Anal. Chem. 2002, 74, 3071-3075
Quantitation of Amphetamine, Methamphetamine, and Their Methylenedioxy Derivatives in Urine by Solid-Phase Microextraction Coupled with Electrospray Ionization-High-Field Asymmetric Waveform Ion Mobility Spectrometry-Mass Spectrometry Margaret A. McCooeye, Zolta´n Mester, Barbara Ells,† David A. Barnett,† Randy W. Purves,† and Roger Guevremont*,†
Institute for National Measurement Standards, National Research Council of Canada, Ottawa, ON, Canada, K1A 0R6
Amphetamine, methamphetamine, and their methylenedioxy derivatives have been identified and measured in a human urine matrix using solid-phase microextraction (SPME) and high-field asymmetric waveform ion mobility spectrometry (FAIMS) in combination with electrospray ionization (ESI) and mass spectrometric detection (MS). Limits of detection in human urine between 200 pg/mL and 7.5 ng/mL have been achieved. The use of a simple extraction method, SPME, combined with the high sensitivity and selectivity of ESI-FAIMS-MS eliminates the need for chromatographic separation and allows for very rapid sample processing.
The use of recreational drugs has become almost commonplace in social settings, such as dance raves and clubs catering to young people1. The stimulant effects of amphetamine (AM) and methamphetamine (MA) have always been popular, but their methylenedioxy derivatives, the so-called designer drugs, 3,4methylenedioxyamphetamine (MDA, Love Drug), 3,4-methylenedioxymethamphetamine (MDMA, Ecstasy), and 3,4-methylenedioxyethylamphetamine (MDEA, Eve) are even more potent. These drugs increase alertness and produce feelings of euphoria, energy, and a desire to socialize. Among users, amphetamine analogues have the reputation of being safe; however, in recent studies they have been associated with hepatotoxicity, neurotoxicity, psychopathology, potential for abuse,2,3 and even death.4 The popularity of these drugs and the potentially dangerous consequences of their use lead to a requirement for their rapid quantitative analysis in biological fluids in clinical and forensic laboratory settings. * To whom correspondence should be addressed. † Current address: Ionalytics Corporation, Ottawa, ON, Canada K1A 0R6. (1) Christophersen, A. S. Toxicology Lett. 2000, 112-113, 127-131. (2) Maurer, H. H.; Bickeboeller-Friedrich, J.; Kraemer, T.; Peters, F. T. Toxicology Lett. 2000, 112-113, 133-142. (3) Ropero-Miller, J. D.; Goldberger, B. A. Toxicology 1998, 18, 727-746. (4) Weinmann, W.; Bohnert, M. Forensic Sci. Int. 1998, 91, 91-101. 10.1021/ac011296+ CCC: $22.00 Published on Web 05/14/2002
© 2002 American Chemical Society
Initial rapid screening of samples is often accomplished with immunoassay methods.5 Positive results undergo a confirmation analysis that must be at least as sensitive, and more specific for the drug of interest, than the initial screening. Presently, the U.S. Department of Health and Human Services Workplace Drug Testing Program requires a limit of quantitation of at least 1000 ng/mL for initial screening for AM, MA, MDA, MDMA, and MDEA in urine and 500 ng/mL for confirmation analysis of these drugs.6 Several reviews7-9 and recent publications10-16 describe both liquid and gas chromatographic methods for confirmation analysis of amphetamines and designer drugs. This screening/ confirmation approach to drug analysis is expensive in terms of both time and materials. Methods for rapid, specific, and sensitive analyses that would eliminate the double-analysis approach are being investigated. Recent studies have used secondary electrospray ionization with ion mobility spectrometric detection17 and nonaqueous capillary electrophoresis with electrochemical detection18 for the analysis of amphetamines and their derivatives, but neither work considered matrix effects. Real samples have been analyzed for this same class of compounds using liquid-liquid extraction followed by nonaqueous capillary electrophoresis with (5) Kintz, P.; Samyn, N. J. Chromatogr. B 1999, 733, 137-143. (6) U.S. Department of Health and Human Services, Substance Abuse and Mental Health Services Administration, Website www.samhsa.gov. (7) Bogusz, M. J. J. Chromatogr. B 1999, 733, 65-91. (8) Maurer, H. H. J. Chromatogr. B 1998, 713, 3-25. (9) Moeller, M. R.; Steinmeyer, S.; Kraemer, T. J. Chromatogr. B 1998, 713, 91-109. (10) Okajima, K.; Namera, A.; Yashiki, M.; Tsukue, I.; Kojima, T. Forensic Sci. Int. 2001, 116, 15-22. (11) Ugland, H. G.; Krough, M.; Rasmussen, K. E. J. Pharm. Biomed. Anal. 1998, 19, 463-475. (12) Namera, A.; Yashiki, M.; Liu, J.; Okajima, K.; Hara, K.; Imamura, T.; Kojima, T. Forensic Sci. Int. 2000, 109, 215-223. (13) Weinmann, W.; Renz, M.; Vogt, S.; Pollack, S. Int. J. Legal Med. 2000, 113, 229-235. (14) Valentine, J. L.; Middleton, R. J. Anal. Toxicol. 2000, 24, 211-222. (15) Kataoka, H.; Lord, H.; Pawliszyn, J. J. Anal. Toxicol. 2000, 24, 257-265. (16) Jurado, C.; Gimenez, M. P.; Soriano, T.; Menendez, M.; Repetto, M. J. Anal. Toxicol. 2000, 24, 11-16. (17) Wu, C.; Siems, W. F.; Hill, H. H., Jr. Anal. Chem. 2000, 72, 396-403. (18) Backofen, U.; Matysik, F.-M.; Hoffman, W.; Lunte, C. E., Fresenius’ J. Anal. Chem. 2000, 367, 359-363.
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electrospray ionization-mass spectrometry19 and by solid-phase extraction using flow injection-ionspray tandem mass spectrometry, with detection limits of
