Abstract
Purpose
To test synthetic cannabinoid (SCs) in parent forms from living human, the hairs seems to be one of the best samples, because of the non-invasiveness upon their collection. The purpose of this study is to establish a method for quantification of MDMB-4en-PINACA and ADB-BUTINACA, the most recently abused SCs in hair samples, using gas chromatography−tandem mass spectrometry (GC−MS/MS).
Methods
The collected hair samples were washed with a detergent solution, following by water and acetone. After drying cutting them into about 2 mm sections, they were ground by a cryogenic grinder into powder. The 50-mg powder with internal standard(s) plus 1 mL methanol were vortexed, and centrifuged to obtain the supernatant layer. After its evaporation and reconstitution with 50 µL methanol, 1-µL aliquot of it was subjected to analysis.
Results
The standard calibration curves were created for both MDMB-4en-PINACA and ADB-BUTINACA in blank hair samples; good linear curves were obtained in the range of 20–20,000 pg/mg with correlation coefficients greater than 0.99. The limits of detection and limits of quantification were 10 and 20 pg/mg, respectively. Other validation parameters were all satisfactory. The concentrations of MDMB-4en-PINACA obtained from 3 authentic subjects and ADB-BUTINACA obtained from 3 authentic subjects were 26.2–806 pg/mg and 63.1–430 pg/mg, respectively.
Conclusions
In the present article, the details of simple and rapid quantification of MDMB-4en-PINACA and ADB-BUTINACA in human scalp hair have been established. To our knowledge, this is the first report for quantification of SCs in hair samples by GC−MS/MS.
References
Auwärter V, Dresen S, Weinmann W, Müller M, Pütz M, Ferreirós N (2009) ‘Spice’ and other herbal blends: harmless incense or cannabinoid designer drugs? J Mass Spectrom 44:832–837. https://doi.org/10.1002/jms.1558
Uchiyama N, Kikura-Hanajiri R, Kawahara N, Goda Y (2009) Identification of a cannabimimetic indole as a designer drug in a herbal product. Forensic Toxicol 27:61–66. https://doi.org/10.1007/s11419-009-0069-y
EMCDDA (2021) European drug report 2021: trends and developments. EMCDDA. https://doi.org/10.2810/18539
EMCDDA (2020) MDMB-4en-PINACA : EMCDDA initial report on the new psychoactive substance methyl 3,3-dimethyl-2-(1-(pent-4-en-1-yl)-1H-indazole-3-carboxamido)butanoate (MDMB-4en-PINACA). EMCDDA. https://doi.org/10.2810/135998
EMCDDA (2020) Risk assessment report on a new psychoactive substance: methyl 3,3-dimethyl-2-{[1-(pent-4-en-1-yl)-1H-indazole-3-carbonyl]amino}butanoate (MDMB-4en-PINACA) in accordance with Article 5c of Regulation (EC) No 1920/2006 (as amended). https://www.emcdda.europa.eu/system/files/publications/13680/emcdda-RAR-MDMB-4en-PINACA_NEW.pdf. Accessed 30 Dec 2021
Cannaert A, Sparkes E, Pike E, Luo JL, Fang A, Kevin RC, Ellison R, Gerona R, Banister SD (2020) Stove CP (2020) synthesis and in vitro cannabinoid receptor 1 activity of recently detected synthetic cannabinoids 4F-MDMB-BICA, 5F-MPP-PICA, MMB-4en-PICA, CUMYL-CBMICA, ADB-BINACA, APP-BINACA, 4F-MDMB-BINACA, MDMB-4en-PINACA, A-CHMINACA, 5F-AB-P7AICA, 5F-MDMB-P7AICA, and 5F-AP7AICA. ACS Chem Neurosci 11:4434–4446. https://doi.org/10.1021/acschemneuro.0c00644
Banister SD, Stuart J, Kevin RC, Edington A, Longworth M, Wilkinson SM, Beinat C, Buchanan AS, Hibbs DE, Glass M, Connor M, McGregor IS, Kassiou M (2015) Effects of bioisosteric fluorine in synthetic cannabinoid designer drugs JWH-018, AM-2201, UR-144, XLR-11, PB-22, 5F-PB-22, APICA, and STS-135. ACS Chem Neurosci 6:1445–1458. https://doi.org/10.1021/acschemneuro.5b00107
Kronstrand R, Norman C, Vikingsson S, Biemans A, Crespo BV, Edwards D, Fletcher D, Gilbert N, Persson M, Reid R, Semenova O, Al Teneiji F, Wu X, Dahlén J, NicDaéid N, Tarbah F, Sutcliffe OB, McKenzie C, Gréen H (2021) The metabolism of the synthetic cannabinoids ADB-BUTINACA and ADB-4en-PINACA and their detection in forensic toxicology casework and infused papers seized in prisons. Drug Test Anal. https://doi.org/10.1002/dta.3203
Sia CH, Wang Z, Goh EML, Tan YL, Fong CY, Moy HY, Chan ECY (2021) Urinary metabolite biomarkers for the detection of synthetic cannabinoid ADB-BUTINACA abuse. Clin Chem 67:1534–1544. https://doi.org/10.1093/clinchem/hvab134
Toronto Research Chemicals (2021) Chemical No. A558240, ADB-BUTINACA. https://www.trc-canda.com/product-detail/?A558240. Accessed 30 Dec 2021
Peters FT, Drummer OH, Musshoff F (2007) Validation of new methods. Forensic Sci Int 165:216–224. https://doi.org/10.1016/j.forsciint.2006.05.021
U.S. Department of Justice, Drug Enforcement Administration, Diversion Control Division (2021) NFLIS-drug 2020 annual report. https://www.nflis.deadiversion.usdoj.gov/nflisdata/docs/NFLISDrug2020AnnualReport.pdf. Accessed 23 Dec 2021
Minakata K, Yamagishi I, Nozawa H, Hasegawa K, Suzuki M, Gonmori K, Suzuki O, Watanabe K (2017) Sensitive identification and quantitation of parent forms of six synthetic cannabinoids in urine samples of human cadavers by liquid chromatography–tandem mass spectrometry. Forensic Toxicol 35:275–283. https://doi.org/10.1007/s11419-017-0354-0
Diao X, Huestis MA (2019) New synthetic cannabinoids metabolism and strategies to best identify optimal marker metabolites. Front Chem 7:109. https://doi.org/10.3389/fchem.2019.00109(open access article)
Dahm P, Thomas A, Rothschild MA, Thevis M, Mercer-Chalmers-Bender K (2022) Phase I-metabolism studies of the synthetic cannabinoids PX-1 and PX-2 using three different in vitro models. Forensic Toxicol. https://doi.org/10.1007/s11419-021-00606-6(open access article)
Franz F, Angerer V, Hermanns-Clausen M, Auwärter V, Moosmann B (2016) Metabolites of synthetic cannabinoids in hair—proof of consumption or false friends for interpretation? Anal Bioanal Chem 408:3445–3452. https://doi.org/10.1007/s00216-016-9422-2
Cho B, Cho HS, Kim J, Sim J, Seol I, Baeck SK, In S, Shin DH, Kim E (2020) Simultaneous determination of synthetic cannabinoids and their metabolites in human hair using LC-MS/MS and application to human hair. Forensic Sci Int 306:110058. https://doi.org/10.1016/j.forsciint.2019.110058
Shi Y, Zhou L, Li L, Liu M, Qiang H, Shen M, Shen B, Chen H, Drummer OH, Liu W, Wu H, Xiang P (2020) Detection of a new tert-leucinate synthetic cannabinoid 5F-MDMB-PICA and its metabolites in human hair: application to authentic cases. Front Chem 8:610312. https://doi.org/10.3389/fchem.2020.610312(open access article)
Liying Z, Min S, Baohua S, Hang C, Xin W, Hongxiao D, Ping X, Yan S (2022) Application of a UPLC-MS/MS method for quantitative analysis of 29 synthetic cannabinoids and their metabolites, such as ADB-BUTINACA and MDMB-4en-PINACA in human hair in real cases. Forensic Sci Int 331:111139. https://doi.org/10.1016/j.forsciint.2021.111139
Hutter M, Kneisel S, Auwärter V, Neukamm MA (2012) Determination of 22 synthetic cannabinoids in human hair by liquid chromatography–tandem mass spectrometry. J Chromatogr B 903:95–101. https://doi.org/10.1016/j.jchromb.2012.07.002
Salomone A, Luciano C, Di Corcia D, Gerace E, Vincenti M (2014) Hair analysis as a tool to evaluate the prevalence of synthetic cannabinoids in different populations of drug consumers. Drug Test Anal 6:126–134. https://doi.org/10.1002/dta.1556
Gottardo R, Sorio D, Musile G, Trapani E, Seri C, Serpelloni G, Tagliaro F (2014) Screening for synthetic cannabinoids in hair by using LC-QTOF MS: a new and powerful approach to study the penetration of these new psychoactive substances in the population. Med Scie Law 54:22–27. https://doi.org/10.1177/0025802413477396(open access article)
Franz F, Jechle H, Angerer V, Pegoro M, Auwärter V, Neukamm MA (2018) Synthetic cannabinoids in hair—pragmatic approach for method updates, compound prevalences and concentration ranges in authentic hair samples. Anal Chim Acta 1006:61–72. https://doi.org/10.1016/j.aca.2017.12.029
Mönch B, Becker R, Nehls I (2013) Quantification of ethyl glucuronide in hair: effect of milling on extraction efficiency. Alcohol Alcohol 48:558–563. https://doi.org/10.1093/alcalc/agt059(open access article)
Kummer N, Wille SMR, Di Fazio V, Fernández DMR, M, Yegles M, Lambert WE.E, Samyn N (2015) Impact of the grinding process on the quantification of ethyl glucuronide in hair using a validated UPLC–ESI-MS-MS method. J Anal Toxicol 39:17–23. https://doi.org/10.1093/jat/bku108(open access article)
Da Rosa Chagas AG, Spinelli E, Fiaux SB, da Silva BA, Rodrigues SV (2017) Particle-size distribution (PSD) of pulverized hair: a quantitative approach of milling efficiency and its correlation with drug extraction efficiency. Forensic Sci Int 277:188–196. https://doi.org/10.1016/j.forsciint.2017.06.008
Gallagher C (2021) Potentially fatal synthetic imitation cannabis detected in State last year: three deaths after substance exposure confirmed in United Kingdom and one in Sweden. The Irish Times 22 Jul 2021. https://www.irishtimes.com/news/crime-and-law/potentially-fatal-synthetic-imitation-cannabis-detected-in-state-last-year-1.4627878. Accessed 23 Dec 2021
Acknowledgements
This study was supported in part by the National Natural Science Foundation of China (Grant No.81860331).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
There are no financial or other relations that could lead to a conflict of interest.
Ethical approval
This study was approved by the Ethical Committee of Inner Mongolia Medical University. The blank hair strands were obtained from healthy volunteers with informed consent. The toxicological analyses of hair samples of the authentic suspects were requested by judicial authorities. All participants were kept anonymous.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Wang, Y., Pan, Y., Yang, H. et al. Quantification of MDMB-4en-PINACA and ADB-BUTINACA in human hair by gas chromatography–tandem mass spectrometry. Forensic Toxicol 40, 340–348 (2022). https://doi.org/10.1007/s11419-022-00615-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11419-022-00615-z