Evidence for linkage position determination in cobalt coordinated pentasaccharides using ion trap mass spectrometry

  • Stefan König
  • Julie A. Leary


A methodology to determine the linkage position of oligosaccharides is presented. In order to illustrate this technique, several oligosaccharides and disaccharides were ionized by electrospray and analyzed in a Paul trap mass spectrometer. Multiple stage tandem mass spectrometry experiments were used to determine linkage and structural information for the following four cobalt coordinated and singly charged ([M+Co−H]+) pentasaccharides: Lacto-N-fucopentaose I, II, III, and V. In order to differentiate between linkage positions, multiple low energy collision induced experiments with mass selected C type ions have been carried out in an ion trap mass spectrometer. Because of the coordination with cobalt, which directs the dissociation pathways, these C type ions undergo specific fragmentation reactions upon low energy collision induced dissociation. These dissociation pathways are unambiguously dependent on their linkage position, thus allowing differentiation between 1→2, 1→3, 1→4, and 1→6 linkage positions throughout the oligomers. Studies on various linked disaccharides and N-acetyl-disaccharides, which are smaller constituents of the pentasaccharides, were used to verify and confirm the results obtained from the pentasaccharides.


GlcNAc Fucose Neutral Loss Dehydro Dissociation Pathway 
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.
    Mass Spectrometry in Biological Sciences: A Tutorial; Gross, M. L., Ed.; Kluwer Academic: Dordrecht, 1992.Google Scholar
  2. 2.
    Methods in Enzymology; McCloskey, J. A., Ed.; Academic: San Diego, CA, 1990; Vol. 193, Chaps 29–40.Google Scholar
  3. 3.
    Biological Mass Spectrometry; Burlingame, A. L.; McCloskey, J. A., Eds.; Proceedings of the Second International Symposium on Mass Spectrometry in the Health and Life Sciences, 1990, Chaps 23–27.Google Scholar
  4. 4.
    Lonngren, J.; Svensson, S. Adv. Carbohydrate Chem. Biochem. 1974, 29, 41.CrossRefGoogle Scholar
  5. 5.
    Glycoconjugates; Composition, Structure, and Function; Allen, H. J.; Kisailus, E. C., Eds.; Dekker: New York, 1992.Google Scholar
  6. 6.
    Lennarz, W. J.; Hart, G. W. Methods in Enzymology; Academic: San Diego, CA, 1994; Vol 230, Chaps 1 and 8.Google Scholar
  7. 7.
    Wormald, M. R.; Rudd, P. M.; Harvey, D. J.; Chang, S.; Scragg, I. G.; Dwek, R. A. Biochemistry 1997, 36, 1370.CrossRefGoogle Scholar
  8. 8.
    Egge, H.; Peter-Katalinic, J.; Karas, M.; Stahl, B. Pure Appl. Chem. 1991, 63, 491.CrossRefGoogle Scholar
  9. 9.
    Nilsson, B. Mol. Biotechnol. 1994, 2, 243.CrossRefGoogle Scholar
  10. 10.
    Aduru, S.; Chait, B. T. Anal. Chem. 1991, 63, 1621.CrossRefGoogle Scholar
  11. 11.
    Krotkiewski, H.; Lisowska, E.; Nilsson, G.; Grönberg, G.; Nilsson, B. Carbohydr. Res. 1993, 239, 35.CrossRefGoogle Scholar
  12. 12.
    Pappas, R. S.; Sweetman, B. J.; Ray, S.; Hellerqvist, C. G. Carbohydr. Res. 1990, 197, 1.CrossRefGoogle Scholar
  13. 13.
    Juhasz, P.; Costello, C. E. J. Am. Soc. Mass Spectrom. 1992, 3, 785.CrossRefGoogle Scholar
  14. 14.
    Bjorndal, H.; Hellerqvist, C. G.; Lindberg, B.; Svensson, S. Angew. Chem. 1970, 82, 643.CrossRefGoogle Scholar
  15. 15.
    Hakomori, S. I. J. Biochem. 1964, 55, 205.Google Scholar
  16. 16.
    Rolf, D.; Gray, G. R. J. Am. Chem. Soc. 1982, 104, 3539.CrossRefGoogle Scholar
  17. 17.
    Hellerqvist, C. G.; Lindberg, B.; Svensson, S.; Holme, T.; Lindberg, A. A. Carbohydr. Res. 1968, 8, 43.CrossRefGoogle Scholar
  18. 18.
    Poppe, L.; Stuike-Prill, R.; Meyer, B.; VanHalbeek, H. J. Biomolecular NMR 1992, 2, 109.CrossRefGoogle Scholar
  19. 19.
    Van Halbeek, H. NMR Spectroscopy in Glycotechnology: Strategies for Characterization of Carbohydrate Primary Structure, Solution Conformation, and Dynamics, Proceedings from the Second International Glycobiology Symposium, 1994, San Francisco, CA.Google Scholar
  20. 20.
    Yamasaki, R.; Bacon, B. Biochemistry 1991, 30, 851.CrossRefGoogle Scholar
  21. 21.
    Carbohydrate Analysis; Chaplin, M. F.; Kennedy, J. F., Eds.; Oxford University: New York, 1994.Google Scholar
  22. 22.
    Bahr, U.; Pfenninger, A.; Karas, M.; Stahl, B. Anal. Chem. 1997, 69, 4530.CrossRefGoogle Scholar
  23. 23.
    Weiskopf, A. S.; Vouros, P.; Harvey, D. J. Rapid Commun. Mass Spectrom. 1997, 11, 1493.CrossRefGoogle Scholar
  24. 24.
    Hofmeister, G. E.; Zhou, Z.; Leary, J. A. J. Org. Chem. 1991, 113, 5964.Google Scholar
  25. 25.
    Staempfli, A. A.; Zhou, Z.; Leary, J. A. J. Org. Chem. 1992, 57, 3590.CrossRefGoogle Scholar
  26. 26.
    Zhou, Z.; Odgen, S.; Leary, J. A. J. Org. Chem. 1990, 55, 5444.CrossRefGoogle Scholar
  27. 27.
    Fura, A.; Leary, J. A. Anal. Chem. 1993, 65, 2805.CrossRefGoogle Scholar
  28. 28.
    Sible, E. M.; Brimmer, S. P.; Leary, J. A. J. Am. Soc. Mass. Spectrom. 1997, 8, 32.CrossRefGoogle Scholar
  29. 29.
    Smith, G.; Pedersen, S. F.; Leary, J. A. J. Org. Chem. 1997, 62, 2152.CrossRefGoogle Scholar
  30. 30.
    Smith, G.; Leary, J. A. J. Am. Chem. Soc. 1996, 118, 3293.CrossRefGoogle Scholar
  31. 31.
    Smith, G.; Leary, J. A. J. Am. Soc. Mass Spectrom. 1996, 7, 953.CrossRefGoogle Scholar
  32. 32.
    Gaucher, S.; Leary, J. A. Anal. Chem. 1998, 70, 3009.CrossRefGoogle Scholar
  33. 33.
    Kohler, M.; Leary, J. A. Anal. Chem. 1995, 67, 3501.CrossRefGoogle Scholar
  34. 34.
    Asam, M. R.; Glish, G. L. J. Am. Soc. Mass. Spectrom. 1997, 8, 987.CrossRefGoogle Scholar
  35. 35.
    Gale, D.; Smith, R. D. Rapid Commun. Mass Spectrom. 1993, 7, 1017.CrossRefGoogle Scholar
  36. 36.
    Domon, B.; Costello, C. E. J. Glycoconjugate 1988, 5, 397.CrossRefGoogle Scholar
  37. 37.
    König, S.; Leary, J. A. Proceedings of the 45th ASMS Conference on Mass Spectrometry and Allied Topics; Palm Springs, CA, 1997.Google Scholar
  38. 38.
    Taw, F.; Brimmer, S.; Leary, J. A. Proceedings of the 44th ASMS Conference on Mass Spectrometry and Allied Topics; Portland, OR, 1996.Google Scholar
  39. 39.
    Egge, H.; Peter-Katalnic, J. Mass. Spectrom. Rev. 1988, 6, 331.CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 1998

Authors and Affiliations

  1. 1.College of ChemistryUniversity of CaliforniaBerkeleyUSA

Personalised recommendations