Journal
CARBOHYDRATE RESEARCH
Volume 388, Issue -, Pages 50-60Publisher
ELSEVIER SCI LTD
DOI: 10.1016/j.carres.2014.02.010
Keywords
Glucose; DMSO; Free energy surface; Condensation; Dehydration
Funding
- NSF CAREER [CBET 1137795]
- Directorate For Engineering
- Div Of Chem, Bioeng, Env, & Transp Sys [1137795] Funding Source: National Science Foundation
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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.
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