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Hemoperfusion is the most effective detoxification approach, and its efficacy critically depends on the adsorbent system. However, most developed adsorbents exhibit poor hemocompatibility, posing risks of coagulation and bacterial infection. Herein, we report a facile and highly biocompatible strategy to fabricate bioactive superstructures for blood purification, enabling toxin removal. The formation of the bioactive superstructures is mediated by the assembly of polydopamine\/Zn\n                    <jats:sup>II<\/jats:sup>\n                    networks on natural polymer templates, followed by surface modification with human serum albumin. The obtained superstructures enable rapid bilirubin clearance owing to the synergistic effects of metal coordination and polyphenol\u2010mediated noncovalent interactions (hydrogen bonding and hydrophobic and electrostatic interactions). Furthermore, these bioactive superstructures exhibit excellent antibacterial efficacy, achieving &gt; 99.9% killing efficiency of both\n                    <jats:italic>Escherichia coli<\/jats:italic>\n                    and\n                    <jats:italic>Staphylococcus aureus<\/jats:italic>\n                    , while enhancing anticoagulant performance by 2.6\u2010fold (compared to the control) through inhibition of platelet adhesion\/activation and modulation of the intrinsic coagulation pathway. This work expands our understanding of metal\u2013phenolic\u2010mediated superstructure assembly. Furthermore, the efficient toxin removal, antibacterial protection, and anticoagulant activity of the developed bioactive superstructures are expected to underpin the rational design of blood\u2010contacting materials based on metal\u2013phenolic complexation.\n                  <\/jats:p>","DOI":"10.1002\/anie.2081750","type":"journal-article","created":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T13:01:23Z","timestamp":1785934883000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Assembly of Bioactive Superstructures via Metal\u2013Phenolic Complexation for Blood Purification"],"prefix":"10.1002","volume":"65","author":[{"given":"Po","family":"Wang","sequence":"first","affiliation":[{"name":"School of Chemical Engineering Sichuan University  Chengdu Sichuan P. R. China"},{"name":"Department of Chemical Engineering The University of Melbourne  Parkville Victoria Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0950-1923","authenticated-orcid":false,"given":"Jingqu","family":"Chen","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering The University of Melbourne  Parkville Victoria Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Siying","family":"Chen","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Sichuan University  Chengdu Sichuan P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Binsha","family":"Peng","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Sichuan University  Chengdu Sichuan P. R. 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China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1086-338X","authenticated-orcid":false,"given":"Xiaojie","family":"Ju","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Sichuan University  Chengdu Sichuan P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wei","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Sichuan University  Chengdu Sichuan P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6073-7632","authenticated-orcid":false,"given":"Dawei","family":"Pan","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Sichuan University  Chengdu Sichuan P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2676-6325","authenticated-orcid":false,"given":"Liangyin","family":"Chu","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Sichuan University  Chengdu Sichuan P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0197-497X","authenticated-orcid":false,"given":"Frank","family":"Caruso","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering The University of Melbourne  Parkville Victoria Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6898-5908","authenticated-orcid":false,"given":"Zhuang","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Sichuan University  Chengdu Sichuan P. R. 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