Fast and Sensitive Chiral Analysis of Amphetamines and Cathinones in Equine Urine and Plasma Using Liquid Chromatography Tandem Mass Spectrometry — Oak Academic Publishing
Research ArticleOpen AccessGoogle Scholar indexed
Fast and Sensitive Chiral Analysis of Amphetamines and Cathinones in Equine Urine and Plasma Using Liquid Chromatography Tandem Mass Spectrometry
A simple, rapid, sensitive and reproducible method for enantiomer analysis of methamphetamine, amphetamine, cathinone and methcathinone was developed and validated. The compounds were extracted from equine plasma and urine using a fast liquid-liquid extraction procedure. Only one milliliter plasma and one hundred microliter urine sample is needed for analysis. The extraction procedure had good recovery (>70%) and the matrix effect was negligible. Enantiomer differentiation and confirmation were achieved using liquid chromatography with chiral stationary phase and mass spectrometry detection. The method demonstrated excellent reproducibility with intra-day and inter-day precision of lower than 5%. The lower limits of detection for all of the compounds studied here were at low pg/mL level for both plasma and urine. This is the first report of the analysis of four chiral compounds in equine plasma and urine. Routine application was demonstrated for (S)- and (R)-enantiomer differentiation.
KeywordsAmphetamines and CathinonesEquine Plasma and UrineChiral AnalysisLiquid Chromatography Tandem Mass Spectrometry
Paul, B.D. and Cole, K.A. (2001) Cathinone (Khat) and Methcathinone (CAT) in Urine Specimens: A Gas Chromatography-Mass Spectrometric Detection Procedure. Journal of Analytical Toxicology, 25, 525-530. http://dx.doi.org/10.1093/jat/25.7.525
Sporkert, F., Pragst, F., Bachus, R., Masuhr, F. and Harms, L. (2003) Determination of Cathinone, Cathine and Norephedrine in Hair of Yemenite Khat Chewers. Forensic Science International, 133, 39-46. http://dx.doi.org/10.1016/S0379-0738(03)00048-3
Strano-Rossi, S., Botre, F., Bermejo, A.M. and Tabernero, M.J. (2009) A Rapid Method for the Extraction, Enantiomeric Separation and Quantification of Amphetamines in Hair. Forensic Science International, 193, 95-100. http://dx.doi.org/10.1016/j.forsciint.2009.09.016
Yi, R., Zhao, S., Lam, G., Sandhu, J., Loganathan, D. and Morrissey, B. (2013) Detection and Elimination Profile of Cathinone in Equine after Norephedrine (Propalin®) Administration Using a Validated Liquid Chromatography— Tandem Mass Spectrometry Method. Analytical and Bioanalytical Chemistry, 405, 9711-9722. http://dx.doi.org/10.1007/s00216-013-7073-0
Mikuma, T., Iwata, Y.T., Miyaguchi, H., Kuwayama, K., Tsujikawa, K., Kanamori, T. and Inoue, H. (2015) The Use of a Sulfonated Capillary on Chiral Capillary Electrophoresis/Mass Spectrometry of Amphetamine-Type Stimulants for Methamphetamine Impurity Profiling. Forensic Science International, 249, 59-65. http://dx.doi.org/10.1016/j.forsciint.2015.01.015
Pasin, D., Bidny, S. and Fu, S. (2015) Analysis of New Designer Drugs in Post-Mortem Blood Using High-Resolution Mass Spectrometry. Journal of Analytical Toxicology, 39, 163-171. http://dx.doi.org/10.1093/jat/bku144
Gambaro, V., Arnoldi, S., Colombo, M.L., Dellacqua, L., Guerrini, K. and Roda, G. (2012) Determination of the Active Principles of Catha Edulis: Quali-Quantitative Analysis of Cathinone, Cathine, and Phenylpropanolamine. Forensic Science International, 217, 87-92. http://dx.doi.org/10.1016/j.forsciint.2011.09.028
Holler, J.M., Vorce, S.P., Bosy, T.Z. and Jacobs, A. (2005) Quantitative and Isomeric Determination of Amphetamine and Methamphetamine from Urine Using a Nonprotic Elution Solvent and R(-)-a-Methoxy-a-Trifluoromethylphenylacetic Acid Chloride Derivatization. Journal of Analytical Toxicology, 29, 652-657. http://dx.doi.org/10.1093/jat/29.7.652
Makino, Y., Ohta, S. and Hirobe, M. (1996) Enantiomeric Separation of Amphetamine by High-Performance Liquid Chromatography Using Chiral Crown Ether-Coated Reversed-Phase Packing: Application to Forensic Analysis. Forensic Science International, 78, 65-70. http://dx.doi.org/10.1016/0379-0738(95)01865-4
Glennon, R.A., Schechter, M.D. and Rosecrans, J.A. (1984) Discriminative Stimulus Properties of S(-)- and R(+)-Cathinone, (+)-Cathine and Several Structural Modifications. Pharmacology Biochemistry & Behavior, 21, 1-3. http://dx.doi.org/10.1016/0091-3057(84)90121-7
Nielsen, J.A. and Schechter, M.D. (1985) Behavioral and Neurochemical Effects of (-)- and (±)-Cathinone: Dose- Response and Time-Course. Progress in Neuro-Psychopharmacology and Biological Psychiatry, 9, 739-743. http://dx.doi.org/10.1016/0278-5846(85)90052-1
Mohr, S., Weib, J.A., Spreitz, J. and Schmid, M.G. (2012) Chiral Separation of New Cathinone- and Amphetamine-Related Designer Drugs by Gas Chromatography-Mass Spectrometry Using Trifluoroacetyl-L-Prolyl Chloride as Chiral Derivatization Reagent. Journal of Chromatography A, 1269, 352-359. http://dx.doi.org/10.1016/j.chroma.2012.09.079
Rasmssen, L.B., Olsen, K.H. and Johansen, S.S. (2006) Chiral Separation and Quantification of R/S-Amphetamine, R/S-Methamphetamine, R/S-MDA, R/S-MDMA, and R/S-MDEA in Whole Blood by GC-EI-MS. Journal of Chromatography B, 842, 136-141. http://dx.doi.org/10.1016/j.jchromb.2006.05.011
Nystrom, I., Trygg, T., Woxler, P., Ahlner, J. and Kronstrand, R. (2005) Quantitation of R-(-)- and S-(+)-Amphetamine in Hair and Blood by Gas Chromatography-Mass Spectrometry: An Application to Compliance Monitoring in Adult-Attention Deficit Hyperactivity Disorder Treatment. Journal of Analytical Toxicology, 29, 682-688. http://dx.doi.org/10.1093/jat/29.7.682
Mislanova, C. and Hutta, M. (2003) Role of Biological Matrices during the Analysis of Chiral Drugs by Liquid Chromatography. Journal of Chromatography B, 797, 91-109. http://dx.doi.org/10.1016/j.jchromb.2003.07.018
Guillarme, D., Bonvin, G., Badoud, F., Schappler, J., Rudaz, S. and Veuthey, J. (2010) Fast Chiral Separation of Drugs Using Columns Packed with Sub-2 μm Particles and Ultra-High Pressure. Chirality, 22, 320-330.
Kasprzyk-Hordern, B., Kondakal, V.V.R. and Baker, D.R. (2010) Enantiomeric Analysis of Drugs of Abuse in Waste-water by Chiral Liquid Chromatography Coupled with Tandem Spectrometry. Journal of Chromatography A, 1217, 4575-4586. http://dx.doi.org/10.1016/j.chroma.2010.04.073
Bagnall, J.P., Evans, S.E., Wort, M.T., Lubben, A.T. and Kasprzyk-Hordern, B. (2012) Using Chiral Liquid Chromatography Quadrupole Time-of-Flight Mass Spectrometry for the Analysis of Pharmaceuticals and Illicit Drugs in Surface and Wastewater at the Enantiomeric Level. Journal of Chromatography A, 1249, 115-129. http://dx.doi.org/10.1016/j.chroma.2012.06.012
Mohr, S., Taschwer, M. and Schmid, M.G. (2012) Chiral Separation of Cathinone Derivatives Used as Recreational Drugs by HPLC-UV Using a Chiralpak AS-H Column as Stationary Phase. Chirality, 24, 486-492. http://dx.doi.org/10.1002/chir.22048
Schwaninger, A.E., Meyer, W.R. and Maurer, H.H. (2012) Chiral Drug Analysis Using Mass Spectrometric Detection Relevant to Research and Practice in Clinical and Forensic Toxicology. Journal of Chromatography A, 1269, 122-135. http://dx.doi.org/10.1016/j.chroma.2012.07.045
Perera, R.W.H., Abraham, I., Gupta, S., Kowalska, P., Lightsey, D., Marathaki, C., Singh, N.S. and Lough, W.J. (2012) Screening Approach, Optimization and Scale-Up for Chiral Liquid Chromatography of Cathinones. Journal of Chromatography A, 1269, 189-197. http://dx.doi.org/10.1016/j.chroma.2012.11.001
Newmeyer, M.N., Concheiro, M. and Huestis, M.A. (2014) Rapid Quantitative Chiral Amphetamine Liquid Chromatography-Tandem Mass Spectrometry: Method in Plasma and Oral Fluid with a Cost-Effective Chiral Derivatizing Reagent. Journal of Chromatography A, 1358, 68-74. http://dx.doi.org/10.1016/j.chroma.2014.06.096
Wang, T., Shen, B., Shi, Y., Xiang, P. and Yu, Z. (2015) Chiral Separation and Determination of R/S-Methamphetamine and Its Metabolite R/S-Amphetamine in Urine Using LC-MS/MS. Forensic Science International, 246, 72-78. http://dx.doi.org/10.1016/j.forsciint.2014.11.009
Taschwer, M., Seidi, Y., Mohr, S. and Schmid, M.G. (2014) Chiral Separation of Cathinone and Amphetamine Derivatives by HPLC/UV Using Sulfated β-Cyclodextrin as Chiral Mobile Phase Additive. Chirality, 26, 411-418. http://dx.doi.org/10.1002/chir.22341
Ribeiro, A.R., Maia, A.S., Cass, Q.B. and Tiritan, M.E. (2014) Enantioseparation of Chiral Pharmaceuticals in Biomedical and Environmental Analyses by Liquid Chromatography: An Overview. Journal of Chromatography B, 968, 8-21. http://dx.doi.org/10.1016/j.jchromb.2014.02.049
Nguyen, L.A., He, H. and Pham-Huy, C. (2006) Chiral Drugs: An Overview. International Journal of Biomedical Science, 2, 85-100.
Hamman, C., Wong, M., Aliagas, I., Ortwine, D.F., Pease, J., Schmid, D.E. and Victorino, J. (2013) The Evaluation of 2 Chiral Stationary Phase and the Utilization of Sub-2.0 μm Coated Polysaccharide Chiral Stationary Phases via Supercritical Fluid Chromatography. Journal of Chromatography A, 1305, 310-319. http://dx.doi.org/10.1016/j.chroma.2013.07.046
The Association of Official Racing Chemists (2015) AORC Guidelines for the Minimum Criteria for Identification by Chromatography and Mass Spectrometry. http://www.aorc-online.org/documents/aorc-ms-criteria-jan-2015/