Molecular Dynamics of Polyrotaxane in Solution Investigated by Quasi-Elastic Neutron Scattering and Molecular Dynamics Simulation: Sliding Motion of Rings on Polymer.

In this study, we investigated the molecular dynamics of polyrotaxane (PR), composed of α-cyclodextrins (CDs) and a poly(ethylene glycol) (PEG) axial chain, in solution by means of quasi-elastic neutron scattering (QENS) measurements and full-atomistic molecular dynamics (MD) simulations. From QENS experiments, we estimated the diffusion coefficients of CD and PEG monomers in PR, which are in quantitative agreement with those obtained by MD simulations. By analyzing the simulation results, we succeeded, for the first time, in observing and quantifying the sliding motion of CD along a PEG chain. The diffusion coefficient for the sliding motion is almost 6 times lower than that of the translational diffusion of CD in PR at room temperature. The retardation of the sliding motion is caused by the energy barrier on PEG produced by molecular interactions between CD and PEG. We propose a simple equation to describe the diffusion coefficient of the sliding dynamics in PR by combining the Einstein-Stokes diffusion model and a one-dimensional jump diffusion model. This work provides a general strategy for the molecular designs to control the sliding motion in PR.