Supramolecular cyclization of semiflexible cylindrical micelles assembled from rod-coil graft copolymers

Uniform toroidal micelles can be constructed via the supramolecular cyclization of semiflexible cylindrical micelles, but revealing the conditions under which the cyclization occurs and the mechanism underlying the cyclization remains a challenge. In this study, we performed Brownian dynamics simulations of the supramolecular cyclization of semiflexible cylindrical micelles formed by rod-coil graft copolymers to obtain the cyclization conditions and understand the cyclization mechanism. It was found that the balance of the bending energy of the polymer backbones with the self-attraction energy between the pendant groups on the polymer backbones plays an important role in the cyclization process. A theoretical model based on this balance is developed to explain the cyclization mechanism, and the conditions required for realizing the supramolecular cyclization are obtained. The proposed mechanism is supported by our experimental findings regarding the supramolecular cyclization of polypeptide cylindrical micelles. The cyclization conditions and the revealed mechanism can guide further preparation of uniform toroidal micelles from semiflexible cylindrical micelles in an end-to-end closure manner.