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Forensic Toxicology
Published in: Forensic Toxicology 1/2020

01-01-2020 | Cannabinoid | Original Article

Identification and imaging of indole-3-carboxamide cannabinoids in hair using matrix-assisted laser-desorption/ionization mass spectrometry

Authors: Houwei Lin, Xiaoyan Zeng, Qian Wang, Yinnan Li, Bin Sun, Ying Wang, Hang Wang

Published in: Forensic Toxicology | Issue 1/2020

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Abstract

Purpose

Different kinds of new synthetic cannabinoids (SCs) have been continuously developed to evade drug monitoring. Segmental hair analysis offers a longer period for retrospective drug detection compared with blood or urine. In this study, matrix-assisted laser-desorption/ionization-Fourier transform ion cyclotron resonance mass spectrometric imaging (MALDI-FT ICR MSI) was developed for direct identification and imaging of synthetic indole-3-carboxamide cannabinoids in hair samples using the positive ion mode.

Methods

The target SCs include N-(adamantan-1-yl)-1-pentyl-1H-indole-3-carboxamide (APICA), N-(1-amino-3-methyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-1H-indole-3-carboxamide (5F-AB-PICA), N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-pentyl-1H-indazole-3-carboxamide (ADB-PINACA) and N-(1-amino -3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-1H-indole-3-carboxamide (5F-ADBICA). The MALDI-MS and MS/MS were first performed on the scraped hair soaked in a mixture of the four SCs after matrix sublimation. This method may provide a detection power for SCs to the 0.1 ng level per 2 cm hair. Target cannabinoids were identified by MS1 and MS2. Matrix deposition methods including airbrush sprayer and sublimation were compared.

Results

The method was then applied in revealing the spatial distribution of APICA and 5F-ADBICA in real hair samples from two drug abusers by comparing MS1 and MS2 spectra. The metabolites of APICA and 5F-ADBICA were also presumed to be present in the positive hair samples. Furthermore, a comprehensive comparison between a MALDI-FT ICR MS and a MALDI time-of-flight–MS instrument was performed in detection-sensitivity and specificity for positive real samples.

Conclusions

The proposed method provides a powerful tool for drug supervision and forensic medicine analysis in a wide time window, and the sample amount required was also decreased.
Appendix
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Literature
1.
Huestis MA (1996) Technical and legal aspects of drugs of abuse testing in hair. In: Kintz P (ed) Drug testing in hair. CRC Press, New York, pp 5–16
2.
Kintz P, Spiehler V, Negrusz A (2008) Alternative specimens. In: Jickells S, Negrusz A (eds) Clark’s analytical forensic toxicology. Pharmaceutical Press, London, pp 153–190
3.
Kieliba T, Lerch O, Andresen-Streichert H, Rothschild MA, Beike J (2019) Simultaneous quantification of THC–COOH, OH–THC, and further cannabinoids in human hair by gas chromatography—tandem mass spectrometry with electron ionization applying automated sample preparation. Drug Test Anal 11:267–278CrossRef
4.
Kłys M, Rojek S, Kulikowska J, Bożek E (2007) Usefulness of multiple opiate and amphetamine analysis of hair segments under methadone therapy using LC-APCI-MS–MS. Forensic Toxicol 25(2):69–75CrossRef
5.
Kuwayama K, Miyaguchi H, Iwata YT, Kanamori T, Tsujikawa K, Yamamuro T, Segawa H, Inoue H (2018) Different localizations of drugs simultaneously administered in a strand of hair by micro-segmental analysis. Drug Test Anal 10:750–760CrossRef
6.
Sugie K, Kurakami D, Akutsu M, Saito K (2018) Rapid detection of tert-butoxycarbonyl-methamphetamine by direct analysis in real time time-of-flight mass spectrometry. Forensic Toxicol 36:261–269CrossRef
7.
Shen M, Xiang P, Shi Y, Pu H, Yan H, Shen BH (2014) Mass imaging of ketamine in a single scalp hair by MALDI-FTMS. Anal Bioanal Chem 406:4611–4616CrossRef
8.
Miki A, Katagi M, Shima N, Kamata H, Tatsuno M, Nakanishi T, Tsuchihashi H, Takubo T, Suzuki K (2011) Imaging of methamphetamine incorporated into hair by MALDI-TOF mass spectrometry. Forensic Toxicol 29:111–116CrossRef
9.
Miki A, Katagi M, Kamata T, Zaitsu K, Tatsuno M, Nakanishi T, Tsuchihashi H, Takubob T, Suzuki K (2011) MALDI-TOF and MALDI-FTICR imaging mass spectrometry of methamphetamine incorporated into hair. J Mass Spectrom 46:411–416CrossRef
10.
Poetzsch M, Steuer AE, Roemmelt AT, Baumgartner MR, Kraemer T (2014) Single hair analysis of small molecules using MALDI-triple quadrupole MS imaging and LC-MS/MS: investigations on opportunities and pitfalls. Anal. Chem 86:11758–11765CrossRef
11.
Zaitsu K, Sato T, Nakanishi T, Tsuchihashi H, Suzuki K (2015) Single-hair analysis of zolpidem on the supposition of its single administration in drug-facilitated crimes. Forensic Toxicol 33:122–130CrossRef
12.
Kamata T, Shima N, Sasaki K, Matsuta S, Takei S, Katagi M, Miki A, Zaitsu K, Nakanishi T, Sato T, Suzuki K, Tsuchihashi H (2015) Time-course mass spectrometry imaging for depicting drug incorporation into hair. Anal Chem 87:5476–5481CrossRef
13.
Nakanishi T, Nirasawa T, Takubo T (2014) Quantitative mass barcode-like image of nicotine in single longitudinally sliced hair sections from long-term smokers by matrix-assisted laser desorption time-of-flight mass spectrometry imaging. J Anal Toxicol 38:349–353CrossRef
14.
Poetzsch M, Baumgartner MR, Steuer AE, Kraemer T (2015) Segmental hair analysis for differentiation of tilidine intake from external contamination using LC-ESI-MS/MS and MALDI-MS/MS imaging. Drug Test Anal 7:143–149CrossRef
15.
Porta T, Grivet C, Kraemer T, Varesio E, Hopfgartner G (2011) Single hair cocaine consumption monitoring by mass spectrometric imaging. Anal Chem 83:4266–4272CrossRef
16.
Flinders B, Cuypers E, Zeijlemaker H, Tytgat J, Heeren RMA (2015) Preparation of longitudinal sections of hair samples for the analysis of cocaine by MALDI-MS/MS and TOF-SIMS imaging. Drug Test Anal 7:859–865CrossRef
17.
Musshoff F, Arrey T, Strupat K (2013) Determination of cocaine, cocaine metabolites and cannabinoids in single hairs by MALDI-fourier transform mass spectrometry-preliminary results. Drug Test Anal 5:361–365CrossRef
18.
Beasley E, Francese S, Bassindale T (2016) Detection and mapping of cannabinoids in single hair samples through rapid derivatization and matrix-assisted laser desorption ionization mass spectrometry. Anal Chem 88:10328–10334CrossRef
19.
Ernalleguen AEK, Enjalbal C, Alvarez JC, Belgacem O, Leonetti G, Lafitte D, Pelissier-Alicot AL (2018) Synthetic cannabinoid isomers characterization by MALDI-MS3 imaging: application to single scalp hair. Anal Chim Acta 1041:87–93CrossRef
20.
Pacher P, Steffens S, Haskó G, Schindler TH, Kunos G (2018) Cardiovascular effects of marijuana and synthetic cannabinoids: the good, the bad, and the ugly. Nat Rev Cardiol 15(3):151–166CrossRef
21.
Martinotti G, Santacroce R, Papanti D, Elgharably Y, Prilutskaya M, Corazza O (2017) Synthetic cannabinoids: psychopharmacology, clinical aspects, psychotic onset. CNS Neurol Disord Drug Targets 16(5):567–575CrossRef
22.
Mills B, Yepes A, Nugent K (2015) Synthetic cannabinoids. Am J Med Sci 350(1):59–62CrossRef
23.
Le Boisselier R, Alexandre J, Lelong-Boulouard V, Debruyne D (2017) Focus on cannabinoids and synthetic cannabinoids. Clin Pharmacol Ther 101(2):220–229CrossRef
24.
Brandt SD, King LA, Evans-Brown M (2014) The new drug phenomenon. Drug Test Anal 6:587–597CrossRef
25.
Longworth M, Banister SD, Mack JBC, Glass M, Connor M, Kassiou M (2016) The 2-alkyl-2H-indazole regioisomers of synthetic cannabinoids AB-CHMINACA, AB-FUBINACA, AB-PINACA, and 5F-ABPINACA are possible manufacturing impurities with cannabimimetic activities. Forensic Toxicol 34:286–303CrossRef
26.
Hess C, Murach J, Krueger L, Scharrenbroch L, Unger M, Madea B, Sydow K (2017) Simultaneous detection of 93 synthetic cannabinoids by liquid chromatography tandem mass spectrometry and retrospective application to real forensic samples. Drug Test Anal 9:721–733CrossRef
27.
Hutter M, Moosmann B, Auwarter V, Neukamm MA (2015) Hair analysis for JWH-018, JWH-122, and JWH-210 after passive in vivo exposure to synthetic cannabinoid smoke. Forensic Toxicol 33:69–76CrossRef
28.
Cannizzaro C, Malta G, Argo A, Brancato A, Roda G, Casagni E, Fumagalli L, Valoti E, Froldi R, Procaccianti P, Gambaro V (2016) Behavioural and pharmacological characterization of a novel cannabinomimetic adamantane-derived indole, APICA, and considerations on the possible misuse as a psychotropic spice abuse, in C57bl/6J mice. Forensic Sci Int 265:6–12CrossRef
29.
Longworth M, Connor M, Banister SD, Kassiou M (2017) Synthesis and pharmacological profiling of the metabolites of synthetic cannabinoid drugs APICA, STS-135, ADB-PINACA, and 5F-ADB-PINACA. ACS Chem Neurosci 8(8):1673–1680CrossRef
30.
Wang H, Wang Y (2017) Matrix-assisted laser desorption/ionization mass spectrometric imaging for the rapid segmental analysis of methamphetamine in a single hair using umbelliferone as a matrix. Anal Chim Acta 975:42–51CrossRef
31.
Wang H, Wang Y, Wang G, Hong LZ (2017) Matrix-assisted laser-desorption/ionization mass spectrometric imaging of olanzapine in a single hair using esculetin as a matrix. J Pharm Biomed Anal 141:123–131CrossRef
32.
Huang X, Zhan LP, Sun J, Xue JJ, Liu HH, Xiong CQ, Nie ZX (2018) Utilizing a mini-humidifier to deposit matrix for MALDI imaging. Anal Chem 90:8309–8313CrossRef
33.
Gemperline E, Rawson S, Li LJ (2014) Optimization and comparison of multiple MALDI matrix application methods for small molecule mass spectrometric imaging. Anal Chem 86:10030–10035CrossRef
34.
Dong YH, Li B, Malitsky S, Rogachev I, Aharoni A, Kaftan F, Svatos A, Francesch P (2016) Sample preparation for mass spectrometry imaging of plant tissues: a review. Front Plant Sci 7:60PubMedPubMedCentral
35.
Sobolevsky T, Prasolov I, Rodchenkov G (2015) Study on the phase I metabolism of novel synthetic cannabinoids, APICA and its fluorinated analogue. Drug Test Anal 7(2):131–142CrossRef
36.
Diao X, Huestis MA (2017) Approaches, challenges, and advances in metabolism of new synthetic cannabinoids and identification of optimal urinary marker metabolites. Clin Pharmacol Ther 101(2):239–253CrossRef
37.
Carlier J, Diao XX, Scheidweiler KB, Huestis MA (2017) Distinguishing intake of new synthetic cannabinoids ADB-PINACA and 5F-ADB-PINACA with human hepatocyte metabolites and high-resolution mass spectrometry. Clin Chem 63:1008–1021CrossRef
38.
Buck A, Balluff B, Voss A, Langer R, Zitzelsberger H, Aichler M, Walch A (2016) Ionization-time-of-flight for metabolite imaging from clinical formalin-fixed and paraffin-embedded tissue samples in comparison to matrix-assisted laser desorption/ionization-fourier transform ion cyclotron resonance mass spectrometry? Anal Chem 88:5281–5289CrossRef
Metadata
Title
Identification and imaging of indole-3-carboxamide cannabinoids in hair using matrix-assisted laser-desorption/ionization mass spectrometry
Authors
Houwei Lin
Xiaoyan Zeng
Qian Wang
Yinnan Li
Bin Sun
Ying Wang
Hang Wang
Publication date
01-01-2020
Publisher
Springer Singapore
Published in
Forensic Toxicology / Issue 1/2020
Print ISSN: 1860-8965
Electronic ISSN: 1860-8973
DOI
https://doi.org/10.1007/s11419-019-00510-0

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