Direct Synthesis of Polymer Vesicles on the Hundred‐Nanometer‐and‐Beyond Scale Using Chemical Oscillations

• Published in: Chemistry : a European journal 2018-07, Vol.24 (42), p.10621-10624
• Main Authors: Bastakoti, Bishnu Prasad, Guragain, Sudhina, Perez‐Mercader, Juan
• Format: Article
• Language: English
• Subjects: Addition polymerization; Assembly; Belousov–Zhabotinsky reaction; Block copolymers; Chain transfer; Chemical synthesis; Chemistry; Macromolecules; Micelles; Organic chemistry; Oscillations; oscillatory chemistry; PISA; Polyethylene glycol; polymer vesicles; Polymerization; Raw materials; self-assembly; Vesicles
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201801633

The direct synthesis of block copolymer vesicles on the scale of tens to hundreds of nanometers using reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization as an effect of chemical oscillations is reported. RAFT polymerization is successfully accomplished between polyethylene glycol containing a RAFT agent (PEG‐CTA) and ethyl acrylate monomer in the presence of the Belousov–Zhabotinsky (B‐Z) reaction in oscillatory mode. The self‐assembly of poly(ethylene glycol)‐b‐poly(ethyl acrylate) unimers gives rise to spherical micelles. The self‐assembled micelles reorganize and transform to vesicles. All the chemistry of polymerization, self‐assembly and self‐organization, of macromolecules takes place in a single pot using only a few simple raw materials in aqueous solution. An amphiphilic diblock copolymer is synthesized using the Belousov–Zhabotinsky (B‐Z) reaction in its oscillatory mode as initiator. As the reaction proceeds, chain extension of the hydrophobic block leads to spontaneous formation of polymer vesicles. All the chemistry of polymerization, self‐assembly, and self‐organization of macromolecules takes place in a single pot using only a few simple raw materials in an aqueous solution (see figure).