Peroxide Formation Research Articles

Analysis of plasma plume parameters in physio-chemical processes of RF plasma jet plume direct in water for the inactivation of Enterococcus bacteria

The contamination of Enterococcus bacterium is widely observed in the living environment and water. The decontamination of drinking water from the bacterial pollution is an important issue in water treatment. Here, the inactivation of Enterococcus bacteria is studied by placing the dielectric barrier discharge structure, with the RF discharge frequency of 13.56 MHz atmospheric pressure argon plasma jet, directly in water, whereas the water around the plasma plume was seething and the bubbles produced stirring all liquid volume. The ability to place a plasma jet nozzle directly in water for 10 min while maintaining a steady and uniform plasma plume, besides water temperature, provides the effectiveness enhancement in the inactivation of bacteria. The absorption of UV radiation in water is effective, and the role of UV radiation of plasma plume was mainly responsible for the destruction of peptidoglycan, which is the outer layer of Enterococcus. Then, the presence of electrons and plasma plume in water leads to the formation of hydroxyl, hydrogen peroxide, and other reactive radicals that are involved in chemical reactions, which lead to the inactivation of micro-organisms. The number of bacteria decreases from the initial value of 16 × 105 MPN/100 ml to less than 1.2 MPN/100 ml. The spectra of the plasma radiation, with the plume length 2 cm within the water, have been analyzed via the first nitrogen negative system N2+B−X. The plume temperature was calculated to be about 64 °C, which has a good agreement with water temperature measured by using a thermometer at about 67 °C after 15 min at maximum 200 W input power of the plasma jet.

Enhanced Microvascular Adaptation to Acute Physical Stress and Reduced Oxidative Stress in Male Athletes Who Consumed Chicken Eggs Enriched with n-3 Polyunsaturated Fatty Acids and Antioxidants-Randomized Clinical Trial.

This randomized interventional study aimed to determine the effects of n-3 polyunsaturated fatty acids, selenium, vitamin E, and lutein supplementation in the form of enriched chicken egg consumption on microvascular endothelium-dependent vasodilation, oxidative stress, and microvascular response to an acute strenuous training session (ASTS) in competitive athletes. Thirty-one male athletes were assigned to a control (n = 17) or a Nutri4 group (n = 14) who consumed three regular or enriched chicken eggs per day, respectively, for 3 weeks. Significantly enhanced endothelium-dependent responses to vascular occlusion (PORH) and iontophoresis of acetylcholine (AChID) were observed in the Nutri4 group but not in the control group after egg consumption. Formation of peroxynitrite and hydrogen peroxide in peripheral blood mononuclear cells, as well as serum concentration of 8-iso prostaglandin F2α, decreased in the Nutri4 group while remaining unchanged in controls. PORH and AChID were reduced post-ASTS compared with pre-ASTS, both before and after the diets, in both groups. However, the range of PORH responsiveness to ASTS (ΔPORH) increased after consumption of enriched eggs. These results suggest that consumption of enriched chicken eggs has a beneficial effect on microvascular endothelium-dependent vasodilation and the reduction of oxidative stress levels in competitive athletes. Also, microvascular adaptation to the ASTS was improved after consumption of Nutri4 eggs.

Time-shift effect of spontaneous combustion characteristics and microstructure difference of dry-soaked coal

The physical and chemical properties of the air-dried residual coal after soaking in the goaf will change, resulting in an increase in its spontaneous combustion tendency. This study aimed to look into the features and mechanism of soaked-dried coal's spontaneous combustion. Five samples of coal were dried to various degrees, and the weight loss features during thermal processing were examined. Based on this, the pore structure and chemical structure characteristics of the coal samples with the highest tendency to spontaneous combustion were quantitatively examined, and the mechanism by which soaking-drying affected the spontaneous combustion heating process of the remaining coal in goaf was investigated in turn. The results show that T1 decreases with the increase of drying time, T2–T6 shows a fluctuating change, and the ignition activation energy of 36-S-Coal is smaller than that of other coal samples. The pore type of 36-S-Coal changes from a one-end closed impermeable pore to an open pore, and the pore group area is large. During the 36 h drying process, the internal channels of the coal were dredged, and a large number of gravels and minerals were precipitated from the pores with the air flow. A large number of gravels were around the pores to form a surface structure that was easy to adsorb various gases. Furthermore, infrared spectroscopy was used to analyze the two coal samples. It was found that soaking and drying did not change the functional group types of coal samples, but the fatty chain degree of 36-S-Coal was reduced to 1.56. It shows that the aliphatic chain structure of coal is changed after 36 h of drying after 30 days of soaking, which leads to the continuous shedding of aliphatic chain branches of residual coal, and the skeleton of coal is looser, which makes the low-temperature oxidation reaction of 36-S-Coal easier. Based on the above results, the coal-oxygen composite mechanism of water-immersed-dried coal is obtained, and it is considered that the key to the spontaneous combustion oxidation process of coal is to provide oxygen atoms and accelerate the formation of peroxides.

Pincer Ligands as Multifunctional Agents for Alzheimer's Copper Dysregulation and Oxidative Stress: A Computational Evaluation.

Alzheimer's disease (AD) is the most common form of dementia worldwide, affecting millions of people around the globe. AD is characterized by different pathologies being beta-amyloid (Aβ) plaque formation, metal ion dysregulation, and oxidative stress (OS) central topics under investigation. Copper-Aβ complexes have been shown to induce catalytic hydrogen peroxide formation and increase OS in the brain leading to neuronal death. Pincer-type compounds are tridentate ligands that coordinate metals in a planar fashion whose properties can be tuned via group substitutions, giving rise to many possibilities in catalysis and drug discovery. In this work we evaluated the potential pharmaceutical activity of 26 pincer compounds in AD's copper ion-related oxidative stress framework. In this sense, four key aspects were considered: 1) Lipinski's rule of five, 2) blood-brain barrier permeation, 3) standard reduction potential (SRP) of the formed copper complexes, and 4) the ligand's affinity towards copper cations. The evaluation of these criteria was performed by means of bioinformatic tools and electronic structure calculations at the DFT level of theory. Our results suggest that two compounds from this set are potential antioxidant agents, whereas five of them are promissory distributor-like compounds in the context of AD.

β-Caryophyllene Inhibits Oxaliplatin-Induced Peripheral Neuropathy in Mice: Role of Cannabinoid Type 2 Receptors, Oxidative Stress and Neuroinflammation.

Peripheral neuropathy is an important adverse effect caused by some chemotherapeutic agents, including oxaliplatin (OXA). OXA-induced peripheral neuropathy (OIPN) is a challenging condition due to diagnostic complexities and a lack of effective treatment. In this study, we investigated the antiallodynic effect of β-caryophyllene (BCP), a cannabinoid type 2 (CB2) receptor agonist, in a mouse model of OIPN. BCP treatment inhibited OXA-induced mechanical and cold allodynia in both preventive and therapeutic drug treatment regimens. Experiments with the CB2 receptor agonist GW405833 confirmed the role of CB2 receptors in OIPN. The CB2 antagonist SR144528 abrogated the anti-nociceptive effect of BCP on mechanical allodynia, without impacting OXA-induced sensitivity to cold. BCP decreased neuroinflammation, as inferred from TNF, IL-1β, IL-6, and IL-10 profiling, and also reduced ROS production, lipid peroxidation, and 4-hydroxynonenal protein adduct formation in the spinal cords of OXA-treated mice. BCP did not affect the antitumor response to OXA or its impact on blood cell counts, implying that the cytotoxicity of OXA was preserved. These results underscore BCP as a candidate drug for OIPN treatment via CB2 receptor-dependent mechanisms, and anti-inflammatory and antioxidant responses in the spinal cord.

8-Oxoguanine-DNA-Glycosylase Gene Polymorphism and the Effects of an Alternating Magnetic Field on the Sensitivity of Peripheral Blood.

The production of reactive oxygen species (ROS) in animals and cells often results from exposure to low-intensity factors, including magnetic fields. Much of the discussion about the initiation of oxidative stress and the role of ROS and radicals in the effects of magnetic fields has centered on radical-induced DNA damage. The DNA concentration in the final solution was determined spectrophotometrically. Typing of the polymorphic variant rs1052133 of the 8-oxoguanin DNA glycosylase (hOGG1) gene was performed by polymerase chain reaction. An enzyme immunoassay was performed to determine the level of 8-oxyguanine in DNA. To process samples exposed to an alternating magnetic field, the authors developed a device for the automated study of biological fluids in an alternating magnetic field. The content of hydrogen peroxide in aqueous solutions of DNA was determined using the spectrophotometric method. It was experimentally determined that an increase in the concentration of hydrogen peroxide in an aqueous medium by 3-5 times under the action of a low-frequency magnetic field reduces the resistance of the genomic material to oxidative modification and the accumulation of 8-oxyguanine in DNA. A model is proposed for the mechanism of action of a low-frequency magnetic field on aqueous solutions of nucleic acids and proteins, which satisfies the model of a chemical oscillator for the transformations of reactive oxygen species in an aqueous medium. The model illustrates the oscillating nature of the processes occurring in an aqueous solution of DNA and makes it possible to predict changes in the concentration of hydrogen peroxide in an aqueous solution of biopolymers, depending on the frequency of the acting low-intensity magnetic field. The key element in the mechanisms involved in the effects of low-intensity magnetic field on living systems is the occurrence of ROS generation in the aquatic environment of chemical oscillators, in which the competition of physical and chemical processes (electron transfers, reactions of decay and addition of radicals, spin magnetically induced conversion, synthesis, and decay of the longest-lived form-hydrogen peroxide) is controlled by a magnetic field.

Functional mimic for catechol oxidase and phenoxazinone synthase: Structural, spectral, electrochemical and catalytic properties of mononuclear copper(II) complex

A promising bioinspired metallocatalyst [Cu(L1)2(L2)] (L1 = P-hydroxybenzoic acid, L2 = N1,N1-dimethylpropane-1,3-diamine) has been produced and characterized in accordance with reports. In the octahedron arrangement around the copper ion, the elongation along one axial direction and one equatorial direction results in a distorted geometry Molecular assembly shows both inter and intra molecular H-bonding along with CH---π interactions evident from the Hirhsfeld surface analysis. The fingerprint plot discloses the relative contribution of percentage of intermolecular contacts (H⋯H, C⋯H and O⋯H) in the complex. The EPR, CV, and UV analyses collectively support that the complex exhibits such activity via oxygen dependant enzymatic radical pathway. Furthermore, these activities are observed under fully aerobic conditions in which 3,5-di-tert-butylcatechol (3,5-DTBC) and 2-amino phenol (2-AP) are used as model substrates. Michaelis-Menten analysis derived from the pseudo first-order reaction kinetics established that this complex shows extremely high catalytic activity towards 3,5- DTBC and 2-AP (Kcat 1.729 × 105 h−1 and 0.260 × 105 h−1). The suggested mechanism has been supported by UV spectra data in which formation of hydrogen peroxide by observing the appearance of spectral band at λmax 353 nm indicates the active participation of molecular oxygen in the catalytic process.

Mechanism of action of the low-frequency electromagnetic field on aqueous solutions of biopolymers

This paper presents the mechanism of signal transformation by which a signal from the magnetic component of the low-frequency electromagnetic field with extremely low energy is changed into chemical and biochemical signals which elicit a biological response in aqueous solutions of biopolymers based on nucleic acids and proteins. A theoretical model developed shows that the basis of oxidative DNA damage and conformational transitions of proteins is a universal mechanism associated with a change in the amount of the most long-lived form - hydrogen peroxide in a chemical oscillator of mutual transformations of reactive oxygen species under the influence of low-intensity electromagnetic field exposure. It has been experimentally established that the quantitative content of hydrogen peroxide in solutions of biopolymers resonantly depends on the frequency of applied field. Conformational changes in proteins are accompanied by an increase in the availability and activity of the nucleophilic centers that are potential targets for reactive oxygen species. Complete unfolding and denaturation of the amino acid chain of the protein under the influence of low-frequency electromagnetic field exposure do not occur. It has been shown that enhanced hydrogen peroxide formation at 3 Hz and 50 Hz leads to oxidative modification of nitrogenous bases in DNA.

Does Coherence Affect the Multielectron Oxygen Reduction Reaction?

The oxygen reduction reaction (ORR) is the key for oxygen-based respiration and the operation of fuel cells. It involves the transmission of two pairs of electrons. We probed what type of interaction between the electrons is required to enable their efficient transfer into the oxygen. We show experimentally that the transfer of the electrons is controlled by the "hidden property" and present a theoretical model suggesting that it is related to coherent phase relations between the two electrons. Using spin polarization electrochemical measurements, with electrodes coated with different thicknesses of chiral coating, we confirm the special relation between the electrons. This relation is destroyed by multiple scattering events that result in the formation of hydrogen peroxide, which indicates a reduction in the ORR efficiency. Another indication for the possible role of coherence is the fluctuations in the reaction efficiency as a function of thickness of the chiral coated electrode.

Proton exchange membranes for polymer electrolyte fuel cells: An analysis of perfluorosulfonic acid and aromatic hydrocarbon ionomers

The design of proton-exchange membranes (PEMs) for high-performance, durable fuel cells and related electrochemical devices requires a delicate balance between high ion-exchange capacity and proton conductivity, while ensuring robust mechanical properties and preserving dimensional, chemical and thermal stability. In addition, low species crossover is desirable to reduce hydrogen peroxide formation. Ionomers used in PEMs can be classified into two main groups: (i) perfluorosulfonic acid (PFSA) polymers, and (ii) aromatic hydrocarbon (HC) polymers. In this work, an analysis of key characteristics of both PEM types is presented, including water uptake, proton conductivity, water transport properties, thermal conductivity, permeability, mechanical properties and chemical and thermal stability, among others. Comparatively, PFSA-based PEMs are undoubtedly the commercial standard due to its proven high proton conductivity and good chemical stability, even though PTFE-reinforced aromatic HC-based PEMs have also started to be commercialized recently. In the last decades, a growing trend is identified toward the development of hybrid and composite ultra-thin PEMs (5–20 μm in thickness) with tailored properties, e.g., incorporating microporous fillers to enhance water uptake and layered reinforced microstructures to improve mechanical properties and chemical stability. PEM design is to be accomplished in an environmentally friendly circular economy with facilitated recycling and re-utilization.

A Detailed Insight into the Effects of Morphologies of Cerium Oxide on Fenton-like Reactions for Different Applications.

As an exceptional Fenton-like reagent, cerium oxide (CeO2 ) finds applications in biomedical science and organic pollutants treatment. The Fenton-like reaction catalyzed by CeO2 typically encompasses two distinct processes: one resembling the classical Fenton reaction, wherein cerium (Ce3+ ) triggers the decomposition of hydrogen peroxide (H2 O2 ) to yield reactive oxygen species (ROS), and the other involves the complexation of H2 O2 on the Ce3+ surface, leading to the formation of peroxides. However, the influence of diverse CeO2 morphologies on these two reaction pathways has not been comprehensively explored. In this study, CeO2 exhibiting three typical morphologies, rods, cubes, and spheres, were prepared. The generation of ROS and peroxides was evaluated using the 3,3,5,5-tetramethylbenzidine (TMB) oxidation reaction and the reduction current of H2 O2 , respectively. Moreover, the impacts of pH variations and CeO2 /H2 O2 concentrations on the production and conversion of these two reaction products were investigated. To corroborate the distinctions between the resultant products and their applicability, apoptosis assays and acid orange 7 (AO7) degradation analyses were performed. Notably, CeO2 rods exhibited the highest proportion of Ce3+ , predominantly engaging in complexation with H2 O2 to foster peroxide formation, thereby facilitating the robust degradation of AO7. However, the generated peroxides appeared to occupy Ce3+ sites, thereby impeding the H2 O2 decomposition process. Conversely, Ce3+ species on the surface of CeO2 cubes were primarily involved in H2 O2 decomposition, leading to heightened ROS production, and thus showcasing substantial potential for damaging A549 tumor cells. It is worth noting that the ability of these Ce3+ species to form peroxides through complexation with H2 O2 was comparatively reduced. In summation, this study sheds light on the intricate interplay between distinct CeO2 morphologies and their divergent impacts on Fenton-like reactions. These findings expand our comprehension of the influences on its reactivity of CeO2 morphologies and open new insights for applications in diverse domains, from organic dye degradation to tumor therapy.

Dipole field in nitrogen-enriched carbon nitride with external forces to boost the artificial photosynthesis of hydrogen peroxide

Artificial photosynthesis is a promising strategy for efficient hydrogen peroxide production, but the poor directional charge transfer from bulk to active sites restricts the overall photocatalytic efficiency. To address this, a new process of dipole field-driven spontaneous polarization in nitrogen-rich triazole-based carbon nitride (C3N5) to harness photogenerated charge kinetics for hydrogen peroxide production is constructed. Here, C3N5 achieves a hydrogen peroxide photosynthesis rate of 3809.5 µmol g−1 h−1 and a 2e− transfer selectivity of 92% under simulated sunlight and ultrasonic forces. This high performance is attributed to the introduction of rich nitrogen active sites of the triazole ring in C3N5, which brings a dipole field. This dipole field induces a spontaneous polarization field to accelerate a rapid directional electron transfer process to nitrogen active sites and therefore induces Pauling-type adsorption of oxygen through an indirect 2e− transfer pathway to form hydrogen peroxide. This innovative concept using a dipole field to harness the migration and transport of photogenerated carriers provides a new route to improve photosynthesis efficiency via structural engineering.

Assessing stability and performance of fluorine-doped tin oxide electrodes for peroxide formation in carbonate-based electrolytes

Hydrogen peroxide (H2O2) is a valuable chemical currently produced industrially on a large scale by the anthraquinone process. Recently, carbonate and/or bicarbonate-induced selective water oxidation to hydrogen peroxide has been suggested as an environmentally friendly alternative. In this manuscript, we discuss the effect of electrolyte concentration and type of cation in selective water oxidation using carbonate-based electrolytes (i.e., Na2CO3, K2CO3 and Cs2CO3) on fluorine-doped tin oxide (FTO) electrodes. Based on the experimental observations and a techno-economic evaluation we reveal that K2CO3 is preferred over Na2CO3 and Cs2CO3 electrolytes. Using 5 M K2CO3 a Faradaic efficiency of > 60 % was achieved at industrially relevant current densities of 100 mA cm−2. Although for 5 M Cs2CO3 electrolytes lower potentials are required at otherwise similar process conditions, a lower efficiency for hydrogen peroxide formation has been observed which is assigned to higher degradation in Cs-containing electrolyte, rendering the use of potassium-based electrolytes more efficient. Independent of the electrolyte used, the electrodes suffered from stability issues as revealed by increasing concentrations of tin in the electrolyte and electrode failure after polarization for several hours. Overall, this work provides detailed knowledge about the impact of electrolyte concentration and type of cation and reveals the importance of appropriate cell design and process operation for meaningful hydrogen peroxide synthesis by mediated-anodic water oxidation.

The Importance of Precise Reaction Condition Control for the Comparison of Photocatalyst Materials on the Example of Hydrogen Peroxide Formation over Polymeric Carbon Nitrides

AbstractIn our study, we aimed to show how different reaction parameters can affect production rates using photocatalytic hydrogen peroxide formation by different polymeric carbon nitrides (PCN). For this purpose, selected materials were first compared under the same reaction conditions and compared with TiO2 (P25). We also show that different light intensities can have a different influence on seemingly similar materials. Since hydrogen peroxide production in the presence of an electron donor proceeds mainly by reduction of oxygen, we also show an influence of the oxygen flow on the formation rates. Thus, with high oxygen fluxes and high intensities of irradiated light, we were able to achieve an H2O2 concentration of 125 mM after about 25 h. Finally, the two best PCN materials were selected to measure light intensity dependence at different wavelengths up to visible light. It was found that they behaved differently at the different wavelengths and thus it could be shown that an exact specification of the reaction parameters is indispensable for comparisons in the literature.

Iodixanol supplementation in freezing extender improves the antioxidant capacity of semen.

The aim of this study was to evaluate the effect of supplementing bovine semen freezing extender with different concentrations of iodixanol on post-thaw sperm characteristics. Six ejaculates of three Nellore bulls were pooled and diluted in commercial extender (BotuBov®) and then divided into 4 groups: control group (without adding iodixanol); groups G1.5, G3, or G6 according to the concentration of iodixanol solution (RedCushion®). After dilution, the samples were cooled and frozen. Post-thaw semen evaluation included sperm motility by CASA immediately after thawing and after 60 min of incubation at 37°C, flow cytometry analysis for integrity of plasma and acrosomal membranes, membrane destabilization and translocation of phosphatidylserine, mitochondrial membrane potential, and formation of intracellular anion superoxide ( ), hydrogen peroxide (H2 O2 ), and membrane lipid peroxidation. The group G6 presented significantly higher (p < .05) total and progressive motility, percentage of plasma and acrosomal membrane integrity, and H2 O2 than control and group G1.5. Furthermore, group G6 showed lower (p < .05) lipid peroxidation than control. In addition, regardless of the concentration used, the percentage of spermatozoa without phosphatidylserine translocation was higher (p < .05) in all iodixanol supplemented groups. In conclusion, iodixanol supplementation preserved the motility and integrity of sperm membranes during cryopreservation and protected against lipid peroxidation.

Peroxide Formation for Voltage Hysteresis in O2-Type Lithium-Rich Layered Oxides

Development of energy storage systems with high energy density is of vital importance for realizing a sustainable society. Although lithium-ion batteries (LIBs) are the state-of-the-art energy storage technology, their energy density is limited in part by the specific capacity of the positive electrode (cathode) materials. For example, conventional cathode materials, i.e., layered transition-metal oxides LiMO2 (M = transition metal), deliver a modest capacity of approximately 160 mAh/g, where the dominant mechanism of charge compensation for lithium-ion (de)intercalation is the valence change of the transition metal. Further increase in the cathode capacity requires an additional redox center.Integrating an anionic-redox (or oxygen-redox) capacity with the conventional cationic-redox capacity is a promising strategy for large-capacity battery cathodes exceeding present technical limits. However, most oxygen-redox cathodes exhibit a large charge/discharge voltage hysteresis (> 0.5 V), resulting in poor energy efficiency and impractical implementation. Considering immediate electron transfer (O2– → O– + e –) against subsequent structural deformation (O–O dimerization), the overall hypothetical mechanism of the oxygen-redox reactions is described as a square scheme (Figure 1) 1: if an oxidized oxide ion (O–) is stable, it directly contributes to a non-polarizing discharge capacity (nonpolarizing O redox).2 Meanwhile, unstable O– dimerize to form stable peroxo-like O2 2–, which may be accelerated by cation migration. The O2 2– dimers provide a polarizing discharge capacity (polarizing O redox) and an unstable reduced dimer (e.g., O2 4–) decomposes to O2–. The O–O dimerization is prone to result in release of O2 gas (O2 evolution) by their excessive oxidation. However, experimental verification of the square scheme is limited in part due to complicated structural changes during the oxygen-redox reactions. For example, O3-type Li1.2Ni0.2Mn0.6O2 (O3: lithium ions occupy octahedral sites between the MO2 layers, and the packing arrangement of the oxide ions is ABCABC) exhibits irreversible structural degradation such as layered-to-spinel transformation and surface cation densification upon cycling.In this work, we focus on O2-type lithium-rich layered transition-metal oxides that possess structural integrity against the oxygen-redox reactions (O2: lithium ions occupy octahedral sites between the MO2 layers and the packing arrangement of the oxide ions is ABCBA). O2-type Li1.12–y Ni0.17Mn0.71O2 delivers a large reversible capacity greater than 200 mAh/g with minimal voltage decay and capacity fading upon cycling. Combination of X-ray absorption/emission spectroscopy, magnetic susceptibility measurements, and density functional theory calculations indicates bond-forming 2O– → O2 2– and bond-cleaving O2 4– → 2O2– processes. These results emphasize the importance of suppressing the formation of O2 2– and maximizing the contribution of the nonpolarizing O2–/O– redox couple to develop energy-efficient oxygen-redox battery electrodes. Furthermore, based on the electrochemical kinetic analysis, particularly for the 2O2– → O2 2– transformation, technical strategies to quantify non-polarizing and energy-efficient oxygen redox will be discussed.References M. Okubo, et al., Acc. Mater. Res. 2021, 3, 33–41.A. Tsuchimoto, et al., Nat. Commun. 2020, 12, 63.K. Kawai, et al., Energy Environ. Sci. 2022, 15, 2591–2600. Figure 1

Simplification of the combustion mechanism of Jatropha biodiesel surrogate fuel and reaction path analysis

The objectives of this study were to explore the evolution process of the chemical reaction pathways in the combustion of a biodiesel surrogate fuel and to reduce the calculation burden in the numerical simulation of this combustion process due to the complicated mechanism. A mixture of methyl decanoate, methyl 9-decanoate, and n-heptane was selected as the Jatropha biodiesel surrogate fuel. A simplified combustion mechanism of the biodiesel comprising 170 components and 737 reaction components was formed by systematically simplifying 3299 components and 10806 reaction mechanisms using a multistep directed relation graph method, path flux analysis, and sensitivity analysis. The simplified mechanism was compared with the detailed mechanism and experimental data to effectively verify the accuracy of the mechanism. The simplified mechanism could reproduce the detailed mechanism, and the results were in good agreement with the experimental data in terms of the ignition time of a methyl decanoate/air mixture in a shock tube, the concentrations of the components generated in the combustion process of the biodiesel in a jet stirred reactor, and the flame propagation speed of methyl decanoate and n-heptane/air mixture. The rate of production analysis method was used to explore the main reaction pathways and the evolution process of important intermediate components in the Jatropha biodiesel surrogate fuel generated at high and low temperatures. Methyl decanoate and methyl 9-decanoate formed hydrogen peroxide ketone and oxy groups mainly through dehydrogenation, oxygenation, and isomerization at low temperatures. The high-temperature stage mainly involved bond-breaking decomposition reactions, partial dehydrogenation, and isomerization reactions of low-temperature reaction products, resulting in the formation of small molecular products.

Size and Electronic Effects on the Performance of (Corrolato)cobalt-Modified Electrodes for Oxygen Reduction Reaction Catalysis.

Considering the worldwide efforts for designing catalysts that are not based on platinum group metals while still reserving the many advantages thereof, this study focused on the many variables that dictate the performance of cathodes used for fuel cells, regarding the efficient and selective reduction of oxygen to water. This was done by investigating two kinds of porous carbon electrodes, modified by molecular cobalt(III) complexes chelated by corroles that differ very much in size and electron-withdrawing capability. Examination of the electronic effect uncovered shifts in the CoII/CoIII redox potentials and also large differences in the affinity of the cobalt center to external ligands. Spontaneous absorption of the catalysts was found to depend on the size of the corrole's substituents (C6F5 ≫ CF3 ≫ H) and the metal's axial ligands (PPh3 versus pyridine), as well as on the porosity of the carbon electrodes (BP2000 > Vulcan). The better-performing cobalt-based catalysts were almost as active and selective as 20% platinum on Vulcan in terms of the onset potential and the only 2-10% undesirable formation of hydrogen peroxide. Durability was also addressed by using the best-performing modified cathode in a proper anion-exchange membrane fuel cell setup, revealing very little voltage change during 12 h of operation.

Novel NADPH Oxidase-2 Inhibitors as Potential Anti-Inflammatory and Neuroprotective Agents.

A family of seven NADPH oxidase enzymes (Nox1-5, Duox1-2) has been implicated in a variety of diseases, including inflammatory lung diseases, neurodegenerative diseases, cardiovascular diseases, and cancer. Here, we report the results of our studies aimed at developing novel brain-permeable Nox2 inhibitors with potential application as neuroprotective agents. Using cell-based assays, we identified a novel Nox2 inhibitor, TG15-132, that prevents PMA-stimulated oxygen consumption and reactive oxygen species (superoxide radical anion and hydrogen peroxide) formation upon acute treatment in differentiated HL60 cells. Long-term treatment with TG15-132 attenuates the induction of genes encoding Nox2 subunits, several inflammatory cytokines, and iNOS in differentiated THP-1 cells. Moreover, TG15-132 shows a relatively long plasma half-life (5.6 h) and excellent brain permeability, with a brain-to-plasma ratio (>5-fold) in rodent models. Additionally, TG15-132 does not cause any toxic effects on vital organs or blood biomarkers of toxicity in mice upon chronic dosing for seven days. We propose that TG15-132 may be used as a Nox2 inhibitor and a potential neuroprotective agent, with possible further structural modifications to increase its potency.

Antioxidant nanoemulsion loaded with latanoprost enables highly effective glaucoma treatment

Glaucoma is the third leading cause of blindness worldwide and is primarily characterized by elevated intraocular pressure (IOP). Common risk factors such as age, myopia, ocular trauma, and hypertension all increase the risk of elevated IOP. Prolonged high IOP not only causes physiological discomfort like headaches, but also directly damages retinal cells and leads to retinal ischemia, oxidative imbalance, and accumulation of reactive oxygen species (ROS) in the retina. This oxidative stress causes the oxidation of proteins and unsaturated lipids, leading to peroxide formation and exacerbating retinal damage. While current clinical treatments primarily target reducing IOP through medication or surgery, there are currently no effective methods to mitigate the retinal cell damage associated with glaucoma. To address this gap, we developed a novel nanoemulsion to co-delivery latanoprost and α-tocopherol (referred to as LA@VNE later) that prolongs ocular retention and enhances retinal permeability through localized administration. By encapsulating latanoprost, an IOP-lowering drug, and α-tocopherol, a potent antioxidant, we effectively reduced ROS accumulation (>1.5-fold in vitro and 2.5-fold in vivo), retinal ganglion cell (RGC) apoptosis (>9 fold), and inflammatory cell infiltration (>1.6 fold). Our approach showed strong biocompatibility and significant potential for clinical translation, providing a promising platform for the treatment of glaucoma.