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Article Abstract

A model system is introduced as a general tool to elaborate on orthogonal templation of dynamic covalent ring-opening polymerization (ODC-TROP). The tool consists of 3 helical peptides as unprecedented templates and semicarbazones as orthogonal dynamic covalent linkers. With difficult-to-control 1,2-dithiolanes, ODC-TROP on the level of short model oligomers occurs with high templation efficiency, increasing and diminishing upon helix stabilization and denaturation, respectively. Further, an anti-templated conjugate with mispositioned monomers gave reduced templation upon helix twisting. Even with the "unpolymerizable" 1,2-diselenolanes, initial studies already afford mild templation efficiency. These proof-of-principle results promise that the here introduced tool, recyclable and enabling late-stage side chain modification, will be useful to realize ODC-TROP of intractable or unknown cyclic dynamic covalent monomers for dynamer materials as well as cellular uptake and signaling applications.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9324982PMC
http://dx.doi.org/10.1002/chem.202200785DOI Listing

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