Accelerated Mechanochemistry in Helical Polymers

Polymer chains, if long enough, are known to undergo bond scission when mechanically stressed. While the mechanochemical response of random coils is well understood, biopolymers and some key synthetic chains adopt well‐defined secondary structures such as helices. To understand covalent mechanochemistry in such structures, poly(γ‐benzyl glutamates) are prepared while regulating the feed‐monomer chirality, producing chains with similar molecular weights and backbone chemistry but different helicities. Such chains are stressed in solution and their mechanochemistry rates compared by following molecular weight change and using a rhodamine mechanochromophore. Results reveal that while helicity itself is not affected by the covalent bond scissions, chains with higher helicity undergo faster mechanochemistry. Considering that the polymers tested differ only in conformation, these results indicate that helix‐induced chain rigidity improves the efficiency of mechanical energy transduction.