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Characterization of oligosaccharide composition and structure by quadrupole ion trap mass spectrometry
Author(s) -
Weiskopf Andrew S.,
Vouros Paul,
Harvey David J.
Publication year - 1997
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/(sici)1097-0231(199709)11:14<1493::aid-rcm40>3.0.co;2-1
Subject(s) - chemistry , quadrupole ion trap , mass spectrometry , oligosaccharide , ion trap , glycosidic bond , collision induced dissociation , ion , tandem mass spectrometry , fragmentation (computing) , mass spectrum , protein mass spectrometry , analytical chemistry (journal) , electrospray ionization , isobaric process , top down proteomics , chromatography , organic chemistry , physics , computer science , thermodynamics , enzyme , operating system
The use of electrospray ionization — quadrupole ion trap mass spectrometry for the characterization of linear oligosaccharides and N‐linked protein oligosaccharide mixtures is described. Tandem mass spectrometry (MS/MS) experiments with orders higher than two offer a number of ways to enhance MS/MS spectra and to derive information not present in MS and MS 2 spectra. Three such methods are presented in this paper. (a) Collisional activation of permethylated oligosaccharide molecular ions (MS 2 ), as illustrated by maltoheptaose, produces abundant fragments from glycosidic bond cleavages which indicate composition and sequence, and weak cross‐ring cleavage products which denote specific linkages within the oligosaccharide. Through the trapping and further dissociation of these fragments (MS n ), cross‐ring cleavage products can be confirmed and their relative abundances increased to facilitate interpretation. (b) The mechanisms of formation of two isobaric ions or ions isobaric with another ion's isotope peaks, such as those present in the MS 2 spectrum of the ribonuclease B oligosaccharide GlcNAc 2 Man 5 can be independently established by separate MS 3 experiments. (c) Ions in the MS 2 spectrum, specific for individual components of an isobaric mixture, can be isolated and characterized by further stages of fragmentation. This is illustrated by two isobaric oligosaccharides from chicken ovalbumin of the composition of HexNAc 5 Hex 5 . These findings indicate the utility of ion trap mass spectrometry towards the facile determination of oligosaccharide composition, sequence, branching and linkage, providing a wealth of structural information not obtainable by other individual methods of carbohydrate mass spectrometry analysis. © 1997 John Wiley & Sons, Ltd.