Journal of the American Society for Mass Spectrometry

, Volume 13, Issue 11, pp 1331–1340

Structural analysis of underivatized neutral human milk oligosaccharides in the negative ion mode by nano-electrospray MSn (Part 1: Methodology)


  • Anja Pfenninger
    • Institute for Pharmaceutical Chemistry, BiocenterJ. W. Goethe University Frankfurt
    • Aventis Pharma Deutschland GmbH
    • Institute for Pharmaceutical Chemistry, BiocenterJ. W. Goethe University Frankfurt
  • Berndt Finke
    • Numico Research Group Germany
  • Bernd Stahl
    • Numico Research Group Germany

DOI: 10.1016/S1044-0305(02)00645-1

Cite this article as:
Pfenninger, A., Karas, M., Finke, B. et al. J. Am. Soc. Spectrom. (2002) 13: 1331. doi:10.1016/S1044-0305(02)00645-1


Underivatized neutral oligosaccharides from human milk were analyzed by nano-electrospray ionization (ESI) using a quadrupole ion trap mass spectrometer (QIT-MS) in the negative-ion mode. Under these conditions neutral oligosaccharides are observed as deprotonated molecules [M − H] with high intensity. CID-experiments of these species with the charge localized at the reducing end lead to C-type fragment ions forming a “new” reducing end. Fragmentations are accompanied by cross-ring cleavages that yield information about linkages of internal monosaccharides. Several isomeric compounds with distinct structural features, such as different glycosidic linkages, fucosylation and branching sites were investigated. The rules governing the fragmentation behavior of this class of oligosaccharides were elucidated and tested for a representative number of certain isomeric glycoforms using the MS/MS and MSn capabilities of the QIT. On the basis of the specific fragmentation behavior of deprotonated molecules, the position of fucoses and the linkage type (Gal β1→3 GlcNAc or Gal β1→4 GlcNAc) could be determined and linear and branched could be differentiated. Rules could be established which can be applied in further investigations of these types of oligosaccharides even from heterogenous mixtures.

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© American Society for Mass Spectrometry 2002