Article
Multidisciplinary Sciences
Rhiannon M. Evans, Natalie Krahn, Bonnie J. Murphy, Harrison Lee, Fraser A. Armstrong, Dieter Soll
Summary: The study investigates the impact of substituting cysteine with selenocysteine on the function of [NiFe]-hydrogenases, revealing that while the activity of the enzymes is reduced after substitution, variants with selenocysteine show significant differences in O-2 tolerance and electrocatalytic properties.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Review
Polymer Science
Nirpesh Dhakal, Bishnu Acharya
Summary: Syngas fermentation offers potential for producing biofuels and bioplastics from microbial fermentation, with a wide range of feedstock options and sustainability. Utilizing various microbial strains and pathways, diverse products can be produced, but factors like techno-economics, syngas impurities may impact the overall process.
Article
Chemistry, Applied
Minglun Cheng, Xiongfei Zhang, Yong Zhu, Mei Wang
Summary: The [FeFe]-hydrogenase model with a rigid and conjugate S-to-S bridge was found to be catalytically active for the selective photochemical reduction of CO2 to CO, with the catalytic selectivity being adjustable by adding triethanolamine. The study proposed a plausible mechanism for the photocatalytic reduction of CO2 to CO and highlighted the importance of electron transfer in the system.
CHINESE JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Analytical
Songjiao Li, Ke Yang, Jiayu Zeng, Yuqing Xia, Dan Cheng, Longwei He
Summary: Carbon monoxide (CO) is an important gaseous transmitter in biological systems and can be used as a therapeutic molecule. In this study, a near-infrared emitting probe (NIR-CORM-3) was designed to selectively and sensitively respond to CO and exhibit outstanding imaging abilities.
Article
Chemistry, Analytical
Liqiang Yan, Cuiping Zhou, Hong Yang
Summary: The analysis of Tricarbonylchloro(glycinato)ruthenium (CORM-3) is of great significance due to its anti-inflammatory and heart-protecting properties in clinical diseases and its role in studying the metabolic mechanism of endogenous carbon monoxide. A small molecule fluorescent probe was developed to detect CORM-3, which showed enhanced near-infrared fluorescence and a large Stokes shift. The probe achieved a detection limit of 0.11 mu M and a linear range of 0 - 175 mu M, and was successfully used for high-resolution fluorescence imaging in living cells and Zebrafish.
SENSORS AND ACTUATORS B-CHEMICAL
(2023)
Article
Chemistry, Analytical
Zongcheng Wang, Shun Yang, Xiuqi Liu, Tingting Yang, Ting Han, Xingrui He, Yuren Jiang, Yuanqiang Hao
Summary: The newly designed fluorescent probe YZ-M5 shows high accuracy and sensitivity in detecting and visualizing selenocysteine, with rapid and strong fluorescence enhancement within 5 minutes. It has a low detection limit and a wide detection range, as well as the ability to identify selenocysteine in living cells and mice.
MICROCHEMICAL JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Sven T. Stripp, Jonathan Oltmanns, Christina S. Mueller, David Ehrenberg, Ramona Schlesinger, Joachim Heberle, Lorenz Adrian, Volker Schuenemann, Antonio J. Pierik, Basem Soboh
Summary: The study demonstrates that the [Fe](CN)2CO cofactor and the [4Fe-4S] cluster of the HypCD complex have redox activities, with potential-dependent interconversion processes. Furthermore, potential-dependent disulfide formation between the metal centers may suggest an electron confurcation step.
BIOCHEMICAL JOURNAL
(2021)
Article
Chemistry, Physical
Wenhao Ren, Wenchao Ma, Xile Hu
Summary: Electrochemical CO reduction can be used to efficiently convert CO2 to chemical fuels. However, current membrane electrode assembly (MEA) CO electrolyzers suffer from low energy efficiency. This study shows that the transport of water and hydroxide ions at the quasi-two-phase interface of the cathode limits the performance of MEA electrolyzers at high current densities. By improving interfacial mass transport, the researchers achieved a lower cell voltage, higher stability, and higher Faradaic yield.
News Item
Chemistry, Multidisciplinary
Nicholas A. A. Fitzpatrick, Patricia Z. Z. Musacchio
Summary: A visible-light photocatalytic diselenide contraction has been developed for the chemoselective functionalization of selenopeptides and proteins under mild conditions, providing a new method for studying post-translational modification of proteins.
Article
Biochemistry & Molecular Biology
Giorgio Caserta, Sven Hartmann, Casey Van Stappen, Chara Karafoulidi-Retsou, Christian Lorent, Stefan Yelin, Matthias Keck, Janna Schoknecht, Ilya Sergueev, Yoshitaka Yoda, Peter Hildebrandt, Christian Limberg, Serena DeBeer, Ingo Zebger, Stefan Frielingsdorf, Oliver Lenz
Summary: In this study, the maturation process of [NiFe]-hydrogenase was investigated using biochemical analysis and various spectroscopic techniques, providing detailed insights into its complex maturation mechanism.
NATURE CHEMICAL BIOLOGY
(2023)
Article
Biotechnology & Applied Microbiology
Yoshinari Imaura, Shunsuke Okamoto, Taiki Hino, Yusuke Ogami, Yuka Adachi Katayama, Ayumi Tanimura, Masao Inoue, Ryoma Kamikawa, Takashi Yoshida, Yoshihiko Sako
Summary: Microbial CO oxidation contributes to global carbon cycling and serves as a remover of toxic CO. Some microbial CO oxidizers have sister relationships with non-CO oxidizers. We discovered a versatile CO oxidizer, Parageobacillus sp. G301, capable of anaerobic and aerobic CO oxidation using both types of CODH. Comparative genomic analysis suggests that CO oxidation genes are not essential in the genus Parageobacillus.
APPLIED AND ENVIRONMENTAL MICROBIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Rhiannon M. Evans, Stephen E. Beaton, Patricia Rodriguez Macia, Yunjie Pang, Kin Long Wong, Leonie Kertess, William K. Myers, Ragnar Bjornsson, Philip A. Ash, Kylie A. Vincent, Stephen B. Carr, Fraser A. Armstrong
Summary: A variant of hydrogenase-2 from E. coli with a mutated arginine residue at its active site forms a tightly-bound diatomic ligand. This ligand is stabilized by hydrogen bonding and removal only occurs after reduction with H-2 and reduced methyl viologen. The R479K variant shows decreased rates in hydrogen oxidation and evolution compared to the native enzyme. Importance rating: 7/10.
Article
Environmental Sciences
Leonid Yurganov, Vadim Rakitin
Summary: Biomass burning has a significant impact on global and hemispheric carbon cycles, and boreal forest fires in Russia and Canada are major sources of carbon dioxide and methane emissions. Although carbon monoxide has minimal greenhouse effect, its concentrations are closely related to CO2 and CH4 emissions. Satellite measurements of CO provide a simple method for estimating emissions. Recent studies have shown record-high CO emissions from biomass burning, with a steady growth rate over the past two decades.
Article
Chemistry, Physical
P. Wakwella, A. R. W. McKellar, N. Moazzen-Ahmadi
Summary: Extensive infrared spectra of the weakly-bound CO-CO dimer were observed in the carbon dioxide nu 3 asymmetric stretch region, analyzing both C-bonded and O-bonded isomers. The splitting of the degenerate CO bend into in-plane and out-of-plane components due to the presence of CO was observed with different values for C- and O-bonded isomers.
Article
Chemistry, Physical
Thomas Mairegger, Haobo Li, Christoph Griesser, Daniel Winkler, Jakob Filser, Nicolas G. Hoermann, Karsten Reuter, Julia Kunze-Liebhaeuser
Summary: Transition metal carbides, especially Mo2C, are efficient electrocatalysts for CO2 reduction. However, in aqueous electrolytes, only the hydrogen evolution reaction occurs due to the formation of a thin oxide layer. In this study, we investigate the CO2 reduction activity of Mo2C in a non-aqueous electrolyte and find a preference for carbon monoxide production. We also observe that the non-aqueous acetonitrile electrolyte determines the catalytic selectivity of CO2 reduction.
Article
Chemistry, Physical
Karolina Czastka, Alaa A. Oughli, Olaf Ruediger, Serena DeBeer
Summary: The ability to observe changes in the enzyme active site during electrocatalysis is important for understanding the mechanism and designing catalysts. This article discusses the development of X-ray absorption spectroscopy (XAS) combined with electrochemistry for studying enzymatic systems. Challenges and opportunities of using operando XAS for enzymatic electrocatalysis are discussed, including low concentration of photoabsorber and protein instability under X-ray beam. The article also highlights methods for immobilizing enzymes on electrodes and maintaining redox control. A case study of [NiFe] hydrogenase is presented. The feasibility of the experiments is demonstrated, but precise redox control and careful discrimination between electrochemically-driven changes and beam damage are required. Opportunities for future applications are discussed.
FARADAY DISCUSSIONS
(2022)
Article
Multidisciplinary Sciences
Delfim Ferreira, Ana C. C. Barbosa, Goncalo P. Oliveira, Teresa Catarino, Sofia S. Venceslau, Ines A. C. Pereira
Summary: Dissimilatory sulfur metabolism is widespread among bacteria and archaea, with DsrAB and other Dsr proteins playing key roles. DsrD acts as an activator of DsrAB and its function is still debated.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Multidisciplinary Sciences
Esther Edwardes Moore, Samuel J. Cobb, Ana Margarida Coito, Ana Rita Oliveira, Ines A. C. Pereira, Erwin Reisner
Summary: Bioelectrochemistry utilizes porous electrode structures to enhance protein loading and electrochemical current response. This study explores the local environment of enzymes within these structures and demonstrates the importance of adjusting the solution conditions to optimize enzyme activity.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Electrochemistry
Natalia Levin, Carla Casadevall, George E. Cutsail, Julio Lloret-Fillol, Serena DeBeer, Olaf Ruediger
Summary: In this study, a molecular Ru-based water oxidation catalyst bearing a polypyridinic backbone was investigated using in situ spectroelectrochemistry coupled with EPR and XAS techniques. The study proposed a water nucleophilic attack mechanism for O-O bond formation, and observed intermediates supporting this mechanism, including a Ru(V) oxo intermediate based on the Py(2)Metacn ligand for the first time.
Article
Chemistry, Analytical
Tamara Guerrero-Esteban, Cristina Gutierrez-Sanchez, Ana M. Villa-Manso, Monica Revenga-Parra, Felix Pariente, Encarnacion Lorenzo
Summary: Given the importance of fast, efficient, and cost-effective detection of SARS-CoV-2 in wastewater to control the pandemic, a new method based on a carbon nanodots-amplified electrochemiluminescence immunosensor has been proposed. The immunosensor showed high specificity and stability, with a detection limit of 1.2 pg/mL, and successfully detected SARS-CoV-2 in river and urban wastewater. This sensing platform provides a feasible and reliable tool for early virus detection and protection of the population.
Article
Chemistry, Analytical
Monica Mediavilla, Monica Revenga-Parra, Cristina Gutierrez-Sanchez, Lourdes Hernandez-Apaolaza, Felix Pariente, Encarnacion Lorenzo
Summary: A new fluorescent assay for total polyphenol determination based on the bioconjugate formed between laccase enzyme and carbon nanodots has been developed. The study showed that bioconjugation does not inhibit enzymatic activity and the decrease in fluorescence is mainly due to electron transfer processes.
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
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, Analytical
Tamara Guerrero-Esteban, Borja L. Sanchez, Lucia Exposito, David Rodriguez-San-Miguel, Felix Zamora, Felix Pariente, Cristina Gutierrez-Sanchez, Encarnacion Lorenzo
Summary: This work presents a novel approach for detecting biogenic amine tyramine using a sensitive and disposable electrochemiluminescent sensor. The sensor is fabricated by modifying a screen-printed carbon electrode surface with two nanomaterials, alpha-Ge nanolayers and AuNP, which synergistically enhance the electrochemiluminescence response. The sensor was characterized using various techniques such as SEM-EDX, EIS, Raman, and AFM. The principle of the biosensor relays on the fact that tyramine molecule acts as an analyte and co-reactant, which interacts with the luminophore [Ru(bpy)(3)](2+) on the sensor surface. The proposed sensor shows a linear response to tyramine concentration, with a detection limit of 2.28 mu M. The sensor successfully detected tyramine in avocado samples, demonstrating its potential for practical applications.
SENSORS AND ACTUATORS B-CHEMICAL
(2023)
