Analytical separations using molecular micelles in open-tubular capillary electrochromatography.

Open-tubular capillary electrochromatography (OT-CEC) is an alternative approach to conventional CEC. The primary advantage of OT-CEC is the elimination of problems associated with frits and silica particles in conventional CEC. This report is an investigation of the utility of using a polymeric surfactant (molecular micelle) for OT-CEC. In this approach, fused-silica capillaries coated with thin films of physically adsorbed charged polymers are developed by use of a polyelectrolyte multilayer (PEM) coating procedure. The PEM coating is constructed in situ by alternating rinses with positively and negatively charged polymers, where the negatively charged polymer is a molecular micelle. This can offer a number of advantages for separation of hydrophobic analytes. In this study, poly(diallyldimethylammonium chloride) was used as the cationic polymer and poly(sodium N-undecanoyl-L-glycinate) was used as the anionic polymer for PEM coating. The performance of the modified capillaries as a separation medium is evaluated by use of seven benzodiazepines as analytes. The run-to-run, day-to-day, week-to-week, and capillary-to-capillary reproducibilities of electroosmotic flow are very good with relative standard deviation values of less than 1% in all cases. In addition, the chromatographic performance of the monomeric form of the molecular micelle is compared for the separation of these analytes. The PEM-coated capillary was remarkably robust with more than 200 runs accomplished in this study. Strong stability against extreme pH values was also observed. The general utility of this approach is discussed in detail.