Isolation of substances by liquid-phase microextraction (LPME) or electromembrane extraction (EME) is becoming more and more important in analytical chemistry. However, the understanding of the mass transfer in LPME and EME is limited, especially for highly concentrated samples. In this work, the mass transfer in LPME and EME from aqueous samples (0.5–200 mg L–1) was studied in terms of recovery, equilibrium time, flux, and mass transfer capacity. In both EME and LPME, high recoveries were achieved at low analyte concentration, and the recoveries decreased at high analyte concentration. For EME, the loss in recovery was partly compensated by increasing the extraction voltage (from 50 to 200 V), while the LPME recovery at high analyte concentration was improved by increasing the extraction time (from 30 to 180 min). EME was superior in terms of equilibrium time and flux, while LPME provided much higher mass transfer capacity especially for highly concentrated samples. Moreover, the recovery was much more sensitive to high analyte concentrations in EME than in LPME, and the EME recovery decreased significantly above 50 mg L–1, indicating that LPME could be used to isolate analytes in a wider concentration range than EME. We believe that this fundamental study will be of great importance for the selection of a suitable membrane-based microextraction technique.

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The wide abuse of barbiturates has aroused extensive public concern. Therefore, the determination of such drugs is becoming essential in therapeutic drug monitoring and forensic science. Herein, a simple, efficient, and inexpensive sample preparation technique, namely, flat membrane-based liquid-phase microextraction (FM-LPME) followed by liquid chromatography-mass spectrometry (LC-MS), was used to determine barbiturates in biological specimens. Factors that may influence the efficiency including organic extraction solvent, pH, and composition of donor and acceptor phases, extraction time, and salt addition to the sample (donor phase) were investigated and optimized. Under the optimized extraction conditions, the linear ranges of the proposed FM-LPME/LC-MS method (with correlation coefficient factors ≥ 0.99) were 7.5–750 ng mL−1 for whole blood, 5.0–500 ng mL−1 for urine, and 25–2500 ng g−1 for liver. Repeatability between 5.0 and 13.7% was obtained and the limit of detection (LOD) values ranged from 1.5 to 3.1 ng mL−1, from 0.6 to 3.6 ng mL−1, and from 5.2 to 10.0 ng g−1 for whole blood, urine, and liver samples, respectively. This method was successfully applied for the analysis of barbiturates in blood and liver from rats treated with these drugs, and excellent sample cleanup was achieved.

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