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Liquid Secondary Ion Mass Spectrometry of Methyl Glycosides of Oligosaccharides Using Matrices Containing Carboxamides
Author(s) -
Kováčik Vladimír,
Hirsch Jan,
Zorić Sandra,
Grützmacher HansFriedrich
Publication year - 1996
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(199610)10:13<1661::aid-rcm680>3.0.co;2-6
Subject(s) - chemistry , molecule , oligosaccharide , mass spectrum , ion , mass spectrometry , dimer , glycosidic bond , collision induced dissociation , crystallography , dissociation (chemistry) , proton affinity , protonation , tandem mass spectrometry , stereochemistry , organic chemistry , chromatography , enzyme
Intense cluster ions corresponding to proton‐bound hetero‐dimers of an amide molecule and an oligosaccharide molecule are observed in the liquid secondary ion mass spectra of methyl glycosides of oligoxylans if a solution of an aliphatic carboxamide in glycerol is used as the liquid matrix. These cluster ions are particularly abundant and persist for a long period if urea (U) or thiourea (TU) is used as the matrix additive. In these cases, cluster ions containing more than one molecule of U or TU and two oligosaccharide molecules are also observed. The intense signal due to the proton‐bound hetero‐dimer between U or TU and the oligosaccharide can be used with advantage for a molecular weight determination. The bonding interactions between a protonated saccharide molecule and a molecule U or TU in the proton‐bound hetero‐dimers are so strong that the urea molecules remain attached to the fragment ions during the decay of metastable cluster ions and even during collision‐induced dissociation. Thus, the mass‐analysed ion kinetic energy spectra of these proton‐bound hetero‐dimers are dominated by abundant cluster ions [B n +U] and [Y m +U] arising from cleavage of the glycosidic bonds within the oligosaccharides. The collisionally‐activated mass spectra of the proton‐bound hetero‐dimers additionally contain peaks of the free ions B n and Y m . Therefore, these spectra clearly reflect the arrangement of the monosaccharide residues in the oligosaccharide and can be used conveniently for structural analysis.