Materials that solidify in response to an initiation stimulus are currently utilized in several biomedical and surgical applications; however, their clinical adoption would be more widespread with improved physical properties and biocompatibility. One chemistry that is particularly promising is based on the thiol–ene addition reaction, a radical-mediated step-growth polymerization that is resistant to oxygen inhibition and thus is an excellent candidate for materials that polymerize upon exposure to aerobic conditions. Here, thiol–ene-based hydrogels are polymerized by exposing aqueous solutions of multi-functional thiol and allyl ether PEG monomers, in combination with enzymatic radical initiating systems, to air. An initiating system based on glucose oxidase, glucose, and Fe2+ is initially investigated where, in the presence of glucose, the glucose oxidase reduces oxygen to hydrogen peroxide which is then further reduced by Fe2+ to yield hydroxyl radicals capable of initiating thiol–ene polymerization. While this system is shown to effectively initiate polymerization after exposure to oxygen, the polymerization rate does not monotonically increase with raised Fe2+ concentration owing to inhibitory reactions that retard polymerization at higher Fe2+ concentrations. Conversely, replacing the Fe2+ with horseradish peroxidase affords an initiating system is that is not subject to the iron-mediated inhibitory reactions and enables increased polymerization rates to be attained.

Autonomously healing materials that utilize thiol−ene polymerization initiated by an environmentally borne reaction stimulus are demonstrated by puncturing trilayered panels, fabricated by sandwiching thiol−ene− trialkylborane resin formulations between solid polymer panels, with high velocity projectiles; as the reactive liquid layer flows into the entrance hole, contact with atmospheric oxygen initiates polymerization, converting the liquid into a solid plug. Using infrared spectroscopy, we find that formulated resins polymerize rapidly, forming a solid polymer within seconds of atmospheric contact. During high-velocity ballistics experiments, additional evidence for rapid polymerization is provided by high-speed video, demonstrating the immediate viscosity increase when the thiol−ene−trialkylborane resins contact atmospheric oxygen, and thermal imaging, where surface temperature measurements reveal the thiol−ene reaction exotherm, confirming polymerization begins immediately upon oxygen exposure. While other approaches for materials self-repair have utilized similar liquid-to-solid transitions, our approach permits the development of materials capable of sealing a breach within seconds, far faster than previously described methods.