Water structure modification by d-(+)-glucose at different concentrations and temperatures-effect of mutarotation

Water structure modification by carbohydrates is essential both in chemistry and life processes and in particular, molecular level interaction of glucose with water is very important. With a view to developing a fundamental knowledge base, thermodynamic parameters derived from measurements of density, viscosity, and refractive index have been analyzed to investigate how d-(+)-glucose alters the structure of water at various concentrations and temperatures. The nature and extent of the interactions have been investigated using apparent molar volume, Jones–Dole constants, changes in free energy (ΔG), changes in entropy (ΔS), and changes in enthalpy (ΔH) for viscous flow. Using measurements from dynamic light scattering (DLS), the sizes of the aggregates were studied. The kinetics of mutarotation have been investigated using polarimetry and the structural effect on water during mutarotation between α-d-glucose and β-d-glucose with time has been explored by near-infrared (NIR) spectroscopy. The spectroscopic results were examined using difference spectroscopy and two-dimensional correlation spectroscopy (2DCOS). The absorption bands of water shift to a higher wavenumber irrespective of the concentration of the solution with time due to the enhancement of the cleavage of hydrogen bonding in water. At high temperatures, three bands in the region 7100–7350 cm(−1) are attributed to the first overtones of the hydrogen-bonded –O–H stretching vibration. Refractive index values indicate an increase in the density of the anomer solutions with time, suggesting an increase in free water concentration. These results provide evidence for more than one water molecule being involved in the mechanism of mutarotation and propose a concerted mechanism for proton transfer.