The role of water in the design of glycosidic linkage flexibility

Naidoo, Kevin J.; Chen, Jeff Yu-Jen

doi:10.1080/00268970310001592692

Cited by 23 publications

(32 citation statements)

References 23 publications

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“…Previous studies have explored the competition between intra- and intermolecular hydrogen bonding in these types of disaccharide compounds using DFT and MD methods 45,46. Moreover, Serianni and coworkers observed the effects of hydrogen bonding on the preferred conformations of glycosidic linkages using NMR couplings and DFT 47.…”

Section: Resultsmentioning

confidence: 99%

Conformational Properties of Methyl β-Maltoside and Methyl α- and β-Cellobioside Disaccharides

et al. 2010

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An investigation of the conformational properties of methyl β-maltoside, methyl α-cellobioside and methyl β-cellobioside disaccharides, using NMR spectroscopy and molecular dynamics (MD) techniques, is presented. Emphasis is placed on validation of a recently presented force field for hexopyranose disaccharides followed by elucidation of the conformational properties of two different types of glycosidic linkages, α-(1→4) and β-(1→4). Both gas-phase and aqueous-phase simulations are performed to gain insight into the effect of solvent on the conformational properties. A number of transglycosidic J-coupling constants and proton-proton distances are calculated from the simulations and are used to identify the percent sampling of the three glycosidic conformations, syn, anti-φ and anti-ψ, and, in turn, describe the flexibility around the glycosidic linkage. The results show the force field to be in overall good agreement with experiment, though some very small limitations are evident. Subsequently, a thorough hydrogen bonding analysis is performed to obtain insights into the conformational properties of the disaccharides. In methyl β-maltoside competition between HO2′-O3 intramolecular hydrogen bonding and intermolecular hydrogen bonding of those groups with solvent lead to increased sampling of syn φ,ψ conformations and better agreement with NMR J-coupling constants. In methyl α and β-cellobioside, O5′-HO6 and HO2′-O3 hydrogen bonding interactions are in competition with intermolecular hydrogen bonding involving the solvent molecules. This competition leads to retention of the O5′-HO3 hydrogen bond and increased sampling of the syn region of the φ/ψ map. Moreover, glycosidic torsions are correlated to the intramolecular hydrogen bonding occurring in the molecules. The present results verify that in the β-(1→4)-linkage intramolecular hydrogen bonding in the aqueous phase is due to the decreased ability of water to successfully compete for the O5′ and HO3 hydrogen bonding moieties in contrast to that occurring between the O5′ and HO6 atoms in this α-(1→4)-linkage.

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Section: Resultsmentioning

confidence: 99%

Conformational Properties of Methyl β-Maltoside and Methyl α- and β-Cellobioside Disaccharides

et al. 2010

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“…125 These observations, along with the results of the H-bond analysis, are in line with the hypothesis that the formation of a solvent-exposed intramolecular H-bond in aqueous environment is an 'opportunistic' consequence of the proximity of two H-bonding groups in a given molecular conformation, rather than a major conformational driving force promoting this proximity. 137,48 The reasoning underlying this hypothesis is that since water is a protic solvent of high dielectric permittivity, it dramatically weakens the strength of intramolecular electrostatic interactions (such as H-bonds) and at the same time, efficiently competes against other solute groups for the formation of H-bonds with a given solute group. Note that this statement concerning the presumably weak conformational driving force associated with H-bonding 48 pertains to small molecules in an aqueous environment.…”

Section: Discussionmentioning

confidence: 99%

“…150 These observations can be easily rationalized if one assumes that the formation of a solvent-exposed intramolecular H-bond in aqueous environment is an 'opportunistic' consequence of the close proximity of two H-bonding groups in a given molecular conformation, rather than a major conformational driving force promoting this proximity. 48,137 Accepting this assumption, the most stable conformation of a disaccharide would be almost exclusively determined by stereoelectronic and steric effects (Section 3.2), while intramolecular H-bonding would play a minor role, that is, only slightly modulate the basic conformational preferences of the specific linkage. This interpretation would explain why (i) the (1?1)-linked trehaloses present no intramolecular H-bonding (no favorably positioned H-bonding groups in the dominant conformation; Fig.…”

Section: Hydrogen Bondingmentioning

confidence: 98%

Conformational properties of glucose-based disaccharides investigated using molecular dynamics simulations with local elevation umbrella sampling

Perić-Hassler

Hansen

Baron

et al. 2010

Carbohydrate Research

131

156

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“…Since the available techniques allow measuring only in a limited range of frequencies, surface elasticity measurements would all lead to the same value, namely to an elastic modulus of zero. In addition there is hardly any data that would allow us to quantify the strength of the intersurfactant H-bond network [21].…”

Section: Discussionmentioning

confidence: 99%

On the Influence of Intersurfactant H-Bonds on Foam Stability: A Study with Technical Grade Surfactants

Ranieri¹,

Preisig²

2018

Tenside Surfactants Detergents

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From the literature on the foam stability of various surfactants with C 12 alkyl chains but different head groups a clear picture emerges: Foams are more stable when hydrogen bonds can form between the head groups, i. e. when the polar head group has a hydrogen bond donor and a proton acceptor. These observations suggest that hydrogen bonds between neighbouring molecules at the surface enhance foam stability. To support this hypothesis, we carried out a systematic foaming study of two types of technical grade surfactants, one of them being capable of forming H-bonds and the other one not. As was the case for the pure surfactants we found again that more stable foams are formed when the head group is capable of forming intersurfactant H-bonds: These results will certainly affect the future design of surfactants.

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The role of water in the design of glycosidic linkage flexibility

Cited by 23 publications

References 23 publications

Conformational Properties of Methyl β-Maltoside and Methyl α- and β-Cellobioside Disaccharides

Conformational Properties of Methyl β-Maltoside and Methyl α- and β-Cellobioside Disaccharides

Conformational properties of glucose-based disaccharides investigated using molecular dynamics simulations with local elevation umbrella sampling

On the Influence of Intersurfactant H-Bonds on Foam Stability: A Study with Technical Grade Surfactants

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