Free Radical Reactions Research Articles

Enhancing Selectivity with Molecularly Imprinted Polymers via Non-Thermal Dielectric Barrier Discharge Plasma.

Molecularly imprinted polymers (MIPs) are synthetic polymers that mimic the functions of antibodies. Though MIPs are promising tools in various areas, achieving high selectivity in MIPs can be difficult. To improve selectivity, various approaches have been implemented; however, the role of polymerization methods or synthetic techniques in enhancing the selectivity of MIPs has not been studied and remains a crucial area for further research. MIPs are typically prepared from free radical reactions. Recently, we found that Dielectric Barrier Discharge (DBD) plasma can be used to initiate the polymerization of vinyl monomers. The DBD plasma method allows the monomers to associate with the template molecules and initiate polymerization with minimal disruption to the positioning of the monomers. We hypothesize that this could be a preferred method to prepare MIPs over the traditional radical reaction that may cause a disturbance of the pre-associated monomers on the templates for the polymerization. Chicken egg white serum albumin (CESA) was used as the template protein for the MIPs. Our results show that in all test conditions, approximately twofold improvement in selectivity was achieved, which is the primary performance metric for MIPs. This enhancement was evident across all categories, including MIPs prepared from various monomer combinations.

Carbon quantum dots assemblies integrated with spatial confined Co nanoparticles for antibiotic degradation via peroxymonosulfate activation

Heterogeneous Co-based materials are well-known for their exceptional catalytic properties in activating peroxymonosulfate (PMS) for the degradation of antibiotic pollutants. However, the potential applications of these materials are often hindered by significant Co nanoparticle aggregation and ion leaching. In this study, a carbon quantum dot-mediated self-assembly strategy was used to fabricate three-dimensional porous sponge-like Co@CDs-x (x represents the calcination tempeatures) catalysts with spatially confined Co nanoparticles. Among the samples, Co@CDs-900 exhibited a remarkable 97.8 % removal efficiency of TC in 11 minutes, with an apparent rate constant of 0.313 min−1. The exceptional performance of Co@CDs-900/PMS can be attributed to its large specific surface area, unique porosity, and abundant catalytically active sites, which generate ample reactive oxygen species for TC degradation. The catalyst demonstrated good degradation capabilities across a wide pH range of 3–11 and various organic pollutants such as tetranitrophenol, oxytetracycline, ciprofloxacin, methyl orange, and rhodamine B. Moreover, Co@CDs-900 maintained high activity even after the 5th cycle due to its magnetic property and spatial confinement effect, preventing catalyst loss and ion leaching during recycling tests. The degradation mechanism involved both free-radical and non-free radical pathways, with SO4•− and 1O2 identified as the primary reactive oxygen species. The degradation intermediates of TC were identified and a plausible degradation pathway was proposed. Toxicity assessment revealed that the Co@CDs-900/PMS system effectively reduced the toxicity of TC post-degradation. This study presents an effective approach for developing sponge-like CDs assemblies with spatially confined metal nanoparticles for activating PMS in antibiotic degradation.

Theoretical evidence for a pH-dependent effect of carbonate on the degradation of sulfonamide antibiotics

Carbonate (CO32−/HCO3−) have a significant impact on advanced oxidation processes (AOPs) by consuming reactive free radicals such as HO• to generate CO3•-. However, research on the mechanisms and kinetics of CO3•- remains limited. This study investigates the degradation mechanism and kinetics of sulfonamide antibiotics (SAs) by CO3•- through theoretical calculations. The calculation results revealed that the effect of CO3•- on SAs degradation is pH-dependent due to the dissociable sulfonamide group (-SO2NH-) of SAs in the common water treatment pH range (3–8). The main reaction type of CO3•- with both neutral and anionic molecules of SAs is single electron transfer reaction. Frontier molecular orbital theory (FMO) illustrated that deprotonation of the sulfonamide group of SAs decreases the charge density on the heterocyclic ring, facilitating the electrophilic addition of CO3•-. The second-order rate constants of the neutral and anionic molecules of SAs with CO3•- were calculated as 7.57 × 101∼1.84 × 108 and 1.81 × 107∼7.94 × 109 M−1 s−1, respectively, resulting in an increase in the apparent reaction rate constants with pH. Stepwise multiple linear regression was employed to predict reactivity with anionic sulfonamide antibiotics (SAs−). Two models with outstanding prediction and stability were developed with coefficients of determination R2 of 0.660 and 0.681, respectively. The degradation kinetics simulation indicated that in the UV/H2O2 process in the presence of carbonate, the degradation rate of SAs increased with pH. Furthermore, the contribution of CO3•- to SMX degradation increased while that of HO• decreased. This study highlights the contribution of carbonates to the micropollutant degradation in the UV/H2O2 process as the model, providing theoretical insights into the development of carbonate-based AOPs.

The conversion of metal ions to metals particles contributes the photoaging of microplastics in aquatic environments

Metals ions enriched on the surface of Microplastics (MPs) may undergo redox reactions under UV irradiation to promote its photoaging. However, there is a paucity of information on studies of the aging behavior of MPs mediated by different metal ions. This study aims to investigate the effects of three different metal ions (Ag+, Cu2+ and Al3+) on the photoaging properties of polypropylene (PP) to enhance our comprehension of their aging in water contaminated by heavy metals. Physicochemical analyses, like the ratio of O/C and carbonyl index (CI), suggested that metal ions accelerated the aging of PP. The correlation model was established between CI and aging time to confirm that the aging sequence of PP in three metal ions solution was Ag+-PP>Cu2+-PP>Al3+-PP. Electron Paramagnetic Resonance (EPR) results showed metal ions enhanced the generation of reactive oxygen species (•O2–, HO• and 1O2) to accelerate aging through free radical pathways. Electronic exchange capability (EEC) and X-Ray Photoelectron Spectroscopy (XPS) confirmed metal particles were on PP, leading to the e-bridge for electronic relays that altered the EEC of PP and accelerated its protonation process. It needs to note the surface plasmon resonance (SPR) effect of metal nanoparticles may also accelerated the photoaging of MPs in UV–vis illumination. For the first time, the study establishes a connection between different valence states metal ion and PP aging, shedding light on interfacial and free radical aging process of MPs. The finding also proposes the potential e-bridge or SPR effect of metal particles may exist in accelerating photoaging reaction of PP in special water bodies contaminated with heavy metals. The environmental implications and ecological risks of this phenomenon warrant greater consideration.

Tungsten-needle intensifies microwave-sustained plasma accelerating direct H2S conversion to H2

Direct sustainable conversion of hydrogen sulfide (H2S) enables collaborative recovery of H and S resources via a metal-enhanced microwave plasma strategy, avoiding the hydrogen waste in the traditional Claus process. However, the metal size effect on microwave plasma property, the optimal process parameters, and the enhancement mechanism remain unclear in H2S conversion. Herein, the optimal tungsten needle (diameter: 1 mm, length: 60 mm, and tip angle: 10°) is experimentally proven for intensifying microwave discharge in multi-mode cavities. Theoretical calculations and plasma distribution reveal that the optimized tungsten needle achieves the ideal coupling with the microwave field, exhibiting extreme electric field augmentation around the needle tip. Tungsten-needle intensifies microwave-sustained plasma, realizing 40.2 % (90.1 %) conversion of 100 % (10 %) concentration H2S to H2 at a low microwave power of 300 W with a good stability of 30 hrs. Low power, large flow rate, and high H2S concentration are beneficial for improving energy efficiency. The excitation of microwave plasma is accompanied by a massive generation of highly energetic electrons. The direct high-energy electron-H2S collision contributes a lot to H2S splitting, especially for high-concentration H2S. In-situ optical emission spectroscopy confirms the vital S and H radicals in the plasma. The free radical reactions triggered by electron collisions are responsible for the production of H2 and S. This work opens an avenue to sustainable and low-carbon hydrogen production from the direct conversion and utilization of H2S.

Degradation pathways and product formation mechanisms of asphaltene in supercritical water

Asphaltene is the compound with the most complex structure and the most difficult degradation in oily sludge, which is the key to limit the efficiency of supercritical water oxidation treatment of oily sludge. In this paper, the supercritical water oxidation process of asphaltene was investigated in terms of free radical reaction, degradation pathway, and product generation mechanism using ReaxFF molecular dynamics simulation method. The results showed that increasing temperature, increasing O2, and increasing H2O have different effects on HO2·generation. Benzene rings undergo fusion and condensation through hydrogenation abstraction and oxygen addition reactions, subsequently breaking down into long-chain alkanes. Increasing O2 can effectively promote the ring-opening of nitrogen-containing heterocycles. -COOH is the most important intermediate fragment for CO and CO2 generation, and there is a reaction competition with -CHO3 and -CO3. When the number of oxygen molecules increases from 300 to 700, the reaction frequency of -CHO3 and -CO3 to generate CO and CO2 increases by 17.14 % and 12.77 %·H2O determines the production of H2 by controlling the number of H·radicals present. As the amount of H2O increases from 500 to 1500, the product ratio of H2 increases from 12.73 % to 21.31 %. Environmental implicationAsphaltene is the most structurally complex organic matter in oily sludge, and its presence makes it difficult for oily sludge to be completely degraded by conventional treatment methods such as pyrolysis and incineration. Polycyclic aromatic hydrocarbons (PAHs) represented by asphaltene increase the carcinogenicity and mutagenicity of oily sludge, and even irreversibly pollute soil and groundwater. Supercritical water oxidation, as an efficient organic waste treatment technology, can realize harmlessness in a green and efficient way. So the study on the mechanism of supercritical water oxidation of asphaltene is of great significance for environmental protection.

Harnessing in vivo synthesis of bioactive multiarylmethanes in Escherichia coli via oxygen-mediated free radical reaction induced by simple phenols

BackgroundXanthenes and multi-aryl carbon core containing compounds represent different types of complex and condensed architectures that have impressive wide range of pharmacological, industrial and synthetic applications. Moreover, indoles as building blocks were only found in naturally occurring metabolites with di-aryl carbon cores and in chemically synthesized tri-aryl carbon core containing compounds. Up to date, rare xanthenes with indole bearing multicaryl carbon core have been reported in natural or synthetic products. The underlying mechanism of fluorescein-like arthrocolins with tetra-arylmethyl core were synthesized in an engineered Escherichia coli fed with toluquinol remained unclear.ResultsIn this study, the Keio collection of single gene knockout strains of 3901 mutants of E. coli BW25113, together with 14 distinct E. coli strains, was applied to explore the origins of endogenous building blocks and the biogenesis for arthrocolin assemblage. Deficiency in bacterial respiratory and aromatic compound degradation genes ubiX, cydB, sucA and ssuE inhibited the mutant growth fed with toluquinol. Metabolomics of the cultures of 3897 mutants revealed that only disruption of tnaA involving in transforming tryptophan to indole, resulted in absence of arthrocolins. Further media optimization, thermal cell killing and cell free analysis indicated that a non-enzyme reaction was involved in the arthrocolin biosynthesis in E. coli. Evaluation of redox potentials and free radicals suggested that an oxygen-mediated free radical reaction was responsible for arthrocolins formation in E. coli. Regulation of oxygen combined with distinct phenol derivatives as inducer, 31 arylmethyl core containing metabolites including 13 new and 8 biological active, were isolated and characterized. Among them, novel arthrocolins with p-hydroxylbenzene ring from tyrosine were achieved through large scale of aerobic fermentation and elucidated x-ray diffraction analysis. Moreover, most of the known compounds in this study were for the first time synthesized in a microbe instead of chemical synthesis. Through feeding the rat with toluquinol after colonizing the intestines of rat with E. coli, arthrocolins also appeared in the rat blood.ConclusionOur findings provide a mechanistic insight into in vivo synthesis of complex and condensed arthrocolins induced by simple phenols and exploits a quinol based method to generate endogenous aromatic building blocks, as well as a methylidene unit, for the bacteria-facilitated synthesis of multiarylmethanes.

Carbonaceous structures as electronic bridges to enhance charge migration and radical reactions in composite photocatalysts: An effective way to achieve efficient mineralization of pollutants

The intrinsic correlation between photo-induced extraction of hole and free radical reactions can facilitate the mineralization of contaminants via promoting the transfer of electrons from the semiconductor to the solution. TiO2/C/g-C3N4 composite photocatalysts are prepared using thermal polycondensation and sol-gel methods in this paper. The introduction of carbon at the interface between the two phases creates charge migration channels that facilitate electron transfer at the interface of semiconductor catalyst as well as collisions of dissolved oxygen to the catalytic sites, which are able to promote catalytic oxidation reactions. Considering Rh-B as target, the removal rate is 97.2±0.2 % within 90 min. The involvement of hydroxyl radicals and superoxide radicals is confirmed by carrying out radical quenching experiments and ESR characterization, suggesting that effective electron transfer synergistically promotes the production of hydroxyl radicals. Therefore, it emphasizes the importance of the indeterminate carbon bridged 2D/3D interface for constructing charge migration channels as well as promoting the efficiency of carrier separation in the process of photocatalytic efficient degradation of dyes.

Efficient Light-Based Bioprinting via Rutin Nanoparticle Photoinhibitor for Advanced Biomedical Applications.

Digital light processing (DLP) bioprinting, known for its high resolution and speed, enables the precise spatial arrangement of biomaterials and has become integral to advancing tissue engineering and regenerative medicine. Nevertheless, inherent light scattering presents significant challenges to the fidelity of the manufactured structures. Herein, we introduce a photoinhibition strategy based on Rutin nanoparticles (Rnps), attenuating the scattering effect through concurrent photoabsorption and free radical reaction. Compared to the widely utilized biocompatible photoabsorber tartrazine (Tar), Rnps-infused bioink enhanced printing speed (1.9×), interlayer homogeneity (58% less overexposure), resolution (38.3% improvement), and print tolerance (3× high-precision range) to minimize trial-and-error. The biocompatible and antioxidative Rnps significantly improved cytocompatibility and exhibited resistance to oxidative stress-induced damage in printed constructs, as demonstrated with human induced pluripotent stem cell-derived endothelial cells (hiPSC-ECs). The related properties of Rnps facilitate the facile fabrication of multimaterial, heterogeneous, and cell-laden biomimetic constructs with intricate structures. The developed photoinhibitor, with its profound adaptability, promises wide biomedical applications tailored to specific biological requirements.

A feasible strategy of Ag nanoparticles-sodium alginate-polyacrylamide-polyvinyl alcohol hydrogel coatings for preventing catheter-associated urinary tract infections

Catheter-associated urinary tract infections (CAUTIs) pose a significant clinical challenge, potentially resulting in complications such as bacteriuria and mortality. Developing coatings with antibacterial and antiadhesive properties for urinary catheters is essential to address these issues. In this study, a novel hydrogel coating composed of silver nanoparticles (Ag NPs), sodium alginate (SA), polyacrylamide (PAAm), and polyvinyl alcohol (PVA) was prepared on polydopamine (PDA)-modified latex urinary catheters using a simple dipping method. The Ag NPs were synthesized via an in-situ reduction of AgNO3 with SA, eliminating the need for additional chemical reductants. The Ag NPs-SA-PAAm-PVA hydrogel-coated urinary catheter demonstrated superior antibacterial and antiadhesive characteristics compared to the bare urinary catheter. The antiadhesive properties of the hydrogel-coated urinary catheter were attributed to its hydrophilicity and lubricity, while the antibacterial effects were linked to the penetration of Ag NPs and Ag+ ions into bacterial structures, disrupting bacterial metabolism through the generation of reactive oxygen species (ROS) and free radicals upon attachment of Ag+ ions to cell walls and membranes. Furthermore, the hydrogel coatings exhibited remarkable mechanical properties, along with good biocompatibility and hemocompatibility. The exceptional antibacterial and antiadhesive properties of the hydrogel-coated urinary catheter hold promise for reducing CAUTIs.

A Reciprocal Relationship between Oxidative Stress, Antioxidants, and Cancer: A Review

Oxidative stress is a defense mechanism that occurs when there is an imbalance between the production of reactive metabolites and free radicals and the antioxidants' ability to eliminate them. Reactive metabolites are free radicals referred to as oxidants or reactive oxygen species (ROS). Cells are harmed by this imbalance, which may influence the entire body. When the intra- and extracellular environmental circumstances in cells change, ROS is essential for stimulating the corresponding signaling pathways. All aspects of carcinogenesis, including prevention and treatment, are tightly associated with reactive species, particularly ROS. Numerous tumor suppressor genes and proto-oncogenes are deregulated by ROS, which also modify several cellular signaling pathways. However, most chemotherapy drugs and even radiation therapy dramatically raise the ROS concentrations in the tumor microenvironment. Antioxidants cause programmed cell death, which is used in cancer treatment; yet people receiving chemotherapy benefit from antioxidants. Nevertheless, the exact processes underlying this anticancer action remain unclear. Many studies carried out in laboratories and on animals revealed high concentrations of exogenic antioxidants, that inhibit the forms of free radical injury linked with the formation of cancer. There haven't been many human clinical trials looking into the potential of dietary supplementation to reduce the risk of cancer development or death. Since there have been studies on the advantages and downsides of antioxidants in the treatment of cancer, several considerations need to be deemed before administering antioxidant supplements. In conclusion, little is known about the mechanism underlying antioxidant effect in cancer treatment.

Nitrogen-Rich Covalent Organic Polymer for Metal-Free Tandem Catalysis and Postmetalation-Actuated High-Performance Water Oxidation.

Development of high-performing catalytic materials for selective and mild chemical transformations through adhering to the principles of sustainability remains a central focus in modern chemistry. Herein, we report the template-free assembly of a thermochemically robust covalent organic polymer (COP: 1) from 2,2'-bipyridine-5,5'-dicarbonyl dichloride and 2,4,6-tris(4-aminophenyl)triazine as [2 + 3] structural motifs. The two-dimensional (2D) layered architecture contains carboxamide functionality, delocalized π-cloud, and free pyridyl-N site-decked pores. Such trifunctionalization benefits this polymeric network exhibiting tandem alcohol oxidation-Knoevenagel condensation. In contrast to common metal-based catalysts, 1 represents a one of a kind metal-free alcohol oxidation reaction via extended π-cloud delocalization-mediated free radical pathway, as comprehensively supported from diverse control experiments. In addition to reasonable recyclability and broad substrate scope, the mild reaction condition underscores its applicability in benign synthesis of valuable product benzylidene malononitrile. Integration of 2,2'-bipyridyl units in this 2D COP favors anchoring non-noble metal ions to devise 1-M (M: Ni2+/ Co2+) that demonstrate outstanding electrochemical oxygen evolution reaction in alkaline media with high chronoamperometric stability. Electrochemical parameters of both 1-Co and 1-Ni outperform some benchmark, commercial, as well as a majority of contemporary OER catalysts. Specifically, the overpotential and Tafel slope (280 mV, 58 mV/dec) for 1-Ni is better than 1-Co (360 mV, 78 mV/dec) because of increased charge accumulation as well as a higher number of active sites compared to the former. In addition, the turnover frequency of 1-Ni is found to be 6 times higher than that of 1-Co and ranks among top-tier water oxidation catalysts. The results provide valuable insights in the field of metal-free tandem catalysis as well as promising electrochemical water splitting at the interface of task-specific functionality fuelling in polymeric organic networks.

Chitosan-derived N-doped carbon supported Cu/Fe co-doped MoS2 nanoparticles as peroxymonosulfate activator for efficient dyes degradation

Peroxymonosulfate (PMS), which is dominated by free radical (SO4•-) pathway, has a good removal effect on organic pollutants in complex water matrices. In this article, a new catalyst (CFM@NC) was synthesized by hydrothermal carbonization method with chitosan (CS) as N and C precursors, and used to activate PMS to degrade dye wastewater. CFM@NC/PMS system can degrade 50 mg·L−1 rhodamine B by 99.59 % within 30 min, and the degradation rate remains as high as 97.32 % after 5 cycles. It has good complex background matrices, acid-base anti-interference ability (pH 2.6–10.1), universality and reusability. It can degrade methyl orange and methylene blue by >98 % within 30 min. The high efficiency of the composite is due to the fact that CS-modified MoS2 as a carrier exposes a large number of active sites, which not only disperses CuFe2O4 nanoparticles and improves the stability of the catalyst, but also provides abundant electron rich groups, which promotes the activation of PMS and the production of reactive oxygen species (ROS). PMS is effectively activated by catalytic sites (Cu+/Cu2+, Fe2+/Fe3+, Mo4+/Mo6+, pyridine N, pyrrole N, edge sulfur and hydroxyl group) to produce a large number of radicals to attack RhB molecules, causing chromophore cleavage, ring opening, and mineralization. Among them, free radical SO4•- is the main ROS for RhB degradation. This work is expected to provide a new idea for the design and synthesis of environmentally friendly and efficient heterogeneous catalysts.

The Effect of Fermentation Time Variation on Antioxidant Activity of Fermented Robusta Coffee Leaves (Coffea canephora Pierre ex A.Froehner) Brew

Antioxidants are electron-donor compounds that can delay, slow down and prevent free radical reactions. Fermentation is a chemical change that occurs due to the activity of microorganisms which can increase the amount of phenols in tea thereby increasing its antioxidant activity. Fermentation is carried out with the help of a Symbiotic Culture of Bacteria and Yeast (SCOBY) culture, which is commonly used in the production of kombucha. Kombucha is a fermented tea drink produced from leaves that contain high phenols such as robusta coffee leaves (Coffea canephora Pierre ex A.Froehner). Factors that affect the fermentation process are pH and fermentation time. This study aimed to explain the effect of fermentation time on the antioxidant activity of fermented robusta coffee leaves brew. Brewed robusta coffee leaves were made by brewing robusta coffee leaves simplicia powder, adding kombucha liquid starter, then fermented for 0; 3; 7; 14; and 21 days, then pH and antioxidant activity was measured using UV-Visible spectrophotometer using the 2,2-dipheny-1,1-picrylhydrazyl (DPPH) at a wavelength of 516 nm. This study showed that 0; 3; 7; 14; and 21 days fermented robusta coffee leaves brew have pH of 6,07; 4,62; 4,07; 3,21; and 2,74, and IC50 values is 285,1645 μg/ml; 219,7012 μg/ml; 192,2325 μg/ml; 187,0434 μg/ml; and 173,9249 µg/ml. There is an effect of fermentation time variation on the antioxidant activity of fermented robusta coffee leaves brew. Keyword: Antioxidant, Fermentation, pH, Robusta coffee leaves, Time variation

TBuOK/TMSOK‐Mediated “Alkyl Halide to Alkyl Free Radical” Transformation for Transition‐Metal‐Free Benzoin α‐C—H Alkylation

Comprehensive SummaryThe alkali tert‐butoxide (tBuOK or tBuONa) mediated generation of aryl free radical from aryl iodide remarks a milestone discovery in the free radical chemistry. However, the equivalent “alkyl halide to alkyl free radical” transformation has not yet been realized in applicable synthesis by similar catalytic tactic. In this paper, the first practical “alkyl halide to alkyl free radical” transformation mediated by tBuOK or TMSOK in the direct α‐C—H alkylation of benzoins is presented. As the parallelly significant issue as aryl free radical generation, the current work, while bringing a rather facile and useful new approach for the synthesis of diverse benzoins, represents also an important step in the alkyl free radical‐based synthesis by displaying the higher generality of simple alkali base mediated radical formation.

Operando Raman Spectroscopy Reveals Degradation Byproducts from Ionomer Oxidation in Anion Exchange Membrane Water Electrolyzers.

This work showcases the discovery of degradation mechanisms for nonplatinum group metal catalyst (PGM free) based anion exchange membrane water electrolyzers (AEMWE) that utilize hydroxide ion conductive polymer ionomers and membranes in a zero gap configuration. An entirely unique and customized test cell was designed from the ground up for the purposes of obtaining Raman spectra during potentiostatic operation. These results represent some of the first operando Raman spectroscopy explorations into the breakdown products that are generated from high oxidative potential conditions with carbonate electrolytes. We provide a unique design and fabrication method for three-dimensional (3D) printable flow cells that enable spatially resolved Raman spectra collection from the electrode surface into the bulk electrolyte. It is proposed that the generation of breakdown products from the hydroxide-conductive ionomers and membranes originates from a multistep, free radical reaction pathway resulting in chain scission of the poly aryl backbone. This hypothesis is backed by the detection of carboxylic and aromatic functional group Raman signals from small molecules that had dissolved and diffused into the bulk electrolyte.

Charge carrier controlled free radical construction efficient photocatalytic self-Fenton system

The photocatalytic self-Fenton technology has demonstrated unique advantages in the low-cost and efficient removal of environmental pollutants. Designing an efficient photocatalytic self-Fenton system (PSFs) to enhance the synergistic effect between photocatalytic H2O2 production and pollutant mineralization processes, as well as understanding the regulatory mechanism of free radical reactions in this process, are crucial for advancing this technology. In this study, an efficient PSFs was developed by coating COFs (TpPa-1) onto the surface of MXene (Ti3C2). Under visible light irradiation, the generation rate of H2O2 reached 983.9 μmol·g−1·h−1, which is 9 times that of pure TpPa-1. Additionally, this led to a significant increase in the removal rate of sulfamethoxazole (SMX) from 25 % to 92 % within 100 min. Photoelectrochemical tests and density functional theory (DFT) calculations confirmed that the incorporation of Ti3C2 not only facilitates efficient charge carrier transport but also enhances the generation of hydroxyl radicals (·OH) and the production of H2O2, thereby improving the photocatalytic self-Fenton removal efficiency of SMX. This research is expected to have a positive impact on the development of efficient PSFs.

Progress of metal-loaded biochar-activated persulfate for degradation of emerging organic contaminants.

In recent years, studies on the degradation of emerging organic contaminants by sulfate radical (SO4-·) based advanced oxidation processes (SR-AOPs) have triggered increasing attention. Metal-loaded biochar (Me-BC) can effectively prevent the agglomeration and leaching of transition metals, and its good physicochemical properties and abundant active sites induce outstanding in activating persulfate (PS) for pollutant degradation, which is of great significance in the field of advanced oxidation. In this paper, we reviewed the preparation method and stability of Me-BC, the effect of metal loading on the physicochemical properties of biochar, the pathways of pollutant degradation by Me-BC-activated PS (including free radical pathways: SO4-·, hydroxyl radical (·OH), superoxide radicals (O2-·); non-free radical pathways: singlet oxygen (1O2), direct electron transfer), and discussed the activation of different active sites (including metal ions, persistent free radicals, oxygen-containing functional groups, defective structures, etc.) in the SR-AOPs system. Finally, the prospect was presented for the current research progress of Me-BC in SR-AOPs technology.

Effects of sodium ions on the tribological and antioxidation properties of borates

A borate ester (BMBS) and its sodium salts (BMBSNa) were synthesized and used as multifunctional lubricant additives in oleic acid. Results showed that BMBSNa possessed better anti-oxidation and tribological properties than BMBS. Worn surfaces analysis revealed that BMBSNa was more favorable to forming boundary film containing h-BN and FeS. Theoretical calculation suggested that BMBSNa had a higher chemical reactivity and better metal adsorption ability than BMBS. Fukui indices showed that sodium ions favor free radical reaction. Radial distribution functions (RDF) indicated that sodium ions help the adsorption of BMBSNa on the iron surface. It can be concluded that sodium ions benefit the oxidation resistance of base oil, and contribute to forming good boundary lubrication film to achieve good tribological properties.

Weak magnetic effect and free radical reaction mechanism on the dissolution of lightweight magnesia in CaO–Al2O3–SiO2 melts

Lightweight magnesia-based refractories play a crucial role in achieving energy savings and carbon reduction in steelmaking furnaces. The primary requirement is to make lightweight magnesia refractories with high corrosion resistance. The introduction of a weak static magnetic field is also a promising way to improve the slag resistance of lightweight refractories in addition to optimizing the composition and structure of the refractories. In this paper, the dissolution behavior of the lightweight magnesia in CaO–Al2O3–SiO2 molten slags at and above 1600 °C under weak static magnetic field is presented. The influence of the weak static magnetic field on the dissolution rate was analyzed, the behavior from the perspective of free radical and kinetics was discussed, and the influence of different calcia–silica weight ratios (C/S) on slag, magnetic flux density and the reaction mechanism are revealed. The results show that the dissolution rate of the lightweight magnesia in the molten slag presents a significantly weak magnetic effect, with a reaction inhibition interval of 2–4 mT in the range of 0–16 mT magnetic field intensity, and the key inhibition threshold surpasses that of alumina. The mechanism of the free radical formation and reaction during magnesia dissolution in high-temperature slag is explained and illustrated. The relationship between the magnetic flux density, superoxide radical content, and dissolution rate is presented, providing theoretical guidance for developing magnetic combined magnesia refractories.