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Conformational changes due to vicinal glycosylation: The branched α-l-Rhap(1–2)[β-d-Galp(1–3)]-β-d-Glc1-OMe trisaccharide compared with its parent disaccharides*

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Grosskurth,  Horst
Department of Molecular Neurobiology, Max Planck Institute for Medical Research, Max Planck Society;

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Dabrowski,  Ursula
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Dabrowski,  Janusz
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Citation

Kozar, T., Nifantev, N. E., Grosskurth, H., Dabrowski, U., & Dabrowski, J. (1998). Conformational changes due to vicinal glycosylation: The branched α-l-Rhap(1–2)[β-d-Galp(1–3)]-β-d-Glc1-OMe trisaccharide compared with its parent disaccharides*. Biopolymers, 46(6), 417-432. doi:10.1002/(SICI)1097-0282(199811)46:6<417:AID-BIP6>3.0.CO;2-V.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002B-9F5F-E
Abstract
Conformations of the α-l-Rhap(1-2)-β-d-Glc1-OMe and β-d-Galp(1-3)-β-d-Glc1-OMe disaccharides and the branched title trisaccharide were examined in DMSO-d6 solution by 1H-nmr. The distance mapping procedure was based on rotating frame nuclear Overhauser effect (NOE) constraints involving C- and O-linked protons, and hydrogen-bond constraints manifested by the splitting of the OH nmr signals for partially deuteriated samples. An “isotopomer-selected NOE” method for the unequivocal identification of mutually hydrogen-bonded hydroxyl groups was suggested. The length of hydrogen bonds thus detected is considered the only one motionally nonaveraged nmr-derived constraint. Molecular mechanics and molecular dynamics methods were used to model the conformational properties of the studied oligosaccharides. Complex conformational search, relying on a regular Φ,Ψ-grid based scanning of the conformational space of the selected glycosidic linkage, combined with simultaneous modeling of different allowed orientations of the pendant groups and the third, neighboring sugar residue, has been carried out. Energy minimizations were performed for each member of the Φ,Ψ grid generated set of conformations. Conformational clustering has been done to group the minimized conformations into families with similar values of glycosidic torsion angles. Several stable syn and anti conformations were found for the 1[RIGHTWARDS ARROW]2 and 1[RIGHTWARDS ARROW]3 bonds in the studied disaccharides. Vicinal glycosylation affected strongly the occupancy of conformational states in both branches of the title trisaccharide. The preferred conformational family of the trisaccharide (with average Φ,Ψ values of 38°, 17° for the 1[RIGHTWARDS ARROW]2 and 48°, 1° for the 1[RIGHTWARDS ARROW]3 bond, respectively) was shown by nmr to be stabilized by intramolecular hydrogen bonding between the nonbonded Rha and Gal residues.