Conformational properties of l-fucose and the tetrasaccharide building block of the sulfated l-fucan from Lytechinus variegatus |
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Affiliation: | 1. Institute of Medical Biochemistry Leopoldo de Meis, University Hospital Clementino Fraga Filho, Federal University of Rio de Janeiro, Rio de Janeiro 21941, RJ, Brazil;2. BioMolecular Sciences Department, School of Pharmacy, University of Mississippi, University, 38677 MS, USA;3. Research Institute of Pharmaceutical Sciences, School of Pharmacy, University of Mississippi, University, 38677 MS, USA;1. Program of Glycobiology, Institute of Medical Biochemistry Leopoldo de Meis, and University Hospital Clementino Fraga Filho, Federal University of Rio de Janeiro, Rio de Janeiro, RJ 21941-913, Brazil;2. Glycosciences Laboratory, Imperial College, Department of Medicine, Burlington Danes Building, Du Cane Road, London W12 0NN, UK;3. EaStCHEM School of Chemistry, Joseph Black Building, The King''s Buildings, University of Edinburgh, Edinburgh EH9 3JJ, United Kingdom,;4. GlycoMar Ltd., European Centre for Marine Biotechnology, Dunstaffnage Marine Laboratory, Oban, Argyll PA37 1QA, United Kingdom,;5. Scottish Association for Marine Science, Scottish Marine Institute, Oban, Argyll PA37 1QA, United Kingdom,;6. Glycosciences Laboratory, Hammersmith Campus, Imperial College London, London W12 0NN, United Kingdom,;12. National Institute of Biological Standards and Controls, South Mimms, Potters Bar, Hertfordshire EN6 3QG, United Kingdom,;8. Complex Carbohydrate Research Center, the University of Georgia, Athens, Georgia 30602, and;9. School of Chemistry, National University of Ireland Galway, University Road, Galway, Ireland;1. Department of BioMolecular Sciences, University of Mississippi, Oxford, Mississippi, USA;2. Department of Microbiology and Immunology, University of Mississippi Medical Center, Jackson, Mississippi, USA;3. Center for Biotechnology and Interdisciplinary Studies, Rensselaer Polytechnic Institute, Troy, New York, USA;4. Research Institute of Pharmaceutical Sciences, School of Pharmacy, University of Mississippi, Oxford, Mississippi, USA |
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Abstract: | Although the 3D structure of carbohydrates is known to contribute to their biological roles, conformational studies of sugars are challenging because their chains are flexible in solution and consequently the number of 3D structural restraints is limited. Here, we investigate the conformational properties of the tetrasaccharide building block of the Lytechinus variegatus sulfated fucan composed of the following structure [l-Fucp4(SO3−)-α(1-3)-l-Fucp2,4(SO3−)-α(1-3)-l-Fucp2(SO3−)-α(1-3)-l-Fucp2(SO3−)] and the composing monosaccharide unit Fucp, primarily by nuclear magnetic resonance (NMR) experiments performed at very low temperatures and using H2O as the solvent for the sugars rather than using the conventional deuterium oxide. By slowing down the fast chemical exchange rates and forcing the protonation of labile sites, we increased the number of through-space 1H–1H distances that could be measured by NMR spectroscopy. Following this strategy, additional conformational details of the tetrasaccharide and l-Fucp in solution were obtained. Computational molecular dynamics was performed to complement and validate the NMR-based measurements. A model of the NMR-restrained 3D structure is offered for the tetrasaccharide. |
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Keywords: | Conformation Fucose NMR spectroscopy Structural glycobiology Sulfated fucan |
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