Role of Intramolecular Hydrogen Bonds in the Intermolecular Hydrogen Bonding of Carbohydrates

Abstract

The cooperativity effects in hydrogen-bonded intermolecular interactions of carbohydrates are examined in this study. The nature of such effects is explored with ab initio quantum mechanical and density functional methods. Calculations are performed for complexes of 1,3-propanediol and n-propanol, which are used as model compounds to analyze hydrogen bond cooperativity in the dimerization of the sugar 1,3-diaxial diol 1,6-anhydro-3-deoxy-3-N-methylamine-β-D-glucopyranose. In addition to the influence of cooperativity in the binding energy, the magnitude of cooperativity effects is also examined from the change in key properties related to the formation of hydrogen bonds between monomers, which include bond lengths, atomic partial charges, electron density at bond critical points, and stretching frequencies. The results reported here provide a basis to discuss the relevance of cooperativity in molecular recognition of carbohydrates.

Energy decomposition in molecular complexes: Implications for the treatment of polarization in molecular simulations

“…55 It also properly reflects the polarization trends in diverse molecular complexes, like cation-p or hydrogen-bonded complexes, 13,56 and compare very well with variational methods in Monte Carlo QM/MM simulations of solvated systems. 57 Moreover, the polarization energies determined from eq.…”

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.…”

Performance of the IEF-MST solvation continuum model in the SAMPL2 blind test prediction of hydration and tautomerization free energies

“…Nevertheless, formation of a single intramolecular hydrogen-bond has a dramatic effect on the solvation properties, as the hydration free energy is reduced to around -14 kcal/mol (a further 3 kcal/mol reduction in DG hyd is predicted for a conformation containing two intramolecular hydrogen-bonds). Clearly, adoption of a single structure for a flexible compound such as glycerol cannot be representative of the conformational distribution in aqueous solution and can therefore lead to a large error in the estimated hydration free energy, as one should expect a delicate equilibrium between different conformations due to the balance between intramolecular and intermolecular hydrogen bonds [28][29][30].…”