Autonomous Ex Novo Chemical Assembly with Blebbing and Division of Functional Polymer Vesicles from a “Homogeneous Mixture”

The chemical energy and radicals from an oscillating chemical reaction are used to synthesize a polymer vesicle from a homogeneous solution of monomeric units. Periodically formed radicals from the Belousov–Zhabotinsky (B–Z) reaction initiate radical polymerization between a polyethylene glycol based chain transfer agent (PEG-CTA) and hydrophilic acrylonitrile monomers in water. The growth of a hydrophobic chain on the hydrophilic PEG chain induces self-assembly of polymeric amphiphiles to form micrometer-sized vesicles entrapping an active oscillating B–Z reaction. In our experimental conditions, the different chemical environments inside and outside the vesicles contribute to enlarge the area and diameter of the resulting self-assembled vesicles and, in some cases, promote blebbing and division.