Matrix Effects on Internal Energy in Desorption Ionization

  • K. L. Busch
  • B. H. Hsu
  • Y.-X. Xie
  • R. G. Cooks
Part of the Springer Series in Chemical Physics book series (CHEMICAL, volume 25)


Desorption ionization (DI) mass spectrometry encompasses a family of techniques in which energization of a condensed phase leads to ejection of ions into the vacuum with subsequent mass analysis and detection [1]. In contrast to the gas—phase ionization methods of electron, chemical, and photo- ionization, DI techniques are by their nature sensitive to the physical and chemical nature of the matrix from which the ions are ejected. Success in the analysis of nonvolatile and thermally fragile molecules has been enough to thrust these techniques into routine use in just a few years. DI spectra of pure compounds can often be interpreted in terms of known gas—phase ion chemistry. This provides evidence for the desorption, from the surface, of intact ions with some degree of internal excitation; the fragmentation processes undergone are then defined by the nature and the amount of the internal energy. Since the ion is in an isolated state, fragmentation processes should be the same as those undergone by ions of the same structure formed directly in the gas phase by chemical ionization [2]. MS/MS experiments have confirmed this premise for particular DI conditions. Ions are isolated by a first stage of mass analysis, and then activated by collision. The masses and relative abundances of the resultant fragment ions (determined by the second stage of mass analysis) match those of the DI spectra. Metastable ion transitions have also been directly observed in DI spectra.


Ammonium Chloride Desorption Ionization Phosphonium Salt Fast Atom Bombardment Mass Spectrometry Liquid Matrice 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    K.L. Busch and R.G. Cooks: Science, in press.Google Scholar
  2. 2.
    H. Grade and R.G. Cooks: J. Am. Chem. Soc. 100, 5615 (1978).CrossRefGoogle Scholar
  3. 3.
    L.K. Liu, K.L. Busch, and R.G. Cooks: Anal. Chem. 53, 109 (1981).CrossRefGoogle Scholar
  4. 4.
    J.L. Pierce, K.L. Busch, R.G. Cooks, and R.A. Walton: Inorg. Chem. 21, 2597 (1982).CrossRefGoogle Scholar
  5. 5.
    S.E. Unger, R.J. Day, and R.G. Cooks: Int. J. Mass Spectrom. Ion Phys. 39, 231 (1981).CrossRefGoogle Scholar
  6. 6.
    B.P. Stimpson, D.S. Simons, and C.A. Evans, Jr.: J. Phys. Chem. 82, 660 (1978).CrossRefGoogle Scholar
  7. 7.
    M. Barber, R.S. Bordoli, G.J. Elliott, R.D. Sedgwick, and A.N. Tyler: Anal. Chem. 54, 645A (1982).Google Scholar
  8. 8.
    K.L. Busch, S.E. Unger, A. Vincze, R.G. Cooks, and T. Keough: J. Am. Chem. Soc. 104, 1507 (1982).CrossRefGoogle Scholar
  9. 9.
    C.R. Blakely, J.J. Carmody, and M.C. Vestal, J. Am. Chem. Soc. 102, 5931 (1980).CrossRefGoogle Scholar
  10. 10.
    K.L. Busch, S.E. Unger, and R.G. Cooks, Proceedings of the Conference on Ion Formation from Organic Solids, University of Münster, October 1980, Springer-Verlag, New York, in press.Google Scholar
  11. 11.
    D.J. Surman and J.C. Vickerman: J. Chem. Res. (S), 170 (1981).Google Scholar
  12. 12.
    M. Barber, R.S. Bordoli, R.D. Sedgwick, and A.N. Tyler: J. Chem. Soc. Chem. Comm., 325 (1981).Google Scholar
  13. 13.
    K.D. Cook, Presented at the Thirtieth Annual Conference on Mass Spectrometry and Allied Topics, Honolulu, HI, 1982, paper MOD7.Google Scholar
  14. 14.
    T.M. Ryan, R.J. Day, and R.G. Cooks: Anal. Chem. 52, 2054 (1980).CrossRefGoogle Scholar
  15. 15.
    U. Giessmann and D.F. Barofsky, Presented at the Thirtieth Annual Conference on Mass Spectrometry and Allied Topics, Honolulu, HI, 1982, paper WPB12.Google Scholar
  16. 16.
    P.J. Arpino and G. Guichon, J. Chromatog. 251, 153 (1982).CrossRefGoogle Scholar
  17. 17.
    S.E. Unger, A. Vincze, R.G. Cooks, R. Chrisman, and L.D. Rothman: Anal. Chem. 53, 976 (1981).CrossRefGoogle Scholar
  18. 18.
    A. Ba-isa, K.L. Busch, R.G. Cooks, A. Vincze, and I. Granoth: Tetrahedron, in press.Google Scholar
  19. 19.
    K.L. Busch and R.G. Cooks, in preparation.Google Scholar
  20. 20.
    D. Zakett, A.E. Schoen, R.G. Cooks, and P.H. Hemberger: J. Am. Chem. Soc. 103, 1295 (1981).CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1983

Authors and Affiliations

  • K. L. Busch
    • 1
  • B. H. Hsu
    • 1
  • Y.-X. Xie
    • 1
  • R. G. Cooks
    • 1
  1. 1.Department of ChemistryPurdue UniversityWest LafayetteUSA

Personalised recommendations