Skip to main content
Log in

Mechanistic studies of multipole storage assisted dissociation

  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

The degree and onset of fragmentation in multipole storage assisted dissociation (MSAD) have been investigated as functions of several hexapole parameters. Strict studies of hexapole charge density (number of ions injected) and hexapole storage time were made possible by placing a pulsed shutter in front of the entrance to the mass spectrometer. The results obtained show that the charge density is the most critical parameter, but also dependencies on storage time, radio-frequency (rf) -amplitude, and pressure are seen. From these data, and from simulations of the ion trajectories inside the hexapole, a mechanism for MSAD, similar to the ones for sustained off-resonance irradiation (SORI), and for low energy collisionally induced dissociation in the collision multipole of a triple quadrupole mass spectrometer, is proposed. It is believed that, at higher charge densities, ions are pushed to larger hexapole radii where the electric potential created by the rf field is higher, forcing the ions to oscillate radially to higher amplitudes and thereby reach higher (but still relatively low) kinetic energies. Multiple collisions with residual gas molecules at these elevated energies then heat up the molecules to their dissociation threshold. Further support for this mechanism is obtained from a comparison of MSAD and SORI spectra which are almost identical in appearance.

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

Access this article

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

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. GilleceCastro, B. L.; Stults, J. T. Methods Enzymol. 1996, 271, 427–448.

    Article  CAS  Google Scholar 

  2. Winston, R. L.; Fitzgerald, M. C. Mass Spectrom. Rev. 1997, 16, 165–179.

    Article  CAS  Google Scholar 

  3. Yates, J. R. Methods Enzymol. 1996, 271, 351–377.

    Article  CAS  Google Scholar 

  4. Roepstorff, P. Curr. Opin. Biotechnol. 1997, 8, 6–13.

    Article  CAS  Google Scholar 

  5. Nordhoff, E.; Kirpekar, F.; Roepstorff, P. Mass Spectrom. Rev. 1996, 15, 67–138.

    Article  Google Scholar 

  6. Crain, P. F.; McCloskey, J. A. Curr. Opin. Biotechnol. 1998, 9, 25–34.

    Article  CAS  Google Scholar 

  7. Dell, A.; Reason, A. J.; Khoo, K. H.; Panico, M.; McDowell, R. A.; Morris, H. R. Methods Enzymol. 1994, 230, 108–132.

    Article  CAS  Google Scholar 

  8. Reinhold, V. N.; Reinhold, B. B.; Chan, S. Methods Enzymol. 1996, 271, 377–402.

    Article  CAS  Google Scholar 

  9. Karas, M.; Hillenkamp, F. Anal. Chem. 1988, 60, 2301–2303.

    Article  Google Scholar 

  10. Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Mass Spectrom. Rev. 1990, 9, 37–70.

    Article  CAS  Google Scholar 

  11. Zubarev, R. A.; Chivanov, V. D.; Håkansson, P.; Sundqvist, B. U. R. Rapid Commun. Mass Spectrom. 1994, 8, 906–912.

    Article  CAS  Google Scholar 

  12. Vorm, O.; Roepstorff, P. Biol. Mass Spectrom. 1994, 23, 734–740.

    Article  CAS  Google Scholar 

  13. Håkansson, K.; Zubarev, R.; Håkansson, P. Rapid Commun. Mass Spectrom. 1998, 12, 705–711.

    Article  Google Scholar 

  14. Lee, T. D.; Shively, J. E. Methods Enzymol. 1990, 193, 361–374.

    Article  CAS  Google Scholar 

  15. Loo, J. A.; Edmonds, C. G.; Udseth, H. R.; Smith, R. D. Anal. Chim. Acta 1990, 241, 167–173.

    Article  CAS  Google Scholar 

  16. Hayes, R. N.; Gross, M. L. Methods Enzymol. 1990, 193, 237–263.

    Article  CAS  Google Scholar 

  17. Kaufmann, R.; Spengler, B.; Lützenkirchen, F. Rapid Commun. Mass Spectrom. 1993, 7, 902–910.

    Article  CAS  Google Scholar 

  18. Piyadasa, C. K. G.; Håkansson, P.; Ariyaratne, T. R.; Barofsky, D. F. Rapid Commun. Mass Spectrom. 1998, 12, 1655–1664.

    Article  CAS  Google Scholar 

  19. Dongre, A. R.; Somogyi, A.; Wysocki, V. H. J. Mass Spectrom. 1996, 31, 339–350.

    Article  CAS  Google Scholar 

  20. Williams, E. R.; Fang, L. L.; Zare, R. N. Int. J. Mass Spectrom. Ion Processes 1993, 123, 233–241.

    Article  CAS  Google Scholar 

  21. Williams, E. R.; Henry, K. D.; McLafferty, F. W.; Shabanowitz, J.; Hunt, D. F. J. Am. Soc. Mass Spectrom. 1990, 1, 413–416.

    Article  CAS  Google Scholar 

  22. Williams, E. R.; Furlong, J. P.; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 1990, 1, 288–294.

    Article  CAS  Google Scholar 

  23. Little, D. P.; Speir, J. P.; Senko, M. W.; O’Connor, P. B.; McLafferty, F. W. Anal. Chem. 1994, 66, 2809–2815.

    Article  CAS  Google Scholar 

  24. Price, W. D.; Schnier, P. D.; Williams, E. R. Anal. Chem. 1996, 68, 859–866.

    Article  CAS  Google Scholar 

  25. Zubarev, R. A.; Kelleher, N. L.; McLafferty, F. W. J. Am. Chem. Soc. 1998, 120, 3265–3266.

    Article  CAS  Google Scholar 

  26. Axelsson, J.; Palmblad, M.; Håkansson, K.; Håkansson, P. Rapid Commun. Mass Spectrom. 1999, 13, 474–477.

    Article  CAS  Google Scholar 

  27. Sannes-Lowery, K.; Griffey, R. H.; Kruppa, G. H.; Speir, J. P.; Hofstadler, S. A. Rapid Commun. Mass Spectrom. 1998, 12, 1957–1961.

    Article  CAS  Google Scholar 

  28. Sannes-Lowery, K. A.; Hofstadler, S. A. J. Am. Soc. Mass Spectrom. 2000, 11, 1–9.

    Article  CAS  Google Scholar 

  29. Axelsson, J.; Håkansson, K.; Palmblad, M.; Håkansson, P. Rapid Commun. Mass Spectrom. 1999, 13, 1550.

    Article  CAS  Google Scholar 

  30. Fohlman, J.; Roepstorff, P. Biomed. Mass Spectrom. 1984, 11, 601.

    Article  Google Scholar 

  31. Gauthier, J. W.; Trautman, T. R.; Jacobson, D. B. Anal. Chim. Acta 1991, 246, 211–225.

    Article  CAS  Google Scholar 

  32. Xu, H. J.; Wada, M.; Tanaka, J.; Kawakami, H.; Katayama, I.; Ohtani, S. Nucl. Instrum. Methods Phys. Res. A 1993, 333, 274–281.

    Article  CAS  Google Scholar 

  33. Vékey, K. Mass Spectrom. Rev. 1995, 14, 195–225.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Kristina Håkansson.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Håkansson, K., Axelsson, J., Palmblad, M. et al. Mechanistic studies of multipole storage assisted dissociation. J Am Soc Mass Spectrom 11, 210–217 (2000). https://doi.org/10.1016/S1044-0305(99)00144-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1016/S1044-0305(99)00144-0

Keywords

Navigation