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Biocatalytical reduction of carbon dioxide for sustainable biofuel production
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Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis
Publication . Oliveira, Ana Rita; Mota, Cristiano; Klymanska, Kateryna; Biaso, Frederic; Romão, Maria Joao; Guigliarelli, Bruno; Pereira, Inês Cardoso; Instituto de Tecnologia Química e Biológica António Xavier (ITQB); UCIBIO - Applied Molecular Biosciences Unit; DQ - Departamento de Química; ACS - American Chemical Society
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.
Biocatalytic reduction of carbon dioxide for sustainable biofuel production
Publication . Oliveira, Ana Rita; Pereira, Inês Cardoso
"The development of sustainable processes to reduce CO2 levels is an urgent and challenging issue faced by our society. The use of CO2 as a feedstock for the production of added-value products, such as formate, represent a promising tool to mitigate CO2 emissions. This approach provides not only a mechanism to reduce harmful CO2 levels, (...)"
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Fundação para a Ciência e a Tecnologia
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COVID/BD/151766/2021