Article
Chemistry, Multidisciplinary
Guanhua Liu, Huaxun Chen, Hao Zhao, Ran Chen, Minghui Yang, Jing Gao, Fengshou Yu, Yanjun Jiang
Summary: A novel enzymatic system for CO2 conversion was designed in this study, which improved efficiency through PEI-enhanced enzyme immobilization and CO2 adsorption. The optimized catalysis system was able to produce 1.118 mM formate after a 3-hour reaction, with a productivity 3.7 times higher than that of the free enzyme system.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Vivek M. Badiani, Samuel J. Cobb, Andreas Wagner, Ana Rita Oliveira, Sonia Zacarias, Ines A. C. Pereira, Erwin Reisner
Summary: This study elucidates the key factors governing the activity and stability of immobilized redox enzymes and the role of film loss, particularly hydrogen bonding, in stabilizing bioelectrode performance. Electrostatic interactions are responsible for enzyme orientation, while hydrogen bonding limits enzyme desorption and improves enzyme stability.
Article
Chemistry, Multidisciplinary
Feilong Li, Silvan Scheller, Michael Lienemann
Summary: Metal-dependent formate dehydrogenases (Me-FDHs) are efficient enzymes for CO2 reduction, which can be used for fossil-free production of chemicals using renewable energy. In this study, the role of nucleophilic selenocysteine residue in Escherichia coli formate dehydrogenase H (EcFDH-H) as a ligand of molybdenum atom was investigated. The presence of selenocysteine was found to enhance the efficient CO2 reduction reaction.
JOURNAL OF CO2 UTILIZATION
(2023)
Review
Chemistry, Multidisciplinary
Marta Meneghello, Christophe Leger, Vincent Fourmond
Summary: Only two enzymes, CO dehydrogenase and formate dehydrogenase, are capable of directly reducing CO2, producing CO and formate respectively. These metalloenzymes are rapid, energy-efficient, and specific in product. Researchers have studied their mechanisms using protein film electrochemistry, and also exploited their catalytic performance to build biotechnological devices.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biotechnology & Applied Microbiology
Jaehyun Cha, Jinhee Lee, Byoung Wook Jeon, Yong Hwan Kim, Inchan Kwon
Summary: This study proposes a CO2 hydrogenation system that utilizes hydrogenase from Ralstonia eutropha H16 (ReSH) and formate dehydrogenase from Methylobacterium extorquens AM1 (MeFDH1) to efficiently convert carbon dioxide in industrial flue gas into formate via a nicotinamide adenine dinucleotide-dependent cascade reaction. The enzyme system is tolerant to inhibitors such as carbon monoxide and oxygen, and it can utilize diverse sources of hydrogen and carbon dioxide.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2023)
Article
Biotechnology & Applied Microbiology
Jaehyun Cha, Hyeonseon Bak, Inchan Kwon
Summary: Researchers have discovered a pair of oxygen-tolerant enzymes that can convert hydrogen and carbon dioxide gases into formate, overcoming the issue of enzyme damage caused by the presence of oxygen in the cheap sources.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2023)
Article
Microbiology
Ji-in Yang, Seong Hyuk Lee, Ji-Young Ryu, Hyun Sook Lee, Sung Gyun Kang
Summary: In this study, the functionality and characteristics of cytoplasmic Fdh3 in the hyperthermophilic archaeon Thermococcus onnurineus NA1 were described. Fdh3 was found to dispose of reducing equivalents by mediating electron transfer between formate and NAD(P)H or ferredoxin. Additionally, Fdh3 exhibited high NADP(+) dependent formate oxidation activity and CO2 reduction activity.
FRONTIERS IN MICROBIOLOGY
(2022)
Article
Chemistry, Physical
Mihai-Cristian Fera, Rita R. Manuel, Ines A. C. Pereira, Jose M. Abad, Antonio L. De Lacey, Marcos Pita
Summary: The electrochemical reduction of CO2 through redox enzymes is a promising method to reduce global CO2 concentrations. In this study, the enzyme Desulfovibrio vulgaris Hildenborough FdhAB formate dehydrogenase was effectively immobilized on MWCNTs-modified low density graphite electrodes using electrostatic interactions and protected with polyethyleneimine (PEI) polymer. The synergistic effect of MWCNTs and PEI resulted in high catalytic current densities and long-term operational stability.
Article
Chemistry, Physical
Haiyang Cui, Lingling Zhang, Dominik Soeder, Xiaomei Tang, Mehdi D. Davari, Ulrich Schwaneberg
Summary: MetRich plays a crucial role in the rapid immobilization of CueO on electrodes, showing high affinity to carbon nanotubes through the synergistic effect of pi-pi stacking and hydrophobic interactions. Fusion of MetRich with CotA enables CotA to rapidly and selectively adsorb on electrode surfaces.
Article
Agricultural Engineering
Yaju Xue, Xiuling Ji, Zhuang Li, Fuqiang Ma, Jingjie Jiang, Yuhong Huang
Summary: This study developed two recombinant mutants with enhanced CO2 reduction activity, leading to improved efficiency in converting CO2 to methanol. Molecular dynamics analysis revealed that increasing the width of the substrate pocket and enhancing the rigidity of C-terminal residues were key factors in improving the enzyme's reduction activity.
BIORESOURCE TECHNOLOGY
(2024)
Article
Chemistry, Multidisciplinary
Xiuling Ji, Yaju Xue, Zhuang Li, Yanrong Liu, Lei Liu, Peter Kamp Busk, Lene Lange, Yuhong Huang, Suojiang Zhang
Summary: The use of ionic liquids as solvents and enzyme stabilizers significantly enhances CO2 conversion rates, providing a new strategy for efficient bioactivation of CO2. By creating a specific ionozyme, key intermediates are formed, enzyme structure is stabilized, and hydride transfer is facilitated, making it an ideal starting point for sustainable carbon cycles.
Article
Chemistry, Multidisciplinary
Matias E. Aguirre, Cristina L. Ramirez, Yesica Di Iorio
Summary: A recyclable bio-composed system was constructed by encapsulating formate dehydrogenase in a ZIF-8 metalorganic framework (MOF) with the presence of magnetite, which overcomes the limitations of enzyme denaturation and the impossibility of biocatalyst recovery. The partial dissolution of ZIF-8 in the enzyme's operation medium can be inhibited by using a magnetic support concentration exceeding 10 mg mL(-1). The bio-friendly immobilization environment does not harm the integrity of the biocatalyst and improves the production of formic acid 3.4-fold compared to the free enzyme due to the concentration effect of MOFs as enzymatic cofactor concentrators. Furthermore, the bio-composed system retains 86% of its activity after five cycles, indicating excellent magnetic recovery and reusability.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Barbara Thijs, Jan Ronge, Johan A. Martens
Summary: This article discusses the concentration requirements of formic acid in the electrochemical production process as a carbon capture and utilization product. It explains how the specifications of electrochemical formic acid production can be matched with the requirements of emerging applications.
Article
Chemistry, Inorganic & Nuclear
Leandro A. A. Faustino, Antonio E. H. Machado, Pedro I. S. Maia, Javier J. J. Concepcion, Antonio Otavio T. Patrocinio
Summary: A novel terpyridine-based Ru(ii) complex was synthesized and its spectroscopic, electrochemical, and catalytic properties were investigated. The complex exhibited two reduction peaks in dry acetonitrile, attributed to consecutive 1 e(-) reduction. Under CO2 atmosphere, a catalytic wave was observed, with CO as the main reduction product. The presence of water improved the catalytic activity and formate production was detected.
DALTON TRANSACTIONS
(2023)
Article
Materials Science, Multidisciplinary
Xiaoqian Wei, Zijian Li, Haeseong Jang, Min Gyu Kim, Qing Qin, Xien Liu
Summary: Surface strain tuning in a coupled heterostructure efficiently enhances the catalytic performance of Bi2O2CO3/ZnO heterojunction catalysts for CO2 electroreduction. Charge transfer from Zn atoms to Bi atoms and compressive stress on the catalyst surface are crucial in promoting CO2 capture, activation, and subsequent electrochemical reduction to formate.
SCIENCE CHINA-MATERIALS
(2023)
Article
Engineering, Chemical
Manuel Canto-Robertos, Carlos Quintal-Franco, Carmen Ponce-Caballero, Marisela Vega-De Lille, Ivan Moreno-Andrade
Summary: The instability of hydrogen production in dark fermentation of food waste was found to be due to the competition of lactic-acid bacteria, specifically Bifidobacterium, which altered the acetic/butyric fermentation process.
BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING
(2023)
Article
Biophysics
Anthony Legrand, Daniel G-Cava, Marie-Dominique Jolivet, Marion Decossas, Olivier Lambert, Vincent Bayle, Yvon Jaillais, Antoine Loquet, Veronique Germain, Marie Boudsocq, Birgit Habenstein, Marisela Velez Tirado, Sebastien Mongrand
Summary: Remorins are a family of plasma membrane phosphoproteins involved in plant interaction mechanisms. Their signaling activity depends on phosphorylation and clustering into membrane domains. This study investigates the role of the intrinsically disordered domain (IDD) in remorin-membrane interaction. The results show that REM1.3 drives the formation of lipid-reorganized nanodomains and the phosphorylation of IDD influences clustering and domain formation.
BIOPHYSICAL JOURNAL
(2023)
Article
Microbiology
Delfim Ferreira, Sofia S. S. Venceslau, Raquel Bernardino, Andre Preto, Lichun Zhang, Jacob R. R. Waldbauer, William D. D. Leavitt, Ines A. C. Pereira
Summary: DsrC is a crucial protein in dissimilatory sulfur metabolism, serving as a co-substrate of the dissimilatory sulfite reductase DsrAB. It has been found to have additional functions beyond sulfite reduction. In this study, the role of DsrC in fermentative growth of Desulfovibrio vulgaris Hildenborough was investigated, and it was found that impairment of DsrC function led to reduced growth and a shift towards more fermentative metabolism.
ENVIRONMENTAL MICROBIOLOGY
(2023)
Article
Chemistry, Physical
Jose M. Abad, Marcos Pita, Antonio L. De Lacey
Summary: Monolayer-Protected Gold Clusters (AuMPCs) have attracted great interest as nanoscale capacitors in aqueous media for various nanobiotechnological applications. However, achieving subattofarad double-layer capacitance and single-electron charging has been challenging. In this study, we successfully synthesized Thioctic Acid Monolayer-Protected Au Clusters (TA-AuMPCs) that exhibited electrochemical single electron quantized capacitance charging in both organic and aqueous solutions. The functional carboxylic groups present in TA-AuMPCs provide a simple strategy for interfacing nanoparticles with biomolecules for biological electron transfer reactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Vladimir Pelmenschikov, Delfim Ferreira, Sofia S. Venceslau, Peter Hildebrandt, Ines A. . C. Pereira, Smilja Todorovic, Smilja Todorovic
Summary: In this study, resonance Raman spectroscopy and density functional theory calculations were used to investigate the structural, electronic, and vibrational properties of the noncubane [4Fe-4S] cluster in heterodisulfide reductase (HdrB). Homology modeling was employed to predict the protein environment of the neighboring clusters in DvHdrB. The results showed that the oxidized [4Fe-4S](3+) cluster adopts a closed conformation in the absence of substrate, but transitions to an open structure upon substrate coordination, accompanied by a ligand switch. This study provides valuable insights for future research on enzymes with this unconventional cofactor.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Analytical
Emiliano Martinez-Perinan, Aitor Dominguez-Saldana, Ana M. Villa-Manso, Cristina Gutierrez-Sanchez, Monica Revenga-Parra, Eva Mateo-Marti, Felix Pariente, Encarnacion Lorenzo
Summary: Carbon nanodots modified with azure A were synthesized and applied as a redox mediator for bioelectrocatalytic reactions. The modified electrodes demonstrated excellent electrocatalytic activity and analytical performance for the detection of NADH and glutamate. The developed biosensor based on immobilized enzyme showed good analytical parameters and successfully analyzed food and biological samples.
SENSORS AND ACTUATORS B-CHEMICAL
(2023)
Article
Chemistry, Analytical
Melisa del Barrio, Emiliano Martinez-Perinan, Cristina Gutierrez-Sanchez, Eva Mateo-Marti, Marcos Pita, Antonio L. De Lacey, Felix Pariente, Encarnacion Lorenzo
Summary: The determination of cholesterol is important for heart disease detection and as a fuel for enzymatic fuel cells. A cholesterol biosensor and peroxide-free biofuel cell was developed using electrocatalytic oxidation of NADH generated during cholesterol dehydrogenase (ChDH) reaction. This alternative method avoids the use of H2O2 biosensing strategies.
SENSORS AND ACTUATORS B-CHEMICAL
(2023)
Article
Chemistry, Multidisciplinary
Samuel J. Cobb, Azim M. Dharani, Ana Rita Oliveira, Ines A. C. Pereira, Erwin Reisner
Summary: The electrolysis of dilute CO2 streams is hampered by low concentrations of dissolved substrate and rapid depletion at the electrolyte-electrocatalyst interface. To address this issue, a bio-inspired strategy mimicking the carboxysome in cyanobacteria is introduced. It utilizes microcompartments with nanoconfined enzymes in a porous electrode to accelerate CO2 hydration kinetics and minimize substrate depletion, enabling efficient reduction of low-concentration CO2 to formate even at atmospheric concentrations. This concept demonstrates the potential of the carboxysome as a blueprint for the reduction of low-concentration CO2 streams to chemicals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Gabriel Luna-Lopez, Melisa del Barrio, Jennifer Fize, Vincent Artero, Ana Margarida Coito, Ines A. C. Pereira, Jose Carlos Conesa, Ana Iglesias-Juez, Antonio L. De Lacey, Marcos Pita
Summary: Clean energy vectors are required to achieve a fossil fuel-free society, reducing both greenhouse effect and pollution. Electrochemical water splitting provides a clean method to obtain green hydrogen, but efficient electrocatalysts are needed to avoid high overpotentials. The combination of inorganic semiconductors with biocatalysts offers an alternative approach for photoelectrochemical H2 production.
BIOELECTROCHEMISTRY
(2023)
Article
Chemistry, Physical
Mihai-Cristian Fera, Rita R. Manuel, Ines A. C. Pereira, Jose M. Abad, Antonio L. De Lacey, Marcos Pita
Summary: The electrochemical reduction of CO2 through redox enzymes is a promising method to reduce global CO2 concentrations. In this study, the enzyme Desulfovibrio vulgaris Hildenborough FdhAB formate dehydrogenase was effectively immobilized on MWCNTs-modified low density graphite electrodes using electrostatic interactions and protected with polyethyleneimine (PEI) polymer. The synergistic effect of MWCNTs and PEI resulted in high catalytic current densities and long-term operational stability.
Article
Ecology
Sinje Neukirchen, Ines A. C. Pereira, Filipa L. Sousa
Summary: Microbial dissimilatory sulfur metabolism plays a significant role in Earth's biochemical sulfur cycle. Comparative genomics and phylogenetic analyses indicate an archaeal origin of the minimal DsrABCMK(N) protein set, with sulfite reduction as its primordial function. The acquisition of additional Dsr proteins increased the complexity of the Dsr pathway. Further discoveries of two types of Qmo complexes allowed microorganisms to use sulfate as an electron acceptor. Chlorobi and Proteobacteria evolved the ability to use the Dsr pathway for sulfur oxidation independently.
Article
Chemistry, Analytical
Ana M. Villa-Manso, Tamara Guerrero-Esteban, Felix Pariente, Celia Toyos-Rodriguez, Alfredo de la Escosura-Muniz, Monica Revenga-Parra, Cristina Gutierrez-Sanchez, Encarnacion Lorenzeo
Summary: A novel immunosensor based on electrochemiluminescence resonance energy transfer (ECL-RET) has been developed for the sensitive determination of N protein of the SARS-CoV-2 coronavirus. The immunosensor utilizes bifunctional core@shell nanoparticles as ECL acceptor and [Ru(bpy)(3)](2+) as ECL donor. It demonstrates a wide linear response to the concentration of N protein with a detection limit of 1.27 pg/mL, high stability, and specificity. The immunosensor has been successfully applied for quantification of N protein in saliva samples and showed consistent results with a commercial colorimetric ELISA kit.
Article
Nanoscience & Nanotechnology
Keyvan Jodeiri, Aleksandra Foerster, Gustavo F. Trindade, Jisun Im, Diego Carballares, Roberto Fernandez-Lafuente, Marcos Pita, Antonio L. De Lacey, Christopher Parmenter, Christopher Tuck
Summary: The drive for miniaturization in enzyme-based bioelectronics has led to the development of 3D microstructured electrodes. Additive manufacturing combined with electroless metal plating allows the production of these electrodes with high surface area. The challenge lies in ensuring strong adhesion between the metal layer and polymer structure, which has been achieved in this study through the introduction of an interfacial adhesion layer.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Laura Fernandez-Lopez, Isabel Cea-Rama, Julia Alvarez-Malmagro, Anna K. Ressmann, Jose L. Gonzalez-Alfonso, Cristina Coscolin, Patrick Shahgaldian, Francisco J. Plou, Jan Modregger, Marcos Pita, Julia Sanz-Aparicio, Manuel Ferrer
Summary: Metal complexes introduced into protein scaffolds can generate versatile biomimetic catalysts with various catalytic properties. In this study, we synthesized and covalently bound a bipyridinyl derivative to the active site of an esterase, resulting in a biomimetic catalyst that exhibits catecholase activity and enantioselective catalytic oxidation of (+)-catechin.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Araceli Lino-Sanchez, Virginia Gonzalez-Velez, Marisela Velez, Julia Aguilar-Pliego
Summary: In this study, we successfully extracted and characterized natural collagen from fish scales. The obtained collagen had high denaturation temperatures and hydroxyproline contents, making it a valuable alternative for biomedical applications.
