Simultaneous enantiomeric determination of MDMA and its phase I and phase II metabolites in urine by liquid chromatography-tandem mass spectrometry with chiral derivatization.

A liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) procedure was developed for the simultaneous determination of enantiomers of the prevalent designer drug 3,4-methylenedioxymethamphetamine (MDMA) and its phase I and phase II metabolites in urine with chiral derivatization. The analytes in urine were directly derivatized with chiral Marfey's reagent, N(α)-(5-fluoro-2,4-dinitrophenyl)-D-leucinamide, without extraction. The diastereomers of the N(α)-(2,4-dinitrophenyl)-D-leucinamide derivatives generated were determined by LC-MS/MS. Satisfactory chromatographic separation was achieved for the enantiomers of MDMA and its metabolites 3,4-methylenedioxyamphetamine, 4-hydroxy-3-methoxymethamphetamine (HMMA), HMMA glucuronide, and HMMA sulfate on a semimicro octadecylsilane column using linear gradient elution. With use of multiple reaction monitoring mode, the limits of detection of these analytes ranged from 0.01 to 0.03 µg/mL. Linear calibration curves were obtained for all enantiomers from 0.1 to 20 µg/mL in urine. The method showed sufficient reproducibility and quantitative ability. This is the first report of a simple LC-MS/MS-based analytical procedure with direct chiral derivatization in aqueous media that allows simultaneous enantiomeric determination of drugs and their metabolites, including glucuronide and sulfate derivatives.

[Studies on the identification of psychotropic substances. IX. Preparation and various analytical data of reference standard of new psychotropic substances, N-ethyl methylenedioxyamphetamine, N-hydroxy methylenedioxyamphetamine, mecloqualone, 4-methylaminorex, phendimetrazine and phenmetrazine].

The reference standards of N-Ethyl methylenedioxyamphetamine, N-Hydroxy methylenedioxy-amphetamine, Mecloqualone, 4-Methylaminorex. Phendimetrazine and Phenmetrazine were chemically prepared from commercial chemicals. Their purities determined by HPLC were more than 99.8%. The standard spectra and chromatograms of the standards such as TLC, UV, IR, HPLC, GC/MS and NMR were measured. For the identification of these six drugs in forensic laboratory, their mass fragmentation and NMR spectra were discussed.

[Studies on the identification of psychotropic substances (VII). Preparation and various analytical data of standard references of some hallucinogens, 3,4-methylenedioxyamphetamine (MDA), 3,4- methylenedioxymethamphetamine (MDMA) and 5-methoxy-3,4- methylenedioxyamphetamine (MMDA)].

The Reference Standards of 3, 4-methylenedioxyamphetamine (MDA), 3, 4-methylenedioxymethamphetamine (MDMA) and 5-methoxy-3,4-methylenedioxyamphetamine (MMDA) were prepared. Their purities determined by HPLC were 99.8% for DMA hydrochloride, 99.8% for MDMA hydrochloride and 99.5% for MMDA hydrochloride. For the identification and determination, various analytical data of the three drugs were measured and studied by TLC, UV, IR, HPLC, GC/MS and NMR.