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Characterization of the glycosidic linkage of underivatized disaccharides by interaction with Pb 2+ ions
Author(s) -
Firdoussi Ahlam El,
Lafitte Marie,
Tortajada Jeanine,
Kone Omar,
Salpin JeanYves
Publication year - 2007
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1220
Subject(s) - chemistry , disaccharide , glycosidic bond , tandem mass spectrometry , mass spectrometry , electrospray ionization , stereochemistry , fragmentation (computing) , ion , electrospray , chromatography , organic chemistry , computer science , enzyme , operating system
Electrospray ionization in combination with tandem mass spectrometry and lead cationization is used to characterize the linkage position of underivatized disaccharides. Lead(II) ions react mainly with disaccharides by proton abstraction to generate [Pb(disaccharide) m − H] + ions ( m = 1–2). At low cone voltages, an intense series of doubly charged ions of general formula [Pb(disaccharide) n ] 2+ are also observed. Our study shows that MS/MS experiments have to be performed to differentiate Pb 2+ ‐coordinated disaccharides. Upon collision, [Pb(disaccharide) − H] + species mainly dissociate according to glycosidic bond cleavage and cross‐ring cleavages, leading to the elimination of C n H 2 n O n neutrals ( n = 2–4). The various fragmentation processes allow the position of the glycosidic bond to be unambiguously located. Distinction between glc‐glc and glc‐fru disaccharides also appears straightforward. Furthermore, for homodimers of D ‐glucose our data demonstrate that the anomericity of the glycosidic bond can be characterized for the 1 → n linkages ( n = 2, 4, 6). Consequently, Pb 2+ cationization combined with tandem mass spectrometry appears particularly useful to identify underivatized disaccharides. Copyright © 2007 John Wiley & Sons, Ltd.