Sensitive detection and structural characterization of trimethyl(p‐aminophenyl)‐ammonium‐derivatized oligosaccharides by electrospray ionization–mass spectrometry and tandem mass spectrometry

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.