Catalytic Active Sites Research Articles

Queuosine biosynthetic enzyme, QueE moonlights as a cell division regulator.

In many organisms, stress responses to adverse environments can trigger secondary functions of certain proteins by altering protein levels, localization, activity, or interaction partners. Escherichia coli cells respond to the presence of specific cationic antimicrobial peptides by strongly activating the PhoQ/PhoP two-component signaling system, which regulates genes important for growth under this stress. As part of this pathway, a biosynthetic enzyme called QueE, which catalyzes a step in the formation of queuosine (Q) tRNA modification is upregulated. When cellular QueE levels are high, it co-localizes with the central cell division protein FtsZ at the septal site, blocking division and resulting in filamentous growth. Here we show that QueE affects cell size in a dose-dependent manner. Using alanine scanning mutagenesis of amino acids in the catalytic active site, we pinpoint residues in QueE that contribute distinctly to each of its functions-Q biosynthesis or regulation of cell division, establishing QueE as a moonlighting protein. We further show that QueE orthologs from enterobacteria like Salmonella typhimurium and Klebsiella pneumoniae also cause filamentation in these organisms, but the more distant counterparts from Pseudomonas aeruginosa and Bacillus subtilis lack this ability. By comparative analysis of E. coli QueE with distant orthologs, we elucidate a unique region in this protein that is responsible for QueE's secondary function as a cell division regulator. A dual-function protein like QueE is an exception to the conventional model of "one gene, one enzyme, one function", which has divergent roles across a range of fundamental cellular processes including RNA modification and translation to cell division and stress response.

Defect-rich CoRu alloy embedded in the porous carbon serving as highly-efficient and bifunctional electrocatalyst for overall water splitting over a wide pH range

Exploring highly-efficient and pH-universal overall water splitting electrocatalysts are critical but keep challenging. Herein, a highly-efficient, dual-function and pH-universal electrocatalyst consisting of CoRu alloy nanoparticles embedded in the carbon matrix (CoRu/C) was successfully synthesized through an acid etching-pyrolysis conversion process using ZIF-67 as a precursor. Benefiting from the rich crystal defects created during the alloy formation process that could serve as active catalytic sites and the optimized electronic structure, the as-obtained CoRu/C electrocatalyst required overpotentials of only 18 and 37 mV to reach a current density of 10 mA cm−2 for hydrogen evolution reaction (HER) and 184 and 170 mV for oxygen evolution reaction (OER) in 1.0 M KOH and 0.5 M H2SO4 aqueous solution, respectively. For practical application, the CoRu/C catalyst only needs a cell voltage of 1.49 and 1.45 V in a two-electrode overall water splitting system to achieve a current density of 10 mA cm−2 in alkaline and acidic medium, respectively. The present work paves a new way for the design and construction of efficient bifunctional electrocatalyst for overall water splitting, and would inspire widespread research interest in the field of energy storage and conversion.

A green perspective for the first electrochemical detection and application of balsalazide via recycled waste core-shell carbon/CdO nanoparticles-based hybrid nanosensor

In this report, a glassy carbon electrode (GCE) modified with carbon-based core–shell structures (CSC) with CdO nanoparticles has been prepared and performed for the electrochemical detection of Balsalazide (BLZ). The electrochemical investigation of BLZ was carefully examined using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) on the bare GCE, and CSC-CdO/GCE. Compared to bare GCE, the proposed CSC-CdO/GCE sensor can remarkably enhance the electrocatalytic activity towards the oxidation of BLZ with an increase in the anodic peak currents. For the optimum of experimental conditions, the influence of supporting electrolyte, the pH, concentration of the nanosensor, and scan rate on the peak potentials and current were investigated on the current response of BLZ before the electrochemical determination of BLZ in commercial human serum and urine samples for GCE, and CSC-CdO/GCE. The limit of detection (LOD) for BLZ in the linear range of 8.00 × 10−9 – 8.00 × 10−5 mol/L was determined as 2.20 × 10−9 mol/L. Recovery measurements assessed the accuracy of the proposed sensor in serum and urine samples. The developed sensor indicated high sensitivity and great stability toward BLZ. Core-shell structures are frequently preferred in sensor applications due to their perfect shapes, active catalytic sites, rapid interfacial transport of pores at different length scales, and their ability to reduce or shorten diffusion action paths. CSC was used as a modification material in this study due to its superior properties and advantages. Since CSC has a high surface area during the electron transfer process, it enables more efficient charge transfer between the electrode and the electrolyte. In the study, CdO nanoparticle modification on the CSC was ensured for a synergistic effect to enhance the surface area, electroactivity, and selectivity. After morphological, physical, and chemical characterization of composite material, electrochemical experiments showed that it is extremely promising because of its wide linear concentration range, low LOD, and nearly no interference with some interfering compounds and ions.

Cu2MoS4 Nanocatalyst-Based Electrochemical Sensor for Ofloxacin Electro-Oxidation: Delineating the Combined Roles of Crystallinity and Morphology on the Analytical Performance.

In this study, we demonstrate the influence of crystallinity and morphology on the analytical performance of various Cu2MoS4 (CMS) nanocatalysts-based electrochemical sensors for the high-efficiency detection of Ofloxacin (OFX) antibiotic. The electrochemical kinetics parameters including peak current response (ΔIp), peak-to-peak separation (ΔEp), electrochemically active surface area (ECSA), electron-transfer resistance (Rct), were obtained through the electrochemical analyses, which indicate the single-crystalline nature of CMS nanomaterials (NMs) is beneficial for enhanced electron-transfer kinetics. The morphological features and the electrochemical results for OFX detection substantiate that by tuning the tube-like to plate-like structures of the CMS NMs, it might noticeably enhance multiple adsorption sites and more intrinsic active catalytic sites due to the diffusion of analytes into the interstitial spaces between CMS nanoplates. As results, highly single-crystalline and plate-shaped morphology structures of CMS NMs would significantly enhance the electrocatalytic OFX oxidation in terms of onset potential (Eonset), Tafel slope, catalytic rate constant (kcat), and adsorption capacity (Γ). The CMS NMs-based electrochemical sensing platform showed excellent analytical performance toward the OFX detection with two ultra-wide linear detection concentration ranges from 0.25-100 and 100-1000 μM, a low detection limit of 0.058 μM, and an excellent electrochemical sensitivity (0.743 μA μM-1 cm-2).

Computational investigation of cis-1,4-polyisoprene binding to the latex-clearing protein LcpK30.

Latex clearing proteins (Lcps) catalyze the oxidative cleavage of the C = C bonds in cis-1,4-polyisoprene (natural rubber), producing oligomeric compounds that can be repurposed to other materials. The active catalytic site of Lcps is buried inside the protein structure, thus raising the question of how the large hydrophobic rubber chains can access the catalytic center. To improve our understanding of hydrophobic polymeric substrate binding to Lcps and subsequent catalysis, we investigated the interaction of a substrate model containing ten carbon-carbon double bonds with the structurally characterized LcpK30, using multiple computational tools. Prediction of the putative tunnels and cavities in the LcpK30 structure, using CAVER-Pymol plugin 3.0.3, fpocket and Molecular Dynamic (MD) simulations provided valuable insights on how substrate enters from the surface to the buried active site. Two dominant tunnels were discovered that provided feasible routes for substrate binding, and the presence of two hydrophobic pockets was predicted near the heme cofactor. The larger of these pockets is likely to accommodate the substrate and to determine the size distribution of the oligomers. Protein-ligand docking was carried out using GOLD software to predict the conformations and interactions of the substrate within the protein active site. Deeper insight into the protein-substrate interactions, including close-contacts, binding energies and potential cleavage sites in the cis-1,4-polyisoprene, were obtained from MD simulations. Our findings provide further justification that the protein-substrate complexation in LcpK30 is mainly driven by the hydrophobic interactions accompanied by mutual conformational changes of both molecules. Two potential binding modes were identified, with the substrate in either extended or folded conformations. Whilst binding in the extended conformation was most favorable, the folded conformation suggested a preference for cleavage of a central double bond, leading to a preference for oligomers with 5 to 6 C = C bonds. The results provide insight into further enzyme engineering studies to improve catalytic activity and diversify the substrate and product scope of Lcps.

Identification of novel single nucleotide variants in the drug resistance mechanism of Mycobacterium tuberculosis isolates by whole-genome analysis

BackgroundTuberculosis (TB) represents a major global health challenge. Drug resistance in Mycobacterium tuberculosis (MTB) poses a substantial obstacle to effective TB treatment. Identifying genomic mutations in MTB isolates holds promise for unraveling the underlying mechanisms of drug resistance in this bacterium.MethodsIn this study, we investigated the roles of single nucleotide variants (SNVs) in MTB isolates resistant to four antibiotics (moxifloxacin, ofloxacin, amikacin, and capreomycin) through whole-genome analysis. We identified the drug-resistance-associated SNVs by comparing the genomes of MTB isolates with reference genomes using the MuMmer4 tool.ResultsWe observed a strikingly high proportion (94.2%) of MTB isolates resistant to ofloxacin, underscoring the current prevalence of drug resistance in MTB. An average of 3529 SNVs were detected in a single ofloxacin-resistant isolate, indicating a mutation rate of approximately 0.08% under the selective pressure of ofloxacin exposure. We identified a set of 60 SNVs associated with extensively drug-resistant tuberculosis (XDR-TB), among which 42 SNVs were non-synonymous mutations located in the coding regions of nine key genes (ctpI, desA3, mce1R, moeB1, ndhA, PE_PGRS4, PPE18, rpsA, secF). Protein structure modeling revealed that SNVs of three genes (PE_PGRS4, desA3, secF) are close to the critical catalytic active sites in the three-dimensional structure of the coding proteins.ConclusionThis comprehensive study elucidates novel resistance mechanisms in MTB against antibiotics, paving the way for future design and development of anti-tuberculosis drugs.

N-doped Ru/Mo2C-based electrocatalyst for outstanding and durable hydrogen evolution reaction with universal pH

The fabrication of Pt-free electrocatalysts with outstanding activity is crucial for reducing the overpotential of the hydrogen evolution reaction (HER) and advancing the next generation of energy technologies. This study introduced a scalable one-pot pyrolysis approach for fabricating N-doped Ru/Mo2C (MCNRx) for HER. The MCNR1 catalyst offered several advantages for electrocatalytic applications and beyond. The N-doped Ru/Mo2C prevented the agglomeration of Mo2C nanomaterials and improved their electronic conductivity. Moreover, the Ru metal was uniformly distributed, providing a large number of active catalytic sites, and the enhanced crystallinity and conductive surfaces generated from the trimesic acid create mass electron migration and facilitate the presence of active centers. The MCNR1 electrocatalyst, designed with the abovementioned advantages, had exceptional performance for HER across a broad pH range. For instance, it achieved a current density of 10 mA cm−2 with an overpotential of 35 mV in 1.0 M KOH, 44 mV in 0.5 M H2SO4, and 196 mV in 1.0 M phosphate-buffered saline (PBS). Furthermore, the electrocatalyst had exceptional long-term stability across all pH levels compared to Pt/C. The synthetic approach devised in this study can be employed for various cost-effective replacements for Pt-based electrocatalysts for HER.

Hexagonal boron nitride-doped carbon membrane as anode for the enhanced adsorption and electrochemical oxidation of phenol

An activated carbon membrane (ACM) doped with hexagonal boron nitride (h-BN) was fabricated by using activated carbon as the raw material and phenolic resin as the binder. The preparation process involves blending raw materials, ball milling, membrane pressing, and high-temperature carbonization. The conductive ACM was employed as an anode to constitute an electrochemical membrane reactor (EMR) for phenol removal. The effect of h-BN doping rate (0–5 wt%) on the properties of ACM was explored. Results showed that ACM1 (1 wt% h-BN) displayed a small pore size (20 nm), high porosity (41.6 %), large specific surface area (446.8 m2/g), and strong mechanical strength (15.4 MPa) compared to the pristine ACM0. The oxygen precipitation potential of ACM1 (2.11 V) was much higher than that of ACM0 (1.53 V), thus reducing oxygen generation at the anode in EMR for phenol degradation. The phenol removal rate of phenol obtained from EMR with ACM1 as the anode at 1.5 V was up to 95.6 %, which was much higher than that for ACM0 (39.3 %). Density functional theory (DFT) calculations and experimental results confirmed that h-BN-doping enhanced the adsorption active sites, and adsorption energy, leading to the high performance of EMR for phenol removal. In addition, the equilibrium adsorption capacity of ACM1 (10.2 mg/g) was much higher than that of ACM0 (3.7 mg/g). The C atoms adjacent to pyridine N in ACM1 were identified as the adsorption and active catalytic sites by X-ray photoelectron spectroscopy (XPS) and DFT calculations. Therefore, this study sheds light on the design and fabrication of conductive carbon membranes for enhanced performance in industrial wastewater treatment.

Enhancement of oxygen evolution reaction by in situ growth PMo12@ZIF-67 on MWCNTs via perylene bisimide-based dispersant

The combination of metal organic frameworks (MOFs) and multi-walled carbon nanotubes (MWCNTs) can significantly improve their electrochemical performance. However, in most cases, chemical pre-treatment of MWCNTs is inevitable, which may compromise the ideal performance of the final composites. Herein, via a noncovalent functionalization method, PMo12@ZIF-67 was in situ grown on the surfaces of MWCNTs with the assistance of a new dispersant containing two triethylenetetramine (TETA) segments. In order to enhance the coordination of Co metal ions with the surface of MWCNTs, phenolic hydroxyl groups were incorporated into the dispersant through reaction with gallic acid (GA). After annealing, homogeneous CNT/Co6Mo6C2/Co composites were obtained, and they showed excellent performance on oxygen evolution reaction (OER). At a current density of 10 mA cm−2, the lowest overpotential is 263 mV, of which the performance is superior to that achieved by other in situ growth methods. The uniform distribution of coordination sites and subsequent in situ growth of MOFs on MWCNTs improved the electrical conductivity of the derivatives, thereby enhanced the utilization of catalytic active sites. This study presents a novel approach for synthesizing carbon-doped electrocatalytic materials, which demonstrates significant potential in various electrochemical applications.

Electrochemical Restructuring Driven Catalytic Cycle of Bi-Based Heterojunctions for High-Performance Lithium-Sulfur Batteries.

Restructuring is an important phenomenon in catalytic reactions. Conversion-type materials with suitable redox potential may undergo in situ electrochemically driven restructurings and induce highly active catalytic sites in a working lithium-sulfur battery. Herein, driven by the electrochemical conversion reaction of BiVO4, a reversible catalytic cycle of Bi/amorphous Li3VO4 (a-Li3VO4) and Bi2S3/a-Li3VO4 heterojunctions is constructed, which targets the oxidation of Li2S and the conversion of polysulfide, respectively. The heterostructures and electrochemically driven size confinement provide abundant sites for shuttle restraining and sulfur conversion. Especially, the p-block Bi and Bi2S3 could dramatically reduce the conversion energy barriers of Li2S and polysulfide by virtue of the p-p orbital hybridization, promoting bidirectional reactions of the sulfur cathode. As a result, the corresponding sulfur cathode possesses a high reversible capacity of 7.5 mAh cm-2 after 120 cycles under a high sulfur loading of 10.3 mg cm-2 with a current density of 0.38 mA cm-2. This study furnishes a feasible scheme to obtain highly effective catalysts for bidirectional sulfur redox by utilizing the electrochemically induced restructuring.

CoFe2O4 nanosheets grown in situ on nickel nanowires for efficient hydrazine oxidation-boosted hydrogen production

The use of the hydrazine oxidation reaction (HzOR) to replace the oxygen evolution reaction (OER), which has a large thermodynamic barrier and a slow kinetic process, is a feasible way to achieve energy saving hydrogen production, but the construction of superior bifunctional catalysts is also challenging. Herein, an array (CoFe2O4@NNWs) of CoFe2O4 nanosheet grown in situ on nickel nanowires (NNWs) has been prepared and showed the excellent performance for hydrogen evolution reaction (HER) and HzOR under alkaline media, which require a lower potential of −91 mV (vs. RHE) for HzOR and 45 mV (vs. RHE) for HER at the current density (j, 10 mA cm−2). The overall hydrazine splitting (OHzS) electrolyzer requires cell voltages of 0.028 V (10 mA cm−2) and 1.227 V (1000 mA cm−2) by using electricity, wind, solar and thermal energies as power sources and had remarkable long-term stability. In addition, the potential of the OHzS is 1.67 V lower than that of OWS at the j of 10 mA cm−2. The excellent performance of CoFe2O4@NNWs is attributed to the fact that the heterojunction fromed by CoFe2O4 and NNWs effectively regulates the electron density of the sample, thereby improving the kinetics of H* adsorption and the N2H4 dehydrogenation, which can be confirmed by DFT. Second, the continuous electron transport channel provided by NNWs improves the electrical conductivity of the sample. In addition, the 2D CoFe2O4 nanosheets grown on NNWs not only expose more catalytic active sites, but also provide a fast channel for the diffusion of the electrolyte.

High-Entropy Lithium Niobate Nanocubes for Photocatalytic Water Splitting under Visible Light.

The vast compositional space available in high-entropy oxide semiconductors offers unique opportunities for electronic band structure engineering in an unprecedented large room. In this work, with wide band gap semiconductor lithium niobate (LiNbO3) as a model system, we show that the substitutional addition of high-entropy metal cation mixtures within the Nb sublattice can lead to the formation of a single-phase solid solution featuring a substantially narrowed band gap and intense broadband visible light absorption. The resulting high-entropy LiNbO3 [denoted as Li(HE)O3] crystallizes as well-faceted nanocubes; atomic-resolution imaging and elemental mapping via transmission electron microscopy unveil a distinct local chemical complexity and lattice distortion, characteristics of high-entropy stabilized solid solution phases. Because of the presence of high-entropy stabilized Co2+ dopants that serve as active catalytic sites, Li(HE)O3 nanocubes can accomplish the visible light-driven photocatalytic water splitting in an aqueous solution containing methanol as a sacrificial electron donor without the need of any additional co-catalysts.

Anion Structure Regulation of Cobalt Silicate Hydroxide Endowing Boosted Oxygen Evolution Reaction.

Transition metal silicates (TMSs) are attempted for the electrocatalyst of oxygen evolution reaction (OER) due to their special layered structure in recent years. However, defects such as low theoretical activity and conductivity limit their application. Researchers always prefer to composite TMSs with other functional materials to make up for their deficiency, but rarely focus on the effect of intrinsic structure adjustment on their catalytic activity, especially anion structure regulation. Herein, applying the method of interference hydrolysis and vacancy reserve, new silicate vacancies (anionic regulation) are introduced in cobalt silicate hydroxide (CoSi), named SV-CoSi, to enlarge the number and enhance the activity of catalytic sites. The overpotential of SV-CoSi declines to 301mV at 10mA cm-2 compared to 438mV of CoSi. Source of such improvement is verified to be not only the increase of active sites, but also the positive effect on the intrinsic activity due to the enhancement of cobalt-oxygen covalence with the variation of anion structure by density functional theory (DFT) method. This work demonstrates that the feasible intrinsic anion structure regulation can improve OER performance of TMSs and provides an effective idea for the development of non-noble metal catalyst for OER.

Stepwise structural evolution toward robust carboranealkynyl-protected copper nanocluster catalysts for nitrate electroreduction.

Atomically precise metal nanoclusters (NCs) are emerging as idealized model catalysts for imprecise metal nanoparticles to unveil their structure-activity relationship. However, the directional synthesis of robust metal NCs with accessible catalytic active sites remains a great challenge. In this work, we achieved bulky carboranealkynyl-protected copper NCs, the monomer Cu13·3PF6 and nido-carboranealkynyl bridged dimer Cu26·4PF6, with fair stability as well as accessible open metal sites step by step through external ligand shell modification and metal-core evolution. Both Cu13·3PF6 and Cu26·4PF6 demonstrate remarkable catalytic activity and selectivity in electrocatalytic nitrate (NO3-) reduction to NH3 reaction, with the dimer Cu26·4PF6 displaying superior performance. The mechanism of this catalytic reaction was elucidated through theoretical computations in conjunction with in situ FTIR spectra. This study not only provides strategies for accessing desired copper NC catalysts but also establishes a platform to uncover the structure-activity relationship of copper NCs.

A Volcano Correlation between Catalytic Activity for Sulfur Reduction Reaction and Fe Atom Count in Metal Center.

Sulfur reduction reaction (SRR) facilitates up to 16 electrons, which endows lithium-sulfur (Li-S) batteries with a high energy density that is twice that of typical Li-ion batteries. However, its sluggish reaction kinetics render batteries with only a low capacity and cycling life, thus remaining the main challenge to practical Li-S batteries, which require efficient electrocatalysts of balanced atom utilization and site-specific requirements toward highly efficient SRR, calling for an in-depth understanding of the atomic structural sensitivity for the catalytic active sites. Herein, we manipulated the number of Fe atoms in iron assemblies, ranging from single Fe atom to diatomic and triatomic Fe atom groupings, all embedded within a carbon matrix. This led to the revelation of a "volcano peak" correlation between SRR catalytic activity and the count of Fe atoms at the active sites. Utilizing operando X-ray absorption and X-ray diffraction spectroscopies, we observed that polysulfide adsorption-desorption and electrochemical conversion kinetics varied up and down with the incremental addition of even a single iron atom to the catalyst's metal center. Our results demonstrate that the metal center with exactly two iron atoms represents the optimal configuration, maximizing atom utility and adeptly handling the conversion of varied intermediate sulfur species, rendering the Li-S battery with a high areal capacity of 23.8 mAh cm-2 at a high sulfur loading of 21.8 mg cm-2. Our results illuminate the pivotal balance between atom utilization and site-specific requirements for optimal electrocatalytic performance in SRR and diverse electrocatalytic reactions.

Strukturelle Einblicke in die Terpencyclasedomänen Zweier Pilzlicher Sesterterpensyntasen und Enzymengineering zur Diversifizierung von Sesterterpenen

AbstractÜber die Strukturen und katalytischen Mechanismen von Sesterterpensynthasen (StTSs) ist wenig bekannt, was das strukturbasierte Engineering von StTSs zur Erweiterung der strukturellen Diversität von Sesterterpenen erheblich erschwert. Wir berichten hier über die Kristallstrukturen der Terpencyclisierungsdomänen (TC) von zwei pilzlichen StTSs: der Sesterfisherol‐Synthase (NfSS) und der Sesterbrasiliatrien‐Synthase (PbSS). Beide TC‐Strukturen enthalten Benzyltriethylammoniumchlorid (BTAC), Pyrophosphat (PPi) und Magnesiumionen (Mg2+), wodurch die katalytisch aktiven Zentren klar definiert sind. Eine Kombination aus Theorie und Experimenten, einschließlich der Modellierung carbokationischer Intermediate, ortsgerichteter Mutagenese und Isotopenmarkierungen, lieferte detaillierte Einblicke in die strukturellen Grundlagen der katalytischen Mechanismen. Strukturbasiertes Engineering von NfSS und PbSS führte zur Bildung von 20 Sesterterpenen, darunter 13 neue Verbindungen und vier Epimerpaare mit unterschiedlichen Konfigurationen an C18. Diese Ergebnisse erweitern die strukturelle Vielfalt von Sesterterpenen und liefern wichtige Erkenntnisse für die zukünftige Forschung im Bereich der synthetischen Biologie.

Structural Insights Into the Terpene Cyclization Domains of Two Fungal Sesterterpene Synthases and Enzymatic Engineering for Sesterterpene Diversification.

Little is known about the structures and catalytic mechanisms of sesterterpene synthases (StTSs), which greatly hinders the structure-based engineering of StTSs for structural diversity expansion of sesterterpenes. We here report on the crystal structures of the terpene cyclization (TC) domains of two fungal StTSs: sesterfisherol synthase (NfSS) and sesterbrasiliatriene synthase (PbSS). Both TC structures contain benzyltriethylammonium chloride (BTAC), pyrophosphate (PPi), and magnesium ions (Mg2+), clearly defining the catalytic active sites. A combination of theory and experiments including carbocationic intermediates modeling, site-directed mutagenesis, and isotope labeling provided detailed insights into the structural basis for their catalytic mechanisms. Structure-based engineering of NfSS and PbSS resulted in the formation of 20 sesterterpenes including 13 new compounds and four pairs of epimers with different configurations at C18. These results expand the structural diversity of sesterterpenes and provide important insights for future synthetic biology research.

Electron-deficient Co7Fe3 induced by interfacial effect of molybdenum carbide boosting oxygen evolution reaction

Developing a high-activity and low-cost catalyst to reduce the anodic overpotential is essential for hydrogen production from water splitting. In this work, a hetero-structured Co7Fe3/Mo2C@C catalyst has been developed to efficiently catalyze oxygen evolution reaction (OER), the overpotential (ƞ10) of Co7Fe3/Mo2C@C-catalyzed OER with current density of 10 mA/cm2 is about 254 mV, substantially lower than the counterparts of Co7Fe3@C-catalyzed OER (ƞ10, 308 mV) and Mo2C@C-catalyzed OER (ƞ10, 439 mV), close to that of OER catalyzed by commercial RuO2. The mechanistic studies reveal that the distinct electron transfer across the Co7Fe3/Mo2C interface results in electron-deficient Co7Fe3, which has been identified as the highly active catalytic sites. Density functional theory (DFT) calculations manifest that Mo2C induces a distinct decrease in electron density on Co7Fe3 and upgrades the d-band centers of Co and Fe in Co7Fe3 towards Fermi energy level, thus substantially lowering the energy barrier of the rate-determining reaction step and conferring significantly improved OER activity on the Co7Fe3/Mo2C@C catalyst.

Synergistic electrochemical catalysis by high-entropy metal phosphide in lithium–sulfur batteries

The shuttle effect and sluggish redox kinetics of polysulfides have hindered the development of lithium–sulfur batteries (LSBs) as premier energy storage devices. To address these issues, a high-entropy metal phosphide (NiCoMnFeCrP) was synthesized using the sol–gel method. NiCoMnFeCrP, with its rich metal species, exhibits strong synergistic effects and provides numerous catalytic active sites for the conversion of polysulfides. These active sites, possessing significant polarity, can bond with polysulfides. In situ ultraviolet–visible were conducted to monitor the dynamic changes in species and concentrations of polysulfides, validating the ability of NiCoMnFeCrP to facilitate the conversion of polysulfides. The batteries with the NiCoMnFeCrP catalyst as functional separators exhibited minimal capacity decay rates of 0.04 % and 0.23 % after 100 cycles at 0 °C and 60 °C, respectively. This indicates that the NiCoMnFeCrP catalyst possesses good thermal stability. Meanwhile, its area capacity can reach 4.78 mAh cm−2 at a high sulfur load of 4.54 mg cm−2. In conclusion, NiCoMnFeCrP achieves the objective of mitigating the shuttle effect and accelerating the kinetics of the redox reaction, thereby facilitating the commercialization of LSBs.

Furosemide Derails Human Lysozyme Fibrillation by Interacting with Aggregation Hot Spots: A Biophysical Comprehension.

Kidney-associated human lysozyme amyloidosis leads to renal impairments;thus, patients are often prescribed furosemide. Based on this fact, the effect of furosemide on induced human lysozyme fibrillation, in vitro, is evaluated by spectroscopic, calorimetric, computational, and cellular-based assays/methods. Results show that furosemide increases the lag phase and decreases the apparent rate of aggregation of human lysozyme, thereby decelerating the nucleation phase and amyloid fibril formation, as confirmed by the decrease in the level of Thioflavin-T fluorescence. Fewer entities of hydrodynamic radii of ∼171 nm instead of amyloid fibrils (∼412 nm) are detected in human lysozyme in the presence of furosemide by dynamic light scattering. Moreover, furosemide decreases the extent of conversion of the α/β structure of human lysozyme into a predominant β-sheet. The isothermal titration calorimetry established that furosemide forms a complex with human lysozyme, which was also confirmed through fluorescence quenching and computational studies. Also, human lysozyme lytic activity is inhibited competitively by furosemide due to the involvement of amino acid residues of the active site in catalysis, as well as complex formation. Conclusively, furosemide interacts with Gln58, Ile59, Asn60, Ala108, and Trp109 of aggregation-prone regions 2 and 4 of human lysozyme, thereby masking its sites of aggregation and generating only lower-order entities that are less toxic to red blood cells than the fibrils. Thus, furosemide slows the progression of amyloid fibrillation in human lysozyme.