{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,26]],"date-time":"2026-08-26T18:14:28Z","timestamp":1787768068155,"version":"build-2784847793"},"reference-count":29,"publisher":"Wiley","issue":"19","license":[{"start":{"date-parts":[[2004,8,17]],"date-time":"2004-08-17T00:00:00Z","timestamp":1092700800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2004,10,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The first electrochemical and infra\u2010red data on the binding of cyanide to the isolated iron\u2013molybdenum cofactor of nitrogenase, FeMoco, is described. It is shown that cyanide stabilises a hitherto unrecognised, low\u2010spin, EPR\u2010active (<jats:italic>S<\/jats:italic>=<jats:styled-content>${{ 1\/2 }}$<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-ueqn-1.gif\" xlink:title=\"equation image\"\/><\/jats:styled-content>), superoxidised form of FeMoco, and we provide the first evidence that carbon monoxide and cyanide bind synergically to the oxidised and semireduced states of the isolated cofactor, states which are unreactive to carbon monoxide alone.<\/jats:p>","DOI":"10.1002\/chem.200400382","type":"journal-article","created":{"date-parts":[[2004,8,17]],"date-time":"2004-08-17T06:12:11Z","timestamp":1092723131000},"page":"4770-4776","source":"Crossref","is-referenced-by-count":24,"title":["Synergic Binding of Carbon Monoxide and Cyanide to the FeMo Cofactor of Nitrogenase: Relic Chemistry of an Ancient Enzyme?"],"prefix":"10.1002","volume":"10","author":[{"given":"Christopher J.","family":"Pickett","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kylie A.","family":"Vincent","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Saad K.","family":"Ibrahim","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carol A.","family":"Gormal","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Barry E.","family":"Smith","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shirley A.","family":"Fairhurst","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stephen P.","family":"Best","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2004,9,22]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1038\/385126a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0969-2126(99)80005-7"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr950055x"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/a901608b"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1073877"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200390033"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi00261a031"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1007\/s002390010061"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/a902371b"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic030108q"},{"key":"e_1_2_6_11_2","doi-asserted-by":"crossref","first-page":"15\u2009967","DOI":"10.1016\/S0021-9258(18)71574-3","volume":"264","author":"Conradson S. D.","year":"1989","journal-title":"J. Biol. Chem."},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00085a022"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1042\/bj2970373"},{"key":"e_1_2_6_14_2","unstructured":"Redox levels of the cofactor successively more reduced than FeMocooxare labelled semireduced (FeMocosemired) reduced (FeMocored) and superreduced (FeMocosuperred) respectively; a more oxidised level is labelled superoxidised (FeMocosuperox)."},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00305a007"},{"key":"e_1_2_6_16_2","unstructured":"All potentials are directly referenced to the saturated calomel reference electrode (SCE) in the NMF electrolyte;E(NHE)=E(SCE)+0.241 V (298 K)."},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)00155-6"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1042\/bj2230783"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39850000323"},{"key":"e_1_2_6_20_2","first-page":"105","volume-title":"Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B","author":"Nakamoto K.","year":"1997"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470166468.ch4"},{"key":"e_1_2_6_22_2","unstructured":"In contrast to the sharp response observed for the FeMoco(SPh)ox\/semiredcouple processIis broadened in the absence of thiophenolate probably due to redox\u2010linked isomerism at the terminal Fe site as discussed previously see reference [15]."},{"key":"e_1_2_6_23_2","unstructured":"Preliminary spectroelectrochemical experiments were conducted in which the potential was stepped out to more negative values so as to access further reduced levels of the cofactor in the presence of CO and CN\u2212. Under these conditions the spectra resembled those obtained for the cofactor under CO alone (see reference [6]). This suggests that cyanide may dissociate from the cofactor at these redox levels."},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00041a038"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.274.6.3331"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/a906391i"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0045-6535(02)00624-0"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi00450a023"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-0728(02)01176-2"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200400382","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200400382","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T12:02:50Z","timestamp":1760270570000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200400382"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2004,9,22]]},"references-count":29,"journal-issue":{"issue":"19","published-print":{"date-parts":[[2004,10,4]]}},"alternative-id":["10.1002\/chem.200400382"],"URL":"https:\/\/doi.org\/10.1002\/chem.200400382","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2004,9,22]]}}}