Skip to main content
SpringerLink
Log in

Protonation in electrospray mass spectrometry: Wrong-way-round or right-way-round?

  • Focus: Electrospray
  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

The term “wrong-way-round ionization” has been used in studies of electrospray ionization to describe the observation of protonated or deprotonated ions when sampling strongly basic or acidic solutions (respectively) where such ions are not expected to exist in appreciable concentrations in solution. Study of the dependence of ionization of the weak base caffeine on the electrospray capillary potential reveals three distinct contributors to wrong-way-round ionization. At near-neutral pH in solutions of low ionic strength, protonation of caffeine results from the surface enrichment of electrolytically produced protons in the surface layer of the droplets from which ions are desorbed. For solutions made strongly basic with ammonia, gas-phase proton transfer from ammonium ions can create protonated caffeine. These two mechanisms have been discussed previously elsewhere. For solutions of high ionic strength at neutral or high pH, the data suggest that discharge-induced ionization is responsible for the production of protonated caffeine. This mechanism probably accounts for some of the wrong-way-round ionization reported elsewhere.

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

Similar content being viewed by others

References

  1. Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Science 1989, 246, 64–71.

    Article  CAS  Google Scholar 

  2. Fenn, J. B. J. Am. Soc. Mass Spectrom. 1993, 4, 524–529.

    Article  CAS  Google Scholar 

  3. Van Berkel, G. J.; Zhou, F.; Aronson, J. T. Int. J. Mass Spectrom. Ion Processes 1997, 162, 55–67.

    Article  Google Scholar 

  4. Van Berkel, G. J. In Electrospray Ionization Mass Spectrometry; Cole, R. B., Ed.; Wiley: New York, 1997; pp 65–105.

    Google Scholar 

  5. Mansoori, B. A.; Volmer, D. A.; Boyd, R. K. Rapid Commun. Mass Spectrom. 1997, 11, 1120–1130.

    Article  CAS  Google Scholar 

  6. Kelly, M. A.; Vestling, M. M.; Fenselau, C. C.; Smith, P. B. Org. Mass Spectrom. 1992, 27, 1143–1147.

    Article  CAS  Google Scholar 

  7. Guevremont, R.; Siu, K. W. M.; Le Blanc, J. C. Y.; Berman, S. S. J. Am. Soc. Mass Spectrom. 1992, 3, 216–224.

    Article  CAS  Google Scholar 

  8. Le Blanc, J. C. Y.; Wang, J.; Guevremont, R.; Siu, K. W. M. Org. Mass Spectrom. 1992, 29, 587–593.

    Article  Google Scholar 

  9. Wang, G.; Cole, R. B. Org. Mass Spectrom. 1994, 29, 419–427.

    Article  CAS  Google Scholar 

  10. Charbonnier, F.; Berthelot, L.; Rolando, C. Anal. Chem. 1999, 71, 1585–1591.

    Article  CAS  Google Scholar 

  11. Loo, J. A.; Udseth, H. R.; Smith, R. D. Rapid Commun. Mass Spectrom. 1988, 2, 207–210.

    Article  CAS  Google Scholar 

  12. Hiraoka, K.; Murata, K.; Kudaka, I. J. Mass. Spectrom. Soc. Jpn. 1995, 43, 127–138.

    CAS  Google Scholar 

  13. Konermann, L.; Collings, B. A.; Douglas, D. J. Biochemistry 1997, 36, 12296–12302.

    Article  CAS  Google Scholar 

  14. Le Blanc, J. C. Y.; Guevremont, R.; Siu, K. W. M. Int. J. Mass Spectrom. Ion Processes 1993, 125, 145–153.

    Article  Google Scholar 

  15. Gatlin, C. L.; Tureček, F. Anal. Chem. 1994, 66, 712–718.

    Article  CAS  Google Scholar 

  16. Zhou, S.; Edwards, A. G.; Cook, K. D.; Van Berkel, G. J. Anal. Chem. 1999, 71, 769–776.

    Article  CAS  Google Scholar 

  17. Tang, L.; Kebarle, P. Anal. Chem. 1993, 65, 3654–3668.

    Article  CAS  Google Scholar 

  18. Enke, C. G. Anal. Chem. 1997, 69, 4885–4893.

    Article  CAS  Google Scholar 

  19. Kebarle, P.; Ho, Y. In Electrospray Ionization Mass Spectrometry; Cole, R. B., Ed.; Wiley: New York, 1997; pp 1–64.

    Google Scholar 

  20. Perrin, D. D. Dissociation Constants of Organic Bases in Aqueous Solution; Butterworths: London, 1965.

    Google Scholar 

  21. Stryer, L. Biochemistry; W. H. Freeman and Company: New York, 1988.

    Google Scholar 

  22. Iribarne, J. V.; Thomson, B. A. J. Chem. Phys. 1976, 64, 2287–2294.

    Article  CAS  Google Scholar 

  23. Thomson, B. A.; Iribarne, J. V. J. Chem. Phys. 1979, 71, 4451–4465.

    Article  CAS  Google Scholar 

  24. CRC Handbook of Chemistry and Physics, 71st ed.; Lide, D. E., Ed.; CRC: Boca Raton, FL, 1990.

    Google Scholar 

  25. Cooks, R. G.; Patrick, J. S.; McLuckey, S. A. Mass Spectrom. Rev. 1994, 13, 287–339.

    Article  CAS  Google Scholar 

  26. Horning, E. C.; Horning, M. G.; Carroll, D. I.; Dzidic, I.; Stillwell, R. N. Anal. Chem. 1973, 45, 936–943.

    Article  CAS  Google Scholar 

  27. Good, A.; Durden, D. A.; Kebarle, P. J. Chem. Phys. 1970, 52, 222–229.

    Article  CAS  Google Scholar 

  28. Sunner, J.; Nicol, G.; Kebarle, P. Anal. Chem. 1988, 60, 1300–1307.

    Article  CAS  Google Scholar 

  29. Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, Suppl. 1.

  30. Lüttgens, U.; Röllgen, F. W.; Cook, K. D. In Methods and Mechanisms for Producing Ions from Large Molecules (NATO ASI Series B, Vol. 269); Standing, K. G.; Ens, W., Eds.; Plenum: New York, 1991; pp 185–193.

    Google Scholar 

  31. Bruins, A. P. Mass Spectrom. Rev. 1991, 10, 53–77.

    Article  CAS  Google Scholar 

  32. Harrison, A. G. Chemical Ionization Mass Spectrometry, 2nd ed.; CRC: Boca Raton, FL, 1992; pp 91–100.

    Google Scholar 

Download references

Author information

Author notes

  1. Shaolian Zhou

    Present address: Department of Medicinal Chemistry, University of Utah, 84112, Salt Lake City, UT

Authors and Affiliations

  1. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, USA

    Shaolian Zhou & Kelsey D. Cook

Authors
  1. Shaolian Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kelsey D. Cook
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kelsey D. Cook.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhou, S., Cook, K.D. Protonation in electrospray mass spectrometry: Wrong-way-round or right-way-round?. J. Am. Soc. Spectrom. 11, 961–966 (2000). https://doi.org/10.1016/S1044-0305(00)00174-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1016/S1044-0305(00)00174-4

Keywords

Search

Navigation