Differentiation of Ca(2+)- and Mg(2+)-coordinated branched trisaccharide isomers: an electrospray ionization and tandem mass spectrometry study.

Three isomeric branched trisaccharides coordinated to calcium and magnesium were analyzed by electrospray ionization followed by tandem mass spectrometry. Studies were undertaken to optimize the singly charged metal coordinated precursor prior to MS/MS and MS/MS/MS experiments. The positioning of the glycosidic linkages between reducing and nonreducing rings could be determined in all three isomers, and the linkage of the fucose ring was obvious in two of the three isomers when calcium was used as the coordinating metal. The ionic radius and charge of the metal appear to be very important in obtaining structural information in these isomers.