Evaluation of a carbohydrate–π interaction in a peptide model system

Abstract

A carbohydrate-pi interaction contributes -0.8 kcal mol(-1) to the stabilization of a beta-hairpin peptide.

Kinetics of Cellobiohydrolase (Cel7A) Variants with Lowered Substrate Affinity

“…Provided that alanine in position 38 interacts negligibly with the cellulose strand (50) and that the overall conformation of the mutant is mainly unchanged, this suggests that Trp-38 contributes Ϫ2 to Ϫ3 kJ/mol to the standard free energy of substrate binding. This value perfectly matches general assessments of the interaction free energy for carbohydrates and aromatic side chains (50,56), but it is lower than the contribution from Trp-38 to ligand binding (Ϫ15.9 kJ/mol) derived from molecular dynamics simulations (57). We note that a similar analysis of the contribution of the CBM (again using the appropriate ratios of parameters from (32).…”

A Combined NMR, Computational, and HPLC Study of the Inclusion of Aromatic and Fluoroaromatic Compounds in Cyclodextrins as a Model for Studying Carbohydrate–Aromatic Interactions

“…From a more general perspective, these results as a whole reinforce the notion [14][15][16][17] that carbohydrate···aromatic binding involves interactions between C-H bonds on the hydrophobic face of the sugar and the π electrons of the aromatic partner. The presence of electron-withdrawing substituents on the aromatic ring hampers in part, or prevents altogether, the binding event.…”

“…[14] This behavior has been taken as a direct demonstration of the existence of sugar-aromatic CH···π interactions, [15] which has also been claimed to bias the conformational behavior of certain glycopeptides in water solution. [16] The presence of three C-H vectors pointing towards the same spatial orientation seems to be a key factor in defining the stabilization of the intermolecular carbohydrate··· aromatic interaction. Nevertheless, preliminary results obtained from a comparison of the NMR spectroscopic data of some of these molecules in water compared with those measured in nonaqueous solvents, such as CD 3 OD or DMSO, [17] seem to indicate a weakening of the observed effects in the NMR spectra, and possibly suggest a role for hydrophobic packing in defining the interaction.…”

Magnitude of CH/O interactions between carbohydrate and water

“…The carbohydrate-aromatic interactions, which are sometimes denoted as CH/p interactions, were used for recognition of carbohydrates by artificial receptors [11][12][13][14]. The carbohydrate-aromatic interactions have been studied extensively both by experimental [15][16][17][18][19][20][21][22][23] and by theoretical [24][25][26][27][28][29][30][31][32][33][34][35] methods. The carbohydrate recognition processes involve desolvation of water molecules from the carbohydrate molecule.…”