Non-aqueous capillary electrophoresis with electrochemical detection (NACE-ED) was applied to the determination of cannabinoids in hair, The effect of different electrolyte compositions on the selectivity of the separation of tetrahydrocannabinol (THC), cannabinol (CBN), cannabidiol (CBD) and tetrahydrocannabinol carboxylic acid (THCA) was studied. Complete electrophoretic resolution was obtained using a strongly basic background electrolyte consisting of 5 mM sodium hydroxide dissolved in acetonitrile-methanol (1:1). Electrochemical detection yielded well defined signals in the oxidation mode. In order to obtain low limits of detection experimental parameters, which determine the sensitivity and the noise level, were optimized, A crucial parameter for sensitive measurements using a wall-tube flow cell as end-column detector is the distance between the capillary outlet and the working electrode. The highest signal-to-noise ratio using a 50 mum I.D. capillary was obtained at a distance of 25 mum. When the capillary outlet was moved away from the working electrode, thus reducing the strength of the separation Field present at the working electrode, a large low frequency noise developed. This rise was attributed to disturbances of the hydrodynamic pattern in the flow cell. Analytical aspects such as sensitivity, reproducibility and selectivity were addressed in this work. The precision of NACE-ED regarding migration time and peak height for a sample containing 1 mug/ml THC was 0.4% and 1.1% (RSD), respectively (n=5). The calibration curve was linear for concentrations ranging between 0.1 and 10 mug/ml (r=0.998). The limit of detection for THC was 37 ng/ml, which is almost two orders of magnitude lower when compared with on-column UV detection. The method was evaluated using hair samples containing cannabinoids as sample material. (C) 2002 Elsevier Science B.V. All rights reserved.
