Ozone Research Articles

Novel oxygen vacancies-rich 3D porous ZnO for highly sensitive 3-hydroxy-2-butanone biomarker gas sensors

Listeriosis can cause human death via infection by Listeria monocytogenes (LMs) with a high fatality rate of 20–30 %. Detection of 3-hydroxy-2-butanone (3H-2B) biomarker of LMs can achieve estimation of LMs content, which is of great significance for human health. Exploring porous metal oxide semiconductors (MOSs) with rich vacancies towards 3H-2B sensing is quite promising for achieving this goal. Herein, we report a highly sensitive 3H-2B sensor based on novel 3D porous ZnO with rich oxygen vacancies which was facilely obtained by sacrificing Zn foam in oxalic acid and subsequent thermal decomposition. The ZnO sensor displays ultrahigh sensor response of Ra/Rg = 328@5 ppm, super-low detection limit of 0.001 ppm, excellent cycling stability and selectivity and good linear response at 120 °C, showing great potential for precise detection of 3H-2B biomarker. The porous structure and increased oxygen vacancies contribute greatly to the adsorption of active oxygen species therefore the sensing reactions on ZnO surface, which accounts for the high sensing performance. Our work provides an ingenious strategy to produce novel 3D ZnO with rich oxygen vacancies as well as new insights for boosting the detection of LMs.

Active lattice oxygen trigger for propane total oxidation: [MnO6] tunnel-restrained Cu2+ chain in α-MnO2

The elimination of propane is particularly important in volatile organic compounds (VOCs) emissions control. We designed a special Cu-type α-MnO2 with tunnel-restrained Cu2+ chain for propane total oxidation. It can effectively elevate the reaction rate and reduce the apparent activation energy. Cu2+ mainly stabilizes as tunnel [CuO4] configurations, changing the charge distribution and ligand field inside the tunnel, compared to the original ionic [KO8] and [KO12] in α-MnO2. The covalency between Cu−O as well as exacerbated Jahn-Teller distortion of [MnO6] occur. The resulting charge transfer of Cu−O−Mn units via bridging O atoms further affects the outside-tunnel properties, specifically, facilitating oxygen vacancy formation and lattice oxygen activation. Moreover, abundant oxygen vacancies can promote the dehydrogenation of propane to generate alcohols at low temperatures. The above intermediates undergo successively oxidation with activated lattice oxygen to produce C3∼C1 carboxylates as temperature elevates.

Normobaric hypoxia accelerates high-intensity intermittent training-induced mitochondrial biogenesis (PGC-1α)- and dynamics (OPA1)-related protein expressions in rat gastrocnemius muscle.

High-intensity intermittent training (HIIT) in a normobaric hypoxic environment enhances exercise capacity, possibly by increasing the mitochondrial content in skeletal muscle; however, the molecular mechanisms underlying these adaptations are not well understood. Therefore, we investigated whether HIIT under normobaric hypoxia can enhance the expression of proteins involved in mitochondrial biogenesis and dynamics in rat gastrocnemius muscle. Five-week-old male Wistar rats (n = 24) were randomly assigned to the following four groups: (1) sedentary under normoxia (20.9% O2) (NS), (2) training under normoxia (NT), (3) sedentary under normobaric hypoxia (14.5% O2) (HS), and (4) training under normobaric hypoxia (HT). The training groups in both conditions were engaged in HIIT on a treadmill five to six days per week for nine weeks. From the fourth week of the training period, the group assigned to hypoxic conditions was exposed to normobaric hypoxia. Forty-eight hours after completing the final training session, gastrocnemius muscles were surgically removed, and mitochondrial enzyme activity and mitochondrial biogenesis and dynamics regulatory protein levels were determined. Citrate synthase (CS) activity and mitochondrial oxygen phosphorylation (OXPHOS) subunits in the gastrocnemius muscle in the HT significantly exceeded those in the other three groups. Moreover, the levels of a master regulator of mitochondrial biogenesis, peroxisome proliferator-activated receptor γ coactivator-1α (PGC-1α), and a mitochondrial fusion-related protein, optic atrophy 1 (OPA1), were significantly increased by HIIT under normobaric hypoxia. Our data indicates that HIIT and normobaric hypoxia increase the expression of mitochondrial biogenesis- and dynamics-related proteins in skeletal muscles.

Mitigating the skin phototoxicity of sonodynamic therapy via singlet oxygen-consuming metal-organic frameworks

Sonodynamic anti-cancer therapy relies on the highly active singlet oxygen to induce potent cell death. However, the non-specific biodistribution of sonosensitizers post systemic administration results in a significant accumulation in the skin, and hence the daylight-induced phototoxicity. Here, we report a smart metal-organic framework-based nanocarrier with titanium dioxide (TiO2) as the sonosensitizer for reduced phototoxicity in the skin. The organic ligand bears the imidazole moiety that can facilely consume singlet oxygen in the skin without compromising the anti-cancer efficacy. The reaction between imidazole moiety and singlet oxygen was confirmed by the density functional theory (DFT). Upon light irradiation, the nanocarrier can significantly reduce the phototoxicity post light irradiation in a range of normal cells in vitro and in a mouse model in vivo. Meanwhile, the ligand contains a disulfide moiety that can deplete glutathione and orchestrate the singlet oxygen-induced toxicity in the CT-26 colon cancer cells. As a result, the nanocarrier showed superior in vivo antitumor efficacy in a CT-26 tumor-bearing mice model, leading to significant suppression of tumor growth and improved animal survival rates. The current work provides a tailored nanoscale particle engineering approach to simultaneously minimize phototoxicity in the skin and sensitize sonodynamic anti-cancer therapy.

Carbonyl Compounds Observed at a Suburban Site during an Unusual Wintertime Ozone Pollution Event in Guangzhou

Carbonyl compounds are important oxygenated volatile organic compounds (VOCs) that play significant roles in the formation of ozone (O3) and atmospheric chemistry. This study presents comprehensive field observations of carbonyl compounds during an unusual wintertime ozone pollution event at a suburban site in Guangzhou, South China, from 19 to 28 December 2020. The aim was to investigate the characteristics and sources of carbonyls, as well as their contributions to O3 formation. Formaldehyde, acetone, and acetaldehyde were the most abundant carbonyls detected, with average concentrations of 7.11 ± 1.80, 5.21 ± 1.13, and 3.00 ± 0.94 ppbv, respectively, on pollution days, significantly higher than those of 2.57 ± 1.12, 2.73 ± 0.88, and 1.10 ± 0.48 ppbv, respectively, on nonpollution days. The Frame for 0-D Atmospheric Modeling (F0AM) box model simulations revealed that local production accounted for 62–88% of observed O3 concentrations during the pollution days. The calculated ozone formation potentials (OFPs) for various precursors (carbonyls and VOCs) indicated that carbonyl compounds contributed 32.87% of the total OFPs on nonpollution days and 36.71% on pollution days, respectively. Formaldehyde, acetaldehyde, and methylglyoxal were identified as the most reactive carbonyls, and formaldehyde ranked top in OFPs, and it alone contributed 15.92% of total OFPs on nonpollution days and 18.10% of total OFPs on pollution days, respectively. The calculation of relative incremental reactivity (RIR) indicates that ozone sensitivity was a VOC-limited regime, and carbonyls showed greater RIRs than other groups of VOCs. The model simulation showed that secondary formation has a significant impact on formaldehyde production, which is primarily controlled by alkenes and biogenic VOCs. The characteristic ratios and backward trajectory analysis also indicated the indispensable impacts of local primary sources (like industrial emissions and vehicle emissions) and regional sources (like biomass burning) through transportation. This study highlights the important roles of carbonyls, particularly formaldehyde, in forming ozone pollution in megacities like the Pearl River Delta region.

Fluidity and structure of aluminate slags for smelting high-alumina iron ores: Effect of CaO/SiO2 mass ratio

Slag regulation is crucial for achieving smelting of high-alumina iron ore in blast furnaces. This study investigated the fluidity and structure of CaO-SiO2–10 wt.%MgO-30 wt.%Al2O3 slag by varying the CaO/SiO2 ratio (1.0–2.0). The results revealed that viscosity decreased with increasing CaO/SiO2 ratio, while the free running temperature, defined as the temperature at which the slag can flow freely, initially increased and then decreased, peaking at the range of 1.2–1.6. Interestingly, the free running temperature of slag at basicity 2.0 (1392 °C) was lower than that at basicity 1.0 (1398 °C). Spectroscopic analysis demonstrated that increasing basicity facilitated greater charge compensation of Al3+ ions, resulting in an increased amount of [AlO4] tetrahedra. Moreover, increasing free oxygen promoted the depolymerization of [SiO4] and [AlO4] tetrahedra, reducing bridging oxygen and increasing non-bridging oxygen. Consequently, the slag's overall polymerization degree decreased. Furthermore, MD simulations identified two distinct fracture mechanisms of bridging oxygen within the Si-O-Si structure.

Engineering of in-plane SnS2–SnO2 nanosheets heterostructures for enhanced H2S sensing

In-plane heterostructures has attracted considerable interest due to exceptional electron transport properties, high specific surface area, and abundant active sites. However, synthesis of in-plane SnS2–SnO2 heterostructures are rarely reported, and the deep investigation of the fine structure on reactivity is of great significance. Here, we propose partial in-situ oxidation strategy to construct the in-plane SnS2–SnO2 heterostructures and the surface properties, the ratio of two components can be finely tuned by precisely adjusting the treatment temperature. In particular, the SnS2–SnO2 heterostructures formed after annealing of SnS2 nanosheets at 350 °C exhibits a unique electronic structure and surface properties due to rich grain boundaries, which exhibits excellent gas sensing performance to H2S (Ra/Rg = 169.81 for 5 ppm H2S at 160 °C, fast response and recovery dynamic (41/101 s), excellent reliability (σ = 0.01) and sensing stability (φ = 0.11 %)). Notably, the in-plane heterostructures endow the material with abundant grain boundaries and effectively regulates the electronic structure of the Sn p-orbital, which facilitate the formation of active oxygen species (O−(ad)), thus contributing to the sensing performance. Our work provides a promising platform to design in-plane heterostructures for various advanced applications.

Gradient and De-Clustered Anionic Redox Enabled Undetectable O2 Formation in 4.5V Sodium Manganese Oxide Cathodes.

Anionic redox chemistry presents a promising approach to enhancing the energy density of oxide cathode materials. However, anionic redox reactions invariably lead to O2 formation, either as free gaseous O2 or trapped molecular O2, which destabilizes the material's structure. Here, this critical challenge is addressed by constructing a crystal structure with both gradient redox activity and de-clustered redox-active oxygen. This design strategy is directly validated by operando differential electrochemical mass spectrometry and ex situ 50K electron paramagnetic resonance, revealing no release of O2 or trapped O2 in the 4.5V P2-type sodium manganese-based layered oxide. Notably, the material exhibits a highly reversible capacity of 247mAhg-1 at 20mAg-1 and exceptional capacity retention of 91.4% after 300 cycles at 300mAg-1. In situ X-ray diffraction further suggests that the absence of O2 formation suppresses the typical P2-O2 phase transition, resulting in a minimal lattice volume change of only 0.5%. Ex situ neutron diffraction studies and theoretical calculations further elucidate that the locally ordered lattice is well-preserved, attributable to reduced cationic migrations during cycling.

Promoting Surface Reconstruction in Spinel Oxides via Tetrahedral-Octahedral Phase Boundary Construction for Efficient Oxygen Evolution.

Understanding the origin of surface reconstruction is crucial for developing highly efficient lattice oxygen oxidation mechanism (LOM) based spinel oxides. Traditionally, the reconstruction has been achieved through electrochemical procedures, such as cyclic voltammetry (CV), linear sweep voltammetry (LSV). In this work, we found that the surface reconstruction in LOM-based CoFe0.25Al1.75O4 catalyst was an irreversible oxygen redox chemical reaction. And a lower oxygen vacancy formation energy (EO-V) could benefit the combination of the activated lattice oxygen atoms with adsorbed water molecular. Motivated by this finding, a strategy of phase boundary construction from Co tetrahedral to octahedral was employed to decrease EO-V in CoFe0.25Al1.75O4. The results showed that as the Co octahedral occupancy ratio rose to 64 %, a 3.5 nm-thick reconstructed layer formed on the catalyst surface with a 158 mV decrease in overpotential. Further experiments indicated that the coexistence of tetrahedral-octahedral (O-T) phase would result in lattice mismatch, promoting non-bonding oxygen states and lowering EO-V. Then more active lattice oxygen combined with H2O molecules to generate hydroxide ions (OH-), followed by soluble cation leaching, which enhanced the reconstruction process. This work provided new insights into the relationship between the intrinsic structure of pre-catalysts and surface reconstruction in LOM-based spinel electrocatalysts.

Supersaturated Doping-Induced Maximized Metal-Support Interaction for Highly Active and Durable Oxygen Evolution.

Metal-support interaction (MSI) is pivotal and ubiquitously used in the development of next-generation catalysts, offering a pathway to enhance both catalytic activity and stability. However, owing to the lattice mismatch and poor solubility, traditional catalysts often exhibit a metal-on-support heterogeneous structure with limited interfaces and interaction and, consequently, a compromised enhancement of properties. Herein, we report a universal and tunable method for supersaturated doping of transition-metal carbides via strongly nonequilibrium carbothermal shock synthesis, characterized by rapid heating and swift quenching. Our results enable ∼20 at. % Ni2FeCo doping in Mo2C, significantly surpassing the thermodynamic equilibrium limit of <3 at. %. The supersaturation ensures more catalytically active NiFeCo doping and sufficient interaction with Mo2C, resulting in the maximized MSI (Max-MSI) effect. The Max-MSI enables outstanding activity and particularly stability in alkaline oxygen evolution reaction, showing an overpotential of 284 mV at 100 mA cm-2 and stable for 700 h, while individual Ni2FeCo and Mo2C only last less than 70 and 10 h (completely dissolved), respectively. In particular, the SD-Mo2C catalyst also exhibits excellent durability at 100 mA cm-2 for up to 400 h in 7 M KOH. Such a significantly improved stability is attributed to the supersaturated doping that led to each Mo atom strongly binding with adjacent heteroatoms, thus elevating the dissolution potential and corrosion resistance of Mo2C at a high current density. Additionally, the highly dispersed NiFeCo also facilitates the formation of dense oxyhydroxide coating during reconstruction, further protecting the integrated catalysts for durable operation. Furthermore, the synthesis has been successfully scaled up to fabricate large (16 cm2) electrodes and is adaptable to nickel foam substrates, indicating promising industrial applications. Our strategy allows the general and versatile production of various highly doped transition-metal carbides, such as Ni2FeCo-doped TiC, NbC, and W2C, thus unlocking the potential of maximized or adjustable MSI for diverse catalytic applications.

Oxidative damage biomarkers and antioxidant enzymes in saliva of patients with peri-implant diseases

Objectives8-hydroxydeoxyguanosine (8-OHdG) and Malondialdehyde (MDA) are commonly used as markers to evaluate oxidative DNA and Lipid damage in disorders including chronic inflammatory diseases. Superoxide dismutase (SOD) and glutathione peroxidase (GPx) protect tissues against oxidative injury from free oxygen radicals generated by various metabolic processes. The aim of this study was to evaluate 8-OHdG and MDA levels, and SOD and GPx activities in whole saliva of patients with peri-implant diseases.Materials and methodsA cross-sectional study was conducted on a sum of 60 age gender balanced; peri-implantitis (n = 20), peri-mucositis (n = 20) and healthy (n = 20) individuals. Unstimulated whole saliva samples were collected and to determine the clinical condition of each subject; the plaque index (PI), gingival index (GI), peri-implant probing pocket depth (PIPD), peri-implant presence of bleeding on probing (BOP) (with/without suppuration) and radiographic signs of crestal bone loss (BL) were measured. The salivary 8-OHdG level was measured using the ELISA method. SOD, GPx activities and MDA levels were determined spectrophotometrically.ResultsA total of 60 individuals had evaluations of 318 implants. In comparison to the peri-mucositis and peri-implantitis groups, the healthy group had significantly lower PI and GI scores (p < 0.001). The PIPD value differed amongst the groups, with the peri-implantitis group having the highest value (p < 0.001). Compared to the peri-mucositis and control groups, the peri-implantitis group had a significantly higher BL score (p < 0.001 and p < 0.001, respectively). The peri-implantitis group showed a significantly higher 8-OHdG level (p < 0.001; p < 0.001 respectively) than the peri-mucositis and control groups. Compared to the peri-mucositis and control groups, the peri-implantitis group had a significantly higher MDA level (p < 0.001 and p < 0.001, respectively). The peri-implantitis group had a significantly higher SOD level (p < 0.001 and p < 0.001, respectively) in comparison to the peri-mucositis and control groups. There was no significant difference in GPx levels between the peri-mucositis and control groups (p > 0.05), while the peri-implantitis group had significantly lower GPx levels than the peri-mucositis and control groups (p < 0.001 and p < 0.001, respectively).ConclusionsElevated levels of oxidative stress in saliva may indicate the onset of pathological bone loss surrounding the implant and may be an indication of peri-implantitis.Clinical relevanceIn peri-implant diseases, changes may occur in the levels of 8-OHdG, MDA, SOD and GPx in saliva, which may lead to a deterioration in the oxidant/antioxidant balance.

Enhancing Thermochemical Energy Storage Performance of Perovskite with Sodium Ion Incorporation

Perovskite materials are promising for thermochemical energy storage due to their ability to undergo redox cycling over a wide temperature range. Although BaCoO3 exhibits excellent air cycling properties, its heat storage capacity in air remains suboptimal. This study introduces Na into the lattice structure to enhance oxygen vacancy formation and mobility. DFT+U simulations of the surface structure of Na-doped BaCoO3−δ indicate that incorporating Na improves surface stability and facilitates the formation of surface oxygen vacancies. NaxBa1−xCoO3−δ compounds were synthesized using a modified sol–gel method, and their properties were investigated. The experimental results demonstrate that Na doping significantly enhances the redox activity of the material. The heat storage capacity increased by above 50%, with the Na0.0625Ba0.9375CoO3−δ solid solution achieving a heat storage density of up to 341.7 kJ/kg. XPS analysis reveals that Na doping increases the concentration of surface defect oxygen, leading to more active oxygen release sites at high temperatures. This enhancement in redox activity aligns with DFT predictions. During high-temperature cycling, the distribution of Na within the material becomes more uniform, and no performance degradation is observed after 300 cycles. Even after 450 cycles, Na0.0625Ba0.9375CoO3−δ retains over 96% of its initial redox activity, significantly outperforming fresh BaCoO3−δ. These findings elucidate the mechanism by which Na doping enhances the thermochemical heat storage performance of BaCoO3−δ and provide new insights for the design of perovskite-based materials.

ROS-responsive injectable hydrogels loaded with exosomes carrying miR-4500 reverse liver fibrosis

The reversal of liver fibrosis requires effective strategies to reduce oxidative stress and inhibition of hepatic stellate cell (HSC) activation. MiR-4500 regulates pathological angiogenesis and collagen mRNA stability, with the potential to inhibit fibrosis. Herein, we explored the inhibition of HSC activation in vitro by exosomes (Exos) carrying miR-4500 and encapsulated ExosmiR−4500 in an intelligent injectable hydrogel with biological activity and reactive oxygen species (ROS) responsiveness for application in oxidative stress environments. Briefly, reversible boronic ester bonds were integrated into gelatin-based hydrogels through dynamic crosslinking of quaternized chitosan (QCS) and 4-carboxyphenylboronic acid (CPBA)-modified gelatin. The QCS-CPBA-Gelatin (QCG) hydrogel scavenged excess ROS from the local microenvironment and released ExosmiR−4500 through the dissociation of boronic ester bonds, providing a favorable microenvironment and in situ sustained-release drug delivery system for ExosmiR−4500. The results showed that QCG@ExosmiR−4500 hydrogel has biocompatibility, biodegradability, and slow-release ability, which could effectively clear ROS and inhibit HSC activation and pathological angiogenesis in vitro and in vivo. Furthermore, transcriptome analysis suggests that the pharmacological mechanism of the QCG@ExosmiR−4500 hydrogel is mainly related to anti-oxidation, anti-angiogenesis, anti-fibrosis processes, and signaling pathways. Thus, our study demonstrates that an intelligently responsive ExosmiR−4500 delivery system based on injectable hydrogels is a promising strategy for the treatment of liver fibrosis.

Взаємозв’язок активності ферментативної та неферментативної ланок антиоксидантної системи організму залежно від тонусу автономної регуляції

The purpose of the study is to establish the nature of the influence of autonomic nervous regulation on the activity of the antioxidant defense system of broiler chickens. For the study of autonomic nervous regulation, Cobb 500 chickens crossbred were used. Autonomic nervous regulation was studied by variation pulsometry in chickens 30-35 days old, after which reference representatives of three types of tone of autonomic regulation were selected: sympathicotonic, normotonic and vagotonic. It was established that the average value of superoxide dismutase activity in sympathicotonic chickens is statistically higher than in normotonic chickens, which indicates a more active oxygen consumption in sympathicotonic chickens. As a result, the formation of superoxide radical increases, which requires more superoxide dismutase to accelerate its neutralization. In 60-day-old sympathicotonic chickens, indicators of superoxide dismutase activity remain at a lower level than in normotonic chickens, and in vagotonic chickens, a downward trend is noted. The indicator of glutathione peroxidase with the predominance of the sympathetic department of autonomic regulation is statistically lower than vago- and normotonic. A correlation was determined between superoxide dismutase and retinol level in 35-day-old normotonic chickens, which indicates the mutual coordination of the work of the enzymatic and non-enzymatic link of the antioxidant system under the condition of balanced autonomous regulation. However, with age, the parasympathetic division of the autonomic nervous system increases the influence on the relationship between superoxide dismutase and retinol in vagotonic chickens, in contrast to normotonic ones. It was found that the level of relationships between catalase and tocopherol increases with age in chickens with a vagotonic type of autonomous regulation. It has been proven that the level of tocopherol and retinol in 35-day-old vagotonic chickens is higher than that of normotonic chickens. Hens of the sympathicotonic and normotonic groups had a lower level of tocopherol in the blood plasma than in vagotonic hens. The level of retinol in the blood plasma of chickens with vagotonic type of autonomous nervous regulation is higher than that of normotonic and sympathicotonic chickens. This indicates the highest level of antioxidant protection in vagotonic chickens, which forms a solid foundation for higher immune status and growth in such birds.

Enhanced electrocatalytic CO2 reduction into formate: Unleashing the effect of engineered bimetallic oxides supported on activated carbon

The excessive concentration of anthropogenic CO2 continuously harms the atmosphere. Consequently, deploying CO2 via the electrochemical reduction approach has become a highly sought-after research thrust area. In this study, a facile, one-pot solution combustion synthesis method (SCSM) was employed for the synthesis of various mixed-metal oxides supported on porous activated carbon (SnO2-CuO@AC). The prepared materials are characterized by analytical and spectroscopic techniques. Electrochemical studies were performed for the SnO2-CuO@AC catalyst to reduce CO2 into formic acid via an electrochemical approach. The in-depth properties of the designed catalysts were analysed by theoretical calculations using FT-IR and XRD data. The SnO2-CuO@AC exhibited improved electrochemical performance with a high current density of −10.77 mAcm−2, a low overpotential of −1.29 V, a lower Tafel slope value of 100 mV/dec. The faradaic efficiency for formic acid was 78.8 % at 1.3 V vs. RHE, with high stability for 9 h. The presence of coordinated active sites and oxygen vacancies, and a lower Tafel slope, also endorses CO2 adsorption and activation, faster electron transfer and boosts CO2 reduction. The significant reactivity toward CO2 reduction is attributed to the intensity of interaction between CO2∗- and the electrocatalyst, followed by kinetic activation toward protonation to obtain the desired product.

Synergistic effect and role of light for efficient photothermocatalytic CO2 reduction by CH4 on Pd/Co-Al1Mg3Ox

Photothermocatalytic CO2 reduction by CH4 converts greenhouse gases into valuable syngas, but limited by high light intensity and carbon deposition. Here, we designed a nanocomposite supporting low content of Pd nanoparticles on Co and Al doped MgO (Pd/Co-Al1Mg3Ox), achieving high production rates of H2 (rH2, 73.04 mmol min−1 g−1) and CO (rCO, 84.80 mmol min−1 g−1) with light-to-fuel efficiency (η, 25.3 %) at relatively low light intensity (81.1 kW m−2). Compared to Pd/Al1Mg3Ox, Pd/Co-Al1Mg3Ox demonstrates improvements of rH2, rCO and η by 6.5, 6.2 and 6.7 times respectively with great durability of 48 hours. This originates from a synergetic effect between Pd and Co-Al1Mg3Ox that the participation of active oxygen from Co-Al1Mg3Ox greatly accelerates carbon species (C*) oxidation. Interestingly, light plays unique roles on Pd/Co-Al1Mg3Ox which not only expedites C* oxidation, activates the oxygen connected to Pd and Co-Al1Mg3Ox, but also reverses rapid thermocatalytic deactivation by boosting CO desorption.

Mechanisms of enhanced performance in Zr4+/Ta5+ codoped rutile-TiO2 ceramics via broadband dielectric spectroscopy.

Aliovalent dopant codoped rutile-TiO2 materials have garnered attention due to their excellent performance properties, characterized by low loss tangent (tanδ), high dielectric permittivity (ε'), and stable ε' over a broad temperature range. This performance is primarily due to the electron-pinned defect-dipoles (EPDDs) of the complex defects [Formula: see text]Ti3+-[Formula: see text]Ti3+BTi. Notably, the excellent dielectric properties in ZrxTa2.5%Ti0.975-xO2 (Zr-TTO) ceramics can be achieved using the traditional mixed oxide method without the EPDDs, due to the absence of A3+ (acceptor doping ions). Instead, the existence of localized free electrons and oxygen vacancies ([Formula: see text]) in Zr-TTO structures, due to doping ions and the sintering process, was confirmed by X-ray photoelectron and Raman spectroscopies. These ceramics exhibited ε'~ 2 × 104 and tanδ < 0.03 at 1kHz and 25°C in the 2.5-10%Zr-TTO samples. Moreover, all ceramics demonstrated a maximum ε' change (∆ε') of less than ±15% over the temperature range suitable for X7R and X8R type ceramic capacitors. Significantly, the change in ε' related to relative humility was calculated to be less than ±0.5% over the range of 50-95% RH, indicating the environmental stability of the dielectric properties, which is essential for capacitor applications. Investigations suggested that at least four mechanisms contributed to this system: the intrinsic effect of ionic polarization, Ti4+ · e- -[Formula: see text]- Ti4+ · e- and Ti4+ · e- - [Formula: see text] defects, interfacial polarization at insulating grain boundaries, and non-Ohmic contact between the surface sample and the metal electrode.

Visible light accelerates skin wound healing and alleviates scar formation in mice by adjusting STAT3 signaling

During the wound healing process, the activation of signal transducer and activator of transcription 3 (STAT3) is considered crucial for the migration and proliferation of epithelial cells, as well as for establishing the inflammatory environment. However, an excessive STAT3 activation aggravates scar formation. Here we show that 450 nm blue light and 630 nm red light can differentially regulate the phosphorylation of STAT3 (p-STAT3) and its downstream cytokines in keratinocytes. Further mechanistic studies reveal that red light promotes wound healing by activating the PI3 kinase p110 beta (PI3Kβ)/STAT3 signaling axis, while blue light inhibits p-STAT3 at the wound site by modulating cytochrome c-P450 (CYT-P450) activity and reactive oxygen species (ROS) generation. In a mouse scar model, skin wound healing can be significantly accelerated with red light followed by blue light to reduce scar formation. In summary, our study presents a potential strategy for regulating epithelial cell p-STAT3 through visible light to address skin scarring issues and elucidates the underlying mechanisms.

Three-dimensional porous SiC/BDD electrode with long-term robustness and enhanced electrochemical degradation performance for refractory organic pollutants

Boron-doped diamond (BDD) electrodes with a three-dimensional (3D) porous network structure can overcome the mass transfer limitations and increase substantially the utilization rate of active oxygen species. Nonetheless, the 3D porous network structure was invariably built using metallic substrates, which inherently have inferior stability because of their non-corrosion resistance and the severe thermal mismatch between BDD films and substrates. Herein, we reported, for the first time, the use of a commercially porous silicon carbide (SiC) as the substrate to construct a 3D SiC/BDD electrode to simultaneously alleviate the problematics of substrate corrosion and thermal mismatch. This novel electrode exhibited a long-term service lifetime of 800 h in 3 M H2SO4 under the current density of 50 mA cm−2, over 500 times longer than the conventional metallic substrate-based BDD electrodes. The optimum p-SiC/BDD electrode exhibited a high oxygen evolution potential of 2.04 V vs. SHE, a low charge transfer resistance of 18.4 Ω, a high mass transfer coefficient of 2.78 × 10−5 m s−1, and a thin diffusion layer thickness of 25.2 μm. The proposed electrode had a threefold larger pseudo-first-order reaction rate constant than a flat BDD electrode, although it consumed just a fourth of the latter’s electric energy. The superior performance was attributable to an increased mass transfer rate confirmed by computational fluid dynamics (CFD) simulations as well as a high yield of reactive oxygen species verified by electron spin resonance (ESR). Furthermore, the proposed SiC/BDD electrode could work effectively under different water matrices in the presence of diverse salt electrolytes, thus paving a new avenue for the structure design of robust non-active anode materials.

Temperature-induced evolution of CuOx clusters in CuOx/TiO2 catalyst for boosting auto-exhaust oxidation

Developing non-noble metal oxides, replacing platinum group catalysts for auto-exhaust purification, where their usage amount exceeds 40 % of global demand, remains a challenge. Herein, we presented a combined approach on the synthesis and application of robust CuOx/TiO2 catalysts with ultra-fine CuOx clusters (ca. 1 nm). The strong interaction between CuOx and TiOx induces favorable interfacial charge accumulation, facilitating the extraction of the interfacial oxygen atoms in Cu2-x-O-Ti4-y chains and the surface lattice oxygen on CuOx clusters. Isotope 18O2 experiments and DFT calculations jointly confirmed that these oxygen atoms preferentially participate in the oxidation through the Mars-van Krevelen mechanism below 250 °C. The resulted oxygen vacancies facilitate the adsorption and activation of O2 molecules, which will participate the oxidation above 250 °C through Eley-Rideal mechanism. The increase in the temperature also drives the synergy of active oxygen species in the interfacial Cu2-x-O-Ti4-y bond chains and on CuOx clusters, cooperatively promoting the conversion of NO to NO2. As a result, the CuOx/TiO2 catalyst exhibits exceptional catalytic performance in soot oxidation, with a four-fold higher reaction rate (4.17 μmol g−1 min−1) than that of single-atom Cu₁-TiO2 catalyst. Such findings provide a novel strategy for the advancement of Cu-based cluster catalysts in environmental applications.