Oxidation Products Research Articles

Efficiently activate peracetic acid by FeS2-anchored molybdenum species for the rapid degradation of sulfamethazine

Peracetic acid (PAA) based advanced oxidation processes are increasingly used as alternative strategies for sulfonamide antibiotics (SAs) degradation. In this study, molybdenum (Mo) species were successfully anchored on the FeS2 surface. This catalyst (Mo-FeS2) could be used as an excellent PAA activator for the removal of sulfamethazine (SMT). Electrochemical measurements revealed that anchored Mo species lowered the electron transfer resistance on the FeS2 surface, and density functional theory (DFT) calculation suggested more electrons can be shifted from FeS2 to Mo, which is prone to transfer electrons for PAA activation. After 30 min reaction, 87.6 % of SMT could be removed by Mo-FeS2/PAA at pH 4, and reactive species (RSs) including HO•, CH3COO• and Fe(IV) were responsible for the SMT degradation. Increasing the dosages of PAA (0.02 – 0.5 mM) or Mo-FeS2 (0.1 – 0.4 g/L) facilitated the SMT degradation. DFT calculation results suggest that the aniline ring of SMT is vulnerable to attack induced by RSs. The degradation pathways of SMT, including Smiles rearrangements, hydroxylation of aniline ring, oxidation of the –NH2 group and coupling reaction, were proposed according to the identified oxidation products. Sulfamethoxazole, sulfadiazine, sulfanilamide and sulfathiazole could also be degraded by Mo-FeS2/PAA (>50 %), suggesting that the Mo-FeS2/PAA would be a competitive strategy for the remediation of SAs-contaminated water.

Relationship between wooden breast severity in broiler chicken, antioxidant enzyme activity and markers of energy metabolism

This study aims to provide new insight on the association between the development of wooden breast myopathy and mitochondrial and glycolytic activity under oxidative stress. Myopathic muscle had higher oxidative stress together with altered glycolytic metabolism and tricarboxylic acid (TCA) cycle. This was evidenced by significantly elevated antioxidant enzyme activities (catalase, superoxide dismutase, and glutathione peroxidase), decreased citrate synthase activity and postmortem glycolytic potential with increasing wooden breast severity. In addition, affected muscles also exhibited higher initial and ultimate pH values as well as reduced total glucose and lactate contents. Citrate synthase activity was negatively correlated to antioxidant enzyme activities. Taken together, we propose that the development of the wooden breast lesion is a chronic process that may be related to the failure of muscle fibers to defend against the excessively generated oxidative products promoted by mitochondrial damage accompanied by impaired TCA cycle. Furthermore, there was a positive correlation between citrate synthase activity and glycolytic potential, which suggests that the wooden breast condition is linked to the overall altered energy metabolism of the muscle, including the oxidative phosphorylation and glycolytic pathways.

Effect of deodorization conditions on fatty acid profile, oxidation products, and lipid-derived free radicals of soybean oil

Oxidative stability is a key quality characteristic of edible oils, and the oil’s antioxidant capacity decreases during the deodorization stage. This study explores the changes in radical formation, molecular structure, oxidative characteristics, fatty acids, and main bioactive compounds in soybean oil during deodorization. The lag phase decreased, whereas the total amount of spins of free radicals increased as the deodorization time increased from 90 to 150 min. The total amount of spins and percentage of alkyl radicals varied dramatically under different times and temperatures (220 ∼ 260 ℃). Results showed that identifying and quantifying the formed radicals can provide useful information for monitoring and controlling oil oxidation in vegetable oil refining systems. Therefore, to control early oxidation events, maximize refined oil product yield, and reduce energy consumption in the refining plant, the priority should be to minimize temperature during the oil refining process and then shorten the deodorization time.

Optimization of Desulfurization Process via Choline Phosphotungstate Coupled with Persulfate Using Response Surface Methodology

Using a simple acid-base neutralization method, a Ch-PW solid catalyst was synthesized by mixing choline hydroxide (ChOH) and phosphotungstic acid (HPW) at a 2:1 molar ratio in an aqueous solution. This catalyst was combined with a 20 wt.% potassium peroxymonosulfate (PMS) solution, using acetonitrile (ACN) as the extraction solvent to create an extraction catalytic oxidative desulfurization system. The optimal desulfurization conditions were determined through response surface methodology, targeting the highest desulfurization rate: 0.99 g of Ch-PW, 1.07 g of PMS, 2.5 g of extraction solvent, at a temperature of 50.48 °C. The predicted desulfurization rate was 90.79%, compared to an experimental rate of 93.64%, with a deviation of 3.04%. A quadratic model correlating the desulfurization rate with the four conditions was developed and validated using ANOVA, which also quantified the impact of each factor on the desulfurization rate: PMS > ACN > Ch-PW > temperature. GC-MS analysis identified the main oxidation product as DBTO2, and the mechanism of desulfurization in this system was further explored.

Optimized Ultraviolet-C Processing Inactivates Pathogenic and Spoilage-Associated Bacteria while Preserving Bioactive Proteins, Vitamins, and Lipids in Human Milk.

Holder pasteurization (HoP) enhances donor human milk microbiological safety but damages many bioactive milk proteins. Though ultraviolet-C irradiation (UV-C) can enhance safety while better preserving some milk proteins, it has not been optimized for dose or effect on a larger array of bioactive proteins. We determined the minimal UV-C parameters that provide >5-log reductions of relevant bacteria in human milk and how these treatments affect an array of bioactive proteins, vitamin E, and lipid oxidation. Treatment at 6000 and 12 000 J/L of UV-C resulted in >5-log reductions of all vegetative bacteria and bacterial spores, respectively. Both dosages improved retention of immunoglobulin A (IgA), IgG, IgM, lactoferrin, cathepsin D, and elastase and activities of bile-salt-stimulated lipase and lysozyme compared with HoP. These UV-C doses caused minor reductions in α-tocopherol but not γ-tocopherol and no increases in lipid oxidation products. UV-C treatment is a promising approach for donor human milk processing.

Modeling the influence of carbon branching structure on secondary organic aerosol formation via multiphase reactions of alkanes

Abstract. Branched alkanes represent a significant proportion of hydrocarbons emitted in urban environments. To accurately predict the secondary organic aerosol (SOA) budgets in urban environments, these branched alkanes should be considered as SOA precursors. However, the potential to form SOA from diverse branched alkanes under varying environmental conditions is currently not well understood. In this study, the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model is extended to predict SOA formation via the multiphase reactions of various branched alkanes. Simulations with the UNIPAR model, which processes multiphase partitioning and aerosol-phase reactions to form SOA, require a product distribution predicted from an explicit gas kinetic mechanism, whose oxygenated products are applied to create a volatility- and reactivity-based αi species array. Due to a lack of practically applicable explicit gas mechanisms, the prediction of the product distributions of various branched alkanes was approached with an innovative method that considers carbon lengths and branching structures. The αi array of each branched alkane was primarily constructed using an existing αi array of the linear alkane with the nearest vapor pressure. Generally, the vapor pressures of branched alkanes and their oxidation products are lower than those of linear alkanes with the same carbon number. In addition, increasing the number of alkyl branches can also decrease the ability of alkanes to undergo autoxidation reactions that tend to form low-volatility products and significantly contribute to alkane SOA formation. To account for this, an autoxidation reduction factor, as a function of the degree and position of branching, was applied to the lumped groups that contain autoxidation products. The resulting product distributions were then applied to the UNIPAR model for predicting branched-alkane SOA formation. The simulated SOA mass was compared to SOA data generated under varying experimental conditions (i.e., NOx levels, seed conditions, and humidity) in an outdoor photochemical smog chamber. Branched-alkane SOA yields were significantly impacted by NOx levels but insignificantly impacted by seed conditions or humidity. The SOA formation from branched and linear alkanes in diesel fuel was simulated to understand the relative importance of branched and linear alkanes with a wide range of carbon numbers. Overall, branched alkanes accounted for a higher proportion of SOA mass than linear alkanes due to their higher contribution to diesel fuel.

Molecular composition of clouds: a comparison between samples collected at tropical (Réunion Island, France) and mid-north (Puy de Dôme, France) latitudes

Abstract. The composition of dissolved organic matter of cloud water has been investigated through non-targeted high-resolution mass spectrometry on only a few samples that were mostly collected in the Northern Hemisphere in the USA, Europe and China. There remains, therefore, a lack of measurements for clouds located in the Southern Hemisphere, under tropical conditions and influenced by forest emissions. As a matter of fact, the comparison of the composition of clouds collected in different locations is challenging since the methodology for the analysis and data treatment is not standardized. In this work, the chemical composition of three samples collected at Réunion Island (REU) during the BIO-MAÏDO field campaign, in the Indian Ocean, with influences from marine, anthropogenic and biogenic (tropical) emissions, is investigated and compared to the chemical composition of samples collected at the Puy de Dôme (PUY) observatory in France. The same methodology of analysis and data treatment was employed, producing a unique dataset for the investigation of the molecular composition of organic matter in cloud water. Besides the analysis of elemental composition, we investigated the carbon oxidation state (OSC) of dissolved organic matter, finding that overall samples collected at PUY are more oxidized than those collected at REU. Molecular formulas were also classified based on stoichiometric elemental ratios, showing the high frequency and abundance of reduced organic compounds, classified as lipids (LipidC), in this matrix, which led to a search for terpene oxidation products in cloud water samples. To better discriminate between samples collected at PUY and REU, statistical analysis (principal component analysis and agglomerative hierarchical clustering) was performed on the ensemble of molecular formulas and their intensities. Samples collected at REU have a different composition from samples collected at PUY, which is mainly linked to different primary sources, the processing of organic matter in cloud water and the influence of different primary emissions at the two locations.

Secondary Lipid Oxidation Products as Modulators of Calpain-2 Functionality In Vitro.

The objective was to understand the impacts of secondary lipid oxidation products on calpain-2 activity and autolysis and, subsequently, to determine the quantity and localization of modification sites. 2-Hexenal and 4-hydroxynonenal incubation significantly decreased calpain-2 activity and slowed the progression of autolysis, while malondialdehyde had minimal impact on calpain-2 activity and autolysis. Specific modification sites were determined with LC-MS/MS, including distinct malondialdehyde modification sites on the calpain-2 catalytic and regulatory subunits. 2-Hexenal modification sites were observed on the calpain-2 catalytic subunit. Intact protein mass analysis with MALDI-MS revealed that a significant number of modifications on the calpain-2 catalytic and regulatory subunits are likely to exist. These observations confirm that specific lipid oxidation products modify calpain-2 and may affect the calpain-2 functionality. The results of these novel experiments have implications for healthy tissue metabolism, skeletal muscle growth, and post-mortem meat tenderness development.

Fostering a Holistic Understanding of the Full Volatility Spectrum of Organic Compounds from Benzene Series Precursors through Mechanistic Modeling.

A comprehensive understanding of the full volatility spectrum of organic oxidation products from the benzene series precursors is important to quantify the air quality and climate effects of secondary organic aerosol (SOA) and new particle formation (NPF). However, current models fail to capture the full volatility spectrum due to the absence of important reaction pathways. Here, we develop a novel unified model framework, the integrated two-dimensional volatility basis set (I2D-VBS), to simulate the full volatility spectrum of products from benzene series precursors by simultaneously representing first-generational oxidation, multigenerational aging, autoxidation, dimerization, nitrate formation, etc. The model successfully reproduces the volatility and O/C distributions of oxygenated organic molecules (OOMs) as well as the concentrations and the O/C of SOA over wide-ranging experimental conditions. In typical urban environments, autoxidation and multigenerational oxidation are the two main pathways for the formation of OOMs and SOA with similar contributions, but autoxidation contributes more to low-volatility products. NOx can reduce about two-thirds of OOMs and SOA, and most of the extremely low-volatility products compared to clean conditions, by suppressing dimerization and autoxidation. The I2D-VBS facilitates a holistic understanding of full volatility product formation, which helps fill the large gap in the predictions of organic NPF, particle growth, and SOA formation.

TS-1 zeolite encapsulated Pt clusters with enhanced electronic metal-support interaction of Pt−O(H)−Ti for nearly-zero-carbon-emitting photocatalytic hydrogen production from methanol

Photocatalytic H2 production from methanol is sustainable, yet challenges remain in avoiding carbon-containing gaseous by-products. Titanium silicalite-1 (TS-1) zeolite possesses attractive photocatalytic performance, but lack of modification strategies due to its microporous framework. Herein, we developed a pre-anchoring strategy to confine ultra-small Pt clusters inside TS-1 with ultra-low loading (0.2 mol%), in which Pt were anchored in Ti−OH nests by electronic metal-support interaction (EMSI). The optimal catalyst achieved a remarkable H2 generation rate of 63.2 mmol g–1 h–1 in CH3OH solutions, along with the production of high-value chemical HCHO as the oxidation product with 96.9% selectivity. Investigations reveal that the EMSI between Pt and Ti facilitated the selective decomposition of CH3OH to H2 and HCHO, leading to a nearly zero-carbon-emission process. Accordingly, we propose a light-driven carbon-negative "CO2→CH3OH→H2" route, coupling CO2 utilization and green H2 production with CH3OH as the intermediate, therefore offering a new perspective for "liquid sunshine".

Bacterial cysteate dissimilatory pathway involves a racemase and d-cysteate sulfo-lyase

The sulfite-reducing bacterium Bilophila wadsworthia, a common human intestinal pathobiont, is unique in its ability to metabolize a wide variety of sulfonates to generate sulfite as a terminal electron acceptor (TEA). The resulting formation of H2S is implicated in inflammation and colon cancer. l-cysteate, an oxidation product of l-cysteine, is among the sulfonates metabolized by B. wadsworthia, although the enzymes involved remain unknown. Here we report a pathway for l-cysteate dissimilation in B. wadsworthia RZATAU, involving isomerization of l-cysteate to d-cysteate by a cysteate racemase (BwCuyB), followed by cleavage into pyruvate, ammonia and sulfite by a d-cysteate sulfo-lyase (BwCuyA). The strong selectivity of BwCuyA for d-cysteate over l-cysteate was rationalized by protein structural modeling. A homolog of BwCuyA in the marine bacterium Silicibacter pomeroyi (SpCuyA) was previously reported to be a l-cysteate sulfo-lyase, but our experiments confirm that SpCuyA too displays a strong selectivity for d-cysteate. Growth of B. wadsworthia with cysteate as the electron acceptor is accompanied by production of H2S and induction of BwCuyA. Close homologs of BwCuyA and BwCuyB are present in diverse bacteria, including many sulfate- and sulfite-reducing bacteria, suggesting their involvement in cysteate degradation in different biological environments.

THE RELATIONSHIP BETWEEN OXIDATIVE STRESS AND NEUROLOGICAL DISORDERS: MINI REVIEW

Oxidative stress is one of the main causes of neuronal dysfunction and death, mainly due to excessive formation of reactive oxygen species and depletion of antioxidant reserves. Oxidative stress is characterized by an imbalance between the production of reactive oxygen species (ROS) and antioxidant defense mechanisms of the body. This process is involved in the onset and development of many neurological diseases. In this review, we analyzed and summarized the results of studies showing the association of neurological diseases, such as stroke, Parkinson’s disease, and other neurological diseases, with excessive formation of oxidative stress products. This article aims to provide an overview of the relationship between oxidative stress and a range of neurological conditions, shedding light on the underlying mechanisms and potential therapeutic implications.

A sensitive Ag+-mediated magnetic relaxation and colorimetry dual-mode sensing platform

To address the relatively low sensitivity of current redox reagent-mediated magnetic relaxation sensing methods, we present a novel Ag+-mediated magnetic sensing platform that enhances the sensitivity by three orders of magnitude. The new sensing platform is based on Ag+-catalyzed oxidation of Mn2+ to KMnO4, accompanied by a distinct color change, which facilitates colorimetric detection. In the case of insufficient Ag+ ions, MnO2 is an additional oxidation product and the KMnO4/MnO2 ratio is dependent on the concentration of Ag+. When combined with a specific quantity of reducing agent, both KMnO4 and MnO2 are reduced to Mn2+ with a large relaxivity, and the concentration of Mn2+ in the resultant solution inversely correlates with the amount of KMnO4 since KMnO4 consumes more reductant during reduction. Consequently, the transverse relaxation rate of the solution exhibits a negative correlation with the Ag+ concentration. Thus, by coupling this Ag+-mediated Mn2+ to KMnO4 transformation with reactions that modulate Ag+ concentration, a dual-mode sensing platform for magnetic relaxation and colorimetry can be realized. Herein, we take H2O2 as an example to verify the detection performance of this sensing platform since H2O2 can oxidize Ag0 in Ag@Fe3O4 nanoparticles to Ag+. Experimental findings demonstrate detection limits of 10 nM and 20 nM for the magnetic relaxation and colorimetry modes, respectively, affirming the excellent sensitivity and the potential practical application of this strategy.

Physical and oxidative stability of flaxseed oil-in-water emulsions prepared by natural lignin-carbohydrate complex

Flaxseed oil, rich in α-linolenic acid, plays a crucial role in various physiological processes. However, its stability presents certain challenges. In this study, the natural lignin-carbohydrate complex (LCC) was used to prepare the physical and oxidative stability of flaxseed oil-in-water emulsions. The LCC was characterized by HPLC, GPC, and FT-IR. The stability of emulsions was evaluated by viscosity, modulus, and micro-morphology changes. Then, the oxidation products were monitored by UV–vis spectrophotometer and HPLC. The results revealed that the high internal phase emulsion (HIPE) was successfully prepared with 2.5 wt% LCC at an oil/water ratio of 75/25 (v/v). Small droplet size (13.361 μm) and high viscosity (36,500 mPa·s) were found even after 30-day storage. Steric interactions of the LCC play a crucial role in ensuring stability, intricately linked to the interfacial properties of the emulsion. Meanwhile, the oxidative stability of α-linolenic acid in the encapsulated flaxseed oil was significantly higher than that in the bulk flaxseed oil. The results revealed that the LCC as a suitable emulsifier opens a new window for the storage of functional lipids rich in polyunsaturated fatty acids.

Effect of Propolis on Salivary Glands After Radiotherapy.

To investigate the effects of increasing propolis doses on salivary glands exposed to radiotherapy (RT). Thirty-seven rats were divided into 4 groups: The control group (G0, n: 7), G1 group (n: 10), G2 group (n: 10), and G3 group (n: 10). The rats in the G1 group received 15 Gray (Gy) RT only to the head and neck area. The rats in the G2 and G3 groups received 15 Gy RT for the head and neck area along with 100mg/kg/ml and 200mg/kg/ml of propolis. The parotid, submandibular, and sublingual glands of rats were immunohistochemically stained with aquaporin-1 (AQP-1) and aquaporin-5 (AQP-5). They were also evaluated for malondialdehyde (MDA), superoxide dismutase (SOD), glutathione peroxidase (GPO), total antioxidant (TAS), and total oxidant status (TOS). AQP-1 and AQP-5 values were highest in G0 group followed by G3, G2, and G1 groups in decreasing order. The MDA and TOS values were highest in G1 group, which was followed by G2, G3, and G0 groups. The highest GPO, SOD, and TAS values were observed in G0 group followed by G3, G2, and G1 groups in decreasing order. It was found that propolis increased antioxidant products and decreased oxidative products in the salivary glands receiving RT in parallel with the dose increase. Similarly, in the groups receiving propolis, an increase in the immune expression of aquaporin molecules was detected in a dose-dependent manner. Based on these data, it could be stated that propolis has a healing effect on the salivary glands exposed to RT.

Integrated drug delivery system loading ROS-generating antitumor drugs for signal-amplified photoacoustic imaging and multimodal tumor therapy

The usefulness of antitumor drugs that produce reactive oxygen species (ROS) in accurate tumor diagnosis and treatment has been underestimated. Here, β-Lapachone (Lapa, antitumor drugs), 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS, precursor photoacoustic agents) and 2, 2′-azobis[2-(2-imidazolin-2-yl) propane] dihydrochloride (AIPH, free radical initiators) were successfully loaded into zeolitic imidazolate framework (ZIF) in situ by a one-pot method and named Lapa/ABTS/AIPH@ZIF-67 nanoparticles (LBIZ NPs). After entering the tumor cell, the ZIF structure of LBIZ NPs is disrupted in the acidic tumor microenvironment, which results in the release of Co2+ and drugs. In one hand, Lapa and Co2+ together increased hydroxyl radicals (•OH) levels to achieve Enhanced-Chemodynamic therapy (ECDT). As the amount of •OH went up, the amount of ABTS•+, the oxidation product of ABTS, would also increase, thus increasing the sensitivity and contrast of photoacoustic imaging. In the other hand, the photothermal effect produced by ABTS•+ induces AIPH to crack and release alkyl radicals (•R) to achieve thermodynamic therapy. The LBIZ NPs achieved more effective tumor treatments by fully utilizing light and heat energy. Hence, this integrated drug delivery system is able to achieve signal-amplified photoacoustic imaging and Enhanced-Chemodynamic/Photothermal/Thermodynamic trimodal combination therapy. This work provides a new insight into the application of ROS-generating antitumor drugs to precise imaging of tumors.

Difference comparison of characteristic aroma compounds between braised pork cooked by traditional open-fire and induction cooker and the potential formation cause under electromagnetic cooking

The characteristic aroma compounds of braised pork were identified through molecular sensory science and PLSR analysis, and the difference between two cooking methods, traditional open-fire (BPF) and induction cooker (BPC), was compared. Seventeen aroma compounds with odor activity values (OAVs) > 1 were identified in both samples. BPF revealed higher OAVs for most of the aroma compounds compared to BPC, and the higher aroma quality. Aroma recombination and omission experiments confirmed that twelve aroma compounds significantly contributed to the characteristic aroma of braised pork, and eight compounds such as hexanal, (E)-2-octenal, and methanethiol were further confirmed as important contributors by PLSR analysis. Furthermore, PLSR analysis clarified the role of aldehydes such as hexanal, (E)-2-octenal, and (E,E)-2,4-decadienal in contributing to fatty attribute, whereas methanethiol was responsible for the meaty aroma. These characteristic aroma compounds mainly derived from lean meat due to its high content of phospholipids, and the exogenous seasonings contributed to the balanced characteristic aroma profile of braised pork by altering the distribution of these characteristic aroma compounds. Variations in heating parameters affected the formation of lipid oxidation and Strecker degradation products, which might explain aroma discrepancy between braised pork cooked by two methods with different heat transfer efficiencies.

Elucidation of the Role of TRPV1, VEGF-A, TXA2, Redox Homeostasis, and Inflammatory Cascades in Protection against Cold Injuries by Herbosomal-Loaded PEG-Poloxamer Topical Formulation.

High-altitude regions, cold deserts, permafrost regions, and the polar region have some of the severest cold conditions on earth and pose immense perils of cold injuries to exposed individuals. Accidental and unintended exposures to severe cold, either unintentionally or due to occupational risks, can greatly increase the risk of serious conditions including hypothermia, trench foot, and cold injuries like frostbite. Cold-induced vasoconstriction and intracellular/intravascular ice crystal formation lead to hypoxic conditions at the cellular level. The condition is exacerbated in individuals having inadequate and proper covering and layering, particularly when large area of the body are exposed to extremely cold environments. There is a paucity of preventive and therapeutic pharmacological modalities that have been explored for managing and treating cold injuries. Given this, an efficient modality that can potentiate the healing of frostbite was investigated by studying various complex pathophysiological changes that occur during severe cold injuries. In the current research, we report the effectiveness and healing properties of a standardized formulation, i.e., a herbosomal-loaded PEG-poloxamer topical formulation (n-HPTF), on frostbite. The intricate mechanistic pathways modulated by the novel formulation have been elucidated by studying the pathophysiological sequelae that occur following severe cold exposures leading to frostbite. The results indicate that n-HPTF ameliorates the outcome of frostbite, as it activates positive sensory nerves widely distributed in the epidermis transient receptor potential vanilloid 1 (TRPV1), significantly (p < 0.05) upregulates cytokeratin-14, promotes angiogenesis (VEGF-A), prominently represses the expression of thromboxane formation (TXA2), and significantly (p < 0.05) restores levels of enzymatic (glutathione reductase, superoxide dismutase, and catalase) and nonenzymatic antioxidants (glutathione). Additionally, n-HPTF attenuates oxidative stress and the expression of inflammatory proteins PGF-2α, NFκB-p65, TNF-α, IL-6, IL-1β, malondialdehyde (MDA), advanced oxidative protein products (AOPP), and protein carbonylation (PCO). Masson's Trichrome staining showed that n-HPTF stimulates cellular proliferation, and increases collagen fiber deposition, which significantly (p < 0.05) promotes the healing of frostbitten tissue, as compared to control. We conclude that protection against severe cold injuries by n-HPTF is mediated via modulation of pathways involving TRPV1, VEGF-A, TXA2, redox homeostasis, and inflammatory cascades. The study is likely to have widespread implications for the prophylaxis and management of moderate-to-severe frostbite conditions.

Completely Inorganic Deep Eutectic Solvents for Efficient and Recyclable Liquid-Liquid Interface Catalysis.

Organic acid-based deep eutectic solvents (DESs) as catalysts always suffer from weak stability and low recyclability due to the accumulation of organic oxidative products in the DES phase. Herein, a completely inorganic deep eutectic solvent (IDES) ZnCl2/PA with zinc chloride (ZnCl2) and phosphoric acid (PA) as precursors is constructed to realize liquid-liquid interface catalysis for desulfurization of fuel and product self-separation for the first time. Owing to the inorganic nature, the organic oxidative products are accumulated at the interface between the IDES and fuel rather than the IDES phase. With this unique feature, the IDES can be reused for at least 15 times without any further treatment in oxidative desulfurization process, showing a state-of-the-art cycle-regeneration stability. Moreover, compared with the reported organic DESs, the IDES also reveals more attractive catalytic oxidative desulfurization performance. Experimental and theoretical studies indicate that the strong coordination Zn···O═P and the strong adsorption energy between IDES and sulfides enhance the activation of H2O2 to reactive oxygen species, leading to the superior catalytic performance in oxidative desulfurization of fuel.

Adaptogenic correction of free radical processes in liver tissue under the exposure to coal-rock dust on the body (experimental study)

Introduction. Damage to the liver under the conditions of long-term exposure to coal-rock dust on the body leads to significant impairment of its metabolic, detoxification, synthetic, and other functions. In this regard, it is relevant to search for early methods of prevention and correction of developing pathological changes in this organ. The purpose of the study is to experimentally study the effect of a complex drug with dihydroquercetin on the activity of free radical processes in the liver of laboratory rats over the dynamics of long-term exposure to coal-rock dust. Materials and methods. The work was carried out on male white rats weighing 200–250 g. The control group was kept under the standard vivarium conditions. The experimental group included rats that inhaled coal-rock dust in a priming chamber daily for 4 hours for 1, 3, 6, and 9 weeks and rats that received a daily complex drug with dihydroquercetin immediately before dust exposure. In the liver tissue, the activity of free radical oxidation and antioxidant defense enzymes (superoxide dismutase and catalase) was determined. Results. Priming rats with coal-rock dust for three weeks led to the gain in the intensity of free radical processes in the liver tissue: the initial level of accumulation of TBA-active oxidation products reliably raised by almost 2 times over the 1st week and 3 times over the 3rd week of the experiment compared to the control. An increase in the intensity of free radical oxidation was accompanied by activation of antioxidant defense enzymes - catalase - by 2.4 times at the 1st week and 1.6 times at the 3rd week of dust exposure. Raising the period of priming with dust up to 9 weeks led to multidirectional changes in oxidative metabolism in the liver tissue: at week 6, a decrease in the activity of superoxide dismutase was almost 3 times; at week 9, to a slight activation of antioxidant enzymes: superoxide dismutase by 55% and catalase by 36%.The most effective use of a complex drug with dihydroquercetin had been shown in short-term mode for three weeks, but not long-term (more than 6 weeks). The maximum antioxidant defense effect of dihydroquercetin was detected at the 3rd week of dust exposure – the level of free radical products decreased by 2 times and the activity of superoxide dismutase increased by 4 times. Limitations. Since the issue of organ-specific effects and the optimal duration of use of dihydroquercetin to increase resistance to free radical damage has been little elaborated, this imposes certain restrictions on its use for the correction and prevention of occupational diseases. Conclusion. The results obtained should be taken into account with long-term use of exogenous antioxidants in the correction and prevention of occupational diseases to support the level of endogenous antioxidant systems in the cell and the protective effect of dihydroquercetin for tissues most sensitive to the action of free radical processes.