Molecular Simulation of Sucrose Solutions near the Glass Transition Temperature

Abstract

The physical properties of aqueous sucrose near the glass transition temperature have been studied using Monte Carlo and molecular dynamics simulations. The sucrose solutions ranged in concentration from 6 to 100 wt% and in temperature from 300 to 600 K. For concentrated solutions (≥ 80 wt%), a parallel tempering Monte Carlo algorithm was implemented to circumvent the slow system dynamics and improve sampling of configuration space. Parallel-tempered density calculations agree more closely with experimental data than conventional NPT results. Our simulations indicate that aqueous sucrose retains two intramolecular hydrogen bonds even in dilute solutions. The two hydrogen bonds detected in crystalline sucrose were also observed in the sucrose solutions of 50 wt% sucrose and greater. The hydration number was calculated for sucrose and compared with that for trehalose. Sucrose is less hydrated than trehalose for all concentrations studied. Using parallel-tempered NPT density results, molecular dynamics simulations were utilized to estimate the diffusion of water near the glass transition for concentrated sugar solutions. Diffusion coefficients in aqueous sucrose appear to be a factor of 2 greater than those in trehalose solutions.