Structural Characterization of Sulfated Glycosaminoglycans by Fast Atom Bombardment Mass Spectrometry: Application to Chondroitin Sulfate

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Abstract
Polysulfated oligosaccharides obtained from enzymatic digests of chondroitin sulfate have been successfully analyzed by positive and negative ion fast atom bombardment mass spectrometry. The spectra show intense cationized molecular ions and fragment ions from which sugar sequence and sites of sulfation can be readily determined. In addition, polymers of 4-O-sulfate and 6-O-sulfate positional isomers may be distinguished by fast atom bombardment mass spectrometry. The mass spectra also indicate the presence of structural homologs of chondroitin sulfate that contain more than one covalently bound sulfate moiety per two sugar residues. The effects of salt concentration, liquid matrix composition and ionization mode (negative versus positive ion abstraction) on the quality and information content of the mass spectra are discussed in detail.