Determining the structure of glycan moieties by mass spectrometry.

Acquisition of mass spectra using fast-atom bombardment (FAB), matrix-assisted laser desorption/ionization (MALDI), and electrospray ionization (ESI) mass spectrometry is summarized in this unit. Molecular weights of the carbohydrates provide information on their composition in terms of isobaric monosaccharide composition, and tables of residue masses are provided to assist these calculations. More detailed structural analysis can be performed by fragmentation; the main fragmentation modes of carbohydrates and their nomenclature are discussed. Fragmentation of negative ions generated by nano-electrospray, in particular, provide very informative spectra and give details such as the position of fucose substitution, branching pattern, and the presence or absence of bisecting GlcNAc residues. Practical details are given for the purification of samples prior to mass spectrometric analysis and for recording FAB, MALDI, and ESI spectra.