Recent advances in structural analysis of gangliosides: primary and secondary structures.

Robert K Yu, T. A. Koerner, P. C. Demou, J. N. Scarsdale, J. H. Prestegard

Research output: Contribution to journalArticle

12 Scopus citations

Abstract

High-field (500 MHz) proton NMR has been used to elucidate the primary and secondary structures of glycosphingolipids (GSLs). Using 2-D J-correlated spectroscopy (2-D SECSY) which establishes scalar couplings of protons, the monosaccharide composition, anomeric configuration and aglycon structures of a GSL can be established. 2-D nuclear Overhauser effect spectroscopy (2-D NOE) then establishes through-space intra- and inter-residue couplings of cross-relaxing protons. We have found that each anomeric proton is involved in NOE couplings with inter- and intra-residue protons. The inter-residue coupling, resulting from interaction of protons across the glycosidic linkage, establishes the n-1 sugar residue and specific glycosidation site to which the n-residue is linked. When such information is known for each residue and is combined, the sequence of the core oligosaccharide is obtained. The sialylation-induced glycosidation shift is then used to establish the site of sialic acid residue attachment in a ganglioside molecule. We have also observed that the anomeric proton inter-residue NOE couplings can be used to suggest the preferred conformation of an oligosaccharide. We have found that the oligosaccharide residue of globoside exists in a unique and rather rigid conformation which could be stabilized by hydrogen bonds and van der Waals interactions. Since GSLs are known to have a receptor role and are implicated in cell-cell recognition, enzyme-substrate interaction and antigen-antibody interaction, the determination of their conformation should be useful in understanding their biological functions.

Original languageEnglish (US)
Pages (from-to)87-102
Number of pages16
JournalAdvances in Experimental Medicine and Biology
Volume174
StatePublished - Jan 1 1984
Externally publishedYes

ASJC Scopus subject areas

  • Biochemistry, Genetics and Molecular Biology(all)

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