Synthetic chemistry originally developed for the manufacture of chemically stable silica polyamine composites was adapted for the modification of fused silica capillaries for application in CE. Polyethyleneimine (PEI) and polyallylamine (PAA) were covalently bonded to the interior surface of fused silica capillaries utilizing 3-chloropropyltrichlorosilane (CPTCS) or 3-glycidoxypropyl-trimethoxysilane (GPTMS) to anchor the polymers to the surface. The surface-bound polymers were subsequently quaternized using methyl iodide (MeI). The resulting modified capillaries were studied using CE, and were shown to provide reproducible, stable, and robust anodic EOF throughout the pH range of 2–10. Surface modifications utilizing CPTCS could be rinsed with up to 6 M HCL or 1 M NaOH without significant loss of surface modifier. The utility of the modified capillaries for the separation of simple anions and cations was demonstrated.

Recent research and development efforts concerning polymeric pseudostationary phases (PSPs) for electrokinetic chromatography are reviewed. The introduction of new materials, characterization of structural effects on performance and selectivity, applications, and the use of polymeric PSPs with mass spectrometric detection are considered. Very interesting results concerning the effects of polymer structure have been reported. Significant developments have also been reported in the development of novel applications of polymeric PSPs, particularly for sample preconcentration using micellar affinity gradient focusing. The use of mass spectrometric detection with electrokinetic chromatography has seen significant development, and recent reports indicate that this is a robust and sensitive approach.