PMID- 15516295
OWN - NLM
STAT- MEDLINE
DCOM- 20050204
LR  - 20190513
IS  - 0146-4760 (Print)
IS  - 0146-4760 (Linking)
VI  - 28
IP  - 6
DP  - 2004 Sep
TI  - Enantiomeric separation and quantitation of (+/-)-amphetamine, 
      (+/-)-methamphetamine, (+/-)-MDA, (+/-)-MDMA, and (+/-)-MDEA in urine specimens 
      by GC-EI-MS after derivatization with (R)-(-)- or 
      (S)-(+)-alpha-methoxy-alpha-(trifluoromethy)phenylacetyl chloride (MTPA).
PG  - 449-55
AB  - In drug testing, the presence of methamphetamine in urine is generally confirmed 
      by a gas chromatography-mass spectrometry (GC-MS) method. Derivatization of the 
      compound to a perfluoroalkylamide, prior to confirmation, typically yields better 
      chromatographic separation. Once methamphetamine is detected, a second GC-MS test 
      is necessary to distinguish positive results from the use of over-the-counter 
      medication, Vicks inhaler, or from use of a prescription drug, selegiline 
      (Deprenyl). R-(-)-Methamphetamine is the urinary product from legitimate use of 
      these medications. The second GC-MS test is to confirm illicit use of 
      (S)-(+)-methamphetamine. In the procedure, the two methamphetamine isomers are 
      changed to the chromatographically separable diastereomers by a chiral 
      derivatizing agent, (S)-(-)-trifluoroacetylprolyl chloride (TPC). But the method 
      has inherent limitations. Racemization of the reagent produces mixed 
      diastereomers even from pure (S)-(+)-methamphetamine. Instead of using TPC, we 
      utilized (R)-(-)-alpha-methoxy-alpha-(trifluoromethyl)phenylacetyl chloride 
      (MTPA) to prepare the amides of diastereomers of methamphetamine. No racemization 
      was observed with this reagent. The method was extended to resolve GC peaks of 
      (R)-(-)- and (S)-(+)-isomers of amphetamine, 3,4-methylenedioxyamphetamine (MDA), 
      N-methyl-MDA (MDMA), and N-ethyl-MDA (MDEA). Three ions from the drug and two 
      ions from the deuterated internal standard were monitored to characterize and 
      quantitate the drugs. For MDEA, only one ion was used. The quantitation was 
      linear over 25 to 5000 ng/mL for MDEA and 25 to 10,000 ng/mL for all other drugs. 
      Correlation coefficients were > 0.996. Precision calculated as the coefficient of 
      variation at the calibrator concentration of 500 ng/mL was within +/- 11% for all 
      drugs. The method was applied to test 43 urine specimens. In 91% of the 
      methamphetamine-positive specimens, only the (S)-(+)-isomer was detected. In all 
      MDMA-positive specimens, the concentrations of (R)-(-)-isomer were greater than 
      the (S)-(+)-isomer indicating longer retention of (R)-(-)-isomer in the human 
      body. The specimen concentrations (R + S) compared well with that of a non-chiral 
      method that used 4-carboethoxyhexafluorobutyryl chloride as derivatizing agent. 
      But the MTPA method has some advantage. It alone can replace the two GC-MS 
      methods needed to confirm the presence of (S)-(+)-isomers of amphetamine and 
      methamphetamine.
FAU - Paul, Buddha D
AU  - Paul BD
AD  - Division of Forensic Toxicology, Office of the Armed Forces Medical Examiner, 
      Armed Forces Institute of Pathology, Rockville, Maryland 20850, USA. 
      paul@afip.osd.mil
FAU - Jemionek, John
AU  - Jemionek J
FAU - Lesser, David
AU  - Lesser D
FAU - Jacobs, Aaron
AU  - Jacobs A
FAU - Searles, Douglas A
AU  - Searles DA
LA  - eng
PT  - Journal Article
PL  - England
TA  - J Anal Toxicol
JT  - Journal of analytical toxicology
JID - 7705085
RN  - 0 (Amphetamines)
RN  - 0 (Indicators and Reagents)
RN  - 0 (Quaternary Ammonium Compounds)
RN  - 40748-21-8 (4-(N-maleimido)benzyltrimethylammonium)
RN  - 44RAL3456C (Methamphetamine)
RN  - 4764-17-4 (3,4-Methylenedioxyamphetamine)
RN  - KE1SEN21RM (N-Methyl-3,4-methylenedioxyamphetamine)
RN  - ML1I4KK67B (3,4-methylenedioxyethamphetamine)
SB  - IM
MH  - 3,4-Methylenedioxyamphetamine/*analogs & derivatives/chemistry/*urine
MH  - Amphetamines/chemistry/*urine
MH  - Chromatography, Gas
MH  - Chromatography, Ion Exchange
MH  - Humans
MH  - Indicators and Reagents
MH  - Methamphetamine/chemistry/*urine
MH  - Military Personnel
MH  - N-Methyl-3,4-methylenedioxyamphetamine/chemistry/*urine
MH  - Quaternary Ammonium Compounds/*chemistry
MH  - Reference Standards
MH  - Spectrometry, Mass, Electrospray Ionization
MH  - Stereoisomerism
MH  - Substance Abuse Detection
EDAT- 2004/11/02 09:00
MHDA- 2005/02/05 09:00
CRDT- 2004/11/02 09:00
PHST- 2004/11/02 09:00 [pubmed]
PHST- 2005/02/05 09:00 [medline]
PHST- 2004/11/02 09:00 [entrez]
AID - 10.1093/jat/28.6.449 [doi]
PST - ppublish
SO  - J Anal Toxicol. 2004 Sep;28(6):449-55. doi: 10.1093/jat/28.6.449.