Skip to main content
SpringerLink
Log in

A Distonic Radical-Ion for Detection of Traces of Adventitious Molecular Oxygen (O2) in Collision Gases Used in Tandem Mass Spectrometers

  • Application Note
  • Published:
Journal of The American Society for Mass Spectrometry

Abstract

We describe a diagnostic ion that enables rapid semiquantitative evaluation of the degree of oxygen contamination in the collision gases used in tandem mass spectrometers. Upon collision-induced dissociation (CID), the m/z 359 positive ion generated from the analgesic etoricoxib undergoes a facile loss of a methyl sulfone radical [•SO2(CH3); 79-Da] to produce a distonic radical cation of m/z 280. The product-ion spectrum of this m/z 280 ion, recorded under low-energy activation on tandem-in-space QqQ or QqTof mass spectrometers using nitrogen from a generator as the collision gas, or tandem-in-time ion-trap (LCQ, LTQ) mass spectrometers using purified helium as the buffer gas, showed two unexpected peaks at m/z 312 and 295. This enigmatic m/z 312 ion, which bears a mass-to-charge ratio higher than that of the precursor ion, represented an addition of molecular oxygen (O2) to the precursor ion. The exceptional affinity of the m/z 280 radical cation towards oxygen was deployed to develop a method to determine the oxygen content in collision gases.

ᅟ

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2

References

  1. Williamson, B.L., Creaser, C.S.: Letter: ion-molecule reactions of the benzoyl ion [C6H5CO]+ with compounds containing the amine functional group in a quadrupole ion trap. Eur. J. Mass Spectrom. 4, 103–106 (1998)

    Article  CAS  Google Scholar 

  2. Horni, A., Hesse, M.: Addition of nucleophiles to fragment ions in mass spectrometers under electrospray-ionization conditions. Helv. Chim. Acta 82, 1969–1977 (1999)

    Article  CAS  Google Scholar 

  3. Tuytten, R., Lemiere, F., Van Dongen, W., Esmans, E.L., Witters, E., Herrebout, W., Van Der Veken, B., Dudley, E., Newton, R.P.: Intriguing mass spectrometric behavior of guanosine under low energy collision-induced dissociation: H2O adduct formation and gas-phase reactions in the collision cell. J. Am. Soc. Mass Spectrom. 16, 1291–1304 (2005)

    Article  CAS  Google Scholar 

  4. Lemr, K., Holčapek, M., Jandera, P.: Oxygen attachment to metal complex ions during their collision induced dissociation in ion trap. Rapid Commun. Mass Spectrom. 14, 1878–1879 (2000)

    Article  CAS  Google Scholar 

  5. Wu, H.-F., Chen, C.-H.: Letter: hydroxide and oxygen atom attachment to dichlorophthalic anhydride in negative-ion chemical ionization with collisionally-activated dissociation in an external-source ion trap mass spectrometer. Eur. J. Mass Spectrom. 8, 329–332 (2002)

    Article  CAS  Google Scholar 

  6. Habicht, S.C., Amundson, L.M., Duan, P., Vinueza, N.R., Kenttämaa, H.I.: Laser-induced acoustic desorption coupled with a linear quadrupole ion trap mass spectrometer. Anal. Chem. 82, 608–614 (2010)

    Article  CAS  Google Scholar 

  7. Kostiainen, R., Auriola, S.: Effect of collision gas pressure and collision energy on reactions between oxygen and the negative molecular ion of tetrachlorodibenzo-p-dioxins in the collision cell of a triple-quadrupole mass spectrometer. Org. Mass Spectrom. 25, 255–259 (1990)

    Article  CAS  Google Scholar 

  8. Yates, B.F., Bouma, W.J., Radom, L.: Detection of the prototype phosphonium (CH2PH3), sulfonium (CH2SH2), and chloronium (CH2ClH) ylides by neutralization-reionization mass spectrometry: a theoretical prediction. J. Am. Chem. Soc. 106, 5805–5808 (1984)

    Article  CAS  Google Scholar 

  9. Yates, B.F., Bouma, W.J., Radom, L.: Distonic radical cations. Guidelines for the assessment of their stability: Presented in part at the 7th IUPAC Conference on Physical Organic Chemisrty, Auckland, New Zealand, August 1984. Tetrahedron 42, 6225–6234 (1986)

    Article  CAS  Google Scholar 

  10. Stirk, K.M., Kiminkinen, L.K.M., Kenttämaa, H.I.: Ion-molecule reactions of distonic radical cations. Chem. Rev. 92, 1649–1665 (1992)

    Article  CAS  Google Scholar 

  11. Tomazela, D.M., Sabino, A.A., Sparrapan, R., Gozzo, F.C., Eberlin, M.N.: Distonoid ions. J. Am. Soc. Mass Spectrom. 17, 1014–1022 (2006)

    Article  CAS  Google Scholar 

  12. Xia, Y., Chrisman, P.A., Pitteri, S.J., Erickson, D.E., McLuckey, S.A.: Ion-molecule reactions of cation radicals formed from protonated polypeptides via gas-phase ion/ion electron transfer. J. Am. Chem. Soc. 128, 11792–11798 (2006)

    Article  CAS  Google Scholar 

  13. Barlow, C.K., Wright, A., Easton, C.J., O'Hair, R.A.J.: Gas-phase ion-molecule reactions using regioselectively generated radical cations to model oxidative damage and probe radical sites in peptides. Org. Biomol. Chem. 9, 3733–3745 (2011)

    Article  CAS  Google Scholar 

  14. Ly, T., Kirk, B.B., Hettiarachchi, P.I., Poad, B.L.J., Trevitt, A.J., Da Silva, G., Blanksby, S.J.: Reactions of simple and peptidic alpha-carboxylate radical anions with dioxygen in the gas phase. Phys. Chem. Chem. Phys. 13, 16314–16323 (2011)

    Article  CAS  Google Scholar 

  15. Tan, L., Xia, Y.: Gas-phase reactivity of peptide thiyl (RSo), perthiyl (RSSo), and sulfinyl (RSOo) radical ions formed from atmospheric pressure ion/radical reactions. J. Am. Soc. Mass Spectrom. 24, 534–542 (2013)

    Article  CAS  Google Scholar 

  16. Crizer, D.M., McLuckey, S.A.: Electron transfer dissociation of amide nitrogen methylated polypeptide cations. J. Am. Soc. Mass Spectrom. 20, 1349–1354 (2009)

    Article  CAS  Google Scholar 

  17. Moore, B.N., Blanksby, S.J., Julian, R.R.: Ion-molecule reactions reveal facile radical migration in peptides. Chem. Commun. 33, 5015–5017 (2009)

    Article  Google Scholar 

  18. Smith, S.A., Kalcic, C.L., Cui, L., Reid, G.E.: Femtosecond laser-induced ionization/dissociation tandem mass spectrometry (fsLID-MS/MS) of deprotonated phosphopeptide anions. Rapid Commun. Mass Spectrom. 27, 2807–2817 (2013)

    Article  CAS  Google Scholar 

  19. Croom, K.F., Siddiqui, M.A.A.: Etoricoxib: a review of its use in the symptomatic treatment of osteoarthritis, rheumatoid arthritis, ankylosing spondylitis, and acute gouty arthritis. Drugs 69, 1513–1532 (2009)

    Article  CAS  Google Scholar 

  20. Harman, D.G., Blanksby, S.J.: Trapping of a tert-adamantyl peroxyl radical in the gas phase. Chem. Commun. 8, 859–861 (2006)

    Article  Google Scholar 

  21. Harman, D.G., Blanksby, S.J.: Investigation of the gas phase reactivity of the 1-adamantyl radical using a distonic radical anion approach. Org. Biomol. Chem. 5, 3495–3503 (2007)

    Article  CAS  Google Scholar 

  22. Kirk, B.B., Harman, D.G., Blanksby, S.J.: Direct observation of the gas-phase reaction of the cyclohexyl radical with dioxygen using a distonic radical ion approach. J. Phys. Chem. A 114, 1446–1456 (2010)

    CAS  Google Scholar 

  23. Kirk, B.B., Harman, D.G., Kenttämaa, H.I., Trevitt, A.J., Blanksby, S.J.: Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase: direct evidence for products and pathways in low temperature benzene oxidation. Phys. Chem. Chem. Phys. 14, 16719–16730 (2012)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Center for Mass Spectrometry, Department of Chemistry, Chemical Biology and Biomedical Engineering, Stevens Institute of Technology, Hoboken, NJ, 07030, USA

    Freneil B. Jariwala, John A. Hibbs, Carl S. Weisbecker, Rahul L. Khade, Yong Zhang & Athula B. Attygalle

  2. Perkin Elmer, Inc., 710 Bridgeport Ave., Shelton, CT, 06484, USA

    John Ressler

Authors
  1. Freneil B. Jariwala
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. John A. Hibbs
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Carl S. Weisbecker
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. John Ressler
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Rahul L. Khade
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yong Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Athula B. Attygalle
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Athula B. Attygalle.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOCX 7509 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Jariwala, F.B., Hibbs, J.A., Weisbecker, C.S. et al. A Distonic Radical-Ion for Detection of Traces of Adventitious Molecular Oxygen (O2) in Collision Gases Used in Tandem Mass Spectrometers. J. Am. Soc. Mass Spectrom. 25, 1670–1673 (2014). https://doi.org/10.1007/s13361-014-0945-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13361-014-0945-5

Key words

Search

Navigation