Proton transfer reactions of matrix-assisted laser desorption/ionization matrix monomers and dimers

  • K. Breuker
  • R. Knochenmuss
  • R. Zenobi


The gas-phase basicities of monomeric and dimeric deprotonated ferulic and sinapic acids, common matrix-assisted laser desorption/ionization (MALDI) matrices, were determined. A new bracketing method based on structure-reactivity correlations was developed for deriving gas-phase basicities from reaction efficiencies. The matrix dimer anions were found to be significantly less basic than the monomer anions, by about 115 kJ/mol. The low basicity of the dimer anion can qualitatively be explained by resonance stabilization. The energies for proton transfer from dimers to monomers are therefore about 1.2 eV lower than for proton transfer between monomers. For the MALDI process, proton transfer reactions involving matrix dimers provide a low energy pathway for matrix and analyte ion formation.


Ferulic Acid Sinapic Acid Proton Transfer Reaction Dime Anion Monomer Anion 
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.
    Karas, M.; Bachmann, D.; Bahr, U.; Hillenkamp, F. Int. J. Mass Spectrom. Ion Processes 1987, 78, 53–68.CrossRefGoogle Scholar
  2. 2.
    Wang, B. H.; Dreisewerd, K.; Bahr, U.; Karas, M.; Hillenkamp, F. J. Am. Soc. Mass Spectrom. 1993, 4, 393–398.CrossRefGoogle Scholar
  3. 3.
    Karas, M.; Bahr, U.; Strupat, K.; Hillenkamp, F.; Tsarbopoulos, A.; Pramanik, B. N. Anal. Chem. 1995, 67, 675–679.CrossRefGoogle Scholar
  4. 4.
    Tang, W.; Nelson, C. M.; Zhu, L.; Smith, L. M. J. Am. Soc. Mass Spectrom. 1997, 8, 218–224.CrossRefGoogle Scholar
  5. 5.
    Jørgensen, T. J. D.; Bojesen, G.; Rahbek-Nielsen, H. Eur. Mass Spectrom. 1998, 4, 39–45.CrossRefGoogle Scholar
  6. 6.
    Nelson, C. M.; Crellin, K.; Berry, J.; Beauchamp, J. L.; Smith, L. M. Proceedings of the 44th ASMS Conference on Mass Spectrometry and Allied Topics; Giordani, A. B.; Ed.; Portland, 1996, p 733.Google Scholar
  7. 7.
    Steenvoorden, R. J. J. M.; Breuker, K.; Zenobi, R. Eur. Mass Spectrom. 1997, 3, 339–346.CrossRefGoogle Scholar
  8. 8.
    Burton, R. D.; Watson, C. H.; Eyler, J. R.; Lang, G. L.; Powell, D. H.; Avery, M. Y. Rapid Commun. Mass Spectrom. 1997, 11, 443–446.CrossRefGoogle Scholar
  9. 9.
    Breuker, K.; Knochenmuss, R.; Zenobi, R. Int. J. Mass Spectrom. 1999, 184, 25–38.CrossRefGoogle Scholar
  10. 10.
    Zhang, K.; Zimmerman, D. M.; Chung-Phillips, A.; Cassady, C. J. J. Am. Chem. Soc. 1993, 115, 10812–10822.CrossRefGoogle Scholar
  11. 11.
    Carr, S. R.; Cassady, C. J. J. Am. Soc. Mass Spectrom. 1996, 7, 1203–1210.CrossRefGoogle Scholar
  12. 12.
    Gorman, G. S.; Amster, I. J. J. Am. Chem. Soc. 1993, 115, 5729–5735.CrossRefGoogle Scholar
  13. 13.
    McKiernan, J. W.; Beltrame, C. E. A.; Cassady, C. J. J. Am. Soc. Mass Spectrom. 1994, 5, 718–723.CrossRefGoogle Scholar
  14. 14.
    Zenobi, R.; Knochenmuss, R. Mass Spectrom. Rev. 1998, 17, 337–366.CrossRefGoogle Scholar
  15. 15.
    Bartmess, J. E. Negative Ion Energetics Data. In NIST Standard Reference Database Number 69; Mallard, W. G.; Linstrom, P. J.; Ed.; National Institute of Standards and Technology: Gaithersburg MD, 1997. ( Scholar
  16. 16.
    Breuker, K.; Knochenmuss, R.; Zenobi, R. Int. J. Mass Spectrom. 1998, 176, 149–159.CrossRefGoogle Scholar
  17. 17.
    Mowry, C. D.; Johnston, M. V. Rapid Commun. Mass Spectrom. 1993, 7, 569–575.CrossRefGoogle Scholar
  18. 18.
    Su, T.; Bowers, M. T. Int. J. Mass Spectrom. Ion Phys. 1973, 12, 347–356.CrossRefGoogle Scholar
  19. 19.
    Witt, M.; Grützmacher, H. F. Int. J. Mass Spectrom. 1997, 164, 93–106.CrossRefGoogle Scholar
  20. 20.
    Bouchoux, G.; Salpin, J. Y.; Leblanc, D. Int. J. Mass Spectrom. 1996, 153, 37–48.CrossRefGoogle Scholar
  21. 21.
    Agmon, N. Int. J. Chem. Kinet. 1981, 13, 333–365.CrossRefGoogle Scholar
  22. 22.
    Atkins, P. W. Physical Chemistry, Fifth Edition; Oxford University Press: Oxford, 1995.Google Scholar
  23. 23.
    Agmon, N.; Levine, R. D. Isr. J. Chem. 1980, 19, 330–336.Google Scholar
  24. 24.
    Lifshitz, C.; Wu, R. L. C.; Tiernan, T. O. J. Am. Chem. Soc. 1978, 100, 2040–2048.CrossRefGoogle Scholar
  25. 25.
    Farneth, W. E.; Braumann, J. I. J. Am. Chem. Soc. 1976, 98, 7891–7898.CrossRefGoogle Scholar
  26. 26.
    Mackay, G. I.; Betowski, L. D.; Payzant, J. D.; Schiff, H. I.; Bohme, D. K. J. Phys. Chem. 1976, 80, 2919–2922.CrossRefGoogle Scholar
  27. 27.
    Mackay, G. I.; Hemsworth, R. S.; Bohme, D. K. Can. J. Chem. 1976, 54, 1624–1642.CrossRefGoogle Scholar
  28. 28.
    Dodd, J. A.; Baer, S.; Moylan, C. R.; Brauman, J. I. J. Am. Chem. Soc. 1991, 113, 5942–5949.CrossRefGoogle Scholar
  29. 29.
    Marshall, A. G.; Hendrickson, C. L.; Jackson, G. S. Mass Spectrom. Rev. 1998, 17, 1–35.CrossRefGoogle Scholar
  30. 30.
    Heeren, R. M. A.; Vékey, K. Rapid Commun. Mass Spectrom. 1998, 12, 1175–1181.CrossRefGoogle Scholar
  31. 31.
    Zubarev, R. A.; Hékansson, P.; Sundqvist, B.; Talrose, V. L. Rapid Commun. Mass Spectrom. 1997, 11, 63–70.CrossRefGoogle Scholar
  32. 32.
    Gorshkov, M. V.; Pasa-Tolic, L.; Smith, R. D. J. Am. Soc. Mass Spectrom. 1999, 10, 15–18.CrossRefGoogle Scholar
  33. 33.
    Knochenmuss, R.; Dubois, F.; Dale, M. J.; Zenobi, R. Rapid Commun. Mass Spectrom. 1996, 10, 871–877.CrossRefGoogle Scholar
  34. 34.
    Knochenmuss, R.; Karbach, V.; Wiesli, U.; Breuker, K.; Zenobi, R. Rapid Commun. Mass Spectrom. 1998, 12, 529–534.CrossRefGoogle Scholar
  35. 35.
    Chen, X.; Carrol, J. A.; Beavis, R. C. J. Am. Soc. Mass Spectrom. 1998, 9, 885–891.CrossRefGoogle Scholar
  36. 36.
    Bökelmann, V.; Spengler, B.; Kaufmann, R. Eur. Mass Spectrom. 1995, 1, 81–93.CrossRefGoogle Scholar
  37. 37.
    Kinsel, G. R.; Edmonson, R. D.; Russel, D. H. J. Mass Spectrom. 1997, 32, 714–722.CrossRefGoogle Scholar
  38. 38.
    Dreisewerd, K. Dissertation, University of Münster, 1994.Google Scholar
  39. 39.
    Beavis, R. C.; Chait, B. T. Chem. Phys. Lett. 1991, 181, 479–484.CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 1999

Authors and Affiliations

  1. 1.Department of Chemistry, Swiss Federal Institute of Technology (ETH)Universitätstrasse 16ZürichSwitzerland

Personalised recommendations