Neue bio-synthetische Hybridkonstrukte zur Aufklärung und Beeinflussung der Wasserstoffkatalyse in [FeFe]-Hydrogenasen
Zusammenfassung der Projektergebnisse
This project part has substantially advanced the biochemical, genetic, synthetic and spectroscopic toolbox for hydrogenase and biomimetic H-cluster research. Key outcomes include: • The characterization of the proton-coupled electron transport in [FeFe]-hydrogenases is presented as the reason for their high catalytic activity. • The discovery of novel oxygen-stable hydrogenases and the explanation of the reason for O2 stability. • New data to help us understand how the biological assembly and coordination of the diiron site of [FeFe]-hydrogenases works. • Development of artificial hydrogen-producing catalysts based on ferredoxin scaffolds. • Development of scalable, safe, and reproducible synthesis of [2FeH] mimics, including isotopically labelled variants. • Integration of novel ligand frameworks based on phosphorus and first-row metals. • Extension of artificial maturation to include Os- and Mn-based multimetallic complexes - representing a new class of functional non-native cofactors. • Identification of previously unknown hydride states in [FeFe] hydrogenases through combined biochemical and spectroscopic efforts. Together, these results provide new pathways for the mechanistic dissection of hydrogenase function. We have not only published our results in peer-reviewed journals, but have also routinely reported on our research for the public in the press. Even NRW Minister President Hendrik Wüst noticed our outstanding results in the field of hydrogen research and visited our joint research laboratory with our Japanese collaboration partners in Osaka 2023. He likewise reported publicly and enthusiastically about our innovative research (press Land NRW).
Projektbezogene Publikationen (Auswahl)
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The roles of long-range proton-coupled electron transfer in the directionality and efficiency of [FeFe]-hydrogenases. Proceedings of the National Academy of Sciences, 117(34), 20520-20529.
Lampret, Oliver; Duan, Jifu; Hofmann, Eckhard; Winkler, Martin; Armstrong, Fraser A. & Happe, Thomas
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Increasing the O2 Resistance of the [FeFe]-Hydrogenase CbA5H through Enhanced Protein Flexibility. ACS Catalysis, 13(2), 856-865.
Rutz, Andreas; Das, Chandan K.; Fasano, Andrea; Jaenecke, Jan; Yadav, Shanika; Apfel, Ulf-Peter; Engelbrecht, Vera; Fourmond, Vincent; Léger, Christophe; Schäfer, Lars V. & Happe, Thomas
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Trapping an Oxidized and Protonated Intermediate of the [FeFe]-Hydrogenase Cofactor under Mildly Reducing Conditions. Inorganic Chemistry, 61(26), 10036-10042.
Senger, Moritz; Duan, Jifu; Pavliuk, Mariia V.; Apfel, Ulf-Peter; Haumann, Michael & Stripp, Sven T.
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A Dynamic Water Channel Affects O2 Stability in [FeFe]‐Hydrogenases. ChemSusChem, 17(3).
Brocks, Claudia; Das, Chandan K.; Duan, Jifu; Yadav, Shanika; Apfel, Ulf‐Peter; Ghosh, Subhasri; Hofmann, Eckhard; Winkler, Martin; Engelbrecht, Vera; Schäfer, Lars V. & Happe, Thomas
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Cyanide Binding to [FeFe]‐Hydrogenase Stabilizes the Alternative Configuration of the Proton Transfer Pathway. Angewandte Chemie International Edition, 62(7).
Duan, Jifu; Hemschemeier, Anja; Burr, David J.; Stripp, Sven T.; Hofmann, Eckhard & Happe, Thomas
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A Conserved Binding Pocket in HydF is Essential for Biological Assembly and Coordination of the Diiron Site of [FeFe]-Hydrogenases. Journal of the American Chemical Society, 146(23), 15771-15778.
Haas, Rieke; Lampret, Oliver; Yadav, Shanika; Apfel, Ulf-Peter & Happe, Thomas
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Mesoporous Electrodes Enhance the Electrocatalytic Performance of [FeFe]‐Hydrogenase. Angewandte Chemie International Edition, 64(5).
Webb, Sophie; Veliju, Astrit; Maroni, Plinio; Apfel, Ulf‐Peter; Happe, Thomas & Milton, Ross D.
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Distinct Valence States of the [4Fe4S] Cluster Revealed in the Hydrogenase Cr HydA1. Angewandte Chemie International Edition, 64(14).
Heghmanns, Melanie; Yadav, Shalini; Boschmann, Sergius; Selve, Victor R.; Veliju, Astrit; Brocks, Claudia; Happe, Thomas; Pantazis, Dimitrios A. & Kasanmascheff, Müge
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Hydrogen‐Producing Catalysts Based on Ferredoxin Scaffolds. Advanced Science, 12(33).
She, Yiting; Engelbrecht, Vera; Kozuch, Jacek; Apfel, Ulf‐Peter; Stripp, Sven T.; Hemschemeier, Anja & Happe, Thomas
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Protein Dynamics Affect O 2 -Stability of Group B [FeFe]-Hydrogenase from Thermosediminibacter oceani. Journal of the American Chemical Society, 147(18), 15170-15180.
Ghosh, Subhasri; Das, Chandan K.; Uddin, Sarmila; Stripp, Sven T.; Engelbrecht, Vera; Winkler, Martin; Leimkühler, Silke; Brocks, Claudia; Duan, Jifu; Schäfer, Lars V. & Happe, Thomas
