Selectivity control in micellar electrokinetic chromatography of small peptides using mixed fluorocarbon-hydrocarbon anionic surfactants.

Electrophoretic mobilities and capacity factors for a group of Trp-containing small peptides were determined by micellar electrokinetic chromatography (MEKC) using mixtures of a fluorocarbon anionic surfactant, lithium perfluorooctane sulfonate, and a hydrocarbon anionic surfactant, lithium dodecyl sulfate. Upon mixing these two surfactants, which have different microenvironments and interactive characteristics, greater control over migration of solutes is achieved. The changes in the composition of mixed micelles such as the mole fraction of the surfactants result in different solute-micelle binding as well as migration times of the micelles (tmc). Consequently, capacity factor, selectivity and elution window (tmc/t0) change with the composition of the mixed micellar system. Another characteristic of the mixtures of fluorocarbon-hydrocarbon surfactants is the possibility of forming two different types of micelles which offers an additional partitioning process for each solute in the MEKC system. Such a unique phenomenon offers a higher degree of selectivity control. This mixed MEKC system is quite effective for the separation of small peptides. It provides an alternative to the free-solution capillary zone electrophoresis system for the separation of charged solutes with nearly identical electrophoretic mobility.