<p>Rotaxanes are a class of mechanically interlocked polymers characterized by the sliding motion of ring molecules along a linear backbone. The dynamic behavior of a ring plays a critical role in determining its material properties. In this study, molecular dynamics simulations were performed to investigate the sliding dynamics of a ring on a rod-coil copolymer in rotaxane. We find that both the mean square displacement <i>g</i><sub>3</sub>(<i>t</i>) and the diffusion coefficient <i>D</i> of the rings are influenced by the rod-to-coil length ratio <i>α</i>, the stretching degree <i>μ</i> of the coil block, and the ring size <i>N</i><sub>ring</sub>. The mean square displacement <i>g</i><sub>3</sub>(<i>t</i>) shows sub-diffusive behavior at intermediate time scales owing to the heterogeneous backbone. The diffusion coefficient exhibits nonmonotonic dependence on <i>α</i> and <i>μ. D</i> first decreased and then increased as <i>a</i> increased, indicating that the ring diffused faster on more homogeneous copolymer chains. <i>D</i> increases with <i>μ</i> under a moderate stretching degree of the coil block, but decreases under near full extension, which demonstrates that the dynamics of the ring are governed by a competition between the chain flattening and the coil block’s fluctuation. Similarly, ring size <i>N</i><sub>ring</sub> has a nonmonotonic influence on the diffusion coefficient <i>D</i>. This study provides molecular-level insights into the manipulation of sliding dynamics in rod-coil-based rotaxanes, thereby offering a theoretical basis for the design of functional slide-ring materials through topological control.</p>

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Sliding Dynamics of Ring Chain on a Rod-Coil Block Copolymer in Rotaxane

  • Si-Yi Yan,
  • Xiang-Hong Wang,
  • Ke Li,
  • Lin-Li He

摘要

Rotaxanes are a class of mechanically interlocked polymers characterized by the sliding motion of ring molecules along a linear backbone. The dynamic behavior of a ring plays a critical role in determining its material properties. In this study, molecular dynamics simulations were performed to investigate the sliding dynamics of a ring on a rod-coil copolymer in rotaxane. We find that both the mean square displacement g3(t) and the diffusion coefficient D of the rings are influenced by the rod-to-coil length ratio α, the stretching degree μ of the coil block, and the ring size Nring. The mean square displacement g3(t) shows sub-diffusive behavior at intermediate time scales owing to the heterogeneous backbone. The diffusion coefficient exhibits nonmonotonic dependence on α and μ. D first decreased and then increased as a increased, indicating that the ring diffused faster on more homogeneous copolymer chains. D increases with μ under a moderate stretching degree of the coil block, but decreases under near full extension, which demonstrates that the dynamics of the ring are governed by a competition between the chain flattening and the coil block’s fluctuation. Similarly, ring size Nring has a nonmonotonic influence on the diffusion coefficient D. This study provides molecular-level insights into the manipulation of sliding dynamics in rod-coil-based rotaxanes, thereby offering a theoretical basis for the design of functional slide-ring materials through topological control.