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Environmentally persistent free radicals (EPFRs) play an important role in aerosol effects on air quality and public health, but their atmospheric abundance and sources are poorly understood. We measured EPFRs contained in PM2.5 collected in Fairbanks, Alaska, in winter 2022. We find that EPFR concentrations were enhanced during surface-based inversion and correlate strongly with incomplete combustion markers, including carbon monoxide and elemental carbon (R2 > 0.75). EPFRs exhibit moderately good correlations with PAHs, biomass burning organic aerosols, and potassium (R2 > 0.4). We also observe strong correlations of EPFRs with hydrocarbon-like organic aerosols, Fe and Ti (R2 > 0.6), and single-particle mass spectrometry measurements reveal internal mixing of PAHs, with potassium and iron. These results suggest that residential wood burning and vehicle tailpipes are major sources of EPFRs and nontailpipe emissions, such as brake wear and road dust, may contribute to the stabilization of EPFRs. Exposure to the observed EPFR concentrations (18 ± 12 pmol m-3) would be equivalent to smoking ∼0.4-1 cigarette daily. Very strong correlations (R2 > 0.8) of EPFR with hydroxyl radical formation in surrogate lung fluid indicate that exposure to EPFRs may induce oxidative stress in the human respiratory tract.

GaCH2, a free radical thought to play a role in the chemical vapor deposition of gallium-containing thin films and semiconductors, has been spectroscopically detected for the first time. The radical was produced in a pulsed discharge jet using a precursor mixture of trimethylgallium vapor in high pressure argon and studied by laser-induced fluorescence and wavelength resolved emission techniques. Partially rotationally resolved spectra of the hydrogenated and deuterated species were obtained, and they exhibit the nuclear statistical weight variations and subband structure expected for a 2A2–2B1 electronic transition. The measured spectroscopic quantities have been compared to our own ab initio calculations of the ground and excited state properties. The electronic spectrum of gallium methylene is similar to the corresponding spectrum of the aluminum methylene radical, which we reported in 2022. [ABSTRACT FROM AUTHOR]

C4F7N/CO2 gas mixtures have attracted extensive attention because of their excellent insulating properties and environmental friendliness. High electrical and thermal stability is an important indicator for evaluating their performance, but there have been few molecular dynamics studies of their decomposition mechanisms. In this study, using ReaxFF molecular dynamics simulations and quantum chemistry theory, the decomposition mechanism of a C4F7N/CO2 gas mixture and the effect of the O2 content on the decomposition of the mixture were simulated on the microscopic level. It was found that there are three main decomposition pathways of C4F7N molecules, of which the generation of C3F4N⋅ and CF3⋅ free radicals is the most likely to occur. COF2 is the main oxygen-containing product of the C4F7N/CO2 gas mixture, and its generation is significantly affected by the simulation time and temperature. COF2 can be regarded as the characteristic decomposition product of the C4F7N/CO2 gas mixture. The addition of O2 slightly promotes the decomposition of C4F7N, whereas the maximum decomposition rate of CO2 decreases by 0.3% and 1% after the addition of 2% and 8% O2, respectively. Relevant results of this research can provide a theoretical basis and guidance for research into the performance of C4F7N/CO2 gas mixtures and practical engineering applications of these mixtures in the future. [ABSTRACT FROM AUTHOR]

Electronic (e-) cigarette formulations containing nicotine salts from a range of organic acid conjugates and pH values have dominated the commercial market. The acids in the nicotine salt formulations may alter the redox environment in e-cigarettes, impacting free radical formation in e-cigarette aerosol. Here, the generation of aerosol mass and free radicals from a fourth-generation e-cigarette device was evaluated at 2 wt % nicotine salts (pH 7, 30:70 mixture propylene glycol to vegetable glycerin) across eight organic acids used in e-liquids: benzoic acid (BA), salicylic acid (SLA), lactic acid (LA), levulinic acid (LVA), succinic acid (SA), malic acid (MA), tartaric acid (TA), and citric acid (CA). Furthermore, 2 wt % BA nicotine salts were studied at the following nicotine to acid ratios: 1:2 (pH 4), 1:1 (pH 7), and 2:1 (pH 8), in comparison with freebase nicotine (pH 10). Radical yields were quantified by spin-trapping and electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra of free radicals in the nicotine salt aerosol matched those generated from the Fenton reaction, which are primarily hydroxyl (OH) radicals and other reactive oxygen species (ROS). Although the aerosol mass formation was not significantly different for most of the tested nicotine salts and acid concentrations, notable ROS yields were observed only from BA, CA, and TA under the study conditions. The e-liquids with SLA, LA, LVA, SA, and MA produced less ROS than the 2 wt % freebase nicotine e-liquid, suggesting that organic acids may play dual roles in the production and scavenging of ROS. For BA nicotine salts, it was found that the ROS yield increased with a higher acid concentration (or a lower nicotine to acid ratio). The observation that BA nicotine salts produce the highest ROS yield in aerosol generated from a fourth-generation vape device, which increases with acid concentration, has important implications for ROS-mediated health outcomes that may be relevant to consumers, manufacturers, and regulatory agencies.

Absolute line strengths of several transitions in the ν1 fundamental band of the hydroxyl radical (OH) have been measured by simultaneous determination of hydrogen peroxide (H2O2) and OH upon laser photolysis of H2O2. Based on the well-known quantum yield for the generation of OH radicals in the 248-nm photolysis of H2O2, the line strength of the OH radicals can be accurately derived by adopting the line strength of the well-characterized transitions of H2O2 and analyzing the difference absorbance time traces of H2O2 and OH obtained upon laser photolysis. Employing a synchronized two-color dual-comb spectrometer, we measured high-resolution time-resolved absorption spectra of H2O2 near 7.9 µm and the OH radical near 2.9 µm, simultaneously, under varied conditions. In addition to the studies of the line strengths of the selected H2O2 and OH transitions, the kinetics of the reaction between OH and H2O2 were investigated. A pressure-independent rate coefficient kOH+H2O2 was determined to be [1.97 (+0.10/−0.15)] × 10−12 cm3 molecule−1 s−1 at 296 K and compared with other experimental results. By carefully analyzing both high-resolution spectra and temporal absorbance profiles of H2O2 and OH, the uncertainty of the obtained OH line strengths can be achieved down to <10% in this work. Moreover, the proposed two-color time-resolved dual-comb spectroscopy provides a new approach for directly determining the line strengths of transient free radicals and holds promise for investigations on their self-reaction kinetics as well as radical–radical reactions. [ABSTRACT FROM AUTHOR]

[Display omitted] • An injectable hydrogel to reduce the postoperative abdominal adhesion is designed. • A third-generation polyamide-amine dendrimer loads the Meloxicam for slow release. • The hydrogel has good in vitro and in vivo biosafety and biodegradability. • MX inhibits inflammatory responses and balances the fibrinolytic system. • The adhesion prevention is proved in a rat abdominal adhesion model. Establishing a physical barrier between the peritoneum and the cecum is an effective method to reduce the risk of postoperative abdominal adhesions. Meloxicam (MX), a nonsteroidal anti-inflammatory drug has also been applied to prevent postoperative adhesions. However, its poor water solubility has led to low bioavailability. Herein, we developed an injectable hydrogel as a barrier and drug carrier for simultaneous postoperative adhesion prevention and treatment. A third-generation polyamide-amine dendrimer (G3) was exploited to dynamically combine with MX to increase the solubility and the bioavailability. The formed G3@MX was further used to crosslink with poly-γ-glutamic acid (γ-PGA) to prepare a hydrogel (GP@MX hydrogel) through the amide bonding. In vitro and in vivo experiments evidenced that the hydrogel had good biosafety and biodegradability. More importantly, the prepared hydrogel could control the release of MX, and the released MX is able to inhibit inflammatory responses and balance the fibrinolytic system in the injury tissues in vivo. The tunable rheological and mechanical properties (compressive moduli: from ∼ 57.31 kPa to ∼ 98.68 kPa;) and high anti-oxidant capacity (total free radical scavenging rate of ∼ 94.56 %), in conjunction with their syringeability and biocompatibility, indicate possible opportunities for the development of advanced hydrogels for postoperative tissue adhesions management. [ABSTRACT FROM AUTHOR]

Herein, inspired by the macrophage's defensive behavior of releasing free radicals to kill bacteria and viruses, a marine antifouling coating with dynamic surfaces is prepared by precise regulation of dynamic covalent bonds. Alkyl radical (R·) derived from oxime-urethane structure attracts and disrupts microbe cell membrane and pili between intimate cells, resulting in excellent anti-biofouling effect. Moreover, the newly exposed coating then continues to break, which ultimately results in the peeling of the layers, thus making barnacles, mussels and other fouling organisms less likely to adhere. [Display omitted] • Macrophage-inspired marine antifouling coating with dynamic surfaces is prepared. • Alkyl radical (R·) derived from oxime-urethane structure offers excellent anti-fouling performance. • The newly exposed coating continues to break making it less likely that fouling organisms will adhere to it. • This study presents a novel methodology for fulfilling the technological gap of marine coatings with dynamic surface. Macrophages can kill bacteria and viruses by releasing free radicals, which provides a possible approach to construct antifouling coatings with dynamic surfaces that release free radicals if the breaking of dynamic covalent bonds is precisely regulated. Herein, inspired by the defensive behavior of macrophages of releasing free radicals to kill bacteria and viruses, a marine antifouling coating composed of polyurethane incorporating dimethylglyoxime (PU x -DMG) is prepared by precise regulation of dynamic oxime-urethane covalent bonds. The obtained alkyl radical (R·) derived from the cleavage of the oxime-urethane bonds manages to effectively suppress the attachment of marine biofouling. Moreover, the intrinsic dynamic surface makes it difficult for biofouling to adhere and ultimately achieves sustainable antifouling property. Notably, the PU 50 -DMG coating not only presents efficient antibacterial and antialgae properties, but also prevents macroorganisms from settling in the sea for up to 4 months. This provides a pioneer broad-spectrum strategy to explore the marine antifouling coatings. [ABSTRACT FROM AUTHOR]

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Advanced oxysulfur radical-based advanced oxidation processes (OSR-AOPs) usually use heterogeneous catalysts to activate sulfite to degrade organic pollutants in water. In this study, we report the mechanism of sulfite activation by amorphous Fe1−xNixS to degrade rhodamine B (RhB) in different pH ranges. Compared with FeS, Fe1−xNixS had a wide pH application range and high activity. For Fe1−xNixS, Ni-doping sped up electron transfer inside the catalyst and the reduced S2− promoted the ≡Fe(III)/≡Fe(II) cycle, which together improved the sulfite activation by Fe1−xNixS. The results indicated a pH dependence of RhB degradation in the Fe1−xNixS/sulfite system. The free radical pathway of SO3˙−, SO5˙− and ˙OH generated in the process was dominant under acidic condition, whereas it was mainly a non-free radical pathway of electron transfer between the catalyst and the pollutant under alkaline conditions. Both free radical and non-free radical pathways existed in Fe1−xNixS/sulfite under neutral conditions. The results shed significant light on promoting sulfite-based AOPs to remove pollutants from water. [ABSTRACT FROM AUTHOR]

Compared with heavy metal catalysts, metal-free catalysts that activate persulfate (PS) for controlling organic pollutants are more economical, environmentally friendly, and safer for human health. Utilizing ZIF-8 particles as templates and polyphosphazene as the precursor, hollow N, P, and O tri-doped carbon microspheres (NPOC) with a hierarchical pore structure were successfully synthesized from ZIF-8@polyphosphazene. Their morphology and structure were investigated by SEM, TEM, TGA, XPS, BET, and FT-IR. Otherwise, NPOC were used as catalysts to activate PS for the oxidative degradation of tetracycline. The dosage of catalyst and oxidant, tetracycline concentration, carbonization temperature, and pH can all have a substantial influence on the oxidative degradation of tetracycline. Free radical testing by EPR reveals that HO˙ and SO4˙− are generated and the radical pathway is dominant in the oxidative degradation process. NPOC exhibited superior catalytic oxidation performance and good reusability, indicating their potential for application for eliminating TC from aqueous solution. [ABSTRACT FROM AUTHOR]

Vinyl‐substituted hydridopolycarbosilane (VHPCS) is widely studied for its low viscosity, abundance of active functional groups, rapid curing, and high ceramic yield. The curing reactions mainly involve the free radical polymerization of vinyl and hydrosilylation reactions, but these reactions typically require high temperatures such as 160–250°C. The curing behavior of VHPCS‐17 with a tert‐butyl peroxybenzoate/Nickel acetylacetonate (TBPB/NIAA) system is investigated using differential scanning calorimetry and in situ Fourier transform infrared. The properties of VHPCS‐17 with different initiator systems and VHPCS with different vinyl contents (under TBPB/NIAA system) are studied using thermogravimetric analysis and x‐ray diffraction. The results demonstrate that the TBPB/NIAA system can facilitate the free radical polymerization of vinyl; moreover, this system decreases the peak temperature of the curing reaction from 251 to 141°C and increases the ceramic yield from 80.49% to 89.88%. The ceramic yield of cured VHPCS increases gradually, reaching 89.88% when the vinyl content is 17%. The grain size of β‐SiC decreases continuously with the increase in vinyl content, while the high‐temperature oxidation‐resistant properties of SiC ceramics obtained from different VHPCSs are not negatively affected. [ABSTRACT FROM AUTHOR]

The photocatalytic oxidation of biomass‐derived benzyl alcohol provides a promising way for the synthesis of benzoic acid, which is an important intermediate with wide applications. To improve the efficiency of photocatalytic benzyl alcohol oxidation to benzoic acid is of great interest. In this work, we propose the utilization of NH2‐UiO‐66‐ID‐Fe catalyst for photocatalytic oxidation of benzyl alcohol to benzoic acid, where NH2‐UiO‐66 is a typically used metal‐organic framework, ID is indole‐2,3‐dione (ID) that has biocompatibility, light absorption property and can be covalently combined with amino‐functionalized substances. The NH2‐UiO‐66‐ID‐Fe catalyst exhibits improved light absorption and photo‐generated electron‐hole separation ability compared with NH2‐UiO‐66. The photocatalytic performance of NH2‐UiO‐66‐ID‐Fe was examined for the oxidation of bio‐based benzyl alcohol under mild conditions of air atmosphere, room temperature and no additive or additional oxidant involved. The results show that the conversion of benzyl alcohol and the selectivity to benzoic acid could both reach over 99 % in 6 h, and the generation rate of benzoic acid per gram of catalyst is 3.36 mmol g−1 h−1. The reaction mechanism was detected by radical trapping method and in situ electron paramagnetic resonance. This study presents an efficient and environmentally benign avenue for the synthesis of carboxylic acid compounds. [ABSTRACT FROM AUTHOR]

This paper aimed at providing new insights into the mechanisms of ozone reactions with a selection of organic compounds, where C–H bonds were single available attack spots (1-propanol, tertiary-butanol, formate and formic acid). The involved method was based on the density functional theory (DFT). The calculations considered reactions occurring in a polar solvent, water (ɛr = 80), and a nonpolar one, cyclohexane (ɛr = 2.02). For all cases, the reaction was triggered by extraction of a hydrogen atom from the active C–H bond by ozone leading to a pair of radicals. Following this reaction, three situations occurred. Diffusion of the radicals from the solvent cage resulting in two free radicals meant H-abstraction. A fast electron transfer between the two radicals within the solvent cage resulting in the corresponding ions pair indicated pseudo hydride transfer. The recombination of the radicals within the solvent cage leading to an organic hydrotrioxide denoted pseudo insertion. In water, the systems might follow all pathways. In cyclohexane, the reaction might occur generally only via H-abstraction and pseudo insertion. An exception was the formate/O3 system, where all pathways might occur. [ABSTRACT FROM AUTHOR]

The new methacrylic azomethine-containing monomers with side chain quinoline moiety were synthesized by reaction of their corresponding alcohols with methacryloyl chloride. The polymers based on new monomers were synthesized by free radical polymerization. Polymers were characterized by 1HNMR spectroscopy, and the results of their photochemical and optical activities are presented. [ABSTRACT FROM AUTHOR]

• The composition and bioactivities of essential oil (EO) from Bulbophyllum kwangtungense were investigated for the first time. • Network pharmacology was utilized to evaluate B. kwangtungense EO potential therapeutic effects. • B. kwangtungense EO can be exploited as nature-derived antioxidant preservatives, synergistic antibiotics, and therapeutic agents against oxidative stress. The present study investigates the chemical composition of the essential oil (EO) from Bulbophyllum kwangtungense Schltr., evaluates its antioxidant, enzyme inhibitory activities, and analyzes its therapeutic mechanisms against oxidative damage through network pharmacology. The main components identified were n -hexadecanoic acid (9.95 %), linalool (9.17 %), 1-hexanol (5.16 %), pentadecanoic acid (4.66 %), (Z)-3-hexen-1-ol (3.39 %), phytol (2.67 %), linoleic acid (2.49 %), 1-hexadecanol (2.39 %), α-curcumene (2.28 %). The 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate) (ABTS), 1,1-diphenyl-2-picryl-hydrazyl radical (DPPH) free radical scavenging capacity was characterized by IC 50 values of 0.43 ± 0.08 mg/mL and 3.87 ± 1.26 mg/mL. The ferric reducing antioxidant power (FRAP) antioxidant value (Trolox equivalent antioxidant concentration) was 116.49 ± 0.26 μM/g. The EO exhibited anti-β-lactamase activity with an IC 50 of 229.4 ± 18.7 μg/mL. The anti-acetylcholinesterase activity was 18.10 ± 2.71% at the 500 μg/mL concentration. The network pharmacology analysis was conducted to reveal potential targets and pathways of oxidative damage involved in the therapeutic effects of our EO. [ABSTRACT FROM AUTHOR]

• Psidium fruits showed antioxidant activities, with a protective effect on DNA. • It may be related to phenolic compounds, flavonoids, tannins and anthocyanins. • Its fruits had no cytotoxicity, except for the P. myrtoides highest concentrations. • Aqueous extracts of Psidium fruits showed no genotoxic effects. • Psidium fruits are potential sources for functional foods, with benefits for health. Psidium cattleianum Sabine and P. myrtoides O. Berg (Myrtaceae) fruits, known as yellow and purple araçá, respectively, are widely consumed fresh and are used in several applications, such as juices, syrups, and ice cream products. Moreover, their extracts and essential oils have been recognized for their biological properties. Here, we evaluated the potential of P. cattleianum and P. myrtoides fruits through antioxidant, cytogenotoxic, and antigenotoxic tests using their aqueous fruit extracts (1.56 to 50.0 mg/mL). Phenolic compounds and flavonoids were present in both Psidium fruit extracts, while tannins and anthocyanins were found only in P. myrtoides. The latter species exhibited higher antioxidant activity when compared to P. cattleianum according to the DPPH and ABTS tests. Psidium cattleianum extracts showed no cytotoxicity (MTT assay), while P. myrtoides was considered cytotoxic only at the highest concentrations (25 and 50 mg/mL). No genotoxic effects were observed for both extracts (3.12, 6.25, and 12.5 mg/mL) using micronucleus test with the fibroblast cell line L929. Additionally, P. cattleianum and P. myrtoides extracts (12.5 mg/mL) reduced nuclear changes induced by MMS in the antigenotoxic assay. Overall, our findings suggest that the analyzed Psidium fruits, particularly the P. myrtoides species, are sources of natural antioxidants, with no genotoxicity (≤ 12.5 mg/mL) and exhibit a protective effect against DNA damage. [ABSTRACT FROM AUTHOR]

The plant Allium ampeloprasum, belonging to the Liliaceae family, is an important source of antioxidant compounds. In this study, the anti -radical and antioxidant activities, as well as the determination of phenolic and flavonoid compounds in the aqueous and alcoholic extracts of this plant, were investigated. In this laboratory study, the aqueous and alcoholic extracts of Allium ampeloprasum were prepared by adding 50 grams of the plant and mixing it in a 1:5 ratio with distilled water or ethanol. The total phenolic and flavonoid content was determined by spectrophotometry, and the antioxidant activity of the plant at different concentrations was measured using the Cuprac method, DPPH free radical scavenging, and ferric reducing antioxidant power (FRAP) assay. Data analysis was performed using SAS software and one -way analysis of variance. Based on the results, the total phenolic content in the aqueous extract was 86.9859 and 23.4 micrograms of gallic acid per milliliter in the alcoholic extract. The total flavonoid content was 42.81 in the aqueous extract and 345.54 micrograms of quercetin per milliliter in the alcoholic extract. Additionally, the total antioxidant capacity in the aqueous extract was 0.2362 and 0.3876 in the alcoholic extract, and the Cuprac method reported 0.0747 in the aqueous extract and 0.1992 in the alcoholic extract. The ferric reducing antioxidant power was 0.1041 in the aqueous extract and 0.0248 in the alcoholic extract, while the DPPH radical scavenging activity was 73.18 in the aqueous extract and 72.95 in the alcoholic extract. According to the study results, Allium ampeloprasum is a good source of antioxidant compounds, and its consumption can reduce oxidative damages in the body and improve health. Moreover, after extraction and purification, it can be used in pharmaceutical and food industries. [ABSTRACT FROM AUTHOR]

Summary: Betaine is a natural antioxidant lacking the ability to scavenge free radicals. Although it has been shown to exert antioxidant function by enhancing the expression of antioxidant enzymes, its mechanism has not yet been elucidated. This study explored the role and mechanism of the transcription factor NF‐E2‐associated factor 2 (Nrf2)‐Kelch‐like epichlorohydrin‐associated Protein 1 (Keap1) antioxidant reaction element (ARE) pathway in betaine‐mediated enhancement of antioxidant enzyme expression. Results derived from real‐time quantitative PCR, Western blot, quantitative methylation‐specific PCR, and inhibitors assay experiments showed that betaine activated the Nrf2‐Keap1‐ARE pathway, leading to an increase in the mRNA level of superoxide dismutase, glutathione peroxidase, and heme oxygenase‐1. The mechanism may involve betaine's promotion of DNA methyltransferase expression, resulting in increased methylation of Keap1 DNA promoter, which ultimately reduces the level of Keap1 mRNA. Therefore, betaine can directly activate the Nrf2‐Keap1‐ARE pathway by increasing the methylation level of Keap1 DNA promoter, thereby improving the expression of antioxidant enzymes. This study will contribute to unveiling a new antioxidant mechanism for betaine. [ABSTRACT FROM AUTHOR]

BACKGROUND: To improve phytol bioavailability, a novel method of magnetic stirring and high‐pressure homogenization (HPH) combination was used to prepare zein/fucoidan‐coated phytol nanoliposomes (P‐NL‐ZF). The characterization, the simulated in vitro digestion, and the antioxidant activity of these phytol nanoliposomes from the different processes have been studied. RESULTS: Based on the results of dynamic light scattering (DLS) and gas chromatography–mass spectrometer (GC–MS) analysis, P‐NL‐ZF prepared through the combination of magnetic stirring and HPH exhibited superior encapsulation efficiency at 76.19% and demonstrated exceptional physicochemical stability under a series of conditions, including storage, pH, and ionic in comparison to single method. It was further confirmed that P‐NL‐ZF by magnetic stirring and HPH displayed a uniform distribution and regular shape through transmission electron microscopy (TEM). Fourier‐transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) analysis showed that electrostatic interactions and hydrogen bonding were the primary driving forces for the formation of composite nanoliposomes. Additionally, an in vitro digestion study revealed that multilayer composite nanoliposomes displayed significant and favorable slow‐release properties (58.21%) under gastrointestinal conditions compared with traditional nanoliposomes (82.36%) and free phytol (89.73%). The assessments of chemical and cell‐based antioxidant activities demonstrated that the coating of zein/fucoidan on phytol nanoliposomes resulted in enhanced effectiveness in scavenging activity of ABTS free radical and hydroxyl radical and mitigating oxidative damage to HepG2 cells. CONCLUSION: Based on our studies, the promising delivery carrier of zein/fucoidan‐coated nanoliposomes is contributed to the encapsulation of hydrophobic natural products and enhancement of their biological activity. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Seminars in Thrombosis and Hemostasis (STH) celebrates 50 years of publishing in 2024. To celebrate this landmark event, STH is republishing some archival material. This article represents the most highly cited paper ever published in STH. The original abstract follows. Blood is a two-phase suspension of formed elements (i.e., red blood cells [RBCs], white blood cells [WBCs], platelets) suspended in an aqueous solution of organic molecules, proteins, and salts called plasma. The apparent viscosity of blood depends on the existing shear forces (i.e., blood behaves as a non-Newtonian fluid) and is determined by hematocrit, plasma viscosity, RBC aggregation, and the mechanical properties of RBCs. RBCs are highly deformable, and this physical property significantly contributes to aiding blood flow both under bulk flow conditions and in the microcirculation. The tendency of RBCs to undergo reversible aggregation is an important determinant of apparent viscosity because the size of RBC aggregates is inversely proportional to the magnitude of shear forces; the aggregates are dispersed with increasing shear forces, then reform under low-flow or static conditions. RBC aggregation also affects the in vivo fluidity of blood, especially in the low-shear regions of the circulatory system. Blood rheology has been reported to be altered in various physiopathological processes: (1) Alterations of hematocrit significantly contribute to hemorheological variations in diseases and in certain extreme physiological conditions; (2) RBC deformability is sensitive to local and general homeostasis, with RBC deformability affected by alterations of the properties and associations of membrane skeletal proteins, the ratio of RBC membrane surface area to cell volume, cell morphology, and cytoplasmic viscosity. Such alterations may result from genetic disorders or may be induced by such factors as abnormal local tissue metabolism, oxidant stress, and activated leukocytes; and (3) RBC aggregation is mainly determined by plasma protein composition and surface properties of RBCs, with increased plasma concentrations of acute phase reactants in inflammatory disorders a common cause of increased RBC aggregation. In addition, RBC aggregation tendency can be modified by alterations of RBC surface properties because of RBC in vivo aging, oxygen-free radicals, or proteolytic enzymes. Impairment of blood fluidity may significantly affect tissue perfusion and result in functional deteriorations, especially if disease processes also disturb vascular properties. [ABSTRACT FROM AUTHOR]

Disrupted lipid metabolism is a characteristic of gliomas. This study utilizes an ultrastructural approach to characterize the prevalence and distribution of lipids within gliomas. This study made use of tissue from IDH1 wild type (IDH1-wt) glioblastoma (n = 18) and IDH1 mutant (IDH1-mt) astrocytoma (n = 12) tumors. We uncover a prevalent and intriguing surplus of lipids. The bulk of the lipids manifested as sizable cytoplasmic inclusions and extracellular deposits in the tumor microenvironment (TME); in some tumors the lipids were stored in the classical membraneless spheroidal lipid droplets (LDs). Frequently, lipids accumulated inside mitochondria, suggesting possible dysfunction of the beta-oxidation pathway. Additionally, the tumor vasculature have lipid deposits in their lumen and vessel walls; this lipid could have shifted in from the tumor microenvironment or have been produced by the vessel-invading tumor cells. Lipid excess in gliomas stems from disrupted beta-oxidation and dysfunctional oxidative phosphorylation pathways. The implications of this lipid-driven environment include structural support for the tumor cells and protection against immune responses, non-lipophilic drugs, and free radicals. [ABSTRACT FROM AUTHOR]

[Display omitted] Reducing iron by hydroxylamine (HA) can promote the generation of reactive oxygen species (ROS) in the Fenton reaction and play a crucial role in the degradation of organic pollutants. However, the performance of this system at wider environmental thresholds is still not sufficiently understood, especially in the highly alkaline environments resulting from human activities. Here, we assessed the impact of solution pH on organic pollutant degradation by goethite with the addition of HA and H 2 O 2. The solid phase variation and ROS generation were analyzed using Mössbauer spectroscopy, X-ray absorption near edge structure spectroscopy, and electron paramagnetic resonance analysis. This study found that under alkaline conditions, the system can continuously scavenge organic pollutants through oxygen-mediated generation of free radicals. At lower pH levels, organic pollutant decomposition, exemplified by the breakdown of bisphenol A (BPA), is primarily driven by the Fenton reaction facilitated by iron. As pH increases, hydroxyl radical (•OH) production decreases, accompanied by decreased BPA removal efficiency. However, the removal efficiency of BPA increased significantly at pH > 9. At pH 12, the removal of BPA exceeded that of the acidic condition after one hour, which is consistent with observations in soil system studies. Unlike the Fenton reaction, which is not sensitive to oxygen content, the removal of BPA under alkaline conditions occurs only under aerobic conditions. H 2 O 2 is hardly involved in the reaction, and the depletion of HA becomes a critical factor in the decomposition of BPA. Importantly, in contrast to acidic conditions, where the dramatic decomposition of BPA occurs mainly in the first 10 min, the decomposition of BPA under alkaline conditions continued to occur over the 2 h of observation until complete removal. For natural systems, the remediation of pollutants depends more on the active time of ROS than on their reactivity. Therefore, this idea can reference pollution remediation strategies in anthropogenically disturbed environments. [ABSTRACT FROM AUTHOR]

This study aimed to select the best conditions for producing a nanoemulsion loaded with an essential oil blend (NEOB) to achieve maximum antimicrobial and antioxidant activities. The NEOB consisted of lemongrass (Cymbopogon citratus; LEO; 60%) and thyme (Thymus vulgaris; TEO; 40%). The effect of ultrasound time exposition at 300 W (5, 18, and 30 min) and essential oil concentration (5, 11, and 20 mg/mL) on these responses was evaluated after obtaining NEOB and after an oxidation assay with UVC-LED exposure. Nanoemulsions were analyzed for their physicochemical and biological properties. Overall, droplet size, zeta potential, minimum inhibitory concentrations (MIC) against Escherichia coli, DPPH free radical scavenging activity, and ferric-reducing antioxidant power were affected by essential oil concentration and/or ultrasound time exposition in a non-linear fashion. The NEOB (average size, 68.88 ± 2.84 nm) with 20.5 mg/mL of essential oil and sonicated for 35.7 min achieved the highest anti-E. coli (MIC, 0.44 mg/mL) and antioxidant activity (FRAP, 1.17 μmol TROLOX equivalent/g), remaining stable even after high UVC-LED doses (6.41 J/cm2 exposure, p < 0.05). This study reveals the promising potential of NEOB obtained from ultrasound for sustainable industrial applications. [ABSTRACT FROM AUTHOR]

Based on the Thermal Decomposition of Xishan coal Experiments and ReaxFF MD Simulations, the study investigated the processes and product changes in the thermal decomposition of coal and the pyrolysis of coal with Na2SO4. The results indicate that the initial temperature of thermal decomposition of Xishan coal is around 300 °C in experiments and approximately 1600 K in molecular simulations. The addition of Na2SO4 advances the initial pyrolysis temperature and promotes the generation of total number and types of products. Xishan coal pyrolysis generates a large number of small molecular gases and free radicals, and the addition of Na2SO4 promotes the generation of CO, CH4, and H2S, as well as the accumulation of a significant number of free radicals. Free Na mainly affects the evolution of N elements, promoting the formation of N into amino groups, and Na easily combines with sulfur-containing intermediates. Through the extraction of sulfur-containing intermediates and the analysis of the influence of free radicals, it was found that S elements Xishan coal ultimately forms H2S. This study microscopically confirms that in the coal with Na2SO4 system, H2S originates from the hybridised sulfur atoms in the carbon chain and free ${\rm SO}_4^{2-}$ SO 4 2 − . [ABSTRACT FROM AUTHOR]

The way that living cells respond to non-ionizing electromagnetic fields (EMF), including static/extremely-low frequency and radiofrequency electromagnetic fields, fits the pattern of 'cellular stress response' – a mechanism manifest at the cellular level intended to preserve the entire organism. It is a set pattern of cellular and molecular responses to environmental stressors, such as heat, ionizing radiation, oxidation, etc. It is triggered by cellular macromolecular damage (in proteins, lipids, and DNA) with the goal of repairing and returning cell functions to homeostasis. The pattern is independent of the type of stressor encountered. It involves cell cycle arrest, induction of specific molecular mechanisms for repair, damage removal, cell proliferation, and cell death if damage is too great. This response could be triggered by EMF-induced alternation in oxidative processes in cells. The concept that biological response to EMF is a 'cellular stress response' explains many observed effects of EMF, such as nonlinear dose- and time-dependency, increased and decreased risks of cancer and neurodegenerative diseases, enhanced nerve regeneration, and bone healing. These responses could be either detrimental or beneficial to health, depending on the duration and intensity of the exposure, as well as specific aspects of the living organism being exposed. A corollary to electromagnetic hypersensitivity syndrome (EHS) could be an inappropriate response of the hippocampus/limbic system to EMF, involving glucocorticoids on the hypothalamic-pituitary-adrenal axis. [ABSTRACT FROM AUTHOR]

The development of highly efficient, solution-processable, and environmentally stable perovskite quantum dots (PQDs) is crucial for their accurate high-resolution patterning and subsequently enabling the practical deployment of PQD based emissive display devices. This study presents an innovative strategy for integrating all-inorganic PQDs and ultraviolet (UV) crosslinkable acrylate polymer at a structural and functional level. The achievement is accomplished by meticulous design and one-pot synthesis of UV-crosslinkable CsPbX3 (X = Cl, Br, I) PQDs solution, which exhibit outstanding environmental stability. Leveraging the solution-processable characteristics of the resulting UV-crosslinkable PQDs, precise patterning of high-resolution (2 µm, 7608 pixels in.−1) and colorful PQDs microarrays can be readily achieved through inkjet printing and high-throughput photolithography (~ 2 µm in pitch line/space patterning). The UV cross-linked process guarantees a homogeneous distribution of PQDs, effectively mitigating coffee ring effect and improving the overall quality of stereoscopic microarrays. The photo-cured PQDs film, which undergoes free radical photopolymerization, displays an impressive photoluminescence quantum yield (PL QY) of up to 89.2%, reaching 98% of the value observed in the solution state. The approach outlined in this research is both cost-effective and pragmatic, exhibiting tremendous promise for diverse system-level integrated optoelectronic devices, such as ultra-high-resolution micro-light-emitting device (micro-LED) displays. [ABSTRACT FROM AUTHOR]

Based on the Thermal Decomposition of Xishan coal Experiments and ReaxFF MD Simulations, the study investigated the processes and product changes in the thermal decomposition of coal and the pyrolysis of coal with Na2SO4. The results indicate that the initial temperature of thermal decomposition of Xishan coal is around 300 °C in experiments and approximately 1600 K in molecular simulations. The addition of Na2SO4 advances the initial pyrolysis temperature and promotes the generation of total number and types of products. Xishan coal pyrolysis generates a large number of small molecular gases and free radicals, and the addition of Na2SO4 promotes the generation of CO, CH4, and H2S, as well as the accumulation of a significant number of free radicals. Free Na mainly affects the evolution of N elements, promoting the formation of N into amino groups, and Na easily combines with sulfur-containing intermediates. Through the extraction of sulfur-containing intermediates and the analysis of the influence of free radicals, it was found that S elements Xishan coal ultimately forms H2S. This study microscopically confirms that in the coal with Na2SO4 system, H2S originates from the hybridised sulfur atoms in the carbon chain and free ${\rm SO}_4^{2-}$ SO 4 2 − . [ABSTRACT FROM AUTHOR]

Highlights Recent studies have shown that graphene nanoplatelets (GNP) absorb free radicals and slow polymer degradation. A study has been conducted to investigate the effects of GNP polarity and concentration on polyethylene stability in ClO2‐containing water. The addition of graphene nanoplatelets SG: high polarity and CG: low polarity improved the thermo‐oxidative stability of bimodal high‐density polyethylene (PE100). As a result of the application of traditional primary and secondary antioxidants, as well as the addition of 0.1% CG, the thermo‐oxidative stability of PE100 was significantly increased, according to the oxidative induction time (OIT). The synergistic thermal stabilization effect of GNP is derived from the free radical scavenging and tortuous path effect of CG. Rheological measurements showed that the appropriate nanofiller and antioxidant combined prevent polymer thermo‐oxidation degradation during melt processing. As a result of 3 weeks of aging in chlorine dioxide‐containing water, the neat sample (PE100) demonstrates only 50% elongation at break, whereas the sample with 0.6 wt% of CG shows 200% elongation at break after 3 weeks, due to the formation of a tortuous barrier and radical scavenging of the CG structures. DPPH assay test confirms the antioxidant scavenging capability of the GNPs. The appropriate nanofiller and antioxidant combined to prevent polymer thermo‐oxidation degradation during melt processing. Low polarity GNP can be dispersed more uniformly in the nanocomposite matrix. Nanocomposite containing lower polarity GNP shows more resistance against thermochemical degradation. [ABSTRACT FROM AUTHOR]

TiO2@BiOCl‐BiOI heterostructure photocatalyst with high photocatalytic activity was prepared by the composite modification and sol‐gel procedure. TiO2 nanoparticles highly dispersed on the surface of TiO2@BiOCl‐BiOI, which provides sufficient active sites for the photocatalytic degradation process. The photodegradation performance of the photocatalyst was evaluated by the removal rate of Congo Red. The researches showed that the degradation effect of TiO2@BiOCl‐BiOI for Congo Red is significantly stronger than that of TiO2 and BiOCl‐BiOI, which is mainly due to the type‐II heterojunction structure of TiO2@BiOCl‐BiOI and its enhanced visible‐light response. The experiments of free radical capture indicated that ⋅O2- ${{{\rm O}}_{2}^{-}}$ and h+ ${{{\rm h}}^{+}}$ are the main active species in the photocatalytic degradation system. This study showed that TiO2@BiOCl‐BiOI can almost completely degrade Congo Red under simulated sunlight, making it the harmless substances such as H2O and CO2. [ABSTRACT FROM AUTHOR]

The selection of appropriate solvents in the extraction process plays a crucial role in determining the nature and quantity of secondary metabolites extracted from medicinal plants. This study investigates the impact of solvent polarity on the extraction yield, phenolic content, and antioxidant properties of seeds from four plants belonging to the Malvaceae family: Abutilon fruticosum, Abutilon pannosum, Sida ovata and Malvastrum coromendelianum. The seed powder of each species was subjected to extraction using solvents with varying polarities, including acetone, chloroform, methanol, and water. Physicochemical analysis, extraction yield, quantitative phenolic content, and antioxidant activity were assessed. Total phenolic content (TPC) was determined using the Folin–Ciocalteu reagent, and antioxidant activity was measured using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. Analysis of variance (ANOVA) revealed that the choice of extracting solvents significantly influenced (p < 0.05) extraction yield, phenolic content, and antioxidant properties. In conclusion, water and methanol emerged as the most effective solvents for achieving high extraction yields, phenolic compound content, and free radical scavenging activities. The results demonstrated a robust correlation between total phenolic content (mg of Gallic acid equivalent/g of sample) and free radical scavenging activity (IC50). The study highlights the substantial impact of solvent type, suggesting the potential benefits of using a combination of polar and nonpolar solvents to enhance the extraction efficiency of phytochemicals, phenolic content and antioxidant quality from medicinal plant seeds. Future investigations should focus on isolating and identifying active secondary metabolites from these extracts. [ABSTRACT FROM AUTHOR]

NH3 is a highly promising zero‐carbon fuel. In this paper, 19 important reactions involving NH3, NH2, and NH in the ammonia system are studied to better establish the combustion reaction mechanism of ammonia. These reactions encompass the reactions of NH3, NH2, and NH with free radicals and inorganic compounds such as O, H, OH, NO, H2O, and O2. Utilizing the transition state theory and Yao‐Lin method, energy barrier diagrams for these reactions are presented, and the harmonic and anharmonic rate constants are calculated over the temperature range from 300 to 4000 K. The calculation results reveal that, in most reactions, the harmonic rate constants exceed the anharmonic rate constants and the experimental results are closer to the anharmonic rate constants. Additionally, the kinetic and thermodynamic parameters are fitted. To summarize, most reactions are significantly influenced by the anharmonic effect. [ABSTRACT FROM AUTHOR]

Taking Gonghe oil shale as raw material, the rapid pyrolysis experiment was carried out using the Py-GC/MS device under different atmospheres. The effects of different pyrolysis atmospheres on the rapid pyrolysis products of Gonghe oil shale were studied. The results show that the H2 atmosphere can not only increase the content of saturated hydrocarbons and reduce the content of unsaturated hydrocarbons but also reduce the content of oxygen-containing heterocyclic compounds. This may be because more H free radicals under the H2 atmosphere are produced to react with the free radical fragments formed by kerogen decomposition. The coupling between H free radicals and free radical fragments can prevent the polymerization among macromolecular free radicals and inhibit the generation of heavy byproducts, which can promote the kerogen pyrolysis and increase the release of volatile matter. In addition, the pyrolysis atmosphere is conducive to the deoxygenation of oxygen-containing heterocyclic compounds to a certain extent. [ABSTRACT FROM AUTHOR]

In order to provide more evidence to understand the termination mechanism in styrene free‐radical polymerization, (1‐bromoethyl) benzene and polystyrene with bromide end group (PSt‐Br) synthesized by atom transfer radical polymerization (ATRP) were used as the model compound and model polymer to study the termination behavior of styrenic radical by atom transfer radical coupling (ATRC), and then the NMR chemical shifts of the head‐to‐head enchainment from coupling termination were obtained. SEC and different NMR measurement methods were used to analyze and characterize the products. It is confirmed that there is no bimolecular disproportionation termination between styrenic free radicals, but only coupling termination to form the head‐to‐head enchainment. The proton and carbon chemical shifts of the head‐to‐head enchainment from coupling termination for (1‐bromoethyl) benzene are 2.7–2.86 ppm and ~47.3 ppm. As for the polystyrene through ATRC from PSt‐Br, the corresponding chemical shifts are 2.61–3.29 ppm and ~46.4 ppm, respectively, they are almost the same as the data in our previous paper (~3.05 ppm, ~46.6 ppm) for polystyrene initiated by BPO, proving that the chain termination in free‐radical polymerization of styrene initiated by BPO occurs through primary termination between chain radical and primary radical rather than bimolecular termination between chain radicals. [ABSTRACT FROM AUTHOR]

Abstract\nHIGHLIGHTSProstate damage can occur in men due to age and genetic factors, especially when exposed to external factors. Radiation (RAD) is a prominent factor leading to oxidative stress and potential prostate damage. Additionally, chloroquine (CQ), used in malaria treatment, can induce oxidative stress in a dose-dependent manner. Therefore, reducing and preventing oxidative damage in prostate tissue caused by external factors is crucial. Rats used in the study were divided into seven groups, CQ, apocynin (APO), RAD, CQ + APO, CQ + RAD, APO + RAD, CQ + APO + RAD. Subsequently, in vivo biochemical parameters of prostate tissues were examined, including reduced glutathione, lipid peroxidation, superoxide dismutase, glutathione reductase, glutathione peroxidase, glutathione-S-transferase activities, and total antioxidant status, total oxidant status, reactive oxygen species, oxidative stress index, advanced oxidation protein products and histologically. The in vivo results presented in our study showed that APO reduced oxidative stress and had a protective effect on prostate tissue in the CQ, RAD, and CQ + RAD groups as a results of biochemical and histological experiments. Additionally, in silico studies revealed a higher binding affinity of diapocynin to target proteins compared to APO. As a histological results, RAD and CQ alone or in combination did not induce damage in prostate tissues, whereas mild histopathological findings such as hyperemia and haemorrhage were observed in all APO-treated groups. The results suggest that the use of APO for the treatment of oxidative damage induced by CQ and RAD in rats.The biochemical and histological experiments showed that apocynin (APO) has reducing effects of oxidative stress in prostate tissue caused by radiation and radiation + chloroquine.In silico models presented to possible inhibitory effects of APO for enzymes which are reason to the production of free radical.The biochemical and histological experiments showed that apocynin (APO) has reducing effects of oxidative stress in prostate tissue caused by radiation and radiation + chloroquine.In silico models presented to possible inhibitory effects of APO for enzymes which are reason to the production of free radical. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Photoinitiators of the oxime ester (OXE) or ketoxime ester (OXE‐CO) type can rapidly undergo N—O bond cleavage and generate free radicals to initiate photopolymerization under LED excitation, occupying an important position in the field of photocuring. However, the commercial OXEs, e.g., OXE 01 and 02 with λmax's at 326 and 344 nm, respectively, still do not well match the emission spectra of LEDs. Developing novel OXEs/OXE‐COs with high photosensitivity for long‐wavelength LEDs has great significance. Here, four new OXEs/OXE‐COs with nitro‐carbazole‐styrene conjugated chromophore were designed, synthesized, and used as photoinitiators. Results demonstrated that all photoinitiators had strong absorption within the UV–vis range (λmax: 381—392 nm, εmax: 8200—11500 M−1·cm−1). Molecular design of the oxime ester cleavage to produce a small volume methyl group and a methacryl group with an unsaturated double bond brings high activity and low migration, respectively, in one‐photon polymerization under 365—450 nm LEDs excitation. Moreover, OXEs/OXE‐COs with PETA exhibited a wide processing window, high resolution (line accuracy~100 nm) and good nano‐patterning capability under 780 nm femtosecond laser irradiation in two‐photon polymerization, indicating their great potential in 2D/3D microfabrication technologies. [ABSTRACT FROM AUTHOR]

Tannery solid waste (TSW) contains 70–90% collagen by weight. The rapid extraction of collagen while preserving its original and unique triple-helical conformation has proved challenging. In this paper, an ionic liquid-synergistic dissolution and regeneration (IL-SDR) method was developed based on a TBAH/DMSO/H2O ternary (TDH) solvent for the rapid recovery of collagen from TSW under mild conditions. A solubility of 10.25% TSW and a collagen recovery yield of 51.2% were achieved in 30 minutes at room temperature. The original triplet helical conformation and the molecular weight of the collagen product were retained, confirmed via FT-IR, circular dichroism, and matrix-assisted laser desorption/ionization time-of-flight analysis. SEM was used to verify that dense and uniform pores could be formed within collagen by adjusting the DMSO content, and cytotoxicity and moisture retention tests demonstrated that the collagen produced via the IL-SDR process is comparable to natural collagen used in cosmetic and skincare applications. Moreover, the TDH solvent demonstrated excellent reproducibility across five cycles, achieving consistent solubility varying from 9.71% to 11.04%. EPR and 1H NMR showed that the OH– in TBAH induced the generation of DMSO˙ free radicals in the TDH solvent, and these radicals were indispensable for the dissolution of TSW. The DMSO content was positively correlated with the concentration of free radicals. A synergistic dissolution mechanism was proposed: DMSO˙ free radicals preferentially cleaved the terminal peptide chains, causing the collagen molecules to be exposed to DMSO. Subsequently, DMSO disrupted the original hydrogen bond network within the collagen molecules. Then, TBAH and DMSO formed hydrogen bonds with the collagen molecules, stabilizing the dissolved collagen and preventing the reformation of the hydrogen bond network between collagen molecules. This work provides an avenue for low-temperature and rapid dissolution of TSW, and reveals an in-depth, atypical dissolution mechanism for collagen-based materials during the IL-SDR process. [ABSTRACT FROM AUTHOR]

Bee-derived pharmaceutical products, including propolis (PRO) and royal jelly (ROJ), possess outstanding pharmacological properties. However, their efficiency in counteracting the deleterious influences of cadmium (Cd) in testes and the relevant mechanisms entail further investigations. Therefore, this study sheds light on the therapeutic efficacy of PRO and ROJ against testicular dysfunction and infertility induced by Cd. Toward this end, 30 mature male Wistar albino rats were randomly divided into six groups (5 animals/group), including (I) control, (II) Cd, (III) PRO, (IV) ROJ, (V) PRO + Cd, and (VI) ROJ + Cd groups. Furthermore, antioxidant factors, semen quality, hormonal levels, steroidogenic enzymes, and genotoxicity were assessed. Moreover, histopathological and ultrastructural attributes and offspring rates were investigated. The Cd-treated group revealed marked reductions in reduced glutathione (GSH), total antioxidant capacity (TAC), and superoxide dismutase (SOD) with an amplification of lipid peroxidation in testes, indicating disruption of the antioxidant defense system. Furthermore, myeloperoxidase (MPO) activity and DNA damage were significantly heightened, implying inflammation and genotoxicity, respectively. Moreover, steroidogenic enzymes, including 17β-Hydroxy Steroid Dehydrogenase 3 (HSD17b3), 3β-Hydroxy Steroid Dehydrogenase 2 (HSD3b2), 17α-hydroxylase/17,20-lyase (CYP17A1), and steroid 5α-reductase 2 (SRD5A2) were markedly diminished accompanied with disorders in luteinizing hormone (LH), follicle-stimulating hormone (FSH), and testosterone. Besides, spermatozoa quality was reduced, associated with a diminution in the diameter of seminiferous tubules. By contrast, PRO or ROJ significantly protected and/or counteracted the Cd-induced pathophysiological consequences, ameliorating antioxidant and inflammatory biomarkers, steroidogenic enzymes, hormonal levels, and sperm properties, along with lessening DNA impairments. Critically, histological and ultrastructural analyses manifested several anomalies in the testicular tissues of the Cd-administered group, including the Leydig and Sertoli cells and spermatozoa. Conversely, PRO or ROJ sustained testicular tissues' structure, enhancing spermatozoa integrity and productivity. Interestingly, treatment with PRO or ROJ improved fertility indices through offspring rates compared to the Cd-animal group. Our data suggest that PRO is a more effective countermeasure than ROJ against Cd toxicity for securing the delicate testicular microenvironment for spermatogenesis and steroidogenesis. [ABSTRACT FROM AUTHOR]

AbstractPolycyclic aromatic hydrocarbons (PAHs) are a group of complex chemicals that are formed and released during incomplete combustion during industrial processes or pyrolysis of the organic matter. Human exposure to PAHs primarily occurs through food consumption. One of the possible causes of formation in food is free radicals. Also, the confirmed mechanism of their toxicity in living organisms is oxidative stress. This complication is also caused by free radicals released during their metabolism. Chronic exposure to PAHs can lead to carcinogenic, teratogenic and mutagenic effects in humans. Consequently, there is a need to minimize the presence of these compounds in food. Research suggests that antioxidants play a crucial role in reducing PAH levels in food. Therefore, formulating food products with the right combination of antioxidants could be an effective strategy to mitigate the formation of PAHs. Moreover, antioxidants have been found to alleviate the toxicity associated with PAHs in the human body. This manuscript discusses the effects and mechanisms of antioxidants in reducing PAH in food products and living organisms. [ABSTRACT FROM AUTHOR]

The utilization of two‐component systems comprising camphorquinone (CQ) and aromatic amines has become prevalent in the photopolymerization. However, there are still concerns about the safety of this CQ/amine system, mainly because of the toxicity associated with the leaching of aromatic amines. In light of these concerns, this study aims to develop novel coinitiator combinations featuring CQ and amines which cannot be leached out of materials, enabling free radical polymerization of representative dentalmethacrylate resins under blue light irradiation. This approach involves the initial design and analysis of hydrogen donors with low C─H bond dissociation energy through molecular modeling. Subsequently, copolymerizable methacrylate functional groups are incorporated via chemical modification, allowing it to act as both coinitiator and copolymerization monomer to achieve low migrationand leachability properties. This work presents, for the first time, the synthesis of the innovative coinitiator and compares its performance with the benchmark CQ/ethyl‐4‐dimethylaminobenzoate (EDB)‐based photoinitiation system (PIS). The results demonstrate the effectiveness of the newly proposed PIS. Finally, an in‐depth investigation is conducted into the reaction mechanism associated with this PIS through molecular orbital calculations and electron spin resonance studies. [ABSTRACT FROM AUTHOR]

Pomegranate (Punica granatum) is a tree of the Punicaceae family that is widespread all over the world and has several types and therapeutic uses. The current study aimed to investigate the phytochemical compounds by GC analysis and carried out physical characterization of the pomegranate seed oil and its self-nanoemulsifying system. Then antioxidant, anti-diabetic, and anti-lipase activities were investigated for both.The pomegranate seed oil was extracted, and its self-nanoemulsifying system was then prepared. Phytochemical compounds were analyzed by GC, and physical characterization was established of the pomegranate seed oil and its self-nanoemulsifying system. Then antioxidant, anti-diabetic, and anti-lipase activities were investigated for both.The GC–MS analysis revealed that punicic acid, β-eleosteric acid, catalpic acid, α-eleosteric acid, and oleic acid were the most predominant compounds in pomegranate seed oil. Other active compounds like linoleic acid, palmitic acid, stearic acid, and α-linolenic acid were detected in trace percentages. The self-nanoemulsifying system was prepared using various concentrations of surfactant (Tween 80), co-surfactant (Span 80), and pomegranate seed oil. The selected formulation had a PDI of 0.229 ± 0.09 and a droplet size of 189.44 ± 2.1 nm. The free radical scavenging activity of pomegranate seed oil, the self-emulsifying system, and Trolox was conducted using DPPH. The oil-self-nanoemulsifying system showed potent antioxidant activity compared to Trolox. Also, pomegranate oil inhibited α-amylase with a weak IC50 value of 354.81 ± 2.3 µg/ml. The oil self-nanoemulsifying system showed potent activity compared to acarbose and had a weaker IC50 value (616.59 ± 2.1 µg/ml) and a potent IC50 value (43.65 ± 1.9 µg/ml) compared to orlistat.Pomegranate seed oil self-nanoemulsifying system could be applied in the future for the preparation of possible oral medications for the prevention and treatment of oxidative stress, diabetes, and obesity due to its high activity against free radical, amylase, and lipase enzymes compared to pomegranate seed oil itself and the references used. This study reveals that self-nanoemulsion systems can enhance oil drug formulations by improving pharmacokinetics and pharmacodynamics, acting as drug reservoirs, and facilitating efficient oil release. [ABSTRACT FROM AUTHOR]

Despite the existence of various therapeutic approaches, diabetes mellitus and its complications have been an increasing burden of mortality and disability globally. Hence, it is necessary to evaluate the efficacy and safety of medicinal plants to support existing drugs in treating diabetes. Xanthones, the main secondary metabolites found in Gentiana dinarica and Gentiana utriculosa, display various biological activities. In in vitro cultured and particularly in genetically transformed G. dinarica and G. utriculosa roots, there is a higher content of xanthones. The aim of this study was to investigate and compare antidiabetic properties of secondary metabolites (extracts) prepared from these two Gentiana species, cultured in vitro and genetically transformed with those collected from nature. We compare HPLC secondary metabolite profiles and the content of the main extract compounds of G. dinarica and G. utriculosa methanol extracts with their ability to scavenge DPPH free radicals and inhibit intestinal α-glucosidase in vitro. Anti-hyperglycemic activity of selected extracts was tested further in vivo on glucose-loaded Wistar rats. Our findings reveal that the most prominent radical scavenging potential and potential to control the rise in glucose level, detected in xanthone-rich extracts, were in direct correlation with an accumulation of xanthones norswertianin and norswertianin-1-O-primeveroside in G. dinarica and decussatin and decussatin-1-O-primeveroside in G. utriculosa. [ABSTRACT FROM AUTHOR]

The natural aromatic polymer lignin and its lignin-like oligomeric fragments have attracted attention for their antioxidant capacity and free radical scavenging activities. In this study, a 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay was employed to assess the antioxidant capacity of fractionated and partially depolymerized organosolv lignin by electron paramagnetic resonance (EPR) and UV-Vis spectroscopy. The results show significant antioxidant activity for both the lignin and oligomeric fragments, with the EPR measurements demonstrating their efficiency in quenching the free radicals. The EPR data were analyzed to derive the kinetic rate constants. The radical scavenging activity (RSA) of lignins was then determined by UV-Vis spectroscopy and the results were compared with the EPR method. This two-method approach improves the reliability and understanding of the antioxidant potential of lignin and its derivatives and provides valuable insights for their potential applications in various industries, including pharmaceuticals, food preservation, and cosmetics. [ABSTRACT FROM AUTHOR]

Because global sulfur emission has escalated, the development of high-efficiency deep desulfurization techniques has become imperative. Herein, to design a high-activity heterogeneous catalyst for the aerobic oxidation desulfurization (AODS) of fuel, Dawson-type polyoxometalate (H6P2W18O62 abbreviated as D-P2W18), characterized by its high activity and strong oxidative capacity, was applied to react with CuCl2·2H2O and H3TZI via a one-pot hydrothermal method. Consequently, blue crystalline H6P2W18O62@[Cu6O(TZI)3(H2O)6]4 (abbreviated as D-P2W18@rht-MOF-1; rht-MOF-1 = [Cu6O(TZI)3(H2O)6]4·nH2O) was afforded. X-ray diffraction analysis indicated that D-P2W18 was successfully encapsulated in two different cages of rht-MOF-1, which is distinct from the crystal structure of Keggin-type POMs@rht-MOF-1. It represents the first crystal structure of Dawson-type POMs@rht-MOF-1. When D-P2W18@rht-MOF-1 was employed as a catalyst for AODS under ambient oxygen pressure with the assistance of surfactant dioctadecyl dimethyl ammonium chloride (DODMAC), it demonstrated remarkable catalytic capability and recyclability for both model fuel and commercial diesel. Further, the AODS reaction mechanism, identified as a free radical oxidation–reduction process, was verified by way of radical quenching experiments, EPR and XPS analysis. This approach offers a feasible route for the synthesis of new Dawson-type POMs@MOFs of heterogeneous catalysts for highly active AODS of fuel. [ABSTRACT FROM AUTHOR]

Styphnolobium japonicum leaves are considered a rich source of flavonoids, which are the prospective basis for various therapeutic effects. However, there has been a lack of comprehensive cytotoxic studies conducted on these leaves. Therefore, this ongoing investigation aimed to detect and isolate the flavonoids present in S. japonicum leaves, and assess their antioxidant and anticancer properties. The defatted extract from S. japonicum leaves was analyzed using HPLC, which resulted in the identification of seven phenolics and six flavonoids. Rutin and quercetin were found to be the most abundant. Furthermore, a comprehensive profile of flavonoids was obtained through UPLC/ESI–MS analysis in negative acquisition mode. Fragmentation pathways of the identified flavonoids were elucidated to gain relevant insights into their structural characteristics. Furthermore, genistein 7-O-glucoside, quercetin 3-O-rutinoside, and kaempferol 3-O-α-L-rhamnopyranosyl-(1 → 6)-β-D-glucopyranosyl-(1 → 2)-β-D-glucopyranoside were isolated and characterized. The defatted extract rich in flavonoids exhibited significant antioxidant, iron-reducing, free radicals scavenging impacts, and remarkable cytotoxicity against the liver cell line (IC50 337.9μg/ mL) and lung cell line (IC50 55.0 μg/mL). Furthermore, the antioxidant and anticancer capacities of the three isolated flavonoids have been evaluated, and it has been observed that their effects are concentration-dependent. The findings of this research highlight the promising impact of flavonoids in cancer therapy. It is recommended that future scientific investigations prioritize the exploration of the distinct protective and therapeutic characteristics of S. japonicum leaves, which hold significant potential as a valuable natural resource. [ABSTRACT FROM AUTHOR]

A theoretical thermodynamic study was conducted to investigate the antioxidant activity and mechanism of 1,3,4-oxadiazol-2-ylthieno[2,3-d]pyrimidin-4-amine derivatives (OTP) using a Density Functional Theory (DFT) approach. The study assessed how solvent environments influence the antioxidant properties of these derivatives. With the increasing prevalence of diseases linked to oxidative stress, such as cancer and cardiovascular diseases, antioxidants are crucial in mitigating the damage caused by free radicals. Previous research has demonstrated the remarkable scavenging abilities of 1,3,4-oxadiazole derivatives, prompting this investigation into their potential using computational methods. DFT calculations were employed to analyze key parameters, including bond dissociation enthalpy (BDE), ionization potential (IP), proton dissociation enthalpy (PDE), and electron transfer enthalpy (ETE), to delineate the antioxidant mechanisms of these compounds. Our findings indicate that specific electron-donating groups such as amine on the phenyl rings significantly enhance the antioxidant activities of these derivatives. The study also integrates global and local reactivity descriptors, such as Fukui functions and HOMO-LUMO energies, to predict the stability and reactivity of these molecules, providing insights into their potential as effective synthetic antioxidants in pharmaceutical applications. [ABSTRACT FROM AUTHOR]

Based on a constant volume combustion system, the effect of dilution ratio changes on the laminar combustion characteristics of C 2 H 5 OH/air mixture was studied under an initial pressure of 1 bar, initial temperatures of 370 K, 400 K, 450 K, and equivalence ratios of 0.7–1.4. A chemical kinetic mechanism for ethanol-carbon dioxide was established, and the combined physical and chemical effects of carbon dioxide were separated. An independent parameter control method was proposed, introducing virtual species FN 2 , ICO 2 , FCO 2 , and KCO 2 , to isolate the dilution effect, thermal effect, direct reaction effect, third-body effect, and transport effect. Simulation analysis using the modified chemical kinetic mechanism revealed that various impacts of CO 2 reduce the peak progress rate and sensitivity coefficient of key elementary reactions. Furthermore, the dilution effect of CO 2 has the greatest influence on the sensitivity coefficients and net progress rates of important elementary reactions. Based on the results of the chemical kinetic simulations, a new global reaction pathway analysis method was created, overcoming the limitations of the Chemkin-pro method. The decomposition pathway of C 2 H 5 OH throughout the combustion process was calculated as C 2 H 5 OH → SC 2 H 4 OH → CH 3 CHO → CH 3 CO → CH 3 → CH 2 O → HCO → CO → CO 2. Changes in initial temperature and dilution ratio do not alter the main decomposition pathway of C 2 H 5 OH. Detailed chemical kinetics and free radical behavior analysis indicate that the LBV of the C 2 H 5 OH/CO 2 /air blends has a linear correlation with [H + O + OH] max. • The relationship curve between dilution ratio and LBV was fitted. • The introduction of virtual matter decouples the five chemical and physical combined effects of CO 2. • The five effects of CO 2 will all reduce the peak of the progress rate of key elemental reactions. • The decomposition pathway of C 2 H 5 OH during the entire combustion process was calculated. • The linear correlation between LBV and [H + O + OH] max of the blends has been verified. [ABSTRACT FROM AUTHOR]

Non-equilibrium plasma is applied for the first time to ignite the ammonium-hydrogen mixture and reduce the NO x /N 2 O emission with effect in this work. Gas chromatography (GC) experiments as well as a detailed kinetic model, including neutral molecules, free radicals, charged particles, vibratory excited states, and electron excited states, are integrated to investigate the kinetic process of ammonia-hydrogen doped ignition and NO x /N 2 O emission facilitated by nanosecond pulsed discharge. The numerical model closely matches the GC-measured values of NH 3 consumption, H 2 increase, and N 2 O production. Pathway fluxes of important species and sensitivity analysis of ignition delay time reveal that the addition of non-equilibrium plasma has an obvious promotion effect on ammonia and hydrogen-doped oxidation and ignition. The initial ignition temperature significantly impacts the ignition delay time, with a more pronounced plasma-promotion effect observed at lower temperatures. Conversely, as the hydrogen mixing ratio increases, the ignition delay time decreases, yet the generation of NO and N 2 O increases. This is attributed to the heightened production of H and NH through elementary reactions such as NH 3 +H NH 2 + H 2 , H + O 2 O + OH, and OH + H 2 H + H 2 O. Nevertheless, NO and N 2 O emissions are reduced by 1-2 orders of magnitude with plasma assistance compared to auto-ignition. The reduction in NO emissions can be attributed to increased consumption in the pathway of NO + NH 2 N 2 + H 2 O and decreased formation in the pathways of HNO + O 2 HO 2 + NO and NH + NO N 2 O + H. Additionally, it was discovered that the electron attachment dissociation reaction e + N 2 O → O− + N 2 predominantly contributes to the reduction of N 2 O. These research findings significantly contribute to advancing our understanding of the kinetics involved in ammonia-hydrogen doped ignition and emissions, particularly with plasma assistance, for potential engine applications. • Kinetic models for plasma-assisted NH 3 /H 2 /air ignition are established. • Measurements of products in plasma-activated NH 3 /H 2 /air pyrolysis are provided. • NO and N 2 O emissions are reduced with plasma assistance compared to auto-ignition. • Pathways for NO and N 2 O generation during NH 3 /H 2 /air ignition are elucidated. [ABSTRACT FROM AUTHOR]

To explore the inhibition effectiveness and mechanisms of pentafluoroethane (C 2 HF 5), carbon dioxide (CO 2), and their blends, 9.5% methane (CH 4)-air mixture explosions under different inhibitors were tested by employing a 20 L spherical explosion system. A quadratic regression model was developed to predict impacts of factors on maximum explosion pressure (p m) through response surface method. The reactions and mechanisms under blended inhibitors were numerically investigated. Results depicted that increasing volume fractions of inhibitor led to decrease in p m , maximum rate of pressure rise, and delay in explosion induction time. Blended inhibitors demonstrated superior inhibition effectiveness, optimal inhibition-environmental was achieved at 4.5% C 2 HF 5 blended with 5.5% CO 2. A quadratic polynomial relation existed among p m , volume fractions of C 2 HF 5 , CO 2 , and CH 4 during the explosion. Key free radicals were weakened and the promoted explosive elementary reactions were primarily inhibited. CH 4 +OH CH 3 +H 2 O and CH 4 +H CH 3 +H 2 were the most diminished reactions by blended inhibitors compared to CO 2 alone. Carbon-containing reactions R82 and R84, and fluorinated reactions R1025 and R1099 reduced the key free radicals, interrupted the chain reactions and promoted the production of HF. Findings will provide new ideas for prevention of CH 4 -air mixture explosions and reduce hazardous effect. • Blended inhibitors demonstrated superior inhibition effectiveness. • The optimal inhibition-environment was achieved with a blend of 4.5% pentafluoroethane with 5.5% carbon dioxide. • A quadratic polynomial relation between maximum explosion pressure and pentafluoroethane volume fraction. • The physical and chemical inhibition mechanism by pentafluoroethane blend with carbon dioxide was revealed. [ABSTRACT FROM AUTHOR]

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This study explored the impact of enzymatic grafting modification on the structure and functional properties of pectin, aiming to provide a scientific foundation for the development of novel food packaging materials with bioactive properties. Using lipase as a catalyst, p-hydroxybenzoic acid and gallic acid were grafted onto pectin molecules. The structure of the modified pectin was characterized using 1H NMR, FTIR, and XPS analytical techniques, and its antioxidant and antibacterial activities were evaluated. The results showed that the grafting rates of p-hydroxybenzoic acid-modified pectin (Hb-Pe) and gallic acid-modified pectin (Ga-Pe) reached 21.8% and 22.9%, respectively. Notably, compared to unmodified pectin, Ga-Pe exhibited significantly (P<0.05) enhanced DPPH free radical scavenging capacity (69.6%) and β-carotene bleaching inhibition capacity (65.5%), while the improvement in antioxidant activity of Hb-Pe was limited, with the two indicators being only 5.54% and 28.6%, respectively. Furthermore, the inhibition zone diameters of the two modified pectins against Escherichia coli and Staphylococcus aureus were 15.7, 13.3 mm (Hb-Pe) and 16.6, 12.6 mm (Ga-Pe), respectively, which were significantly (P<0.05) higher than those of unmodified pectin. This study confirms that enzymatic grafting modification can effectively enhance the bioactivity of pectin, providing a new approach for extending the shelf life of food products. [ABSTRACT FROM AUTHOR]