Ozonolysis of ketoprofen in polluted water: Reaction pathways, kinetics, removal efficiency, and health effects.

Ketoprofen (KET), as a non-steroidal anti-inflammatory drug frequently detected in aqueous environments, is a threat to human health due to its accumulation and low biodegradability, which requires the transformation and degradation of KET in aqueous environments. In this paper, the reaction process of ozone-initiated KET degradation in water was investigated using density functional theory (DFT) method at the M06-2X/6-311++g(3df,2p)//M06-2X/6-31+g(d,p) level. The detailed reaction path of KET ozonation is proposed. The thermodynamic results show that ozone-initiated KET degradation is feasible. Under ultraviolet irradiation, the reaction of ozone with water can also produce OH radicals (HO·) that can react with KET. The degradation reaction of KET caused by HO· was further studied. The kinetic calculation illustrates that the reaction rate (1.99 × 10-1 (mol/L)-1 sec-1) of KET ozonation is relatively slow, but the reaction rate of HO· reaction is relatively high, which can further improve the degradation efficiency. On this basis, the effects of pollutant concentration, ozone concentration, natural organic matter, and pH value on degradation efficiency under UV/O3 process were analyzed. The ozonolysis reaction of KET is not sensitive to pH and is basically unaffected. Finally, the toxicity prediction of oxidation compounds produced by degradation reaction indicates that most of the degradation products are harmless, and a few products containing benzene rings are still toxic and have to be concerned. This study serves as a theoretical basis for analyzing the migration and transformation process of anti-inflammatory compounds in the water environment.

Hydroxyl radicals dominated the reduction of antibiotic resistance genes by inactivating Gram-negative bacteria during soil electrokinetic treatment.

Antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) are emerging contaminants that widely exist in the environment. Effective reduction of ARB and ARGs from soil and water could be achieved by electrokinetic remediation (EKR) technology. In water, hydroxyl radicals (·OH) are proved to play a major role in the EKR process; while the reduction mechanism of ARB and ARGs is still unclear in soil. In this study, different concentrations of hydroxyl radical scavengers (salicylic acid) were added to the EKR system to explore the possible role of ·OH in the reduction of ARB and ARGs. The results showed that generally, ·OH played a more vital role in the reduction of ARB (65.24-72.46%) compared to the reduction of total cultivable bacteria (57.50%). And ·OH contributed to a higher reduction of sul genes (60.94%) compared to tet genes (47.71%) and integrons (36.02%). It was found that the abundance of Gram-negative bacteria (Chloroflexi, Acidobacteria and norank_c_Acidobacteria) was significantly reduced, and the correlation between norank_f_Gemmatimonadaceae and sul1 was weakened in the presence of ·OH. Correlation analysis indicated that the abundance of ARGs (especially sul1) was closely related to the Gram-negative bacteria (Proteobacteria, Acidobacteria, and Gemmatimonadetes) in the soil EKR treatment. Moreover, changes in bacterial community structure affected the abundance of ARB and ARGs indirectly. Overall, this study revealed the reduction mechanism of ARB and ARGs by ·OH in the soil EKR system for the first time. These findings provide valuable support for soil remediation efforts focusing on controlling antibiotic resistance.

Biomonitoring of Heavy Metal Toxicity in Freshwater Canals in Egypt Using Creeping Water Bugs (Ilyocoris cimicoides): Oxidative Stress, Histopathological, and Ultrastructural Investigations.

The abundance of metal pollutants in freshwater habitats poses serious threats to the survival and biodiversity of aquatic organisms and human beings. This study intends for the first time to assess the pernicious influences of heavy metals in Al Marioteya canal freshwater in Egypt, compared to Al Mansoureya canal as a reference site utilizing the creeping water bug (Ilyocoris cimicoides) as an ecotoxicological model. The elemental analysis of the water showed a significantly higher incidence of heavy metals, including cadmium (Cd), cobalt (Co), chromium (Cr), nickel (Ni), and lead (Pb), in addition to the calcium (Ca) element than the World Health Organization's (WHO) permitted levels. The Ca element was measured in the water samples to determine whether exposure to heavy metals-induced oxidative stress engendered Ca deregulation in the midgut tissues of the creeping water bug. Remarkably, increased levels of these heavy metals were linked to an increase in chemical oxygen demand (COD) at the polluted site. Notably, the accumulation of these heavy metals in the midgut tissues resulted in a substantial reduction in antioxidant parameters, including superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), and ascorbate peroxidase (APOX), along with a marked rise in malondialdehyde (MDA), cytochrome P450, and protein carbonyl levels. These results clearly indicate a noticeable disturbance in the antioxidant defense system due to uncontrollable reactive oxygen species (ROS). Notably, the results demonstrated that oxidative stress caused disturbances in Ca levels in the midgut tissue of I. cimicoides from polluted sites. Furthermore, the comet and flow cytometry analyses showed considerable proliferations of comet cells and apoptotic cells in midgut tissues, respectively, exhibiting prominent correlations, with pathophysiological deregulation. Interestingly, histopathological and ultrastructural examinations exposed noticeable anomalies in the midgut, Malpighian tubules, and ovarioles of I. cimicoides, emphasizing our findings. Overall, our findings emphasize the potential use of I. cimicoides as a bioindicator of heavy metal pollution in freshwater to improve sustainable water management in Egypt.

The Effects of Maca (Lepidium meyenii Walp) on Cellular Oxidative Stress: A Systematic Review and Meta-Analysis.

Lepidium meyenii Walp (LmW) or Maca, including its bioactive components such as macamides, among others, has demonstrated antioxidant effects. However, the effect size (ES) of LmW on oxidative stress has not been qualitatively described and calculated. The primary objective of this systematic review and meta-analysis was to review and qualitatively describe the studies published up to 2023 that supplemented LmW to control cellular oxidative stress; the secondary objective was to calculate the ES of the different interventions. The search was designed following the PRISMA® guidelines for systematic reviews and meta-analyses and performed in the Web of Science, Scopus, SPORTDiscus, PubMed, and MEDLINE until 2023. The selection of studies included randomized controlled trials, with tests and post-tests, both in vitro and in vivo in animals and humans. The methodological quality and risk of bias were evaluated with the CAMARADES tool. The main variables were reduced glutathione, glutathione peroxidase, superoxide dismutase, and malondialdehyde. The analysis was conducted with a pooled standardized mean difference (SMD) through Hedges' g test (95% CI). Eleven studies were included in the systematic review and eight in the meta-analysis. They revealed a small effect for reduced glutathione (SMD = 0.89), a large effect for glutathione peroxidase (SMD = 0.96), a moderate effect for superoxide dismutase (SMD = 0.68), and a moderate effect for malondialdehyde (SMD = -0.53). According to the results, the phytochemical compounds of LmW effectively controlled cellular oxidative stress, mainly macamides. It was also determined that a higher dose of LmW generated a greater antioxidant effect. However, information concerning humans is scarce.

Effect of UV Radiation and Temperature on Radical Scavenging Activity of Hippophaë rhamnoides L. and Vaccinium oxycoccos L. Fruit Extracts.

New active ingredients, including those of plant origin, which could protect the skin against various harmful factors, such as UV radiation and free radicals responsible for skin ageing, are still being sought. The present study was focused on the antioxidant activity of Hippophaë rhamnoides L. and Vaccinium oxycoccos L. fruit glycolic extracts. Investigations were also carried out to evaluate the effect of UVA radiation and the storage of the sea buckthorn and European cranberry extracts at an elevated temperature of 50 °C on their interactions with free radicals. The kinetics of the interactions of the extracts with DPPH were assessed using electron paramagnetic resonance (EPR) spectroscopy. The sea buckthorn and European cranberry extracts quench the EPR signal of DPPH free radicals, which indicates their antioxidant potential. The EPR method further showed that a mixture of sea buckthorn and cranberry extracts in a volume ratio of 2:1 was more potent in quenching free radicals compared to a mixture of these extracts in a ratio of 1:2. Our findings demonstrate that long-term UVA radiation exposure reduces the ability of sea buckthorn and cranberry extracts to interact with free radicals. Moreover, storage at elevated temperatures does not affect the interaction of sea buckthorn extract with free radicals, while it alters the ability of cranberry extract to interact with free radicals. This study has demonstrated that an important factor in maintaining the ability to scavenge radicals is the storage of raw materials under appropriate conditions. H. rhamnoides and V. oxycoccos extracts can be used as valuable raw materials with antioxidant properties in the pharmaceutical and cosmetic industries.

Changes in Electron Paramagnetic Resonance Parameters Caused by Addition of Amphotericin B to Cladosporium cladosporioides Melanin and DOPA-Melanin-Free Radical Studies.

Cladosporium cladosporioides are the pigmented soil fungi containing melanin. The aim of this work was to determine the influence of amphotericin B on free radicals in the natural melanin isolated from pigmented fungi Cladosporium cladosporioides and to compare it with the effect in synthetic DOPA-melanin. Electron paramagnetic resonance (EPR) spectra were measured at X-band (9.3 GHz) with microwave power in the range of 2.2-70 mW. Amplitudes, integral intensities, linewidths of the EPR spectra, and g factors, were analyzed. The concentrations of free radicals in the tested melanin samples were determined. Microwave saturation of EPR lines indicates the presence of pheomelanin in addition to eumelanin in Cladosporium cladosporioides. o-Semiquinone free radicals in concentrations ~1020 [spin/g] exist in the tested melanin samples and in their complexes with amphotericin B. Changes in concentrations of free radicals in the examined synthetic and natural melanin point out their participation in the formation of amphotericin B binding to melanin. A different influence of amphotericin B on free radical concentration in Cladosporium cladosporioides melanin and in DOPA-melanin may be caused by the occurrence of pheomelanin in addition to eumelanin in Cladosporium cladosporioides. The advanced spectral analysis in the wide range of microwave powers made it possible to compare changes in the free radical systems of different melanin polymers. This study is important for knowledge about the role of free radicals in the interactions of melanin with drugs.

Light Emission from Fe2+-EGTA-H2O2 System Depends on the pH of the Reaction Milieu within the Range That May Occur in Cells of the Human Body.

A Fe2+-EGTA(ethylene glycol-bis (ß-aminoethyl ether)-N,N,N',N'-tetraacetic acid)-H2O2 system emits photons, and quenching this chemiluminescence can be used for determination of anti-hydroxyl radical (•OH) activity of various compounds. The generation of •OH and light emission due to oxidative damage to EGTA may depend on the buffer and pH of the reaction milieu. In this study, we evaluated the effect of pH from 6.0 to 7.4 (that may occur in human cells) stabilized with 10 mM phosphate buffer (main intracellular buffer) on a chemiluminescence signal and the ratio of this signal to noise (light emission from medium alone). The highest signal (4698 ± 583 RLU) and signal-to-noise ratio (9.7 ± 1.5) were noted for pH 6.6. Lower and higher pH caused suppression of these variables to 2696 ± 292 RLU, 4.0 ± 0.8 at pH 6.2 and to 3946 ± 558 RLU, 5.0 ± 1.5 at pH 7.4, respectively. The following processes may explain these observations: enhancement and inhibition of •OH production in lower and higher pH; formation of insoluble Fe(OH)3 at neutral and alkaline environments; augmentation of •OH production by phosphates at weakly acidic and neutral environments; and decreased regeneration of Fe2+-EGTA in an acidic environment. Fe2+-EGTA-H2O2 system in 10 mM phosphate buffer pH 6.6 seems optimal for the determination of anti-•OH activity.

Activated carbon fiber loaded nano zero-valent iron for Microcystis aeruginosa removal: Performance and mechanisms.

Cyanobacterial blooms caused by Microcystis aeruginosa threaten environmental safety and daily life. In this study, an activated carbon fiber-supported nano zero-valent iron composite (ACF-nZVI) was developed to remove Microcystis aeruginosa. The results showed that nZVI was evenly distributed on the activated carbon fibers, preventing aggregation and oxidation. ACF-nZVI achieved a removal efficiency of more than 90 % within a pH range of 3-7. During the reaction, H2O2, which was generated by Fe0, was activated to form ·OH and ·O-2, which dismantled antioxidant enzymes and induced lipid peroxidation. Additionally, ACF-nZVI destroyed the cell wall and membrane, resulting in protein and humus leakage and causing 92.34 % cell damage and death. In this study, an environmentally friendly and stable nanomaterial was developed, offering a novel approach for the safe, cost-effective, and efficient removal of cyanobacteria.

A free radical interlocking co-deposition strategy based on the oxidative pyrolysis mechanism of polyethylene terephthalate to achieve green energy recovery.

Accidental combustion and energy recovery of polyethylene terephthalate (PET) result in the formation of harmful organic substances and excessive emissions of CO2 and CO. This paper presents our recent efforts to unravel the formation mechanism of these harmful substances during the PET combustion process using thermal analysis and simulation calculations (DFT, CDFT, and ReaxFF). Our findings reveal that PET oxidative pyrolysis produces free radicals, harmful small molecule gases, and CO2. The interaction between aromatic free radicals and oxygen initiates unstable peroxy bonds, triggering uncontrollable chain exothermic reactions and producing oxygenated polycyclic aromatic hydrocarbon (OPAH) precursors. We propose a straightforward and eco-friendly free radical interlocking co-deposition inhibition strategy for PET by incorporating polycarbonate (PC). This strategy aims to facilitate green energy recovery by curbing OPAH formation and reducing CO2 and CO emissions during PET waste combustion. Our investigation into the oxidative pyrolysis of PET challenges conventional wisdom dominated by C-H bond fracture, paving the way for efficient, low-pollution green energy recovery.

Effect of Cl2 Radical on Dry Development of Spin-Coated Metal Oxide Resist.

In this study, the effects of Cl2 radicals on dry development of spin-coated metal oxide resist (MOR) and changes in its surface binding states were investigated to verify the mechanism of dry development. Dry development characteristics of tin hydroxide (Tin OH), which is one of the MOR candidates for next generation lithography, were investigated as functions of process time and temperature using a Cl2 radicals source. Non-UV-exposed Tin OH film showed a linear etch rate (1.77 nm/min) from the initial thickness of ∼50 nm, while the UV-exposed film showed slower etch behavior (1.46 nm/min) in addition to the increase of film thickness for up to 3 min during the Cl2 radical dry development. UV-exposed photoresist (PR) contained more oxygen (Sn-O bonding) in the film due to the removal of butyl compounds from the clusters during the UV exposure process. Therefore, due to the lower reaction of chlorine radicals with Sn-O in the UV-exposed Tin OH than the other bindings, the non-UV-exposed PR was preferentially removed compared to the UV-exposed PR. As the temperature decreases, the overall etch rate decreases, but the difference in etch rate between exposed and unexposed Tin OH becomes larger. Finally, at a substrate temperature of -20 °C, the non-UV-exposed Tin OH with a thickness of 50 nm was completely removed, while ∼30 nm thick PR remained for UV-exposed Tin OH. Eventually, a negative tone development was possible with Cl2 radical plasma due to the difference in activation energy between the UV-exposed and non-UV-exposed films. It is believed that dry development using Cl2 radicals will be one of the most important process techniques for next-generation patterning to remove problems such as pattern leaning, line edge roughness, residue, etc., caused by wet development.

Investigating In Silico and In Vitro Therapeutic Potential of Diosmetin as the Anti-Parkinson Agent.

AIM: This study aimed to investigate how diosmetin interacts with seven target receptors associated with oxidative stress (OS) and validate its antioxidant properties for the potential management of Parkinson's disease (PD). BACKGROUND: In PD, the degeneration of dopaminergic cells is strongly influenced by OS. This stressor is intricately connected to various mechanisms involved in neurodegeneration, such as mitochondrial dysfunction, neuroinflammation, and excitotoxicity induced by nitric oxide. OBJECTIVE: The aim of this research was to establish a molecular connection between diosmetin and OS-associated target receptors was the goal, and it investigated how this interaction can lessen PD. MATERIAL AND METHODS: Seven molecular targets - Adenosine A2A (AA2A), Peroxisome Proliferator- Activated Receptor Gamma (PPARγ), Protein Kinase AKT1, Nucleolar Receptor NURR1, Liver - X Receptor Beta (LXRß), Monoamine Oxidase - B (MAO-B) and Tropomyosin receptor kinase B (TrkB) were obtained from RCSB. Molecular docking software was employed to determine molecular interactions, while antioxidant activity was assessed through in-vitro assays against various free radicals. RESULTS: Diosmetin exhibited interactions with all seven target receptors at their binding sites. Notably, it showed superior interaction with AA2A and NURR1 compared to native ligands, with binding energies of -7.55, and -6.34 kcal/mol, respectively. Additionally, significant interactions were observed with PPARγ, AKT1, LXRß, MAO-B, and TrkB with binding energies of -8.34, -5.42, -7.66, -8.82, -8.45 kcal/mol, respectively. Diosmetin also demonstrated antioxidant activity against various free radicals, particularly against hypochlorous acid (HOCl) and nitric oxide (NO) free radicals. CONCLUSION: Diosmetin possibly acts on several target receptors linked to the pathophysiology of PD, demonstrating promise as an OS inhibitor and scavenger.

Theoretical investigation on the oxidation mechanism of methylglyoxal in the aqueous phase.

The oxidation mechanism of methylglyoxal (CH3COCHO) in the aqueous phase plays a crucial role in the formation of secondary organic aerosols (SOA). To date, the investigations of reaction mechanisms of MG in the aqueous phase still needs to be refined, and the oxidation mechanisms of MG in the existence of various oxidants (e.g., H2O2, O3, ∙NO3, etc.) are in controversy. In this paper, we investigated the hypothesis that small-molecule organic acids are the primary products in cloud water and fog droplets, while large-molecule organic acids and oligomers play crucial roles in wet aerosols. Specifically, the hydration reaction, oxidation mechanism and oligomerization reaction of MG in aqueous phase were investigated on a theoretical basis. It has been indicated that the hydration reaction is a significant initiating reaction of MG in the atmospheric aqueous phase, whose generated hydrated compounds played a critical part in the process of forming oligomers. The aqueous oxidation reaction of MG could form a variety of organic acids, including pyruvic acid, formic acid, acetic acid, and oxalic acid. In the presence of OH radicals, pyruvic acid was the main first-generation production, which undergoes further reactions to form acetic acid, oxalic acid, and mesoxalic acid. Acetic acid was mainly derived from the reaction of OH radicals with pyruvic acid, whereas oxalic and mesoxalic acids were mainly generated by the OH radical reaction for MG and pyruvic acid. Of these, the formation of acetic acid was thermodynamically most favorable. Additionally, the reactions of MG with other oxidants also provided the possible pathways for pyruvic acid production. At 298 K, we calculated the rate constants for the reaction of MGHY with NO3, OH, HO2 radicals, and O3 to be 4.48 × 108, 2.54 × 107, 1.26 × 10-2, and 4.38 × 10-4 M-1 s-1, with atmospheric aqueous phase lifetimes (τ) of 4.43, 3.12 × 103, 2.21 × 1011, and 3.17 × 108 h, respectively. The theoretical results from this work will facilitate the explanation for the MG reaction process in the aqueous phase so as to further correctly estimate the relationship between the aqueous phase chemistry of MG and the formation of SOA.

Phosphate ligand-mediated production of reactive oxygen species during oxygenation of Fe(II)-phosphate complexes.

Reactive oxygen species (ROS) production upon the oxygenation of reduced iron minerals is of critical importance to redox cycles of Fe and the fate of refractory organic contaminants. The environmental impact factors during this process, however, have been underappreciated. In this study, prominently enhanced production of hydroxyl radicals (•OH) was observed by oxygenation of Fe(II) with 5-50 mM phosphate. The results of spin trap electron spin resonance (ESR) experiment showed that Fe(II)-phosphate complexes facilitated the generation of •OH. The degradation experiment of p-nitrophenol (PNP) confirmed that •OH formation was dominated by a consecutive one-electron O2 reduction (90.2-96.9 %), and the quantification of PNP degradation products revealed that Fe(II)/phosphate molar ratios regulated the O2 activation pathways for O2•- or •OH production. The further experimental and theoretical investigation demonstrated that the coordination of phosphate with Fe(II) plays a dual role in ROS generation that facilitated O2•- formation by lowering the energy barrier for Fe(II) oxidation and altered the reaction pathway of •OH formation due to its occupation of sites for electron transfer. The present work highlights an important role of natural oxyanions in O2 activation by Fe(II) and raises the possibility of in situ degradation of contaminants in subsurface environment.

Reno-protective potential of sudachitin to mitigate paraquat instigated renal toxicity via regulating Nrf2/Keap1 pathway: An inflammatory, apoptotic and histopathological assessment.

This investigation was executed to assess the protective effects of SCN to counteract PQ instigated renal damage in albino rats (Rattus norvegicus). Twenty-four rats were apportioned in 4 different groups i.e., a control group, PQ (5mg/kg) intoxicated, PQ (5mg/kg) + SCN (20mg/kg) exposed & SCN (20mg/kg) only administrated group. Our findings explored that exposure to PQ lessened the expressions of Nrf2 and its cytoprotective genes while escalating the expression of keap1. Furthermore, PQ intoxication reduced the enzymatic activity of superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GSR), & glutathione (GSH), while upregulating the levels of malondialdehyde (MDA) & reactive oxygen species (ROS). Moreover, intoxication to PQ significantly increased the levels of neutrophil gelatinous-associated lipocalin (NGAL), urea, kidney injury molecule-1(KIM-1) as well as creatine while reducing creatine clearance. Additionally, exposure to PQ upregulated the levels of inflammatory markers including interleukin-6 (IL-6), tumor necrosis- α (TNF- α), nuclear factor- κB (NF-κB), interleukin 1beta (IL-1ß), & cyclo-oxygenase-2 (COX-2). Moreover, PQ administration upregulated the expression of Bax and Caspase-3 while downregulating the expressions of Bcl-2. Besides, PQ exposure prompted various histopathological damages in renal tissues. Nonetheless, SCN substantially restored aforementioned alterations in renal tissues owing to its anti-oxidative, anti-inflammatory and anti-apoptotic potential.

Lipid radicals and oxidized cholesteryl esters in low- and high-density lipoproteins in patients with ß-thalassemia: Effects of iron overload and iron chelation therapy.

Iron overload results in lipid peroxidation (LPO) and the oxidative modification of circulating lipoproteins, which contributes to cardiovascular complications in patients with ß-thalassemia. Investigating LPO may provide opportunities for the development of novel therapeutic strategies; however, the chemical pathways underlying iron overload-induced LPO in ß-thalassemia lipoproteins remain unclear. In this study, we identified various species of lipid radicals (L•), the key mediators of LPO, and oxidized cholesteryl esters (oxCE) derived from the in vitro oxidation of major core lipids, cholesteryl linoleate (CE18:2) and cholesteryl arachidonate (CE20:4); the levels of these radical products in low-density lipoproteins (LDL) and high-density lipoproteins (HDL) were measured and compared between ß-thalassemia patients and healthy subjects by using a specific fluorescent probe for L• with a liquid chromatography-tandem mass spectrometric method. Our results demonstrated that iron overload substantially decreased the levels of CE18:2 and CE20:4 substrates and α-tocopherol, resulting in higher levels of full-length and short-chain truncated L• and oxCE products. In particular, CE epoxyallyl radicals (•CE-O) were observed in the lipoproteins of ß-thalassemia, revealing the pathological roles of iron overload in the progression of LPO. In addition, we found that intermission for two weeks of iron chelators can increase the production of these oxidized products; therefore, suggesting the beneficial effects of iron chelators in preventing LPO progression. In conclusion, our findings partly revealed the primary chemical pathway by which the LPO of circulating lipoproteins is influenced by iron overload and affected by iron chelation therapy. Moreover, we found that •CE + O shows potential as a sensitive biomarker for monitoring LPO in individuals with ß-thalassemia.

Unveiling chlorine's role: How it shapes the formation and light-activated oxygen dynamics of chlorophenol-derived environmental persistent free radicals.

Environmental persistent free radicals (EPFRs) derived from chlorophenols, triggered by light or heat exposure, pose significant ecological concerns, yet the impact of chlorine substituents on EPFRs formation and reactivity remains inadequately understood. Through an intentional synthesis of chlorophenol-derived EPFRs with varying chlorine contents and positioning, we elucidated the role of chlorine in the photoactivation of molecular oxygen. Our combined experimental and theoretical analysis reveals that these EPFRs are primarily oxygen-centered phenoxy radicals, establishing a direct link between chlorine substitution patterns and their ability to activate molecular oxygen under visible light. Increased chlorine content enhances EPFRs formation by elevating the positive charge on the phenolic hydroxyl group's hydrogen atom, facilitating its removal. Moreover, the capability of EPFRs to activate molecular oxygen was directly correlated with chlorine content, with 2,3,5,6-tetrachlorophenol-derived EPFRs showcasing the highest activity. This activity is attributed to their structural propensity for TCSQ·- species generation. Furthermore, our study established a significant correlation between the toxicity and activity of EPFRs, emphasizing the critical role of halogen substituents in determining the reactivity of EPFRs. These insights contribute to our understanding of their environmental and toxicological ramifications, underscoring the imperative for continued research aimed at mitigating their detrimental impacts.

Recent Applications of Sulfonium Salts in Synthesis and Catalysis.

The use of sulfonium salts in organic synthesis has experienced a dramatic increase during the last years that can arguably be attributed to three main factors; the development of more direct and efficient synthetic methods that make easily available sulfonium reagents of a wide structural variety, their intrinsic thermal stability, which facilitates their structural modification, handling and purification even on large scale, and the recognition that their reactivity resembles that of hypervalent iodine compounds and therefore, they can be used as replacement of such reagents for most of their uses. This renewed interest has led to the improvement of already existing reactions, as well as to the discovery of unprecedented transformations; in particular, by the implementation of photocatalytic protocols. This review aims to summarize the most recent advancements on the area focusing on the work published during and after 2020. The scope of the methods developed will be highlighted and their limitations critically evaluated.

The mechanism of UV accelerated aging of polyvinyl chloride in marine environment: The role of free radicals.

This study systematically investigated the photo-aging of polyvinyl chloride (PVC) in deionized water, estuary water, and seawater. As the concentration of Cl- increases, the carbonyl index (CI) of PVC during photo aging also increases, indicating that Cl- plays a dominant role in PVC photoaging in the environment, which enhance carbonyl index and •OH radical accumulation. Unlike previous studies, this study discovered that halogen radicals were also generated during PVC aging. Compared to •OH radicals, halogen radicals exhibit stronger selectivity and are more conducive to the photo aging of PVC. Additionally, it was found that PVC shows specific toxicity to Paramecia caudatum at various concentrations both before and after aging, affecting the reproduction process of Paramecia caudatum. This study elucidates the mechanism by which anions in natural water bodies affect the rate of PVC aging, providing a scientific basis for understanding the photodegradation of MPs in the ocean.

Highly Efficient Near-Infrared Luminescent Radicals with Emission Peaks over 750 nm.

Purely organic molecules exhibiting near-infrared (NIR) emission possess considerable potential for applications in both biological and optoelectronic technological domains, owing to their inherent advantages such as cost-effectiveness, biocompatibility, and facile chemical modifiability. However, the repertoire of such molecules with emission peaks exceeding 750 nm and concurrently demonstrating high photoluminescence quantum efficiency (PLQE) remains relatively scarce due to the energy gap law. Herein, we report two open-shell NIR radical emitters, denoted as DMNA-Cz-BTM and DMNA-PyID-BTM, achieved through the strategic integration of a donor group (DMNA) onto the Cz-BTM and PyID-BTM frameworks, respectively. We found that the donor-acceptor molecular structure allows the two designed radical emitters to exhibit a charge-transfer excited state and spatially separated electron and hole levels with non-bonding characteristics. Thus, the high-frequency vibrations are effectively suppressed. Besides, the reduction of low-frequency vibrations is observed. Collectively, the non-radiative decay channel is significantly suppressed, leading to exceptional NIR PLQE values. Specifically, DMNA-Cz-BTM manifests an emission peak at 758 nm alongside a PLQE of 55%, whereas DMNA-PyID-BTM exhibits an emission peak at 778 nm with a PLQE of 66%. Notably, these represent the pinnacle of PLQE among metal-free organic NIR emitters with emission peaks surpassing 750 nm.

Radical-Based Enantioconvergent Reductive Couplings of Racemic Allenes and Aldehydes.

Transition metal-catalyzed radical-based enantioconvergent reactions have become a powerful strategy to synthesize enantiopure compounds from racemic starting materials. However, existing methods primarily address precursors with central chirality, neglecting those with axial chirality. Herein, we describe the enantioconvergent reductive coupling of racemic allenes with aldehydes, facilitated by a photoredox, chromium, and cobalt triple catalysis system. This method selectively affords one product from sixteen possible regio- and stereoisomers. The protocol leverages CoIII-H mediated hydrogen atom transfer (MHAT) and Cr-catalyzed radical-polar crossover for efficient stereoablation of axial chirality and asymmetric addition, respectively. Supported by mechanistic insights from control experiments, deuterium labeling, and DFT calculations, our approach offers synthetic chemists a valuable tool for creating enantioenriched chiral homoallylic alcohols, promising to advance radical-based strategies for synthesizing complex chiral molecules.