2013
DOI: 10.1021/ja4054702
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Stabilization of Branched Oligosaccharides: Lewisx Benefits from a Nonconventional C–H···O Hydrogen Bond

Abstract: Although animal lectins usually show a high degree of specificity for glycan structures, their single-site binding affinities are typically weak, a drawback which is often compensated in biological systems by an oligovalent presentation of carbohydrate epitopes. For the design of monovalent glycomimetics, structural information regarding solution and bound conformation of the carbohydrate lead represents a valuable starting point. In this paper, we focus on the conformation of the trisaccharide Le(x) (Gal[Fucα… Show more

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Cited by 74 publications
(100 citation statements)
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“…4F), as has been found previously in structures of Le x (37) and sLe x (38) oligosaccharides. The presence of this hydrogen bond is indicated by the distance between Fuc-H5 and Gal-O5 of 2.2-2.3 Å within the ensemble, which is significantly shorter than the sum of the corresponding van der Waals radii (2.6 Å), and further supported by the characteristic NMR chemical shift of Fuc-H5 (∼4.8 ppm) (37,38).…”
Section: Resultsmentioning
confidence: 83%
See 1 more Smart Citation
“…4F), as has been found previously in structures of Le x (37) and sLe x (38) oligosaccharides. The presence of this hydrogen bond is indicated by the distance between Fuc-H5 and Gal-O5 of 2.2-2.3 Å within the ensemble, which is significantly shorter than the sum of the corresponding van der Waals radii (2.6 Å), and further supported by the characteristic NMR chemical shift of Fuc-H5 (∼4.8 ppm) (37,38).…”
Section: Resultsmentioning
confidence: 83%
“…However, Fuc stabilizes the core Le x trisaccharide in a binding-competent conformation by forming an intracarbohydrate C-H···O hydrogen bond to Gal6S (Fig. 4F), together with hydrophobic interactions (37,38,43), and may thus indirectly contribute to affinity by decreasing the entropic penalty of fixing multiple conformational degrees of freedom upon binding.…”
Section: Discussionmentioning
confidence: 99%
“…In another biomolecular context, CH··O HBs appear to be quite prominent in oligosaccharides and carbohydrates [197] where they can amount to some 40 % of the total interaction energy, and can lock particular configurations [198]. The interactions between RNA bases and phosphate include CH··O HBs [199] as do 2-deoxyribonucleosides [200,201].…”
Section: Serine Proteasesmentioning
confidence: 99%
“…Nor is it necessary that the bridging H atom be covalently bound to a highly electronegative atom, as SH and ClH can participate as well [46][47][48][49][50][51]. In fact, even the C atom with an electronegativity comparable to H, has been shown to be a potent proton donor in certain circumstances [52][53][54][55][56][57][58][59]. With specific regard to CH··O HBs, a good deal has been learned about them in recent years.…”
Section: Introductionmentioning
confidence: 99%
“…Recent work [67] has shown for example, that a CH··O HB can override the normal trans-planar conformational preferences of α-fluoroamides. In the biological realm too, CH···O HBs play quite an important role [53,[68][69][70][71][72][73][74][75] in systems varying from interhelical interactions in proteins to structures of oligosaccharides and carbohydrates and nucleic acids [76][77][78][79]. There is some evidence that CH··O HBs may play a previously overlooked role in the structure of such protein stalwarts as the β-sheet [80,81].…”
Section: Introductionmentioning
confidence: 99%