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While the biotechnological process using\n                    <jats:italic>Clostridium<\/jats:italic>\n                    <jats:italic>autoethanogenum<\/jats:italic>\n                    to transform syngas (H\n                    <jats:sub>2<\/jats:sub>\n                    , CO\n                    <jats:sub>2<\/jats:sub>\n                    and CO) is blooming, scientific debates remain on the ethanol biosynthesis pathway. Here, we experimentally validated that ethanol production is initiated through a tungsten-dependent aldehyde:ferredoxin oxidoreductase (AFOR), which reduces acetate to acetaldehyde. The reaction, thermodynamically unfavorable under standard conditions, has been considered by many as unsuitable in vivo but is rather approved by metabolic modeling. To answer this riddle, we demonstrated that the thermodynamic coupling of CO oxidation and ethanol synthesis allows acetate reduction. The experiments, performed with native CO dehydrogenase and AFOR, highlighted the key role of ferredoxin in stimulating the activity of both metalloenzymes and electron shuttling. The crystal structure of holo AFOR, refined to 1.59-\u00c5 resolution, and its biochemical characterization provide new insights into the cofactor chemistry and the specificities of this enzyme, fundamental to sustainable biofuel production.\n                  <\/jats:p>","DOI":"10.1038\/s41589-025-02055-3","type":"journal-article","created":{"date-parts":[[2025,10,29]],"date-time":"2025-10-29T10:52:10Z","timestamp":1761735130000},"page":"28-36","update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Carbon-monoxide-driven bioethanol production operates through a tungsten-dependent catalyst"],"prefix":"10.1038","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4389-5786","authenticated-orcid":false,"given":"Olivier N.","family":"Lemaire","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6208-1983","authenticated-orcid":false,"given":"M\u00e9lissa","family":"Belhamri","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-6157-4442","authenticated-orcid":false,"given":"Anna","family":"Shevchenko","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3382-8969","authenticated-orcid":false,"given":"Tristan","family":"Wagner","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2025,10,29]]},"reference":[{"key":"2055_CR1","doi-asserted-by":"publisher","first-page":"345","DOI":"10.1007\/BF00303591","volume":"161","author":"J Abrini","year":"1994","unstructured":"Abrini, J., Naveau, H. & Nyns, E.-J. Clostridium autoethanogenum, sp. nov., an anaerobic bacterium that produces ethanol from carbon monoxide. Arch. Microbiol. 161, 345\u2013351 (1994).","journal-title":"Arch. Microbiol."},{"key":"2055_CR2","doi-asserted-by":"publisher","first-page":"00427","DOI":"10.1128\/mBio.00427-16","volume":"7","author":"F Liew","year":"2016","unstructured":"Liew, F. et al. Insights into CO2 fixation pathway of Clostridium autoethanogenum by targeted mutagenesis. mBio 7, 00427\u201300416 (2016).","journal-title":"mBio"},{"key":"2055_CR3","doi-asserted-by":"publisher","first-page":"3020","DOI":"10.1039\/C5GC02708J","volume":"18","author":"E Marcellin","year":"2016","unstructured":"Marcellin, E. et al. Low carbon fuels and commodity chemicals from waste gases\u2014systematic approach to understand energy metabolism in a model acetogen. Green. Chem. 18, 3020\u20133028 (2016).","journal-title":"Green. 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