Abstract
A complex mixture of isomeric neutral oligosaccharides from pooled human milk was analyzed by nano-electrospray ionization (ESI) in a quadrupole ion trap mass spectrometer (QIT-MS) in the negative ion mode. Since deprotonated molecules of neutral oligosaccharides follow distinct fragmentation rules, which have been elucidated by using model compounds (see [1]), spectra obtained from consecutive CID experiments allowed the differentiation of isomers out of this highly complex mixture. With this method new human milk oligosaccharides of previously unknown isomeric structures have been identified, e.g., the occurence of three isomeric fucosylated lacto-N-hexaoses could be determined precisely, which have not been described before: (1) Fuc (α1 → 2) Gal (β1 → 3) GlcNac (β1 → 3) Gal (β1 → 4) GlcNac (β1 → 3) Gal (β1 → 4) Glc, (2) Gal (β1 → 4) GlcNAc [(α1 → 3) Fuc] (β1 → 3) Gal (β1 → 4) GlcNac (β1 → 3) Gal (β1 → 4) Glc, (3) Gal (β1 → 4) GlcNAc (β1 → 3) Gal (β1 → 4) GlcNac [(α1 → 3) Fuc] (β1 → 3) Gal (β1 → 4) Glc.
Article PDF
Similar content being viewed by others
References
Pfenninger, A.; Karas, M.; Finke, B.; Stahl, B.; Sawatzki, G. J. Am. Soc. Mass Spectrom. in press.
Dwek, R. A. Chem. Rev. 1996, 96, 683.
Stahl, B.; Thurl, S.; Zeng, J.; Karas, M.; Hillenkamp, F.; Steup, M.; Sawatzki, G. Anal. Biochem. 1994, 223, 218.
Finke, B.; Stahl, B.; Pfenninger, A.; Karas, M.; Daniel, H.; Sawatzki, G. Anal. Chem. 1999, 71, 3755.
Newburg, D. S.; Street, J. M. Nutrit. Today 1987, 32, 191.
Varki, A. Glycobiol. 1993, 3, 97.
Kennedy, J. F. Carbohydrate Chemistry; Clarendon Press: Oxford, 1988; 269.
Fievre, S.; Wieruszeski, J.; Michalski, J.; Lemoine, J.; Montreuil, J.; Strecker, G. Biochem. Biophys. Res. Commun. 1991, 177, 720.
Paul, W. Angew. Chem. 1990, 102, 780.
March, R. E. J. Mass Spectrom. 1997, 32, 351.
Cooks, R. G.; Glish, G. L.; McLuckey, S. A.; Kaiser, R. E. Chem. Eng. News 1991, 69, 26.
Amster, I. J. J. Mass Spectrom. 1996, 31, 1325.
Spengler, B. J. Mass Spectrom. 1997, 32, 1019.
Spengler, B.; Kirsch, D.; Kaufmann, R.; Lemoine, J. J. Org. Mass Spectrom. 1994, 29, 782.
Bahr, U.; Karas, M.; Schubert-Zsilavecz, M. Proceedings of the 46th ASMS Conference on Mass Spectrometry and Allied Topics; Orlando, FL, May/June, 1998.
Bahr, U.; Pfenninger, A.; Karas, M. Anal. Chem. 1997, 69, 4530.
Stahl, B.; Thurl, S.; Zeng, J.; Karas, M.; Hillenkamp, F.; Steup, M.; Sawatzki, G. Anal. Biochem. 1994, 223, 218.
Thurl, S.; Offermanns, J.; Müller-Werner, B.; Sawatzki, G. J. Chromatogr. 1991, 568, 291.
Thurl, S.; Müller-Werner, B.; Sawatzki, G. Anal. Biochem. 1996, 235, 202.
Bier, M. E.; Schwartz, J. C. In Electrospray Ionization Mass Spectrometry. Cole, R. B., Ed.; John Wiley and Sons: New York, 1997; p 235.
Kunz, C.; Rudolf, S. Acta Paediatr. 1993, 82, 903.
Yamashita, K.; Tachibana, Y.; Kobata, A. J. Biol. Chem. 1977, 252, 5408.
Dua, V. K.; Goso, K.; Dube, V. E.; Bush, C. A. J. Chromatogr. 1985, 328, 259.
Kobata, A.; Ginsburg, V. Arch. Biochem. Biophys. 1972, 150, 273.
Sabharwal, H.; Nilsson, B.; Grönberg, G.; Chester, M. A.; Dakour, J.; Sjöblad, S.; Lundblad, A. Arch. Biochem. Biophys. 1988, 265, 390.
Sabharwal, H.; Nilsson, B.; Chester, M. A.; Lindh, F.; Grönberg, G.; Sjöblad, S.; Lundblad, A. Carbohydr. Res. 1988, 178, 145.
Bruntz, R.; Dabrowski, U.; Dabrowski, J.; Ebersold, A.; Peter-Katalinic, J.; Egge, H. Biol. Chem. Hoppe-Seyler 1997, 369, 257.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Pfenninger, A., Karas, M., Finke, B. et al. Structural analysis of underivatized neutral human milk oligosaccharides in the negative ion mode by nano-electrospray MSn (Part 2: Application to isomeric mixtures). J. Am. Soc. Spectrom. 13, 1341–1348 (2002). https://doi.org/10.1016/S1044-0305(02)00646-3
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/S1044-0305(02)00646-3