{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,3]],"date-time":"2026-10-03T20:58:53Z","timestamp":1791061133497,"version":"4.1.0"},"reference-count":27,"publisher":"American Association for the Advancement of Science (AAAS)","issue":"5609","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Science"],"published-print":{"date-parts":[[2003,2,14]]},"abstract":"<jats:p>\n                    NiFe-hydrogenases have an Ni-Fe site in which the iron has one CO and two CN groups as ligands. Synthesis of the CN ligands requires the activity of two hydrogenase maturation proteins: HypF and HypE. HypF is a carbamoyltransferase that transfers the carbamoyl moiety of carbamoyladenylate to the COOH-terminal cysteine of HypE and thus forms an enzyme-thiocarbamate. HypE dehydrates the\n                    <jats:italic>S<\/jats:italic>\n                    -carbamoyl moiety in an adenosine triphosphate\u2013dependent process to yield the enzyme thiocyanate. Chemical model reactions corroborate the feasibility of this unprecedented biosynthetic route and show that thiocyanates can donate CN to iron. This finding underscores a striking parallel between biochemistry and organometallic chemistry in the formation of an iron-cyano complex.\n                  <\/jats:p>","DOI":"10.1126\/science.1080972","type":"journal-article","created":{"date-parts":[[2003,2,13]],"date-time":"2003-02-13T17:06:30Z","timestamp":1045155990000},"page":"1067-1070","source":"Crossref","is-referenced-by-count":195,"title":["Taming of a Poison: Biosynthesis of the NiFe-Hydrogenase Cyanide Ligands"],"prefix":"10.1126","volume":"299","author":[{"given":"Stefanie","family":"Reissmann","sequence":"first","affiliation":[{"name":"Department Biologie I, Mikrobiologie, University of Munich, Maria-Ward-Strasse 1a, D-80638 Munich, Germany."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Elisabeth","family":"Hochleitner","sequence":"additional","affiliation":[{"name":"Max-Planck Institut fu\u0308r Biochemie, Abteilung Proteinchemie, Am Klopferspitz, D-82152 Martinsried, Germany."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haofan","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Arizona, Post Office Box 210041, Tucson, AZ 85721-0041, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Athanasios","family":"Paschos","sequence":"additional","affiliation":[{"name":"Department Biologie I, Mikrobiologie, University of Munich, Maria-Ward-Strasse 1a, D-80638 Munich, Germany."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Friedrich","family":"Lottspeich","sequence":"additional","affiliation":[{"name":"Max-Planck Institut fu\u0308r Biochemie, Abteilung Proteinchemie, Am Klopferspitz, D-82152 Martinsried, Germany."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Richard S.","family":"Glass","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Arizona, Post Office Box 210041, Tucson, AZ 85721-0041, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"August","family":"Bo\u0308ck","sequence":"additional","affiliation":[{"name":"Department Biologie I, Mikrobiologie, University of Munich, Maria-Ward-Strasse 1a, D-80638 Munich, Germany."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"221","reference":[{"key":"e_1_3_1_2_2","doi-asserted-by":"crossref","first-page":"455","DOI":"10.1016\/S0168-6445(01)00063-8","volume":"25","author":"Vignais P. 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Soc."},{"key":"e_1_3_1_15_2","unstructured":"Dehydration of citrullines to cyanamides with p -toluenesulfonyl chloride and pyridine i.e. RNHCONH 2 \u2192 RNHCN was reported in a chemical simulation of arginine biosynthesis and the urea cycle (23)."},{"key":"e_1_3_1_16_2","unstructured":"For evidence supporting the relevancy of modeling the active site of [NiFe] hydrogenase with Fp complexes see (24)."},{"key":"e_1_3_1_17_2","doi-asserted-by":"crossref","first-page":"361","DOI":"10.1016\/S0022-328X(00)82417-1","volume":"186","author":"Jungbauer A.","year":"1980","unstructured":"Jungbauer A., Behrens H., J. Organomet. Chem. 186, 361 (1980).","journal-title":"J. Organomet. Chem."},{"key":"e_1_3_1_18_2","unstructured":"Although this reaction may involve nucleophilic displacement by iron of thiolate at the cyano carbon atom an electron transfer mechanism is also possible."},{"key":"e_1_3_1_19_2","unstructured":"There are two possibilities for the origin of the CO ligands: hydrolysis of a CN ligand and transfer of a carbamoyl group to iron followed by deamination. Hydrolysis of a CN ligand is analogous to the known hydrolysis of iron isocyanides to iron carbonyl complexes (25). Deamination of carboxamido iron complexes is also known (26)."},{"key":"e_1_3_1_20_2","doi-asserted-by":"crossref","first-page":"5819","DOI":"10.1016\/S0040-4039(98)01149-6","volume":"39","author":"Simpson J. S.","year":"1998","unstructured":"Simpson J. S., Garson M. J., Tetrahedron Lett. 39, 5819 (1998).","journal-title":"Tetrahedron Lett."},{"key":"e_1_3_1_21_2","doi-asserted-by":"crossref","first-page":"4843","DOI":"10.1016\/S0040-4039(00)93475-0","volume":"32","author":"Pham A. 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Acta 2 391 (1968).","DOI":"10.1016\/S0020-1693(00)87067-X"},{"key":"e_1_3_1_28_2","unstructured":"We thank the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie for supporting the research of A.B. and the donors of the Petroleum Research Fund administered by American Chemical Society for support of this research (ACS-PRF 37202-AC3 R.S.G. and H.W.)."}],"container-title":["Science"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.science.org\/doi\/pdf\/10.1126\/science.1080972","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,1,9]],"date-time":"2024-01-09T23:27:39Z","timestamp":1704842859000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.science.org\/doi\/10.1126\/science.1080972"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2003,2,14]]},"references-count":27,"journal-issue":{"issue":"5609","published-print":{"date-parts":[[2003,2,14]]}},"alternative-id":["10.1126\/science.1080972"],"URL":"https:\/\/doi.org\/10.1126\/science.1080972","relation":{"has-review":[{"id-type":"doi","id":"10.3410\/f.1012394.185367","asserted-by":"object"}]},"ISSN":["0036-8075","1095-9203"],"issn-type":[{"value":"0036-8075","type":"print"},{"value":"1095-9203","type":"electronic"}],"subject":[],"published":{"date-parts":[[2003,2,14]]}}}