Abstract

Mass spectrometric methodologies which use electrospray ionization (ESI) for oligosaccharide structural determination and which are linked to classical procedures, such as reductive amination, have been established. Several derivatives of a model oligosaccharide were prepared and their ionization efficiencies in electrospray ionization (ESI) and fast-atom bombardment (FAB) mass spectrometry were investigated. The trimethyl-(p-aminophenyl)ammonium (TMAPA) derivatives showed extremely high sensitivity in positive-ion ESI-MS and gave Y- and Z-series sequence ions by ESI tandem mass spectromety (MS/MS). This study suggests that TMAPA-derivatized oligosaccharides used in ESI-MS and ESI-MS/MS would be effective for structural characterization of oligosaccharides that are available only in limited quantities.

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