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To address this limitation, we developed a bioorthogonal prodrug activation strategy within an SF patch via tetrazine functionalization (SF\u2010Tz). This platform enables the spatiotemporally controlled release of trans\u2010cyclooctene (TCO)\u2010caged dexamethasone (TCO\u2010Dex) via inverse electron\u2010demand Diels\u2010Alder reactions. The SF\u2010Tz platform was engineered through optimized carboxylation and tetrazine conjugation protocols, achieving high grafting density of tetrazine while preserving the native SF's mechanical strength. In vitro analyses demonstrated efficient TCO\u2010Dex activation (78.0% within 24\u00a0h), accompanied by significant suppression of pro\u2010inflammatory cytokines (TNF\u2010\n                    <jats:italic>\u03b1<\/jats:italic>\n                    : 76.0% reduction; IL\u20106: 95.0% reduction) and increase in\u00a0anti\u2010inflammatory IL\u201010 secretion (239.7% increase). Macrophage polarization assays demonstrated a 21.2% suppression of CD86+ M1 macrophages and a 13.8% promotion of CD206+ M2 macrophage, confirming their anti\u2010inflammatory efficacy through phenotypic reprogramming. In a rat abdominal wall defect model, the SF\u2010Tz patch mediated local release of Dex achieved marked reductions in inflammation, accelerated collagen deposition, and successful defect closure within 28 days. Notably, systemic toxicity markers remained within physiological ranges, validating the biocompatibility of this approach. This bioorthogonal strategy uniquely combines SF's inherent biocompatibility with programmable immunomodulation, establishing a translational platform for treating chronic wounds and complex tissue defects requiring precise inflammatory control.\n                  <\/jats:p>","DOI":"10.1002\/adhm.71275","type":"journal-article","created":{"date-parts":[[2026,5,23]],"date-time":"2026-05-23T06:21:27Z","timestamp":1779517287000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Bioorthogonally Active Silk Fibroin Patch Facilitate Immunomodulatory Prodrug Activation for Tissue Repair"],"prefix":"10.1002","volume":"15","author":[{"given":"Xinnan","family":"Xie","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yingchun","family":"Guo","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yaqin","family":"Li","sequence":"additional","affiliation":[{"name":"Department of Obstetrics and Gynecology Beijing Key Laboratory of Female Pelvic Floor Disease Research Peking University People's Hospital  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yue","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Obstetrics and Gynecology Beijing Key Laboratory of Female Pelvic Floor Disease Research Peking University People's Hospital  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiuli","family":"Sun","sequence":"additional","affiliation":[{"name":"Department of Obstetrics and 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