On-column liquid–liquid–liquid microextraction coupled with base stacking as a dual preconcentration method for capillary zone electrophoresis

A simple and efficient dual preconcentration method of on-column liquid–liquid–liquid microextraction (LLLME) coupled with base stacking was developed for capillary zone electrophoresis (CZE) in this paper. Four N-methyl carbamates were used as target compounds to evaluate the enrichment means. The carbamates in sample solutions (donor phase) were extracted into a dodecanol phase immobilized on a porous hollow fiber, hydrolyzed and back extracted into 0.20 μL running buffer (acceptor phase) of 30 mmol/L methylamine hydrochloride (pH 11.6) containing 0.5 mmol/L tetradecyltrimethylammonium bromide inside the hollow fiber, stacked further with 0.5 mol/L NaOH injected at −10 kV for 60 s, and separated by CZE. Analytical parameters affecting the LLLME, base stacking and CZE were investigated, including sample solution volume, pH and temperature, extraction time, stirring rate, buffer component, buffer pH, NaOH concentration, stacking time, etc. The enrichment factors of the carbamates were higher than 1100. The relative standard deviation (RSD) of peak height and limits of detection (LODs) were 4.5–5.5% (n = 6) and 2–4 ng/mL (S/N = 3) for standard solutions, respectively. The proposed method was applied to the analysis of vegetable and fruit samples with the RSD less than 6.0% (n = 3) and LODs of 6–10 ng/g (S/N = 3). The calibration solutions were prepared by diluting the stock solutions with blank sample solutions, and the calibration concentrations ranged from 0.012 to 1.0 μg/mL (r > 0.9951). The analytical results demonstrated that the LLLME coupled with base stacking was a simple, convenient and reliable on-column sample pretreatment method for the analysis of anionic analytes in CZE.