| Publication Type |
Journal Article |
| Title |
Conformational Plasticity in Glycomimetics: Fluorocarbamethyl-L-idopyranosides Mimic the Intrinsic Dynamic Behaviour of Natural Idose Rings |
| Authors |
Luca Unione Bixue Xu Dolores Diaz Sonsoles Martin-Santamaria Ana Poveda Joao Sardinha Amélia P. Rauter Yves Bleriot Yongmin Zhang F. Javier Canada Matthieu Sollogoub Jesus Jimenez-Barbero |
| Groups |
HC |
| Journal |
CHEMISTRY-A EUROPEAN JOURNAL |
| Year |
2015 |
| Month |
July |
| Volume |
21 |
| Number |
29 |
| Pages |
10513-10521 |
| Abstract |
Sugar function, structure and dynamics are intricately correlated. Ring flexibility is intrinsically related to biological activity; actually plasticity in L-iduronic rings modulates their interactions with biological receptors. However, the access to the experimental values of the energy barriers and free-energy difference for conformer interconversion in water solution has been elusive. Here, a new generation of fluorine-containing glycomimetics is presented. We have applied a combination of organic synthesis, NMR spectroscopy and computational methods to investigate the conformational behaviour of idose- and glucose-like rings. We have used low-temperature NMR spectroscopic experiments to slow down the conformational exchange of the idose-like rings. Under these conditions, the exchange rate becomes slow in the (FNMR)-F-19 spectroscopic chemical shift timescale and allows shedding light on the thermodynamic and kinetic features of the equilibrium. Despite the minimal structural differences between these compounds, a remarkable difference in their dynamic behaviour indeed occurs. The importance of introducing fluorine atoms in these sugars mimics is also highlighted. Only the use of (FNMR)-F-19 spectroscopic experiments has permitted the unveiling of key features of the conformational equilibrium that would have otherwise remained unobserved. |
| DOI |
http://dx.doi.org/10.1002/chem.201501249 |
| ISBN |
|
| Publisher |
|
| Book Title |
|
| ISSN |
0947-6539 |
| EISSN |
1521-3765 |
| Conference Name |
|
| Bibtex ID |
ISI:000357328200034 |
| Observations |
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