Synergetic Manipulation Mechanism of Single-Atom M-N4 and M-OH (M = Mn, Fe, Co, Ni) Sites for Ozone Activation: Theoretical Prediction and Experimental Verification.

Carbon-based single-atom catalysts (SACs) have been gradually introduced in heterogeneous catalytic ozonation (HCO), but the interface mechanism of O3 activation on the catalyst surface is still ambiguous, especially the effect of a surface hydroxyl group (M-OH) at metal sites. Herein, we combined theoretical calculations with experimental verifications to comprehensively investigate the O3 activation mechanisms on a series of conventional SAC structures with N-doped nanocarbon substrates (MN4-NCs, where M = Mn, Fe, Co, Ni). The synergetic manipulation effect of the metal atom and M-OH on O3 activation pathways was paid particular attention. O3 tends to directly interact with the metal atom on MnN4-NC, FeN4-NC, and NiN4-NC catalysts, among which MnN4-NC has the best catalytic activity for its relatively lower activation energy barrier of O3 (0.62 eV) and more active surface-adsorbed oxygen species (Oads). On the CoN4-NC catalyst, direct interaction of O3 with the metal site is energetically infeasible, but O3 can be activated to generate Oads or HO2 species from direct or indirect participation of M-OH sites. The experimental results showed that 90.7 and 82.3% of total organic carbon (TOC) was removed within 40 min during catalytic ozonation of p-hydroxybenzoic acid with MnN4-NC and CoN4-NC catalysts, respectively. Phosphate quenching, catalyst characterization, and EPR measurement further supported the theoretical prediction. This contribution provides fundamental insights into the O3 activation mechanism on SACs, and the methods and ideals could be helpful for future studies of environmental catalysis.

Unexpectedly Enhanced Organics Removal in Persulfate Oxidation with High Concentration of Sulfate: The Origin and the Selectivity.

Massive anions in high saline wastewater are primary factors that restricted the efficiency of pollutant degradation in advanced oxidation processes (AOPs). Herein, we reported the influence laws of different anions at high concentration on the electron-transfer process in the activation of persulfate, and especially, the sulfate anion exhibited the excellent promotion effect. Depending on the ionic charge, polarizability, and size, the anions exerted diverse effects on the dispersed phase and zeta potential of carbonaceous catalysts, which further embodied in the removal of pollutants. Based on the differences of reaction rate constant in water solution and high saline solution, the order was ClO4- < NO3- < Cl- < SO42- < CO32-, obeying the Hofmeister series. The enhancement of the sulfate anion was widely confirmed with different carbonaceous catalysts and pollutants with various structures. It could be attributed to the higher oxidation capacity, the faster interfacial electron transfer, and the better catalyst dispersion in the high sulfate environment. On the other hand, the decrease of zeta potential of the catalyst induced by sulfate reinforced the electrostatic attraction or repulsion with pollutants, which caused the selectivity of the sulfate promotion effect. Overall, this study provides new insights into the mechanism of influence of anions on AOPs, which refreshed the cognition of the role of sulfate on pollutant degradation, and helps guide the treatment design of high salinity wastewater.

Single-Atom Mn-N4 Site-Catalyzed Peroxone Reaction for the Efficient Production of Hydroxyl Radicals in an Acidic Solution.

The peroxone reaction between O3 and H2O2 has been deemed a promising technology to resolve the increasingly serious water pollution problem by virtue of the generation of superactive hydroxyl radicals (•OH), but it suffers greatly from an extremely limited reaction rate constant under acidic conditions (ca. less than 0.1 M-1 s-1 at pH 3). This article describes a heterogeneous catalyst composed of single Mn atoms anchored on graphitic carbon nitride, which effectively overcomes such a drawback by altering the reaction pathway and thus dramatically promotes •OH generation in acid solution. Combined experimental and theoretical studies demonstrate Mn-N4 as the catalytically active sites. A distinctive catalytic pathway involving HO2• formation by the activation of H2O2 is found, which gets rid of the restriction of HO2- as the essential initiator in the conventional peroxone reaction. This work offers a new pathway of using a low-cost and easily accessible single-atom catalyst (SAC) and could inspire more catalytic oxidation strategies.

Composite material derived from ZIF-67 and biochar promotes ozonation of 4-nitrophenol.

Cobalt 2-methylimidazole (ZIF-67) have abundant nitrogen and cobalt elements, which can be used as an excellent precursor for catalyst synthesis. In this study, a new Co, N co-doped carbon-based catalyst (Co-N-BC) was synthesized from ZIF-67 and biochar, which can significantly improve the degradation of 4-nitrophenol (4-NP) in catalytic ozonation. The mineralization rate of 4-NP achieves 65.8% within 60 min. The catalyst showed high recycling stability in the four cycles of reuse experiment. Different operating parameters, such as solution pH, the concentration of O3 and 4-NP, have been studied in the Co-N-BC catalytic ozonation. O3, O2-· and ·OH are determined as the main reactive species for 4-NP degradation, and ·OH is especially responsibly for 4-NP mineralization. The existence of inorganic ions, such as Cl-, NO2-, CO32- and PO43-, all significantly inhibited the degradation of 4-NP to different extend, respectively. The effect of substituent on a series of organics with similar structure of 4-NP was also investigated in Co-N-BC catalytic ozonation. This study provides a new composite material for heterogeneous catalytic ozonation, which is very promising in 4-NP contained complex wastewater treatment.

Facile synthesis of nitrogen and sulfur co-doped hollow microsphere polymers from benzothiazole containing wastewater for water treatment.

Advanced oxidation is a very efficient method in wastewater treatment, but it is a waste of resources to directly oxide the high concentration of valuable organics into carbon dioxide and water. In this paper, the combination of persulfate and wet air oxidation was developed to recover organics from high concentration of wastewater, along with high mineralization of the residual organics. Nitrogen and sulfur co-doped hollow spherical polymers with narrow size distribution was recovered from the simulated benzothialzole (BTH) wastewater in this facile way, along with chemical oxygen demand (COD) removal rate higher than 90%. The formation route of the polymers was intensively studied based on detailed analysis of different kinds of reaction intermediates. The polymers can be further carbonized into co-doped hollow carbon microsphere, which showed better performance in organic contaminants removal than a commercial activated carbon both in adsorption or catalytic persulfate oxidation. This proposed a new strategy to simultaneously combine oxidation and polymerization for resource recovery from wastewater with high concentration of heterocyclic compounds.

Preparation of three-layer flaxseed gum/chitosan/flaxseed gum composite coatings with sustained-release properties and their excellent protective effect on myofibril protein of rainbow trout.

Plant essential oils lose their activity due to unstable chemical properties and volatility, and the coating can improve their stability by encapsulating. The three-layer coatings were prepared by tape casting method with flaxseed gum (FG) and chitosan (CS) as film-forming materials, eugenol (EG) and laurel essential oil (LEO) as preservatives. The composite coatings were characterized, and their physicochemical properties, release properties, antibacterial and antioxidant properties were determined. Meanwhile, the protective effect of the composite coatings on rainbow trout fillets myofibril protein was studied. The mechanical properties of the FG/CS/FG coatings are better than FG coating. The release of EG and LEO from the coatings are followed simple diffusion mechanism. After added essential oils, the antibacterial and antioxidant properties of the composite coatings are significantly enhanced. In the preservation process of the rainbow trout fillets, the composite coatings can reduce the carbonyl content, increase the sulfhydryl content and Ca2+-ATPase activity. The ß-sheet content is 6.09%-15.63% higher than that of control, indicating the coatings are helpful to maintain the order of myofibril protein. The composite coatings slowed down the decrease of antioxidant enzyme activity, thus delay the protein oxidation. Because of long-term antibacterial and antioxidant properties, the composite coatings have potential value in food preservation or food packaging materials.

Identification of feature genes and pathways for Alzheimer's disease via WGCNA and LASSO regression.

While Alzheimer's disease (AD) can cause a severe economic burden, the specific pathogenesis involved is yet to be elucidated. To identify feature genes associated with AD, we downloaded data from three GEO databases: GSE122063, GSE15222, and GSE138260. In the filtering, we used AD for search keywords, Homo sapiens for species selection, and established a sample size of > 20 for each data set, and each data set contains Including the normal group and AD group. The datasets GSE15222 and GSE138260 were combined as a training group to build a model, and GSE122063 was used as a test group to verify the model's accuracy. The genes with differential expression found in the combined datasets were used for analysis through Gene Ontology (GO) and The Kyoto Encyclopedia of Genes and Genome Pathways (KEGG). Then, AD-related module genes were identified using the combined dataset through a weighted gene co-expression network analysis (WGCNA). Both the differential and AD-related module genes were intersected to obtain AD key genes. These genes were first filtered through LASSO regression and then AD-related feature genes were obtained for subsequent immune-related analysis. A comprehensive analysis of three AD-related datasets in the GEO database revealed 111 common differential AD genes. In the GO analysis, the more prominent terms were cognition and learning or memory. The KEGG analysis showed that these differential genes were enriched not only in In the KEGG analysis, but also in three other pathways: neuroactive ligand-receptor interaction, cAMP signaling pathway, and Calcium signaling pathway. Three AD-related feature genes (SST, MLIP, HSPB3) were finally identified. The area under the ROC curve of these AD-related feature genes was greater than 0.7 in both the training and the test groups. Finally, an immune-related analysis of these genes was performed. The finding of AD-related feature genes (SST, MLIP, HSPB3) could help predict the onset and progression of the disease. Overall, our study may provide significant guidance for further exploration of potential biomarkers for the diagnosis and prediction of AD.

Generation of Marker-Free Transgenic Rice Resistant to Rice Blast Disease Using Ac/Ds Transposon-Mediated Transgene Reintegration System.

Rice blast is one of the most serious diseases of rice and a major threat to rice production. Breeding disease-resistant rice is one of the most economical, safe, and effective measures for the control of rice blast. As a complement to traditional crop breeding, the transgenic method can avoid the time-consuming process of crosses and multi-generation selection. In this study, maize (Zea mays) Activator (Ac)/Dissociation (Ds) transposon vectors carrying green fluorescent protein (GFP) and red fluorescent protein (mCherry) genetic markers were used for generating marker-free transgenic rice. Double fluorescent protein-aided counterselection against the presence of T-DNA was performed together with polymerase chain reaction (PCR)-based positive selection for the gene of interest (GOI) to screen marker-free progeny. We cloned an RNAi expression cassette of the rice Pi21 gene that negatively regulates resistance to rice blast as a GOI into the Ds element in the Ac/Ds vector and obtained marker-free T1 rice plants from 13 independent transgenic lines. Marker-free and Ds/GOI-homozygous rice lines were verified by PCR and Southern hybridization analysis to be completely free of transgenic markers and T-DNA sequences. qRT-PCR analysis and rice blast disease inoculation confirmed that the marker-free transgenic rice lines exhibited decreased Pi21 expression levels and increased resistance to rice blast. TAIL-PCR results showed that the Ds (Pi21-RNAi) transgenes in two rice lines were reintegrated in intergenic regions in the rice genome. The Ac/Ds vector with dual fluorescent protein markers offers more reliable screening of marker-free transgenic progeny and can be utilized in the transgenic breeding of rice disease resistance and other agronomic traits.

Effect of scrubbing by NaClO backwashing on membrane fouling in anammox MBR.

NaClO based chemically enhanced backwash (CEB) is often administered to maintain membrane permeability during the operation of MBR. However, the effect and working mechanism of NaClO concentrations in CEB were rarely investigated. The current investigation examined the changes in membrane resistance, permeate production and membrane morphology with or without CEB in an anammox MBR to reveal the scrubbing effect of different NaClO concentrations (0-596 mg/L). Good cleaning effect indicated by membrane fouling rate of 1.98-2.26 kPa/day and membrane permeate production of 80-88 L was observed when NaClO concentration of 149-596 mg/L was used. The best cleaning effect was observed when 298 mg/L of NaClO was used. To explore the mechanism of CEB action, backwashing foulants were also analyzed. Insoluble EPS transformed into soluble forms like S-EPS or SMP after the sludge was exposed to NaClO. The NaClO based CEB removed 112-675 mg of polysaccharide (PS)/m2 in foulants at NaClO concentration of 149-596 mg/L, which was significantly higher than the value obtained by pure water (35 mg PS/m2). The possible mechanisms behind the detachment of soluble PS seemed as oxidation and sterilization by NaClO. The current investigation provides useful guidelines on NaClO concentrations applied during CEB for anammox MBR.