A theoretical study of glucose mutarotation in aqueous solution.
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.
Silva
Alexander M
AM
Departamento de Química, Universidade Federal Rural do Rio de Janeiro, BR 465 km 7, Seropédica, RJ 23890-000, Brazil.
da Silva
Edilson C
EC
da Silva
Clarissa O
CO
D005947:Glucose / Q000737:chemistry*; D007536:Isomerism; D007700:Kinetics; D008958:Models, Molecular; D008962:Models, Theoretical; D015394:Molecular Structure; D011522:Protons; D012996:Solutions / Q000737:chemistry; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D011522:Protons; D012996:Solutions; D014867:Water; D005947:Glucose