Insights into the solvation of glucose in water, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) and its possible implications on the conversion of glucose to platform chemicals

Cellulosic biomass derived molecules such as glucose can be converted into specific platform chemicals like 5-hydroxymethylfurfural (HMF), levulinic acid and gamma valerolactone (GVL). The solvation medium plays an important role in the selective conversion of glucose to these platform chemicals and it is shown that the addition of co-solvents increases the selectivity towards desired products and minimizes the formation of undesired condensation/polymerization products and humins. Hence, it becomes imperative to understand the implications of the solvation of glucose by co-solvents on glucose conversion reactions. In the present paper, we implement OPLS-AA force-field based molecular dynamics simulations to investigate the solvation of glucose in water, in the presence of dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF) and tetrahydrofuran (THF). The local arrangement of solvents around the glucose molecule is analyzed using 2-dimensional radial pair distribution functions and 3-dimensional volumetric maps. Additionally, lifetimes and activation free energies of hydrogen bonds between solvents and glucose and the tendency of glucose molecules to agglomerate were studied. It was observed that all the aforementioned co-solvents compete with water to be in the first solvation shell of glucose and significant amount of water is pushed to the second coordination shell. Though fewer water molecules are directly coordinated with glucose in the presence of co-solvents, they are bound strongly to it. Additionally, DMSO, THF and DMF tend to localize more around the hydrogen atom of the hydroxyl groups of selected carbon atoms of glucose. This preferential arrangement of co-solvents and water around glucose may play a role in facilitating the reaction pathway for the formation of HMF and levulinic acid and may reduce the likelihood of glucose' degradation to unwanted dehydration/rehydration products. Increasing the proportion of co-solvents also increases the hydrogen bond lifetimes between water and glucose and reduces the mobility of glucose molecules within the solvent. The reduced mobility of glucose molecules in the presence of co-solvents might be correlated to the experimentally observed reduction in the rate of formation of polymerization/condensation products and humins.