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Increased intramitochondrial free iron is a key feature of various liver diseases, leading to oxidative stress, mitochondrial dysfunction, and liver damage. Polydatin is a polyphenol with a hepatoprotective effect, which has been attributed to its ability to enhance mitochondrial oxidative metabolism and antioxidant defenses, thereby inhibiting reactive oxygen species (ROS) dependent cellular damage processes and liver diseases. However, it has not been explored whether polydatin is able to exert its effects by protecting the phospholipid cardiolipin against damage from excess iron. Cardiolipin maintains the integrity and function of electron transport chain (ETC) complexes and keeps cytochrome c bound to mitochondria, avoiding uncontrolled apoptosis. Therefore, the effect of polydatin on oxidative lipid damage, ETC activity, cytochrome levels, and ROS production was explored in iron-exposed rat liver mitochondria. Fe2+ increased lipid peroxidation, decreased cardiolipin and cytochromes c + c1 and aa3 levels, inhibited ETC complex activities, and dramatically increased ROS production. Preincubation with polydatin prevented all these effects to a variable degree. These results suggest that the hepatoprotective mechanism of polydatin involves the attenuation of free radical production by iron, which enhances cardiolipin levels by counteracting membrane lipid peroxidation. This prevents the loss of cytochromes, improves ETC function, and decreases mitochondrial ROS production. [ABSTRACT FROM AUTHOR]

Water from Madín Dam in Mexico has been shown to contain a wide variety of pollutants such as drugs, pesticides, personal care products and compounds that are released into the environment as waste from production processes. In this work, the effect of the main process variables on the percentage of total organic carbon (TOC) removal in water samples from the Madín reservoir was studied by applying a photo-Fenton treatment catalyzed with iron-pillared clays. The catalyst was characterized by XRD, N2 physisorption, DRS and XPS. The sampling and characterization of the water from the Madín reservoir was carried out according to Mexican standards. The system for treatment tests was 0.1 L of reaction volume and a controlled temperature of 23–25 °C, and the reaction system was kept under constant stirring. After 4 h of treatment time under UV light, the TOC removal was 90%, and it was 60% under Vis light. The main ROS involved in the photo-Fenton process driven by UVC light were hydroxyl radicals, while hydroperoxyl radicals predominate in the Vis-light-driven process. Evidence of superoxide anion participation was not found. The toxicity of untreated and treated water was assessed on Danio rerio specimens, and it was observed to be reduced after the photo-Fenton treatment. [ABSTRACT FROM AUTHOR]

The widespread presence and use of Bisphenol A (BPA) in aquatic environments has caused significant ecological damage. Coal gangue (CG), a byproduct of coal mining, poses a major environmental concern due to its vast land occupation and potential for pollution. A magnetic recyclable geopolymer (MnFe2O4-CGP) using coal gangue geopolymer (CGP) as the carrier was successfully synthesized and was evaluated for its ability to Fenton-like degrade BPA. The characterization techniques revealed the successful incorporation of spherical MnFe2O4 onto the CGP surface and that CGP serves as an excellent platform for the immobilization and dispersion of MnFe2O4. The degradation rate reached 100% within 60 min at pH = 5, 15 mmol/L H2O2, 0.6 g/L catalyst, and 50 mg/L BPA, significantly higher than MnFe2O4 and CGP alone. It was indicated that the degradation rate of BPA in MnFe2O4-CGP composites was 0.1121 min−1, which was consistent with the first-order kinetic model. The saturation magnetization of MnFe2O4-CGP was measured to be 10.96 emu/g, enabling convenient recovery. MnFe2O4-CGP exhibited excellent stability, as the degradation rate of BPA remained above 95% even after five reaction cycles. This efficiency may be due to the MnFe2O4-CGP induced generation of reactive radicals. Quenching and EPR radical trapping experiments unequivocally confirmed that the reactive radical was hydroxyl radical (•OH). These results indicate that MnFe2O4-CGP has potential application prospects as a magnetic recyclable geopolymer composite in Fenton-like catalysis. [ABSTRACT FROM AUTHOR]

In this study, the mechanism of the reaction between 4-methyl aniline and hydroxyl free radicals was computed using the M06-2X and CCSD(T) methods, along with the 6-311++G(3df,2p) basis set. The kinetics of the reaction were calculated utilizing the transition state theory and the microcanonical Rice–Ramsperger–Kassel–Marcus theory. The calculated results revealed that NH-C6H4-CH3 was the key product of the system. The total rate coefficient of the system, k_total = 2.04 × 10−18 T2.07 exp[(11.2 kJ/mol)/RT] cm3/s, was found under the 300–2000 K interval, with P = 760 Torr. At the ambient conditions, the velocity of this reaction was about ten times larger than that of the reaction between C6H5CH3 and hydroxyl free radicals, but it was smaller than the aniline + OH rate. [ABSTRACT FROM AUTHOR]

Ionizing radiation induces many different types of DNA lesions. But one of its characteristics is to produce complex DNA damage, of which tandem DNA damage has received much attention, owing to its promise of distinctive biological properties. Oxidative stresses in response to inflammation in tissues and metal-catalyzed reactions that result in generation of radicals also form these DNA lesions. In this minireview, we have summarized the formation of the tandem lesions as well as the replication and repair studies carried out on them after site-specific synthesis. Many of these lesions are resistant to the traditional base excision repair, so that they can only be repaired by the nucleotide excision repair pathway. They also block DNA replication and, when lesion bypass occurs, it may be significantly error-prone. Some of these tandem DNA lesions may contribute to ageing, neurological diseases, and cancer. [ABSTRACT FROM AUTHOR]

Benzene is the typical volatile organic compound (VOC) of indoor and outdoor air pollution, which harms human health and the environment. Due to the stability of their aromatic structure, the catalytic oxidation of benzene rings in an environment without an external energy input is difficult. In this study, the efficient degradation of benzene at room temperature was achieved by constructing Ag and Ni bimetallic active site catalysts (AgNi/BCN) supported on boron–carbon–nitrogen aerogel. The atomic-scale Ag and Ni are uniformly dispersed on the catalyst surface and form Ag/Ni-C/N bonds with C and N, which were conducive to the catalytic oxidation of benzene at room temperature. Further catalytic reaction mechanisms indicate that benzene reacted with ·OH to produce R·, which reacted with O2 to regenerate ·OH. Under the strong oxidation of ·OH, benzene was oxidized to form alcohols, carboxylic acids, and eventually CO2 and H2O. This study not only significantly reduces the energy consumption of VOC catalytic oxidation, but also improves the safety of VOC treatment, providing new ideas for the low energy consumption and green development of VOC treatment. [ABSTRACT FROM AUTHOR]

The present work used the Behnajady–Modirshahla–Ghanbary (BMG) kinetic model to determine the initial reaction rates (1/m), which were used to calculate the activation energy (Ea) from the decolorization of synthetic dyes by Fenton processes (Fe2+/H2O2, Fe2+/H2O2/reducer and Fe3+/H2O2/reducer). When increasing the temperature and adding Fe3+-reducing compounds (3-Hydroxyanthranilic Acid, Hydroquinone, Gallic Acid, Cysteine or Ascorbic Acid), increases in the 1/m values were observed. When studying the classical Fenton reaction (Fe2+/H2O2), almost all added reducers had decreased Ea. For example, 3-Hydroxyanthranilic Acid decreased the Ea related to the decolorization of the Phenol Red dye by 39%, while Ascorbic Acid decreased the Ea of Safranin T decolorization by 23%. These results demonstrate that the reducers increased the initial reaction rate and decreased the energy barrier to improve Fenton-based decolorization of dyes. When comparing the reaction systems in presence of reducers (Fen+/H2O2/reducer), the reactions initially containing Fe2+ presented lower Ea than reactions catalyzed by Fe3+. That way, the activation energy obtained through the 1/m values of the BMG model highlighted the pro-oxidant effect of reducers in Fenton processes to degrade dyes. [ABSTRACT FROM AUTHOR]

Micro–nanobubbles (MNBs) can generate ·OH in situ, which provides a new idea for the safe and efficient removal of pollutants in water supply systems. However, due to the difficulty in obtaining stable MNBs, the generation efficiency of ·OH is low, and the removal efficiency of pollutants cannot be guaranteed. This paper reviews the application research of MNB technology in water security from three aspects: the generation process of MNBs in water, the generation rule of ·OH during MNB collapse, and the control mechanisms of MNBs on pollutants and biofilms. We found that MNB generation methods are divided into chemical and mechanical (about 10 kinds) categories, and the instability of the bubble size restricts the application of MNB technology. The generation of ·OH by MNBs is affected by the pH, gas source, bubble size, temperature, and external stimulation. And the pH and external stimulus have more influence on ·OH generation in situ than the other factors. Adjusting the pH to alkaline or acidic conditions and selecting ozone or oxygen as the gas source can promote ·OH generation. MNB collapse also releases a large amount of energy, during which the temperature and pressure can reach 3000 K and 5 Gpa, respectively, making it efficient to remove ≈90% of pollutants (i.e., trichloroethylene, benzene, and chlorobenzene). The biofilm can also be removed by physical, chemical, and thermal effects. MNB technology also has great application potential in drinking water, which can be applied to improve water quality, optimize household water purifiers, and enhance the taste of bottled water. Under the premise of safety, after letting people of different ages taste water samples, we found that compared with ordinary drinking water, 85.7% of people think MNB water is softer, and 73.3% of people think MNB water is sweeter. This further proves that MNB water has a great prospect in drinking water applications. This review provides innovative theoretical support for solving the problem of drinking water safety. [ABSTRACT FROM AUTHOR]

Nowadays, antibiotics are widely used, increasing the risk of contamination of the water body and further threatening human health. The traditional water treatment process is less efficient in degrading antibiotics, and the advanced oxidation process (AOPs) is cleaner and more efficient than the traditional biochemical degradation process. The combined ozone/peroxymonosulfate (PMS) advanced oxidation process (O3/PMS) based on sulfate radical (SO4•−) and hydroxyl radical (•OH) has developed rapidly in recent years. The O3/PMS process has become one of the most effective ways to treat antibiotic wastewater. The reaction mechanism of O3/PMS was reviewed in this paper, and the research and application progress of the O3/PMS process in the degradation of antibiotics in drinking water and wastewater effluent were evaluated. The operation characteristics and current application range of the process were summarized, which has a certain reference value for further research on O3/PMS process. [ABSTRACT FROM AUTHOR]

Surface processes such as coatings, corrosion, photocatalysis, and tribology are greatly diversified by acid–base interactions at the surface overlayer. This study focuses on the action of a metallic copper surface as an electron donor/acceptor related to the inactivation of viruses. It was found that regarding Cu2O or Cu materials, electrostatic interaction plays a major role in virus inactivation. We applied the TPPE method to clarify the mechanism of electron transfer (ET) occurring at light-irradiated copper surfaces. The TPPE characteristics were strongly influenced by the environments, which correspond to the temperature and environment dependence of the total count of emitted electrons in the incident light wavelength scan (PE total count, NT), the photothreshold, and further the activation energy (ΔE) analyzed from the Arrhenius plot of NT values obtained in the temperature increase and subsequent temperature decrease processes. In this study, we re-examined the dependence of the TPPE data from two types of Cu metal surfaces: sample A, which was mechanically abraded in alcohols, water, and air, and sample C, which was only ultrasonically cleaned in these liquids. The NT for both samples slowly increased with increasing temperature, reached a maximum (NTmax) at 250 °C (maximum temperature, Tmax), and after that, decreased. For sample A, the NTmax value decreased in the order H2O > CH3OH > C2H5OH > (CH3)2CHOH > C3H7OH, although the last alcohol gave Tmax = 100 °C, while with sample C, the NTmax value decreased in the order C3H7OH > (CH3)2CHOH > C2H5OH > CH3OH > H2O. Interestingly, both orders of the liquids were completely opposite; this means that a Cu surface can possess a two-way character. The NT intensity was found to be strongly associated with the change from the hydroxyl group (–Cu–OH) to the oxide oxygen (O2−) in the O1s spectra in the XPS measurement. The difference between the above orders was explained by the acid–base interaction mode of the –Cu–OH group with the adsorbed molecule on the surfaces. The H2O adsorbed on sample A produces the electric dipole –CuOδ−Hδ+ ⋅⋅⋅ :OH2 (⋅⋅⋅ hydrogen bond), while the C3H7OH and (CH3)2CHOH adsorbed on sample C produce RO−δHδ+ ⋅⋅⋅ :O(H)–Cu− (R = alkyl groups). Gutmann's acceptor number (AN) representing the basicity of the liquid molecules was found to be related to the TPPE characteristics: (CH3)2CHOH (33.5), C2H5OH (37.1), CH3OH (41.3), and H2O (54.8) (the AN of C3H7OH could not be confirmed). With sample A, the values of NTmaxa and ΔEaUp1 both increased with increasing AN (Up1 means the first temperature increase process). On the other hand, with sample C, the values of NTmaxc and ΔEcUp1 both decreased with increasing AN. These findings suggest that sample A acts as an acid, while sample C functions as a base. However, in the case of both types of samples, A and C, the NTmax values were found to increase with increasing ΔEUp1. It was explained that the ΔEUp1 values, depending on the liquids, originate from the difference in the energy level of the hydroxyl group radical at the surface denoted. This is able to attract electrons in the neighborhood of the Fermi level of the base metal through tunnelling. After that, Auger emission electrons are released, contributing to the ET in the overlayer. These electrons are considered to have a strong ability of reducibility. [ABSTRACT FROM AUTHOR]

Recently, granular activated carbon (GAC) has shown its effectiveness as a cathode material for in situ ROS generation. Here, we present an electrochemically modified GAC cathode using electrode polarity reversal (PR) approach for enhanced H2O2 decomposition via 2-electron oxygen reduction reaction (2e-ORR). The successful GAC modification using PR necessitates tuning of the operational parameters such as frequency, current, and time intervals between the PR cycles. This modification enhances the GAC hydrophilicity by increasing the density of surface oxygen functionalities. After optimization of the electrode polarity, using the 20 (No PR)-2 (PR) interval and 140 mA current intensity, the •OH concentration reaches 38.9 μ M compared to the control (No PR) (28.14 μ M ). Subsequently, we evaluated the enhanced •OH generation for the removal of glyphosate, a persistent pesticide used as a model contaminant. The modified GAC using PR removed 67.6% of glyphosate compared to 40.6% by the unmodified GAC without PR, respectively. The findings from this study will advance the utilization of GAC for in situ ROS synthesis, which will have direct implications on increasing the effectiveness of electrochemical water treatment systems. [ABSTRACT FROM AUTHOR]

Tissue inflammation drives the infiltration of innate immune cells that generate reactive species to kill bacteria and recruit adaptive immune cells. Neutrophil activation fosters the release of myeloperoxidase (MPO) enzyme, a heme-containing protein generating hypochlorous acid (HOCl) from hydrogen peroxide (H2O2) and chloride ions. MPO-dependent oxidant formation initiates bioactive oxidation and chlorination products and induces oxidative post-translational modifications (oxPTMs) on proteins and lipid oxidation. Besides HOCl and H2O2, further reactive species such as singlet oxygen and nitric oxide are generated in inflammation, leading to modified proteins, potentially resulting in their altered bioactivity. So far, knowledge about multiple free radical-induced modifications of MPO and its effects on HOCl generation is lacking. To mimic this multi-oxidant microenvironment, human MPO was exposed to several reactive species produced simultaneously via argon plasma operated at body temperature. Several molecular gas admixes were used to modify the reactive species type profiles generated. MPO was investigated by studying its oxPTMs, changes in protein structure, and enzymatic activity. MPO activity was significantly reduced after treatment with all five tested plasma gas conditions. Dynamic light scattering and CD-spectroscopy revealed altered MPO protein morphology indicative of oligomerization. Using mass spectrometry, various oxPTMs, such as +1O, +2O, and +3O, were determined on methionine and cysteine (Cys), and -1H-1N+1O was detected in asparagine (Asp). The modification types identified differed between argon-oxygen and argon-nitrogen plasmas. However, all plasma gas conditions led to the deamidation of Asp and oxidation of Cys residues, suggesting an inactivation of MPO due to oxPTM-mediated conformational changes. [ABSTRACT FROM AUTHOR]

We examined the reaction of hydroxyl radicals (HO•) and sulfate radical anions (SO4•−), which is generated by ionizing radiation in aqueous solutions under anoxic conditions, with an alternating GC doubled-stranded oligodeoxynucleotide (ds-ODN), i.e., the palindromic 5′-d(GCGCGC)-3′. In particular, the optical spectra of the intermediate species and associated kinetic data in the range of ns to ms were obtained via pulse radiolysis. Computational studies by means of density functional theory (DFT) for structural and time-dependent DFT for spectroscopic features were performed on 5′-d(GCGC)-3′. Comprehensively, our results suggest the addition of HO• to the G:C pair moiety, affording the [8-HO-G:C]• detectable adduct. The previous reported spectra of one-electron oxidation of a variety of ds-ODN were assigned to [G(-H+):C]• after deprotonation. Regarding 5′-d(GCGCGC)-3′ ds-ODN, the spectrum at 800 ns has a completely different spectral shape and kinetic behavior. By means of calculations, we assigned the species to [G:C/C:G]•+, in which the electron hole is predicted to be delocalized on the two stacked base pairs. This transient species was further hydrated to afford the [8-HO-G:C]• detectable adduct. These remarkable findings suggest that the double-stranded alternating GC sequences allow for a new type of electron hole stabilization via delocalization over the whole sequence or part of it. [ABSTRACT FROM AUTHOR]

Triclosan (TCS), a broad-spectrum bacteriostatic agent with bactericidal and disinfectant properties, is one of the emerging pollutants of great interest. The electrically activated persulfate-coupled carbon membrane system was studied in this paper. The removal of triclosan achieved 90% within 40 min. Complete degradation can be achieved within 90 min. The electrode was characterized by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The optimal reaction conditions were explored. The catalytic mechanism of the reaction was investigated. It was proved that hydroxyl radicals, sulfate radicals, and singlet oxygen were the main reactive oxygen species in the reaction process by the free radical quenching experiment and electron paramagnetic resonance spectrometer. The degradation path and mechanism of triclosan were investigated. [ABSTRACT FROM AUTHOR]

Ferrocene has been the most used organometallic moiety introduced in organic and bioinorganic drugs to cure cancers and various other diseases. Following several pioneering studies, two real breakthroughs occurred in 1996 and 1997. In 1996, Jaouen et al. reported ferrocifens, ferrocene analogs of tamoxifen, the chemotherapeutic for hormone-dependent breast cancer. Several ferrocifens are now in preclinical evaluation. Independently, in 1997, ferroquine, an analog of the antimalarial drug chloroquine upon the introduction of a ferrocenyl substituent in the carbon chain, was reported by the Biot-Brocard group and found to be active against both chloroquine-sensitive and chloroquine-resistant strains of Plasmodium falciparum. Ferroquine, in combination with artefenomel, completed phase IIb clinical evaluation in 2019. More than 1000 studies have been published on ferrocenyl-containing pharmacophores against infectious diseases, including parasitic, bacterial, fungal, and viral infections, but the relationship between structure and biological activity has been scarcely demonstrated, unlike for ferrocifens and ferroquines. In a majority of ferrocene-containing drugs, however, the production of reactive oxygen species (ROS), in particular the OH. radical, produced by Fenton catalysis, plays a key role and is scrutinized in this mini-review, together with the supramolecular approach utilizing drug delivery nanosystems, such as micelles, metal–organic frameworks (MOFs), polymers, and dendrimers. [ABSTRACT FROM AUTHOR]

Tetraphenylethene derivatives (TPEs) are used as luminescence probes for the detection of metal ions and biomolecules. These sensors function by monitoring the increase in the photoluminescence (PL) intensity of the TPEs resulting from aggregation-induced emission (AIE) upon interaction with the analytes. The AIE behavior of the sensors was investigated by measuring their PL. In this study, PL, PL lifetime, and confocal laser scanning microscopy measurements were carried out as part of our in-depth investigation of AIE behavior of TPEs for the detection of biomolecules and radical species. We used 1,1,2,2-tetrakis(4-((trimethylammonium)alkoxy)phenyl)tetraphenylethene tetrabromide (TPE-C(m)N+Me3Br−, m = 2, 4, and 6, where m denotes the number of methylene groups in the alkyl chain) and TPE-C(m)N+Me3TCNQ−• (TCNQ−• is the 7,7′,8,8′-tetracyanoquinodimethane anion radical) as luminescent probes for the detection of bovine serum albumin (BSA), DNA, and the hydroxyl radical (•OH) generated from Fenton's reagent. The sensing performance of TPE-C(m)N+Me3Br− for BSA and DNA was found to depend on the length of the alkyl chains (m). UV-vis and PL measurements revealed that the responses of TPE-C(m)N+Me3Br− and TPE-C(4)N+TCNQ−• to Fenton's reagent depended on the solvent. The electrochemical properties of the TPE derivatives prepared in this study were additionally investigated via cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Nanostructured oxides (SiO2, TiO2) were synthesized using the sol–gel method and modified with noble metal nanoparticles (Pt, Au) and ruthenium dye to enhance light harvesting and promote the photogeneration of reactive oxygen species, namely singlet oxygen (1O2) and hydroxyl radical (•OH). The resulting nanostructures were embedded in a transparent polyvinyl alcohol (PVA) hydrogel. Morphological and structural characterization of the bare and modified oxides was performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), UV–Vis spectroscopy, and X-ray photoelectron spectroscopy (XPS). Additionally, electrokinetic potential measurements were conducted. Crystallinity data and elemental analysis of the investigated systems were obtained through X-ray diffraction and X-ray fluorescence analyses, while the chemical state of the elements was determined using XPS. The engineered materials, both as simple powders and embedded in the hydrogel, were evaluated for their ability to generate reactive oxygen species (ROS) under visible and simulated solar light irradiation to establish a correlation with their antibacterial activity against Staphylococcus aureus. The generation of singlet oxygen (1O2) by the samples under visible light exposure can be of significant importance for their potential use in biomedical applications. [ABSTRACT FROM AUTHOR]

Hydroxyl radicals (OH) play a crucial role in plasma-bio applications. As pulsed plasma operation is preferred, and even expanded to the nanosecond range, it is essential to study the relationship between OH radical production and pulse characteristics. In this study, we use optical emission spectroscopy to investigate OH radical production with nanosecond pulse characteristics. The experimental results reveal that longer pulses generate more OH radicals. To confirm the effect of pulse properties on OH radical generation, we conduct computational chemical simulations, focusing on two types of pulse properties: pulse instant power and pulse width. The simulation results show that, similar to the experimental results, longer pulses generate more OH radicals. In the nanosecond range, reaction time is critical for OH radical generation. In terms of chemical aspects, N2 metastable species mainly contribute to OH radical generation. It is a unique behavior observed in nanosecond range pulsed operation. Furthermore, humidity can turn over the tendency of OH radical production in nanosecond pulses. In a humid condition, shorter pulses are advantageous for generating OH radicals. Electrons play key roles in this condition and high instant power contributes to them. [ABSTRACT FROM AUTHOR]

Azo dyes such as Congo red can easily cause cancer when they come into contact or are absorbed by the human body, so it is urgent to find a fast and simple method for degrading Congo red. In order to better achieve this research goal, an ultrasonic method was used to degrade Congo red solution in a rotating flow field. The concentration of hydroxyl radical in the solution was significantly increased under the action of ultrasonic cavitation, chemical action of zero valent iron, and mechanochemistry. Under the strong oxidation of hydroxyl radical and the reduction of nano zero valent iron peeled off in the reaction process, the reaction speed is significantly accelerated and should promote the reaction. The effect of increasing stirring and adding iron powder particles on ultrasonic cavitation was studied by numerical simulation, and the yield of hydroxyl radical in the system was measured by fluorescence analysis. The experimental results show that, first, the rotating field formed by mixing increases the uniformity of ultrasonic sound field distribution and the amplitude of sound pressure, and it improves the cavitation intensity. In the effective dispersion area, the strong ultrasonic wave can form a temporary high-energy microenvironment in the suspension through cavitation, generate high strength shockwaves and micro jets, and thus significantly deagglomerate the iron powder aggregates. The addition of iron powder particles then provides a complementary Fenton reagent for the degradation reaction. The concentration of hydroxyl radicals in the solution was significantly increased by the synergy of the two actions. The degradation rate of Congo red reached more than 99% after 30 min of reaction. [ABSTRACT FROM AUTHOR]

The development of novel approaches to the remotion of pharmaceuticals in wastewater is a subject of concern due to their effect on living beings and the environment. Advanced oxidation processes and the use of relevant catalysts are feasible treatment alternatives that require further development. The development of suitable heterogeneous catalysts is a necessity. This work proposes the synthesis of an iron catalyst in a deep eutectic solvent (Fe-DES) composed of choline chloride and citric acid, which was physically and chemically characterized using SEM-EDS and TEM, FTIR, RAMAN, XRD and XPS. The characterisation confirmed the presence of iron in the form of hematite. Fe-DES was shown to be a multipurpose catalyst that can be applied in the removal of sulfamethoxazole as a reagent in the Fenton and electro-Fenton processes and as an activator of peroxymonosulfate (PMS) processes. After testing the catalyst with the aforementioned techniques, the best result was achieved by combining these processes in an electro-PMS, with great efficiency achieved by dual activation of the PMS with the catalyst and electric field, attaining total elimination at natural pH in 90 min. Furthermore, the degradation was confirmed by the detection of short-chain carboxylic acids (oxalic, succinic, and acetic) and reduction in toxicity values. These results confirm the suitability of Fe-DES to degrade high-priority pharmaceutical compounds. [ABSTRACT FROM AUTHOR]

The influences of various factors on blood lead to the formation of extra reactive oxygen species (ROS), resulting in the disruption of morphology and functions of red blood cells (RBCs). This study considers the mechanisms of the mechanochemical synergism of O H • free radicals, which are most active in the initiation of lipid peroxidation (LPO) in RBC membranes, and H 2 O 2 molecules, the largest typical diffusion path. Using kinetic models of differential equations describing C H 2 O 2 t   and C O H • t , we discuss two levels of mechanochemical synergism that occur simultaneously: (1) synergism that ensures the delivery of highly active free radicals O H • to RBC membranes and (2) a positive feedback system between H 2 O 2 and O H • , resulting in the partial restoration of spent molecules. As a result of these ROS synergisms, the efficiency of LPO in RBC membranes sharply increases. In blood, the appearance of O H • free radicals is due to the interaction of H 2 O 2 molecules with free iron ions ( F e 2 + ) which arise as a result of heme degradation. We experimentally established the quantitative dependences of C O H •   C H 2 O 2 using the methods of spectrophotometry and nonlinear curve fitting. This study extends the analysis of the influence of ROS mechanisms in RBC suspensions. [ABSTRACT FROM AUTHOR]

An aromatic substrate for hydroxylation by hydroxyl radicals (•OH) was investigated. The probe, N,N'-(5-nitro-1,3-phenylene)-bis-glutaramide, and its hydroxylated product do not bind either iron(III) or iron(II), and so they do not interfere with the Fenton reaction. A spectrophotometric assay based on the hydroxylation of the substrate was developed. The synthesis and purification methods of this probe from previously published methodologies were improved upon, as well as the analytical procedure for monitoring the Fenton reaction through its use, enabling univocal and sensitive •OH detection. The assay was utilised to demonstrate that the iron(III) complexes of long-chain fatty acids lack Fenton activity under biological conditions. [ABSTRACT FROM AUTHOR]

The development of catalysts continues to have a significant influence on science today since we can utilize them to efficiently destroy some contaminants. A study in this field is justified because there is a dearth of comprehensive literature on the creation of SrTiO3-based photocatalysts. Related to this topic, here we report the facile preparation of a structure-modified SrTiO3 photocatalyst, by incorporating CuWO4. Within the case of the CuWO4-modified samples (0.5–3 wt% nominal CuWO4 content), the photo-oxidation of phenol, as a contaminant, was more than two times higher than the initial SrTiO3. However, the photocatalytic activity does not change linearly with increasing CuWO4 content, and the CWS2.5 (2.5 wt% nominal CuWO4 content and 4.25 wt% measured content) has the highest photo-activity under the applied conditions. The reason for the better activity was the increased recombination time of charge separation on the catalyst surface. Slower recombination can result in more water being oxidized to hydroxyl radicals, leading to the faster decomposition of the phenol. [ABSTRACT FROM AUTHOR]

This Special Issue includes manuscripts on mechanistic understanding, development, and implementation of advanced oxidation processes (AOPs) for the removal of contaminants of emerging concern in water and wastewater treatment. The main goal was successfully achieved under the joint effort of authors, anonymous reviewers, and editorial managers. Totally, one review and 15 research papers are included in the Special Issue. These are mainly focused on catalyst synthesis, reactor design, treatment performance, kinetic modeling, reaction mechanisms, and by-product formation during electrochemical, photocatalytic, plasma, persulfate, chlorine, ozone-based, and Fenton-related AOPs at different scales. This Special Issue received attention from researchers from different parts of the world such as Argentina, Brazil, Canada, China, Germany, India, Mexico, and the USA. The guest editors are happy to see that all papers presented are innovative and meaningful, and hope that this Special Issue can promote mechanistic understanding and engineering applications of AOPs for the removal of contaminants of emerging concern in water. [ABSTRACT FROM AUTHOR]

Laundry wastewater is supposed to be one of the most important sources of surfactants and microplastics in the wastewater treatment plant. Consequently, the aim of the study was evaluating the performance and mechanism of the electro-hybrid ozonation–coagulation (E-HOC) process for the removal of surfactants and microplastics. In this study, the efficiency of the E-HOC process for surfactant and microplastic removal was examined at different current densities and ozone dosages. Under the optimal reaction conditions (current density 15 mA·cm−2, ozone dosage 66.2 mg·L−1), both the removal efficiency of surfactant and microplastic can reach higher than 90%. Furthermore, the mechanism of surfactant and microplastic removal was investigated by electron paramagnetic resonance (EPR) and Fourier transform infrared spectroscopy (FT-IR). The results showed that the E-HOC (carbon fiber cathode) system can produce more reactive oxygen species (ROS), which can significantly improve the removal of the contaminants. In addition, the shape, size and abundance of the microplastics were analyzed. It was found that the shape of the microplastics in laundry wastewater is mainly fiber. Microplastics less than 50 μm account for 46.9%, while only 12.4% are larger than 500 μm. The abundance of microplastics in laundry wastewater ranges between 440,000 and 1,080,000 items per 100 L. The analysis of microplastics by FT-IR showed that most of the microplastics in laundry wastewater were polyethylene, nylon and polyester. These results indicated that the E-HOC process can effectively remove surfactants and microplastics from laundry wastewater. [ABSTRACT FROM AUTHOR]

For potential use in wastewater management and health control, this study investigates the disinfection effectiveness of bulk ultrafine bubbles (UFBs) with different bubble number densities and solution pH. Initially, neutral UFB solutions with different bubble concentrations were mixed with E. coli suspension for 120 min, but these solutions did not achieve sterilization. The bubble number density did not affect the disinfection ability of the neutral solution. Next, the pH of the UFB solutions was fixed at 5, 7, and 9. When mixed with E. coli suspension, the acidic UFB solutions reduced the colony counts by 12% after 30 min of cultivation and by 66% after 60 min of cultivation. The colony counts increased slightly in neutral and significantly in alkaline UFB solutions. The acidic UFB solutions had lower zeta potentials and smaller number densities after cultivation, implying that the number density reduced through bubble coalescence rather than increased by bubble collapse. Additionally, the UFBs exhibited insignificant fluorescence intensity, suggesting that the colony counts increased by generated ∙OH radicals. This study revealed that the effect of UFB on E. coli significantly depends on the solution pH. Further, an acidified solvent achieves a bactericidal effect, whereas a neutral or alkaline solvent enhances the growth effect. This result is important when using actual wastewater. [ABSTRACT FROM AUTHOR]

Mitochondrial (mt) DNA and nuclear (n) DNA have known structures and roles in cells; however, they are rarely compared under specific conditions such as oxidative or degenerative environments that can create damage to the DNA base moieties. Six purine lesions were ascertained in the mtDNA of wild type (wt) CSA (CS3BE–wtCSA) and wtCSB (CS1AN–wtCSB) cells and defective counterparts CS3BE and CS1AN in comparison with the corresponding total (t) DNA (t = n + mt). In particular, the four 5′,8–cyclopurine (cPu) and the two 8–oxo–purine (8–oxo–Pu) lesions were accurately quantified by LC–MS/MS analysis using isotopomeric internal standards after an enzymatic digestion procedure. The 8–oxo–Pu levels were found to be in the range of 25–50 lesions/107 nucleotides in both the mtDNA and tDNA. The four cPu were undetectable in the mtDNA both in defective cells and in the wt counterparts (CSA and CSB), contrary to their detection in tDNA, indicating a nonappearance of hydroxyl radical (HO•) reactivity within the mtDNA. In order to assess the HO• reactivity towards purine nucleobases in the two genetic materials, we performed γ–radiolysis experiments coupled with the 8–oxo–Pu and cPu quantifications on isolated mtDNA and tDNA from wtCSB cells. In the latter experiments, all six purine lesions were detected in both of the DNA, showing a higher resistance to HO• attack in the case of mtDNA compared with tDNA, likely due to their different DNA helical topology influencing the relative abundance of the lesions. [ABSTRACT FROM AUTHOR]

Proteus mirabilis is a common cause of catheter-associated urinary tract infections (CAUTIs). In this study, we verified the effectiveness of amikacin or gentamicin and ascorbic acid (AA) co-therapy in eliminating uropathogenic cells, as well as searched for the molecular basis of AA activity by applying chromatographic and fluorescent techniques. Under simulated physiological conditions, a combined activity of the antibiotic and AA supported the growth (threefold) of the P. mirabilis C12 strain, but reduced catheter colonization (≤30%) in comparison to the drug monotherapy. Slight modifications in the phospholipid and fatty acid profiles, as well as limited (≤62%) 2',7'-dichlorofluorescein fluorescence, corresponding to the hydroxyl radical level, allowed for the exclusion of the hypothesis that the anti-biofilm effect of AA was related to membrane perturbations of the C12 strain. However, the reduced (≤20%) fluorescence intensity of propidium iodide, as a result of a decrease in membrane permeability, may be evidence of P. mirabilis cell defense against AA activity. Quantitative analyses of ascorbic acid over time with a simultaneous measurement of the pH values proved that AA can be an effective urine acidifier, provided that it is devoid of the presence of urease-positive cells. Therefore, it could be useful in a prevention of recurrent CAUTIs, rather than in their treatment. [ABSTRACT FROM AUTHOR]

Naproxen is a widely used non-steroidal anti-inflammatory drug poorly metabolized in the human body, thus resulting in its presence in domestic wastewaters. It is resistant to conventional wastewater treatment, making new methods necessary. Pulsed corona discharge, an energy-efficient advanced oxidation process, was experimentally studied for the oxidation of naproxen in various operation conditions, showing high energy efficiencies in a wide span of pH levels, concentrations, and pulse repetition frequencies. Surfactants present in treated solutions appeared to enhance the degradation rate. The research results contribute to the knowledge of the method's chemistry and technology, supporting its full-scale implementation. [ABSTRACT FROM AUTHOR]

The impacts of natural antioxidants, including ferulic acid, diallyl sulfide, α-tocopherol, and rutin, at a level of 0.2 g/kg on lipid and protein oxidation of minced yak meat in a hydroxyl-radical-generating system were investigated, and the effectiveness was compared with synthetic antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT). The exposure of yak meat to oxidative stress from 12 h to 24 h elevated lipid and protein oxidation. Treatments with antioxidants resulted in significantly lower peroxides, conjugated dienes, and thiobarbituric acid-reactive substances, and were also effective in retarding the formation of carbonyl groups, reducing the loss of sulfhydryl groups and protecting α-helix contents, of which ferulic acid and rutin were the most effective. Myosin heavy chain underwent lower degradation in the samples treated with ferulic acid or rutin compared with the oxidized control and other antioxidant treatments, while that of the BHT treatment showed a similar intensity with oxidized control at 24 h of oxidation. The physical stability of myofibrillar proteins in samples with antioxidants from high to low was rutin, ferulic acid, α-tocopherol, and BHT~diallyl sulfide. These results indicate that rutin and ferulic acid may be promising antioxidants in inhibiting the oxidative reactions during the processing of yak meat. [ABSTRACT FROM AUTHOR]

On the basis of the decolorization caused by the reaction of active oxygen species (AOSs) with methylene blue (MB), our group recently developed colorimetric indicators for hydroxyl radical (OH radical) by embedding MB in polymer thin films made of water-soluble pullulan or sodium alginate. In the present work, to elucidate the reason for the selective decolorization induced by the OH radical compared with other AOSs, such as ozone (O3) and hydrogen peroxide (H2O2), density-functional-theory calculations were performed at the B3LYP/6-31G(d) level for these AOSs and MB and its complexes with pullulan or sodium alginate model molecules. A frontier orbital analysis revealed that the π orbital of MB tends to delocalize on the whole molecule upon complexing with pullulan and sodium alginate, while the energy level is lower than the lowest unoccupied molecular orbital levels of O3 and H2O2 but higher than the singly occupied molecular orbital level of the OH radical. The results support the observation that only the OH radical, as the strongest oxidant, can react with MB in the polymer matrices. The selective decolorization of MB-dyed polymer films by the OH radical is due to not only the steric hindrance in the polymer matrix but also the perturbation of the π orbital of MB through the interaction with the polymer molecules. [ABSTRACT FROM AUTHOR]

Catalyst development still has a major impact on science today, as we can use catalysts to break down certain pollutants in an energy-efficient way. There is no comprehensive literature on the development of SrTiO3-based photocatalysts, so study in this area is justified. Related to this topic, here we report the facile preparation of surface-modified SrTiO3 photocatalyst, performed by plasmonic copper deposition. In the case of the copper-modified samples (0.25–3 wt.% Cu content), the photooxidation of phenol, as model contaminant, was almost 4–5 times higher than the bare SrTiO3. However, the photocatalytic activity was not linearly related to copper content, since the highest photoactivity was achieved at 1 wt.% copper content. The reason for the better activity was the plasmonic effect of copper, which increases the recombination time of charge separation on the catalyst surface. During slower recombination, more water is oxidized to hydroxyl radicals, which can lead to faster degradation of phenol. [ABSTRACT FROM AUTHOR]

The ultraviolet (UV)/H2O2, UV/O3, UV/peroxodisulfate (PDS) and UV/peroxymonosulfate (PMS) methods are called UV-based advanced oxidation processes. In the UV/H2O2 and UV/O3 processes, the free radicals generated are hydroxyl radicals (•OH), while in the UV/PDS and UV/PMS processes, sulfate radicals (SO4•−) predominate, accompanied by •OH. SO4•− are considered to be more advantageous than •OH in degrading organic substances, so the researches on activation of PDS and PMS have become a hot spot in recent years. Especially the utilization of UV-activated PDS and PMS in removing antibiotics in water has received much attention. Some influencing factors and mechanisms are constantly investigated and discussed in the UV/PDS and UV/PMS systems toward antibiotics degradation. However, a systematic review about UV/PDS and UV/PMS in eliminating antibiotics is lacking up to now. Therefore, this review is intended to present the properties of UV sources, antibiotics, and PDS (PMS), to discuss the application of UV/PDS (PMS) in degrading antibiotics from the aspects of effect, influencing factors and mechanism, and to analyze and propose future research directions. [ABSTRACT FROM AUTHOR]

The consequences of aging and disease conditions in tissues involve reactive oxygen species (ROS) and related molecular alterations of different cellular compartments. We compared a murine model of immunodeficient (SCID) xenografted young (4 weeks old) and old (17 weeks old) mice with corresponding controls without tumor implantation and carried out a compositional evaluation of brain tissue for changes in parallel DNA and lipids compartments. DNA damage was measured by four purine 5′,8-cyclo-2′-deoxynucleosides, 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxo-dG), and 8-oxo-7,8-dihydro-2′-deoxyadenosine (8-oxo-dA). In brain lipids, the twelve most representative fatty acid levels, which were mostly obtained from the transformation of glycerophospholipids, were followed up during the aging and disease progressions. The progressive DNA damage due to age and tumoral conditions was confirmed by raised levels of 5′S-cdG and 5′S-cdA. In the brain, the remodeling involved a diminution of palmitic acid accompanied by an increase in arachidonic acid, along both age and tumor progressions, causing increases in the unsaturation index, the peroxidation index, and total TFA as indicators of increased oxidative and free radical reactivity. Our results contribute to the ongoing debate on the central role of DNA and genome instability in the aging process, and on the need for a holistic vision, which implies choosing the best biomarkers for such monitoring. Furthermore, our data highlight brain tissue for its lipid remodeling response and inflammatory signaling, which seem to prevail over the effects of DNA damage. [ABSTRACT FROM AUTHOR]

Iron–manganese silicate (IMS) was synthesized by chemical coprecipitation and used as a catalyst for ozonating acrylic acid (AA) in semicontinuous flow mode. The Fe-O-Mn bond, Fe-Si, and Mn-Si binary oxide were formed in IMS on the basis of the results of XRD, FTIR, and XPS analysis. The removal efficiency of AA was highest in the IMS catalytic ozonation processes (98.9% in 15 min) compared with ozonation alone (62.7%), iron silicate (IS) catalytic ozonation (95.6%), and manganese silicate catalytic ozonation (94.8%). Meanwhile, the removal efficiencies of total organic carbon (TOC) were also improved in the IMS catalytic ozonation processes. The IMS showed high stability and ozone utilization. Additionally, H2O2 was formed in the process of IMS catalytic ozonation. Electron paramagnetic resonance (EPR) analysis and radical scavenger experiments confirmed that hydroxyl radicals (•OH) were the dominant oxidants. Cl−, HCO3−, PO43−, Ca2+, and Mg2+ in aqueous solution could adversely affect AA degradation. In the IMS catalytic ozonation of AA, the surface hydroxyl groups and Lewis acid sites played an important role. [ABSTRACT FROM AUTHOR]

Simple Summary: The Fenton reaction generates the hydroxyl radical (•OH), which is the most reactive and toxic reactive oxygen species and widely recognized as a key player in oxidative stress. To clarify whether this highly reactive molecule travels to its biological target, the effects of the site of the Fenton reaction on cytotoxicity were investigated. Cytotoxicity induced by the Fenton reaction was affected by the distribution of iron ions surrounding and/or being incorporated into cells. Cytotoxicity was enhanced when the Fenton reaction occurred inside cells. Instead of enhancing cytotoxicity, extracellular iron ions exerted protective effects against the cytotoxicity of extracellular hydrogen peroxide in an ion concentration-dependent manner. Distance had a negative impact on the reactivity of extracellular •OH and biologically effective targets. Furthermore, an assessment of plasmid DNA breakage showed that the Fenton reaction system did not effectively induce DNA breakage. The impact of the site of the Fenton reaction, i.e., hydroxyl radical (•OH) generation, on cytotoxicity was investigated by estimating cell lethality in rat thymocytes. Cells were incubated with ferrous sulfate (FeSO4) and hydrogen peroxide (H2O2), or pre-incubated with FeSO4 and then H2O2 was added after medium was replaced to remove iron ions or after the medium was not replaced. Cell lethality in rat thymocytes was estimated by measuring cell sizes using flow cytometry. High extracellular concentrations of FeSO4 exerted protective effects against H2O2-induced cell death instead of enhancing cell lethality. The pre-incubation of cells with FeSO4 enhanced cell lethality induced by H2O2, whereas a pre-incubation with a high concentration of FeSO4 exerted protective effects. FeSO4 distributed extracellularly or on the surface of cells neutralized H2O2 outside cells. Cytotoxicity was only enhanced when the Fenton reaction, i.e., the generation of •OH, occurred inside cells. An assessment of plasmid DNA breakage showed that •OH induced by the Fenton reaction system did not break DNA. Therefore, the main target of intracellularly generated •OH does not appear to be DNA. [ABSTRACT FROM AUTHOR]

Octogen (HMX) is widely used as a high explosive and constituent in plastic explosives, nuclear devices, and rocket fuel. The direct discharge of wastewater generated during HMX production threatens the environment. In this study, we used the electrochemical oxidation (EO) method with a PbO2-based anode to treat HMX wastewater and investigated its degradation performance, mechanism, and toxicity evolution under different conditions. The results showed that HMX treated by EO could achieve a removal efficiency of 81.2% within 180 min at a current density of 70 mA/cm2, Na2SO4 concentration of 0.25 mol/L, interelectrode distance of 1.0 cm, and pH of 5.0. The degradation followed pseudo-first-order kinetics (R2 > 0.93). The degradation pathways of HMX in the EO system have been proposed, including cathode reduction and indirect oxidation by •OH radicals. The molecular toxicity level (expressed as the transcriptional effect level index) of HMX wastewater first increased to 1.81 and then decreased to a non-toxic level during the degradation process. Protein and oxidative stress were the dominant stress categories, possibly because of the intermediates that evolved during HMX degradation. This study provides new insights into the electrochemical degradation mechanisms and molecular-level toxicity evolution during HMX degradation. It also serves as initial evidence for the potential of the EO-enabled method as an alternative for explosive wastewater treatment with high removal performance, low cost, and low environmental impact. [ABSTRACT FROM AUTHOR]

The scavenging activity of hydroxyl radicals, produced by the Fenton reaction, is commonly used to quantify the antioxidant capacity of plant extracts. In this study, three Fenton systems (Fe/phosphate buffer, Fe/quinolinic acid and Fe/phosphate buffer/quinolinic acid) and the thermal degradation of peroxydisulfate were used to produce hydroxyl radicals; the hydroxyl radical scavenging activity of plant extracts (ginger, blueberry juices and green tea infusion) and chemical compounds (EGCG and GA) was estimated by spin trapping with DMPO (5,5-dimethyl-1-pyrroline N-oxide) and EPR (Electron Paramagnetic Resonance) spectroscopy. Phosphate buffer was used to mimic the physiological pH of cellular systems, while quinolinic acid (pyridine-2,3-dicarboxylic acid) facilitates the experimental procedure by hindering the spontaneous oxidation of Fe(II). The EC50 (the concentration of chemical compounds or plant extracts which halves the intensity of the DMPO–OH adduct) values were determined in all the systems. The results show that, for both the chemical compounds and the plant extracts, there is not a well-defined order for the EC50 values determined in the four hydroxyl radical generating systems. The interactions of phosphate buffer and quinolinic acid with the antioxidants and with potential iron-coordinating ligands present in the plant extracts can justify the observed differences. [ABSTRACT FROM AUTHOR]

Ozone micro/nanobubbles with catalytic processes are widely used in the treatment of refractory organic wastewater. Micro/nanobubble technology overcomes the limitations of ozone mass transfer and ozone utilization in the application of ozone oxidation, and effectively improves the oxidation efficiency of ozone. The presence of micro/nanobubbles keeps the catalyst particles in a dynamic discrete state, which effectively increases the contact frequency between the catalyst and refractory organic matter and greatly improves the mineralization efficiency of refractory organic matter. This paper expounds on the characteristics and advantages of micro/nanobubble technology and summarizes the synergistic mechanism of microbubble nanoparticles and the mechanism of catalyst ozone micro/nanobubble systems in the treatment of refractory organics. An interaction mechanism of nanoparticles and ozone microbubbles is suggested, and the proposed theories on ozone microbubble systems are discussed with suggestions for future studies on systems of nanoparticles and ozone microbubbles. [ABSTRACT FROM AUTHOR]

Background and Objectives: The Japanese herbal medicine Yokukansan (YKS) has analgesic properties and is used for various pain disorders. The purpose of the present study was to investigate the effects of YKS in Hunner-type interstitial cystitis (HIC) using an experimental rat model of HIC and to explore its antioxidant activity and role as the underlying mechanism of action. Materials and Methods: The antioxidant capacity of YKS was evaluated by determining its hydroxyl radical (·OH) scavenging capacity using electron spin resonance (ESR). Next, the effects of YKS administration were explored using a toll-like receptor-7 agonist-induced rat model of HIC. The von Frey test was performed to assess bladder pain. Three days after HIC induction, the bladder was removed, and the expression of oxidative stress parameters in the bladder wall was investigated (reactive oxygen metabolites (ROMs), ·OH, and 8-hydroxy-2′-deoxyguanosine (8-OhdG)). Results: YKS had a ·OH scavenging capacity according to the ESR study. In the von Frey test, a significant decrease in the withdrawal threshold was observed in the HIC group compared with the control group; however, the decrease was ameliorated by the administration of YKS. Oxidative stress parameters showed increasing tendencies (ROMs test and 8-OHdG) or a significant increase (·OH) in the HIC group compared with the control group; however, the increase was significantly suppressed by the administration of YKS. Conclusions: These findings suggest that YKS is effective against HIC and that its antioxidant activity is involved in the mechanism of action. [ABSTRACT FROM AUTHOR]

The elimination of organic contaminants from natural resources is extremely important to ensure their (re-)usability. In this report, the degradation of a model pharmaceutical compound, theophylline, is compared between natural and laboratory-controlled environments. While the concentration of H2O2 variably affected the degradation efficiency (approximately from 8 to 20 min for complete degradation) in the photo-irradiation experiments, the inorganic compounds (NaNO3, KH2PO4 and ZnSO4) present in the medium seemed to affect the degradation by scavenging hydroxyl radicals (•OH). The end-product studies using high-resolution mass spectrometry (HRMS) ruled out the involvement of secondary radicals in the degradation mechanism. The quantitative calculation with the help of authentic standards pointed out the predominant role of hydroxylation pathways, especially in the initial stages. Although a noticeable decline in the degradation efficiency was observed in river water samples (complete degradation after 25 min with an approximately 20% total organic carbon (TOC) removal), appreciable TOC removal (70%) was eventually achieved after prolonged irradiation (1 h) and in the presence of additional H2O2 (5 times), revealing the potential of our technique. The results furnished in this report could be considered as a preliminary step for the construction of •OH-based wastewater treatment methodologies for the remediation of toxic pollutants from the real environment. [ABSTRACT FROM AUTHOR]

Photocatalytic studies on contaminant degradation in water suspension generally suggest that the degradation reaction mainly takes place on the surface of the photocatalysts rather than in the water phase. The mechanism of selective degradation is often difficult to distinguish concerning the contribution of adsorption and radical selectivity. This study is thus designed to investigate the roles of two types of hydroxyl radicals, adsorbed hydroxyl radical (·OHa) and free hydroxyl radical (·OHf), on the selective degradation of catechol (CT) and resorcinol (RE). CT and RE are significantly different in adsorption on a TiO2 photocatalyst with a highly exposed {001} facet. CT can be selectively degraded by TiO2 and was highly correlated with adsorption. Free radical quenching experiment results showed that the degradation of CT can be identified as the combined effect of both ·OHa and ·OHf, while the degradation of RE was mainly due to the ·OHf. Electron paramagnetic resonance coupled with spin trapping agents was used to detect the relative concentration of hydroxyl radicals in all the photocatalytic degradation processes. After a series analysis, we proposed that the mechanism of selective degradation mainly depends on the concentration of ·OHf for the pollutant molecules with weak adsorption on the catalyst surface. [ABSTRACT FROM AUTHOR]

Catechin is an extensively investigated plant flavan-3-ol with a beneficial impact on human health that is often associated with antioxidant activities and iron coordination complex formation. The aim of this study was to explore these properties with FeII and FeIII using a combination of nanoelectrospray-mass spectrometry, differential pulse voltammetry, site-specific deoxyribose degradation assay, FeII autoxidation assay, and brine shrimp mortality assay. Catechin primarily favored coordination complex formation with Fe ions of the stoichiometry catechin:Fe in the ratio of 1:1 or 2:1. In the detected Fe–catechin coordination complexes, FeII prevailed. Differential pulse voltammetry, the site-specific deoxyribose degradation, and FeII autoxidation assays proved that coordination complex formation affected catechin's antioxidant effects. In situ formed Fe–catechin coordination complexes showed no toxic activities in the brine shrimp mortality assay. In summary, catechin has properties for the possible treatment of pathological processes associated with ageing and degeneration, such as Alzheimer's and Parkinson's diseases. [ABSTRACT FROM AUTHOR]

This study systematically investigated the oxidative treatment of five selected pesticides, alachlor (ALA), carbendazim (CAR), diuron (DIU), pyrimethanil (PYR), and tebuconazole (TEB), by comparing their relative reactivities as a function of three different oxidative treatment processes (i.e., chlorine (HOCl), ozone (O3), and ozone/hydrogen peroxide (O3/H2O2)) under various oxidant dosages, reaction times, and pH conditions. For oxidative treatment, pesticide standards were spiked into rainwater. The removal efficiency of the selected pesticides varied considerably depending on the oxidative treatment processes. HOCl, O3, and O3/H2O2 treatments were highly effective at eliminating CAR (>80%) and PYR (>99%), while they were not significantly effective in removing TEB (<20%). In the case of DIU, HOCl (81%) was shown to be more effective than O3 (24%) and O3/H2O2 (49%). The removal efficiency of ALA was in the order of O3/H2O2 (49%) > O3 (20%) > HOCl (8.5%). The effect of increasing the solution pH from 5.0 to 9.0 on pesticide degradation varied between the oxidative treatment processes. Additionally, NH4+, NO2−, and humic acid in rainwater significantly inhibited pesticide degradation. [ABSTRACT FROM AUTHOR]

The copper–phenanthroline complex CuI(Phen)2 was the first artificial nuclease studied in biology. The mechanism responsible for this activity involves CuII(Phen)2 and H2O2. Even if H2O2/Cu systems have been extensively studied in biology and oxidative chemistry, most of these studies were carried out at physiological pH only, and little information is available on the generation of radicals by the H2O2/CuII-Phen system. In the context of paper pulp bleaching to improve the bleaching ability of H2O2, this system has been investigated, mostly at alkaline pH, and more recently at near-neutral pH in the case of dyed cellulosic fibers. Hence, this paper aims at studying the production of radicals with the H2O2/CuII-Phen system at near-neutral and alkaline pHs. Using the EPR/spin-trapping method, HO• formation was monitored to understand the mechanisms involved. DMPO was used as a spin-trap to form DMPO–OH in the presence of HO•, and two HO• scavengers were compared to identify the origin of the observed DMPO–OH adduct, as nucleophilic addition of water onto DMPO leads to the same adduct. H2O2 decomposition was enhanced by the addition of CuII–Phen (and only slightly by addition of CuSO4), reaching a level similar to the Fenton reagent at near-neutral pH. This evidences the role of Phen, which improves the effect of CuII by tuning the electronic structure and structural properties of the corresponding CuII complexes. [ABSTRACT FROM AUTHOR]

Myocardial infarction and cerebral ischemic stroke during the process of arterial thrombosis are prominently causes of death worldwide. Platelets are anucleated cells and play a critical factor in these diseases. Columbianadin (CBN), a coumarin derivative from plants, inhibits effective platelet activation. In this study, platelet function analysis revealed that the closure time of the platelet plug in human whole blood significantly prolonged by CBN, whereas CBN did not pointedly prolong the bleeding time in mice. BAY11-7082 (an inhibitor of IκB kinase) and MG-132 (an inhibitor of proteasome) inhibited collagen-stimulated platelet aggregation and ATP-release in human platelets, BAY11-7082 exhibited a higher potency than MG-132. Moreover, CBN markedly reduced NF-κB activation (e.g., IκBα and p65 phosphorylation) and reversed IκBα degradation in activated platelets. We investigated intercellular signaling events between mitogen-activated protein kinases and NF-κB, and found that BAY11-7082 abolished JNK1/2 and ERK1/2 phosphorylation. Interestingly, SP600125 (an inhibitor of JNK) but not PD98059 (an inhibitor of ERK) had no effect in NF-κB activation in activated platelets. Moreover, CBN but not BAY11-7082 significantly reduced hydroxyl radical (HO●) formation in platelets. Therefore, we propose that CBN inhibits NF-κB activation in human platelets and could present a potent clinical treatment for thromboembolic diseases. [ABSTRACT FROM AUTHOR]

Alzheimer's disease (AD) is the most common neurodegenerative disease worldwide and has a high incidence in the elderly. Unfortunately, there is no effective therapy for AD owing to its complicated pathogenesis. However, the development of lipid-lowering anti-inflammatory drugs has heralded a new era in the treatment of Alzheimer's disease. Several studies in recent years have shown that lipid metabolic dysregulation and neuroinflammation are associated with the pathogenesis of AD. 3-Hydroxyl 3-methylglutaryl CoA reductase (HMGCR) is a rate-limiting enzyme in cholesterol synthesis that plays a key role in cholesterol metabolism. HMGCR inhibitors, known as statins, have changed from being solely lipid-lowering agents to neuroprotective compounds because of their effects on lipid levels and inflammation. In this review, we first summarize the main regulatory mechanism of HMGCR affecting cholesterol biosynthesis. We also discuss the pathogenesis of AD induced by HMGCR, including disordered lipid metabolism, oxidative stress, inflammation, microglial proliferation, and amyloid-β (Aβ) deposition. Subsequently, we explain the possibility of HMGCR as a potential target for AD treatment. Statins-based AD treatment is an ascent field and currently quite controversial; therefore, we also elaborate on the current application prospects and limitations of statins in AD treatment.

In dead biological tissues such as human hair, the ability of antioxidants to minimise autoxidation is determined by their chemical reactions with reactive oxygen species. In order to improve our understanding of factors determining such antioxidant properties, the mechanistic chemistry of four phenolic antioxidants found in tea and rosemary extracts (epicatechin, epigallocatechin gallate, rosmarinic and carnosic acids) has been investigated. The degradation of N -acetyl alanine by photochemically generated hydroxyl radicals was used as a model system. A relatively high concentration of the antioxidants (0.1 equivalent with respect to the substrate) tested the ability of the antioxidants to intercept both initiating hydroxyl radicals (preventive action) and propagating peroxyl radicals (chain-breaking action). LC-MS data showed the formation of hydroxylated derivatives, quinones and hydroperoxides of the antioxidants. The structure of the assignment was aided by deuterium exchange experiments. Tea polyphenolics (epicatechin and epigallocatechin gallate) outperformed the rosemary compounds in preventing substrate degradation and were particularly effective in capturing the initiating radicals. Carnosic acid was suggested to act mostly as a chain-breaking antioxidant. All of the antioxidants except for rosmarinic acid generated hydroperoxides which was tentatively ascribed to the insufficient lability of the benzylic C-H bond of rosmarinic acid.

For covalent attachment-supported α-diimine catalysts, on the basis of ensuring the thermal stability and activity of the catalysts, the important problem is that the active group on the catalyst can quickly react with the support, anchoring it firmly on the support, shortening the loading time, reducing the negative impact of the support on the active centers, and further improving the polymer morphology, which makes them suitable for use in industrial polymerization temperatures. Herein, we synthesized a α-diimine nickel(II) catalyst bearing four hydroxyl substituents. The hydroxyl substituents enable the catalyst to be immobilized firmly on silica support by covalent linkage in 5-10 min. Compared with the toluene solvent system, the homogeneous catalysts show high activity and thermal stability in hexane solvent at the same conditions. Compared with homogeneous catalysts, heterogeneous catalysis leads to improvements in catalyst lifetime, polymer morphology control, catalytic activity, and the molecular weight of polyethylene (up to 679 kg/mol). The silica-supported catalysts resulted in higher melting temperatures as well as lower branching densities in polyethylenes. Even at 70 °C, the polyethylene prepared by S-CatA-2 still exhibits dispersed particle morphology, and there is no phenomenon of reactor fouling, which is suitable for industrial polymerization processes.

Oxidative stress signaling is essential for plant adaptation to hostile environments. Previous studies revealed the essentiality of hydroxyl radicals (HO•)-induced activation of massive K+ efflux and a smaller Ca2+ influx as an important component of plant adaptation to a broad range of abiotic stresses. Such activation would modify membrane potential making it more negative. Contrary to these expectations, here, we provide experimental evidence that HO• induces a strong depolarization, from 􀀀130 to 􀀀70 mV, which could only be explained by a substantial HO•-induced efflux of intracellular anions. Application of Gd3+ and NPPB, non-specific blockers of cation and anion conductance, respectively, reduced HO•-induced ion fluxes instantaneously, implying a direct block of the dual conductance. The selectivity of an early instantaneous HO•-induced whole cell current fluctuated from more anionic to more cationic and vice versa, developing a higher cation selectivity at later times. The parallel electroneutral efflux of K+ and anions should underlie a substantial leak of the cellular electrolyte, which may affect the cell's turgor and metabolic status. The physiological implications of these findings are discussed in the context of cell fate determination, and ROS and cytosolic K+ signaling. [ABSTRACT FROM AUTHOR]