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

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.

[1]  André M Deelder,et al.  Mass spectrometry of proton adducts of fucosylated N-glycans: fucose transfer between antennae gives rise to misleading fragments. , 2006, Rapid communications in mass spectrometry : RCM.

[2]  Yassir A. Ahmed,et al.  Glycomics profiling of heparan sulfate structure and activity. , 2010, Methods in enzymology.

[3]  N. Volpi Advances in chondroitin sulfate analysis: application in physiological and pathological States of connective tissue and during pharmacological treatment of osteoarthritis. , 2006, Current pharmaceutical design.

[4]  C. Bertozzi,et al.  Biosynthesis of L-selectin ligands: sulfation of sialyl Lewis x-related oligosaccharides by a family of GlcNAc-6-sulfotransferases. , 2001, Biochemistry.

[5]  M. Bäckström,et al.  High-throughput and high-sensitivity nano-LC/MS and MS/MS for O-glycan profiling. , 2009, Methods in molecular biology.

[6]  S. Kumar,et al.  Circulatory half-life but not interaction with the lutropin/chorionic gonadotropin receptor is modulated by sulfation of bovine lutropin oligosaccharides. , 1992, Proceedings of the National Academy of Sciences of the United States of America.

[7]  N. Packer,et al.  Graphitized carbon LC-MS characterization of the chondroitin sulfate oligosaccharides of aggrecan. , 2007, Analytical chemistry.

[8]  H. Narimatsu,et al.  Enrichment method of sulfated glycopeptides by a sulfate emerging and ion exchange chromatography. , 2009, Analytical chemistry.

[9]  J. Zaia,et al.  The role of mobile protons in negative ion CID of oligosaccharides , 2007, Journal of the American Society for Mass Spectrometry.

[10]  D. Spillmann,et al.  Heparan Sulfate Domain Organization and Sulfation Modulate FGF-induced Cell Signaling* , 2010, The Journal of Biological Chemistry.

[11]  Hiroto Kawashima,et al.  Roles of sulfated glycans in lymphocyte homing. , 2006, Biological & pharmaceutical bulletin.

[12]  N. Packer,et al.  MUC5B glycosylation in human saliva reflects blood group and secretor status. , 2005, Glycobiology.

[13]  J. Kamerling,et al.  Sulfated di-, tri- and tetraantennary N-glycans in human Tamm-Horsfall glycoprotein. , 1998, European journal of biochemistry.

[14]  J. Zaia,et al.  Tandem mass spectrometric determination of the 4S/6S sulfation sequence in chondroitin sulfate oligosaccharides. , 2001, Analytical chemistry.

[15]  Catherine E. Costello,et al.  Tandem mass spectrometric strategies for determination of sulfation positions and uronic acid epimerization in chondroitin sulfate oligosaccharides , 2003, Journal of the American Society for Mass Spectrometry.

[16]  G. Conrad,et al.  On-target derivatization of keratan sulfate oligosaccharides with pyrenebutyric acid hydrazide for MALDI-TOF/TOF-MS. , 2008, Journal of mass spectrometry : JMS.

[17]  Martin Pabst,et al.  Influence of electrosorption, solvent, temperature, and ion polarity on the performance of LC-ESI-MS using graphitic carbon for acidic oligosaccharides. , 2008, Analytical chemistry.

[18]  Koichi Tanaka,et al.  Ionic liquid matrixes optimized for MALDI-MS of sulfated/sialylated/neutral oligosaccharides and glycopeptides. , 2008, Analytical chemistry.

[19]  A. Antonopoulos,et al.  On-line liquid chromatography-electrospray ionisation mass spectrometry for kappa-carrageenan oligosaccharides with a porous graphitic carbon column. , 2007, Journal of chromatography. A.

[20]  L. Lasky,et al.  Identification of a carbohydrate-based endothelial ligand for a lymphocyte homing receptor , 1991, The Journal of cell biology.

[21]  G. Hansson,et al.  Sequencing of sulfated oligosaccharides from mucins by liquid chromatography and electrospray ionization tandem mass spectrometry. , 2000, Analytical chemistry.

[22]  Catherine A. Hayes,et al.  UniCarb-DB: a database resource for glycomic discovery , 2011, Bioinform..

[23]  D. Vigetti,et al.  New electrophoretic and chromatographic techniques for analysis of heparin and heparan sulfate , 2008, Electrophoresis.

[24]  M. Bäckström,et al.  Enhanced detection of sialylated and sulfated glycans with negative ion mode nanoliquid chromatography/mass spectrometry at high pH. , 2010, Analytical chemistry.

[25]  B. Ernst,et al.  False sugar sequence ions in electrospray tandem mass spectrometry of underivatized sialyl-Lewis-type oligosaccharides , 1997 .

[26]  N. Karlsson,et al.  Liquid chromatography-electrospray mass spectrometry as a tool for the analysis of sulfated oligosaccharides from mucin glycoproteins. , 1999, Journal of chromatography. A.

[27]  Yue Sun,et al.  A Conspicuous Connection: Structure Defines Function for the Phosphatidylinositol-Phosphate Kinase Family , 2007, Critical reviews in biochemistry and molecular biology.

[28]  J. Baenziger,et al.  Pituitary glycoprotein hormone oligosaccharides: structure, synthesis and function of the asparagine-linked oligosaccharides on lutropin, follitropin and thyrotropin. , 1988, Biochimica et biophysica acta.

[29]  J. Zaia,et al.  The influence of sialylation on glycan negative ion dissociation and energetics , 2006, Journal of the American Society for Mass Spectrometry.

[30]  R. Dwek,et al.  "Internal residue loss": rearrangements occurring during the fragmentation of carbohydrates derivatized at the reducing terminus. , 2002, Analytical chemistry.

[31]  K. Khoo,et al.  Enabling techniques and strategic workflow for sulfoglycomics based on mass spectrometry mapping and sequencing of permethylated sulfated glycans. , 2009, Glycobiology.

[32]  N. Karlsson,et al.  Sulphated mucin oligosaccharides from porcine small intestine analysed by four-sector tandem mass spectrometry. , 1996, Journal of mass spectrometry : JMS.

[33]  S. Tomatsu,et al.  Analytical method for the determination of disaccharides derived from keratan, heparan, and dermatan sulfates in human serum and plasma by high-performance liquid chromatography/turbo ionspray ionization tandem mass spectrometry. , 2007, Analytical Biochemistry.

[34]  V. Korolik,et al.  Mucins in the mucosal barrier to infection , 2008, Mucosal Immunology.

[35]  S. Carrington,et al.  INTERACTION OF EIMERIA TENELLA WITH INTESTINAL MUCIN IN VITRO , 2007, The Journal of parasitology.

[36]  N. Packer,et al.  Use of graphitised carbon negative ion LC-MS to analyse enzymatically digested glycosaminoglycans. , 2005, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[37]  K. Hård,et al.  The Asn-linked carbohydrate chains of human Tamm-Horsfall glycoprotein of one male. Novel sulfated and novel N-acetylgalactosamine-containing N-linked carbohydrate chains. , 1992, European journal of biochemistry.