High-yielding and controlled dissociation of glycosides producing B- and C-ion species under collision-induced dissociation MS/MS conditions and use in structural determination.

Collision-induced dissociation (CID) in mass spectrometry is a powerful technique with which to understand gas-phase chemical reactions. A mass spectrometer is used to carry out the reaction, isolation, and analysis. On the other hand, structural analysis of glycan structures is of extreme importance in the analysis of biomolecules, such as glycoproteins and glycolipids. In the analysis of glycan structures based on CID, certain ion species, including B-/Y-, C-/Z-, and A-/X-ions, are produced. Among these ions, we are interested in C-ion species that carry a glycosyl oxygen atom at the anomeric center and that possibly provide information regarding anomeric configuration. A method for generating C-ion species when necessary is thus considered to be important; however, none is currently available. In this study, synthetic glycosides carrying a series of aglycons were analyzed with the aim of identifying suitable glycosides with which to produce C-ions to be used in the structural determination of oligosaccharides. The results showed a 4-aminobutyl group was an excellent candidate. Furthermore, the use of C-ion species obtained in this manner in the structural characterization of a ganglioside, GM3, is described. The type of glycoside is believed to be valuable not only in structural analysis but also in biological investigation, because of the existing amino functionality that has been proven to be useful by enabling the generation of conjugates with other molecules and materials.