title: Sensitive, rapid and validated gas chromatography/negative ion chemical ionization-mass spectrometry assay including derivatisation with a novel chiral agent for the enantioselective quantification of amphetamine-type stimulants in hair.
abstract: A novel chiral derivatisation agent, (2S,4R)-N-heptafluorobutyryl-4-heptafluorobutoyloxy-prolyl chloride, was used for the indirect resolution of amphetamine (AM), methamphetamine (MA), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethylamphetamine (MDEA) enantiomers using gas chromatography coupled to mass spectrometry operating in the negative-ion chemical ionization mode (GC/MS-NICI). This new chiral derivatisation reagent was readily obtained in optically pure form after a simple two-step synthesis. Optimal derivatisation was accomplished in 15 min at room temperature in a carbonate buffer and the resulting diastereoisomers were base line separated by GC in 12 min only. No racemization was observed during the derivatisation. The method was applied and fully validated for the enantiomeric quantification of amphetamines and methylenedioxylated amphetamines in hair. The analyses of 24 hair specimens from suspected ATS abusers showed that 24 cases were positive for MA and/or AM enantiomers and that in most cases the concentrations of (S)-MA and (S)-AM exceeded those of the corresponding (R)-enantiomers. One hair specimen was tested positive for both enantiomers of MDMA and MDA.
authors.affiliation: National Laboratory of Health, Toxicology Division, University of Luxembourg, 162A avenue de la Faïencerie, L-1511 Luxembourg, Luxembourg. liliane.martins@uni.lu
authors.forename: Liliane Ferreira
authors.initials: LF
authors.lastname: Martins
authors.forename: Michel
authors.initials: M
authors.lastname: Yegles
authors.forename: Heesun
authors.initials: H
authors.lastname: Chung
authors.forename: Robert
authors.initials: R
authors.lastname: Wennig
mesh_terms: D000662:Amphetamines / Q000032:analysis / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006197:Hair / Q000737:chemistry*; D006801:Humans; D008694:Methamphetamine / Q000032:analysis / Q000737:chemistry; D015394:Molecular Structure; D018817:N-Methyl-3,4-methylenedioxyamphetamine / Q000032:analysis / Q000737:chemistry; D015203:Reproducibility of Results; D013237:Stereoisomerism
chemical_list: D000662:Amphetamines; D008694:Methamphetamine; D018817:N-Methyl-3,4-methylenedioxyamphetamine