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Tandem mass spectrometric analysis of fixed‐charge derivatized oligosaccharides
Author(s) -
Domon B.,
Mueller D. R.,
Richter W. J.
Publication year - 1994
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210291204
Subject(s) - chemistry , fragmentation (computing) , tandem mass spectrometry , tandem , ion , mass spectrometry , dissociation (chemistry) , reductive amination , yield (engineering) , fast atom bombardment , collision induced dissociation , analytical chemistry (journal) , medicinal chemistry , chromatography , organic chemistry , materials science , catalysis , computer science , metallurgy , composite material , operating system
Various derivatives of a set of three isomeric (linear and branched) pentasaccharides (LNF‐1, LNF‐2 and LNF‐3) were prepared and investigated by high‐performance tandem mass spectrometry in order to compare their collision‐induced dissociation (CID) behaviour. The fast atom bombardment tandem mass spectra of [M + H] + ions of peracetylated derivatives mainly display fragments containing the non‐reducing terminus (B‐type ions) and allow a straightforward assignment of sugar sequence and branching together with the identification of some interglycosidic linkages. Permethylated derivatives, which better accommodate the mass range of tandem mass spectrometers in the case of larger oligosaccharides, yield similar results, i.e. predominance of B ions, but the necessary information has to be retrieved from incomplete B i and Y i ion series. By contrast, CID of permethyl or peracetyl derivatives carrying a preformed charge due to prior reductive amination of the oligosaccharides with trimethyl( p ‐aminophenyl)ammonium chloride yields exclusively fragment ions comprising the reducing end. In this case, the four distinct series of fragments observed involve charge‐remote fragmentation processes. As a consequence, the spectral patterns are not significantly affected by the nature of the sugar O‐substituents additionally introduced (i.e. methyl or acetyl).