Modular addition strategy-regulated polymerization-induced self-assembly: an <i>in silico</i> 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 <i>in silico</i> experiments on a well-established PISA system. Two categories of modular addition strategies, <i>i.e.</i>, 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.