Characterization of Methyl- and Acetyl-Ni Intermediates in Acetyl CoA Synthase Formed during Anaerobic CO 2 and CO Fixation
The Wood-Ljungdahl Pathway is a unique biological mechanism of carbon dioxide and carbon monoxide fixation proposed to operate through nickel-based organometallic intermediates. The most unusual steps in this metabolic cycle involve a complex of two distinct nickel-iron-sulfur proteins: CO dehydroge...
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| Veröffentlicht in: | Journal of the American Chemical Society 2023-06, Vol.145 (25), p.13696-13708 |
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| container_title | Journal of the American Chemical Society |
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| creator | Can, Mehmet Abernathy, Macon J Wiley, Seth Griffith, Claire James, Christopher D Xiong, Jin Guo, Yisong Hoffman, Brian M Ragsdale, Stephen W Sarangi, Ritimukta |
| description | The Wood-Ljungdahl Pathway is a unique biological mechanism of carbon dioxide and carbon monoxide fixation proposed to operate through nickel-based organometallic intermediates. The most unusual steps in this metabolic cycle involve a complex of two distinct nickel-iron-sulfur proteins: CO dehydrogenase and acetyl-CoA synthase (CODH/ACS). Here, we describe the nickel-methyl and nickel-acetyl intermediates in ACS completing the characterization of all its proposed organometallic intermediates. A single nickel site (Ni
) within the A cluster of ACS undergoes major geometric and redox changes as it transits the planar Ni
, tetrahedral Ni
-CO and planar Ni
-Me and Ni
-Ac intermediates. We propose that the Ni
intermediates equilibrate among different redox states, driven by an electrochemical-chemical (EC) coupling process, and that geometric changes in the A-cluster linked to large protein conformational changes control entry of CO and the methyl group. |
| doi_str_mv | 10.1021/jacs.3c01772 |
| format | Article |
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) within the A cluster of ACS undergoes major geometric and redox changes as it transits the planar Ni
, tetrahedral Ni
-CO and planar Ni
-Me and Ni
-Ac intermediates. We propose that the Ni
intermediates equilibrate among different redox states, driven by an electrochemical-chemical (EC) coupling process, and that geometric changes in the A-cluster linked to large protein conformational changes control entry of CO and the methyl group.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.3c01772</identifier><identifier>PMID: 37306669</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Acetyl Coenzyme A - chemistry ; Aldehyde Oxidoreductases - metabolism ; Anaerobiosis ; Carbon Dioxide - metabolism ; Carbon Monoxide - chemistry ; Iron-Sulfur Proteins - chemistry ; Nickel - chemistry ; Nitric Oxide Synthase - metabolism</subject><ispartof>Journal of the American Chemical Society, 2023-06, Vol.145 (25), p.13696-13708</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1309-a5358c53719c1140440af07a83f6f17043d70a908ee1de2dba4a6b3fc5eea2783</citedby><cites>FETCH-LOGICAL-c1309-a5358c53719c1140440af07a83f6f17043d70a908ee1de2dba4a6b3fc5eea2783</cites><orcidid>0000-0002-0455-2086 ; 0000-0002-4132-3565 ; 0000-0003-3938-8906 ; 0000-0002-2447-5153 ; 0000-0002-3100-0746 ; 0000-0002-2764-2279 ; 0000-0002-5960-8040 ; 0000-0001-7443-0554 ; 0000-0002-6207-6380 ; 0000000241323565 ; 0000000227642279 ; 0000000262076380 ; 0000000259608040 ; 0000000204552086 ; 0000000339388906 ; 0000000224475153 ; 0000000174430554 ; 0000000231000746</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,2752,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37306669$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/1985558$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Can, Mehmet</creatorcontrib><creatorcontrib>Abernathy, Macon J</creatorcontrib><creatorcontrib>Wiley, Seth</creatorcontrib><creatorcontrib>Griffith, Claire</creatorcontrib><creatorcontrib>James, Christopher D</creatorcontrib><creatorcontrib>Xiong, Jin</creatorcontrib><creatorcontrib>Guo, Yisong</creatorcontrib><creatorcontrib>Hoffman, Brian M</creatorcontrib><creatorcontrib>Ragsdale, Stephen W</creatorcontrib><creatorcontrib>Sarangi, Ritimukta</creatorcontrib><title>Characterization of Methyl- and Acetyl-Ni Intermediates in Acetyl CoA Synthase Formed during Anaerobic CO 2 and CO Fixation</title><title>Journal of the American Chemical Society</title><addtitle>J Am Chem Soc</addtitle><description>The Wood-Ljungdahl Pathway is a unique biological mechanism of carbon dioxide and carbon monoxide fixation proposed to operate through nickel-based organometallic intermediates. The most unusual steps in this metabolic cycle involve a complex of two distinct nickel-iron-sulfur proteins: CO dehydrogenase and acetyl-CoA synthase (CODH/ACS). Here, we describe the nickel-methyl and nickel-acetyl intermediates in ACS completing the characterization of all its proposed organometallic intermediates. A single nickel site (Ni
) within the A cluster of ACS undergoes major geometric and redox changes as it transits the planar Ni
, tetrahedral Ni
-CO and planar Ni
-Me and Ni
-Ac intermediates. We propose that the Ni
intermediates equilibrate among different redox states, driven by an electrochemical-chemical (EC) coupling process, and that geometric changes in the A-cluster linked to large protein conformational changes control entry of CO and the methyl group.</description><subject>Acetyl Coenzyme A - chemistry</subject><subject>Aldehyde Oxidoreductases - metabolism</subject><subject>Anaerobiosis</subject><subject>Carbon Dioxide - metabolism</subject><subject>Carbon Monoxide - chemistry</subject><subject>Iron-Sulfur Proteins - chemistry</subject><subject>Nickel - chemistry</subject><subject>Nitric Oxide Synthase - metabolism</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNo9kE1PwzAMhiMEYmNw44wiznTko2naY1UxmDTYAThXbprSTFs6JUFi8Odpt8HJr-VHtvwgdE3JlBJG71eg_JQrQqVkJ2hMBSORoCw5RWNCCItkmvARuvB-1bcxS-k5GnHJSZIk2Rj9FC04UEE78w3BdBZ3DX7Wod2tIwy2xrnSoc8vBs9tT210bSBoj409jnDR5fh1Z0MLXuNZNyC4_nTGfuDcgnZdZRQulpjt9_VhZr72py7RWQNrr6-OdYLeZw9vxVO0WD7Oi3wRKcpJFoHgIlWCS5opSmMSxwQaIiHlTdJQSWJeSwIZSbWmtWZ1BTEkFW-U0BqYTPkE3R72dj6Y0isTtGpVZ61WoaRZKoQYoLsDpFznvdNNuXVmA25XUlIOostBdHkU3eM3B3z7WfUP_8N_ZvkvCdF4xA</recordid><startdate>20230628</startdate><enddate>20230628</enddate><creator>Can, Mehmet</creator><creator>Abernathy, Macon J</creator><creator>Wiley, Seth</creator><creator>Griffith, Claire</creator><creator>James, Christopher D</creator><creator>Xiong, Jin</creator><creator>Guo, Yisong</creator><creator>Hoffman, Brian M</creator><creator>Ragsdale, Stephen W</creator><creator>Sarangi, Ritimukta</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0002-0455-2086</orcidid><orcidid>https://orcid.org/0000-0002-4132-3565</orcidid><orcidid>https://orcid.org/0000-0003-3938-8906</orcidid><orcidid>https://orcid.org/0000-0002-2447-5153</orcidid><orcidid>https://orcid.org/0000-0002-3100-0746</orcidid><orcidid>https://orcid.org/0000-0002-2764-2279</orcidid><orcidid>https://orcid.org/0000-0002-5960-8040</orcidid><orcidid>https://orcid.org/0000-0001-7443-0554</orcidid><orcidid>https://orcid.org/0000-0002-6207-6380</orcidid><orcidid>https://orcid.org/0000000241323565</orcidid><orcidid>https://orcid.org/0000000227642279</orcidid><orcidid>https://orcid.org/0000000262076380</orcidid><orcidid>https://orcid.org/0000000259608040</orcidid><orcidid>https://orcid.org/0000000204552086</orcidid><orcidid>https://orcid.org/0000000339388906</orcidid><orcidid>https://orcid.org/0000000224475153</orcidid><orcidid>https://orcid.org/0000000174430554</orcidid><orcidid>https://orcid.org/0000000231000746</orcidid></search><sort><creationdate>20230628</creationdate><title>Characterization of Methyl- and Acetyl-Ni Intermediates in Acetyl CoA Synthase Formed during Anaerobic CO 2 and CO Fixation</title><author>Can, Mehmet ; Abernathy, Macon J ; Wiley, Seth ; Griffith, Claire ; James, Christopher D ; Xiong, Jin ; Guo, Yisong ; Hoffman, Brian M ; Ragsdale, Stephen W ; Sarangi, Ritimukta</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1309-a5358c53719c1140440af07a83f6f17043d70a908ee1de2dba4a6b3fc5eea2783</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Acetyl Coenzyme A - chemistry</topic><topic>Aldehyde Oxidoreductases - metabolism</topic><topic>Anaerobiosis</topic><topic>Carbon Dioxide - metabolism</topic><topic>Carbon Monoxide - chemistry</topic><topic>Iron-Sulfur Proteins - chemistry</topic><topic>Nickel - chemistry</topic><topic>Nitric Oxide Synthase - metabolism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Can, Mehmet</creatorcontrib><creatorcontrib>Abernathy, Macon J</creatorcontrib><creatorcontrib>Wiley, Seth</creatorcontrib><creatorcontrib>Griffith, Claire</creatorcontrib><creatorcontrib>James, Christopher D</creatorcontrib><creatorcontrib>Xiong, Jin</creatorcontrib><creatorcontrib>Guo, Yisong</creatorcontrib><creatorcontrib>Hoffman, Brian M</creatorcontrib><creatorcontrib>Ragsdale, Stephen W</creatorcontrib><creatorcontrib>Sarangi, Ritimukta</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Can, Mehmet</au><au>Abernathy, Macon J</au><au>Wiley, Seth</au><au>Griffith, Claire</au><au>James, Christopher D</au><au>Xiong, Jin</au><au>Guo, Yisong</au><au>Hoffman, Brian M</au><au>Ragsdale, Stephen W</au><au>Sarangi, Ritimukta</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Characterization of Methyl- and Acetyl-Ni Intermediates in Acetyl CoA Synthase Formed during Anaerobic CO 2 and CO Fixation</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J Am Chem Soc</addtitle><date>2023-06-28</date><risdate>2023</risdate><volume>145</volume><issue>25</issue><spage>13696</spage><epage>13708</epage><pages>13696-13708</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The Wood-Ljungdahl Pathway is a unique biological mechanism of carbon dioxide and carbon monoxide fixation proposed to operate through nickel-based organometallic intermediates. The most unusual steps in this metabolic cycle involve a complex of two distinct nickel-iron-sulfur proteins: CO dehydrogenase and acetyl-CoA synthase (CODH/ACS). Here, we describe the nickel-methyl and nickel-acetyl intermediates in ACS completing the characterization of all its proposed organometallic intermediates. A single nickel site (Ni
) within the A cluster of ACS undergoes major geometric and redox changes as it transits the planar Ni
, tetrahedral Ni
-CO and planar Ni
-Me and Ni
-Ac intermediates. We propose that the Ni
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| fulltext | fulltext |
| identifier | ISSN: 0002-7863 |
| ispartof | Journal of the American Chemical Society, 2023-06, Vol.145 (25), p.13696-13708 |
| issn | 0002-7863 1520-5126 |
| language | eng |
| recordid | cdi_osti_scitechconnect_1985558 |
| source | ACS Publications; MEDLINE |
| subjects | Acetyl Coenzyme A - chemistry Aldehyde Oxidoreductases - metabolism Anaerobiosis Carbon Dioxide - metabolism Carbon Monoxide - chemistry Iron-Sulfur Proteins - chemistry Nickel - chemistry Nitric Oxide Synthase - metabolism |
| title | Characterization of Methyl- and Acetyl-Ni Intermediates in Acetyl CoA Synthase Formed during Anaerobic CO 2 and CO Fixation |
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