Biopolymers such as proteins and nucleic acids are the key building blocks of life. Synthetic polymers have nevertheless revolutionized our everyday life through their robust synthetic accessibility. Combining the unmatched functionality of biopolymers with the robustness of tailorable synthetic polymers holds the promise to create materials that can be designed ad hoc for a wide array of applications. Radical polymerization is the most widely applied polymerization technique in both fundamental science and industrial polymer production. While this polymerization technique is robust and well controlled, it generally yields unfunctional all-carbon backbones. Combinations of natural polymers such as peptides, with synthetic polymers, are thus limited to tethering peptides onto the side chains or chain ends of the latter. This synthetic limitation is a critical restraint, considering that the function of biopolymers is programmed into the sequence of their main chain (i.e., primary structure). Here, we report the radical copolymerization of peptides and synthetic comonomers yielding synthetic polymers with defined peptide sequences embedded into their main chain. Key was the development of a solid-phase peptide synthesis (SPPS) approach to generate synthetic access to peptide conjugates containing allylic sulfides. Following cyclization, the obtained peptide monomers can be readily copolymerized with N,N-dimethylacrylamide (DMA)�controlled by reversible addition−fragmentation chain transfer (RAFT). Importantly, the developed synthetic strategy is compatible with all 20 standard amino acids and uses exclusively standard SPPS chemicals or chemicals accessible in one-step synthesis�prerequisite for widespread and universal application.

Incorporation of photolabile moieties into the polymer backbone holds promise to remotely‐control polymer degradation. However, suitable synthetic avenues are limited, especially for radical polymerizations. Here we report a strategy to program photodegradability into vinylic polymers by exploiting the wavelength selectivity of photocycloadditions for radical ring‐opening polymerization (rROP). Irradiation of coumarin terminated allylic sulfides with UVA light initiated intramolecular [2+2] photocycloaddition producing cyclic macromonomers. Subsequent RAFT‐mediated rROP with methyl acrylate yielded copolymers that inherited the photoreactivity of the cyclic parent monomer. Irradiation with UVB initiated efficient photocycloreversion of the coumarin dimers, causing polymer degradation within minutes under UVB light or days under sunlight exposure. Our synthetic strategy may pave the way to insert photolabile linkages into vinylic polymers, tuning degradation for specific wavelengths.

Incorporation of photolabile moieties into the polymer backbone holds promise to remotely-control polymer degradation. However, suitable synthetic avenues are limited, especially for radical polymerizations. Here we report a strategy to program photodegradability into vinylic polymers by exploiting the wavelength selectivity of photocycloadditions for radical ring-opening polymerization (rROP). Irradiation of coumarin terminated allylic sulfides with UVA light initiated intramolecular [2+2] photocycloaddition producing cyclic macromonomers. Subsequent RAFTmediated rROP with methyl acrylate yielded copolymers that inherited the photoreactivity of the cyclic parent monomer. Irradiation with UVB initiated efficient photocycloreversion of the coumarin dimers, causing polymer degradation within minutes under UVB light or days under sunlight exposure. Our synthetic strategy may pave the way to insert photolabile linkages into vinylic polymers, tuning degradation for specific wavelengths.