Carbohydrate Hydrogen-Bonding Cooperativity − Intramolecular Hydrogen Bonds and Their Cooperative Effect on Intermolecular Processes − Binding to a Hydrogen-Bond Acceptor Molecule

Abstract

The high hydroxy (OH) group content in carbohydrates makes the study of carbohydrate OH···XH and OH···X Hbond energetics fundamental to understanding of carbohydrate recognition. There is, however, a relative lack of knowledge concerning the factors that allow a carbohydrate to participate in recognition events stabilised by intermolecular H bonds. We therefore present here a systematic study on the factors that determine the formation of a well-defined intramolecular H-bonding network between carbohydrate hydroxy groups, and its cooperative or anti-cooperative influence on selected intermolecular processes mediated by H bonds. With this in mind, we first determined the H-bonding networks of a series of carbohydrate derivatives − monoalcohols, 1,2-and 1,3-diols and amidoalcohols − by 1 H NMR and FT-IR spectroscopy. The hydroxy groups of these compounds showed different abilities to form intramolecular H bonds, depending on their relative positions and configurations on

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

“…Note that this statement concerning the presumably weak conformational driving force associated with H-bonding 48 pertains to small molecules in an aqueous environment. It may not be applicable to larger systems (e.g., due to H-bonding cooperativity effects [240][241][242]196,[243][244][245][246][247][248][249][250][251][252] in extended chains or reduced local solvation in folded chains) and to other environments (e.g., crystals, fibers, solutions with non-polar solvents, or vacuum). In addition, this hypothesis does not imply that intramolecular H-bonding has no effect on the physico-chemical properties of a specific sugar, because many of these properties are actually defined by a change of environment relative to the bulk aqueous environment at high dilution.…”

Hydrogen bond coupling in sodium dihydrogen triacetate

“…For instance, carbohydrate-protein receptor interaction in molecular recognition is controlled by hydrogen bonds of O-H… O type and their couplings. This means that the intramolecular and/or intermolecular hydrogen bonds coupling (HBC) in carbohydrates can affect their reactivity toward other molecules [1]. Replacement of one or more hydrogen atoms (of the hydrogen bond) by deuterium ones reflects the coupling in multiple hydrogenbonded systems.…”

Conformation, dynamics, solvation and relative stabilities of selected β-hexopyranoses in water: a molecular dynamics study with the gromos 45A4 force field

“…This is mainly because (i) hydroxyl protons are difficult to detect via NMR spectroscopy 37,[109][110][111][112] (chemical exchange, mutual overlap, overlap with solvent signal); (ii) hydroxyl group vibrations are difficult to characterize via infrared (IR) spectroscopy 110,[113][114][115] (dual hydrogen-bond donoracceptor character, mutual overlap, overlap with solvent bands). Furthermore, X-ray crystallography provides limited reference information in the solid state, because the hydroxyl protons are invisible in these experiments (weak diffraction centers, orientational averaging).…”

“…124,132,133,135,137 Electrostatic effects: Electrostatic effects, mainly intramolecular hydrogen-bonding, are strongly sensitive to the nature and polarity of the solvent. Experimentally, intramolecular hydrogen-bonds in an aqueous environment can be detected only indirectly, for example, via NMR 37,[109][110][111][112]115,[124][125][126][138][139][140][141][142][143][144][145][146][147][148][149] or IR 110,[113][114][115]144,[149][150][151][152][153] spectroscopy. However, most studies to date have investigated model compounds (e.g., monosaccharide analogs) and only provided qualitative information on the existence or absence of a hydrogen-bond.…”

“…However, most studies to date have investigated model compounds (e.g., monosaccharide analogs) and only provided qualitative information on the existence or absence of a hydrogen-bond. Based on these studies, it appears that intramolecular hydrogen-bonds in aldohexopyranoses can be broadly classified into three groups in order of decreasing strength: 110,113,115,154 (i) six-membered hydrogenbonded 'rings' between 1,3-syn-diaxial hydroxyl groups; 101,102,110,114,121,122,125,126,141,[144][145][146][147][148]150,155,156 (ii) five-membered hydrogen-bonded 'rings' between cis-vicinal (axial-equatorial) hydroxyl groups; 121,150 and (iii) five-membered hydrogen-bonded 'rings' between transvicinal (diequatorial) hydroxyl groups. 121,150 Hydrogen-bonding interactions are strong in vacuum or in solvents of low polarity, 121,122,125,126,144,149,155 but probably represent rather weak conformational driving forces in aqueous environment.…”