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Peroxymonosulfate (PMS) driven by halloysite nanotubes (HNTs) modified with nanomanganese cobaltate (MnCo

Persulfate oxidation has been increasingly integrated with membrane separation for water purification, whereas the oxidizing ability of persulfate is relatively limited, and appropriate activation methods are urgently required. In this work, a novel catalyst of carbon nanofiber (CNF) supported CuO (CuO@CNF) was synthesized for peroxymonosulfate (PMS) activation. The micro-morphology showed that CuO nanoparticles were well dispersed on the CNF support, which solved the agglomeration problem of nanoparticles and improved the catalytic ability. Furtherly, PMS oxidation activated by CuO@CNF was proposed as a pre-processing means for improving ultrafiltration (UF) water purification efficiency and mitigating membrane fouling. The prepared CuO@CNF was more efficient than individual CNF and CuO in activating PMS for the reduction of various typical natural organic matter, improving permeation flux, and mitigating membrane fouling. The fouling control efficiencies were also verified by characterizing the membrane surface functional groups. The CuO@CNF catalyst could signally promote the oxidative capacity by generating a series of reactive oxygen species, thus enhancing the removal of organics with varying species and molecular weight ranges in surface water. With respect to the fouling condition, the specific permeation flux after filtration was improved from 0.25 to 0.61, with the removal rate of reversible fouling resistance reached 89.6%. The fouling mechanism was apparently altered, with both standard and complete blocking dominated throughout the filtration process. The findings are beneficial for the development of new strategies to improve membrane-based water purification efficiency.

Potential leaching of Co ions could decrease the catalytic activity and cause secondary pollution of water, thereby threatening ecological safety and human health. In response, the in-situ generation of well-dispersed Co

The agricultural waste-derived biochar can be used as an effective green catalyst for peroxymonosulfate (PMS) activation to utilize the biomass resource. Herein, nitrogen-doped microtubes porous graphitic carbon (N-MPGC) derived from loofah sponge was facilely prepared via the impregnation-calcination method. The amount of N doping was positively correlated with the catalytic performance of N-MPGC. The obtained N-MPGC-2 as a metal-free carbon catalyst showed excellent ability for rhodamine B (RhB) degradation via PMS activation with the pseudo-first-order reaction rate constant (k) of 0.293 min

Commercial cannabis oil products are widely available in Canada even though there is a significant gap in scientific information regarding them. Oils, such as vegetable oils, are known to undergo oxidative changes through free radical mechanisms when they are heated or aged, but the cannabis oils used in this study did not have expiry dates or best-before usage dates. This led to the question of how these products would be affected with time. We hypothesized that cannabis oils would produce increased concentrations of free radicals in aging-simulated conditions, which would be related to a decrease in cannabidiol (CBD) or Δ

Red mud of low cost is regarded as a promising alternative to heterogeneous catalysts for activating peroxymonosulfate (PMS) to degrade m-cresol. Improper valence states of metal oxides and coated active substances in red mud greatly hampered its wide application. To solve this problem, the modified red mud (WRMG/700) was prepared by the pyrolysis reduction of glucose in N2 atmosphere. X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectrum (XPS) analysis confirmed the production of Fe3O4, MnO and NiO in red mud and their gathering on the surface of particles. WRMG/700 exhibited the excellent performance toward PMS activation for the m-cresol degradation with 99.02% degradation efficiency and a pH-independent catalytic activity between initial pH 3–8. The removal efficiency of COD increased with the reaction time under the optimized degradation conditions. The free radical scavenging experiments and electron paramagnetic resonance (EPR) test confirmed 1O2 played a dominant role during m-cresol degradation in the WRMG/700/PMS system, implying m-cresol degradation was a non-radical oxidation process. Accordingly, the possible reaction mechanism was proposed. WRMG/700 retained its activation performance even after five recycles. This study showed a low cost and simple operation process for m-cresol elimination.

The combination of peroxymonosulfate (PMS) activation by hetero-catalysis and electrolysis (EC) attracted incremental concerns as an efficient antibiotics degradation method. In this work, carbon embedding iron (C@Fe) catalysts growing on nickel foam (NF) composite cathode (C@Fe/NF) was prepared via in-situsolvothermal growth and carbonization method and used to activate PMS toward sulfamethoxazole (SMX) degradation. The EC-[C@Fe/NF(II)]-PMS system exhibited an excellent PMS activation, with 100% SMX removal efficiency achieving within 30 min. Reactive oxygen species (ROS) generation and their roles in SMX degradation were confirmed by quenching experiments and electron paramagnetic resonance. It was found that singlet oxygen (

Oxidation is one of the most common degradation pathways for active pharmaceutical ingredients (APIs) in pharmaceutical formulations, mostly involving 1-electron processes via peroxy radicals and 2-electron processes by peroxides. In liquid pharmaceutical formulations, several factors can impact oxidative instabilities including pH, excipient impurities, headspace oxygen, and the potential for photo-oxidation. Photo-oxidation can be particularly challenging to characterize given the number of oxidative mechanisms which can occur. This was observed during formulation development of a new chemical entity, MK-1454, where a degradation peak was observed during photostability studies which was not previously observed during peroxide and peroxyradical forced stress studies.To gain a fundamental understanding of reactive oxygen species generation and its role in degradation of MK-1454, experiments were performed with materials which either generate or measure reactive oxygen species including organic hydroperoxides, singlet oxygen, and superoxide to fundamentally understand a photodegradation mechanism which was observed in the original formulation. LC-MS experiments further elucidated the structure and mechanism of this observed degradation pathway.A clear relationship between the decrease in dissolved oxygen after light exposure and the loss of MK-1454 was established. The data indicate that singlet oxygen is the most likely contributor of a particular photodegradation product. The singlet oxygen was generated by the inactive ingredients in the formulation, and LC-MS confirm this as the most likely pathway.This work highlights the importance of understanding photochemical degradation of APIs in solution formulations and provides approaches which can better elucidate those mechanisms and thereby control strategies.

The necessary step of directly adding hydrogen peroxide (H

Current research has widely applied heteroatom doping for the promotion of catalyst activity in peroxymonosulfate (PMS) systems; however, the relationship between heteroatom doping and stimulated activation mechanism transformation is not fully understood. Herein, we introduce nitrogen and sulfur doping into a Co@rGO material for PMS activation to degrade tetracycline (TC) and systematically investigate how heteroatom doping transformed the activation mechanism of the original Co@rGO/PMS system. N was homogeneously inserted into the reduced graphene oxide (rGO) matrix of Co@rGO, inducing a significant increase in the degradation efficiency without affecting the activation mechanism transformation. Additionally, S doping converted Co

The mechanisms underlying the inactivation of Leuconostoc mesenteroides glucose 6-phosphate dehydrogenase (G6PDH) induced by peroxyl radicals (ROO

In this work, the response surface methodology (RSM) was used to model and optimize the hydroxylamine (HA) enhanced Fe(II)/peroxymonosulfate (PMS) process. The enhanced effect of HA on the degradation efficiency of Orange II (AO7) in the Fe(II)/PMS system was quantitatively analyzed. Pareto analysis showed that the individual and interactive effects of HA, Fe(II) and PMS were of the following order: HA > Fe(II) > PMS and Fe(II)/PMS > HA/PMS > Fe(II)/HA. The optimal conditions of HA/Fe(II)/PMS system were as follows: Fe(II) concentration was 34.0 μM, HA concentration was 0.4 mM, and PMS concentration was 0.9 mM. When the initial pH was 4.0–6.0, the degradation efficiency of AO7 in the HA/Fe(II)/PMS system was significantly higher than that in the Fe(II)/PMS system (P < 0.05). Hydroxylamine enhances the degradation of AO7 in the Fe(II)/PMS system by reducing Fe(III) to Fe(II). The results of quenching experiment showed that SO4•− was the dominating reactive oxygen species (ROS) in the HA/Fe(II)/PMS system. In the HA/Fe(II)/PMS system, CO32− and humic acid inhibited the degradation efficiency of AO7. This work provides a novel mathematical model for the degradation of AO7 in the HA/Fe(II)/PMS system, which can be popularized and applied in similar experiments.

Developing advanced heterogeneous catalysts with atomically dispersed active sites is an efficient strategy to boost the kinetics of peroxymonosulfate (PMS) activation for micropollutant removal. Here, we report a binary Mo

Poor angiogenesis at injury site is a major problem in chronic wounds, which could lead to limbs amputation in adverse cases. To overcome this issue, several efforts have made in literature and by our group as well to develop pro-angiogenic agents. For this purpose, metal oxides due to their oxidative potential have been studied and found very attractive agents. Cerium oxides are proven to be non-toxic and their biological studies have already proved their importance in preventing chronic inflammation, and neurological diseases among several others by modulating the intracellular reactive oxygen species. In current study, we report the synthesis and neovascularization activity of cerium oxide and cerium peroxide nanoparticles when loaded into chitosan and collagen hydrogel. The hydrogels were characterized by FTIR, SEM and XRD. The pro-angiogenic behavior of these hydrogels was studied by in-vivo CAM assay. It was found that cerium peroxide loaded material showed significantly increase in angiogenesis as compared to cerium oxide loaded materials. It was demonstrated that cerium peroxide hydrogels enhanced the angiogenic capability in CAM assay as compared to cerium oxide and hence holds good potential for chronic ulcer and burn wounds healing.

This study provided insight on the design of co-doped graphitic carbon nitride (g-C

UV/peroxymonosulfate (UV/PMS) advanced oxidation process has attracted significant attention for removal of micropollutants in water. However, during practical water treatment applications, the PMS treatment must be performed before the UV treatment to achieve full contact. In this study, sulfamethoxazole (SMX) was selected as the target micropollutant. Four different operational approaches, including UV alone, PMS alone, simultaneous UV/PMS and sequential PMS-UV, were compared for their differences in SMX removal and disinfection by-product (DBP) formation potentials during chlorine-driven disinfection. Among the four approaches, UV/PMS and PMS-UV achieved over 90% removal efficiencies for SMX without substantial differences. For raw water, the trichloronitromethane (TCNM) formation potential after treatment with PMS-UV was lower than that after UV/PMS treatment. The time interval over which the PMS-UV process was conducted had little effect on the final removal efficiency for SMX. However, a brief (5 min) pre-PMS treatment significantly reduced the TCNM formation potential and the genotoxicity from DBPs. The formation risk for TCNM during chlorination increased markedly with increasing PMS dosages, and the appropriate dosage under these experimental conditions was suggested to be 0.5-1.0 mmol/L. Under alkaline conditions, PMS-UV treatment can enhance SMX degradation as well as dramatically reduced the formation potentials for haloketones, haloacetonitriles and halonitromethanes. This study suggests that proper optimization of UV/PMS processes can remove SMX and reduce its DBP formation.

Recombinant rice quiescin sulfhydryl oxidase (rQSOX) has the potential to improve the flour processing quality, but the mechanisms remain unclear. The effects of rQSOX on bread quality, dough rheology, and gluten structure and composition, with glucose oxidase as a positive control, were investigated. rQSOX addition could improve the dough processing quality, as proved by enhanced viscoelastic properties of dough as well as a softer crumb, higher specific volume, and lower moisture loss of bread. These beneficial effects were attributed to gluten protein polymerization and gluten network strengthening, evidenced by the improved concentration of SDS-insoluble gluten and formation of large gluten aggregates and the increased α-helix and β-turn conformation. Furthermore, decreased free sulfhydryl and increased dityrosine in gluten as well as improved H

An Fe(OTf)

Whitening agents, such as hydrogen peroxide and carbamide peroxide, are currently used in clinical applications for dental esthetic and dental care. However, the free radicals generated by whitening agents cause pathological damage; therefore, their safety issues remain controversial. Furthermore, whitening agents are known to be unstable and short-lived. Since 2001, nanoparticles (NPs) have been researched for use in tooth whitening. Importantly, nanoparticles not only function as abrasives but also release reactive oxygen species and help remineralization. This review outlines the historical development of several NPs based on their whitening effects and side effects. NPs can be categorized into metals or metal oxides, ceramic particles, graphene oxide, and piezoelectric particles. Moreover, the status quo and future prospects are discussed, and recent progress in the development of NPs and their applications in various fields requiring tooth whitening is examined. This review promotes the research and development of next-generation NPs for use in tooth whitening.

This study used coagulation sludge from a landfill leachate treatment to prepare a modified coagulation sludge (MCS) catalyst by the limited oxygen pyrolysis method, and the adsorption, degradation efficiency, and reaction mechanism of bisphenol A (BPA) in the MCS activated peroxymonosulfate (MCS/PMS) process were investigated. The pyrolysis temperature determined the adsorption capacity and the activation ability of MCS. At a pyrolysis temperature of 300 °C for 2 h, the MCS300-2 test material had the best adsorption capacity for BPA, while MCS450-2 prepared at a pyrolysis temperature of 450 °C for 2 h had a better catalytic performance towards PMS. In the MCS/PMS process, BPA (20 mg/L) could be completely degraded at 120 min under room temperature when the initial pH = 7, PMS dosage = 3 g/L, and MCS dosage = 0.3 g/L. Radical quenching experiments indicated that both hydroxyl radical (·OH) and sulfate radical (SO

In natural photosynthesis, the light-driven splitting of water into electrons, protons and molecular oxygen forms the first step of the solar-to-chemical energy conversion process. The reaction takes place in photosystem II, where the Mn4CaO5 cluster first stores four oxidizing equivalents, the S0 to S4 intermediate states in the Kok cycle, sequentially generated by photochemical charge separations in the reaction center and then catalyzes the O-O bond formation chemistry1-3. Here, we report room temperature snapshots by serial femtosecond X-ray crystallography to provide structural insights into the final reaction step of Kok's photosynthetic water oxidation cycle, the S3→[S4]→S0 transition where O2 is formed and Kok's water oxidation clock is reset. Our data reveal a complex sequence of events, which occur over micro- to milliseconds, comprising changes at the Mn4CaO5 cluster, its ligands and water pathways as well as controlled proton release through the hydrogen-bonding network of the Cl1 channel. Importantly, the extra O atom Ox, which was introduced as a bridging ligand between Ca and Mn1 during the S2→S3 transition4-6, disappears or relocates in parallel with Yz reduction starting at approximately 700 μs after the third flash. The onset of O2 evolution, as indicated by the shortening of the Mn1-Mn4 distance, occurs at around 1,200 μs, signifying the presence of a reduced intermediate, possibly a bound peroxide.

In this study, we proposed an advanced oxidation process of pyrite (FeS

In this study, the previously overlooked effects of contaminants' molecular structure on their degradation efficiencies and dominant reactive oxygen species (ROS) in advanced oxidation processes (AOPs) are investigated with a peroxymonosulfate (PMS) activation system selected as the typical AOP system. Averagely, degradation efficiencies of 19 contaminants are discrepant in the CoCaAl-LDO/PMS system with production of SO

The superior catalytic property of single-atom catalysts (SACs) renders them highly desirable in the energy and environmental fields. However, using SACs for water decontamination is hindered by their limited spatial distribution and density on engineered surfaces and low stability in complex aqueous environments. Herein, we present copper SACs (Cu

Sinorhizobium meliloti infects the host plant alfalfa to induce formation of nitrogen-fixation root nodules, which inevitably elicit reactive oxygen species (ROS) bursts and organic peroxide generation. The MarR family regulator OhrR regulates the expression of chloroperoxidase and organic hydrogen resistance protein, which scavenge organic peroxides in free-living S. meliloti cells. The single mutant of ohrR genes SMc01945 (ohrR1) and SMc00098 (ohrR2) lacked symbiotic phenotypes. In this work, we identified the novel ohrR gene SMa2020 (ohrR3) and determined that ohrR genes are important for rhizobial infection, nodulation and nitrogen fixation with alfalfa. By analysing the phenotypes of the single, double and triple deletion mutants of ohrR genes, we demonstrate that ohrR1 and ohrR3 slightly affect rhizobial growth, but ohrR2 and ohrR3 influence cellular resistance to the organic peroxide, tert-butyl hydroperoxide. Deletion of ohrR1 and ohrR3 negatively affected infection thread formation and nodulation, and consequently, plant growth. Correspondingly, the expression of the ROS detoxification genes katA and sodB as well as that of the nitrogenase gene nifH was downregulated in bacteroids of the double and triple deletion mutants, which may underlie the symbiotic defects of these mutants. These findings demonstrate that OhrR proteins play a role in the S. meliloti-alfalfa symbiosis.

Nitrogen doping could improve the catalytic performance of carbon materials, in which the nitrogen configuration could be used as active sites for peroxymonosulfate (PMS) activation. Herein, this paper studied how to turn waste to "treasure" by agriculture waste pomelo peel to prepare nitrogen-doped biochar and successfully applied it to advanced oxidation field. The effects of the sodium bicarbonate (NaHCO

SUMMARY Objective This study investigated the influence of the viscosity and kind of thickener of 35% hydrogen peroxide bleaching gels on the tooth (color change, demineralization of enamel, and permeation) and on the gel [reactive oxygen species (ROS), pH, and peroxide concentration]. Methods and Materials Two hundred forty specimens were divided into groups of bleaching gels with different thickeners (CAR, carbomer; ASE, alkali swellable emulsion; MSA, modified sulfonic acid polymer; SSP, semisynthetic polysaccharide; PAC, particulate colloids) in three viscosities (low: 50,000 cP; medium: 250,000 cP; high: 1,000,000 cP). Color change (ΔEab), demineralization of enamel by Knoop microhardness (KHN) reduction analysis, and peroxide permeation (PP) were analyzed in the specimens, while pH, peroxide concentration (PC), and ROS were evaluated in the gels. Data were analyzed by two-way ANOVA (α=0.05). Results The higher viscosity gels reduced ΔEab, PP, enamel softening, and ROS in relation to the lower viscosity gels. However, the drop in pH and PC were higher in the more viscous gels. Gels with MSA produced higher ΔEab compared with SSP and ASE. The PP was higher for PAC, and smaller for SSP and CAR. The KHN reduction was higher for CAR and smaller for PAC. The higher pH reduction was seen for ASE and CAR, and the smaller for SSP. The PC reduction was higher for SSP and smaller for CAR. More ROS were observed for MSA and fewer for ASE. Conclusions Increased gel viscosity was associated with reduced color change, permeation, demineralization of enamel, and ROS, and led to increased peroxide decomposition and pH alteration during the treatment. The kind of thickener significantly interfered with the treatment effects.

Ohrs (organic hydroperoxide resistance proteins) are antioxidant enzymes that play central roles in the response of microorganisms to organic peroxides. Here, we describe recent advances in the structure, catalysis, phylogeny, regulation, and physiological roles of Ohr proteins and of its transcriptional regulator, OhrR, highlighting their unique features. Ohr is extremely efficient in reducing fatty acid peroxides and peroxynitrite, two oxidants relevant in host-pathogen interactions. The highly reactive Cys residue of Ohr, named peroxidatic Cys (C

SUMMARY Aim The study evaluated the efficacy and potential erosion of non-peroxide strips compared to hydrogen peroxide (HP) whitening strips (WSs). Methods Color evaluation samples (N=64) were distributed into four groups and treated according to manufacturer’s directions. NC: Negative control treated with water; BT: Non-peroxide Brilliant Dissolving Strips; FM: Non-peroxide Fancymay Teeth WSs; WS: Crest 3D Brilliance HP White Strips. A contact-type spectrophotometer was used to measure color at baseline (T1), 1-day posttreatment (T2), and 1-week posttreatment (T3). Teeth were cut to a rectangular block for micro-CT erosion assessment. The samples (N=30) were divided into five groups. In addition to the four groups for color assessment, a positive control (PC) treated with 0.25% citric acid was added. The samples were scanned, reconstructed, and measured for erosion depth using a micro-CT analysis program software. Kruskal-Wallis test was used to determine differences in color change and erosion depth among the groups. Tests of hypotheses were two-sided with an alpha level of 0.05. Results The mean ΔE*ab at 1-day/1-week posttreatment were 2.4/2.5, 2.8/2.9, 2.8/3.2, and 8.6/11.0 for NC, BT, FM, and WS, respectively. There was a statistically significant difference for ΔE*ab at 1-day and 1-week posttreatment (p0.05). Mean erosion depths in microns were 0.52, 0.58, 0.42, 0.49, and 29.55 for NC, BT, FM, WS, and PC, respectively. There was a statistically significant difference among the groups (p=0.004). Group PC had the greatest erosion, while the other groups had negligible erosion that did not differ from each other (p>0.05). Conclusion Peroxide WSs had superior whitening efficacy compared to non-peroxide strips. None of the tested products compromised tooth structure integrity through enamel erosion.

The innate cartilage extracellular matrix is avascular and plays a vital role in innate chondrocytes. Recapping the crucial components of the extracellular matrix in engineered organs via polymeric gels and bioinspired approaches is promising for improving the regenerative aptitude of encapsulated cartilage/chondrocytes. Conventional gel formation techniques for polymeric materials rely on employing oxidative crosslinking, which is constrained in this avascular environment. Further, poor mechanical properties limit the practical applications of polymeric gels and reduce their therapeutic efficacy. Herein, the purpose of this study was to develop a bioadhesive gel possessing dual crosslinking for engineering cartilage. Tyramine (TYR) was first chemically conjugated to the alginate (ALG) backbone to form an ALG-TYR precursor, followed by the addition of calcium peroxide (CaO

The reaction of singlet oxygen (

Peroxides (H

Stable tricyclic aminoperoxides can be selectively assembled via a catalyst-free three-component condensation of β,δ'-triketones, H

The enzyme BesC from the β-ethynyl-L-serine biosynthetic pathway in Streptomyces cattleya fragments 4-chloro-L-lysine (produced from L-Lysine by BesD) to ammonia, formaldehyde, and 4-chloro-L-allylglycine and can analogously fragment L-Lys itself. BesC belongs to the emerging family of O(2)-activating non-heme-diiron enzymes with the “heme-oxygenase-like” protein fold (HDOs). Here we show that binding of L-Lys or an analog triggers capture of O(2) by the protein’s diiron(II) cofactor to form a blue μ-peroxodiiron(III) intermediate analogous to those previously characterized in two other HDOs, the olefin-installing fatty acid decarboxylase, UndA, and the guanidino-N-oxygenase domain of SznF. The ~ 5- and ~ 30-fold faster decay of the intermediate in reactions with 4-thia-L-Lys and (4RS)-chloro-DL-lysine than in the reaction with L-Lys itself, and the primary deuterium kinetic isotope effects (D-KIEs) on decay of the intermediate and production of L-allylglycine in the reaction with 4,4,5,5-[(2)H]-L-Lys, suggest that the peroxide intermediate or a reversibly connected successor complex abstracts a hydrogen atom from C4 to enable olefin formation. Surprisingly, the sluggish substrate L-Lys can dissociate after triggering the intermediate to form, thereby allowing one of the better substrates to bind and react. The structure of apo BesC and the demonstrated linkage between Fe(II) and substrate binding suggest that the triggering event involves an induced ordering of ligand-providing helix 3 (α3) of the conditionally stable HDO core. As previously suggested for SznF, the dynamic α3 also likely initiates the spontaneous degradation of the diiron(III) product cluster after decay of the peroxide intermediate, a trait emerging as characteristic of the nascent HDO family.

Organic peroxides play a vital role in the formation, evolution, and health impacts of atmospheric aerosols, yet their molecular composition and fate in the particle phase remain poorly understood. Here, we identified, using iodometry-assisted liquid chromatography mass spectrometry, a large suite of isomer-resolved peroxide monomers (C

This study demonstrated that peroxymonosulfate (PMS) activated by Fe(II)/citric acid (CA) could effectively degrade trichloroethylene (TCE) in the presence of Tween-80 (TW-80) or sodium dodecyl sulfate (SDS). Significant TCE removal of 91.6% (90.1%) with 1.3 g L

Lignin is one of the most abundant naturally occurring polymers and can produce value-added products such as vanillin and p-coumaric acid. In the current work, in-situ depolymerization of lignin for its valorization in a microbial peroxide-producing cell (MPPC) system was performed. It is an electrochemical cell that requires no external energy to produce H

Burning lignocellulosic biomass wastes in an outdoor atmosphere has placed heavy burden on ecological environment and increased risk on human health. Converting solid agricultural wastes into functional materials is a research hotspot. In this study, N-doped and CoO-loaded carbocatalyst (CoO-N/BC) was successfully synthesized from the cotton stalk biomass via a simple synthesis process of impregnation and carbonization. Compared with cotton stalk biomass derived pristine biochar, the CoO-N/BC possessed a higher specific surface area (466.631 m2 g-1 vs 286.684 m2 g-1) as well as a better catalytic performance in the activation of peroxymonosulfate (PMS) for CIP degradation. The superior catalytic efficiency was ascribed to the directional flow of electrons on the well-organized carbon network of CoO-N/BC, which accelerated electron migration and improved electron conduction ability. Based on the results of radical quenching experiment and electron paramagnetic resonance (EPR), both radical and non-radical process conjointly led to the stepwise decomposition of CIP, and singlet oxygen (1O2) mediated non-radical pathway was discovered to play a dominant role. Besides, the carbon-bridge mediated non-radical pathway was proved to accelerate this degradation process through the experiments of prolong the time of adding CIP at different time intervals. Nitrogen doped sites and CoO active sites as well as defects formed in sp2-hybridized carbon network were supposed to be the active sites for PMS. Furthermore, EIS and LSV were employed to confirm the electron transfer mediated non-radical process of reaction system. This work provides a modified strategy for the disposition of lignocellulosic biomass wastes and illuminates the underlying mechanism of heterogeneous catalysis by CoO-N/BC.

Here, we report a hydrothermally treated green leaves (Moringa oleifera) extract exploited as an efficient and highly sensitive catalyst to catalyze the chemiluminescence (CL) reaction of luminol. In the absence of enhancer, this green and hydrothermally treated catalyst was found to significantly enhance the CL intensity ~3.5-fold compared with the traditionally used K

Coupling membrane filtration with peroxymonosulfate (PMS) activation is promising to overcome the selectivity-permeability trade-off in membrane-based water treatment. However, the PMS catalytic efficiency of membrane still needs improvement to offset the insufficient reaction time during filtration process. Herein, an oxidized carbon nanotube intercalated nitrogen doped reduced graphene oxide (NRGO-OCNT) membrane with PMS activation function was firstly designed and prepared, which confined PMS activation in membrane interlayer for enhanced water treatment. The influence of confinement scale on membrane performance was studied through changing the OCNT intercalation ratio. Under the optimal confinement condition, the NRGO-OCNT membrane filtration integrated with PMS activation (MFPA) could realize 100% 4-chlorophenol removal at a high permeate flux of 290.2 L m−2 h−1 bar−1 (retention time of only 0.36 s), whose performance was 2.8, 1.7 and 5.0 times higher than that of filtration alone, NRGO MFPA (excessive confinement) and NRGO-OCNT powder-based batch reaction (no confinement), respectively. Moreover, NRGO-OCNT MFPA preferentially removed smaller-sized organics which easily entered and diffused in confined interlayer. The outstanding performance of NRGO-OCNT MFPA was owing to the nanoconfinement effect in appropriate confined interspacing, where the mass transfer rate of reactants was greatly boosted for enhanced generation of SO4 − and OH towards pollutant.

P-nitrophenol (PNP), a widely used compound, is harmful to the environment and human health. In this study, four iron-based Prussian blue analogs (PBAs) were prepared by coprecipitation (Co-Fe PBA, Mn-Fe PBA, Cu-Fe PBA and Fe-Fe PBA). The Co-Fe PBA exhibited high peroxymonosulfate (PMS) activation performance for PNP degradation, removing over 90% of PNP in 60 min at an optimal pH of 7, temperature at 30 ℃, initial concentration of 20 mg/L, PBA dose of 0.2 g/L and PMS dose of 1 g/L. The physicochemical properties of the Co-Fe PBA were investigated by various characterization methods. The catalytic activity of PBA and the influence of various process parameters and water quality on the catalytic reaction were investigated to elucidate the mechanism of p-nitrophenol degradation by PBA-activated persulfate. Moreover, the mechanism of accelerated degradation of PNP under HCO3- conditions and the role of major reactive oxides were determined by EPR measurement methods and free radical trapping experiments. HCO3- was found to directly activate PMS to produce reactive oxygen species, and 1O2, ∙OH and SO4∙- were all greatly increased. This work presents a promising green heterogeneous catalyst for the degradation of emerging contaminants (ECs) in real wastewater with natural organic matter and coexisting anions by PMS activation.

The mechanism of reaction of DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) with ·CH

In this study, a new hollow nanotube material, 30% Co–CHNTs was prepared by the impregnation–chemical reduction–calcination method. This material can be used as a peroxymonosulfate (PMS) activator to catalyse the degradation of sulfamethoxazole (SMX). The best reaction conditions that correspond to the degradation rate of SMX, up to 97.5%, are as follows: the concentration of SMX is 10 mg L−1, the amount of catalyst is 0.20 g L−1, the dosage is 1.625 mM, and the solution pH is 6.00. X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical emission spectrometry (ICP-OES) show that the calcined composites mainly stimulate an increase in the content of bivalent cobalt in PMS and reduce the leaching of cobalt ions after the reaction. Additionally, the 30% Co–CHNTs + PMS reaction system exhibits a reasonable SMX degradation rate in a natural organic matter solution and excellent stability after three repeated experiments. Furthermore, the possible degradation mechanism in the 30% Co–CHNTs + PMS reaction system was analysed through electron paramagnetic resonance (EPR) and free-radical capture experiments, and it was observed that the non-radical degradation of 1O2 plays a leading role in SMX degradation. Finally, according to the nine degradation intermediates detected by liquid chromatography-mass spectrometry (LC–MS), four possible SMX degradation routes were proposed. This study proved that a 30% Co–CHNTs heterogeneous catalyst is easily prepared, inexpensive, and environmentally friendly and has potential application in antibiotic wastewater treatment.

The redox behavior of metal active sites determines the rate of heterogeneous catalysis in peroxymonosulfate activation. Previous reports focused on the construction of catalysts for accelerating interfacial electron transfer. In this work, a new strategy was proposed for facilitating valence cycles of Cu

SUMMARY Objectives To systematically review the literature on color stability of resin-based composites (RBC) after in vitro bleaching protocols and to assess the influence of bleaching protocols by meta-regression analysis on RBC color stability, and the association with clinical and experimental characteristics. Methods The electronic search was conducted in MEDLINE/PubMed, Scopus, and Web of Science databases and included English language studies that evaluated and reported color differences (CIELAB values) of RBC after in vitro bleaching procedures using hydrogen peroxide and/or carbamide peroxide. Results Database search for color change of RBC after bleaching retrieved 1335 eligible papers after removing duplicates. After initial screening, 66 articles were assessed for full-text reading with final inclusion of 23 published papers. A meta-regression analysis showed that storage time (p≤0.01), color measuring device (p≤0.01), and background color (p≤0.01) had influenced on color changes of RBC. The bleaching protocol (bleaching agent and time of application) did not influence on color changes of RBC (p>0.01). Conclusions There is evidence that RBC change color after bleaching, but the change is not clinically significant.

Bacterial luciferase (Lux) catalyzes oxidation of reduced flavin mononucleotide (FMN) and aldehyde to form oxidized FMN and carboxylic acid via molecular oxygen with concomitant light generation. The enzyme is useful for various detection applications in biomedical experiments. Upon reacting with oxygen, the reduced FMN generates C4a-peroxy-FMN (FMNH-C4a-OO

BACKGROUND Most very premature newborns (< 32 weeks of gestation) receive parenteral nutrition (PN) that is inherently contaminated with peroxides. Oxidative stress induced by PN is associated with bronchopulmonary dysplasia, a main pathological complication in these babies who have weak antioxidant capacity to detoxify peroxides because of their glutathione deficiency. In animals, glutathione supplementation of PN prevented oxidative stress and alveolar loss (the main characteristic of bronchopulmonary dysplasia). Of its two forms - disulfide (GSSG) and free thiol (GSH) - GSSG was used because of its better stability in PN. However, a 30% loss of GSSG in PN is observed. The potentially high therapeutic benefits of GSSG supplementation on the health of very premature babies makes the study of its stability highly important. MATERIALS AND METHODS GSSG was incubated in combination with the following components of PN: dextrose, multivitamins, Primene, Travasol, as well as with cysteine, cystine and peroxides for 24h. Total glutathione in these solutions was measured 0-24h after the addition of GSSG. RESULTS The combination of cysteine and multivitamins caused the maximum loss of glutathione. The stability of GSSG was not affected by multivitamins. The cysteine was responsible for about 20% of the loss of GSSG, in presence of multivitamins the loss reached more than 70%. Removing the cysteine prevented the degradation of glutathione. CONCLUSION GSSG reacts with cysteine to form cysteine-glutathione disulfide, another suitable glutathione substrate for preterm neonates. The study confirms that GSSG added to PN can potentially provide a precursor to de novo synthesis of glutathione in vivo. This article is protected by copyright. All rights reserved.

Human mitochondrial manganese superoxide dismutase (MnSOD) is a major player in alleviating oxidative stress within the mitochondria, which is a characteristic of a wide range of human diseases. Here, the methods leading to the structural visualization of the evasive peroxo complex of MnSOD by integrating cryotrapping and neutron protein crystallography are described., Structurally identifying the enzymatic intermediates of redox proteins has been elusive due to difficulty in resolving the H atoms involved in catalysis and the susceptibility of ligand complexes to photoreduction from X-rays. Cryotrapping ligands for neutron protein crystallography combines two powerful tools that offer the advantage of directly identifying hydrogen positions in redox-enzyme intermediates without radiolytic perturbation of metal-containing active sites. However, translating cryogenic techniques from X-ray to neutron crystallo­graphy is not straightforward due to the large crystal volumes and long data-collection times. Here, methods have been developed to visualize the evasive peroxo complex of manganese superoxide dismutase (MnSOD) so that all atoms, including H atoms, could be visualized. The subsequent cryocooling and ligand-trapping methods resulted in neutron data collection to 2.30 Å resolution. The P6122 crystal form of MnSOD is challenging because it has some of the largest unit-cell dimensions (a = b = 77.8, c = 236.8 Å) ever studied using high-resolution cryo-neutron crystallography. The resulting neutron diffraction data permitted the visualization of a dioxygen species bound to the MnSOD active-site metal that was indicative of successful cryotrapping.

A metal-free method for the Minisci-type arylation of heterocycles with aryl acyl peroxides has been reported. This strategy enables the rapid and simple synthesis of a series of Minisci-type adducts from commercially available starting materials without metal catalysts. A free-radical-pathway mechanism is suggested for this transformation.

Our study aimed to investigate the impact of various emulsifiers, namely whey protein isolate (WPI), soy protein isolate (SPI), and Tween 80 (Tw), on their ability to encapsulate cannabis oil with maltodextrin as the wall material. The physicochemical properties of the powder, the stability of the cannabinoids, and their bioaccessibility during static