Biomimetic radical polymerization via cooperative assembly of segregating templates

Segregation and templating approaches have been honed by billions of years of evolution to direct many complex biological processes. Nature uses segregation to improve biochemical control by organizing reactants into defined, well-regulated environments, and the transfer of genetic information is a primary function of templating. The ribosome, wherein messenger RNA is translated into polypeptides, combines both techniques to allow for ideal biopolymer syntheses. Herein is presented a biomimetic segregation/templating approach to synthetic radical polymerization. Polymerization of a nucleobase-containing vinyl monomer in the presence of a complementary block copolymer template of low molecular weight yields high molecular weight ( M w up to ~400,000 g mol −1 ), extremely low polydispersity (≤1.08) daughter polymers. Control is attained by segregation of propagating radicals in discrete micelle cores (via cooperative assembly of dynamic template polymers). Significantly reduced bimolecular termination, combined with controlled propagation along a defined number of templates, ensures unprecedented control to afford well-defined high molecular weight polymers. Nature synthesizes proteins and nucleic acids by polymerization methods that use well-regulated and segregated templates. Now, synthetic block-copolymer templates have been designed to assemble in a biomimetic fashion to segregate, and thus control, the synthetic radical polymerization of complementary nucleobase-containing vinyl monomers, to yield high-molecular-weight, low-polydispersity polymer chains.