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Facile synthesis of multiblock copolymers containing sequence‐controlled peptides and well‐defined vinyl polymers via nitroxide‐mediated polymerization

Precisely incorporating a wide range of structural and functional multiblocks along the polymer backbone is a significant challenge in polymer chemistry and offers promising opportunities to design highly ordered materials, including controlled polymer folding. Herein we report a facile and versatile strategy for preparing functional multiblock copolymers composed of sequential peptides and well‐defined vinyl polymers with a narrow polydispersity. We develop cyclic oligopeptides containing an alkoxyamine bond in the framework. Using this type of cyclic initiator, peptide‐containing multiblock copolymers are successfully synthesized by nitroxide‐mediated polymerization of styrene. To demonstrate the versatility of this method, radical (co)polymerizations were carried out for different monomers (p‐chlorostyrene, 4‐vinylpyridine, and styrene/acrylonitrile) and by three different cyclic peptide initiators with specific amino acid sequences. The resultant multiblock copolymer is foldable via intramolecular interactions between peptide blocks. We believe that this approach will bring a significant advance in the field of controlled polymer synthesis for complex structures as well as single chain foldings.

Authors:   Shin-nosuke Nishimura, Nobuyuki Higashi, Tomoyuki Koga
Journal:   Chemistry - A European Journal
Year:   2017
Pages:   n/a
DOI:   10.1002/chem.201703655
Publication date:   10-Aug-2017
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