Modular addition strategy-regulated polymerization-induced self-assembly: an in silico experiment

We propose a modular addition strategy-regulated polymerization-induced self-assembly (PISA) system to effectively control the reaction kinetics and self-assembly morphologies. We validated this strategy by performing in silico experiments on a well-established PISA system. Two categories of modular addition strategies, i.e., the multistep addition strategy and the constant rate addition strategy, were investigated. Results showed that the modular addition operation of macromolecular chain transfer agents (macro-CTAs) effectively regulated the width of the molecular weight distribution for the hydrophobic PSt block, which further led to an assembly of vesicle structures with irregular aspherical cavities. Besides, we found a new transition pathway for the formation of vesicles, which involved generation of small vesicles in the early stage followed by a gradual growth in the intermediate and late stages. In the constant rate addition strategy, with the increase in the addition rate of macro-CTA, we found that the morphology basically tended to change from a micellar structure to a vesicle structure. This study holds potential to inspire future work toward the improvement of experimental techniques in PISA-relevant systems.