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, 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)
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)
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)
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)
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
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, 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)
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, 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
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
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
Biochemistry & Molecular Biology
Pei-Hua Zhao, Xiao-Li Gu, Xiao Tan, Bo Jin, Yang Guo
Summary: Researchers have developed bulky oxadithiolate-bridged [FeFe]-hydrogenase mimics with chelating diphosphines, obtaining new asymmetrically diphosphine-substituted diiron model complexes through substitutions with various diphosphines and characterizing them through multiple methods.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2022)
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
Jacob H. Artz, Oleg A. Zadvornyy, David W. Mulder, Stephen M. Keable, Aina E. Cohen, Michael W. Ratzloff, S. Garrett Williams, Bojana Ginovska, Neeraj Kumar, Jinhu Song, Scott E. McPhillips, Catherine M. Davidson, Artem Y. Lyubimov, Natasha Pence, Gerrit J. Schut, Anne K. Jones, S. Michael Soltis, Michael W. W. Adams, Simone Raugei, Paul W. King, John W. Peters
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Biochemistry & Molecular Biology
Jacob H. Artz, Monika Tokmina-Lukaszewska, David W. Mulder, Carolyn E. Lubner, Kirstin Gutekunst, Jens Appel, Brian Bothner, Marko Boehm, Paul W. King
JOURNAL OF BIOLOGICAL CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Bryant Chica, Jesse Ruzicka, Hayden Kallas, David W. Mulder, Katherine A. Brown, John W. Peters, Lance C. Seefeldt, Gordana Dukovic, Paul W. King
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Nanoscience & Nanotechnology
Di Huang, Chaiwat Engtrakul, Sanjini Nanayakkara, David W. Mulder, Sang-Don Han, Meng Zhou, Hongmei Luo, Robert C. Tenent
Summary: This study combines multiple scientific methods to investigate the degradation products and electrochemical behavior of cathode materials in lithium-ion batteries in various electrolytes, revealing that the mechanism of Mn dissolution is partially dependent on the lithium salt anion.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Physics, Applied
Yinan Liu, William K. Schenken, Lakshmi Krishna, Ahmad A. A. Majid, Thomas E. Furtak, Michael Walker, Carolyn A. Koh, P. Craig Taylor, Reuben T. Collins
Summary: This study explores a two-step process for synthesizing silicon clathrate film on a diamond silicon wafer and identifies key factors impacting film quality. Two approaches are systematically developed to minimize the effects of defective structures, resulting in high-quality clathrate surfaces and films for more reliable optical measurements. Techniques presented in this work pave the way for Si clathrate thin film to be an optically efficient alternative crystalline form of Si in optoelectronic applications.
APPLIED PHYSICS REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Bryant Chica, Jesse Ruzicka, Lauren M. Pellows, Hayden Kallas, Effie Kisgeropoulos, Gregory E. Vansuch, David W. Mulder, Katherine A. Brown, Drazenka Svedruzic, John W. Peters, Gordana Dukovic, Lance C. Seefeldt, Paul W. King
Summary: The [8Fe-7S] P-cluster of nitrogenase MoFe protein plays a role in electron transfer during the catalytic production of ammonia. By using photochemical reduction and EPR analysis, it was found that the formation of P+intermediates during electron transfer can be trapped and studied. The results demonstrate the coupling between spin-state transitions and changes in P-cluster oxidation state during electron transfer in MoFe protein.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Courtney E. Wise, Anastasia E. Ledinina, David W. Mulder, Katherine J. Chou, John W. Peters, Paul W. King, Carolyn E. Lubner
Summary: Electron bifurcation is an energy-conserving process widely utilized in biochemistry, which generates high-energy products from substrates with lower reducing potential. The energetic challenge of the first bifurcation event, with a thermodynamically uphill step, is resolved by elucidating the unusually low two-electron potential of the bifurcating flavin.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Meeting Abstract
Biochemistry & Molecular Biology
Courtney E. Wise, Anastasia E. Ledinina, David W. Mulder, John W. Peters, Paul W. King, Carolyn E. Lubner
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
(2022)
Correction
Chemistry, Multidisciplinary
Sharon L. Smolinski, Carolyn E. Lubner, Zhanjun Guo, Jacob H. Artz, Katherine A. Brown, David W. Mulder, Paul W. King
Summary: This correction article by Sharon L. Smolinski et al. focuses on the influence of electron utilization pathways on photosystem I photochemistry in Synechocystis sp. PCC 6803. The study reveals that different electron utilization pathways have distinct effects on the photochemical process of photosystem I, which is of great significance for further understanding the mechanism of photosynthesis.
Article
Chemistry, Multidisciplinary
Gregory E. Vansuch, David W. Mulder, Bryant Chica, Jesse L. Ruzicka, Zhi-Yong Yang, Lauren M. Pellows, Mark A. Willis, Katherine A. Brown, Lance C. Seefeldt, John W. Peters, Gordana Dukovic, Paul W. King
Summary: Experimental evidence shows that the addition of hydrogen is associative with the E-4(2N(2)H) state, thereby revealing a key step in the mechanism of N-2 reduction catalyzed by the enzyme nitrogenase.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Gregory E. Vansuch, David W. Mulder, Bryant Chica, Jesse L. Ruzicka, Zhi-Yong Yang, Lauren M. Pellows, Mark A. Willis, Katherine A. Brown, Lance C. Seefeldt, John W. Peters, Gordana Dukovic, Paul W. King
Summary: Photodriven electron delivery in the frozen state using CdS quantum dots in complex with MoFe protein reveals details of the E-state species and tests the stability of E-4(2N2H). The results establish that the oxidative addition of H-2 to the E-4(2N2H) state follows an associative reaction mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Sharon L. Smolinski, Carolyn E. Lubner, Zhanjun Guo, Jacob H. Artz, Katherine A. Brown, David W. Mulder, Paul W. King
Summary: The ability of cyanobacteria to adapt to changing photon flux and nutrient availability conditions is due to the controlled management of reducing power. In the absence of ORR1, the photochemical activity of PSI is modulated in coordination with the decrease in electron demand.
Article
Chemistry, Multidisciplinary
Carolyn E. Lubner, Jacob H. Artz, David W. Mulder, Aisha Oza, Rachel J. Ward, S. Garrett Williams, Anne K. Jones, John W. Peters, Ivan I. Smalyukh, Vivek S. Bharadwaj, Paul W. King
Summary: Redox cofactors play a crucial role in mediating electron transfer in biological enzymes. One example is the [FeFe]-hydrogenase I from Clostridium acetobutylicum, which utilizes a terminal, non-canonical, His-coordinated, [4Fe-4S] cluster to mediate interfacial electron transfer. Substituting His for Cys in this enzyme results in changes in electron transfer properties and reactivity, demonstrating the importance of His coordination in controlling electron exchange.
Review
Chemistry, Multidisciplinary
David W. Mulder, John W. Peters, Simone Raugei
Summary: Catalytic bias refers to the propensity of a reaction catalyst to accelerate the rate of reaction differently in one direction versus the other under non-equilibrium conditions. Enzyme's inherent bias in biocatalysis is advantageous for promoting efficiency and coordination, while directional catalytic bias is sought after in industrial chemical catalysis.
CHEMICAL COMMUNICATIONS
(2021)
Article
Materials Science, Multidisciplinary
William K. Schenken, Yinan Liu, Lakshmi Krishna, Ahmad A. A. Majid, Carolyn A. Koh, P. Craig Taylor, Reuben T. Collins