Mechanism Of Oxidation Research Articles

Oxidative stress mechanism by gold compounds: a close look at total ROS increase and the inhibition of antioxidant enzymes.

The antitumor activity of various gold compounds is a promising field of investigation, attracting researchers seeking potential clinical candidates. To advance this research, they explore the complex mechanisms of action of these compounds. Since the discovery of the strong inhibition of thioredoxin reductase by auranofin, the primary mechanism explored has been the inhibition of this enzyme. This inhibition disrupts the redox balance in cells, promoting oxidative stress and triggering cell death. In this review, we analyzed studies from the past decade that measured cellular ROS increase and examined the coordination structures of gold compounds. We also correlate ROS increase with the inhibition of redox-regulating enzymes, thioredoxin reductase and glutathione reductase, to elucidate the relationship between these cellular effects and chemical structures. Our data compilation reveals that different structures exhibit varying efficacy: some significantly increase ROS production and inhibit thioredoxin reductase or glutathione reductase, while others elevate ROS levels without affecting these target enzymes, suggesting alternative mechanisms of action. This review consolidates critical evidence, enhancing our understanding of the mechanisms by which these gold complexes act and providing valuable insights for developing new therapeutic strategies against tumor cells.

Water vapor oxidation of SiC layer of tristructural isotropic particles

AbstractTristructural isotropic (TRISO) fuel particles, developed for use in high‐temperature gas‐cooled nuclear reactors, can be subjected to oxidizing environments in off‐normal accident scenarios. In this study, surrogate TRISO fuel particles were oxidized at 1000–1350°C for 4 h in 20 kPa water vapor atmosphere balanced with ultrahigh‐purity helium gas. The oxide scale morphology and thickness were studied via scanning electron microscopy, focused ion beam, and transmission electron microscopy. The oxide thickness increased as the oxidation temperature was increased. Although the oxide scale at 1000°C was completely amorphous, pockets of crystalline oxide were observed on particles oxidized at 1200 and 1300°C. Kinetic analysis was performed to deduce the oxidation mechanism by determining the apparent activation energy using linear regression analysis. The oxidation mechanism was consistent for temperatures from 1000 to 1200°C with an activation energy of 412.4 ± 8.8 kJ/mol. The activation energy then dropped to approximately 201 ± 7.1 kJ/mol for temperatures 1200–1350°C. Therefore, there is a change in oxidation mechanism at ∼1200°C. This change is attributed to the existence of a network of significant bubbles in the oxide layer at higher temperatures, which serve as rapid diffusion pathways for the transport of oxidants from the surface to the SiC/SiO2 interface, instead of relying on the bulk diffusion through the SiO2 layer at lower temperatures where only small bubbles are present along the SiC/SiO2 interface.

Selective conversion of thermal decomposition products of ammonium perchlorate by amorphous CoSnOx

The directional transformation of products in the multiphase decomposition process of ammonium perchlorate (AP) still faces significant challenges, one of which is the conversion of greenhouse gas N2O. Furthermore, additional elucidation of the structure and potential catalytic mechanisms of catalysts with high thermal stability is imperative for the aforementioned process. This study proposes a cobalt-based amorphous oxide with high thermal stability for catalysing the thermal decomposition of AP and achieving the transformation of catalytic products from N2O to NO (and its derivatives). The results indicate that the type of catalytic decomposition products is related to the structural transformation of the catalyst, suggesting a synergistic oxidation mechanism by active oxygen and lattice oxygen. The peak decomposition temperature of AP has dropped to near the limit of 257.2 °C, TG-IR test and MD simulation results indicate the selective generation of NO under the lattice oxygen mechanism. In addition, kinetic calculations elucidated the transition of catalysts from amorphous to crystalline state in catalysis. Finally, suggestions were made for the current characterization techniques of catalysts. This study offers a reference point for the catalyst design of AP decomposition-oriented products, which is beneficial for the transition to more environmentally-friendly products.

Environmentally Benign Synthesis of Magnetic Fe3O4 Nanoparticle/Carbon Black/Copper‐Quercetin Rods for Sensitive, Disposable Electrochemical Sensor for Mitoxantrone

AbstractPhenolic compounds have a variety of activities but are most famous for their antioxidant and metal‐chelating properties. We explore the green synthesis and application of Fe3O4 nanoparticles, carbon black (CB), and copper‐quercetin (Cu−Q) composite for a disposable electrochemical sensor for mitoxantrone. Fe3O4 was synthesised using Camellia sinensis leaf extract. The copper‐quercetin was synthesised by titrating copper acetate solution with quercetin monohydrate solution at room temperature. Equal amounts of Fe3O4, CB, and Cu−Q were mixed to form Fe3O4‐CB/Cu−Q. The Fe3O4‐CB/Cu−Q/SPE has the lowest detection limit (55.47 pM) compared to previous mitoxantrone sensors. The average recovery was 102.2 %, with an RSD of 4.67 % in serum. The sensor maintained an average accuracy of 98.99 % in the presence of the interfering agent. The detection limit of the new sensor is about five times lower than that of the previous Fe3O4 and carbon black electrode. Therefore, it can be suggested that the Copper‐quercetin complex contributed significantly to the electrode's sensitivity. This research is the first to report the three oxidation potentials for mitoxantrone consistent with mitoxantrone's complex oxidation mechanism. Also, this is the first report on using copper‐quercetin as an electrode material for electrode chemical detection. Furthermore, this is the first green‐derived sensor for mitoxantrone.

Tailoring the Charge Transfer‐Driven Oxidation in van der Waals Ferroelectric NbOI2 Through Hetero‐Interface Engineering

Abstract2D transition metal halide oxides (TMHOs) have attracted much interest due to their intriguing ferroelectrics and excellent nonlinear optics, however, their susceptibility to oxidation makes their basic research and practical application a challenge. Therefore, it is crucial to understand the oxidation mechanism and explore effective strategies for protection. Here, taking van der Waals (vdWs) ferroelectric NbOI2 as an example, oxidation mechanisms and tuning the oxidation behaviors of NbOI2 and its heterostructures by a variety of in situ experiments and first‐principles calculations are discovered. The ambient‐pressure X‐ray photoelectron spectra reveal a self‐limiting oxidation in isolated NbOI2, driven by spontaneously formed iodine vacancies that react with oxygen molecules due to their lower formation and adsorption energies. For the heterostructures with a lower Fermi level (such as WSe2) than transition state VI@NbOI2 (NbOI2 rich in I‐vacancies), the charge transfer from NbOI2 to WSe2 drives the continuous and complete oxidation of NbOI2 flakes. Moreover, the heterostructures with a higher Fermi level (such as graphene) than VI@NbOI2 can weaken the oxidation of NbOI2. By linking the energy band structures to oxidation behavior, the work offers a new oxidation mechanism of 2D air‐sensitive materials and a crucial strategy for improving their chemical stability.

Proton-Coupled Electron Transfer between a Pendant Thiol and a Ferrous Dioxygen Adduct.

The mechanism of thiol oxidation by O2, as catalyzed by ferrous porphyrins, is investigated by trapping intermediates of the transformation at low temperatures and subsequently characterizing them using continuous wave and pulsed electron paramagnetic resonance and resonance Raman spectroscopy. A Fe(III)-O2•- species is initially formed in an iron porphyrin with a pendant thiol functional group, which undergoes proton-coupled electron transfer (PCET) (not HAT) to form an Fe(III)-OOH species. Following O-O bond homolysis, this forms a Fe(IV)═O species with concomitant oxidation of the thiol to an RSO3H group.

Engineering heterojunction noble metal (NM)@ZnO catalyst for improved CH4 photocatalytic oxidation

The photo-oxidation of methane into value-oxygenated products using H2O2 and H2O as an oxidant under atmospheric pressure represents a desired sustainable strategy for the production of commodity chemicals. However, controlling the products and maintaining high yields poses significant challenges. In this study, we propose an efficient strategy involving the design of noble metal (Au, Pd)/ZnO photocatalysts to enhance the productivity of oxygenates through CH4 photocatalytic oxidation. The prominent product, CH3OH, is achieved with a high yield of 1900 μmol/g. The unique combination and porous structures of Au/ZnO synergistically promote its conversion performance. Additionally, photoluminescence results provide direct evidence of the main intermediates involved in producing CH3OH and multi-carbon oxygenates. The findings of this research offer valuable insights into the fundamental oxidation mechanisms underlying photocatalytic CH4 conversion.

Curcumin-encapsulated glucan nanoparticles as an oxidative stress modulator against human hepatic cancer cells

In Hepatitis B patients, the virus targets liver cells, leading to inflammation and liver damage, which can result in severe complications such as liver failure, cirrhosis, and liver cancer. Therapeutic options for liver disease are currently limited. Curcumin, a polyphenol with potential protective effects against chronic diseases like cancer, suffers from poor water solubility, restricting its pharmacological applications. This study explores the encapsulation of curcumin in glucan nanoparticles (NPs) and its impact on oxidative stress in liver cancer cells. Two sizes of curcumin-loaded glucan NPs, GC111 (111 nm) and GC398 (398 nm), were produced with nearly 100 % encapsulation efficiency. Cytotoxicity studies revealed that particle size influences the extent of observed effects, with GC111 NPs causing a greater reduction in cell viability. Additionally, the smaller GC111 NPs demonstrated a higher capacity to induce oxidative stress in cancer cells by stimulating the production of ROS, NO, and the chemokine RANTES in a concentration-dependent manner. These findings suggest that the smaller GC111 NPs are promising candidates for future studies aimed at evaluating oxidative stress-induced tumor cell death mechanisms.

Engineered Core-Shell SiC@SiO2 Nanofibers for Enhanced Electromagnetic Wave Absorption Performance.

To enable SiC material to achieve high electromagnetic wave (EMW) absorption performance, solving its impedance mismatch with EMW is necessary. Therefore, a novel approach is proposed for the precise control of impedance matching by adjusting the shell thickness of SiO2 nanolayers on the surface of SiC nanofibers (NFs). High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) reveals the atomic scale oxidation process of SiC, providing fresh insights into the oxidation mechanism. By oxidizing to construct a heterogeneous core-shell structure nanofiber (NF) can effectively lock the incident EMW inside the NF through the generated charges gathered at the interface, forming an electronic barrier that prevents the outward propagation of EMWs. The produced SiC@SiO2 NFs-3 exhibits exceptional EMW absorption properties, including an impressive minimum reflection loss (RLmin) of -53.09dB and a broad maximum effective absorption bandwidth (EABmax) of 8.85GHz. These findings not only deepen understanding of the oxidation mechanism of SiC but also offer valuable insights for further enhancing the EMW absorption capabilities of SiC materials, paving the way for their application in advanced EMW technologies.

Unveiling the Mechanism of Glycerol Oxidation to Lactic Acid on Pt/Sn-MFI Zeolite: an In situ Solid-state NMR Study

Unveiling the Mechanism of Glycerol Oxidation to Lactic Acid on Pt/Sn-MFI Zeolite: an In situ Solid-state NMR Study

Nd3+ induces three-dimensional hierarchical rosette-shaped Bi3O4Br to generate abundant oxygen vacancies for enhanced photocatalytic activity

Three-dimensional hierarchical rosette-shaped Bi3O4Br has been successfully prepared by a one-step hydrothermal method for the first time, in which the doping of Nd3+ into the matrix of Bi3O4Br induces abundant oxygen vacancies and triggers energy-band hybridization to produce new dopant levels, which can efficiently receive photo-excited electrons and inhibit the complexation of photogenerated carriers. Impressively, the doped energy levels act as “springboards” for photogenerated electron jumps, exacerbating the inhomogeneity of charge distribution and accelerating charge separation. In addition, the fine-tuning of Nd3+ improves the band structure and photocatalytic performance of Nd/Bi3O4Br. Notably, the unique 3D rosette-like Bi3O4Br could enhance the adsorption capacity of the catalyst and provide more opportunities for the introduction of Nd3+ to induce the generation of abundant oxygen vacancies. Both experimental and density functional theory (DFT) results reveal the synergistic effect of energy band hybridization and oxygen vacancies. In addition, comparative experiments showed that Nd/Bi3O4Br enhanced the maximum removal efficiency of heavy metal mercury by 29.66 % relative to Bi3O4Br under visible light. The present work reveals the reaction mechanism of photocatalytic oxidation for mercury removal, which provides a new direction for realizing energy conversion and environmental purification in the future.

Threshold voltage instability of SiC MOSFETs under very‐high temperature and wide gate bias

AbstractThreshold voltage (VTH) instability affects the reliability of silicon carbide (SiC) MOSFETs. In this article, the influence of gate bias (VGS) and high temperature on VTH instability is investigated under wide VGS and very‐high temperature range (150°C to 275°C). The degradation mechanism of gate oxide under coupling of different electrical and thermal stress is revealed. When the device is subjected to +VGS, the relationship between VTH shift and temperature is not monotonic and there is a temperature turning point. This is mainly related to the capture/release and generation of electron traps. However, the VTH shift increases sharply and gate oxide breakdown for the device bias at +35 V, which is related to Fowler–Nordheim (F–N) tunnelling effect. For a large −VGS, the VTH shift is very small. Moreover, when the negative VGS decreases, the VTH shift is positively correlated with temperature, which may result from the activation and charge exchange of hole traps. However, the influence of moving ions changes the temperature dependence of VTH shift for the device bias at −30 V. Finally, the devices of different manufacturers are studied and similar change patterns are found. This finding provides guidance for the further application of SiC MOSFETs under high temperatures and different voltages.

Oxidative Processes and Xenobiotic Metabolism in Plants: Mechanisms of Defense and Potential Therapeutic Implications.

Plants are continuously exposed to environmental challenges, including pollutants, pesticides, and heavy metals, collectively termed xenobiotics. These substances induce oxidative stress by generating reactive oxygen species (ROS), which can damage cellular components such as lipids, proteins, and nucleic acids. To counteract this, plants have evolved complex metabolic pathways to detoxify and process these harmful compounds. Oxidative stress in plants primarily arises from the overproduction of hydrogen peroxide (H2O2), superoxide anions (O2•-), singlet oxygen (1O2), and hydroxyl radicals (•OH), by-products of metabolic activities such as photosynthesis and respiration. The presence of xenobiotics leads to a notable increase in ROS, which can result in cellular damage and metabolic disruption. To combat this, plants have developed a strong antioxidant defense mechanism that includes enzymatic antioxidants that work together to eliminate ROS, thereby reducing their harmful effects. In addition to enzymatic defenses, plants also synthesize various non-enzymatic antioxidants, including flavonoids, phenolic acids, and vitamins. These compounds effectively neutralize ROS and help regenerate other antioxidants, offering extensive protection against oxidative stress. The metabolism of xenobiotic substances in plants occurs in three stages: the first involves modification, which refers to the chemical alteration of xenobiotics to make them less harmful. The second involves conjugation, where the modified xenobiotics are combined with other substances to increase their solubility, facilitating their elimination from the plant. The third stage involves compartmentalization, which is the storage or isolation of conjugated xenobiotics in specific parts of the plant, helping to prevent damage to vital cellular functions. Secondary metabolites found in plants, such as alkaloids, terpenoids, and flavonoids, play a vital role in detoxification and the defense against oxidative stress. Gaining a deeper understanding of the oxidative mechanisms and the pathways of xenobiotic metabolism in plants is essential, as this knowledge can lead to the formulation of plant-derived strategies aimed at alleviating the effects of environmental pollution and enhancing human health by improving detoxification and antioxidant capabilities, as discussed in this review.

Mechanical properties and first-principle calculation investigation of ZrHfNbTa series refractory high entropy alloys prepared by a combined process

ABSTRACT Refractory high-entropy alloys (RHEAs) are widely used in aerospace engine, gas turbine high-temperature components, capacitors and catalysis. The study presents a combined process for preparing ZrHfNbTa series RHEAs. HEAs powders were prepared from metal oxide by molten salt electro-deoxidation process, and the bulk HEAs were prepared by vacuum hot-pressing sintering process. The study aimed to explore the alloying mechanism of mixed metal oxide in molten salt electro-deoxidation process to optimise the properties. The hardness and wear resistance of the bulk alloy were tested. The test results show that the hardness of ZrHfNbTa and VZrHfNbTa bulk RHEAs prepared by this process is 1251 and 1603 HV. According to the friction surface characterisation of bulk alloy, VZrHfNbTa HEA has better wear resistance than ZrHfNbTa. Based on the first-principle calculation results, the doping of V element produces a strong hybridisation of electron orbitals in RHEAs, which can effectively improve the mechanical properties of RHEAs.

Analysis of the evolution of placental oxidative stress research from a bibliometric perspective.

Research on placental oxidative stress is pivotal for comprehending pregnancy-related physiological changes and disease mechanisms. Despite recent advancements, a comprehensive review of current status, hotspots, and trends remains challenging. This bibliometric study systematically analyzes the evolution of placental oxidative stress research, offering a reference for future studies. To conduct a comprehensive bibliometric analysis of the literature on placental oxidative stress to identify research hotspots, trends, and key contributors, thereby providing guidance for future research. Relevant data were retrieved from the Web of Science Core Collection database and analyzed using VOSviewer, CiteSpace, and the bibliometrix package. An in-depth analysis of 4,796 publications was conducted, focusing on publication year, country/region, institution, author, journal, references, and keywords. Data collection concluded on 29 April 2024. A total of 4,796 papers were retrieved from 1,173 journals, authored by 18,835 researchers from 4,257 institutions across 103 countries/regions. From 1991 to 2023, annual publications on placental oxidative stress increased from 7 to 359. The United States (1,222 publications, 64,158 citations), the University of Cambridge (125 publications, 13,562 citations), and Graham J. Burton (73 publications, 11,182 citations) were the most productive country, institution, and author, respectively. The journal Placenta had the highest number of publications (329) and citations (17,152), followed by the International Journal of Molecular Sciences (122 publications). The most frequent keywords were "oxidative stress," "expression," "pregnancy," "preeclampsia," and "lipid peroxidation." Emerging high-frequency keywords included "gestational diabetes mellitus," "health," "autophagy," "pathophysiology," "infection," "preterm birth," "stem cell," and "inflammation." Over the past 3decades, research has concentrated on oxidative stress processes, antioxidant mechanisms, pregnancy-related diseases, and gene expression regulation. Current research frontiers involve exploring pathophysiology and mechanisms, assessing emerging risk factors and environmental impacts, advancing cell biology and stem cell research, and understanding the complex interactions of inflammation and immune regulation. These studies elucidate the mechanisms of placental oxidative stress, offering essential scientific evidence for future intervention strategies, therapeutic approaches, and public health policies.

Oxidation anisotropy of 4H-SiC wafers during chemical-mechanical polishing

4H silicon carbide (4H-SiC) wafers are widely used in high-power, high-temperature, and high-frequency electronics owing to their excellent physical and electrical properties. In the processing of 4H-SiC wafers, chemical-mechanical polishing (CMP) is commonly employed to realize atomic-scale smoothness, damage-free surface, and global planarization. The CMP process is the synergy of wet oxidation and mechanical grinding, whose efficiency significantly relies on the oxidation process. Therefore, understanding the wet oxidation mechanism of Si face and C face of 4H-SiC wafers is critical to high-efficiency double-side CMP. In this work, the anisotropic CMP performance of Si face and C face of 4H-SiC wafers are investigated. It has been found that the material removal rate of the C face is 2–3 times that of the Si face. The thicknesses of the transient oxide layer on the C face and Si face are 8.71 nm and 3.50 nm, respectively. X-ray photoelectron spectroscopy analysis reveals that the oxygen content on the C face is higher than that on the Si face after wet KMnO4 oxidation. This indicates that the C face of 4H-SiC is easier to oxidize, which results in more oxides that that on the Si face of 4H-SiC. Our work shows that accelerating the oxidation of the Si face of 4H-SiC wafers during the simultaneous double-sided CMP process is crucial for the efficient polishing of 4H-SiC wafers.

A Practical Study on the Relationship between Serum Iron Elevation and Liver Enzymes Plus Other Factors in Patients with Beta-Thalassemia

Thalassemia is a genetic condition characterized by faulty hemoglobin synthesis and low hemoglobin concentration. Overload of iron is an unavoidable condition experienced by severe thalassemia patients as a result of excessive blood transfusions. We looked at impaired liver function in thalassemia individuals with Iraq as a result of these issues. Our findings demonstrated serum activity in hepatocytes, as well as a large rise in GOT and AIP in patients with elevated iron levels and a substantial rise in TSB. All of these elements may work together or independently to create chronic liver disease by causing damage in cells via oxidative mechanisms.

Oxygen Plasma Triggered Co-O-Fe Motif in Prussian Blue Analogue for Efficient and Robust Alkaline Water Oxidation.

In the context of oxygen evolution reaction (OER), the construction of high-valent transition metal sites to trigger the lattice oxygen oxidation mechanism is considered crucial for overcoming the performance limitations of traditional adsorbate evolution mechanism. However, the dynamic evolution of lattice oxygen during the reaction poses significant challenges for the stability of high-valent metal sites, particularly in high-current-density water-splitting systems. Here, we have successfully constructed Co-O-Fe catalytic active motifs in cobalt-iron Prussian blue analogs (CoFe-PBA) through oxygen plasma bombardment, effectively activating lattice oxygen reactivity while sustaining robust stability. Our spectroscopic and theoretical studies reveal that the Co-O-Fe bridged motifs enable a unique double-exchange interaction between Co and Fe atoms, promoting the formation of high-valent Co species as OER active centers while maintaining Fe in a low-valent state, preventing its dissolution. The resultant catalyst (CoFe-PBA-30) requires an overpotential of only 276 mV to achieve 1000 mA cm-2. Furthermore, the assembled alkaline exchange membrane electrolyzer using CoFe-PBA-30 as anode material achieves a high current density of 1 A cm-2 at 1.76 V and continuously operates for 250 hours with negligible degradation. This work provides significant insights for activating lattice oxygen redox without compromising structure stability in practical water electrolyzers.

Oxygen Plasma Triggered Co‐O‐Fe Motif in Prussian Blue Analogue for Efficient and Robust Alkaline Water Oxidation

In the context of oxygen evolution reaction (OER), the construction of high‐valent transition metal sites to trigger the lattice oxygen oxidation mechanism is considered crucial for overcoming the performance limitations of traditional adsorbate evolution mechanism. However, the dynamic evolution of lattice oxygen during the reaction poses significant challenges for the stability of high‐valent metal sites, particularly in high‐current‐density water‐splitting systems. Here, we have successfully constructed Co‐O‐Fe catalytic active motifs in cobalt‐iron Prussian blue analogs (CoFe‐PBA) through oxygen plasma bombardment, effectively activating lattice oxygen reactivity while sustaining robust stability. Our spectroscopic and theoretical studies reveal that the Co‐O‐Fe bridged motifs enable a unique double‐exchange interaction between Co and Fe atoms, promoting the formation of high‐valent Co species as OER active centers while maintaining Fe in a low‐valent state, preventing its dissolution. The resultant catalyst (CoFe‐PBA‐30) requires an overpotential of only 276 mV to achieve 1000 mA cm‐2. Furthermore, the assembled alkaline exchange membrane electrolyzer using CoFe‐PBA‐30 as anode material achieves a high current density of 1 A cm‐2 at 1.76 V and continuously operates for 250 hours with negligible degradation. This work provides significant insights for activating lattice oxygen redox without compromising structure stability in practical water electrolyzers.

Operando XANES Reveals the Chemical State of Iron-Oxide Monolayers During Low-Temperature CO Oxidation.

We have used grazing incidence X-ray absorption near edge spectroscopy (XANES) to investigate the behavior of monolayer FeOxfilms on Pt(111) under near ambient pressure CO oxidation conditions with a total gas pressure of 1 bar. Spectra indicate reversible changes during oxidation and reduction by O2 and CO at 150ºC, attributed to a transformation between FeO bilayer and FeO2 trilayer phases. The trilayer phase is also reduced upon heating in CO+O2, consistent with a Mars-van-Krevelen type mechanism for CO oxidation. At higher temperatures, the monolayer film dewets the surface, resulting in a loss of the observed reducibility. A similar iron oxide film prepared on Au(111) shows little sign of reduction or oxidation under the same conditions. The results highlight the unique properties of monolayer FeO and the importance of the Pt support in this reaction. The study furthermore demonstrates the power of grazing-incidence XAFS for in situ studies of these model catalysts under realistic conditions.