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Here, a \u03b2-ketoester-functionalized keto-enamine covalent organic framework (COF) is developed as a structurally defined support for arginine-directed immobilization of unspecific peroxygenase (UPO). The crystalline periodicity and post-synthetic addressability of the COF lattice enable precise placement of anchoring groups at the enzyme\u2212support interface. The grafted \u03b2-ketoester groups react with surface arginine residues under mild aqueous conditions, forming a robust covalent linkage without external activating agents or toxic cross-linkers. Compared with physical adsorption and lysine-directed epoxy coupling, the arginine-directed strategy offers higher enzyme loading, reduced leaching, and improved reusability, while raising the catalytic efficiency (kcat\/KM) toward ABTS oxidation 1.8-fold. Spectroscopic and molecular dynamics analyses indicate that arginine-directed anchoring rigidifies the enzyme and biases the heme channel toward a more open average geometry, offering a structural rationale for the enhanced turnover. The immobilized UPO also shows improved productivity in representative hydroxylation, sulfoxidation, and halogenation reactions. These results establish the identity of the anchoring residue as a tunable interfacial design parameter for COF-supported biocatalytic materials.<\/jats:p>","DOI":"10.1021\/acsami.6c14068","type":"journal-article","created":{"date-parts":[[2026,9,12]],"date-time":"2026-09-12T03:01:33Z","timestamp":1789182093000},"page":"51464-51474","source":"Crossref","is-referenced-by-count":1,"title":["Engineering the Enzyme\u2212Support Interface: Arginine-Directed Anchoring of Peroxygenase on a \u03b2-Ketoester Covalent Organic Framework"],"prefix":"10.1021","volume":"18","author":[{"given":"Wanzheng","family":"Wu","sequence":"first","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510641"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yikang","family":"Lu","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510641"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6036-4058","authenticated-orcid":true,"given":"Aitao","family":"Li","sequence":"additional","affiliation":[{"name":"Hubei University , , #368 Youyi Road , ,","place":["Wuhan, China, 430062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuxia","family":"Pang","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510641"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3941-7287","authenticated-orcid":true,"given":"Hongming","family":"Lou","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510641"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xueqing","family":"Qiu","sequence":"additional","affiliation":[{"name":"Guangdong University of Technology , , ,","place":["Guangzhou, China, 510006"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6721-536X","authenticated-orcid":true,"given":"Zhixian","family":"Li","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510641"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,11]]},"reference":[{"issue":"2","key":"2026102013064614500_cit1","doi-asserted-by":"publisher","first-page":"798","DOI":"10.1002\/anie.201507881","article-title":"Peroxygenase-Catalyzed Oxyfunctionalization Reactions Promoted by the Complete Oxidation of Methanol","volume":"55","author":"Ni","year":"2016","journal-title":"Angew. 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