Dispersive liquid–liquid microextraction prior to field-amplified sample injection for the sensitive analysis of 3,4-methylenedioxymethamphetamine, phencyclidine and lysergic acid diethylamide by capillary electrophoresis in human urine

A novel capillary zone electrophoresis (CZE) with ultraviolet detection method has been developed and validated for the analysis of 3,4-methylenedioxymethamphetamine (MDMA), lysergic acid diethylamide (LSD) and phencyclidine (PCP) in human urine. The separation of these three analytes has been achieved in less than 8 min in a 72-cm effective length capillary with 50-μm internal diameter. 100 mM NaH2PO4/Na2HPO4, pH 6.0 has been employed as running buffer, and the separation has been carried out at temperature and voltage of 20 °C, and 25 kV, respectively. The three drugs have been detected at 205 nm. Field amplified sample injection (FASI) has been employed for on-line sample preconcentration. FASI basically consists in a mismatch between the electric conductivity of the sample and that of the running buffer and it is achieved by electrokinetically injecting the sample diluted in a solvent of lower conductivity than that of the carrier electrolyte. Ultrapure water resulted to be the better sample solvent to reach the greatest enhancement factor. Injection voltage and time have been optimized to 5 kV and 20 s, respectively. The irreproducibility associated to electrokinetic injection has been correcting by using tetracaine as internal standard. Dispersive liquid–liquid microextraction (DLLME) has been employed as sample treatment using experimental design and response surface methodology for the optimization of critical variables. Linear responses were found for MDMA, PCP and LSD in presence of urine matrix between 10.0 and 100 ng/mL approximately, and LODs of 1.00, 4.50, and 4.40 ng/mL were calculated for MDMA, PCP and LSD, respectively. The method has been successfully applied to the analysis of the three drugs of interest in human urine with satisfactory recovery percentages.