The diluted aqueous solvation of carbohydrates as inferred from molecular dynamics simulations and NMR spectroscopy

The purpose of this paper is to review our understanding of the dilute hydration (aqueous solvation) behaviour of disaccharide compounds. To this end we discuss and scrutinize the results that have been obtained for the three model disaccharides: maltose, sucrose and trehalose from experimental NMR studies and from theoretical molecular dynamics studies in explicit aqueous solutions. The focus is on the description of molecular hydration features that will influence macroscopic entities such as diffusion and relaxation: residence times of hydration waters, hydration numbers and hydration densities. The principles of molecular dynamics simulation are briefly outlined while a detailed presentation is given of the key features that characterise hydration: the solvation of the glycosidic linkage, the radial hydration of the solute, the water density anisotropy around the solute, the residential behaviour of water molecules in the periphery of the solute, and rotational and translational diffusion coefficients. With respect to the use of NMR in characterising the structure and dynamics of the hydration, the hydrodynamic theory of rotational and translational diffusion of biomolecules as well as the use of pulse field gradient spin echo experiments are briefly presented. The NMR-defined rotational diffusion coefficients (D(r)) and the experimentally determined translational diffusion (D(t)) coefficients are reported for 4% (w/w) solutions of sucrose, trehalose and maltose. These results are compared with theoretical data obtained from molecular dynamics simulations of sucrose, trehalose and maltose under identical conditions (concentration, temperature, etc.). With our present level of knowledge we can propose that although carbohydrates share a number of hydration characteristics, evidence is accumulating in support of the notion that it is not the amount or overall hydration but rather the detailed individual carbohydrate-water interaction that is likely to determine carbohydrate structure and functionality.