In Situ Covalent Reinforcement of a Benzene‐1,3,5‐Tricarboxamide Supramolecular Polymer Enables Biomimetic, Tough, and Fibrous Hydrogels and Bioinks

In natural tissues, toughness is often imparted via the combination of fibrous noncovalent self‐assembly with key covalent bond formation. This controlled combination of supramolecular and covalent interactions remains difficult to engineer, yet can provide a clear strategy for advanced biomaterials.

Here, a synthetic supramolecular/covalent strategy is investigated for creating a tough hydrogel that embodies the hierarchical fibrous architecture of the extracellular matrix (ECM). A benzene‐1,3,5‐tricarboxamide (BTA) hydrogelator is developed with synthetically addressable norbornene handles that self‐assembles to form a and viscoelastic hydrogel. Inspired by collagen's covalent cross‐linking of fibrils, the mechanical properties are reinforced by covalent intra‐ and interfiber cross‐links.