To investigate the amphiphilicity of cellulose, a series of molecular dynamics simulations were performed with a cellulose nanocrystal and a water-octane interfacial system. Assuming that the axis of cellulose is parallel to the water-octane interface, the freedoms of motion of the nanocrystal were restricted to two, the distance from the interface and the orientation around the axis. The mean force and the mean torque on the nanocrystal were evaluated with sufficiently long simulation at each crystal configuration, and their numerical integration gave a smooth free energy surface as the potential of mean force. The cellulose sample used here was found to be much more hydrophilic than oleophilic with the free energy difference ΔFw→o=318 kcal/mol. Three adsorption states with local minimum of adsorption free energy are distinguished in the free energy surface-the direct contact type which is similar to previously reported one, the hydrophilic-surface/water/octane type where a thin water layer is sandwiched between the surface and the octane phase, and the oleophilic/water/octane type where a thin water layer also exists. Water molecules in these water layers contribute to stabilize the adsorption states by taking a special orientational order and slow self-diffusion.
Keywords: adsorption free energy; amphiphilicity; cellulose nanocrystal; confined liquid; molecular dynamics simulation; potential of mean force.