期刊
GLYCOBIOLOGY
卷 25, 期 5, 页码 535-547出版社
OXFORD UNIV PRESS INC
DOI: 10.1093/glycob/cwu184
关键词
conformation; MD; NMR; NOE; oligosaccharides; spin relaxation; sulfated fucan
资金
- Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq)
- Fundacao de Amparo a Pesquisa do Estado do Rio de Janeiro (FAPERJ)
- CNPq [141872/2013-6]
- US National Institutes of Health (NIH) [P41 GM103390]
- NIH [P41 GM103390, R01 GM094919]
- Science Foundation of Ireland [08/IN.1/B2070]
Sulfated fucans from sea urchin egg jelly express well-defined chemical structures that vary with species. This species specificity regulates the sperm acrosome reaction, a critical step to assure intraspecific fertilization. In addition, these polysaccharides are involved in other biological activities such as anticoagulation. Although sulfation patterns are relevant to the levels of response in both activities, conformation and dynamics of these glycans are also contributing factors. However, data about these features of sulfated fucans are very rare. To address this, we have employed nuclear magnetic resonance experiments combined with molecular dynamics on structurally defined oligosaccharides derived from two sulfated fucans. The results have indicated that the oligosaccharides are flexible in solution. Ring conformation of their composing units displays just the C-1(4) chair configuration. In a particular octasaccharide, composed of two tetrasaccharide sequences, inter-residual hydrogen bonds play a role to decrease dynamics in these repeating units. Conversely, the linking disaccharide [-3)-alpha-L-Fucp-2(OSO3-)-(1-3)-alpha-L-Fucp-4(OSO3-)-(1-] located right between the two tetrasaccharide units has amplified motions suggested to be promoted by electrostatic repulsion of sulfates on opposite sides of the central glycosidic bond. This conjunction of information about conformation and dynamics of sulfated fucan oligosaccharides provides new insights to explain how these glycans behave free in solution and influenced by sulfation patterns. It may also serve for future studies concerning structure-function relationship of sulfated fucans, especially those involving sea urchin fertilization and anticoagulation.
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