Charge/radical site initiation versus coulombic repulsion for cleavage of multiply charged ions. Charge solvation in poly(alkene glycol) ions

  • Blas A. Cerda
  • Kathrin Breuker
  • David M. Horn
  • Fred W. McLafferty
Article

Abstract

Electrospray ionization of poly(ethylene glycol) (PEG) followed by separation with Fourier-transform mass spectrometry traps (PEG100 + nH)n+ ions. Both collisionally activated dissociation (CAD) and electron capture dissociation (ECD) of these ions (n = 5, 6, 7) produce PEGx fragment ions in which the x values correspond closely to those for an equal distribution of charges in the linear polymer ion, e.g., for n = 7, near x = 1, 17, 34, 50, 67, 83, and 100. However, positions intermediate between these charges should represent the maximum coulombic repulsion, so this is not a specific driving force for fragmentation, which is instead consistent with charge site (CAD) or radical site (ECD) initiation. These conclusions were confirmed by studies of a variety of other poly(alkene glycol) polymers. For these, the ECD spectra of the protonated species are consistent with the predicted charge solvation by the ion’s oxygen atoms.

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References

  1. 1.
    Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Science 1989, 246, 64–71.CrossRefGoogle Scholar
  2. 2.
    Loo, J. A.; Udseth, H. R.; Smith, R. D. Rapid Commun. Mass Spectrom. 1988, 2, 207–210. Gauthier, J. W.; Trautman, T. R.; Jacobsen, D. B. Anal. Chim. Acta 1991, 246, 211–225. Senko, M. W.; Speir, J. P.; McLafferty, F. W. Anal. Chem. 1994, 66, 2801–2808.CrossRefGoogle Scholar
  3. 3.
    Little, D. P.; Speir, J. P.; Senko, M. W.; O’Connor, P. B.; McLafferty, F. W. Anal. Chem. 1994, 66, 2809–2815.CrossRefGoogle Scholar
  4. 4. (a)
    Zubarev, R. A.; Kelleher, N. L.; McLafferty, F. W. J. Am. Chem. Soc. 1998, 120, 3265–3266.CrossRefGoogle Scholar
  5. 4. (b)
    Zubarev, R. A.; Kruger, N. A.; Fridricksson, E. K.; Lewis, M. A.; Horn, D. M.; Carpenter, B. K.; McLafferty, F. W. J. Am. Chem. Soc. 1999, 121, 2857–2862.CrossRefGoogle Scholar
  6. 4. (c)
    Zubarev, R. A.; Horn, D. M.; Fridricksson, E. K.; Kelleher, N. L.; Kruger, N. A.; Lewis, M. A.; Carpenter, B. K.; McLafferty, F. W. Anal. Chem. 2000, 72, 563–573.CrossRefGoogle Scholar
  7. 5.
    Senko, M. W.; Speir, J. P.; McLafferty, F. W. Anal. Chem. 1994, 66, 2801–2808.CrossRefGoogle Scholar
  8. 6.
    Schnier, P. D.; Gross, D. S.; Williams, E. R. J. Am. Chem. Soc. 1995, 117, 6747–6757. Jockush, R. B.; Schnier, P. D.; Price, W. D.; Strittmatter, E. F.; Demirev, P. A.; Williams, E. R. Anal. Chem. 1997, 69, 1119–1126.CrossRefGoogle Scholar
  9. 7.
    Schaaff, T. G.; Cargile, B. J.; Stephenson, J. L., Jr.; McLuckey, S. A. Anal. Chem. 2000, 72, 899–907.CrossRefGoogle Scholar
  10. 8.
    Loo, J. A.; Edmonds, C. G.; Smith, R. D. Anal. Chem. 1993, 65, 425–436.CrossRefGoogle Scholar
  11. 9.
    Miteva, M.; Demirev, P. A.; Karshikoff, A. D. J. Phys. Chem. B 1997, 101, 9645–9650.CrossRefGoogle Scholar
  12. 10.
    Dongre, A. R.; Somogyi, A.; Wysocki, V. H. J. Mass Spectrom. 1996, 31, 339–350. Nair, H.; Somogyi, A.; Wysocki, V. H. J. Mass Spectrom. 1996, 31, 1141–1148. de Maaijer-Gielbert, J.; Gu, C.; Somogyi, A.; Wysockii, V. H.; Kistemaker, P. G.; Weeding, T. L. J. Am. Soc. Mass Spectrom. 1999, 10, 414–422.CrossRefGoogle Scholar
  13. 11.
    Burlet, O.; Orkiszewski, R. S.; Ballard, K. D.; Gaskell, S. J. Rapid Commun. Mass Spectrom. 1992, 6, 658–662. Cox, K. A.; Gaskell, S. J.; Morris, M.; Whiting, A. J. Am. Soc. Mass Spectrom. 1996, 7, 522–531.CrossRefGoogle Scholar
  14. 12.
    Rockwood, A. L.; Busman, M.; Smith, R. D. Int. J. Mass Spectrom. Ion Processes 1991, 111, 103–129.CrossRefGoogle Scholar
  15. 13.
    Cerda, B. A.; Horn, D. M.; Breuker, K.; Carpenter, B. K.; McLafferty, F. W. Eur. Mass Spectrom. 1999, 5, 335–338.CrossRefGoogle Scholar
  16. 14.
    von Helden, G.; Wyttenbach, T.; Bowers, M. T. Science 1995, 267, 1483–1485. Gidden, J.; Wyttenbach, T.; Jackson, A. T.; Scrivens, J. H.; Bowers, M. T. J. Am. Chem. Soc. 2000, 122, 4692–4699.CrossRefGoogle Scholar
  17. 15.
    McLafferty, F. W. Chem. Commun. 1966, 78–80.Google Scholar
  18. 16.
    McLafferty, F. W.; Turecek, F. Interpretation of Mass Spectra, 4th ed.; University Science Books: Mill Valley, CA, 1993.Google Scholar
  19. 17.
    Beu, S. C.; Senko, M. W.; Quinn, J. P.; Wampler, F. M., III; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 1993, 4, 557–565.CrossRefGoogle Scholar
  20. 18.
    Marshall, A. G.; Wang, T. C. L.; Ricca, T. L. J. Am. Chem. Soc. 1985, 107, 7893–7897.CrossRefGoogle Scholar
  21. 19.
    Horn, D. M.; Zubarev, R. A.; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 2000, 11, 320–332.CrossRefGoogle Scholar
  22. 20.
    Lattimer, R. P. Int. J. Mass Spectrom. Ion Processes 1992, 116, 23–36.CrossRefGoogle Scholar
  23. 21.
    Cerda, B. A.; Horn, D. M.; Breuker, K.; McLafferty, F. W. J. Am. Chem. Soc., submitted.Google Scholar
  24. 22.
    Horn, D. M.; Ge, Y.; McLafferty, F. W. Anal. Chem. 2000, 72, 4778–4784.CrossRefGoogle Scholar
  25. 23.
    Tasaki, K. J. Am. Chem. Soc. 1996, 118, 8459–8469.CrossRefGoogle Scholar
  26. 24.
    Reimann, C. T.; Quist, A. P.; Kopniczky, J.; Sundvist, B. U. R.; Erlandsson, R.; Tengvall, P. Nucl. Instrum. Methods Phys. Res. B 1994, 88, 29–34.CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 2001

Authors and Affiliations

  • Blas A. Cerda
    • 1
  • Kathrin Breuker
    • 1
  • David M. Horn
    • 1
  • Fred W. McLafferty
    • 1
  1. 1.Department of Chemistry and Chemical BiologyCornell UniversityIthacaUSA

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