Topology-Directed Coassembly of Linear and Cyclic Amphiphilic Diblock Copolymers: A Monte Carlo Study

The self-assembly behaviors of the mixtures composed of linear and cyclic AB diblock copolymers in A-selective solvents are investigated by means of Monte Carlo simulation. The simulation results indicate that a typical morphological transition of the aggregate from sphere to cylinder, to lamella, and then to vesicle can be achieved via solely adjusting the molar fraction of the cyclic diblock copolymers in the mixture. Furthermore, the simulation results show that under the condition that the pure cyclic and linear diblock copolymers can both form vesicles, the structure characteristics (e.g., the inner radius and hydrophobic membrane thickness of the vesicle) and the formation pathway of the vesicles formed by the mixtures can also be regulated via solely changing the molar fraction of the cyclic diblock copolymers in the mixture. It is worth noting that the inner radius of the vesicle can be considerably increased by increasing the molar fraction of the cyclic diblock copolymers in the mixture, which results in a remarkable increase in the inner capacity of the vesicle. This phenomenon has a unique significance in the field of drug delivery. Our simulation works can provide a new approach to the preparation of polymer materials with novel properties and functions.