Advertisement

The classification of Cannabis hemp cultivars by thermal desorption direct analysis in real time mass spectrometry (TD-DART-MS) with chemometrics

  • Wen Dong
  • Jian Liang
  • Isabella Barnett
  • Paul C. Kline
  • Elliot Altman
  • Mengliang ZhangEmail author
Research Paper

Abstract

Cannabis has been cultivated as a source of food, fiber, and medicine globally, so the classification of Cannabis cultivars based on their chemical fingerprints is important to standardize and control the quality of Cannabis, ensure that patients receive a full and consistent spectrum of therapeutic benefits, and promote the further implementation of Cannabis-based products in clinical uses. In this study, a high-throughput analytical method, thermal desorption direct analysis in real time mass spectrometry (TD-DART-MS), was employed to classify various Cannabis hemp cultivars with multivariate analysis. Cannabis plant materials from four cultivars were analyzed directly by TD-DART-MS without solvent extraction. The total run time was 15 min including 8 min for data acquisition and 7 min for cooling down the thermal stage. Data preprocessing strategy such as data transformation was evaluated on the TD-DART-MS data set and cubic root transform has shown significant improvement to the classification. TD-DART-MS data was then processed by principal component analysis (PCA) and the results were compared with those from liquid chromatography-mass spectrometry (LC-MS) data. The samples were clustered based on cultivars by PCA, and the validation samples collected 2 months later were also grouped together with the original samples by cultivars after mean-centering the data sets. Partial least squares discriminant analysis (PLS-DA) models were constructed with the TD-DART-MS data sets and a 99.3 ± 0.3% classification accuracy was obtained from 100 independent bootstrapped Latin partition evaluations. Our results indicate that TD-DART-MS may be used as a screening tool for the classification of Cannabis cultivars.

Graphical abstract

Keywords

Cannabis hemp Direct analysis in real time mass spectrometry Chemometrics Classification Liquid chromatography-mass spectrometry Principal component analysis 

Notes

Acknowledgments

The authors acknowledge IonSense, Inc. for the support and assistance on DART ion source and BioChromato, Inc. for offering IonRocket device for thermal desorption DART-MS experiments.

Funding information

Isabella Barnett received support from a MTSU Undergraduate Research Experience and Creative Activity (URECA) grant. This research received additional funding from GreenWay Herbal Products, LLC.

Compliance with ethical standards

Conflict of interest

Elliot Altman has equity ownership in GreenWay Herbal Products, LLC. The other authors declare that they have no conflict of interest

Supplementary material

216_2019_2200_MOESM1_ESM.pdf (194 kb)
ESM 1 (PDF 194 kb)

References

  1. 1.
    McPartland JM. Cannabis systematics at the levels of family. Genus, and Species. 2018;3(1):203–12.  https://doi.org/10.1089/can.2018.0039.CrossRefGoogle Scholar
  2. 2.
    McPartland JM, Guy GWJTBR. Models of Cannabis taxonomy, cultural bias, and conflicts between scientific and vernacular names. 2017;83(4):327–381. doi: https://doi.org/10.1007/s12229-017-9187-0.CrossRefGoogle Scholar
  3. 3.
    Whiting PF, Wolff RF, Deshpande S, Di Nisio M, Duffy S, Hernandez AV, et al. Cannabinoids for medical use: a systematic review and meta-analysis. JAMA. 2015;313(24):2456–73.  https://doi.org/10.1001/jama.2015.6358.CrossRefPubMedGoogle Scholar
  4. 4.
    Tanda G, Munzar P, Goldberg SR. Self-administration behavior is maintained by the psychoactive ingredient of marijuana in squirrel monkeys. Nat Neurosci. 2000;3(11):1073–4.  https://doi.org/10.1038/80577.CrossRefPubMedGoogle Scholar
  5. 5.
    Russo EB. Taming THC: potential cannabis synergy and phytocannabinoid-terpenoid entourage effects. Br J Pharmacol. 2011;163(7):1344–64.  https://doi.org/10.1111/j.1476-5381.2011.01238.x.CrossRefPubMedPubMedCentralGoogle Scholar
  6. 6.
    Small E, Cronquist A. A practical and natural taxonomy for Cannabis. Taxon. 1976;25(4):405–35.  https://doi.org/10.2307/1220524.CrossRefGoogle Scholar
  7. 7.
    Hazekamp A, Fischedick JT. Cannabis - from cultivar to chemovar. Drug Test Anal. 2012;4(7–8):660–7.  https://doi.org/10.1002/dta.407.CrossRefPubMedGoogle Scholar
  8. 8.
    ElSohly MA, Stanford DF, Murphy TP. Chemical fingerprinting of Cannabis as a means of source identification. In: ElSohly MA, editor. Marijuana and the cannabinoids. Totowa, NJ: Humana Press; 2007. p. 51–66.CrossRefGoogle Scholar
  9. 9.
    Jin D, Jin S, Yu Y, Lee C, Chen J. Classification of Cannabis cultivars marketed in Canada for medical purposes by quantification of cannabinoids and terpenes using HPLC-DAD and GC-MS. J Anal Bioanal Tech. 2017;8(1):349.CrossRefGoogle Scholar
  10. 10.
    Citti C, Linciano P, Panseri S, Vezzalini F, Forni F, Vandelli MA, et al. Cannabinoid profiling of hemp seed oil by liquid chromatography coupled to high-resolution mass spectrometry. Front Plant Sci. 2019;10:120.  https://doi.org/10.3389/fpls.2019.00120.CrossRefPubMedPubMedCentralGoogle Scholar
  11. 11.
    Choi YH, Kim HK, Hazekamp A, Erkelens C, Lefeber AWM, Verpoorte R. Metabolomic differentiation of Cannabis sativa cultivars using 1H NMR spectroscopy and principal component analysis. J Nat Prod. 2004;67(6):953–7.  https://doi.org/10.1021/np049919c.CrossRefPubMedGoogle Scholar
  12. 12.
    Wang X, Harrington PB, Baugh SF. Effect of preprocessing high-resolution mass spectra on the pattern recognition of Cannabis, hemp, and liquor. Talanta. 2018;180:229–38.  https://doi.org/10.1016/j.talanta.2017.12.032.CrossRefPubMedGoogle Scholar
  13. 13.
    Musah RA, Domin MA, Walling MA, Shepard JR. Rapid identification of synthetic cannabinoids in herbal samples via direct analysis in real time mass spectrometry. Rapid Commun Mass Sp. 2012;26(9):1109–14.  https://doi.org/10.1002/rcm.6205.CrossRefGoogle Scholar
  14. 14.
    Lesiak AD, Musah RA, Domin MA, Shepard JR. DART-MS as a preliminary screening method for “herbal incense”: chemical analysis of synthetic cannabinoids. J Forensic Sci. 2014;59(2):337–43.  https://doi.org/10.1111/1556-4029.12354.CrossRefPubMedGoogle Scholar
  15. 15.
    Lesiak AD, Cody RB, Dane AJ, Musah RA. Rapid detection by direct analysis in real time-mass spectrometry (DART-MS) of psychoactive plant drugs of abuse: the case of Mitragyna speciosa aka “Kratom”. Forensic Sci Int. 2014;242:210–8.  https://doi.org/10.1016/j.forsciint.2014.07.005.CrossRefPubMedGoogle Scholar
  16. 16.
    Marino MA, Voyer B, Cody RB, Dane AJ, Veltri M, Huang L. Rapid identification of synthetic cannabinoids in herbal incenses with DART-MS and NMR. J Forensic Sci. 2016;61(S1):S82–91.  https://doi.org/10.1111/1556-4029.12932.CrossRefPubMedGoogle Scholar
  17. 17.
    Gross JH. Direct analysis in real time--a critical review on DART-MS. Anal Bioanal Chem. 2014;406(1):63–80.  https://doi.org/10.1007/s00216-013-7316-0.CrossRefPubMedGoogle Scholar
  18. 18.
    Harris GA, Fernandez FM. Simulations and experimental investigation of atmospheric transport in an ambient metastable-induced chemical ionization source. Anal Chem. 2009;81(1):322–9.  https://doi.org/10.1021/ac802117u.CrossRefGoogle Scholar
  19. 19.
    Sisco E, Forbes TP. Rapid detection of sugar alcohol precursors and corresponding nitrate ester explosives using direct analysis in real time mass spectrometry. Analyst. 2015;140(8):2785–96.  https://doi.org/10.1039/c4an02347a.CrossRefPubMedGoogle Scholar
  20. 20.
    Barnett I, Bailey FC, Zhang M. Detection and classification of ignitable liquid residues in the presence of matrix interferences by using direct analysis in real time mass spectrometry. J Forensic Sci. 2019;64:1486–94.  https://doi.org/10.1111/1556-4029.14029.CrossRefPubMedGoogle Scholar
  21. 21.
    Maric M, Marano J, Cody RB, Bridge C. DART-MS: a new analytical technique for forensic paint analysis. Anal Chem. 2018;90(11):6877–84.  https://doi.org/10.1021/acs.analchem.8601067.CrossRefPubMedGoogle Scholar
  22. 22.
    Sisco E, Verkouteren J, Staymates J, Lawrence J. Rapid detection of fentanyl, fentanyl analogues, and opioids for on-site or laboratory based drug seizure screening using thermal desorption DART-MS and ion mobility spectrometry. Forensic Chem. 2017;4:108–15.  https://doi.org/10.1016/j.forc.2017.04.001.CrossRefPubMedPubMedCentralGoogle Scholar
  23. 23.
    Aloglu AK, Harrington PB, Sahin S, Demir C. Prediction of total antioxidant activity of Prunella L. species by automatic partial least square regression applied to 2-way liquid chromatographic UV spectral images. Talanta. 2016;161:503–10. doi: https://doi.org/10.1016/j.talanta.2016.09.014.CrossRefGoogle Scholar
  24. 24.
    Harrington PB, Laurent C, Levinson DF, Levitt P, Markey SP. Bootstrap classification and point-based feature selection from age-staged mouse cerebellum tissues of matrix assisted laser desorption/ionization mass spectra using a fuzzy rule-building expert system. Anal Chim Acta. 2007;599(2):219–31.  https://doi.org/10.1016/j.aca.2007.08.007.CrossRefPubMedPubMedCentralGoogle Scholar
  25. 25.
    Wang ZF, Chen P, Yu LL, Harrington PD. Authentication of organically and conventionally grown basils by gas chromatography/mass spectrometry chemical profiles. Anal Chem. 2013;85(5):2945–53.  https://doi.org/10.1021/ac303445v.CrossRefPubMedPubMedCentralGoogle Scholar
  26. 26.
    Sigman ME, Williams MR, Castelbuono JA, Colca JG, Clark CD. Ignitable liquid classification and identification using the summed-ion mass spectrum. Instrum Sci Technol. 2008;36(4):375–93.  https://doi.org/10.1080/10739140802151440.CrossRefGoogle Scholar
  27. 27.
    Adutwum LA, Abel RJ, Harynuk J. Total ion spectra versus segmented total ion spectra as preprocessing tools for gas chromatography - mass spectrometry data. J Forensic Sci. 2018;63(4):1059–68.  https://doi.org/10.1111/1556-4029.13657.CrossRefPubMedGoogle Scholar
  28. 28.
    Wang M, Wang YH, Avula B, Radwan MM, Wanas AS, van Antwerp J, et al. Decarboxylation study of acidic cannabinoids: a novel approach using ultra-high-performance supercritical fluid chromatography/photodiode array-mass spectrometry. Cannabis Cannabinoid Res. 2016;1(1):262–71.  https://doi.org/10.1089/can.2016.0020.CrossRefPubMedPubMedCentralGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryMiddle Tennessee State UniversityMurfreesboroUSA
  2. 2.Research Center for Traditional Chinese Medicine Resourcing and Ethnic Minority MedicineJiangxi University of Traditional Chinese MedicineNanchangChina
  3. 3.Forensic Science Program, College of Basic and Applied SciencesMiddle Tennessee State UniversityMurfreesboroUSA
  4. 4.Tennessee Center for Botanical Medicine ResearchMiddle Tennessee State UniversityMurfreesboroUSA
  5. 5.Department of BiologyMiddle Tennessee State UniversityMurfreesboroUSA

Personalised recommendations