Mass spectrometric characterization of oligo- and polysaccharides and their derivatives

Abstract

Mass spectrometry has become a key technique for the structural analysis of carbohydrates. Due to their special properties and requirements carbohydrates and especially chemically modified carbohydrates occupy a position between biopolymers and synthetic polymers. Charged analytes can be obtained by adduct formation with appropriate small ions or by various labeling procedures. Besides molecular mass profiling, tandem mass spectrometry can give more detailed structural information including sugar constituents, sequence and interresidue linkage positions, and some information on stereochemistry. Substitution patterns of polysaccharide derivatives are also studied by ESI IT-MS and MALDI ToF-MS. In this review, ion formation of carbohydrates, their chemical modification, fragmentation pathways of various analyte species, and the applicability of MS for quantitative evaluations are discussed. Mainly ESI applications are presented, but where of general significance MALDI-MS applications are also outlined. Examples of application are given, excluding the well-reviewed area of biologically important O- and N-linked glycans. Molecular mass determination and structural analysis of heteroglycans are followed by examples of cellulose and starch derivatives. © 2011 Springer-Verlag Berlin Heidelberg.