Facile One‐Pot Synthesis of Functional Giant Polymeric Vesicles Controlled by Oscillatory Chemistry

We introduce a novel application of an oscillatory chemical reaction to the synthesis of block copolymers. The Belousov–Zhabotinsky (B‐Z) reaction is coupled with the polymerization of an amphiphilic block copolymer. Radicals generated in the B‐Z reaction initiate the polymerization between a polyethylene glycol (PEG) macroreversible addition‐fragmentation chain‐transfer agent and butyl acrylate monomers. The attachment of a hydrophobic block on PEG leads to self‐assembly and formation of spherical micelles. The nanoscale micelles transform into submicrometer vesicles and grow to giant vesicles as a consequence of the oscillatory behavior of the B‐Z reaction. The one‐pot synthesis of an amphiphilic di‐block copolymer and retention of oscillatory behavior for the B‐Z reaction with the formation of giant vesicles bring a new insight into possible pathways for the synthesis of active functional microreactors in the range from hundreds of nanometers to tens of micrometers. Get into the swing of things: An oscillatory chemical reaction is used to synthesize self‐assembling active giant polymeric vesicles in one pot. The hydrophobic block on polyethylene glycol (PEG) undergoes self‐assembly to form vesicles. The green squiggly line represents the PEG, the red star is the chain transfer agent (CTA), the yellow diamonds are components of the Belousov‐Zhabotinsky reaction, and the purple spheres are monomer units.