Simultaneous chiral separation of 3,4‐methylenedioxymethamphetamine (MDMA), 3‐4‐methylenedioxyamphetamine (MDA), 3,4‐methylenedioxyethylamphetamine (MDE), ephedrine, amphetamine and methamphetamine by capillary electrophoresis in uncoated and coated capillaries with native β‐cyclodextrin as the chiral selector: Preliminary application to the analysis of urine and hair

Abstract

The importance of the chiral analysis of amphetamine-related substances in both clandestine preparations and biological samples is widely recognized. For this purpose, capillary electrophoresis was successfully applied by several authors, but only few reports concerned ring-substituted amphetamines, which represent the main components of "ecstasy", a widely abused "recreational" substance. In the present work, the simultaneous chiral analysis of ephedrine, amphetamine, methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA), 3-4-methylenedioxyamphetamine (MDA) and 3,4-methalenedioxyethylamphetamine (MDE) is reported, by using capillary electrophoresis with native beta-cyclodextrin (15 mM) as the chiral selector. After preliminary tests at different pH values (phosphate buffer 100 mM, pH 2.5-9.0) and with bare or coated fused-silica capillaries, the optimized conditions were: pH 2.5 phosphate, uncoated capillary (45 cm x 50 microm inner diameter), potential 10 kV. Detection was either by fixed wavelength (200 nm) or multiwavelength (190-400 nm) UV absorbance. Under these conditions, good resolution was obtained for all the analytes, with excellent chiral selectivity and efficiency. The sensitivity for the individual enantiomers was better than 0.2 microg/mL, analytical precision was characterized by relative standard deviation values < 0.8% (< or = 0.15% with internal standardization) for migration times intra-day and < 2.0% (< or = 0.54% with internal standardization) day-to-day; linearity, in the range 0.156-40 microg/mL, and accuracy were also satisfactory. After a simple liquid-liquid extraction, urine samples could be analyzed with a sensitivity well below the recommended NIDA cut-off of 500 ng/mL. For hair samples, it was necessary to increase the sensitivity by applying a field-amplified sample stacking procedure, which allowed the chiral determination of MDA, MDMA and MDE at concentrations occurring in real samples from ecstasy users, with the possibility of recording UV spectra of the peaks.

Evaluation of drug incorporation into hair segments and nails by enantiomeric analysis following controlled single MDMA intakes

“…1, who was a CYP2D6 poor metabolizer, had the highest R/S-MDMA ratio in the hair segment corresponding to the time of intake and the nail scraping whereas the ratio in the nail clipping was in the range of the extensive CYP2D6 metabolizers ( Figure 3A). To our knowledge, there are two reports on chiral analysis of MDMA and MDA in hair samples from suspected or self-declared MDMA users [41][42][43]. Enantiomeric ratios for MDMA and MDA from our controlled intake study are in concordance with hair findings reported by Martins et al from a study with self-declared MDMA users after controlled MDMA administration [41].…”

Chiral Capillary Electrophoresis of Amphetamine-Type Stimulants

“…6,7) However, few reports have focused on DMA, even though the analysis of DMA is required in Japanese drug abuse situations.…”

Applications de l'électrophorèse capillaire en toxicologie clinique et médico-légale

“…De nombreuses études sont décrites sur le plasma ou sur l'urine pour les dérivés amphétaminiques et analogues (22,37), la méthaqualone (58) Avec l'utilisation de sélecteurs chiraux dans le tampon de migration, TEC s'est énormément développée. Elle est devenue une technique simple et peu coûteuse pour la séparation et l'analyse des énantiomères.…”

“…L'équipe de Thormann est certainement encore la plus active dans l'analyse des milieux biologiques (10-12) et il décrit dans une revue de la littérature sur les années 1997 et 1998 les progrès récents de TEC et les applications en routine en toxicologie clinique et médico-légale. Des études plus spécifiques se développent : TEC est en train de devenir l'approche la plus commune pour l'analyse chirale de nombreux médicaments et substances illicites (13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25) (28). Cependant, l'injection directe de l'échantillon reste peu appliquée à l'analyse toxicologique de prélè-vements biologiques en raison de la faible concentration des xénobiotiques.…”