Stacking in electrophoresis by electroosmotic flow-assisted admicelle to solvent microextraction

An in-line sample concentration method for capillary electrophoresis called admicelle to solvent microextraction was proposed. In this technique, analytes were trapped in the cetyltrimethylammonium bromide admicelles formed in situ on the negatively charged capillary surface. A solvent plug was then partially injected hydrodynamically to collapse the admicelles, which liberated and focused the analytes at the solvent front. Voltage was applied across the capillary, completing the stacking process. Various solvents, namely, methanol, ethanol, and acetonitrile, were investigated. The optimal solvent for solvent to admicelle microextraction was 30% acetonitrile in 24 mM sodium tetraborate (pH 9.2). Sample injection time and solvent to sample injection ratio were also optimised. For this demonstration, the optimum sample injection time and solvent to sample injection ratio were 320 s and 1:2, respectively. Using the optimum conditions, UV detection sensitivity was enhanced 132-176-fold for the model anions. The LOQ, %intra-/inter-day (n = 6/n = 12, 2 days) repeatability, and linearity (R²) of admicelle to solvent microextraction were 0.08-2 µg/mL, 1.9-3.9%, 2.8-4.9%, and 0.992, respectively. Admicelle to solvent microextraction was applied to the analysis of various fortified water samples, with good repeatability (%RSD = 0.5-3.6%), and no matrix interferences.