Structure and dynamics of 1,2-dimethoxyethane and 1,2-dimethoxypropane in aqueous and non-aqueous solutions: A molecular dynamics study

Herein, we report a comparative modelling study of 1,2-dimethoxyethane (DME) and 1,2-dimethoxypropane (DMP) at 298 K and 318 K in the liquid state, water mixtures, and at infinite dilution condition in water, methanol, carbon tetrachloride, and n-heptane. Both DME and DMP are united-atom models compatible with GROMOS/OPLS force fields. Calculated thermodynamic and structural properties of the pure DME and DMP liquids resulted in excellent agreement with the experimental data. In aqueous solutions, densities, diffusion coefficients, and concentration dependent conformers of DME, were in agreement with experimental data. The calculated free energy of solvation (Delta G(hyd)) at 298 K is equal to -22.1 +/- 0.8 kJ mol(-1) in good agreement with the experimental value of 20.2 kJ mol(-1). In addition, the free energy of solvation of DME in non-aqueous solvents follows the trend methanol approximate to water < carbon tetrachloride < n-heptane, consistently with the dielectric constant of the solvents. On contrary, the presence of an extra methyl group on chiral carbon makes DMP less soluble than DME in water (Delta G(hyd) = -16.0 +/- 1.1 kJ mol(-1)) but more soluble in non-polar solvents as n-heptane. Finally, for the DMP the chiral discrimination of the two enantiomers was calculated as solvation free energy difference of one DMP isomer in the solution of the other. The obtained value of Delta Delta G(RS) = -3.7 +/- 1.4 kJ mol(-1) indicates a net chiral discrimination of the two enantiomers. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3643417]