Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis

Detalhes bibliográficos
Autor(a) principal: Oliveira, Ana Rita
Data de Publicação: 2022
Outros Autores: Mota, Cristiano, Klymanska, Kateryna, Biaso, Frederic, Romão, Maria Joao, Guigliarelli, Bruno, Pereira, Inês Cardoso
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10362/150943
Resumo: Funding Information: This work was also funded by the French national research agency (ANR─MOLYERE project, grant number 16-CE-29-0010-01) and supported by the computing facilities of the CRCMM, “Centre Régional de Compétences en Modélisation Moléculaire de Marseille”. The authors are grateful to the EPR facilities at the French EPR network RENARD (IR CNRS 3443, now INFRANALYTICS, FR2054) and the Aix-Marseille University EPR center. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.
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spelling Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during CatalysisBiochemistryMolecular MedicineFunding Information: This work was also funded by the French national research agency (ANR─MOLYERE project, grant number 16-CE-29-0010-01) and supported by the computing facilities of the CRCMM, “Centre Régional de Compétences en Modélisation Moléculaire de Marseille”. The authors are grateful to the EPR facilities at the French EPR network RENARD (IR CNRS 3443, now INFRANALYTICS, FR2054) and the Aix-Marseille University EPR center. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.Metal-dependent formate dehydrogenases are important enzymes due to their activity of CO2reduction to formate. The tungsten-containing FdhAB formate dehydrogenase from Desulfovibrio vulgaris Hildenborough is a good example displaying high activity, simple composition, and a notable structural and catalytic robustness. Here, we report the first spectroscopic redox characterization of FdhAB metal centers by EPR. Titration with dithionite or formate leads to reduction of three [4Fe-4S]1+clusters, and full reduction requires Ti(III)-citrate. The redox potentials of the four [4Fe-4S]1+centers range between -250 and -530 mV. Two distinct WVsignals were detected, WDVand WFV, which differ in only the g2-value. This difference can be explained by small variations in the twist angle of the two pyranopterins, as determined through DFT calculations of model compounds. The redox potential of WVI/Vwas determined to be -370 mV when reduced by dithionite and -340 mV when reduced by formate. The crystal structure of dithionite-reduced FdhAB was determined at high resolution (1.5 Å), revealing the same structural alterations as reported for the formate-reduced structure. These results corroborate a stable six-ligand W coordination in the catalytic intermediate WVstate of FdhAB.Instituto de Tecnologia Química e Biológica António Xavier (ITQB)UCIBIO - Applied Molecular Biosciences UnitDQ - Departamento de QuímicaRUNOliveira, Ana RitaMota, CristianoKlymanska, KaterynaBiaso, FredericRomão, Maria JoaoGuigliarelli, BrunoPereira, Inês Cardoso2023-03-20T22:22:17Z2022-07-152022-07-15T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article9application/pdfhttp://hdl.handle.net/10362/150943eng1554-8929PURE: 55678537https://doi.org/10.1021/acschembio.2c00336info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-03-11T05:33:21Zoai:run.unl.pt:10362/150943Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T03:54:22.355850Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
title Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
spellingShingle Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
Oliveira, Ana Rita
Biochemistry
Molecular Medicine
title_short Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
title_full Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
title_fullStr Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
title_full_unstemmed Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
title_sort Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
author Oliveira, Ana Rita
author_facet Oliveira, Ana Rita
Mota, Cristiano
Klymanska, Kateryna
Biaso, Frederic
Romão, Maria Joao
Guigliarelli, Bruno
Pereira, Inês Cardoso
author_role author
author2 Mota, Cristiano
Klymanska, Kateryna
Biaso, Frederic
Romão, Maria Joao
Guigliarelli, Bruno
Pereira, Inês Cardoso
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Instituto de Tecnologia Química e Biológica António Xavier (ITQB)
UCIBIO - Applied Molecular Biosciences Unit
DQ - Departamento de Química
RUN
dc.contributor.author.fl_str_mv Oliveira, Ana Rita
Mota, Cristiano
Klymanska, Kateryna
Biaso, Frederic
Romão, Maria Joao
Guigliarelli, Bruno
Pereira, Inês Cardoso
dc.subject.por.fl_str_mv Biochemistry
Molecular Medicine
topic Biochemistry
Molecular Medicine
description Funding Information: This work was also funded by the French national research agency (ANR─MOLYERE project, grant number 16-CE-29-0010-01) and supported by the computing facilities of the CRCMM, “Centre Régional de Compétences en Modélisation Moléculaire de Marseille”. The authors are grateful to the EPR facilities at the French EPR network RENARD (IR CNRS 3443, now INFRANALYTICS, FR2054) and the Aix-Marseille University EPR center. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.
publishDate 2022
dc.date.none.fl_str_mv 2022-07-15
2022-07-15T00:00:00Z
2023-03-20T22:22:17Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
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dc.identifier.uri.fl_str_mv http://hdl.handle.net/10362/150943
url http://hdl.handle.net/10362/150943
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 1554-8929
PURE: 55678537
https://doi.org/10.1021/acschembio.2c00336
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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instacron:RCAAP
instname_str Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
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reponame_str Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
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repository.name.fl_str_mv Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
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