermediate to those of the BGE coions used. Besides the expected behavior, where the analytes provide either tailing or fronting zones, unusual behavior with extraordinary zone broadening is also observed in some cases. The explanation for this effect is that binary BGE systems involve, as a physico-chemical rule, a region where the analytes are forced by one coion to give tailing zones and simultaneously by the other coion to give fronting zones. The result of this "schizophrenic" situation is extraordinary zone broadening and deterioration of the detection record. A series of experiments is presented showing in a telling way the electromigration behavior of the discussed type of zones as well as the ways to remedy the deterioration of the peak shape by a mere slight changing of the quantitative composition of the BGE used.