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
Chemistry, Physical
Sanaz Normohammadi, Farzaneh Bahmani, Lida Fotouhi, Mehdi Khoshfetrat
Summary: The engineered nickel nanocone-modified NiMoO4 hybrid on Ni foam substrate demonstrates enhanced capacitance performance, high specific capacitance, and cycling durability, making it a promising electrode material for stable supercapacitors.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Physical
Sunil R. Kadam, Sirshendu Ghosh, Ronen Bar-Ziv, Maya Bar-Sadan
Summary: A cost-effective technique was developed to synthesize Mo2C microspheres with optimized HER catalysis performance in alkaline media, showing reduced overpotentials and high stability.
APPLIED SURFACE SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Palraj Kalimuthu, Dominik Hege, Agnieszka Winiarska, Yvonne Gemmecker, Maciej Szaleniec, Johann Heider, Paul V. Bernhardt
Summary: In contrast to molybdenum enzymes, tungsten enzymes have lower redox potentials and can perform reversible redox transformations. However, the electrochemical properties of tungsten enzymes have received less attention. In this study, the tungsten enzyme aldehyde oxidoreductase (AOR) from Aromatoleum aromaticum was immobilized on a glassy carbon electrode. The system showed electrocatalytic oxidation of aromatic and aliphatic aldehydes in the presence of electron transfer mediators. The different mediators had different electron transfer rates and methylene blue acted as a two-electron acceptor. This work demonstrates a highly energy efficient catalytic process for aldehyde oxidation at low applied electrochemical potential.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Green & Sustainable Science & Technology
J. S. Arya Nair, S. Saisree, K. Y. Sandhya
Summary: This study demonstrates the synthesis of a partially reduced graphene oxide-nano-molybdenum disulfide composite (prGO-MoS2) with ultra-fast Pb(II) removal capability. The prGO-MoS2 exhibits high removal efficiency and selectivity, with the ability to decrease the concentration of Pb(II) from 10,000 ppb to 0.8642 ppb within a short time. It has the fastest removal speed and the second-highest adsorption capacity among reported materials for Pb(II) removal.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
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)
Review
Chemistry, Analytical
Nur Melis Kilic, Sima Singh, Gulsu Keles, Stefano Cinti, Sevinc Kurbanoglu, Dilek Odaci
Summary: Electrochemistry is an interdisciplinary science that has applications in various domains. The use of biosensors to measure biological or biochemical processes is critical in medical and biotechnological fields. There are electrochemical biosensors available for healthcare applications such as glucose, lactate, and nucleic acid detection. Enzyme-based biosensors using carbon-based nanomaterials are highly sensitive and selective, with fast reaction times. However, they can be influenced by environmental factors and the cost of enzymes and their immobilization can hinder their widespread use. This review discusses the design and applications of enzyme-based electrochemical nanobiosensors.
Article
Chemistry, Analytical
Javad Gilnezhad, Ali Firoozbakhtian, Morteza Hosseini, Sadra Adel, Guobao Xu, Mohammad Reza Ganjali
Summary: We developed a glucose sensor using nickel-samarium nanoparticles-decorated MXene layered double hydroxide (MXene/Ni/Sm-LDH), which showed high electro-catalytic activity for glucose oxidation. The sensor demonstrated an extended linear range, with a detection limit of 0.24 muM and sensitivity values of 1673.54 muA mM-1cm-2 and 1519.09 muA mM-1cm-2 at concentrations of 0.01 mM and 1 mM, respectively. The sensor also exhibited good repeatability, high stability, and applicability for real sample analysis, as demonstrated by successful glucose detection in human sweat.
ANALYTICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Inderpal Yadav, Ved Prakash, Ram R. Kaswan, Mannar R. Maurya, Muniappan Sankar
Summary: Two new beta-functionalized oxidomolybdenum(V) corroles have been synthesized and characterized. These corroles exhibit excellent catalytic activity for the oxidative bromination of phenols and show excellent thermal and chemical stabilities.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Vadim Krivitsky, Eran Granot, Yoav Avidor, Ella Borberg, Ralf T. Voegele, Fernando Patolsky
Summary: This article introduces a fast, sensitive, and reliable electrochemical sensing platform for the detection of airborne soybean rust spores. The platform utilizes a specific biotinylated aptamer to bind and detect the spores, which are then incubated with a streptavidin-alkaline phosphatase agent to produce p-nitrophenol for detection.
Review
Chemistry, Analytical
Nurgul K. Bakirhan, Burcu D. Topal, Goksu Ozcelikay, Leyla Karadurmus, Sibel A. Ozkan
Summary: Electrochemical biosensors have gained wider interest in analytical techniques due to their practicality, sensitivity, and fast response. They can be integrated with labs-on-chips to create excellent point of care analytical platforms. These sensors are suitable for detecting a wide range of analytes and have unique features such as molecular recognition, user friendliness, small reagent volume requirement, low cost, and applicability to point of care tests. Recent research has focused on using nanomaterials and polymers to enhance the performance of electrochemical biosensors.
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
V. Saska, U. Contaldo, I. Mazurenko, A. de Poulpiquet, E. Lojou
Summary: The nature, composition and concentration of electrolytes play a crucial role in electrocatalysis involving redox enzymes. In this study, the effect of different electrolyte compositions with increasing ionic strengths on the stability and activity of the bilirubin oxidase (BOD) from Myrothecium verrucaria was investigated. It was found that the catalytic current decreased reversibly with increasing salt concentrations on carbon nanotube-modified electrodes, while on gold electrodes modified with self-assembled thiols, the catalytic current decreased reversibly when the enzyme was adsorbed and increased when the enzyme was covalently attached.
BIOELECTROCHEMISTRY
(2023)
Article
Chemistry, Analytical
Jianru Wang, Xue Chen, Dengfeng Qu, Xiaofan Zhang, Li Wang, Zongxia Guo, Shufeng Liu
Summary: In this study, a simple and easy-to-operate biosensor with a tunable dynamic range was developed for diagnostic applications. The biosensor utilized an enzyme-responsive electrochemical DNA biosensor that only required one immobilization probe. The immobilization probe, designed with a hairpin-like structure, contained independent target recognition and enzyme-responsive domains. The biosensor showed extended dynamic range, lowered detection limit, and better discrimination ability, making it a promising tool for diagnostic applications and drug monitoring.
ANALYTICA CHIMICA ACTA
(2023)
Article
Chemistry, Analytical
Yi Feng, Yuting Zhao, Jun Ge
Summary: Metal-organic frameworks (MOFs) are promising carriers for enzymes and other biomolecules due to their stability, selectivity, and controllability. However, enzyme-MOF complexes often result in decreased enzyme activity and substrate affinity. In this study, enzyme-MOF composites were synthesized using ZIF-8, with adjusted sizes leading to enhanced substrate affinity and enzyme activity, showing potential for efficient biosensors in biomedicine.
ANALYTICA CHIMICA ACTA
(2021)
Article
Biotechnology & Applied Microbiology
Saki Mori, Yohei Kitta, Hiroaki Sakamoto, Eiichiro Takamura, Shin-ichiro Suye
Summary: The study aimed to develop a high-power biodevice that retains enzyme structure and activity by interposing gold nanoparticles (AuNPs) between the enzyme and the electrode. The research found that the enzymatic and electrochemical properties differed among AuNPs of different diameters, and the enzyme adsorbed on 20 nm AuNPs exhibited the best electrochemical characteristics.
BIOTECHNOLOGY LETTERS
(2021)
Article
Chemistry, Physical
Matthew N. Podgorski, Joshua S. Harbort, Joel H. Z. Lee, Giang T. H. Nguyen, John B. Bruning, William A. Donald, Paul Bernhardt, Jeffrey R. Harmer, Stephen G. Bell
Summary: In this study, it was found that mutating a highly conserved threonine residue in CYP199A4 to glutamate can convert it to a peroxygenase and improve its peroxygenase activity. The crystal structure of the mutant demonstrated a change in spin state upon substrate binding, which was linked to the modification of the oxygen-binding groove and the retention of the iron-bound aqua ligand. The detailed characterization of this engineered heme peroxygenase will aid in the development of new methods for the selective C-H bond activation using heme enzymes.
Article
Chemistry, Multidisciplinary
Madeleine J. Fort, Sophia M. Click, Evan H. Robinson, Felix M. C. He, Paul Bernhardt, Sandra J. Rosenthal, Janet E. Macdonald
Summary: Light-induced charge separation plays a crucial role in solar harvesting technologies, and the internal reorganization energy has a profound impact on charge transfer rates. Experimental and theoretical studies demonstrate that reducing the reorganization energy can greatly increase charge transfer rates, even more significantly than the driving force. This suggests that careful design of redox mediators to minimize reorganization energy is a promising approach to enhance the efficiency of quantum dot applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Plant Sciences
Taizong Wu, Angela A. Salim, Zeinab G. Khalil, Paul V. Bernhardt, Robert J. Capon
Summary: This study identified 13 new macrocyclic spirotetronates, glenthmycins A-M (1-13), with potential antibacterial activity against multidrug-resistant bacteria, such as MRSA and VRE. Furthermore, a semisynthetic derivative, glenthmycin K 9-valerate (26), showed potent inhibitory effects on a wide range of Gram-positive pathogens.
JOURNAL OF NATURAL PRODUCTS
(2022)
Article
Chemistry, Multidisciplinary
Palraj Kalimuthu, Dominik Hege, Agnieszka Winiarska, Yvonne Gemmecker, Maciej Szaleniec, Johann Heider, Paul V. Bernhardt
Summary: In contrast to molybdenum enzymes, tungsten enzymes have lower redox potentials and can perform reversible redox transformations. However, the electrochemical properties of tungsten enzymes have received less attention. In this study, the tungsten enzyme aldehyde oxidoreductase (AOR) from Aromatoleum aromaticum was immobilized on a glassy carbon electrode. The system showed electrocatalytic oxidation of aromatic and aliphatic aldehydes in the presence of electron transfer mediators. The different mediators had different electron transfer rates and methylene blue acted as a two-electron acceptor. This work demonstrates a highly energy efficient catalytic process for aldehyde oxidation at low applied electrochemical potential.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Medicinal
Mahendiran Dharmasivam, Busra Kaya, Tharushi Wijesinghe, Mahan Gholam Azad, Miguel A. Gonzalvez, Mohammad Hussaini, Jason Chekmarev, Paul Bernhardt, Des R. Richardson
Summary: A novel and selective antitumor agent, 3-thiosemicarbazone (PPP44mT), and its analogues with distinctive properties were synthesized and characterized. The inclusion of a styrene moiety prevented the oxidation of oxy-myoglobin or oxy-hemoglobin, which is different from other potent thiosemicarbazones such as DpC or Dp44mT. PPP44mT and its Cu(II) complexes exhibited immediate cytotoxicity against SK-N-MC tumor cells, while [Zn(PPP44mT)2] showed delayed antiproliferative efficacy and superior inhibition of cyclin D1 expression compared to DpC or Dp44mT.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Miguel A. Gonzalvez, Craig M. Williams, Manuel Martinez, Paul V. Bernhardt
Summary: Organocopper(II) reagents are a relatively unexplored frontier in copper catalysis. This study investigates the stability and reactivity of Cu-II-C bonds, proposing two main pathways for their cleavage: homolysis and heterolysis. Experimental results provide insights into the reaction pathways of organocopper(II) complexes, which are relevant to their application as catalysts in C-C bond forming reactions.
INORGANIC CHEMISTRY
(2023)
Article
Genetics & Heredity
Young C. Song, Sophie I. Holland, Matthew Lee, Gao Chen, Frank E. Loffler, Michael J. Manefield, Philip Hugenholtz, Ulrike Kappler
Summary: In this study, a comparative analysis of 10 members of the Dehalobacteriia revealed that Dehalobacterium formicoaceticum is the only species capable of anaerobic fermentation of dichloromethane (DCM). Other species in this class do not possess this ability. Common traits of the Dehalobacteriia include the use of amino acids as carbon and energy sources, energy generation through electron-bifurcating protein complexes, and the presence of S-layer proteins. It was also found that D. formicoaceticum can use serine as a growth substrate in the absence of DCM, and the abundance of electron-bifurcating protein complexes and S-layer proteins is high during growth on DCM. Overall, the Dehalobacteriia are low-abundance fermentative scavengers in anoxic habitats.
MICROBIAL GENOMICS
(2023)
Article
Chemistry, Multidisciplinary
Anthony Wiskich, Trevor Rapson
Summary: The prospects of recent methods of ammonia production without fossil fuels are discussed. These novel biological and electrochemical pathways still need significant improvements to compete with electricity-powered Haber-Bosch. Qualitative discussions about on-farm synthesis and centralized green ammonia production are presented, considering the economics of scale.
Article
Chemistry, Inorganic & Nuclear
Masnun Naher, Chuyi Su, Jeffrey R. Harmer, Craig M. Williams, Paul V. Bernhardt
Summary: The utility and scope of Cu-catalyzed halogen atom transfer chemistry have been exploited in a variety of fields. This study demonstrates the ability to modulate the reactivity of the Cu catalyst using electrochemistry, resulting in unprecedented rate acceleration in Cu-catalyzed bulk electrosynthesis.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Tyler Fahrenhorst-Jones, Dehui Kong, Jed M. Burns, Gregory K. Pierens, Paul V. Bernhardt, G. Paul Savage, Craig M. Williams
Summary: It is found that seco-1-Azacubane-2-carboxylic acid can undergo amide bond formation at both the N- and C-termini using proline-based bioactive molecule templates as a concept platform.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Palraj Kalimuthu, Sheron Hakopian, Dimitri Niks, Russ Hille, Paul V. Bernhardt
Summary: In this study, an electrocatalytically active formate oxidation/CO2 reduction system was developed based on FdsDABG from Cupriavidus necator, providing new insights into the kinetics of the enzyme catalytic mechanism.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Review
Biochemistry & Molecular Biology
Jennifer Hosmer, Alastair G. McEwan, Ulrike Kappler
Summary: Acetate, as an important anti-inflammatory modulator, can affect host-microbe interactions, human health, inflammation, and outcomes of microbial infections. This mini-review provides a summary of the metabolic pathways of acetate in bacteria and human cells, the functions of acetate in bacterial cells, and the impact of microbially derived acetate on human immune function.
EMERGING TOPICS IN LIFE SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Tyler Fahrenhorst-Jones, David L. Marshall, Jed. M. Burns, Gregory K. Pierens, Robert E. Hormann, Allison M. Fisher, Paul V. Bernhardt, Stephen J. Blanksby, G. Paul Savage, Philip E. Eaton, Craig M. Williams
Summary: Highly strained cage hydrocarbons have been widely used to explore chemical stability and reactivity, probe physical properties, and as bioactive molecules and in materials discovery. However, the nitrogenous congeners have received less attention. This study presents the synthesis of 1-azahomocubane and its comprehensive characterization, physical property analysis, and chemical reactivity investigation. The findings suggest that nitrogen is well tolerated in a highly strained environment.
Article
Chemistry, Multidisciplinary
Jeffrey R. Harmer, Sheron Hakopian, Dimitri Niks, Russ Hille, Paul V. Bernhardt
Summary: This article investigates the redox properties of an oxygen-tolerant and molybdenum-dependent formate dehydrogenase, providing insights into the highly efficient catalytic activity of formate oxidation and CO2 reduction associated with the enzyme.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Paul V. Bernhardt
Summary: The accurate measurement of protein redox potentials is an important task. Traditional methods have significant experimental errors. This paper proposes an automated approach that combines continuous scanning potential with time-resolved UV-vis spectroscopy, allowing for fast and accurate measurement of protein redox potentials.
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)