Article
Biochemistry & Molecular Biology
Martin L. Kirk, Jesse Lepluart, Jing Yang
Summary: Resonance Raman spectroscopy is a powerful tool for studying the geometric and electronic structure of metalloproteins. This review focuses on the enzymes sulfite oxidase, dimethyl sulfoxide reductase, xanthine oxidase, and carbon monoxide dehydrogenase, and highlights how resonance Raman studies have provided detailed insight into the nature of these metalloenzyme active sites.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Cassandra Gates, Haley Varnum, Catherine Getty, Natalie Loui, Ju Chen, Martin L. Kirk, Jing Yang, Sharon J. Nieter Burgmayer
Summary: The study reports a complex compound that is structurally similar to the molybdenum cofactor in pyranopterin molybdenum enzymes, and reveals its electronic structure and properties. Protonation has a significant impact on the electronic structure and redox potential of the compound.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Sinan Al-Attar, Julia Rendon, Marlon Sidore, Jean-Pierre Duneau, Farida Seduk, Frederic Biaso, Stephane Grimaldi, Bruno Guigliarelli, Axel Magalon
Summary: This study reports the mechanistic importance of a set of conserved residues lining the substrate entry tunnel in Escherichia coli nitrate reductase A (Nar), a paradigmatic enzyme of the Mo/W-bisPGD superfamily, and reveals their pivotal role in substrate affinity and proton transfer to the Mo active site. The research suggests that motion of Glu-581 side chain and surrounding polar residues control hydration inside the protein core, proton transfer, and substrate selectivity towards the active site, providing an additional determinant for tuning reactivity and selectivity in Nar. It is proposed that a gating mechanism is at play in several other members of the superfamily.
Article
Engineering, Environmental
Ying Gao, Wenda Shi, Caicai Lu, Jianbo Guo, Yuanyuan Song
Summary: This study investigated the enhancement effect and mechanism of MoO3 and silicomolybdic acid (SiMo12) on perchlorate bioreduction. The bioreduction rates of perchlorate were increased by 1.92-fold and 1.33-fold with the addition of SiMo12 and MoO3 respectively. The electrochemical activity and resistance were improved by SiMo12 and MoO3, indicating accelerated electron transfer. The secretion of intracellular and membrane cytochrome c, as well as the extracellular polymeric substance, were increased by SiMo12. Perchlorate reductase A (PcrA) was promoted by both SiMo12 and MoO3, while the mRNA reverse expression levels of perchlorate reductase O (PcrO) and perchlorate reductase Q (PcrQ) were only affected by SiMo12. This work provides a reliable strategy for accelerating perchlorate reductase in wastewater bio-treatment.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2023)
Article
Biochemistry & Molecular Biology
Victor N. Nemykin, Jared R. Sabin, Brian W. Kail, Anup Upadhyay, Michael P. Hendrich, Partha Basu
Summary: The EPR investigation of mononuclear cis- and trans-(L1O)MoOCl2 complexes reveals a difference in their spin Hamiltonian parameters due to the different ligand fields created by the heteroscorpionate donor atoms. DFT calculations were used to determine the values and orientations of the g and A tensors in various isomeric mononuclear oxo-molybdenum(V) complexes. The results showed that the use of a hybrid exchange-correlation functional with 25% of the Hartree-Fock exchange provided the best agreement between theory and experiment. The influence of ligand fields on the energies and contributions of molybdenum d orbitals to the g and A tensors and their relative orientations were analyzed using a simplified ligand-field approach.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2023)
Review
Agronomy
Sergey A. Bursakov, Pavel Yu. Kroupin, Gennady I. Karlov, Mikhail G. Divashuk
Summary: Optimizing all constituent conditions for high and even maximum yields is a recent trend in agriculture. Legumes, with their unique characteristics and symbiotic nodule bacteria, play a special role in storing protein and other important components for human and animal nutrition, as well as industry and agriculture. Molybdenum supply improves seed quality and promotes efficient use of molybdenum-containing enzymes in the plant and nodules, thereby enhancing nitrogen supply and avoiding competition with other trace elements.
Review
Biochemistry & Molecular Biology
Ralf R. Mendel
Summary: Molybdenum (Mo) is an essential micronutrient for plants, animals, and microorganisms, and it plays a crucial role in the biological activity of Mo enzymes through the formation of molybdenum cofactor (Moco). Mo enzymes and Moco are involved in vital transformations in the metabolism of nitrogen, sulfur, and carbon compounds. This review provides a personal perspective on the history, genetics, biochemistry, chemical structure, and biosynthesis of Moco. It also discusses human Moco deficiency and the possibility of life without Moco.
Article
Biotechnology & Applied Microbiology
Thomas Perli, Daan N. A. van der Vorm, Mats Wassink, Marcel van den Broek, Jack T. Pronk, Jean-Marc Daran
Summary: This study identified and expressed Moco biosynthesis genes in a non-conventional yeast for broadening the biocatalytic repertoire of industrial yeast. Engineered S. cerevisiae strain successfully utilized nitrate as nitrogen source for growth, showing competitiveness in co-culture with spoilage yeast.
METABOLIC ENGINEERING
(2021)
Article
Chemistry, Analytical
Simon M. Wikeley, Pablo Lozano-Sanchez, Marco Caffio, Tony D. James, Frank Marken
Summary: This paper presents the use of boronic acid-based synthetic organic receptor molecules attached to graphene in a new electrochemical sensor concept. The sensor utilizes surface redox polymer indicator displacement and graphene foam electrodes. The sensor shows a concentration-dependent Faradaic current response to lactic acid and can be optimized using impedance spectroscopy based on interfacial electron transfer resistance. Surface-active components from human serum are found to modify the sensor response without affecting its performance.
SENSORS AND ACTUATORS B-CHEMICAL
(2023)
Review
Biochemistry & Molecular Biology
Russ Hille
Summary: This passage provides a personal perspective on the establishment of the reaction mechanism of xanthine oxidase and related enzymes in several laboratories, including the author's.
Article
Biochemistry & Molecular Biology
Iulia V. Savina, Anton A. Ivanov, Darya V. Evtushok, Yakov M. Gayfulin, Andrey Y. Komarovskikh, Mikhail M. Syrokvashin, Mariia N. Ivanova, Igor P. Asanov, Ilia V. Eltsov, Natalia V. Kuratieva, Yuri V. Mironov, Michael A. Shestopalov
Summary: This study presents the synthesis and characterization of new chalcogenide molybdenum clusters. The oxidized and reduced forms of the clusters have similar geometries and can be reversibly transformed into each other. Comprehensive characterization reveals the different charge states and magnetic properties of molybdenum in the clusters. DFT calculations contribute to the understanding of the chemistry of molybdenum chalcogenide clusters.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Ana Rita Oliveira, Cristiano Mota, Kateryna Klymanska, Frederic Biaso, Maria Joao Romao, Bruno Guigliarelli, Ines Cardoso Pereira
Summary: The study investigated the structure and catalytic mechanism of metal-dependent formate dehydrogenases, revealing their high activity and structural stability. Spectroscopic and crystallographic analysis determined the redox characteristics and structural changes of the metal centers.
ACS CHEMICAL BIOLOGY
(2022)
Article
Chemistry, Physical
YouJin Min, Oleksiy Penkov, Mahdi Khadem, Dae-Eun Kim
Summary: It has been found that the hardness of the substrate coating significantly affects the tribological performance of graphene films and the formation of an effective lubricating transfer film. Under certain hardness conditions, graphene can significantly reduce the friction coefficient and wear rate.
Article
Chemistry, Physical
Yangdan Tao, Di Wang, Xinyu He, Hongzheng Chen, Chang-Zhi Li
Summary: Doping of solution-processed molybdenum oxide hole transport layers enabled the efficient and stable organic solar cells.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Engineering, Environmental
Jie Li, Yi Li, Pengli Chen, Kuppusamy Sathishkumar, Yumiao Lu, Saraschandra Naraginti, Yunbo Wu, Haisuo Wu
Summary: This study investigated the facilitated biological nitrate removal using ecofriendly green synthesized reduced graphene oxide (rGO) as an electron shuttle. The addition of rGO significantly enhanced the nitrate removal by donating electrons, and the rGO-biofilm showed increased photocurrent response. The study also identified several dominant genera involved in the denitrification process. Overall, the findings suggest that green synthesized rGO can be used as an ecofriendly electron shuttle for facilitated biological denitrification.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2022)
Article
Electrochemistry
Asmaa Hadj Ahmed, Jean-Vincent Daurelle, Vincent Fourmond
Summary: Protein Film Electrochemistry is a technique that directly connects enzymes to an electrode to measure their catalytic turnover rate through electrical current. Previous research has proposed a new design to improve the transport of enzymatic substrates, and this study uses computational fluid dynamics to explore the effects of various cell parameters and suggests an empirical formula to predict mass-transport coefficient and wall shear stress on the electrode.
ELECTROCHIMICA ACTA
(2022)
Review
Chemistry, Multidisciplinary
Sven T. Stripp, Benjamin R. Duffus, Vincent Fourmond, Christophe Leger, Silke Leimkueshler, Shun Hirota, Yilin Hu, Andrew Jasniewski, Hideaki Ogata, Markus W. Ribbe
Summary: Gases like H-2, N-2, CO2, and CO are important feedstock for green energy conversion and as sources of nitrogen and carbon. However, their industrial transformation and production require significant energy input, whereas nature efficiently converts them at ambient conditions using gas-processing metalloenzymes (GPMs). In this review, the importance of the cofactor/protein interface in GPMs is emphasized, and the effects of second and outer coordination sphere on catalytic activity are discussed.
Article
Chemistry, Multidisciplinary
Yeseul Park, Zohar Eyal, Peter Pekker, Daniel M. Chevrier, Christopher T. Lefevre, Pascal Arnoux, Jean Armengaud, Caroline L. Monteil, Assaf Gal, Mihaly Posfai, Damien Faivre
Summary: This study reports the periplasmic biomineralization of copper sulfide nanoparticles produced by the magnetotactic bacterium Desulfamplus magnetovallimortis strain BW-1. It reveals previously unknown possibilities for intracellular biomineralization and holds promise for biological metal recovery.
Article
Chemistry, Multidisciplinary
Marta Meneghello, Alexandre Uzel, Marianne Broc, Rita R. Manuel, Axel Magalon, Christophe Leger, Ines A. C. Pereira, Anne Walburger, Vincent Fourmond
Summary: Metal-based formate dehydrogenases are enzymes that require molybdenum or tungsten ions to catalyze the conversion between formate and CO2. The coordination of the metal ion in the active form prevents direct binding of formate to the metal. The study's findings provide strong evidence for the hypothesis that the oxidation of formate occurs in the second coordination sphere of the metal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Inorganic & Nuclear
Cheriehan Hessin, Jules Schleinitz, Nolwenn Le Breton, Sylvie Choua, Laurence Grimaud, Vincent Fourmond, Marine Desage-El Murr, Christophe Leger
Summary: Potential inversion refers to the phenomenon where the second electron transfer is easier than the first, and it is significant for understanding enzyme catalysis and developing efficient catalysts. Currently, there is a lack of analytical predictions to interpret voltammetric peak potentials when potential inversion occurs, and cyclic voltammograms are often analyzed without considering overfitting or estimating error. In this study, a theory for voltammetry of two-electron redox species in the irreversible limit is formulated and applied to analyze the voltammetry of a nickel complex with redox-active ligands, highlighting the intrinsic underdetermination of the model. Characterizing the thermodynamics of two-electron electron-transfer reactions is crucial for catalyst design.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Raphael J. Labidi, Bruno Faivre, Philippe Carpentier, Giulia Veronesi, Albert Solei-Daura, Ragnar Bjornsson, Christophe Leïger, Philipp Gotico, Yun Li, Mohamed Atta, Marc Fontecave
Summary: In this study, the performance of the orange protein (Orp) as a catalyst for photocatalytic reduction of protons into H-2 under visible light irradiation was investigated. It was found that Orp exhibited excellent photocatalytic activity in the presence of ascorbate as the sacrificial electron donor and [Ru(bpy)(3)]Cl-2 as the photosensitizer. Density functional theory (DFT) calculations were used to propose a consistent reaction mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Correction
Chemistry, Multidisciplinary
Vincent Fourmond, Carole Baffert, Kateryna Sybirna, Thomas Lautier, Abbas Abou Hamdan, Sebastien Dementin, Philippe Soucaille, Isabelle Meynial-Salles, Herve Bottin, Christophe Leger
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Andrea Fasano, Chloe Guendon, Aurore Jacq-Bailly, Arlette Kpebe, Jeremy Wozniak, Carole Baffert, Melisa del Barrio, Vincent Fourmond, Myriam Brugna, Christophe Leger
Summary: The observation that some homologous enzymes have the same active site but very different catalytic properties demonstrates the importance of long-range effects in enzyme catalysis. In this study, the catalytic bias and sensitivity of hydrogenase 1 (Hyd 1) were found to be determined by the catalytic subunit rather than the electron transfer chain, and the proximal cluster was confirmed to play a role in the enzyme's resistance to long-term exposure to O-2. This research provides insights into the structure-function relationships of hydrogenases and offers possibilities for engineering useful hydrogenases with desired properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Correction
Chemistry, Multidisciplinary
Vincent Fourmond, Carole Baffert, Kateryna Sybirna, Thomas Lautier, Abbas Abou Hamdan, Philippe Soucaille, Isabelle Meynial-Salles, Christophe Leger
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Brandon P. Russell, David J. Vinyard
Summary: The Mn4CaO5 oxygen-evolving complex in Photosystem II is crucial for water oxidation. D1 residue R334 participates in proton release and interacts with PsbO. A D1-R334G mutant destabilizes the OEC but stabilizes the S2 intermediate.
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
(2024)
Article
Biochemistry & Molecular Biology
Alexander A. Bulychev, Tatiana S. Strelets
Summary: Excitable cells of higher plants and characean algae respond to stressful stimuli by generating action potentials that influence chlorophyll fluorescence and photosynthesis for an extended period of time. While plant leaves exhibit a reversible depression in the efficiency of photosystem II reaction after an individual action potential, characean algae show long-lasting oscillations of photosystem II reaction efficiency after firing an action potential. This study investigates the possible mechanisms behind these oscillations and suggests that they are a result of metabolic rearrangements in chloroplasts and the cyclosis cessation-recovery cycle induced by calcium influx during action potentials. The findings also indicate that fluidic communications between different cell regions play a role in these oscillations, and the inhibition of oscillations occurs when these communications are restricted or eliminated.
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
(2024)
Article
Biochemistry & Molecular Biology
Dmitry Zlenko, Elena A. Protasova, Georgy Tsoraev, Nikolai N. Sluchanko, Dmitry A. Cherepanov, Thomas Friedrich, Baosheng Ge, Song Qin, Eugene G. Maksimov, Andrew B. Rubin
Summary: The conformation of chromophores in isolated phycobiliproteins is heterogeneous, but not in the entire phycobilisome (PBS). Under low-energy excitation, there is no significant uphill energy transfer from the core to the peripheral rods of the PBS, while transfer from the terminal emitters to bulk allophycocyanin chromophores is highly probable.
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
(2024)
Article
Biochemistry & Molecular Biology
Makio Yokono, Chiyo Noda, Jun Minagawa
Summary: This paper investigates the energy transfer between Photosystem II and Photosystem I in Arabidopsis thaliana, and finds that the fast spillover is reversibly regulated depending on pH.
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
(2024)