Hydrophobic TaOx Species Overlayer Tuning Light-Driven Methane Chlorination with Inorganic Chlorine.

Halogenated methane serves as a universal platform molecule for building high-value chemicals. Utilizing sodium chloride solution for photocatalytic methane chlorination presents an environmentally friendly method for methane conversion. However, competing reactions in gas-solid-liquid systems leads to low efficiency and selectivity in photocatalytic methane chlorination. Here, an in situ method is employed to fabricate a hydrophobic layer of TaOx species on the surface of NaTaO3. Through in-situ XPS and XANES spectra analysis, it is determined that TaOx is a coordination unsaturated species. The TaOx species transforms the surface properties from the inherent hydrophilicity of NaTaO3 to the hydrophobicity of TaOx/NaTaO3, which enhances the accessibility of CH4 for adsorption and activation, and thus promotes the methane chlorination reaction within the gas-liquid-solid three-phase system. The optimized TaOx/NaTaO3 photocatalyst has a good durability for multiple cycles of methane chlorination reactions, yielding CH3Cl at a rate of 233 µmol g-1 h-1 with a selectivity of 83%. In contrast, pure NaTaO3 exhibits almost no activity toward CH3Cl formation, instead catalyzing the over-oxidation of CH4 into CO2. Notably, the activity of the optimized TaOx/NaTaO3 photocatalyst surpasses that of reported noble metal photocatalysts. This research offers an effective strategy for enhancing the selectivity of photocatalytic methane chlorination using inorganic chlorine ions.

Application of ultrasonic-enhanced active seed crystals in the removal of sodium oxalate from alumina refinery waste liquor.

When organic matter, especially sodium oxalate (Na2C2O4), accumulates to a certain extent, it will seriously affect the alumina production process in the refinery and therefore urgently needs to be removed. This work attempts to illuminate the benefits of ultrasonic intensification of the crystallization process of Na2C2O4, taking the alumina refinery waste liquor, i.e., flat plate washing liquor, as a case study. The effects of different operating parameters (seed crystal addition amount, caustic soda concentration, reaction time, ultrasonic power) on the crystallization behavior and yield are discussed, and it is found that ultrasonic can increase the Na2C2O4 removal rate to 70.4%. The addition of ultrasonic promotes the morphological evolution of Na2C2O4 and is of great significance to the optimization of the components of the precipitated Na2C2O4. Specifically, the proportion of Na2C2O4 in the crystallized product reaches 64% with conventional conditions, while it reaches 77% with ultrasonic conditions. Therefore, ultrasonic can greatly reduce the alkali loss caused by the crystallization process of Na2C2O4 in flat plate washing liquor, which has great economic benefits.

Cypermethrin induces Sertoli cell apoptosis through endoplasmic reticulum-mitochondrial coupling involving IP3R1-GRP75-VDAC1.

A widely used type II pyrethroid pesticide cypermethrin (CYP) is one of endocrine disrupting chemicals (EDCs) with anti-androgenic activity to induce male reproductive toxicology. However, the mechanisms have not been fully elucidated. This study was to explore the effects of CYP on apoptosis of mouse Sertoli cells (TM4) and the roles of endoplasmic reticulum (ER)-mitochondria coupling involving 1,4,5-trisphosphate receptor type1-glucose-regulated protein 75-voltage-dependent anion channel 1 (IP3R1-GRP75-VDAC1). TM4 were cultured with different concentrations of CYP. Flow cytometry, calcium (Ca2+) fluorescent probe, transmission electron microscopy and confocal microscopy, and western blot were to examine apoptosis of TM4, mitochondrial Ca2+, ER-mitochondria coupling, and expressions of related proteins. CYP was found to increase apoptotic rates of TM4 significantly. CYP was shown to significantly increase expressions of cleaved caspase-3, cleaved poly ADP-ribose polymerase (PARP). Concentration of mitochondrial Ca2+ was increased by CYP treatment significantly. CYP significantly enhanced ER-mitochondria coupling. CYP was shown to increase expressions of IP3R, Grp75 and VDAC1 significantly. We suggest that CYP induces apoptosis in TM4 cells by facilitating mitochondrial Ca2+ overload regulated by ER-mitochondria coupling involving IP3R1-GRP75-VDAC1. This study identifies a novel mechanism of CYP-induced apoptosis in Sertoli cells.

Transcription factors BZR2/MYC2 modulate brassinosteroid and jasmonic acid crosstalk during pear dormancy.

Bud dormancy is an important physiological process during winter. Its release requires a certain period of chilling. In pear (Pyrus pyrifolia), the abscisic acid (ABA)-induced expression of DORMANCY-ASSOCIATED MADS-box (DAM) genes represses bud break, whereas exogenous gibberellin (GA) promotes dormancy release. However, with the exception of ABA and GA, the regulatory effects of phytohormones on dormancy remain largely uncharacterized. In this study, we confirmed brassinosteroids (BRs) and jasmonic acid (JA) contribute to pear bud dormancy release. If chilling accumulation is insufficient, both 24-epibrassinolide (EBR) and methyl jasmonic acid (MeJA) can promote pear bud break, implying that they positively regulate dormancy release. BRASSINAZOLE RESISTANT 2 (BZR2), which is a BR-responsive transcription factor, inhibited PpyDAM3 expression and accelerated pear bud break. The transient overexpression of PpyBZR2 increased endogenous GA, JA, and JA-Ile levels. In addition, the direct interaction between PpyBZR2 and MYELOCYTOMATOSIS 2 (PpyMYC2) enhanced the PpyMYC2-mediated activation of Gibberellin 20-oxidase genes PpyGA20OX1L1 and PpyGA20OX2L2 transcription, thereby increasing GA3 contents and accelerating pear bud dormancy release. Interestingly, treatment with 5 µm MeJA increased the bud break rate, while also enhancing PpyMYC2-activated PpyGA20OX expression and increasing GA3,4 contents. The 100 µm MeJA treatment decreased the PpyMYC2-mediated activation of the PpyGA20OX1L1 and PpyGA20OX2L2 promoters and suppressed the inhibitory effect of PpyBZR2 on PpyDAM3 transcription, ultimately inhibiting pear bud break. In summary, our data provide insights into the crosstalk between the BR and JA signaling pathways that regulate the BZR2/MYC2-mediated pathway in the pear dormancy release process.

Synergistic Spatial Confining Effect and O Vacancy in WO3 Hollow Sphere for Enhanced N2 Reduction.

Visible-light-driven N2 reduction into NH3 in pure H2O provides an energy-saving alternative to the Haber-Bosch process for ammonia synthesizing. However, the thermodynamic stability of N≡N and low water solubility of N2 remain the key bottlenecks. Here, we propose a solution by developing a WO3-x hollow sphere with oxygen vacancies. Experimental analysis reveals that the hollow sphere structure greatly promotes the enrichment of N2 molecules in the inner cavity and facilitates the chemisorption of N2 onto WO3-x-HS. The outer layer's thin shell facilitates the photogenerated charge transfer and the full exposure of O vacancies as active sites. O vacancies exposed on the surface accelerate the activation of N≡N triple bonds. As such, the optimized catalyst shows a NH3 generation rate of 140.08 µmol g-1 h-1, which is 7.94 times higher than the counterpart WO3-bulk.

Low-cost flexible textile electrocatalyst for overall water splitting.

Through the braidability of cotton fiber and the richness of surface functional groups, cotton fiber can be woven into any shape, and catalytically active centers can be stably anchored on the fibers. During the electrocatalytic overall water splitting (OWS) process, catalyst shedding and activity reduction can be effectively avoided.

Combining ozone and ultrasound technology to remove S2- in Bayer liquor.

High content sulfur (S2-) in Bayer liquor can increase alkali consumption, accelerate equipment corrosion, especially seriously affect alumina production. The removal of S2- in Bayer liquor is studied using ultrasonic enhanced ozone method, which significantly improves the removal efficiency. Results indicate that the best removal efficiency of 93.83 % is obtained with reaction duration of 20 min, oxygen flow rate of 80 L/h, ultrasonic power of 60 W and reaction temperature of 60 °C. The comparative analysis shows that the removal efficiency of S2- is 25.34 % higher than that of ozone (O3) system after introducing ultrasound (US), indicating that US accelerates the mass transfer process of O3 and increases the hydroxyl radicals (OH) content. For further explanation of the mechanism of US/O3 system, EPR and XPS spectra are applied to analyze the content of free radical and the form of sulfur in Bayer liquor, indicating that the content of free radical in US/O3 system is more than US and O3 systems, and all sulfur is converted to SO42- after full oxidation.

Metal to non-metal sites of metallic sulfides switching products from CO to CH4 for photocatalytic CO2 reduction.

The active center for the adsorption and activation of carbon dioxide plays a vital role in the conversion and product selectivity of photocatalytic CO2 reduction. Here, we find multiple metal sulfides CuInSnS4 octahedral nanocrystal with exposed (1 1 1) plane for the selectively photocatalytic CO2 reduction to methane. Still, the product is switched to carbon monoxide on the corresponding individual metal sulfides In2S3, SnS2, and Cu2S. Unlike the common metal or defects as active sites, the non-metal sulfur atom in CuInSnS4 is revealed to be the adsorption center for responding to the selectivity of CH4 products. The carbon atom of CO2 adsorbed on the electron-poor sulfur atom of CuInSnS4 is favorable for stabilizing the intermediates and thus promotes the conversion of CO2 to CH4. Both the activity and selectivity of CH4 products over the pristine CuInSnS4 nanocrystal can be further improved by the modification of with various co-catalysts to enhance the separation of the photogenerated charge carrier. This work provides a non-metal active site to determine the conversion and selectivity of photocatalytic CO2 reduction.

MicroRNA­30a­5p regulates cypermethrin-induced apoptosis of Sertoli cells by targeting KLF9 in vitro.

Cypermethrin (CYP) has been identified as one kind of endocrine-disrupting chemicals (EDCs) to induce male reproduction damage. This study aimed to investigate the effects and mechanisms of miR-30a-5p on CYP induced apoptosis of TM4 mouse Sertoli cells in vitro. In the present study, 0 µM, 10 µM, 20 µM, 40 µM and 80 µM CYP were used to treat TM4 cells for 24 h. The apoptosis of TM4 cells, the expression level of miR-30a-5p, the protein expressions and the interaction between miR-30a-5p and KLF9 were detected by flow cytometry, quantitative Real-Time PCR, Western blot and luciferase reporter assays. CYP induced apoptosis of TM4 cells, inhibited expression of miR-30a-5p in TM4 cells, and overexpression of miR-30a-5p partially recovered CYP induced cells apoptosis. Furthermore, KLF9 was a potential downstream target of miR-30a-5p predicted by publicly available databases. KLF9 expression level in TM4 cells was significantly elevated after treatment with CYP, and the induction was inhibited by miR-30a-5p mimics transfection. Meanwhile, dual-luciferase reporter assay demonstrated that miR-30a-5p directly targeted KLF9-3'UTR. Moreover, in the presence of CYP, the apoptosis regulator p53 expression was also increased in TM4 cells. Overexpression miR-30a-5p or down-regulation of KLF9 both attenuated the induction of CYP on p53 expression. Overall, the present study demonstrated that miR-30a-5p regulated CYP induced TM4 cells apoptosis by targeting KLF9/p53 axis.

Microreactor-based micro/nanomaterials: fabrication, advances, and outlook.

Micro/nanomaterials are widely used in optoelectronics, environmental materials, bioimaging, agricultural industries, and drug delivery owing to their marvelous features, such as quantum tunneling, size, surface and boundary, and Coulomb blockade effects. Recently, microreactor technology has opened up broad prospects for green and sustainable chemical synthesis as a powerful tool for process intensification and microscale manipulation. This review focuses on recent progress in the microreactor synthesis of micro/nanomaterials. First, the fabrication and design principles of existing microreactors for producing micro/nanomaterials are summarized and classified. Afterwards, typical examples are shown to demonstrate the fabrication of micro/nanomaterials, including metal nanoparticles, inorganic nonmetallic nanoparticles, organic nanoparticles, Janus particles, and MOFs. Finally, the future research prospects and key issues of microreactor-based micro/nanomaterials are discussed. In short, microreactors provide new ideas and methods for the synthesis of micro/nanomaterials, which have huge potential and inestimable possibilities in large-scale production and scientific research.

High-Performance Layered CaV4O9-MXene Composite Cathodes for Aqueous Zinc Ion Batteries.

Due to their reliability, affordability and high safety, rechargeable aqueous zinc ion batteries (ZIBs) have garnered a lot of attention. Nevertheless, undesirable long-term cycle performance and the inadequate energy density of cathode materials impede the development of ZIBs. Herein, we report a layered CaV4O9-MXene (Ti3C2Tx) composite assembled using CaV4O9 nanosheets on Ti3C2Tx and investigate its electrochemical performance as a new cathode for ZIBs, where CaV4O9 nanosheets attached on the surface of MXene and interlamination create a layered 2D structure, efficiently improving the electrical conductivity of CaV4O9 and avoiding the stacking of MXene nanosheets. The structure also enables fast ion and electron transport. Further discussion is conducted on the effects of adding MXene in various amounts on the morphology and electrochemical properties. The composite shows an improved reversible capacity of 274.3 mA h g-1 at 0.1 A g-1, superior rate capabilities at 7 A g-1, and a high specific capacity of 107.6 mA h g-1 can be delivered after 2000 cycles at a current density of 1 A g-1. The improvement of the electrochemical performance is due to its unique layered structure, high electrical conductivity, and pseudo capacitance behavior.

Interface Density Engineering on Heterogeneous Molybdenum Dichalcogenides Enabling Highly Efficient Hydrogen Evolution Catalysis and Sodium Ion Storage.

Constructing active heterointerfaces is powerful to enhance the electrochemical performances of transition metal dichalcogenides, but the interface density regulation remains a huge challenge. Herein, MoO2 /MoS2 heterogeneous nanorods are encapsulated in nitrogen and sulfur co-doped carbon matrix (MoO2 /MoS2 @NSC) by controllable sulfidation. MoO2 and MoS2 are coupled intimately at atomic level, forming the MoO2 /MoS2 heterointerfaces with different distribution density. Strong electronic interactions are triggered at these MoO2 /MoS2 heterointerfaces for enhancing electron transfer. In alkaline media, the optimal material exhibits outstanding hydrogen evolution reaction (HER) performances that significantly surpass carbon-covered MoS2 nanorods counterpart (η10 : 156 mV vs 232 mV) and most of the MoS2 -based heterostructures reported recently. First-principles calculation deciphers that MoO2 /MoS2 heterointerfaces greatly promote water dissociation and hydrogen atom adsorption via the O-Mo-S electronic bridges during HER process. Moreover, benefited from the high pseudocapacitance contribution, abundant "ion reservoir"-like channels, and low Na+ diffusion barrier appended by high-density MoO2 /MoS2 heterointerfaces, the material delivers high specific capacity of 888 mAh g-1 , remarkable rate capability and cycling stability of 390 cycles at 0.1 A g-1 as the anode of sodium ion battery. This work will undoubtedly light the way of interface density engineering for high-performance electrochemical energy conversion and storage systems.

Plasmon Au/K-doped defective graphitic carbon nitride for enhanced hydrogen production.

Knowledge of the photocatalytic H2-evolution mechanism is of critical importance for water splitting, and for designing active catalysts for a sustainable energy supply. In this study, we prepared plasmon Au-modified K-doped defective graphitic carbon nitride (Au/KCNx) and then applied it in photocatalytic hydrogen-production tests. The hydrogen-production rate of the Au/KCNx photocatalyst (8.85 mmol g-1 h-1) was found to be almost 104 times higher than that of Au/g-C3N4 (0.085 mmol g-1 h-1), together with an apparent quantum efficiency of 12.8% at 420 nm. It could significantly improve the photocatalytic activities of the Au/KCNx sample, which was attributed to the synergistic effects of the plasmon effect, potassium doping, and nitrogen vacancy. In addition, the Au/KCNx photocatalyst had a large surface area, which was beneficial for photogenerated carrier separation and transfer. The novel strategy proposed here is a potential new method for the development of graphitic carbon nitride photocatalysts with obviously enhanced activities.

Engineering active heterojunction architecture with oxygenated-Co, Mo bimetallic sulfide heteronanosheet and graphene oxide for peroxymonosulfate activation.

Bimetallic sulfides have distinctive catalytic property in activating peroxymonosulfate (PMS) for water remediation. Polyoxometalates as potential precursors have rarely been reported for the catalytic degradation of refractory organic pollutants. Herein, a composite catalyst of Co-Mo bimetallic sulfides supported onto graphene oxide (O-CoMoS/GO) with a heterojunction architecture was synthesized through a hydrothermal strategy with polyoxometalates ((NH4)4[CoIIMo6O24H6]·6H2O) as the precursor and applied in the PMS activation. This material showed a superior performance for the catalytic degradation of the model organic pollutant, 4-chlorophenol (rapidly removed within 10 min with an apparent reaction rate constant of 0.5458 min-1). O-CoMoS/GO outperformed most of the reported catalysts in terms of activity and had a strong tolerance towards common organic and inorganic compounds in water, and could perform well in different real water systems. Experimental and theoretical results indicated that the introduction of GO could achieve the enrichment of electrons on the metals and reduce the d band center (εd) of Co close to the Fermi level (εF), thereby facilitating the interfacial electron transfer process. The activation mechanism was due to the as-prepared bimetallic sulfides and the formation of heterojunction structure with GO, where Co(II) as the active center could be regenerated by the adjacent Mo element (as co-catalyst) and by gathering electrons from GO through the Co/Mo-O-C coupling. This work provides insights into the design of bimetallic sulfide catalysts in activating PMS for water remediation.

Engineering interface structures for heterojunction photocatalysts.

Solar photocatalysis is the most ideal solution to global energy concerns and environmental deterioration nowadays. The heterojunction combination has become one of the most successful and effective strategies to design and manufacture composite photocatalysts. Heterojunction structures are widely documented to markedly improve the photocatalytic behavior of materials by enhancing the separation and transfer of photogenerated charges, widening the light absorption range, and broadening redox potentials, which are attributed to the presence of both build-in electric fields at the interface of two different materials and the complementarity between different electron structures. So far, a large number of heterojunction photocatalytic materials have been reported and applied for water splitting, reduction of carbon dioxide and nitrogen, environmental cleaning, etc. This review outlines the recent accomplishments in the design and modification of interface structures in heterojunction photocatalysts, aiming to provide some useful perspectives for future research in this field.

Abnormalities of hsa-mir-16 and hsa-mir-124 Affect Mitochondrial Function and Fatty Acid Metabolism in Tetralogy of Fallot.

BACKGROUND: Tetralogy of Fallot (TOF) is the most common cyanotic congenital heart disease in clinical practice. It is mainly due to cardiovascular hypoplasia during embryonic development. The study aimed to find the etiology of TOF. METHODS: Through the mRNA expression profile analysis of the GSE35776 dataset, differentially expressed genes (DEGs) were found, and the functional analysis and protein-protein interaction (PPI) network analysis were then performed on DEGs. Likewise, the hub genes and functional clusters of DEGs were analyzed using the PPI network. Differentially expressed miRNAs were analyzed from the GSE35490 dataset, followed by miRNet predicted transcription factors (TFs) and target genes. The key TF-miRNA-gene interaction mechanism was explored through the found significant difference between genes and target genes. RESULTS: A total of 191 differentially expressed genes and 57 differentially expressed miRNAs were identified. The main mechanisms involved in TOF were mitochondria-related and energy metabolism- related molecules and pathways in GO and KEGG analysis. This discovery was identical in TFs and target genes. The key miRNAs, hsa-mir-16 and hsa-mir-124, were discovered by the Venn diagram. A co-expression network with the mechanism of action centered on two miRNAs was made. CONCLUSION: Hsa-mir-16 and hsa-mir-124 are the key miRNAs of TOF, which mainly regulate the expression of NT5DC1, ECHDC1, HSDL2, FCHO2, and ACAA2 involved in the conversion of ATP in the mitochondria and the metabolic rate of fatty acids (FA). Our research provides key molecules and pathways into the etiology of TOF, which can be used as therapeutic targets.

Ultrafast charge separation in a WC@C/CdS heterojunction enables efficient visible-light-driven hydrogen generation.

The rapid recombination of photogenerated carriers and strong photocorrosion have considerably limited the practical application of CdS in the field of photocatalysis. Loading a cocatalyst has been widely utilized to largely enhance photocatalytic activity. In the present work, a WC@C cocatalyst was prepared by a novel molten salt method and explored as an efficient noble-metal-free cocatalyst to significantly enhance the photocatalytic hydrogen evolution rate of CdS nanorods. The WC@C/CdS composite photocatalyst with a 7 wt% content of WC@C showed the highest photocatalytic hydrogen evolution rate of 8.84 mmol g-1 h-1, which was about 21 and 31 times higher than those of CdS and 7 wt% Pt/CdS under visible light irradiation. A high apparent quantum efficiency (AQY) of 55.28% could be achieved under 420 nm monochromatic light. Furthermore, the photocatalytic activity of the 7 wt% WC@C/CdS photocatalyst exhibited good stability for 12 consecutive cycles of the photocatalytic experiment with a total reaction time of 42 h. The excellent photocatalytic performance of the photocatalyst was attributed to the formation of a Schottky junction and the loading cocatalyst, which not only accelerated the separation of the photogenerated carrier but also provided a reactive site for hydrogen evolution. This work revealed that WC@C could act as an excellent cocatalyst for enhancing the photocatalytic activity of CdS nanorods.

Boosting the photocatalytic activity and stability of Cu2O for CO2 conversion by LaTiO2N.

Cu2O is one of the most promising photocatalysts for visible light driven CO2 conversion, but its practical application in artificial photosynthesis is challenged to severe photocorrosion. Herein, a Cu2O/LaTiO2N composite is successfully synthesized by loading Cu2O on LaTiO2N through an ascorbic acid reduction method, which significantly improves the stability and activity of Cu2O for visible light driven photocatalytic CO2 conversion, and shows higher photocatalytic performance than most Cu2O-based photocatalysts reported. The superior photocatalytic performance is attributed to the formation of type-II heterojunction between Cu2O and LaTiO2N, which facilitates the separation and transfer of photogenerated electrons and holes. This work provides an effective strategy for the construction of stable and efficient Cu2O-based photocatalysts.

Phosphorus doped and defect modified graphitic carbon nitride for boosting photocatalytic hydrogen production.

The enhancement of photogenerated carrier separation efficiency is a significant factor in the improvement of photocatalyst performance in photocatalytic hydrogen evolution. Heteroatom doping and defect construction have been considered valid methods to boost the photocatalytic activity of graphitic carbon nitride. Herein, we report graphitic carbon nitride modified with P doping and N defects (PCNx), and the effects of doping and defects were investigated in photocatalytic H2 evolution. Its hydrogen evolution rate can reach up to about 59.1 µmol h-1, which is more than 123.1 times higher than pristine graphitic carbon nitride under visible light irradiation. Importantly, the apparent quantum efficiency reaches 8.73% at 420 nm. The excellent performance of the PCNx photocatalyst was attributed to the following aspects: (I) the large BET surface area of PCNx affords more active sites for H2 production and (II) the introduction of P and N defects can accelerate the charge carrier separation and transfer efficiency, leading to more efficient photocatalytic hydrogen production. The photocatalyst showed obviously enhanced activities.

In Situ Fabrication of N-Doped ZnS/ZnO Composition for Enhanced Visible-Light Photocatalytic H2 Evolution Activity.

For achieving the goal of peaking carbon dioxide emissions and achieving carbon neutrality, developing hydrogen energy, the green and clean energy, shows a promising perspective for solving the energy and ecological issues. Herein, firstly, we used the hydrothermal method to synthesize the ZnS(en)0.5 as the precursor. Then, ZnS/ZnO composite was obtained by the in situ transformation of ZnS(en)0.5 with heat treatment under air atmosphere. The composition, optical property, morphology, and structural properties of the composite were characterized by X-ray photoemission spectroscopy (XPS), Ultraviolet-visible absorption spectra (Uv-vis Abs), Scanning electron microscopy (SEM) and Transmission electron microscopy image (TEM). Moreover, the content of ZnO in ZnS/ZnO was controlled via adjustment of the calcination times. The visible-light response of ZnS/ZnO originated from the in situ doping of N during the transformation of ZnS(en)0.5 to ZnS/ZnO under heat treatment, which was verified well by XPS. Photocatalytic hydrogen evolution experiments demonstrated that the sample of ZnS/ZnO-0.5 h with 6.9 wt% of ZnO had the best H2 evolution activity (1790 µmol/h/g) under visible light irradiation (λ > 400 nm), about 7.0 and 12.3 times that of the pure ZnS and ZnO, respectively. The enhanced activities of the ZnS/ZnO composites were ascribed to the intimated hetero-interface between components and efficient transfer of photo-generated electrons from ZnS to ZnO.