Sliding Dynamics of a Small Charged Ring Chain on the Diblock Polyelectrolyte in Poly[2]catenane in the Presence of Counterions.

Abstract

In this study, we investigate the sliding dynamics of small charged ring chains along the rigid central cyclic diblock polyelectrolyte of AnBn in radial charged poly[2]catenane in the presence of counterions using molecular dynamics simulations and the Lifson-Jackson formula, and our aim is to study the effects of electrostatical interaction strength, the size of the charged small ring chain, and the rigid block length of the diblock polyelectrolyte on the sliding dynamics of a small ring chain threaded on the rigid diblock polyelectrolyte. The mean-square displacement g3(t) of a small ring chain sliding along the rigid diblock polyelectrolyte of A10B10 exhibits oscillating behavior at short time scales for the moderate electrostatical interaction strength, while for the weak or strong electrostatic interactions, it is normal subdiffusion at short time scales. For n = 1, the diffusion coefficient D of the small ring chain sliding along the rigid diblock polyelectrolyte of A1B1 decreases monotonically as the relative electrostatic interaction strength A increases from A = 0.25-4. However, for n ≠ 1, the diffusion coefficient D of the small ring chain sliding along the rigid diblock polyelectrolyte of AnBn first decreases and then increases with the increase of A, and the nonmonotonous relationship between D and A becomes more obvious for larger n. In view of the free energy potential, the sliding diffusion of a small ring chain is governed by both the width of the free energy potential well and the height of the free energy potential barrier. According to the potential of mean force (PMF) of the small ring chain sliding along the rigid diblock polyelectrolyte, we find that our results are in good agreement with the theoretical analysis using the Lifson-Jackson formula. These results may help us to understand the diffusion motion of a ring chain in radial poly[n]catenanes from a fundamental point of view and control the sliding dynamics in molecular designs.