The oligosaccharide moieties of glycolipids and glycoproteins represent a diverse set of structures hypothesized to play roles in membrane surface reception, differentiation, and stabilization. Yet structural characterization of oligosaccharides has lagged behind that of other biological macromolecules, in part through the lack of suitable analytical methodology. It is the objective of this proposal to develop new methodology for the structural analysis of cell surface oligosaccharides and make preliminary application to constituent, monosaccharides, disaccharides, and higher oligomers. These applications will be carried out in ordered phases which bear analogy to biological membranes in an effort to elucidate not only conformation but surface association properties. The new methodology relies on the geometry dependence of quadrupole splittings in deuterium nmr spectra of molecules in magnetic field ordered liquid crystal environments. Multiple quantum nmr methods will be developed which allow assignment of quadruple doublets to specific sites in multiply labeled compounds. Algorithms for interpretation of these splittings in terms of molecular conformation will be developed. Information derived on preferred conformations and preferred modes of membrane association will be combined to improve an understanding of physiological and pathological processes dependent on recognition of membrane surface oligosaccharides.
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