Open-tubular admicellar electrochromatography of charged analytes

Fundamental studies on the separation of cationic and anionic analytes in open-tubular admicellar electrochromatography (OT-AMEC) using cetyltrimethylammonium bromide (CTAB) and fused silica capillaries are presented. OT-AMEC was compared with open-tubular admicellar liquid chromatography (OT-AMLC) by running the two methods using the same mobile phases. The mobile phases were buffered at pH ≥ 6 and contained a low concentration (above the critical surface aggregation concentration and below the critical micelle concentration) of CTAB. The stationary pseudophase of CTAB admicelles were formed at the solid surface and liquid-interface inside the capillary by simply conditioning the capillary with the mobile phase. Separations were performed in a 30 cm (21.5 cm to UV detector) long and 50 μm inner diameter capillary, using low pressure (50 mbar) in OT-AMLC and high voltage (15 kV at negative polarity) in OT-AMEC. The appropriate equations for the experimental estimation of retention factor (k) values of analytes were discussed. For anionic analytes, k in OT-AMEC were carefully determined by considering the observed interaction between CTAB monomers and tested analytes. The calculated k for each analyte was found similar in OT-AMLC and OT-AMEC, although the mechanism of retention was not entirely different due to the contribution of electrophoresis in OT-AMEC. Studies on the addition of a typical (i.e., acetonitrile) and atypical modifier (i.e., nonyl-β-glucoside) into the mobile phase, and sample focusing with >10x improvement in peak height under isocratic conditions were also conducted.