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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\u20101,3,5\u2010tricarboxamide (BTA) hydrogelator is developed with synthetically addressable norbornene handles that self\u2010assembles to form a and viscoelastic hydrogel. Inspired by collagen's covalent cross\u2010linking of fibrils, the mechanical properties are reinforced by covalent intra\u2010 and interfiber cross\u2010links. At over 90% water, the hydrogels withstand up to 550% tensile strain, 90% compressive strain, and dissipated energy with recoverable hysteresis. The hydrogels are shear\u2010thinning, can be 3D bioprinted with good shape fidelity, and can be toughened via\u00a0covalent cross\u2010linking. These materials enable the bioprinting of human mesenchymal stromal cell (hMSC) spheroids and subsequent differentiation into chondrogenic tissue. Collectively, these findings highlight the power of covalent reinforcement\u00a0of supramolecular fibers, offering a strategy for the bottom\u2010up design of dynamic, yet tough, hydrogels and bioinks.<\/jats:p>","DOI":"10.1002\/adma.202301242","type":"journal-article","created":{"date-parts":[[2023,6,27]],"date-time":"2023-06-27T23:24:41Z","timestamp":1687908281000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":46,"title":["In Situ Covalent Reinforcement of a Benzene\u20101,3,5\u2010Tricarboxamide Supramolecular Polymer Enables Biomimetic, Tough, and Fibrous Hydrogels and Bioinks"],"prefix":"10.1002","volume":"35","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1895-1800","authenticated-orcid":false,"given":"Shahzad","family":"Hafeez","sequence":"first","affiliation":[{"name":"Department of Complex Tissue Regeneration MERLN Institute for Technology\u2010Inspired Regenerative Medicine Maastricht University  P.O. 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Box 616 Maastricht 6200 MD The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hans","family":"Duimel","sequence":"additional","affiliation":[{"name":"Maastricht MultiModal Molecular Imaging Institute  P.O. Box 616 Maastricht 6200 MD The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2371-4615","authenticated-orcid":false,"given":"Clemens","family":"van Blitterswijk","sequence":"additional","affiliation":[{"name":"Department of Complex Tissue Regeneration MERLN Institute for Technology\u2010Inspired Regenerative Medicine Maastricht University  P.O. 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