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Sulfate migration in oligosaccharides induced by negative ion mode ion trap collision-induced dissociation

Artikel i vetenskaplig tidskrift
Författare Diarmuid T. Kenny
Samah Issa
Niclas G. Karlsson
Publicerad i Rapid Communications in Mass Spectrometry
Volym 25
Nummer/häfte 18
Sidor 2611-2618
ISSN 0951-4198
Publiceringsår 2011
Publicerad vid Institutionen för biomedicin
Institutionen för biomedicin, avdelningen för medicinsk kemi och cellbiologi
Sidor 2611-2618
Språk en
Länkar dx.doi.org/10.1002/rcm.5157
Ämneskategorier Medicinsk bioteknologi (med inriktning mot cellbiologi (inklusive stamcellsbiologi), molekylärbiologi, mikrobiologi, biokemi eller biofarmaci)

Sammanfattning

Migration of sulfate groups between hydroxyl groups was identified after collision-induced dissociation (CID) of sulfated oligosaccharides in an ion trap mass spectrometer in negative ion mode. Analysis of various sulfated oligosaccharides showed that this was a common phenomenon and was particularly prominent in sulfated oligosaccharides also containing sialic acid. It was also shown that the level of migration was increased when the sulfate was positioned on the flexible areas of the oligosaccharides not involved in the pyranose ring, such as the extra-cyclic C-6 carbon of hexoses or N-acetylhexosamines, or on reduced oligosaccharide. This suggested that migration is dependent on the spatial availability of the sulfate in the ion trap during collision. It is proposed that the migration is initiated when the negatively charged -SO3 – residue attached to the oligosaccharide precursor becomes protonated by a CID-induced proton transfer. This is supported by the CID fragmentation of precursor ions depleted of acidic protons such as doubly charged [M – 2H]2– ions or the sodiated [M + Na – 2H]– ions of oligosaccharides containing one sulfate and one sialic acid in the same molecule. Compared to the CID fragmentation of their monocharged [M – H]– ions, no migration was observed in CID of proton depleted precursors. Alternative fragmentation parameters to suppress migration of sulfated oligosaccharides also showed that it was not present when sulfated oligosaccharides were fragmented by HCD (High-Energy C-trap Dissociation) in an Orbitrap mass spectrometer.

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