Analytical and Bioanalytical Chemistry

, Volume 400, Issue 8, pp 2631–2639 | Cite as

Use of proton transfer reaction time-of-flight mass spectrometry for the analytical detection of illicit and controlled prescription drugs at room temperature via direct headspace sampling

  • B. Agarwal
  • F. Petersson
  • S. Jürschik
  • P. Sulzer
  • A. Jordan
  • T. D. Märk
  • P. Watts
  • C. A. MayhewEmail author
Original Paper


The first reported use of proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) for the detection of a range of illicit and prescribed drugs is presented here. We describe the capabilities of PTR-TOF-MS to detect the following commonly used narcotics—ecstasy (N-methyl-3,4-methylenedioxyamphetamine), morphine, codeine, cocaine and heroin—by the direct sampling of the headspace above small solid quantities (approximately 50 mg) of the drugs placed in glass vials at room temperature, i.e. with no heating of the sample and no pre-concentration. We demonstrate in this paper the ability to identify the drugs, both illicit and prescribed, using PTR-TOF-MS through the accurate m/z assignment of the protonated parent molecule to the second decimal place. We have also included in this study measurements with an impure sample of heroin, containing typical substances found in “street” heroin, to illustrate the use of the technology for more “real-world” samples. Therefore, in a real-world complex chemical environment, a high level of confidence can be placed on the detection of drugs. Although the protonated parent is observed for all drugs, the reactant channel leading to this species is not the only one observed and neither is it necessarily the most dominant. Details on the observed fragmentation behaviour are discussed and compared to electrospray ionisation MSn studies available in the literature.


Drug detection PTR-TOF-MS Illicit drugs Heroin Cocaine Ecstasy Morphine Codeine 



CAM and PW wish to acknowledge the EPSRC (EP/E027571/1) which in part supported this work. Work was partially supported by the Leopold Franzens Universität, Innsbruck, the Ionicon Analytik GmbH, Innsbruck, the FWF and FFG, Wien and the European Commission, Brussels. FP and SJ acknowledge the support of the Community under a Marie Curie Industry-Academia Partnership and Pathways (grant agreement no. 218065).


  1. 1.
    Mayhew CA, Sulzer P, Petersson F, Haidacher S, Jordan A, Märk L, Watts P, Märk TD (2010) Int J Mass Spectrom 289:58–63CrossRefGoogle Scholar
  2. 2.
    Lai H, Corbin I, Almirall JR (2008) Anal Bioanal Chem 392:105–113CrossRefGoogle Scholar
  3. 3.
    Petersson F, Sulzer P, Mayhew CA, Watts P, Jordan A, Märk L, Märk TD (2009) Rapid Commun Mass Spectrom 23:3875–3880CrossRefGoogle Scholar
  4. 4.
    Lokhnauth JK, Snow NH (2005) J Sep Sci 28(7):612–618CrossRefGoogle Scholar
  5. 5.
    Miki A, Tatsuno M, Katagi M, Nishikawa M, Tsuchihashi H (1997) Jpn J Forensic Toxicol 15(2):142Google Scholar
  6. 6.
    Carroll JJ, Le T, DeBono R (2004) Am Lab 36(4):32–34Google Scholar
  7. 7.
    Debono R, Stefanou S, Davis M, Walia G (2002) Pharm Technol North Am 26(4):72, 74, 76, 78Google Scholar
  8. 8.
    Lawrence AH (1989) Anal Chem 61(4):343–349CrossRefGoogle Scholar
  9. 9.
    Keller T, Keller A, Tutsch-Bauer E, Monticelli F (2006) Forensic Sci Int 161(2–3):130–140CrossRefGoogle Scholar
  10. 10.
    Kanu AB, Haigh PE, Hill HH Jr (2005) Anal Chim Acta 553(1–2):148–159CrossRefGoogle Scholar
  11. 11.
    Eiceman GA, Karpas Z (2005) Ion mobility spectrometry, 2nd edn. CRC, Boca RatonCrossRefGoogle Scholar
  12. 12.
    Kanu AB, Hill HH Jr (2007) Talanta 73:692–699CrossRefGoogle Scholar
  13. 13.
    Brown P, Watts P, Märk TD, Mayhew CA (2010) Int J Mass Spectrom 294:103–111CrossRefGoogle Scholar
  14. 14.
    Ionicon Analytik (2010) Innsbruck.
  15. 15.
    Jordan A, Haidacher S, Hanel G, Hartungen E, Märk L, Seehauser H, Schottkowsky R, Sulzer P, Märk TD (2009) Int J Mass Spectrom 286:122–128CrossRefGoogle Scholar
  16. 16.
    Popkie HE, Koski WS, Kaufman JJ (1976) J Am Chem Soc 98:1342–1345CrossRefGoogle Scholar
  17. 17.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, revision D.01. Gaussian Inc., WallingfordGoogle Scholar
  18. 18.
    Nacson S, Harrison AG, Davidson WR (1986) Org Mass Spectrom 21:317–319CrossRefGoogle Scholar
  19. 19.
    Schoon N, Amelynck C, Debie E, Bulttinck P, Arijs E (2007) Int J Mass Spectrom 263:127–136CrossRefGoogle Scholar
  20. 20.
    Raith K, Neubert R, Poeknapo C, Boettcher C, Zenk MH, Schmidt J (2003) J Am Soc Mass Spectrom 14:1262–1269CrossRefGoogle Scholar
  21. 21.
    Zhang Z, Yan B, Liu K, Bo T, Liao Y, Liu H (2008) Rapid Commun Mass Spectrom 22:2851–2862CrossRefGoogle Scholar
  22. 22.
    Hopkinson AC, Mackay GI, Bohme DK (1979) Can J Chem 57:2996–3004CrossRefGoogle Scholar
  23. 23.
    Cordell L, Willis KA, Wyche KP, Blake RS, Ellis AM, Monks PS (2007) Anal Chem 79:8359–8366CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • B. Agarwal
    • 1
  • F. Petersson
    • 2
  • S. Jürschik
    • 1
  • P. Sulzer
    • 2
  • A. Jordan
    • 2
  • T. D. Märk
    • 1
    • 2
  • P. Watts
    • 3
  • C. A. Mayhew
    • 3
    Email author
  1. 1.Institut für Ionenphysik und Angewandte PhysikLeopold Franzens Universität InnsbruckInnsbruckAustria
  2. 2.Ionicon Analytik Gesellschaft m.b.HInnsbruckAustria
  3. 3.School of Physics and AstronomyUniversity of BirminghamBirminghamUK

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