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.

Cannabinoid 2 receptor activation protects against diabetic cardiomyopathy through inhibition of AGE/RAGE-induced oxidative stress, fibrosis, and inflammasome activation.

Oxidative stress, fibrosis, and inflammasome activation from AGE-RAGE interaction contribute to diabetic cardiomyopathy (DCM) formation and progression. Our study revealed the impact of ß-caryophyllene (BCP) on activating CB2 receptors against diabetes complications and investigated the underlying cell signaling pathways in mice. The murine model of DCM was developed by feeding high-fat diet with streptozotocin injections. After the development of diabetes, the animals received a 12-week oral BCP treatment at a dosage of 50 mg/kg/body weight. BCP treatment showed significant improvement in glucose tolerance, insulin resistance, and enhanced serum insulin levels in diabetic animals. BCP treatment effectively reversed the heart remodeling and restored the phosphorylated troponin I and SERCA2a expression. Ultrastructural examination showed reduced myocardial cell injury in DCM mice treated with BCP. The preserved myocytes were found associated with reduced expression of AGE/RAGE in DCM mice hearts. BCP treatment mitigated oxidative stress by inhibiting expression of NOX4 and activating PI3K/AKT/Nrf2 signaling. BCP suppressed cardiac fibrosis and endothelial-to-mesenchymal transition (EndMT) in DCM mice by inhibiting TGF-ß/Smad signaling. Further, BCP treatment suppressed NLRP3 inflammasome activation in DCM mice and alleviated cellular injury to the pancreatic tissues evidenced by significant elevation of the number of insulin-positive cells. To demonstrate CB2 receptor dependent mechanism of BCP, another group of DCM mice were pretreated with AM630, a CB2 receptor antagonist AM630 and AM630 was observed to abrogate the beneficial effects of BCP in DCM mice. Taken together, BCP showed the potential to protect the myocardium and pancreas of DCM mice mediating CB2 receptor dependent mechanisms. Significance Statement 1. ß-caryophyllene (BCP), a cannabinoid type 2 receptor (CB2R) agonist. 2. BCP attenuates diabetic cardiomyopathy via activating CB2R in mice 3. CB2R activation by BCP shows strong protection against fibrosis and inflammasome activation 4. It regulates AGE/RAGE and PI3K/Nrf2/Akt signaling in mice.

E-peroxone with a novel GDE decorated with hydrophobic membrane for the degradation of pyridine: Stability, byproducts and toxicity.

E-peroxone process is an emerging electrochemical oxidation process, based on ozone and the in-situ cathodic generation of H2O2, but the stability of cathode is one of the key restraining factors. In this study, we designed a multilayer gas diffusion electrode (GDE) decorated with a commercial hydrophobic membrane for the degradation of pyridine. It was found that a proper control of membrane pore sizes and hot-pressing temperature can significantly promote the GDE stability. Subsequently, key operational parameters of the constructed E-peroxone system were investigated, including the ozone concentration, current density, pH value, electrolyte type and initial concentration of pyridine. The degradation pathways were proposed according to six identified transformation products. The toxicity variation along the degradation progress was evaluated with microbial respiration tests and Toxicity Estimation Software Tool (T.E.S.T.) calculation and an efficient detoxification capacity of E-peroxone was observed. This research provides a theoretical basis and technical support for the development of highly efficient and stable E-peroxone system for the elimination of toxic organic contaminants.

PDK4-mediated Nrf2 inactivation contributes to oxidative stress and diabetic kidney injury.

Diabetic kidney disease (DKD) is often featured with redox dyshomeostatis. Pyruvate dehydrogenase kinase 4 (PDK4) is the hub for DKD development. However, the mechanism by which PDK4 mediates DKD is poorly understood. The current work aimed to elucidate the relationship between PDK4 and DKD from the perspective of redox manipulation. Oxidative stress was observed in the human proximal tubular cell line (HK-2 cells) treated with a high concentration of glucose and palmitic acid (HGL). The mechanistic study showed that PDK4 could upregulate Kelch-like ECH-associated protein 1 (Keap1) in HGL-treated HK-2 cells through the suppression of autophagy, resulting in the depletion of nuclear factor erythroid 2-related factor 2 (Nrf2), the master regulator of redox homeostasis. At the cellular level, pharmacological inhibition or genetic knockdown of PDK4 could boost Nrf2, followed by the increase of a plethora of antioxidant enzymes and ferroptosis-suppression enzymes. Meanwhile, the inhibition or knockdown of PDK4 remodeled iron metabolism, further mitigating oxidative stress and lipid peroxidation. The same trend was observed in the DKD mice model. The current work highlighted the role of PDK4 in the development of DKD and suggested that PDK4 might be a promising target for the management of DKD.

Enhancing heterogeneous Fenton-like catalysis through pyrrolidine modification of Fe2O3-CuO composites with oxygen-vacancy defects.

Enhancing the generation of reactive hydroxyl radicals (•OH) is crucial for overcoming the limitations of the low reactivity of heterogeneous Fenton Fe-based catalysts. Researchers have explored various methods to modify catalyst structures to enhance reactivity, yet often at the expense of stability. Herein, suitable carbon and nitrogen-codoped Fe2O3-CuO composites were synthesized via pyrolysis method, demonstrating high Fenton reaction activity and remarkable stability. Experimental findings and density functional theory calculations (DFT) revealed that the presence of oxygen vacancies on the catalyst surface facilitated an increase in exposed FeNC active sites, promoting electron transfer and the accelerating the rate of •OH generation. Moreover, carbon and nitrogen, particularly in the form of pyrrole nitrogen bonded to Fe imparted exceptional stability to the FeNC active sites, mitigating their dissolution. Additionally, the Fe-based catalysts exhibited strong magnetism, enabling easy separation from the reaction solution while maintaining a high degradation efficiency for various organic pollutants, even in the presence of multiple anions. Furthermore, a comprehensive mechanism for methylene blue (MB) degradation was identified, enhancing the potential practical applications of these catalysts.

Activation of peracetic acid by electrodes using biogenic electrons: A novel energy- and catalyst-free process to eliminate pharmaceuticals.

Peracetic acid (PAA) has received increasing attention as an alternative oxidant for wastewater treatment. However, existing processes for PAA activation to generate reactive species typically require external energy input (e.g., electrically and UV-mediated activation) or catalysts (e.g., Co2+), inevitably increasing treatment costs or introducing potential new contaminants that necessitate additional removal. In this work, we developed a catalyst-free, self-sustaining bioelectrochemical approach within a two-chamber bioelectrochemical system (BES), where a cathode electrode in-situ activates PAA using renewable biogenic electrons generated by anodic exoelectrogens (e.g., Geobacter) degrading biodegradable organic matter (e.g., acetic acid) in wastewater at the anode. This innovative BES-PAA technique achieved 98 % and 81 % removal of 2 µM sulfamethoxazole (SMX) in two hours at pH 2 (cation exchange membrane) and pH 6 (bipolar membrane) using 100 µM PAA without external voltage. Mechanistic studies, including radical quenching, molecular probe validation, electron spin resonance (ESR) experiments, and density functional theory (DFT) calculations, revealed that SMX degradation was driven by reactive species generated via biogenic electron-mediated OO cleavage of PAA, with CH3C(O)OO• contributing 68.1 %, •OH of 18.4 %, and CH3C(O)O• of 9.4 %, where initial formation of •OH and CH3C(O)O• rapidly reacts with PAA to produce CH3C(O)OO•. The presence of common water constituents such as anions (e.g., Cl-, NO3-, and H2PO4-) and humic acid (HA) significantly hinders SMX removal via the BES-PAA technique, whereas CO32- and HCO3- ions have a comparatively minor impact. Additionally, the study investigated the removal of various pharmaceuticals present in secondary treated municipal wastewater, attributing differences in removal efficiency to the selective action of CH3C(O)OO•. This research demonstrates a novel PAA activation method that is ecologically benign, inexpensive, and capable of overcoming catalyst deactivation and secondary pollution issues.

Efficient degradation of sulfadiazine by UV-triggered electron transfer on oxalic acid-functionalized corn straw biochar for activating peroxyacetic acid: Performance, mechanism, and theoretical calculation.

A novel UV/oxalic acid functionalized corn straw biochar (OCBC)/peroxyacetic acid (PAA) system was built to degrade sulfadiazine from waters. 94.7 % of SDZ was removed within 30 min by UV/OCBC/PAA. The abundant surface functional groups and persistent free radicals (PFRs) on OCBC were responsible for these performances. Cyclic voltammetry (CV) and other characterization analysis revealed, under UV irradiation, the addition of OCBC served as electron donor, which might promote the reaction of electrons with PAA. The quenching and electron paramagnetic resonance (EPR) tests indicated that R-O•, 1O2 and •OH were generated. Theoretical calculations indicated sulfonamide bridge was vulnerable under the attacks of reactive species. In addition, high removal effect achieved by 5 reuse cycles and different real waters also suggested the sustainability of UV/OCBC/PAA. Overall, this study provided a feasible approach to remove SDZ with high mineralization efficiency, in addition to a potential strategy for resource utilization of corn straw.

--Redox Transformations of the OX063 Radical in Biological Media: Oxidative Decay of Initial Trityl with Further Formation of Structurally-Modified TAM.

Being a low-toxic and hydrophilic representative of TAM, OX063 has shown its suitability for in-vivo and in-cell EPR experiments and design of spin labels. Using 13C labeling, we investigated the course of oxidative degradation of OX063 into quinone-methide (QM) under the influence of superoxide as well as further thiol-promoted reduction of QM into TAM radical, which formally corresponds to substitution of a carboxyl function by a hydroxyl group. We found these transformations being quantitative in model reactions mimicking specific features of biological media and confirmed the presence of these reactions in the blood and liver homogenate of mice in vitro. The emergence of the trityl with the hydroxyl group can be masked by an initial TAM in EPR spectra and may introduce distortions into EPR-derived oximetry data if they have been obtained for objects under hypoxia. 13C labeling allows one to detect its presence, considering its different hyperfine splitting constant on 13C1 (2.04 mT) as compared to OX063 (2.30 mT). The potential involvement of these reactions should be considered when using TAM in spin-labeling of biopolymers intended for subsequent EPR experiments, as well as in the successful application of TAM in experiments in vivo and in cell.

Zero-Bias Anti-Ohmic Behaviour in Diradicaloid Molecular Wires.

Open-shell materials bearing multiple spin centres provide a key route to efficient charge transport in single-molecule electronic devices. They have narrow energy gaps, and their molecular orbitals align closely to the Fermi level of the metallic electrodes, thus allowing efficient electronic transport and higher conductance. Maintaining and stabilising multiple open-shell states - especially in contact with metallic electrodes - is however very challenging, generally requiring a continuous chemical or electrochemical potential to avoid self-immolation of the open-shell character. To overcome this issue, we designed, synthesised, and measured the conductance of a series of bis(indeno) fused acenes, where stability is imparted by a close-shell quinoidal conformation in resonance with the diradical electronic configuration. We show here that these compounds have anti-ohmic behaviour, with conductance increasing with increasing molecular length, at an unprecedented rate and across the entire bias window ([[EQUATION]]). Density Functional Theory (DFT) calculations support our findings, showing the rapidly narrowing HOMO-LUMO gap, unique to these diradicaloid structures, is responsible for the observed behaviour. Our results provide a framework for achieving efficient transport in neutral compounds and demonstrate the promise that diradicaloid materials have in single-molecule electronics, owing to their great stability and unique electronic structure.

Catalytic Ozonation of Pharmaceuticals Using CeO2-CeTiOx-Doped Crossflow Ultrafiltration Ceramic Membranes.

The removal of persistent organic micropollutants (OMPs) from secondary effluent in wastewater treatment plants is critical for meeting water reuse standards. Traditional treatment methods often fail to adequately degrade these contaminants. This study explored the efficacy of a hybrid ozonation membrane filtration (HOMF) process using CeO2 and CeTiOx-doped ceramic crossflow ultrafiltration ceramic membranes for the degradation of OMPs. Hollow ceramic membranes (CM) with a 300 kDa molecular weight cut-off (MWCO) were modified to serve as substrates for catalytic nanosized metal oxides in a crossflow and inside-out operational configuration. Three types of depositions were tested: a single layer of CeO2, a single layer of CeTiOx, and a combined layer of CeO2 + CeTiOx. These catalytic nanoparticles were distributed uniformly using a solution-based method supported by vacuum infiltration to ensure high-throughput deposition. The results demonstrated successful infiltration of the metal oxides, although the yield permeability and transmembrane flow varied, following this order: pristine > CeTiOx > CeO2 > CeO2 + CeTiOx. Four OMPs were examined: two easily degraded by ozone (carbamazepine and diclofenac) and two recalcitrant (ibuprofen and pCBA). The highest OMP degradation was observed in demineralized water, particularly with the CeO2 + CeTiOx modification, suggesting O3 decomposition to hydroxyl radicals. The increased resistance in the modified membranes contributed to the adsorption phenomena. The degradation efficiency decreased in secondary effluent due to competition with the organic and inorganic load, highlighting the challenges in complex water matrices.

Towards advanced removal of organics in persulfate solution by heterogeneous iron-based catalyst: A review.

Heterogeneous iron-based catalysts have drawn increasing attention in the advanced oxidation of persulfates due to their abundance in nature, the lack of secondary pollution to the environment, and their low cost over the last a few years. In this paper, the latest progress in the research on the activation of persulfate by heterogeneous iron-based catalysts is reviewed from two aspects, in terms of synthesized catalysts (Fe0, Fe2O3, Fe3O4, FeOOH) and natural iron ore catalysts (pyrite, magnetite, hematite, siderite, goethite, ferrohydrite, ilmenite and lepidocrocite) focusing on efforts made to improve the performance of catalysts. The advantages and disadvantages of the synthesized catalysts and natural iron ore were summarized. Particular interests were paid to the activation mechanisms in the catalyst/PS/pollutant system for removal of organic pollutants. Future research challenges in the context of field application were also discussed.

Critical roles of low-molecular-weight organic acid in enhancing hydroxyl radical production by ferrous oxidation on γ-Al2O3 mineral surface.

Recognizing the pervasive presence of alumina minerals and low-molecular-weight organic acids (LMWOAs) in the environment, this study addressed the gap in the interaction mechanisms within the ternary system involving these two components and Fe(II). Specifically, the impacts of LMWOAs on hydroxyl radicals (•OH) production and iron species transformation during Fe(II) oxidation on γ-Al2O3 mineral surface were examined. Results demonstrated that adding 0.5 mM oxalate (OA) or citrate (CA) to the γ-Al2O3/Fe(II) system (28.1 µM) significantly enhanced •OH production by 1.9-fold (51.9 µM) and 1.3-fold (36.2 µM), respectively, whereas succinate (SA) exhibited limited effect (30.7 µM). Raising OA concentration to 5 mM further promoted •OH yield to 125.0 µM after 24 h. Deeper analysis revealed that CA facilitated the dissolution of adsorbed Fe(II) and its subsequent oxygenation by O2 through both one- and two-electron transfer mechanisms, whereas OA enhanced the adsorption of dissolved Fe(II) and more efficient two-electron transfer for H2O2 production. Additionally, LMWOAs presence favored the formation of iron minerals with poor crystallinity like ferrihydrite and lepidocrocite rather than well-crystallized forms such as goethite. The distinct impacts of various LMWOAs on Fe(II) oxidation and •OH generation underscore their unique roles in the redox processes at mineral surface, consequently modulating the environmental fate of prototypical pollutants like phenol.

Photostability of Phenoxazine Derivatives.

Phenoxazine is a commonly used molecular building block, for example in optoelectronic applications and pharmaceuticals. However, it is highly susceptible to rapid photodegradation, especially in halogenated solvents. In the present study, we identify the degradation products in both halogenated and non-halogenated solvents by UV/Vis absorption, NMR spectroscopy and mass spectrometry. We also propose a substitution strategy aimed at effectively suppressing the high photoreactivity. Kinetic studies show that the quantum yield of photodegradation Ï• differs by a factor of more than 1000 between trisubstituted derivatives and N-substituted phenoxazine.

Unravelling structural features of small molecules for photochemical transformation of environmental contaminants.

Small molecules, including natural metabolites, organic matter decomposition products, and engineered oxidation byproducts, are widespread in aquatic environment. However, the limited understanding of the photochemical interactions of these small molecules with water pollutants hampers the development of effective environmental protection strategies. This study explores the structural features governing the photochemical transformation of toxic oxyanions by α- and ß-dicarbonyl compounds. By integrating experimental observations with quantum chemical calculations, a robust correlation network was constructed. The correlation network reveals that the reactivity of small organic molecules with oxyanions could be quantitively predicted by their intrinsic properties, such as electronic transition energy, bond dissociation energy, molecular softness, molecular orbital gap, atomic charge, and molecular surface local ionization energy. This network maps the relationship between the molecular architecture of chemicals and their photochemical behaviors. This perspective offers fresh insights into the photochemical behaviors of small molecules in diverse environmental and chemical contexts and are helpful for developing advanced water treatment strategies toward a sustainable future.

Supramolecular Chiral Aggregation of Porphyrin Induced by Photo-Generated Triphenylamines Radical Cations.

Here, it is shown that photoirradiation triggered chiral J-aggregates formation of an achiral anionic porphyrin, TPPS (tetrakis(4-sulfonatophenyl) porphyrin), in the presence of chiral triphenylamine (TPA) derivatives. A series of chiral triarylamines linked with aromatic rings is designed through urea or amide bonds. UV-irradiation of self-assembled urea-linked triphenylamine derivatives causes the formation of persistent radical cations in the chlorinated solvents, which subsequently induces the aggregation of TPPS. Transferring chirality of TPA derivatives to achiral TPPS J-aggregates leads to the chiral assemblies with remarkable chiroptical signals. The experimental results demonstrate that, TPA derivatives linked by the urea bond can effectively promote the aggregation of TPPS rather than those with the amide bond although the photo-generated radical cations are both produced. It is suggested that the urea-linked TPA derivatives are more favorable to stable radical cations and thus cause the formation of TPPS chiral J-aggregation. This work may open up an avenue for designing photo-modulated chiral supramolecular assemblies.

Enhanced sorption and destruction of PFAS by biochar-enabled advanced reduction process.

The biochar-enabled advanced reduction process (ARP) was developed for enhanced sorption (by biochar) and destruction of PFAS (by ARP) in water. First, the biochar (BC) was functionalized by iron oxide (Fe3O4), zero valent iron (ZVI), and chitosan (chi) to produce four biochars (BC, Fe3O4-BC, ZVI-chi-BC, and chi-BC) with improved physicochemical properties (e.g., specific surface area, pore structure, hydrophobicity, and surface functional groups). Batch sorption experimental results revealed that compared to unmodified biochar, all modified biochars showed greater sorption efficiency, and the chi-BC performed the best for PFAS sorption. The chi-BC was then selected to facilitate reductive destruction and defluorination of PFAS in water by ARP in the UV-sulfite system. Adding chi-BC in UV-sulfite ARP system significantly enhanced both degradation and defluorination efficiencies of PFAS (up to ∼100% degradation and ∼85% defluorination efficiencies). Radical analysis using electron paramagnetic resonance (EPR) spectroscopy showed that sulfite radicals dominated at neutral pH (7.0), while hydrated electrons (eaq-) were abundant at higher pH (11) for the efficient destruction of PFAS in the ARP system. Our findings elucidate the synergies of biochar and ARP in enhancing PFAS sorption and degradation, providing new insights into PFAS reductive destruction and defluorination by different reducing radical species at varying pH conditions.

Natural Attenuation of 2,4-Dichlorophenol in Fe-Rich Soil during Redox Oscillations: Anoxic-Oxic Coupling Mechanism.

Natural attenuation of organic contaminants can occur under anoxic or oxic conditions. However, the effect of the coupling anoxic-oxic process, which often happens in subsurface soil, on contaminant transformation remains poorly understood. Here, we investigated 2,4-dichlorophenol (2,4-DCP) transformation in Fe-rich soil under anoxic-oxic alternation. The anoxic and oxic periods in the alternating system showed faster 2,4-DCP transformation than the corresponding control single anoxic and oxic systems; therefore, a higher transformation rate (63.4%) was obtained in the alternating system relative to control systems (27.9-42.4%). Compared to stable pH in the alternating system, the control systems presented clear OH- accumulation, caused by more Fe(II) regeneration in the control anoxic system and longer oxygenation in the control oxic system. Since 2,4-DCP was transformed by ion exchangeable Fe(II) in soil via direct reduction in the anoxic process and induced ·OH oxidation in the oxic process, OH- accumulation was unbeneficial because it competed for proton with direct reduction and inhibited •OH generation via complexing with Fe(II). However, the alternating system exhibited OH--buffering capacity via anoxic-oxic coupling processes because the subsequent oxic periods intercepted Fe(II) regeneration in anoxic periods, while shorter exposure to O2 in oxic periods avoided excessive OH- generation. These findings highlight the significant role of anoxic-oxic alternation in contaminant attenuation persistently.

Cytomegalovirus-induced peroxynitrite promotes virus entry and contributes to pathogenesis in a murine model of infection.

There are no licensed vaccines for human cytomegalovirus (HCMV), and current antiviral drugs that target viral proteins are toxic and prone to resistance. Targeting host pathways essential for virus replication provides an alternate strategy that may reduce opportunities for drug resistance to occur. Oxidative stress is triggered by numerous viruses including HCMV. Peroxynitrite is a reactive nitrogen species that is formed during oxidative stress. Herein, we identified that HCMV rapidly induces the generation of intracellular peroxynitrite upon infection in a manner partially dependent upon xanthine oxidase generation. Peroxynitrite promoted HCMV infection in both cell-free and cell-associated infection systems in multiple cell types. Inhibiting peroxynitrite within the first 24 hours of infection prevented HCMV replication and peroxynitrite promoted cell entry and pp65 translocation into the host cell nuclei. Furthermore, using the murine cytomegalovirus model, we demonstrated that antagonizing peroxynitrite significantly reduces cytomegalovirus replication and pathogenesis in vivo. Overall, our study highlights a proviral role for peroxynitrite in CMV infection and implies that RNS and/or the mechanisms that induce their production could be targeted as a novel strategy to inhibit HCMV infection. IMPORTANCE: Human cytomegalovirus (HCMV) causes significant disease in individuals with impaired or immature immune systems, such as transplant patients and after congenital infection. Antiviral drugs that target the virus directly are toxic and are susceptible to antiviral drug resistance due to virus mutations. An alternate strategy is to target processes within host cells that are required by the virus for replication. Herein, we show that HCMV infection triggers a highly reactive molecule, peroxynitrite, during the initial stages of infection. Peroxynitrite was required for the initial entry of the virus into the cell and promotes virus replication in multiple cell types, suggesting a broad pro-viral function. Importantly, targeting peroxynitrite dramatically inhibited cytomegalovirus replication in cells in the laboratory and in mice, suggesting that therapeutic targeting of this molecule and/or the cellular functions it regulates could represent a novel strategy to inhibit HCMV infection.

Photochemical Initiation and Reactions of Thiyl Radicals Studied with SH2' Radical Traps.

A radical trapping method based on an SH2' homolytic substitution reaction was applied to study the mechanism of a photochemical spirocyclisation of indole-ynones in the presence of thiols. Starting material, products and a range of trapped radical intermediates were simultaneously detected in reaction mixtures by mass spectrometry (MS). The trapped intermediates included both initiating and main chain propagating radicals. These data made it possible to propose a self-initiation mechanism consistent with the originally postulated photoexcitation of an intramolecular electron donor-acceptor complex of the substrate. The effect of thiol structure on the MS peak intensity of the reaction components was rationalised in terms of the relative stability of the radical intermediates. The results were compared to a simpler related reaction, a photochemical thiol-ene addition where reagents, products and trapped intermediate radicals were also detected by MS. Relative MS peak intensities were again explained by a combination of electronic and steric effects on the stability of intermediate radicals. Overall, SH2' radical trapping was demonstrated to be a powerful experimental technique for providing mechanistic evidence on photochemical and other organic radical reactions.

In Vitro Protective Effect of Pea-Derived Peptides (PPs) via the Keap1/Nrf2 Signaling Pathway on Alpha-Gliadin-Sensitizing Peptide Induced Cacao-2 Cells.

SCOPE: Celiac disease (CD) is an allergic intestinal disease caused mainly by gliadin in wheat, which is widespread in the population and currently lacks effective treatment. α-Gliadin peptides cause cellular damage by substantially increasing cellular reactive oxygen species (ROS) levels. METHODS AND RESULTS: This study investigates the protective effect of 11 pea-derived peptides (PPs) on ɑ-gliadin peptide (P31-43) treated Caco-2 cells. Results show that cells treated with PP2, PP5, and PP6 peptides significantly reduce the cell mortality caused by P31-43. Three PPs significantly reduce the P31-43-induced decrease in ROS levels to control levels, and there is no difference between them and the vitamin C (Vc) group. The results in terms of antioxidant-related enzymes show that PPs significantly decrease superoxide dismutase activity (SOD), glutathione reductases (GR), and glutathione (GSH)/oxidized glutathione (GSSG) levels, thus significantly enhancing the antioxidant level of cells. By studying the key proteins of the Kelch-like ECH-associated protein 1 (Keap1)/NF-E2-related factor 2 (Nrf2) pathway, it is found that PPs activate the Keap1/Nrf2 signaling pathway. CONCLUSION: The study finds that peptides from peas can effectively alleviate ɑ-gliadin peptide-induced cell damage. The discovery of these food-derived peptides provides novel potential solutions for the prevention and treatment of CD.