Solution self-assembly behavior of rod-alt-coil alternating copolymers via simulations

Alternating copolymers (ACPs) have shown several attractive unique characteristics in solution self-assembly due to their special alternating structure. With the introduction of rod segments, much more complexity and multifunctionality can be achieved in the self-assembly of rod-alt-coil ACPs. Herein, we have performed a simulation study on the self-assembly of rod-alt-coil ACPs in dilute solution through dissipative particle dynamics (DPD) simulations. A morphological phase diagram was constructed as a function of rod and coil length, in which diverse assemblies were found, such as bicontinuous micelles and perforated membranes. Furthermore, the alignment of rod segments in the assemblies has been disclosed in detail. And, we deeply investigated the effects of rod length, coil length and π-π interaction strength on the self-assembly morphologies and rod alignment. With the increase of rod length, a disorder-order transition was observed, and π-π interactions could facilitate the orderly alignment of rods. Besides, our simulation results showed good agreement with available experiments. Furthermore, the unique characteristics in the self-assembly of rod-alt-coil alternating copolymers were discussed; in particular we found that the alternating molecular structures of ACPs could promote the orderly alignment of rod segments. We believe that the current work can provide a solid theoretical foundation for further experimental studies.