Free energy landscape for glucose condensation and dehydration reactions in dimethyl sulfoxide and the effects of solvent

The mechanisms and free energy surfaces (FES) for the initial critical steps during proton-catalyzed glucose condensation and dehydration reactions were elucidated in dimethyl sulfoxide (DMSO) using Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations. Glucose condensation reaction is initiated by protonation of C1-OH whereas dehydration reaction is initiated by protonation of C2-OH. The mechanisms in DMSO are similar to those in aqueous solution. The DMSO molecules closest to the C1-OH or C2-OH on glucose are directly involved in the reactions and act as proton acceptors during the process. However, the energy barriers are strongly solvent dependent. Moreover, polarization from the long-range electrostatic interaction affects the mechanisms and energetics of glucose reactions. Experimental measurements conducted in various DMSO/Water mixtures also show that energy barriers are solvent dependent in agreement with our theoretical results. (C) 2014 Elsevier Ltd. All rights reserved.