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.