Flow chemistry controls self-assembly and cargo in Belousov-Zhabotinsky driven polymerization-induced self-assembly

Amphiphilic block-copolymer vesicles are increasingly used for medical and chemical applications, and a novel method for their transient self-assembly orchestrated by periodically generated radicals during the oscillatory Belousov-Zhabotinsky (BZ) reaction was recently developed. Here we report how combining this one pot polymerization-induced self-assembly (PISA) method with a continuously stirred tank reactor (CSTR) strategy allows for continuous and reproducible control of both the PISA process and the chemical features (e.g. the radical generation and oscillation) of the entrapped cargo. By appropriately tuning the residence time (tau), target degree of polymerization (DP) and the BZ reactants, intermediate self-assembly structures are also obtained (micelles, worms and nano-sized vesicles). Simultaneously, the chemical properties of the cargo at encapsulation are known and tunable, a key advantage over batch operation. Finally, we also show that BZ-driven polymerization in CSTR additionally supports more non-periodic dynamics such as bursting.