Synthesis, Selective Decoration, and Photocrosslinking of <scp>Self‐Immolative</scp> Poly(Thioester)‐ <scp>PEG</scp> Hydrogels

Self-immolative polymers are a class of that undergo linear depolymerization the main chain, often triggered by single initial degradation event. Chain-unzipping immolation processes followed low-ceiling-temperature yield regenerated monomers, demonstrating remarkable potential these in development reversible and recyclable materials. In this work, we describe synthesis an amino-acid-derived poly(thioester) self-immolative polymer with pendent functional groups allowing for selective decoration backbone solubilizing reactive subsequent post-polymerization modification. Crosslinking norbornene-functionalized, water-soluble derivatives via thiol-ene photoclick reaction yielded mechanically robust hydrogels within 15 s light exposure. These networks were capable response to deprotonation end-capping thiol, unzipping along constituent monomers larger molecular weight crosslinker fragments. Finally, degelation rates controlled pH temperature aqueous buffers. At physiological temperature, complete approximately 20 wt% was observed after 16 h, raising buffer 10 resulted network dissolution 5 h. © 2022 Society Industrial Chemistry.