Abstract
Stir-bar sorptive extraction (SBSE) is a unique method; a sample solution is stirred with a stir bar covered with polydimethylsiloxane. It generally gives clean extract and high recovery rates and is used for analysis of various compounds. In this study, we established a detailed procedure for analysis of 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THCA), the main metabolite of Δ9-tetrahydrocannabinol, in human urine by liquid chromatography-tandem mass spectrometry (LC-MS-MS) using SBSE with liquid desorption. For quantitative analysis, an external calibration method was used. A urine sample was fi rst hydrolyzed under strong alkaline conditions, followed by SBSE with a Twister stir bar at about pH 3. The analyte was desorbed from the bar with a small amount of ethyl acetate. After evaporation of the solvent, it was reconstituted in water-methanol mixture for LC-MS-MS analysis in the selected reaction monitoring mode. The calibration curve for THCA was linear in the range of 10–200 ng/ml urine. The lower limit of detection was 1.3 ng/ml. The mean recovery rate was as high as 76.5%. The intraassay accuracy and precision data were satisfactory. The present method established in this study is useful for identifi cation and quantitation of THCA in forensic toxicology, although some improvements of the procedure should be investigated. To our knowledge, this is fi rst report dealing with SBSE for THCA analysis.
References
de Oliveira GL, Voloch MH, Sztulman GB, Neto ON, Yonamine M (2008) Cannabinoid contents in cannabis products seized in São Paulo, Brazil, 2006–2007. Forensic Toxicol 26:31–35
Uchiyama N, Kikura-Hanajiri R, Kawahara N, Goda Y (2009) Identifi cation of a cannabimimetic indole as a designer drug in a herbal product. Forensic Toxicol 27:61–66
Dewey WL (1986) Cannabinoid pharmacology. Pharmacol Rev 38:151–178
Yamamoto I, Watanabe K, Narimatsu S, Matsunaga K, Kijima T, Hiraiwa K, Yoshimura H (1990) A GC-MS method for determination of Δ9-tetrahydrocannabinol-11-oic-acid in human urine. Eisei Kagaku 36:149–152
Williams PL, Moffat AC (1980) Identifi cation in human urine of Δ9-tetrahydrocannabinol-11-oic acid glucuronide: a tetrahydrocannabinol metabolite. J Pharm Pharmacol 32:445–448
Huestis MA, Cone EJ (1998) Urinary excretion half-life of 11-nor-9-carboxy-Δ9-tetrahydrocannabinol in humans. Ther Drug Monit 20:570–576
Castiglioni S, Zuccato E, Crisci E, Chiabrando C, Fanelli R, Bagnati R (2006) Identifi cation and measurement of illicit drugs and their metabolites in urban wastewater by liquid chromatography-tandem mass spectrometry. Anal Chem 78:8421–8429
Dixit V, Dixit VM (1991) Solid-phase extraction of 11-nor-delta-9-tetrahydrocannabinol-9-carboxylic acid from human urine with gas chromatographic-mass spectrometric confirmation. J Chromatogr 567:81–91
Oikawa H, Sasaki Y, Takahashi M, Nakamura S (2001) Analysis of methamphetamine in urine by SBSE (stir bar sorptive extraction). Jpn J Forensic Toxicol 19:166–167
Tienpont B, David F, Desmet K, Sandra P (2002) Stir bar sorptive extraction-thermal desorption-capillary GC-MS applied to biological fl uids. Anal Bioanal Chem 373:46–55
Queiroz RHC, Bertucci C, Malfará WR, Dreossi SAC, Chaves AR, Valério DAR, Queiroz MEC (2008) Quantifi cation of carbamazepine, carbamazepine-10,11-epoxide, phenytoin and phenobarbital in plasma samples by stir bar-sorptive extraction and liquid chromatography. J Pharm Biomed Anal 48: 428–434
Yokota K, Shuto M, Obara T, Asai K, Tachibana K, Arizono K (2008) Determination of bisphenol A and related compounds in canned foods by stir bar sorptive extraction with derivatization and thermal desorption system-GC/MS. Jpn J Food Chem 15:116–121
Stopforth A, Grobbelaar CJ, Crouch AM, Sandra P (2007) Quantifi cation of testosterone and epitestosterone in human urine samples by stir bar sorptive extraction-thermal desorption-gas chromatography/mass spectrometry: application to HIV-positive urine samples. J Sep Sci 30:257–265
Almeida C, Nogueira JMF (2006) Determination of steroid sex hormones in water and urine matrices by stir bar sorptive extraction and liquid chromatography with diode array detection. J Pharm Biomed Anal 41:1303–1311
Benijts T, Vercammen J, Dams R, Tuan HP, Lambert W, Sandra P (2001) Stir bar sorptive extraction-thermal desorption-capillary gas chromatography-mass spectrometry applied to the analysis of polychlorinated biphenyls in human sperm. J Chromatogr B 755:137–142
Blasco C, Fernández M, Picó Y, Font G (2004) Comparison of solid-phase microextraction and stir bar sorptive extraction for determining six organophosphorus insecticides in honey by liquid chromatography-mass spectrometry. J Chromatogr A 1030:77–85
Popp P, Bauer C, Wennrich L (2001) Application of stir bar sorptive extraction in combination with column liquid chromatography for the determination of polycyclic aromatic hydrocarbons in water samples. Anal Chim Acta 436:1–9
Hoeck EV, David F, Sandra P (2007) Stir bar sorptive extraction for the determination of pyrethroids in water samples. A comparison between thermal desorber, in a split/splitless inlet and by liquid desorption. J Chromatogr A 1157:1–9
Weinmann W, Vogt S, Georke R, Müller C, Bromberger A (2000) Simultaneous determination of THC-COOH and THCCOOH-glucuronide in urine samples by LC/MS/MS. Forensic Sci Int 113:381–387
Weinmann W, Goerner M, Vogt S, Goerke R, Pollak S (2001) Fast confi rmation of 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) in urine by LC/MS/MS using negative atmospheric-pressure chemical ionisation (APCI). Forensic Sci Int 121:103–107
Grauwiler SB, Scholer A, Drewe J (2007) Development of a LC/MS/MS method for the analysis of cannabinoids in human EDTA-plasma and urine after small doses of Cannabis sativa extracts. J Chromatogr B 850:515–522
Fernández MdMR, Wille SMR, Samyn N, Wood M, Lopéz-Rivadulla M, De Boeck G (2009) On-line solid-phase extraction combined with liquid chromatography-tandem mass spectrometry for high throughput analysis of 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid in urine. J Chromatogr B 877:2152–2157
Hawks RL, Chiang CN (1986) Examples of specifi c drug assays. In: Hawks RL, Chiang CN (eds) Urine testing for drugs of abuse, NIDA research monograph 73. National Institute on Drug Abuse, Rockville, MD, pp 84–114
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Goto, Y., Araki, T., Fuchigami, T. et al. Analysis of 11-nor-9-carboxy-Δ9-tetrahydrocannabinol in urine by LC-MS-MS after stir-bar sorptive extraction and liquid desorption. Forensic Toxicol 28, 38–42 (2010). https://doi.org/10.1007/s11419-009-0081-2
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DOI: https://doi.org/10.1007/s11419-009-0081-2