Article
Chemistry, Multidisciplinary
Yu Zhang, Lizhi Tao, Toby J. Woods, R. David Britt, Thomas B. Rauchfuss
Summary: This research shows that the active HydA1 can be biosynthesized without the maturases HydG and HydE by using a synthetic cluster.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Batuhan Balci, Roark D. O'Neill, Eric M. Shepard, Adrien Pagnier, Alexander Marlott, Michael T. Mock, William E. Broderick, Joan B. Broderick
Summary: We investigated the maturation of [FeFe]-hydrogenase by using a synthetic complex [Fe-2(& mu;-SH)(2)(CN)(2)(CO)(4)](2-) and the components of glycine cleavage system together with HydF, without the presence of the maturases HydE and HydG. This semisynthetic and fully-defined maturation process offers new insights into the biosynthesis of H-cluster.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Roman Rohac, Lydie Martin, Liang Liu, Debashis Basu, Lizhi Tao, R. David Britt, Thomas B. Rauchfuss, Yvain Nicolet
Summary: FeFe-hydrogenases use a unique H cluster to convert H-2 into protons and low-potential electrons. The [2Fe](H) center is where the reaction occurs and is built stepwise by maturating enzymes, with HydE performing complex modifications of complex-B to produce a precursor to the [2Fe](H) center.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Eric M. Shepard, Stella Impano, Benjamin R. Duffus, Adrien Pagnier, Kaitlin S. Duschene, Jeremiah N. Betz, Amanda S. Byer, Amanda Galambas, Elizabeth C. McDaniel, Hope Watts, Shawn E. McGlynn, John W. Peters, William E. Broderick, Joan B. Broderick
Summary: The study demonstrates that Clostridium acetobutylicum HydG catalyzes the formation of multiple equivalents of free CO and CN-, and suggests that the dangler iron is not essential but may affect relevant catalysis. Free CO/CN- are essential species in hydrogenase maturation.
DALTON TRANSACTIONS
(2021)
Review
Microbiology
Simone Morra
Summary: FeFe-hydrogenases are complex metalloenzymes that play a key role in microbial energy metabolism. They use protons from water as terminal electron acceptors to dissipate excess reducing equivalents and produce hydrogen. FeFe-hydrogenases also have additional physiological functions, such as H-2 uptake, H-2 sensing, and CO2 fixation. Recent advancements in identifying and characterising novel FeFe-hydrogenases have expanded our understanding of their multiple roles and mechanisms.
FRONTIERS IN MICROBIOLOGY
(2022)
Review
Chemistry, Multidisciplinary
Julian T. Kleinhaus, Florian Wittkamp, Shanika Yadav, Daniel Siegmund, Ulf-Peter Apfel
Summary: This review provides an overview of developments in [FeFe]-hydrogenase research, focusing on synthetic mimics and their application within the native enzymatic environment.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Physical
Alexander Schleusener, Mathias Micheel, Stefan Benndorf, Markus Rettenmayr, Wolfgang Weigand, Maria Waechtler
Summary: The combination of CdSe nanoparticles with [FeFe]-hydrogenase mimics has been shown to efficiently generate hydrogen under light-driven conditions, with fast electron transfer processes observed on sub-picosecond and sub-10 picosecond time scales. However, rapid recombination of electrons is also observed, highlighting the importance of sacrificial agents or protons to stabilize charge separation in real catalytic environments.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Hassan Abul-Futouh, Daniel Costabel, Konrad Hotzel, Phil Liebing, Helmar Goeris, Wolfgang Weigand, Kalina Peneva
Summary: This report presents the synthesis and characterization of a mimic of [FeFe]-hydrogenase, named [Fe-2(CO)(6){μ-bdtf}] (2, bdtf = 3,4-dimercaptobenzaldehyde), obtained from the reaction between 3,4-dimercaptobenzaldehyde and Fe-3(CO)(12). Different ligands, such as PPh3 and P(OMe)(3), were used to modify complex 2, resulting in mono- and disubstituted complexes [Fe-2(CO)(5)PPh3{μ-bdtf}] (3), [Fe-2(CO)(4)(PPh3)(2){μ-bdtf}] (4), and [Fe-2(CO)(4)(P(OMe)(3))(2){μ-bdtf}] (5). The structures of complexes 2-5 were determined by X-ray diffraction analysis. The electrochemistry and catalytic activity of these mimics towards proton reduction were evaluated by cyclic voltammetry, with all complexes showing potential for hydrogen formation in the presence of weak acid, such as acetic acid (AcOH).
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Holly J. Redman, Ping Huang, Michael Haumann, Mun Hon Cheah, Gustav Berggren
Summary: In this study, a molecular mimic of the [FeFe]-hydrogenase was used to explore sustainable sources of hydrogen. Characterization of the produced species was carried out using various spectroscopy techniques. The results revealed the potential of the compound to generate biologically relevant iron-oxidation states and facilitate H-2 gas formation.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Juneina Omeiri, Lydie Martin, Anthony Usclat, Mickael V. Cherrier, Yvain Nicolet
Summary: [FeFe]-hydrogenases efficiently catalyze the reversible oxidation of molecular hydrogen, thanks to the intricate H-cluster in their active site. The synthesis of this active site involves the assembly of multiple proteins. Despite the instability of complex B, a biomimetic analogue has been used to study its structure. By encapsulating and stabilizing the complex B product generated by HydG, the structure of complex B has been successfully determined, highlighting the transient interaction between HydG and HydE.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Marco Lorenzi, Joe Gellett, Afridi Zamader, Moritz Senger, Zehui Duan, Patricia Rodriguez-Macia, Gustav Berggren
Summary: Artificial maturation of hydrogenases provides a path to generate semi-synthetic enzymes with novel catalytic properties. This study prepared enzymes containing a synthetic asymmetric mono-cyanide cofactor and investigated their structure and reactivity. The choice of host enzyme was found to have a significant impact on reactivity, and the study showed that synthetic manipulations of the active-site can increase inhibitor tolerance.
Article
Chemistry, Multidisciplinary
Maria Alessandra Martini, Konstantin Bikbaev, Yunjie Pang, Christian Lorent, Charlotte Wiemann, Nina Breuer, Ingo Zebger, Serena DeBeer, Ingrid Span, Ragnar Bjornsson, James A. Birrell, Patricia Rodriguez-Macia
Summary: [FeFe] hydrogenase variants with a mutation in the proton transfer pathway can form two new active site states with a CN- ligand bound to the apical position of [2Fe](H). These states can be generated by either cannibalization from damaged [2Fe](H) subclusters or addition of exogenous CN-. This study provides the first detailed characterization of the interaction between exogenous CN- and [FeFe] hydrogenases.
Article
Chemistry, Multidisciplinary
Melanie Heghmanns, Andreas Rutz, Yury Kutin, Vera Engelbrecht, Martin Winkler, Thomas Happe, Muege Kasanmascheff
Summary: In this study, the active center of CbA5H, the H-cluster, was characterized using multifrequency continuous wave and pulsed electron paramagnetic resonance spectroscopy. It was found that under oxidizing conditions, an additional radical species dominates the spectra. The generation of this radical signal depends on the presence of an intact H-cluster and a complete proton transfer pathway.
Article
Chemistry, Multidisciplinary
Ashleigh T. Castner, Ben A. Johnson, Seth M. Cohen, Sascha Ott
Summary: This study focuses on the preparation and characterization of a redox-active PCN-700-based MOF that mimics the [FeFe] hydrogenase enzyme, revealing similarities and limitations in the MOF-enzyme analogy. The dual-functionalized MOF shows nonideal interactions between linkers and restricted mobility of charge-compensating redox-inactive counterions upon successive charging, leading to absent expected redox features in cyclic voltammetry. These nonlinear effects may play an important role in MOFs for catalytic applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Philipp Buday, Chizuru Kasahara, Elisabeth Hofmeister, Daniel Kowalczyk, Micheal K. Farh, Saskia Riediger, Martin Schulz, Maria Wachtler, Shunsuke Furukawa, Masaichi Saito, Dirk Ziegenbalg, Stefanie Grafe, Peter Bauerle, Stephan Kupfer, Benjamin Dietzek-Ivansic, Wolfgang Weigand
Summary: Inspired by natural [FeFe] hydrogenases, a compact and precious metal-free photosensitizer-catalyst dyad (PS-CAT) was designed for photocatalytic hydrogen evolution under visible light. The interaction between PS-CAT and the sacrificial donor was studied through spectroscopy and electrochemical techniques. The formation of an active species was confirmed by operando EPR spectroscopy, driving the photocatalysis effectively (TON approximately 210).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Simon J. George, Jose A. Hernandez, Emilio Jimenez-Vicente, Carlos Echavarri-Erasun, Luis M. Rubio
CHEMICAL COMMUNICATIONS
(2016)
Article
Chemistry, Inorganic & Nuclear
Song Gao, Simon J. George, Zhao-Hui Zhou
DALTON TRANSACTIONS
(2016)
Article
Biochemistry & Molecular Biology
Stephen W. Ragsdale, Li Yi, Guenes Bender, Nirupama Gupta, Yan Kung, Lifen Yan, Troy A. Stich, Tzanko Doukov, Lars Leichert, Paul M. Jenkins, Christopher M. Bianchetti, Simon J. George, Stephen P. Cramer, R. David Britt, Ursula Jakob, Jeffrey R. Martens, George N. Phillips, Catherine L. Drennan
BIOCHEMICAL SOCIETY TRANSACTIONS
(2012)
Article
Biochemistry & Molecular Biology
Jon M. Kuchenreuther, Yisong Guo, Hongxin Wang, William K. Myers, Simon J. George, Christine A. Boyke, Yoshitaka Yoda, E. Ercan Alp, Jiyong Zhao, R. David Britt, James R. Swartz, Stephen P. Cramer
Article
Biochemistry & Molecular Biology
Bruna P. Selbach, Alexander H. Chung, Aubrey D. Scott, Simon J. George, Stephen P. Cramer, Patricia C. Dos Santos
Article
Chemistry, Inorganic & Nuclear
Lifen Yan, Christie H. Dapper, Simon J. George, Hongxin Wang, Devrani Mitra, Weibing Dong, William E. Newton, Stephen P. Cramer
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2011)
Article
Biochemistry & Molecular Biology
Simon J. George, Brett M. Barney, Devrani Mitra, Robert Y. Igarashi, Yisong Guo, Dennis R. Dean, Stephen P. Cramer, Lance C. Seefeldt
JOURNAL OF INORGANIC BIOCHEMISTRY
(2012)
Article
Chemistry, Multidisciplinary
Devrani Mitra, Simon J. George, Yisong Guo, Saeed Kamali, Stephen Keable, John W. Peters, Vladimir Pelmenschikov, David A. Case, Stephen P. Cramer
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2013)
Article
Chemistry, Multidisciplinary
Aubrey D. Scott, Vladimir Pelmenschikov, Yisong Guo, Lifen Yan, Hongxin Wang, Simon J. George, Christie H. Dapper, William E. Newton, Yoshitaka Yoda, Yoshihito Tanaka, Stephen P. Cramer
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2014)
Article
Multidisciplinary Sciences
Jon M. Kuchenreuther, William K. Myers, Troy A. Stich, Simon J. George, Yaser NejatyJahromy, James R. Swartz, R. David Britt
Article
Multidisciplinary Sciences
Jon M. Kuchenreuther, William K. Myers, Daniel L. M. Suess, Troy A. Stich, Vladimir Pelmenschikov, Stacey A. Shiigi, Stephen P. Cramer, James R. Swartz, R. David Britt, Simon J. George
Article
Physics, Applied
Simon J. George, Matthew H. Carpenter, Stephan Friedrich, Robin Cantor
JOURNAL OF LOW TEMPERATURE PHYSICS
(2020)
Article
Instruments & Instrumentation
Linda Vogt, Julien J. H. Cotelesage, Charles J. Titus, Samin Sharifi, Albert E. Butterfield, Peter Hillman, Ingrid J. Pickering, Graham N. George, Simon J. George
Summary: Oxygen K-edge X-ray absorption spectroscopy is commonly used for studying solid materials, but studying liquid samples faces challenges of high-vacuum conditions and oxygen contamination. A new modular sample holder design allows for encapsulating liquid samples under high-vacuum conditions and provides a protocol for minimizing background oxygen contamination.
JOURNAL OF SYNCHROTRON RADIATION
(2021)
Article
Chemistry, Multidisciplinary
Linda Vogt, Julien J. H. Cotelesage, Natalia Dolgova, Charles J. Titus, Samin Sharifi, Simon J. George, Ingrid J. Pickering, Graham N. George