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To unravel the origin of NO\u2010to\u2010N<jats:sub>2<\/jats:sub>O reduction activity of non\u2010heme diiron enzymes, herein we report a strong second\u2010coordination\u2010sphere interaction between a conserved Tyr<jats:sub>197<\/jats:sub> and the key iron\u2013nitrosyl intermediate of Tm FDP (flavo\u2013diiron protein), which leads to decreased reaction barriers towards N\u2013N formation and N\u2013O cleavage in NO reduction. This finding supports the direct coupling of diiron dinitrosyl as the N\u2013N formation mode in our QM\/MM modeling, and reconciles the mechanistic controversy of external reduction between FDPs and synthetic biomimetics of the iron\u2013nitrosyls. This work highlights the application of QM\/MM <jats:sup>57<\/jats:sup>Fe M\u00f6ssbauer modeling in elucidating the structural features of not only first, but also second coordination spheres of the key transient species involved in NO\/O<jats:sub>2<\/jats:sub> activation by non\u2010heme diiron enzymes.<\/jats:p>","DOI":"10.1002\/anie.201812343","type":"journal-article","created":{"date-parts":[[2019,1,30]],"date-time":"2019-01-30T06:11:35Z","timestamp":1548828695000},"page":"3795-3799","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":52,"title":["Origin of Nitric Oxide Reduction Activity in Flavo\u2013Diiron NO Reductase: Key Roles of the Second Coordination Sphere"],"prefix":"10.1002","volume":"58","author":[{"given":"Jiarui","family":"Lu","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) CAS Key Laboratory of Photochemistry CAS Research\/Education Center for Excellence in Molecular Sciences Institute of Chemistry Chinese Academy of Sciences  Beijing 100190 China"},{"name":"Department of Chemistry Renmin University of China  Beijing 100872 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bo","family":"Bi","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) CAS Key Laboratory of Photochemistry CAS Research\/Education Center for Excellence in Molecular Sciences Institute of Chemistry Chinese Academy of Sciences  Beijing 100190 China"},{"name":"University of Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenzhen","family":"Lai","sequence":"additional","affiliation":[{"name":"Department of Chemistry Renmin University of China  Beijing 100872 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0483-8786","authenticated-orcid":false,"given":"Hui","family":"Chen","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) CAS Key Laboratory of Photochemistry CAS Research\/Education Center for Excellence in Molecular Sciences Institute of Chemistry Chinese Academy of Sciences  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2019,2,14]]},"reference":[{"key":"e_1_2_2_1_1","first-page":"109","volume":"43","author":"Moncada S.","year":"1991","journal-title":"Pharmacol. 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In QM\/MM calculations the QM region includes key residues of both the first and the second coordination sphere of the diiron site. See the Supporting Information for computational details."},{"key":"e_1_2_2_41_1","unstructured":"For results of mononitrosyls see the Supporting Information."},{"key":"e_1_2_2_42_1","unstructured":"Protein environment has very minor effect on the calculated M\u00f6ssbauer parameters (Supporting Information Table\u2005S2)."},{"key":"e_1_2_2_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp902288q"},{"key":"e_1_2_2_44_1","unstructured":"Other diiron-bound hyponitrite intermediates in theD-npathway are all kinetically less favourable in the following N\u2013O cleavage step (Supporting Information Figure\u2005S7)."},{"key":"e_1_2_2_45_1","unstructured":"Accordingly earlier transition states of N\u2013N formation (TS1) and N\u2013O cleavage (TS2) were obtained in theD-nthan inD-apathway (Supporting Information Figure\u2005S4)."},{"key":"e_1_2_2_46_1","unstructured":"Other diiron-bound hyponitrite intermediates in theD-n\u2032pathway are either much less stable or have much higher reaction barriers in the following N\u2013O cleavage step (Supporting Information Figure\u2005S10)."},{"key":"e_1_2_2_47_1","unstructured":"N\u2013O cleavage transition state is earlier inD-n\u2032pathway than inD-a\u2032pathway (Supporting Information Figure\u2005S5)."},{"key":"e_1_2_2_48_1","unstructured":"\u00a0"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b02997"},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b03292"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b11322"},{"key":"e_1_2_2_52_1","unstructured":"\u00a0"},{"key":"e_1_2_2_53_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.05.007"},{"key":"e_1_2_2_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar400256u"},{"key":"e_1_2_2_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b05549"},{"key":"e_1_2_2_56_1","unstructured":"From the FDP structures listed in ref.\u2005[6] there is only one FDP homologue (FDP fromM. thermoautotrophicum) lacking the Tyr residue near Tyr197. 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