Synthesis of AB Diblock Copolymers by Atom‐Transfer Radical Polymerization (ATRP) and Living Polymerization of α‐Amino Acid‐N‐Carboxyanhydrides

The synthesis of poly(methyl acrylate)-block-poly(gamma-benzyl-L-glutamate) (PMA-b-PBLG) diblock copolymers, using atom-transfer radical polymerization (ATRP) of methyl acrylate and living polymerization of gamma-benzyl-L-glutamate-N-carboxyanhydride (Glu-NCA) is described. Amido-amidate nickelacycle end groups were incorporated onto amino-terminated poly(methyl acrylates), and the resulting complexes were successfully used as macroinitiators for the growth of polypeptide segments. This method allows the controlled preparation of polypeptide-block-poly(methyl acrylate) diblock architectures with control over polypeptide chain length and without the formation of homopolypeptide contaminants.