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Evidence of Ca 2 +-Dependent Carbohydrate Association through Ion Spray Mass Spectrometry
Content Provider | Semantic Scholar |
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Author | Siuzdak, Gary Ichikawa, ' Yoshitaka Caulfield, J. M. Munoz, Benito Wong, C. -H. Nicolaou, K. C. |
Copyright Year | 2001 |
Abstract | The interactions of the cell-surface carbohydrate, Lex (Gal-& 1+4-( Fuc-a1+3)-GlcNAc) and the Lexcontaining glycosphingolipid, Lex-LacCer, and their analogues were examined by ion spray mass spectrometry. Both Lex and Lex-LacCer complexed the divalent cations, Ca2+, Mn2+, and Mg2+, to form [nLex + cation2+]2+ and [nLexLacCer + cation2+J2+ ( n = 1, 2, or 3) with greater stability observed for the dimer ( n = 2) relative to the trimer ( n = 3). No evidence of association was obtained when these compounds were analyzed under the same conditions in the presence of monovalent cations, Li+, Na+, and K+. Collision-induced decomposition (CID) experiments were performed on the noncovalent dimers, [2Lex-LacCer + Ca2+J2+ and [2Lex + Ca2+J2+, with results indicating that the Ca2+ complexation site was within the Lex moiety. Furthermore, CID results implied, through the loss of one or both fucose residues from the intact dimers, that both fucose residues may be exposed on the Lex and Lex-LacCer dimers. Lex-LacCer was also found to associate with LacCer, GalCer, or Cer in the presence of the divalent cations. CID studies further implied that the binding affinity of Lex-LacCer with Lex-LacCer was greater than that with LacCer, and decreased in order with GalCer and Cer. Space-filling models and energy minimization calculations of Lex in its solution conformation with Ca2+ affirmed that the molecules may bind through Ca2+ in a homotypic interaction. This predilection for homotypic Lex interactions may correlate to the biological utility of this surface carbohydrate in the cellular adhesion process. |
File Format | PDF HTM / HTML |
Alternate Webpage(s) | https://masspec.scripps.edu/publications/public_pdf/14_art.pdf |
Language | English |
Access Restriction | Open |
Subject Keyword | Antigens, CD15 CER Computer Calcium ion Carbohydrates Cations Cations, Divalent Cations, Monovalent Cell Adhesion Collision-Induced Dissociation Configuration interaction Domino tiling Efimov state Energy minimization Experiment FUT4 wt Allele Fucose Galactosylceramides Glycosphingolipids Ions Lex (software) Manganese Cation (2+) Potassium Processor affinity Pyrimidine Dimers Sodium Spectrometry lithium cation |
Content Type | Text |
Resource Type | Article |