A multi-scale framework for predicting α-cyclodextrin assembly on polyethylene glycol axles.

Controlling the distribution of rings on polymer axles, such as α-cyclodextrin (αCD) on polyethylene glycol (PEG), is paramount in imparting robust mechanical properties to slide-ring gels and polyrotaxane-based networks. Previous experiments demonstrated that the functionalization of polymer ends could modulate the coverage of αCDs on PEG. To explore the design rule, we propose a multi-scale framework for predicting αCD assembly on bare and functionalized PEG. Our approach combines all-atom molecular dynamics with two-dimensional (2D) umbrella sampling to compute the free energy landscapes of threading αCDs onto PEG with ends functionalized by various moieties. Together with the predicted free energy landscapes and a lattice treatment for αCD and polymer diffusion in dilute solutions, we construct a kinetic Monte Carlo (kMC) model to predict the number and intra-chain distribution of αCDs along the polymer axle. Our model predicts the effects of chain length, concentration, and threading barrier on the supramolecular structure of end-functionalized polypseudorotaxane. With simple modifications, our approach can be extended to explore the design rule of polyrotaxane-based materials with advanced network architectures.