PubMed · 13809636
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E CHERASKIN, L MANSON-HING. 1960. The normal glucose-tolerance pattern.. https://doi.org/10.1016/0030-4220(60)90009-8
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A vibrational analysis using FTIR and Raman spectroscopies was carried out on aqueous glucose solutions with a wide range of solute molar fractions and temperatures. The analysis was aimed at revealing structural changes in the local hydrogen-bonding (HB) network of liquid water, correlating these with the conservative properties of biomolecules, and comparing them with those of other sugars. The results of our measurements clearly show that the action of glucose is 2-fold; on one hand, there is a linkage with free hydroxyls of water; on the other, there is a slight lessening of the ordered (tetrahedral) H-bonded assembly of bulk H(2)O. These opposite effects do not balance each other, so the average HB interaction strength decreases on increasing glucose concentration. As a result, there is a reduction in the temperature dependence of solutions structure. In our opinion, this could be related to the low bioprotective action of this carbohydrate.
In this work the mechanism of glucose mutarotation is investigated in aqueous solution considering the most likely pathways proposed from experimental work. Two mechanisms are studied. The first involves an intramolecular proton transfer as proposed by textbooks of organic chemistry, and the second uses one solvent water molecule to assist proton transfer. Both mechanisms are studied in the gas phase and in aqueous solution with the help of a polarizable continuum model, which is adopted to introduce the electrostatic nonspecific influence of bulk solvent. The structures are fully characterized through the calculation of the corresponding vibrational frequencies. The rate coefficients for each mechanism are calculated following transition-state theory in both the gas phase and in aqueous solution. Values computed for the water-assisted pathway in the continuum solvent agree best with the experimental results.