Ozone Research Articles

Polyaniline layered N-doped carbon-coated iron oxide nanocapsules for extremely active Li-ion battery anode and oxygen evolution reaction

We report the effective synthesis of polyaniline (PANi)-layered nitrogen-doped carbon-coated Fe3O4 (FNC@PANi) nanocapsules (NCs) for electrocatalysis of oxygen evolution reaction (OER) as well as anode material for lithium (Li)-ion batteries (LIBs) via a simple hydrothermal method and oxidative polymerization technique. The prepared FNC@PANi NCs revealed a dual core-shell structure, in which an intermediate carbon layer allowed excellent electrical conduction between the Fe3O4 NCs and PANi. The dual core-shell structure also allowed the Fe3O4 NCs to expand freely during the Li-ion insertion/extraction and OER processes without breaking the outer layer, thus providing a high surface area (147.85 m2 g−1) and enhanced electrical conductivity. These properties facilitate the application of the dual core-shell FNC@PANi NCs as an advanced electrode material for LIBs, delivering a high reversible specific capacity of 1556.48 mAh g−1 at 0.1 A g−1, excellent rate performance (896.96 mAh g−1 at 1 A g−1), and durable cycling life (680.12 mAh g−1 at 5 A g−1 for 3000 cycles). The dual core-shell FNC@PANi NCs exhibited high electrocatalytic activity in the OER, with a small Tafel slope of 108.7 mV dec−1 owing to synergistic effects between the copious active sites of the Fe3O4 NCs and the carbon core-shell structure and a modest overpotential of 219 mV at 10 mA cm−2. The electrodes showed excellent stability over 10 h, as determined by chronopotentiometry at 10 mA cm−1. The resultant dual-core-shell FNC@PANi NCs are efficient iron-oxide-based electrode materials for LIBs and OER electrocatalysts.

Reconstruction of High Entropy Alloys on a Metal–Organic Framework Approaching Active Oxygen Reduction Electrocatalysts

Reconstruction of High Entropy Alloys on a Metal–Organic Framework Approaching Active Oxygen Reduction Electrocatalysts

Ozone Pollution in the North China Plain during the 2016 Air Chemistry Research in Asia (ARIAs) Campaign: Observations and a Modeling Study

To study air pollution in the North China Plain (NCP), the Air Chemistry Research in Asia (ARIAs) campaign conducted airborne measurements of air pollutants in spring 2016. High pollutant concentrations, with O3 > 100 ppbv, CO > 500 ppbv, and NO2 > 10 ppbv, were observed. CMAQ simulations with the 2010 EDGAR emissions capture the spatial and temporal variations in ozone and its major precursors such as NO2 and VOCs, with significant underestimation. Differences between CMAQ simulations and satellite observations reflect changes in anthropogenic emissions, decreased NOx emissions in megacities such as Beijing, but slight increases in other cities and rural areas. CMAQ also underestimates HCHO and CO, suggesting adjustments of the 2010 EDGAR emissions are necessary. HCHO/NO2 column ratios derived from OMI measurements and CMAQ simulations show that VOC-sensitive chemistry dominates the ozone photochemical production in eastern China, suggesting the importance of tightening regulations on anthropogenic VOC emissions. After adjusting emissions based on satellite observations, better model performance was achieved. Because of the VOC-sensitive environment in ozone chemistry over the NCP, the underestimation of anthropogenic emissions could be important for CMAQ simulations, while future study and regulations should focus on VOC emissions with continuous controls on NOx emissions in China.

Enhanced Oxygen Evolution and Zinc-Air Battery Performance via Electronic Spin Modulation in Heterostructured Catalysts.

Beyond optimizing electronic energy levels, the modulation of the electronic spin configuration is an effective strategy, often overlooked, to boost activity and selectivity in a range of catalytic reactions, including the oxygen evolution reaction (OER). This electronic spin modulation is frequently accomplished using external magnetic fields, which makes it impractical for real applications. Herein, spin modulation is achieved by engineering Ni/MnFe2O4 heterojunctions, whose surface is reconstructed into NiOOH/MnFeOOH during the OER. NiOOH/MnFeOOH shows a high spin state of Ni, which regulates the OH- and O2 adsorption energy and enables spin alignment of oxygen intermediates. As a result, NiOOH/MnFeOOH electrocatalysts provide excellent OER performance with an overpotential of 261 mV at 10 mA cm-2. Besides, rechargeable zinc-air batteries based on Ni/MnFe2O4 show a high open circuit potential of 1.56 V and excellent stability for more than 1000 cycles. This outstanding performance is rationalized using density functional theory calculations, which show that the optimal spin state of both Ni active sites and oxygen intermediates facilitates spin-selected charge transport, optimizes the reaction kinetics, and decreases the energy barrier to the evolution of oxygen. This study provides valuable insight into spin polarization modulation by heterojunctions enabling the design of next-generation OER catalysts with boosted performance.

Optimizing the Microstructure and Properties of Fe–Ni–Cu–Mo–C Sintered Steel by TiB2

The Fe–Ni–Cu–Mo–C powder metallurgy sintered steels with TiB2 reinforced were prepared by the conventional powder metallurgy techniques. This study explored the influence of incremental TiB2 additions, ranging from 0.1 to 0.6 wt.%, on the microstructure and properties of these steels. The results reveal that the microstructures primarily consist of martensite, Ni-rich austenite, Cu-rich pearlite, TiB2, and Ti–O rich nanoparticles. The latter form via a reaction between TiB2 and free oxygen. Notably, both the density and impact strength of the steels showed enhancement with increasing TiB2 content. The optimal values, 7.25 g/cm3 for density and 17.23 J/cm2 for impact strength, were observed at a TiB2 concentration of 0.5%. The hardness and ultimate tensile strength also increased steadily, reaching maxima of 38.7 and 1083.7 MPa at 0.6% TiB2, respectively. However, excessive TiB2 led to the formation of a net-like B-containing eutectic network, adversely affecting the steel properties. Steels with 0.5% TiB2 exhibited excellent wear resistance. At 200 rpm, the dominant failure mode was abrasive wear, which shifted to adhesive wear with oxidation at 400 rpm, followed by abrasive wear.

Lattice-confined Ag over MnCoLDH accelerated catalytic oxidation of formaldehyde at ambient temperature: The novel pathway with different oxygen species

Catalytic oxidation of formaldehyde (HCHO) at ambient temperature represents a cost-effective and efficient strategy for indoor HCHO removal. Although precious metal-based catalysts have been considered practical for oxidizing gaseous HCHO indoors, the limited activity of Ag-based catalysts can be attributed to their typical +1 and 0 valence states, as well as their single electron transport pathway. This characteristic impedes the reestablishment of the low state during oxygen activation, thereby resulting in catalyst deactivation. The present study successfully incorporated Ag atoms into manganese-cobalt layered double hydroxide (MnCoLDH) through doping, resulting in the development of a catalyst that exhibited complete formaldehyde oxidation activity at 30 °C. Lattice-confined Ag enables continuous activation of oxygen, while LDH facilitates the sustained provision of surface hydroxyl groups. The roles and mechanisms of surface hydroxyl groups, adsorbed oxygen, and lattice oxygen in the oxidation of formaldehyde were investigated using in-situ DRIFTS. By comparing Ag with the impregnation method, the confinement of Ag within the lattice enables continuous activation of oxygen. This study presents a viable strategy for designing efficient catalysts for volatile organic compounds (VOCs) removal by utilizing active lattice oxygen species.

Iron anchored carbon–nitrogen catalyst for enhanced activation performance of peroxymonosulfate: Synergy of 1O2 and high-valent iron

Herein, Iron anchored in carbon–nitrogen nanosheets (Fe-CNx) catalysts were synthesized successfully through one-step in situ pyrolysis for activating peroxymonosulfate (PMS) to degrade sulfachloropyridazine (SCP). Fe-CN800/PMS could realized the complete removal SCP in 20 min (kobs = 0.644 min−1). Its reaction rates were 214.7 times higher than that in PMS system. Additionally, Fe-CN800 could effectively activate PMS in a wide range of pH (3–10.6). The relationship between the content of Fe-CNx functional groups and the catalytic performance indicated that C = O and Fe-N4 were the main active sites. The structural–functional association between active sites and reactive oxygen species (ROS) was revealed by regression analysis and Density Functional Theory calculations, indicating that C = O stimulated 1O2 production, while HV-Fe was derived from C = O and Fe-N4. Moreover, the PMS activation was enhanced via electron transfer between Fe(II) and Fe(III). Based on LC-MS and Fukui index, the action of ROS during SCP decomposition was analyzed, and proposed three probable pathways for SCP degradation. The transformation pattern of the structure and toxicity of the intermediates was revealed via T.E.S.T. analysis, and plant growth experiments showed that the effect of the treated SCP solution on Brassica napus significantly decreased. Finally, Fe-CN800 exhibited excellent stability, with SCP removal remaining above 95 % in five cycles and Fe leaching concentrations lower than ones which have been reported catalysts. This work provided new insights for the precise design of more efficient PMS catalysts. It will provide a fundamental basis for the practical application in wastewater treatment based on PMS-AOPs.

Hyperoxic-hypoxic Paradox: Breast Cancer Microenvironment and an Innovative Treatment Strategy.

A small therapeutic range of oxygen is required for effective metabolism. As a result, hypoxia (low oxygen concentration) is one of the most potent inducers of gene expression, metabolic alterations, and regenerative processes, such as angiogenesis, stem cell proliferation, migration, and differentiation. The cellular response is controlled by sensing the increased oxygen levels (hyperoxia) or hypoxia via specific chemoreceptor cells. Surprisingly, changes in free oxygen concentration instead of absolute oxygen levels may be regarded as a deficiency of oxygen at the cellular level. Recurrent intermittent hyperoxia may trigger many mediators of cellular pathways typically generated during hypoxia. The dilemma of hyperoxic-hypoxic conditions is known as the hyperoxic-hypoxic paradox. According to the latest data, the hypoxic microenvironment, crucial during cancer formation, has been demonstrated to play a key role in regulating breast cancer growth and metastasis. Hypoxic circumstances cause breast cancer cells to respond in a variety of ways. Transcription factors are identified as hypoxia-inducible factors (HIFs) that have been suggested to be a factor in the pathobiology of breast cancer and a possible therapeutic target, driving the cellular response to hypoxia. Breast cancer has a dismal prognosis due to a high level of resistance to practically all well-known cancer management that has been related to hypoxia-based interactions between tumor cells and the stromal milieu. We attempt to review the enigma by exploring the starring roles of HIFs in breast cancer, the HIF paradox, and the hyperoxic-hypoxic enigma.

A first-principles study of the oxygen reduction reaction activity of Pt with TM-N-C support

Developing highly active oxygen reduction reaction (ORR) electrocatalysts is of great significance for energy storage and conversion. In this study, we systematically investigated the effect of transition metal and nitrogen co-doped carbon (TM-N-C) as active support on ORR of Pt by density functional theory (DFT) calculations. Pt with TM-N-C supports (Pt/TM-SACs) exhibited enhanced ORR activity than Pt supported on carbon (Pt/C). The superior ORR activity is attributed to the TM-Nx structure, which can regulate the electronic structure of Pt. Moreover, the coordinated N is significantly correlated with the interaction between Pt and TM-N-C support. These findings provide insights for further exploration of ORR catalysts with active support.

CNT/Nafion functionalized Ti/SnO2-Sb/β-PbO2-CNT/Nafion composite electrode toward highly active and robust degradation of octadecylamine and 4-dodecylmorpholine in real high-salinity system

The efficient removal of recalcitrant organics in high-salinity systems, specifically brine, poses a significant challenge for electrochemically advanced oxidation processes in terms of both activity and stability. Herein, a composite electrode comprising of CNT/Nafion functionalized Ti/SnO2-Sb/β-PbO2-CNT/Nafion was developed for efficient and stable removal of octadecylamine (ODA) and 4-dodecylmorpholine (DMP) in a real high-salinity environment. The degradation efficiencies of ODA and DMP on the composite electrode can reach 100 % within 60 min, respectively. The total organic carbon (TOC) removal efficiency of ODA and DMP was significantly improved to 78 % and 66 % with remarkably low energy consumption (0.414 and 1.402 kWh/g TOC), respectively. The electrochemical characterizations demonstrate that the composite electrode exhibits improved electrochemical activity (oxygen evolution potentials = 1.791 V) and electrode surface area (ECSA = 20 cm2), while maintaining reduced charge transfer resistance (Rct = 18.21 Ω/cm2) and enhanced corrosion-resistant capacity (corrosion potential = 1.115 V). Based on recycling and accelerated lifespan testing, the composite electrode demonstrates exceptional stability and recyclability. Additionally revealed was the linked stability mechanism. The electrocatalytic degradation of ODA and DMP begins with the removal of amino and morpholine rings, and then the decomposition of the carbon chains. Gas chromatography-mass spectrometry (GC–MS) and theoretical calculations were used to identify intermediate products generated during the degradation of ODA and DMP, and possible degradation pathways were provided in high-salinity systems, respectively. This work offered a fresh perspective on electrocatalytic oxidation for a real high-salinity system that is more efficient and stable.

Synthesis of surficial-modified green biochar catalyst generated by biogas residue biochar and potential application for catalytic ozonation degradation of ciprofloxacin

This study synthesized novel, green, and easily recoverable surface-modified economical catalysts via hydrothermal treatment (HT) successfully, utilizing biogas residue biochar (BRB), a food waste product from anaerobic fermentation, pyrolyzed at 500 °C for 50 min. Using autoclaves, a total of six solutions were prepared, each having 1 g fine-grinded BRB, surficial modified by adding glycerol (GL) (10 or 20 mL) and SDI water (70 or 60 mL), and heated in an oven at 240 °C, 180 °C, and 120 °C for 24 h. Afterward, the catalysts showed the potential for degradation of widely used emerging pollutants like ciprofloxacin. Taking advantage of catalytic surface modification, the catalytic ozonation degradation was more effective than that of a single ozonation. However, under similar conditions, catalyst amount 0.20 g, ozone dose 15 mg L−1, and ciprofloxacin 80 mg L−1, the performance of the 10 mL GL-180 °C catalyst was excellent. It showed a 92.45%–94.41% optimum removal rate in the 8–10 min interval. After five continuous cycles, the 10 mL GL-180 °C catalyst exhibited excellent stability and reusability. XPS, FT-IR, BET, XRD, and SEM before and after the reaction confirmed the successful synthesis and degradation mechanism. A possible degradation pathway was unrevealed based on a liquid chromatography-mass spectrometer (LC-MS) and scavenger test, proving the significant roles of superoxide radicals (O2•-), hydroxyl radicals (•OH), and singlet oxygen (1O2). Further, Electron paramagnetic resonance (EPR) analysis confirmed the presence of active oxygen species. Subsequently, 10 mL GL-180 °C showed promising degradation for the actual water environment, such as groundwater (73.55%) and river water (64.74%). This work provides a valuable economic strategy to convert biogas residue biochar into a low-cost catalyst for organic pollutant decomposition.

Synergistic Pore Structure and Active Site Modulation in Co-N-C Catalysts Enabling Stable Zinc-Air Batteries.

Development of cheap, highly active, and durable nonprecious metal-based oxygen electrocatalysts is essential for metal-air battery technology, but achieving the balance of oxygen evolution reaction (OER)/oxygen reduction reaction (ORR) bifunctional performance and long-term durability is still a great challenge. Using a typical Co-N-C catalyst as a model, herein, we introduced ammonium chloride into nitrogen-doped carbon materials containing metal elements during the pyrolysis process (Co-N-C/AC), which not only increases the active area but also realizes the accurate customization of the active site (pyridine nitrogen and cobalt oxide species) so as to achieve the balance of the OER/ORR bifunctional sites. The synthesized Co-N-C/AC bifunctional catalyst with a three-dimensional porous structure exhibits a smaller potential gap of 0.72 V. The peak power density of the aqueous cell at a current density of 308 mA cm-2 is 203 mW cm-2. The cycle life (≈3900 h) is longer than those of other recently reported aqueous Zn-air batteries (ZABs). The peak power density of the Co-N-C/AC-based quasi-solid-state ZAB reaches 550 mW cm-2 for ∼72 h. This work shows a feasible path for the practical application of ZABs by balancing the bifunctional electrocatalysts by tailoring the active site reasonably.

DESTRUCTION OF VITAMIN B12 DURING INTERACTION WITH ACTIVE OXYGEN SPECIES

One of the most attractive molecular systems in the world of chemistry and medicine is vitamin B12, which was originally discovered as a factor against deficiency (pernicious) anemia. Deficiency of this essential vitamin leads to a decrease in the number of red blood cells in the blood and a drop in hemoglobin levels. The article provides a brief overview of the processes leading to the destruction of vitamin B12 caused by hypoxia, the action hypochlorous acid, superoxide anion radical, hydrogen peroxide, hydroxyl radical, peroxynitrite. Under conditions of hypoxia, oxygen transport in the electron transport chain may be disrupted, resulting in the reduction of oxygen on ubiquinone to a superoxide radical under the action of electrons that have not reached cytochrome oxidase. Oxidative stress develops, during which oxygen-containing radicals are formed, which can cause irreversible changes in the vitamin and lead to loss of biological activity. Hydrogen peroxide formed as a result of step-by-step protonation of the formed superoxide-anion radicals can act as such oxidants. Hydrogen peroxide, in turn, is capable of reacting with metals of variable oxidation state to form a reactive hydroxyl radical, producing the Fenton reaction. In addition, hypochlorous acid formed by the enzyme myeloperoxidase in the presence of hydrogen peroxide and chloride anion, as well as peroxynitrite, an active oxidant obtained by reacting the superoxide–anion radical with nitrogen (II) oxide, can act as oxidants. The latter is produced in large quantities under hypoxia conditions due to an increase in the activity of endothelial nitric oxide synthetase. The publications devoted to the influence of various oxidants on the stability of vitamin B12 are considered. For citation: Erina A.A., Borodulin V.B., Dereven’kov I.A., Makarov S.V., Ischenko A.A. Destruction of vitamin B12 during interaction with active oxygen species. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 7. P. 6-18. DOI: 10.6060/ivkkt.20246707.7043.

Au nanoparticles decorated ZnIn2S4/WO3 core-shell heterostructures as highly sensitive and selective ethylene glycol gas sensors

Ethylene glycol (EG) is extensively utilized as anti-freezer and deicer, which would bring potential health risk under unintentional exposures especially with hazardous inhalation of EG aerosols or vapors. In this study, ZnIn2S4 (ZIS)/WO3 core-shell nanofibrous heterostructure loaded with optimized Au nanoparticles (NPs) was prepared for superiorly sensitive and selective EG gas sensing. The ternary Au/ZIS/WO3 heterostructures exhibited an excellent response (Ra/Rg=98.92) to 50 ppm EG, demonstrating an enhancement of 3.5 times compared to the binary ZIS/WO3, and a substantial improvement of 59.5 and 24.1 times compared to pure WO3 and ZIS, respectively. The ternary Au/ZIS/WO3 heterostructures also possessed an extremely low detection limit of 6 ppb, as well as excellent selectivity, repeatability, and long-term stability. This exceptional gas sensing performance can be attributed to its distinctive ternary Au/ZIS/WO3 heterostructures with high specific surface areas. This unique structure not only facilitate the activation of abundant active oxygen species, but also promote the spillover effect of Au and enhance effective electronic distribution, thereby providing more EG adsorption sites, which was confirmed by density functional theory calculation. The synergistic effect arising from the metal-semiconductor interface and the core-shell heterostructure presents a novel avenue for advancing high-performance sensor technologies.

The impact of multi-decadal changes in VOC speciation on urban ozone chemistry: a case study in Birmingham, United Kingdom

Abstract. Anthropogenic non-methane volatile organic compounds (VOCs) in the United Kingdom have been substantially reduced since 1990, which is, in part, attributed to controls on evaporative and vehicle tailpipe emissions. Over time, other sources with a different speciation (for example, alcohols from solvent use and industry processes) have grown in both relative importance and, in some cases, in absolute terms. The impact of this change in speciation and the resulting photochemical reactivities of VOCs are evaluated using a photochemical box model constrained by observational data during a summertime ozone event (Birmingham, UK) and apportionment of sources based on the UK National Atmospheric Emission Inventory (NAEI) data over the period 1990–2019. Despite road transport sources representing only 3.3 % of UK VOC emissions in 2019, road transport continued being the sector with the largest influence on the local O3 production rate (P(O3)). Under case study conditions, the 96 % reduction in road transport VOC emissions that has been achieved between 1990 and 2019 has likely reduced daytime P(O3) by ∼ 1.67 ppbv h−1. Further abatement of fuel fugitive emissions was modeled to have had less impact on P(O3) reduction than abatement of VOCs from industrial processes and solvent use. The long-term trend of increased emissions of ethanol and methanol has somewhat weakened the benefits of reducing road transport emissions, increasing P(O3) by ∼ 0.19 ppbv h−1 in the case study. Abatement of VOC emissions from multiple sources has been a notable technical and policy success in the UK, but some future benefits (from an ozone perspective) of the phase-out of internal combustion engine passenger cars may be offset if domestic and commercial solvent use of VOCs continue to increase.

Multienzyme Mimicking Cascade Mn3O4 Catalyst to Augment Reactive Oxygen Species Elimination and Colorimetric Detection: A Study of Phase Variation upon Calcination Temperature.

Over decades, nanozyme has served as a better replacement of bioenzymes and fulfills most of the shortcomings and intrinsic disadvantages of bioenzymes. Recently, manganese-based nanomaterials have been highly noticed for redox-modulated multienzyme mimicking activity and wide applications in biosensing and biomedical science. The redox-modulated multienzyme mimicking activity was highly in tune with their size, surface functionalization, and charge on the surface and phases. On the subject of calcination temperature to Mn3O4 nanoparticles (NPs), its phase has been transformed to Mn2O3 NPs and Mn5O8 NPs upon different calcination temperatures. Assigning precise structure-property connections is made easier by preparing the various manganese oxides in a single step. The present study has focused on the variation of multienzyme mimicking activity with different phases of Mn3O4 NPs, so that they can be equipped for multifunctional activity with greater potential. Herein, spherical Mn3O4 NPs have been synthesized via a one-step coprecipitation method, and other phases are obtained by direct calcination. The calcination temperature varies to 100, 200, 400, and 600 °C and the corresponding manganese oxide NPs are named M-100, M-200, M-400, and M-600, respectively. The phase transformation and crystalline structure are evaluated by powder X-ray diffraction and selected-area electron diffraction analysis. The different surface morphologies are easily navigated by Fourier transform infrared, field-emission scanning electron microscopy, and high-resolution transmission electron microscopy analysis. Fortunately, for the mixed valence state of Mn3O4 NPs, all phases of manganese oxide NPs showed multienzyme mimicking activity including superoxide dismutase (SOD), catalase, oxidase (OD), and peroxidase; therefore, it offers a synergistic antioxidant ability to overexpose reactive oxygen species. Mn3O4 NPs exhibited good SOD-like enzyme activity, which allowed it to effectively remove the active oxygen (O2•-) from cigarette smoke. A sensitive colorimetric sensor with a low detection limit and a promising linear range has been designed to detect two isomeric phenolic pollutants, hydroquinone (H2Q) and catechol (CA), by utilizing optimized OD activity. The current probe has outstanding sensitivity and selectivity as well as the ability to visually detect two isomers with the unaided eye.

Purinergic Receptor Antagonists Inhibit Hemolysis Induced by Clostridium perfringens Alpha Toxin.

Clostridium perfringens alpha toxin (CPA), which causes yellow lamb disease in sheep and gas gangrene and food poisoning in humans, is produced by all types of C. perfringens and is the major virulence determinant of C. perfringens type A. CPA induces hemolysis in many species, including humans, murines, sheep and rabbits, through its enzymatic activity, which dissolves the cell membrane. Recent studies have shown that some pore-forming toxins cause hemolysis, which is achieved by the activation of purinergic receptors (P2). However, the relationship between P2 receptors and non-pore-forming toxin hemolysis has not been investigated. In the present study, we examined the function of P2 receptors in CPA toxin hemolysis and found that CPA-induced hemolysis was dependent on P2 receptor activation, and this was also true for Staphylococcus aureus β-Hemolysin, another non-pore-forming toxin. Furthermore, we use selective P2 receptor antagonists to demonstrate that P2X1 and P2X7 play important roles in the hemolysis of human and murine erythrocytes. In addition, we found that redox metabolism was mainly involved in CPA-induced hemolysis using metabolomic analysis. We further demonstrate that CPA activates P2 receptors and then activates NADPH oxidase through the PI3K/Akt and MEK1/ERK1 pathways, followed by the production of active oxygen to induce hemolysis. These findings contribute to our understanding of the pathological effects of CPA, clarify the relationship between P2 activation and non-pore-forming toxin-induced hemolysis, and provide new insights into CPA-induced hemolysis.

Long-lasting, fast-switchable photochromism in Na0.5Bi0.5TiO3 induced by photocatalytic memory effect, and its subsequently enhanced piezoelectric response and catalytic performances

A ferroelectric ceramic material of Na0.5Bi0.5TiO3 was found to possess a pronounced, long-lasting, and fast-switchable photochromic behavior responsive to visible light. The working mechanism of its photochromism could be attributed to an interesting photocatalytic memory effect, during which photogenerated electrons were trapped by Bi3+/Ti4+ and oxygen vacancies generated in Na0.5Bi0.5TiO3. The release kinetics of trapped electrons could be modulated by controlling environment conditions to make its photochromism phenomenon both long-lasting and fast-switchable to meet various application requirements. In the meantime, the photochromism process changed its inner electronic structure, resulting in stronger oxidation capability, increased piezoelectric response, improved charge carrier separation and transfer, and more active oxygen species production. Thus, its photocatalytic, piezocatalytic and photopiezocatalytic performances were all significantly enhanced as demonstrated by its TC-HCl degradation performances. This work offered a novel approach to search for and design inorganic photochromic materials with good reversibility for various technical applications.

The Characteristics of Structural Properties and Diffusion Pathway of Alkali in Sodium Trisilicate: Nanoarchitectonics and Molecular Dynamic Simulation.

Based on nanoarchitectonics and molecular dynamics simulations, we investigate the structural properties and diffusion pathway of Na atoms in sodium trisilicate over a wide temperature range. The structural and dynamics properties are analyzed through the radial distribution function (RDF), the Voronoi Si- and O-polyhedrons, the cluster function fCL(r), and the sets of fastest (SFA) and slowest atoms (SSA). The results indicate that Na atoms are not placed in Si-polyhedrons and bridging oxygen (BO) polyhedrons; instead, Na atoms are mainly placed in non-bridging oxygen (NBO) polyhedrons and free oxygen (FO) polyhedrons. Here BO, NBO, and FO represent O bonded with two, one, and no Si atoms, respectively. The simulation shows that O atoms in sodium trisilicate undergo numerous transformations: NBF0 ↔ NBF1, NBF1 ↔ NBF2, and BO0 ↔ BO1, where NBF is NBO or FO. The dynamics in sodium trisilicate are mainly distributed by the hopping and cooperative motion of Na atoms. We suppose that the diffusion pathway of Na atoms is realized via hopping Na atoms alone in BO-polyhedrons and the cooperative motion of a group of Na atoms in NBO- and FO-polyhedrons.

Ozonolysis of Terpene Flavor Additives in Vaping Emissions: Elevated Production of Reactive Oxygen Species and Oxidative Stress.

The production of e-cigarette aerosols through vaping processes is known to cause the formation of various free radicals and reactive oxygen species (ROS). Despite the well-known oxidative potential and cytotoxicity of fresh vaping emissions, the effects of chemical aging on exhaled vaping aerosols by indoor atmospheric oxidants are yet to be elucidated. Terpenes are commonly found in e-liquids as flavor additives. In the presence of indoor ozone (O3), e-cigarette aerosols that contain terpene flavorings can undergo chemical transformations, further producing ROS and reactive carbonyl species. Here, we simulated the aging process of the e-cigarette emissions in a 2 m3 FEP film chamber with 100 ppbv of O3 exposure for an hour. The aged vaping aerosols, along with fresh aerosols, were collected to detect the presence of ROS. The aged particles exhibited 2- to 11-fold greater oxidative potential, and further analysis showed that these particles formed a greater number of radicals in aqueous conditions. The aging process induced the formation of various alkyl hydroperoxides (ROOH), and through iodometric quantification, we saw that our aged vaping particles contained significantly greater amounts of these hydroperoxides than their fresh counterparts. Bronchial epithelial cells exposed to aged vaping aerosols exhibited an upregulation of the oxidative stress genes, HMOX-1 and GSTP1, indicating the potential for inhalation toxicity. This work highlights the indirect danger of vaping in environments with high ground-level O3, which can chemically transform e-cigarette aerosols into new particles that can induce greater oxidative damage than fresh e-cigarette aerosols. Given that the toxicological characteristics of e-cigarettes are mainly associated with the inhalation of fresh aerosols in current studies, our work may provide a perspective that characterizes vaping exposure under secondhand or thirdhand conditions as a significant health risk.