Review
Chemistry, Physical
James A. Birrell, Patricia Rodriguez-Macia, Adrian Hery-Barranco
Summary: This article introduces how to use infrared spectroscopy and thermodynamic schemes to simulate the redox behaviour of the active site H-cluster in [FeFe] hydrogenases, and discusses the applicability of these models to other metalloenzymes and molecular catalysts.
Article
Chemistry, Physical
Monica L. K. Sanchez, Seth Wiley, Edward Reijerse, Wolfgang Lubitz, James A. Birrell, R. Brian Dyer
Summary: The FeFe hydrogenases are efficient catalysts for hydrogen conversion, with a unique active site containing a [4Fe-4S] electron relay and a diiron cluster ligated by CO, CN-, and ADT ligands. The study using TRIR spectroscopy on the CrHydA1 hydrogenase revealed that a modification with PDT ligand inhibits the enzyme from proceeding through the catalytic cycle. The results suggest that the first electron transfer step is pH-independent, supporting a simple electron transfer mechanism rather than a proton-coupled event.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Moritz Senger, Jifu Duan, Mariia V. Pavliuk, Ulf-Peter Apfel, Michael Haumann, Sven T. Stripp
Summary: The H-cluster is the catalytic cofactor of [FeFe]-hydrogenase, and its diiron site can be studied by IR spectroscopy. Previous research identified an oxidized and protonated H-cluster species, HoxH, which is influenced by pH and the presence of external reductants. Recent studies suggest that the accumulation of HoxH is not dependent on specific reductants, but rather on the protonation state and deprotonation ability of the H-cluster.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Inorganic & Nuclear
James A. Birrell, Patricia Rodriguez-Macia, Edward J. Reijerse, Maria Alessandra Martini, Wolfgang Lubitz
Summary: This review provides an overview of the research history and progress on hydrogenases, focusing on their structure, mechanism of action, and catalytic cycle. It compares the studies on the simple enzyme containing the active site H-cluster and enzymes containing additional iron-sulfur clusters.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Simone Morra, Jifu Duan, Martin Winkler, Philip A. Ash, Thomas Happe, Kylie A. Vincent
Summary: By maintaining individual crystals of [FeFe]-hydrogenase under electrochemical control and probing them via Fourier Transform Infrared (FTIR) microspectroscopy, it is possible to precisely tune the redox potential and reveal variations in the distribution of redox states at the active site. This approach offers high sensitivity and precise redox control, facilitating the detection and characterisation of low abundance species and new redox intermediates within a narrow window of conditions.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Andreas Rutz, Chandan K. Das, Andrea Fasano, Jan Jaenecke, Shanika Yadav, Ulf-Peter Apfel, Vera Engelbrecht, Vincent Fourmond, Christophe Leger, Lars Schaefer, Thomas Happe
Summary: The active site of [FeFe]-hydrogenases degrades upon contact with oxygen, but the protein structure of a certain hydrogenase (CbA5H) allows its active site to be protected, reducing degradation caused by oxygen. By modifying the surface residue, the hydrogenase's resistance to oxygen can be increased.
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
Moritz Senger, Tobias Kernmayr, Marco Lorenzi, Holly J. Redman, Gustav Berggren
Summary: This study reveals that small molecules in solution can interfere with mechanistic investigations by affecting the stability of catalytic states and producing off-cycle states. The researchers demonstrate the formation of the hydride state in wild-type [FeFe]-hydrogenases treated with H-2 and discover a new state induced by common low pH buffers, the role of which in catalysis remains unclear.
CHEMICAL COMMUNICATIONS
(2022)
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)
Review
Chemistry, Physical
Matteo Sensi, Carole Baffert, Vincent Fourmond, Luca de Gioia, Luca Bertini, Christophe Leger
Summary: This review presents evidence that hydrogenases are photosensitive, focusing on FeFe hydrogenases with their active site called the H-cluster, consisting of a [4Fe4S] cluster and a diiron site. It discusses the effects of UV-visible light irradiation on the enzyme and warns about FeFe hydrogenase photoinhibition when using them for artificial photosynthesis.
SUSTAINABLE ENERGY & FUELS
(2021)
Review
Biochemistry & Molecular Biology
Jason W. Sidabras, Sven T. Stripp
Summary: This article reviews 25 years of scientific literature on [FeFe]-hydrogenase and provides a personal account on essential research papers and review articles regarding catalytic mechanism, O-2 sensitivity, and the in vivo synthesis of the active site cofactor. It also highlights future directions in structural biology and molecular biophysics and aims to inspire young investigators in the competitive field of [FeFe]-hydrogenase research.
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
(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
Armel F. T. Waffo, Christian Lorent, Sagie Katz, Janna Schoknecht, Oliver Lenz, Ingo Zebger, Giorgio Caserta
Summary: This study used cryogenic infrared and electron paramagnetic resonance spectroscopy to decipher the structural basis of the Ni-a-L intermediates in the regulatory [NiFe]-hydrogenase from Cupriavidus necator, revealing the importance of the protein scaffold in fine-tuning proton and electron dynamics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kim Greis, Carla Kirschbaum, Martin I. Taccone, Michael Goetze, Sandy Gewinner, Wieland Schoellkopf, Gerard Meijer, Gert von Helden, Kevin Pagel
Summary: mRNA-based vaccines have become crucial during the COVID-19 pandemic. This study investigates the mechanism of backbone cleavage of RNA strands and the tautomerization of cytosine in the gas phase using experimental and theoretical approaches. The findings have important implications for the development and analysis of mRNA vaccines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
David W. White, Daniel Esckilsen, Seung Kyu Lee, Stephen W. Ragsdale, R. Brian Dyer
Summary: This study reports a light-driven photocatalytic system for efficient reduction of carbon dioxide to carbon monoxide using CODH II and CdSe/CdS nanocrystals. High quantum yields and turnover frequencies were achieved by incorporating a low-potential redox mediator. This provides new insights into the mechanism of the enzyme.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Monica L. K. Sanchez, Seth Wiley, Edward Reijerse, Wolfgang Lubitz, James A. Birrell, R. Brian Dyer
Summary: The FeFe hydrogenases are efficient catalysts for hydrogen conversion, with a unique active site containing a [4Fe-4S] electron relay and a diiron cluster ligated by CO, CN-, and ADT ligands. The study using TRIR spectroscopy on the CrHydA1 hydrogenase revealed that a modification with PDT ligand inhibits the enzyme from proceeding through the catalytic cycle. The results suggest that the first electron transfer step is pH-independent, supporting a simple electron transfer mechanism rather than a proton-coupled event.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Nanoscience & Nanotechnology
Jana M. Becker, Anna Lielpetere, Julian Szczesny, Joao R. C. Junqueira, Patricia Rodriguez-Macia, James A. Birrell, Felipe Conzuelo, Wolfgang Schuhmann
Summary: The development of electrodes for efficient CO2 reduction is crucial, and the use of enzymes as catalysts offers high catalytic activity and selectivity. In this study, a bioelectrode using a low-potential redox polymer was used for the selective reduction of CO2 to CO, achieving high catalytic current densities and good stability.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Physical
Brooke A. Andrews, R. Brian Dyer
Summary: This study directly observed the hydride transfer in DHFR enzymes from Escherichia coli and Homo sapiens using presteady-state kinetics. The results revealed that the hydride transfer rate in DHFR from E. coli is faster than previously recorded, and the rate in the human enzyme can be directly observed using advanced stopped-flow instrumentation. Additionally, the study found that the hydride transfer rates in both enzymes are pH-dependent, and the human enzyme exhibits a temperature dependence.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Biology
Chris Furlan, Nipa Chongdar, Pooja Gupta, Wolfgang Lubitz, Hideaki Ogata, James N. Blaza, James A. Birrell
Summary: Electron bifurcation is a fundamental energy conservation mechanism in nature that allows endergonic reactions to be driven by exergonic ones. In this study, the structure of HydABC, an electron-bifurcating [FeFe] hydrogenase, was determined using electron cryo-microscopy. The structure revealed a heterododecamer with a central electron transfer pathway, providing insights into the mechanism of electron bifurcation in HydABC. Based on these findings, a possible mechanism of electron bifurcation in HydABC was proposed.
Article
Chemistry, Multidisciplinary
Carl Schiller, Daniel Sieh, Nils Lindenmaier, Michel Stephan, Natascha Junker, Edward Reijerse, Alexander A. Granovsky, Peter Burger
Summary: The rare intermolecular cleavage of C-C bonds was observed in a study on a late transition-metal terminal nitrido complex, which undergoes insertion of the nitrido nitrogen atom into the aromatic C-C bond of ferrocene upon oxidation. The reaction path was confirmed using isotope labeling experiments and various spectroscopic techniques. The high reactivity of the oxidized complex can be attributed to its increased electrophilicity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiuxiu Yang, Edward J. Reijerse, Nils Noethling, Daniel J. SantaLucia, Markus Leutzsch, Alexander Schnegg, Josep Cornella
Summary: In this study, we synthesized, isolated, and characterized two cationic organobismuth(II) compounds with N,C,N pincer frameworks, which mimic crucial intermediates in bismuth radical processes. X-ray crystallography revealed a monomeric Bi(II) structure, and SQUID magnetometry combined with NMR and EPR spectroscopy provided evidence for a paramagnetic S = 1/2 state. High-resolution multifrequency EPR at the X-, Q-, and W-band allowed for precise assignment of the full g- and 209Bi A-tensors. Experimental data and DFT calculations showed that both complexes are metal-centered radicals with minimal delocalization onto the ligands.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Shengyang Ni, Jiyao Yan, Srija Tewari, Edward J. Reijerse, Tobias Ritter, Josep Cornella
Summary: Here, a regioselective, late-stage two-step arene halogenation method is introduced. The unusual Ni(I)/(III) catalysis is achieved through the combination of aryl thianthrenium and Ni redox properties, which has not been achieved with other (pseudo)halides. The catalyst is generated in situ from inexpensive NiCl2 center dot 6(H2O) and zinc without the need for supporting ligands.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Mauro Mato, Davide Spinnato, Markus Leutzsch, Hye Won Moon, Edward J. J. Reijerse, Josep Cornella
Summary: This article explores the use of a low-valency bismuth complex to undergo oxidative addition reactions with redox-active alkyl-radical precursors, resembling the behavior of transition metals. Mechanistic investigations of this reactivity lead to the development of a bismuth-catalyzed C(sp(3))-N cross-coupling reaction that operates under mild conditions and accommodates synthetically relevant NH-heterocycles as coupling partners.
Article
Multidisciplinary Sciences
Yue Pang, Nils Noethling, Markus Leutzsch, Liqun Kang, Eckhard Bill, Maurice van Gastel, Edward Reijerse, Richard Goddard, Lucas Wagner, Daniel SantaLucia, Serena DeBeer, Frank Neese, Josep Cornella
Summary: In this work, the synthesis and characterization of a monocoordinate bismuthinidene compound with a rigid and bulky ligand were reported. Despite showing diamagnetic properties in all magnetic measurements, multiconfigurational quantum chemical calculations revealed that the compound's ground state is dominated by a spin triplet. The apparent diamagnetism is explained by an extremely large spin-orbit coupling-induced positive zero-field splitting.
Article
Chemistry, Multidisciplinary
Mauro Mato, Paolo Cleto Bruzzese, Fumiya Takahashi, Markus Leutzsch, Edward J. J. Reijerse, Alexander Schnegg, Josep Cornella
Summary: This article reports the ability of a well-defined organobismuth(I) complex to undergo formal oxidative addition with a wide range of aryl electrophiles. This reaction, analogous to the transition metal chemistry and catalysis, has been largely underexplored in the context of main group elements.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Nipa Chongdar, Patricia Rodriguez-Macia, Edward J. Reijerse, Wolfgang Lubitz, Hideaki Ogata, James A. Birrell
Summary: This study investigates the influence of the protein environment on the catalytic, spectroscopic, and redox properties of [FeFe] hydrogenases. Mutations at the non-conserved serine 267 site resulted in a significant decrease in activity and a lower redox potential for the [4Fe-4S] subcluster. These findings highlight the important role of the secondary coordination sphere in tuning the catalytic properties of [FeFe] hydrogenases.
Article
Chemistry, Multidisciplinary
Mahendra K. Sharma, Sonia Chabbra, Christoph Woelper, Hanns M. Weinert, Edward J. Reijerse, Alexander Schnegg, Stephan Schulz
Summary: This study reports the synthesis of two L(X)Ga-substituted diphosphenes and their reactivity, showing that carbene coordination can modulate their electronic structure and oxidation properties.