A Simple Model System for the Study of Carbohydrate−Aromatic Interactions

Terraneo, Giancarlo; Potenza, Donatella; Canales, Ángeles; Jiménez‐Barbero, Jesús; Baldridge, Kim K.; Bernardi, Anna

doi:10.1021/ja066633g

Cited by 101 publications

(55 citation statements)

References 58 publications

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“…However, recently, evidence has come to light for an enthalpically driven 'non-classical' hydrophobic effect and this may play a role in lectin-saccharide binding events [39,40]. Moreover, a variety of model studies have indicated roles for CH-p [41][42][43][44][45] and other apolar interactions [46,47] in carbohydrate recognition. Having said all this, the pattern of polar contacts is surely also important, and it is safest to assume that polar and apolar interactions work in concert to achieve biological carbohydrate recognition.…”

Section: Synthetic Lectin Design Principlesmentioning

confidence: 99%

Progress in biomimetic carbohydrate recognition

Walker

Joshi

Davis

2009

Cell. Mol. Life Sci.

109

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The importance of carbohydrate recognition in biology, and the unusual challenges involved, have lead to great interest in mimicking saccharide-binding proteins such as lectins. In this review, we discuss the design of artificial carbohydrate receptors, focusing on those which work under natural (i.e. aqueous) conditions. The problem is intrinsically difficult because of the similarity between substrate (carbohydrate) and solvent (water) and, accordingly, progress has been slow. However, recent developments suggest that solutions can be found. In particular, the "temple" family of carbohydrate receptors show good affinities and excellent selectivities for certain all-equatorial substrates. One example is selective for O-linked beta-N-acetylglucosamine (GlcNAc, as in the O-GlcNAc protein modification), while another is specific for beta-cellobiosyl and closely related disaccharides. Both show roughly millimolar affinities, matching the strength of some lectin-carbohydrate interactions.

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Section: Synthetic Lectin Design Principlesmentioning

confidence: 99%

Progress in biomimetic carbohydrate recognition

Walker

Joshi

Davis

2009

Cell. Mol. Life Sci.

109

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“…Dispersion interactions between carbohydrates and aromatic moieties were also detected by solution NMR [15], [23]–[28] and other experimental methods [29]–[31].…”

Section: Introductionmentioning

confidence: 99%

Stacking Interactions between Carbohydrate and Protein Quantified by Combination of Theoretical and Experimental Methods

et al. 2012

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Carbohydrate – receptor interactions are an integral part of biological events. They play an important role in many cellular processes, such as cell-cell adhesion, cell differentiation and in-cell signaling. Carbohydrates can interact with a receptor by using several types of intermolecular interactions. One of the most important is the interaction of a carbohydrate's apolar part with aromatic amino acid residues, known as dispersion interaction or CH/π interaction. In the study presented here, we attempted for the first time to quantify how the CH/π interaction contributes to a more general carbohydrate - protein interaction. We used a combined experimental approach, creating single and double point mutants with high level computational methods, and applied both to Ralstonia solanacearum (RSL) lectin complexes with α-l-Me-fucoside. Experimentally measured binding affinities were compared with computed carbohydrate-aromatic amino acid residue interaction energies. Experimental binding affinities for the RSL wild type, phenylalanine and alanine mutants were −8.5, −7.1 and −4.1 kcal.mol−1, respectively. These affinities agree with the computed dispersion interaction energy between carbohydrate and aromatic amino acid residues for RSL wild type and phenylalanine, with values −8.8, −7.9 kcal.mol−1, excluding the alanine mutant where the interaction energy was −0.9 kcal.mol−1. Molecular dynamics simulations show that discrepancy can be caused by creation of a new hydrogen bond between the α-l-Me-fucoside and RSL. Observed results suggest that in this and similar cases the carbohydrate-receptor interaction can be driven mainly by a dispersion interaction.

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“…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.…”

Section: Introductionmentioning

confidence: 99%

Magnitude of CH/O interactions between carbohydrate and water

2012

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The interaction energy potentials for six orientations of the fucose-water complex were calculated for evaluating the magnitude of the CH/O interactions in the complex. The calculations show that the C-H bonds of the nonpolar surface of fucose prefer to have contact with the oxygen atom of the water. The substantial attraction exists between the C-H bonds of fucose and water. The interaction energy calculated for the fucose-water complex at the MP2/aug-cc-pVTZ level is -2.55 kcal/mol. The CH/ O interactions in the fucose-water complex are significantly larger than those in the cyclohexane-water complex (-1.13 kcal/mol), which shows that the oxygen atoms of fucose enhance the CH/O interactions. The electrostatic and dispersion interactions are responsible for the attraction in the CH/O interactions in the fucose-water complex, while the electrostatic contributions to the attraction in the CH/O interactions in the cyclohexane-water complex is small. The DFT-SAPT calculations also show that the electrostatic interactions are responsible for the larger attraction in the fucose-water complex. These results suggest that the nature of the CH/O interactions between carbohydrate and water is significantly different from that of the CH/O interactions between saturated hydrocarbon and water.

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A Simple Model System for the Study of Carbohydrate−Aromatic Interactions

Cited by 101 publications

References 58 publications

Progress in biomimetic carbohydrate recognition

Progress in biomimetic carbohydrate recognition

Stacking Interactions between Carbohydrate and Protein Quantified by Combination of Theoretical and Experimental Methods

Magnitude of CH/O interactions between carbohydrate and water

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