Oxidation Rate Research Articles

Single-Entity Electrochemistry of N-Doped Graphene Oxide Nanostructures for Improved Kinetics of Vanadyl Oxidation.

N-doped graphene oxides (GO) are nanomaterials of interest as building blocks for 3D electrode architectures for vanadium redox flow battery applications. N- and O-functionalities have been reported to increase charge transfer rates for vanadium redox couples. However, GO synthesis typically yields heterogeneous nanomaterials, making it challenging to understand whether the electrochemical activity of conventional GO electrodes results from a sub-population of GO entities or sub-domains. Herein, single-entity voltammetry studies of vanadyl oxidation at N-doped GO using scanning electrochemical cell microscopy (SECCM) are reported. The electrochemical response is mapped at sub-domains within isolated flakes and found to display significant heterogeneity: small active sites are interspersed between relatively large inert sub-domains. Correlative Raman-SECCM analysis suggests that defect densities are not useful predictors of activity, while the specific chemical nature of defects might be a more important factor for understanding oxidation rates. Finite element simulations of the electrochemical response suggest that active sub-domains/sites are smaller than the mean inter-defect distance estimated from Raman spectra but can display very fast heterogeneous rate constants >1cms-1. These results indicate that N-doped GO electrodes can deliver on intrinsic activity requirements set out for the viable performance of vanadium redox flow battery devices.

Differential contributions of the gut microbiota and metabolome to pathomechanisms in ulcerative colitis: an in vitro analysis

ABSTRACT The gut microbiota has been implicated in onset and progression of ulcerative colitis (UC). Here, we assess potential causal involvement of the microbiota and -associated fecal water (FW) metabolome in altering key functional parameters of the colonic epithelium. Fecal samples were collected from N = 51 healthy controls (HC), N = 36 patients with active UC (UC-A), and N = 41 subjects in remission N = 41 (UC-R). Using in vitro incubation experiments, the FW metabolome’s impact on butyrate oxidation rates/gene expression and cell death (cytotoxicity) of HT-29 cells, cytokine production by PBMC, and barrier integrity of Caco2 monolayers was evaluated. The FW metabolome from patients and individuals hosting the Bacteroides 2 (Bact2) enterotype (69% of UC-A, 31% of UC-R, 3% of HC), characterized by lower levels of median- and short-chain fatty acids and furan compounds, left butyrate oxidation rates unaltered but affected associated gene expression profiles. UC patients/Bact2-carriers’ FW lowered PBMC IL-8 production and increased IL-1β production. Patients’ FW increased cytotoxicity, associated with sulfide compound levels. Bact2 carriers’ FW, displaying higher levels of bile acids, lowered barrier function upon incubation of monolayers. The FW metabolome of patients and individuals hosting a dysbiotic microbiota could contribute to the disruption of functional processes of the colonic epithelium as observed in UC.

Screening Anti-Rheumatoid Arthritis Synovitis Effective Ingredients of Total Flavonoid From Artemisia argyi Folium Based on Spectrum-Effect Relationship.

Flavonoids are the main nonvolatile component responsible for the anti-rheumatoid arthritis (RA) synovitis activities of Artemisia argyi Folium. However, the effective ingredient remains unidentified. Spectrum-effect relationships analysis was a reliable and efficient strategy for herbal effective ingredient discovery. This study aimed to screen the effective ingredients within the total flavonoid from Artemisia argyi Folium (TFAA) that exhibit anti-RA synovitis activities based on spectrum-effect relationship. TFAA was obtained through ethanol extraction and subsequent purification with D101 resin from 15 distinct batches of Artemisia argyi Folium. The fingerprint of TFAA was established using HPLC, and its efficacy against RA synovitis was evaluated by determining the inhibition rate of nitric oxide (NO) on MH7A synovioblast induced by TNF-α. Common peaks were identified using HPLC-MS/MS and authentic standards. The spectrum-effect relationships between the fingerprints and efficacy were analyzed by gray relational analysis (GRA), canonical correlation analysis (CCA), and partial least squares regression analysis (PLSR) to pinpoint the peaks responsible for the anti-RA synovitis activity, and the results were further verified by invitro anti-RA synovitis experiments and molecular docking studies. The fingerprint revealed 14 common peaks, and 12 compounds were identified, including four caffeoylquinic acids and eight flavonoids. Among them, five flavonoids-X10 (hispidulin), X11 (jaceosidin), X12 (centaureidin), X13 (eupatilin), and X14 (casticin)-were highly relevant to anti-RA synovitis activity. Verification experiments confirmed their inhibitory effect on NO production and cytokine secretion in MH7A cells, showing anti-RA synovitis potential, which was consistent with the established spectrum effect relationship. The underlying mechanism might be related to the inhibition of iNOS. Hispidulin, jaceosidin, centaureidin, eupatilin, and casticin were the key effective ingredient of TFAA responsible for its anti-RA synovitis effects. These compounds can serve as quality control markers for Artemisia argyi Folium and as lead compounds for anti-RA synovitis treatment.

Metabolic Effects of Sodium Thiosulfate During Resuscitation from Trauma and Hemorrhage in Cigarette-Smoke-Exposed Cystathionine-γ-Lyase Knockout Mice

Background: Acute and chronic pre-traumatic cigarette smoke exposure increases morbidity and mortality after trauma and hemorrhage. In mice with a genetic deletion of the H2S-producing enzyme cystathione-γ-lyase (CSE−/−), providing exogenous H2S using sodium thiosulfate (Na2S2O3) improved organ function after chest trauma and hemorrhagic shock. Therefore, we evaluated the effect of Na2S2O3 during resuscitation from blunt chest trauma and hemorrhagic shock on CSE−/− mice with pre-traumatic cigarette smoke (CS) exposure. Since H2S is well established as being able to modify energy metabolism, a specific focus was placed on whole-body metabolic pathways and mitochondrial respiratory activity. Methods: Following CS exposure, the CSE−/− mice underwent anesthesia, surgical instrumentation, blunt chest trauma, hemorrhagic shock for over 1 h (target mean arterial pressure (MAP) ≈ 35 ± 5 mmHg), and resuscitation for up to 8 h comprising lung-protective mechanical ventilation, the re-transfusion of shed blood, fluid resuscitation, and continuous i.v. noradrenaline (NoA) to maintain an MAP ≥ 55 mmHg. At the start of the resuscitation, the mice randomly received either i.v. Na2S2O3 (0.45 mg/gbodyweight; n = 14) or the vehicle (NaCl 0.9%; n = 11). In addition to the hemodynamics, lung mechanics, gas exchange, acid–base status, and organ function, we quantified the parameters of carbohydrate, lipid, and protein metabolism using a primed continuous infusion of stable, non-radioactive, isotope-labeled substrates (gas chromatography/mass spectrometry) and the post-mortem tissue mitochondrial respiratory activity (“high-resolution respirometry”). Results: While the hemodynamics and NoA infusion rates did not differ, Na2S2O3 was associated with a trend towards lower static lung compliance (p = 0.071) and arterial PO2 (p = 0.089) at the end of the experiment. The direct, aerobic glucose oxidation rate was higher (p = 0.041) in the Na2S2O3-treated mice, which resulted in lower glycemia levels (p = 0.050) and a higher whole-body CO2 production rate (p = 0.065). The mitochondrial respiration in the heart, kidney, and liver tissue did not differ. While the kidney function was comparable, the Na2S2O3-treated mice showed a trend towards a shorter survival time (p = 0.068). Conclusions: During resuscitation from blunt chest trauma and hemorrhagic shock in CSE−/− mice with pre-traumatic CS exposure, Na2S2O3 was associated with increased direct, aerobic glucose oxidation, suggesting a switch in energy metabolism towards preferential carbohydrate utilization. Nevertheless, treatment with Na2S2O3 coincided with a trend towards worsened lung mechanics and gas exchange, and, ultimately, shorter survival.

Kinetic and Mechanistic Investigation of L‐Phenylalanine Oxidation by Alkaline Cu(III) Periodate in CPC Micellar Medium

ABSTRACTAmino acid oxidation is fascinating because different oxidants produce diverse compounds. No research has examined how metal catalysts affect amino acid oxidation by diperiodatocuprate (III) (DPC) in micellar environments. This research is crucial to understanding amino acids in redox processes and identifying active species of Ru(III) and DPC. The study will evaluate how cationic surfactant affects Ru(III)‐facilitated L‐phenylalanine (L‐Pheala) oxidation utilizing DPC in an alkaline medium. The reaction's advancement has been assessed employing the pseudo‐first‐order condition as a gauge for [OH−], [DPC], ionic strength, [L‐Pheala], [Ru(III)], [IO4−], [Surfactant], and temperature. L‐Pheala and DPC interact stoichiometrically in a ratio of 1:4. Across the spectrum of concentrations examined, the reported reaction reflects less than unit order kinematics in relation to both [L‐Pheala] (0.61 in the aqueous medium and 0.58 in the CPC micellar medium) and [OH−] (0.47 in the aqueous medium and 0.51 in the CPC micellar medium), first‐order reliance on the [DPC] and [Ru(III)], and negative fractional‐order for [IO4−] (−0.54 in the aqueous medium and −0.56 in the CPC micellar medium). A zero salt effect is suggested by the observed constancy in oxidation rate with the inclusion of electrolytes. The oxidation rate is significantly enhanced by Ru(III) solution (as a catalyst) at ppm concentration. Cetylpyridinium chloride (CPC) micellar media facilitate an additional enhancement (four times) in the rate of the reaction. CPC thus exhibits an excellent compatibility with Ru(III) for the L‐Pheala oxidation using (DPC).

Distinct pathway of multiferroic silver-decorated zinc ferrite nanocatalyst performance for Acinate insecticide oxidation

The current study investigating the preparation and application of a Multiferroic nano-scale silver zinc ferrite substance (Ag0.5Zn0.5Fe2O4 nanocatalyst) has been established. Multiferroic silver zinc ferrite substance is prepared by co-precipitation technique as hybridized composite. This synethsized nanoparticles was characterized via X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) as well as Scanning Electron Miscospopy (SEM). Such nanoparticles are used as a sustainable recyclable photo-Fenton’s reagent precursor for treating insecticide in wastewater. The results revealed a high Acinate oxidation rate reached to 97% removal within 40 min of irradiance time. To increase the performance, the operating variables are optimized. pH 3.0 and 40 and 400 mg/L for Ag0.5Zn0.5Fe2O4 and hydrogen peroxide, respectively are identified as the optimum values. Also, kinetics and thermodynamic are evaluated and the reaction is subsequent the first-order kinetics model and exothermic and non-spontaneous in nature with a low energy barrier of 35.02 kJ/mol. The advantage of Ag0.5Zn0.5Fe2O4 catalyst is its sustainability since it recovered for multiple reuse with a high activity reached to 80% removal rate after six cyclic use compared to 97% of fresh catalyst use.

A numerical study of internal transport in oxidizing liquid core–shell iron particles

In an effort to improve the understanding of the rate-limiting mechanisms in liquid iron particle combustion, this study investigates the impact of internal transport within a core–shell structure. The two-dimensional axisymmetric transient continuum model as presented in previous publication (Thijs et al., 2023) is extended, such that the boundary layer between the particle and the gas, surface processes at the particle–gas interface, as well as the internal oxide layer within the particle, considering the transport of reactive O and Fe ions, are resolved. Information from the equilibrium phase diagram, which is included as supplementary data, is used to determine oxidation rate of the particle. The study reveals that finite-rate internal transport significantly alters the temperature evolution compared to models assuming infinitely fast transport. At elevated oxygen concentrations, internal transport becomes rate-limiting, restricting the maximum particle temperature. The core–shell assumption leads to a higher local oxidation degree at the particle–gas interface than the average in the particle, reducing the overall oxygen consumption rate. The maximum particle temperature is reached when heat loss exceeds heat release. Although internal transport limits the maximum temperature, the initial heating rate remains overestimated, suggesting that the initial phase is not solely limited by external oxygen diffusion, and the L2-gas surface is not at thermodynamic equilibrium. The model does not account for the particle size effect on maximum temperature as observed in some experiments. A hypothetical explanation is that internal convection, more pronounced in larger particles, may reduce the internal transport limitation, leading to higher maximum temperatures in larger particles.Novelty and significanceThis study advances the understanding of oxidation rate-limiting mechanisms in liquid iron particle combustion by numerically investigating the impact of internal transport within a core–shell structure. By using a two-dimensional axisymmetric transient continuum model, the research reveals that finite-rate internal transport significantly affects temperature evolution of an oxidizing micron-sized iron particle, particularly at elevated oxygen concentrations where it becomes rate-limiting. The findings demonstrate that a finite-rate internal transport leads to a higher local oxidation degree at the particle–gas interface, reducing the oxygen consumption rates. The study highlights that finite-rate internal transport limits the maximum particle temperature at elevated oxygen concentrations, a trend observed in isolated iron particle combustion experiments. Furthermore, this study provides a hypothetical explanation for the experimentally observed particle size effects on the maximum particle temperature, emphasizing the role of internal convection in larger particles

Greenly Synthesized Conducting Polymer Nanotunnels with Metal-Hydroxide Nanobundles in Single Dais for Unmitigated Water Oxidation.

Electrochemical water splitting required efficient electrocatalysts to produce clean hydrogen fuel. Here, we adopted greenway coprecipitation (GC) method to synthesize conducting polymer (CP) nanotunnel network affixed with luminal-abluminal CoNi hydroxides (GC-CoNiCP), namely, GC-Co1Ni2CP, GC-Co1.5Ni1.5CP, and GC-Co2Ni1CP. The active catalyst, GC-Co2Ni1CP/GC, has low oxygen evolution reaction (OER) overpotential (307 mV) and a smaller Tafel slope (47 mV dec-1) than IrO2 (125 mV dec-1). The electrochemical active surface area (EASA) normalized linear sweep voltammetry (LSV) curve exhibited outstanding intrinsic activity of GC-Co2Ni1CP, which required 285 mV to attain 10 mA cm-2. At 1.54 V, the estimated turnover frequency (TOF) of GC-Co2Ni1CP/GC (0.017337 s-1) was found to be 3-fold higher than that of IrO2 (0.0014 s-1). Furthermore, the GC-Co2Ni1CP/NF consumed a very low overpotential (281 mV) with a small Tafel slope of 121 mV dec-1. The ultrastability of GC-Co2Ni1CP for industrial application was confirmed by durability at 10 and 100 mA cm-2 for the OER (GC/NF-8 h, 2.0%/100 h, 2.2%) and overall water splitting (100 h, 3.8%), which implies that GC-Co2Ni1CP had adequate kinetics to address the elevated rates of water oxidation. The effect of pH and addition of tetramethylammonium cation (TMA+) reveal that GC-Co2Ni1CP follows the lattice oxygen mechanism (LOM). The solar-powered water electrolysis at 1.55 V supports the efficacy of GC-Co2Ni1CP in the solar-to-hydrogen conversion. The environmental impact studies and solar-driven water electrolysis proved that GC-CoNiCP has excellent greenness and efficiency, respectively.

Bioenergetic suppression by redox-active metabolites promotes antibiotic tolerance in Pseudomonas aeruginosa

The proton-motive force (PMF), consisting of a pH gradient and a membrane potential (ΔΨ) underpins many processes essential to bacterial growth and/or survival. Yet bacteria often enter a bioenergetically diminished state characterized by a low PMF. Consequently, they have increased tolerance for diverse stressors, including clinical antibiotics. Despite the ubiquity of low metabolic rates in the environment, the extent to which bacteria have agency over entry into such a low-bioenergetic state has received relatively little attention. Here, we tested the hypothesis that production of redox-active metabolites (RAMs) could drive such a physiological transition. Pseudomonas aeruginosa is an opportunistic pathogen that produces phenazines, model RAMs that are highly toxic in the presence of molecular oxygen (O2). Under oxic conditions, the phenazines pyocyanin and phenazine-1-carboximide, as well as toxoflavin-a RAM produced by Burkholderia species-suppress the ΔΨ in distinct ways across distributions of single cells, reduce the efficiency of proton pumping, and lower cellular adenosine-triphosphate (ATP) levels. In planktonic culture, the degree and rate by which each RAM lowers the ΔΨ correlates with the protection it confers against antibiotics that strongly impact cellular energy flux. This bioenergetic suppression requires the RAM's presence and corresponds to its cellular reduction rate and abiotic oxidation rate by O2; it can be reversed by increasing the ΔΨ with nigericin. RAMs similarly impact the bioenergetic state of cells in (hyp)oxic biofilm aggregates. Collectively, these findings demonstrate that bacteria can suppress their bioenergetic state by the production of endogenous toxins in a manner that bolsters stress resilience.

Transport properties of high Mach number hypersonic air plasmas

Abstract The collisional and transport properties of hypersonic plasmas have been simulated by an air plasma chemistry model, which includes collisions with electrons, ions and neutral species, elastic scattering, vibrational relaxation and a transport model. Species and thermal fluxes at the surface of the vehicle have been investigated as a function of post-shock gas temperature and species sticking coefficient for a fixed altitude of 50 km. At temperatures below about 5,000 K, the leading species are vibrationally excited nitrogen molecules, while at higher temperatures the molecular nitrogen and atomic oxygen dominate. Large fluxes of oxygen atoms have been observed in the simulations, on the order of 10^20 cm^-2s^ -1, which may lead to high rates of surface oxidation. Another subject of this study is temperature equilibration. For electrons, equilibration takes tens of microseconds, while the vibrational temperature equilibration time vary widely; from a few microseconds to hundreds of microseconds, depending on the gas temperature. Finally, the adiabatic parameter  was calculated for post-shock gas temperatures 5,000 K and 10,000 K and total gas density 1.2×10^17 cm^(-3). For post-shock gas temperature 5,000 K, only a slight reduction of gamma from the ideal gas value of ~1.4 is observed, while for 10,000 K it drops to ~1.26, which has a considerable impact on plasma properties. It was further established that the vibrational kinetics plays a leading role. While a single excited vibrational level of the N2 molecule captures the salient properties of the plasma, a detailed vibration kinetics is required for high-fidelity simulations.

Kinetic Analysis of Molten Oxide Reduction Using Bottom-Blown Hydrogen Injection

Hydrogen-based smelting reduction has received widespread attention as an important technology for realizing low-carbon development in hydrogen metallurgy. In this study, the thermodynamics of smelting reduction was firstly analyzed by using FactSage 8.1 thermodynamic software, on the basis of which smelting reduction experiments of iron oxides by using bottom-blown hydrogen were carried out. The experiments used oxidized pellets as experimental materials, and the effects of the reduction process were analyzed in terms of the reduction temperature, the reduction time, and the hydrogen flow rate. The experimental results show that under the experimental conditions of a temperature of 1550 °C and a hydrogen flow rate of 0.2 Nm3/h, the reduction rate of iron oxides in the process of reducing iron oxides by hydrogen is significantly faster in the first 10 min than after 10 min. The hydrogen utilization rate reached a maximum of 41.87%, then decreased continuously and finally maintained at about 20%. Using the method of model fitting, it was found that the hydrogen-based molten reduction conformed to the phase boundary reaction model (Gα=1−(1−α)1/2), the corresponding mechanism function is fα=2(1−α)1/2, where α stands for the reduction conversion, and the reaction rate constant k(T) is 2.37 × 10−4 s−1 under the experimental conditions.

Aging delays the suppression of lipolysis and fatty acid oxidation in the postprandial period.

Plasma glycerol and free fatty acid concentrations decrease following oral glucose consumption, but changes in the rate of lipolysis during an oral glucose tolerance test (OGTT) have not been documented in conjunction with changes in fatty acid (FA) oxidation or reesterification rates in healthy individuals. After a 12-h overnight fast, 15 young (21-35 yr; 7 men and 8 women) and 14 older (60-80 yr; 7 men and 7 women) participants had the forearm vein catheterized for primed continuous infusion of [1,1,2,3,3-2H]glycerol. A contralateral hand vein was catheterized for arterialized blood sampling. Indirect calorimetry was performed simultaneously to determine total FA and carbohydrate (CHO) oxidation rates (Rox). Total FA reesterification rates (Rs) were estimated from tracer-measured lipolytic and FA oxidation rates. After a 90-min equilibration period, participants underwent a 120-min, 75-g OGTT. Glycerol rate of appearance (Ra), an index of lipolysis, decreased significantly from baseline 5 min postchallenge in young participants and 30 min in older participants. At 60 min, FA Rox decreased in both groups, but was significantly higher in older participants. Between 5 and 90 min, CHO Rox was significantly lower in older participants. In addition, FA Rs was significantly lower in older participants at 60 and 90 min. The area under the curve (AUC) for FA Rox was greater than that for FA Rs in older, but not in young participants. Our results indicate that, in aging, the postprandial suppression of lipolysis and FA oxidation are delayed such that FA oxidation is favored over CHO oxidation and FA reesterification.NEW & NOTEWORTHY To our knowledge, our investigation is the first to demonstrate changes in lipolysis during an oral glucose tolerance test (OGTT) in healthy young and older individuals. Plasma glycerol and free fatty acid concentrations changed after glycerol rate of appearance (Ra), indicating that plasma concentrations are incomplete surrogates of the lipolytic rate. Moreover, simultaneous determinations of substrate oxidation rates are interpreted to indicate that metabolic inflexibility in aging is characterized by delayed changes in postprandial substrate utilization related to the lipolytic rate.

A three-stage oxidation method improves sludge dewaterability by achieving sustained oxidation and phased enhanced coagulation: Ingeniously using H2O2 as a “converter”

Sludge reduction is essential for mitigating the environmental hazards associated with sludge. The use of ferric chloride (Fe(III)) catalyzed ferrate (Fe(VI)) can significantly enhance sludge dewaterability by increasing the Fe(VI) oxidation rate and maintaining in-situ enhanced coagulation. However, its weak oxidation ability at the sludge’s original pH limits its practical application. To address this, hydrogen peroxide (H2O2) strengthened Fe(VI)/Fe(III) was employed to efficiently improve sludge dewaterability without pH adjustment, thereby enhancing the environmental utilization capacity of sludge. Compared to raw sludge, the treatment of Fe(VI)/Fe(III)–H2O2 resulted in approximately the 95% reduction in specific resistance to filtration (SRF) and increased the bioavailable phosphorus (P) content in dewatered sludge. During the oxidation process, highly reactive species such as tetravalent iron (Fe(IV)) and hydroxyl radicals (OH) were generated, facilitating the release of tightly bound water in extracellular polymeric substances (EPS). Importantly, the oxidation process was divided into three stages (persistent moderate oxidation — fast strong oxidation — sustained weak oxidation) based on the predominant reactive species (Fe(IV) or OH). This division promoted more robust and more durable oxidation processes. Phased enhanced coagulation occurred during the oxidation process. The gradual increase in Fe(III) content led to the re-flocculation of damaged EPS, enlarging the size of sludge drainage pores/channels and improving water discharge efficiency. Additionally, the costs and carbon emissions of chemicals for the Fe(VI)/Fe(III)–H2O2 process were 18% and 52% lower than those of the traditional Fenton method. This study not only achieves the goals of sludge reduction and resource collection but also provides insights into selecting sludge conditioning methods that meet pollution reduction and carbon emission reduction requirements.

Regulation of Microlocalization of Antioxidants by Surfactant Micelles in Oil-in-Water Emulsions.

The mass transport effect of aqueous micelles on antioxidants and oxidation products in emulsions may alter the rate, degree, and pathway of lipid oxidation. In this study, the dynamic mass transport of oxidation products and endogenous tocopherol during storage at different micelle concentrations was monitored by UV-vis spectrophotometry and high-performance liquid chromatography. Furthermore, the microlocalization of tocopherol in micelles was investigated using 1H nuclear magnetic resonance and nuclear Overhauser effect spectroscopy, fluorescence measurements, and molecular dynamics simulation. It was demonstrated that high-concentration micelles enhanced the emulsion stability by promoting the mass transport of hydroperoxides and endogenous antioxidants. The enhancement of micelles was a superposition effect of concentration, interaction sites, and binding force between tocopherols and Tween 20 molecules. Tween 20 concentration-induced favorable changes of microlocalization of tocopherol and dynamic mass transport demonstrated a new integrated perspective to control lipid oxidation.

Combined transcriptome and proteome profiling reveal cell-type-specific functions of Drosophila garland and pericardial nephrocytes

Drosophila nephrocytes are specialised cells that share critical functional, morphological, and molecular features with mammalian podocytes. Accordingly, nephrocytes represent a preferred invertebrate model for human glomerular disease. Here, we established a method for cell-specific isolation of the two types of Drosophila nephrocytes, garland and pericardial cells, from animals of different developmental stages and ages. Mass spectrometry-based proteomics and RNA-Seq-based transcriptomics were applied to characterise the proteome and transcriptome of the respective cells in an integrated and complementary manner. We observed characteristic changes in the proteome and transcriptome due to cellular ageing. Furthermore, functional enrichment analyses suggested that larval and adult nephrocytes, as well as garland and pericardial nephrocytes, fulfil distinct physiological functions. In addition, the pericardial nephrocytes were characterised by transcriptomic and proteomic profiles suggesting an atypical energy metabolism with very low oxidative phosphorylation rates. Moreover, the nephrocytes displayed typical signatures of extensive immune signalling and showed an active antimicrobial response to an infection. Factor-specific comparisons identified novel candidate proteins either expressed and secreted by the nephrocytes or sequestered by them. The data generated in this study represent a valuable basis for a more specific application of the Drosophila model in analysing renal cell function in health and disease.

The oxidation-dissolution behavior of Cr-coated Zr alloy in high temperature water

The corrosion and dissolution behavior of Cr-coated Zr alloy were investigated in high temperature water under varying dissolved oxygen (DO) and temperatures. Results demonstrate that the oxidation and dissolution rates of Cr coatings increase significantly with higher DO levels and temperature, while the Zr substrate remains unaffected by DO concentration. At DO levels below 10 ppb, Cr coatings exhibit high stability, but at 300 ppb DO, rapid corrosion/dissolution and spallation occur. The electrochemical potential (ECP) shifts in response to temperature and DO, driving the dissolution mechanism through three distinct region: steady-state, field-assisted dissolution (FAD), and complete dissolution. During the FAD period, a porous nanocrystalline Cr2O3 layer with residual Cr forms, characterized by non-uniform dissolution due to preferential oxidation at grain boundaries and microstructural defects. The soluble HCrO4− ions form at the base of the porous layer, followed by partial recrystallization at the surface, leading to the development of a thin Cr2O3 crystalline layer.

Development of silver dichromate-geopolymer composite: An innovative catalyst for simultaneous desulfurization and denitrogenation for cleaner petroleum fuel

Rising global energy demands necessitate cleaner fuel technologies due to stringent environmental regulations. Emerging techniques like oxidative desulfurization and denitrogenation offer advantages over traditional hydrotreatment, selectively oxidizing sulfur and nitrogen compounds without damaging hydrocarbon structures. This research employs nano-crystalline silver dichromate-geopolymer composites catalysts prepared by direct precipitation, sonochemical, surfactant-assisted and surfactant assisted sonochemical routes for oxidizing sulfur and nitrogen compounds in fuel oil. Surfactant assisted preparation aided in generating catalysts with controlled size, while sonochemical synthesis facilitated uniform dispersion of the particles. The uniform dispersion, controlled particle size, and low agglomeration along with unclogged pores aided the sonochemically prepared catalyst in demonstrating superior catalytic performance over other counterparts in individual sulfur oxidation tests. In contrast, due to the high rate of oxidation and high affinity to occupy active sites, the catalyst prepared by surfactant assisted sonochemical route performed better than its sonochemical counterpart in individual nitrogen compound oxidation tests. The prepared catalysts were thoroughly characterized by different analytical characterization techniques. Single component oxidation resulted in 80.86 and 98.94% conversion of sulfur and nitrogen, while simultaneous oxidation resulted in 58.41% sulfur oxidation and 95.69% nitrogen conversion. Due to the cavitation effect, efficient mixing and a high local temperature and pressure created due to the introduction of ultrasound, the conversion rose to 88.02 and 98.02% for sulfur and nitrogen, respectively. Post oxidation, the oxidation products were removed by extraction, leading to 100% removal of nitrogen and 85% removal of sulfur. The proposed mechanism suggested the oxidation of both the compounds to occur through the formation of active Cr(VI)-peroxo species.

Additive manufactured ODS-FeCrAl steel achieves high corrosion resistance in lead-bismuth eutectic (LBE)

Developing corrosion resistant alloys used in lead-bismuth eutectic (LBE) is essential for lead-cooled fast reactors (LFRs). In this work, additive manufacturing was applied to fabricate oxide dispersion-strengthened FeCrAl steels (ODS and Y-ODS), and the latter contains 1.5 wt.% Y2O3 nanoparticles. After exposure in LBE at 450 °C for 1000 hours, both alloys generate a compact, uniform and stable Cr2O3/Al2O3 protective oxide layer (below 200 nm). Benefits from the quick transient oxidation rate at the initial stage, the oxide layer realizes a slow oxidation kinetics and achieves high corrosion resistance to LBE attack. More importantly, the addition of Y2O3 induce the formation of Y-Al-O-type oxide nanoparticles which provides an additional source of Al3+ at the interface and promotes the growth of an internal oxide layer within Al2O3, and thus subsequently the oxides layer demonstrates remarkable stability. This study highlights the potential application of additive manufacturing in advanced materials for LFRs.

Breaking the Limitations of Activity and Stability in Powdered Materials for Oxygen Evolution Reaction: The Critical Role of Catalyst-Inducing Seeds

Powdered catalysts are extensively employed in industrial-scale energy conversion devices but struggle with weak powder-substrate adhesion and inherent instability in gas-evolving and highly oxidative oxygen evolution reactions (OER). This work introduces an innovative strategy in which powdered materials serve a critical role as catalyst-inducing seeds to break these limitations. Specifically, powdered Ti2CTx MXene with anchored cobalt single atoms (Co-SAs) shows negligible catalytic activity on its own but serves as catalyst-inducing seeds, significantly enhancing the catalytic activity of the conductive FeNi substrate. Mechanistic studies demonstrate that Co-SAs accelerate the oxidation rate of Ti2CTx, leading to the micro-battery corrosion behavior between oxidized Co/Ti2CTx and FeNi alloy, which generates highly OER-active corrosion products tightly bonded to FeNi alloy, thereby enhancing catalytic activity and ensuring stability. The prepared porous electrode shows a low overpotential of 303mV to deliver an ultra-high current density of 1000mAcm-2 and maintains activity for 1200hours under high current density conditions, rivaling advanced self-supporting electrodes. Moreover, replacing Co in Co/Ti2CTx with metals like Fe, Ni or Mn, yields comparable effects, suggesting the scalability of catalyst-inducing seeds. This approach breaks traditional limitations of powdered materials in OER, offering an effective pathway to engineer advanced catalytic electrodes.

Tracking hydrothermal particles from the ridge axis to the sediment column along the Endeavour segment of the Juan de Fuca Ridge

Elemental fluxes associated with mid-ocean ridge hydrothermal systems are thought to be important in the ocean budgets of many elements but quantitative models of these fluxes, and how they vary in space and time due to different boundary conditions, are in their infancy. This is especially true for non-conservative elements that can be involved in multiple processes transforming them between the dissolved and particulate phases both in the water column and after sedimentation. To help develop a more robust database for parameterizing the processes operating, we undertook a coupled sediment trap and sediment core study of hydrothermal sediments on the west flank of the Endeavour segment of the Juan de Fuca Ridge. Sediment traps deployed in the Main Endeavour Field (MEF) and 3 and 9 km southwest of this field, along the mean flow direction of the hydrothermal plume, show that the rate of change of the concentration of sulfide-associated elements (Cu, Zn, Cd, Pb, Ag, As, Mo) in sediment settling from the plume differs between elements. We interpret this as indicating both different dissolution rates of phases containing these elements and different rates of scavenging of these elements from seawater. Scavenging is most readily tracked using elements for which the scavenged fraction is large relative to the hydrothermally derived fraction. For such elements, the relative efficiency of scavenging from seawater (REE > Cr > Ni > V > P > U) matches that previously reported from the TAG system on the Mid-Atlantic ridge despite different vent fluid and seawater chemistries that are expected to lead to both differing roles of Fe-sulfide and Fe-oxyhydroxides and different Fe oxidation rates. In the sediment trap samples collected 9 km off-axis, but not in those collected 3 km off-axis, the Mn and Ti concentrations correlate strongly despite these samples having much higher Mn concentrations than background sediment. Since Ti is sourced almost entirely from background terrigenous material such a correlation was not expected. The most reasonable explanation for this is that aggregation of hydrothermally derived particles with terrigenous material settling through the water column controls removal of hydrothermally derived particles from the water column. Changes in sediment composition with depth in the off-axis sediment core, along with differences between the composition of material from the sediment core and the off-axis sediment traps, are interpreted as indicating large post-deposition changes in sediment composition. For example, much or all of the Mn, P, As and Mo carried to the sediments with hydrothermally derived particles is released back into the water column during diagenesis. In contrast, V and REE concentrations in the sediment core are higher than those in the off-axis sediment trap samples, which may be due to continued scavenging in a benthic boundary layer post-deposition. Overall these data are interpreted as indicating that the net loss of many elements from the non-buoyant plume may not be a proxy for loss from the ocean, and a better understanding of post-depositional processes in hydrothermal settings may be important in understanding cycling of the aforementioned elements, and likely others, in seawater.