The identification of a unique set of advanced materials that can bear extraordinary loads for use in bone and tooth repair will inevitably unlock unlimited opportunities for clinical use. Herein, the design of high-performance thermosets is reported based on triazine-trione (TATO) monomers using light-initiated thiol-yne coupling (TYC) chemistry as a polymerization strategy. In comparison to traditional thiol-ene coupling (TEC) systems, TYC chemistry has yielded highly dense networks with unprecedented mechanical properties. The most promising system notes 4.6 GPa in flexural modulus and 160 MPa in flexural strength, an increase of 84% in modulus and 191% in strength when compared to the corresponding TATO system based on TEC chemistry. Remarkably, the mechanical properties exceed those of polylactide (PLA) and challenge poly(ether ether ketone) PEEK and today's methacrylate-based dental resin composites. All the materials display excellent biocompatibility, in vitro, and are successfully: i) molded into medical devices for fracture repair, and ii) used as bone adhesive for fracture fixation and as tooth fillers with the outstanding bond strength that outperform methacrylate systems used today in dental restoration application. Collectively, a new era of advanced TYC materials is unfolded that can fulfill the preconditions as bone fixating implants and for tooth restorations.

A library of dendritic-linear-dendritic (DLD) materials comprising linear poly(ethylene glycol) and hyperbranched dendritic blocks based on 2,2-bis(hydroxymethyl) propionic acid is successfully synthesized and post-functionalized with peripheral allyl groups. Reactive DLDs with pseudo-generations of 3 to 6 (G3-G6) are isolated in large scale allowing their thorough evaluation as important components for the development of biomedical adhesives. Due to their branched nature and inherent degradable ester-bonds, promising biomaterial resins are accomplished with suitable viscosity, eliminating the excessive use of co-solvents. By utilizing benign high-energy visible light initiated thiol-ene coupling chemistry, DLDs together with tris[2-(3-mercaptopropionyloxy) ethyl] isocyanurate and surgical mesh enable the fabrication of soft tissue adhesive patches (STAPs) within a total irradiation time of 30 s. The STAPs display the ability to create good adhesion to wet soft tissue and encouraging results in cytotoxicity tests. All crosslinked materials are also found to degrade after being stored in human blood plasma and phosphate buffered saline. The proposed benign methodology coupled with the promising features of the crosslinked materials is herein envisioned as a soft tissue adhesive with properties that do not exist in currently available tissue adhesives.