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However, enzymatic mechanisms underpinning Cu(II) bioreduction were unclear. Here, the oxidation of hydrogen as electron donor was essential for Cu(II) bioreduction by\n                    <jats:italic>S. oneidensis<\/jats:italic>\n                    and hydrogenase deletion mutants were used to demonstrate the critical role of the periplasmic [NiFe] hydrogenase, HyaB. Wild type (WT) cultured cells coupled hydrogen oxidation to biosynthesis of Cu(0)\/Cu(I)\u2010NPs within the periplasm (identified using XRD and TEM with SAED, EDS, EELS);\n                    <jats:italic>\u0394hyaB<\/jats:italic>\n                    mutants did not produce CuNPs. Biosynthesized CuNPs were catalytically active for the cycloaddition of methyl azidoacetate and 1\u2010hexyne, confirming the potential for microbial revalorization of Cu(II)\u2010containing wastewaters, by forming catalytically active nanomaterials. Identifying HyaB, as a key mediator for Cu(II) reduction in\n                    <jats:italic>S. oneidensis<\/jats:italic>\n                    is an important first step towards\u00a0developing industrial bioprocesses for Cu(II) recovery and CuNP synthesis, offering a template for improvements using engineering biology. Interestingly,\n                    <jats:italic>c<\/jats:italic>\n                    \u2010type cytochromes, critical for reduction of other metals, were unable to fully reduce Cu(II)\n                    <jats:sub>(aq)<\/jats:sub>\n                    \u00a0in vivo despite being capable of Cu(II) reduction under in vitro conditions. In fact, Cu inhibited outer membrane cytochrome mediated reduction of Pd(II), and this\u00a0may impact bioreduction of mixed metal solutions\/effluents.\n                  <\/jats:p>","DOI":"10.1002\/smll.202500210","type":"journal-article","created":{"date-parts":[[2025,7,14]],"date-time":"2025-07-14T07:10:11Z","timestamp":1752477011000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Hydrogenase Mediated Biosynthesis of Catalytically Active Cu Nanoparticles"],"prefix":"10.1002","volume":"21","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2053-6972","authenticated-orcid":false,"given":"Natalie","family":"Byrd","sequence":"first","affiliation":[{"name":"Department of Earth and Environmental Sciences The University of Manchester  Manchester M13 9PL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2663-6918","authenticated-orcid":false,"given":"Christopher","family":"Egan Morriss","sequence":"additional","affiliation":[{"name":"Department of Earth and Environmental Sciences The University of Manchester  Manchester M13 9PL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7713-8150","authenticated-orcid":false,"given":"Joseph","family":"Parker","sequence":"additional","affiliation":[{"name":"Department of Materials University of Manchester  Oxford Road Manchester M13 9PL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rongsheng","family":"Cai","sequence":"additional","affiliation":[{"name":"Lanzhou Institute of Chemical Physics Chinese Academy of Sciences  Lanzhou 730000 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7029-3764","authenticated-orcid":false,"given":"Elliott J.","family":"Nunn","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Manchester  Manchester M13 9QQ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0764-5453","authenticated-orcid":false,"given":"Jessica H.","family":"van Wonderen","sequence":"additional","affiliation":[{"name":"School of Biological Sciences University of East Anglia  Norwich Research Park Norwich NR4 7TJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5913-7157","authenticated-orcid":false,"given":"Jennifer S.","family":"Cavet","sequence":"additional","affiliation":[{"name":"School of Biological Sciences Faculty of Biology Medicine and Health University of Manchester  Manchester M13 9QQ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5861-9269","authenticated-orcid":false,"given":"Fabio","family":"Parmeggiani","sequence":"additional","affiliation":[{"name":"Department of Chemistry Materials and Chemical Engineering \u201cG. Natta\u201d Politecnico di Milano  Milan 20131 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1438-4116","authenticated-orcid":false,"given":"Richard L.","family":"Kimber","sequence":"additional","affiliation":[{"name":"Department of Earth and Environmental Sciences The University of Manchester  Manchester M13 9PL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9250-7770","authenticated-orcid":false,"given":"Jeffrey A.","family":"Gralnick","sequence":"additional","affiliation":[{"name":"Department of Plant and Microbial Biology University of Minnesota\u2010Twin Cities  St. Paul MN 55108 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas A.","family":"Clarke","sequence":"additional","affiliation":[{"name":"School of Biological Sciences University of East Anglia  Norwich Research Park Norwich NR4 7TJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5509-6706","authenticated-orcid":false,"given":"Sarah J.","family":"Haigh","sequence":"additional","affiliation":[{"name":"Department of Materials University of Manchester  Oxford Road Manchester M13 9PL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0719-0498","authenticated-orcid":false,"given":"Jonathan R.","family":"Lloyd","sequence":"additional","affiliation":[{"name":"Department of Earth and Environmental Sciences The University of Manchester  Manchester M13 9PL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,7,14]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1371\/journal.pbio.0040268"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1128\/AEM.02463-10"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1128\/AEM.00747-07"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3ra44143a"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1462-2920.2007.01438.x"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1472-4669.2008.00146.x"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-319-18570-5_2"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.3389\/fcimb.2013.00073"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/smll.201703145"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jclepro.2019.118978"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.resconrec.2020.104861"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr300527g"},{"key":"e_1_2_8_13_1","unstructured":"B.Forrest in WTW Mining Risk Review Vol. https:\/\/www.wtwco.com\/en\u2010gb\/insights\/2023\/05\/copper\u2010the\u2010core\u2010of\u2010the\u2010green\u2010revolution(accessed: May 2023)."},{"key":"e_1_2_8_14_1","unstructured":"Pickens N. 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