Preparation of Hydrophobic Au Catalyst and Application in One-Step Oxidative Esterification of Methacrolein to Methyl Methacrylate.

The water produced during the oxidative esterification reaction occupies the active sites and reduces the activity of the catalyst. In order to reduce the influence of water on the reaction system, a hydrophobic catalyst was prepared for the one-step oxidative esterification of methylacrolein (MAL) and methanol. The catalyst was synthesized by loading the active component Au onto ZnO using the deposition-precipitation method, followed by constructing the silicon shell on Au/ZnO using tetraethoxysilane (TEOS) to introduce hydrophobic groups. Trimethylchlorosilane (TMCS) was used as a hydrophobic modification reagent to prepare hydrophobic catalysts, which exhibited a water droplet contact angle of 111.2°. At a temperature of 80 °C, the hydrophobic catalyst achieved a high MMA selectivity of over 95%. The samples were characterized using XRD, N2 adsorption, ICP, SEM, TEM, UV-vis, FT-IR, XPS, and water droplet contact angle measurements. Kinetic analysis revealed an activation energy of 22.44 kJ/mol for the hydrophobic catalyst.

Go-Game Image Recognition Based on Improved Pix2pix.

Go is a game that can be won or lost based on the number of intersections surrounded by black or white pieces. The traditional method is a manual counting method, which is time-consuming and error-prone. In addition, the generalization of the current Go-image-recognition methods is poor, and accuracy needs to be further improved. To solve these problems, a Go-game image recognition based on an improved pix2pix was proposed. Firstly, a channel-coordinate mixed-attention (CCMA) mechanism was designed by combining channel attention and coordinate attention effectively; therefore, the model could learn the target feature information. Secondly, in order to obtain the long-distance contextual information, a deep dilated-convolution (DDC) module was proposed, which densely linked the dilated convolution with different dilated rates. The experimental results showed that compared with other existing Go-image-recognition methods, such as DenseNet, VGG-16, and Yolo v5, the proposed method could effectively improve the generalization ability and accuracy of a Go-image-recognition model, and the average accuracy rate was over 99.99%.

Application of functional metal anionic Lewis acid ionic liquids in the alkylation of chlorobenzene/SOCl2.

4,4'-Dichlorodiphenyl sulfoxide is the main raw material for the manufacture of polysulfone, polyether sulfone and other engineering plastics. It is also an intermediate for medicines, dyes and pesticides, which has been widely utilized in engineering plastics, fine chemicals and other fields. The alkylation of chlorobenzene with thionyl chloride can give 4,4'-dichlorodiphenyl sulfoxide as a product using Lewis acidic ionic liquids. In this work, metal-based methylimidazolium ionic liquids were synthesized, which were found to be efficient catalysts for alkylation reactions. The molar ratio of different metal chlorides to 1-butyl-3-methyl imidazole chloride and the influence of different metal chlorine additives on the catalytic Lewis acid center were investigated. The fissionable species of AlCl3 in ionic liquids will enhance the acidity of ionic liquids and, thus, promote the catalytic performance of ionic liquids. Under the optimized reaction conditions, the conversion rate of excess chlorobenzene was 45.3% and the selectivity of 4,4'-dichlorodiphenyl sulfoxide was 31.9%.

Facile preparation of single-atom Ru catalysts via a two-dimensional interface directed synthesis technique for the NRR.

Through the catalysis system design of in situ Ru SACs (single atoms) anchored on a rGO/NC two-dimensional interface, we successfully realized the SA-Ru@rGO/NC electrocatalyst with high metal loading density at a relatively low temperature. The largest NH3 yield of 110.1 µg h-1 mgcat-1 and FE of 17.9% were achieved at -0.3 V under ambient conditions. The electronic environment of the catalyst was regulated by the electronic metal-support interaction, and the use of SACs had the advantages of inhibiting the hydrogen evolution reaction (HER) and enhancing N2 adsorption, which effectively improved the performance of electrocatalytic nitrogen fixation.

Study on the mechanism of Ginseng-Gegen for mesenteric lymphadenitis based on network pharmacology.

Background: This study aimed to determine the main active ingredients of the Ginseng-Gegen (Panax Ginseng-Radix Puerariae) drug pair, to predict relevant action targets, and to establish a network of "drug-active ingredients-targets", to ultimately explore the mechanism of Ginseng-Gegen in the treatment of mesenteric lymphadenitis. Methods: The Traditional Chinese Medicine Systems Pharmacology (TCMSP) platform was used to screen the chemical constituents of Ginseng-Gegen, and the active ingredient targets were retrieved by UniProt database. The databases of GeneCards and the Online Mendelian Inheritance in Man (OMIM) were applied to search for mesenteric lymphadenitis-related targets. Cytoscape software was used to construct the network of active ingredient-action targets. The biological functions of the targets were analyzed in the Database for Annotation, Visualization, and Integrated Discovery (DAVID) database. Results: A total of 26 potential active ingredients of the Ginseng-Gegen drug pair were screened, with 128 drug-related targets and 255 mesenteric lymphadenitis-related targets. After matching, 23 potential targets were obtained for treating mesenteric lymphadenitis. Among them, MOL012297 (puerarin), MOL005344 (ginsenoside Rh2), and MOL000358 (beta-sitosterol) were linked to 3 or more key target genes. They were supposed to be important ingredients of Ginseng-Gegen in the treatment of mesenteric lymphadenitis. Conclusions: Ginseng-Gegen is related to oxidative stress and inflammation, and it is a part of the nuclear factor κB (NF-κB) signaling pathway, tumor necrosis factor (TNF) signaling pathway, and the advanced glycation end products/receptor for advanced glycation end products (AGE-RAGE) signaling pathway. These biological processes and signaling pathways may be potential mechanisms of Ginseng-Gegen for treating mesenteric lymphadenitis.

Modified high-efficiency carbon material for deep degradation of phenol by activating persulfate.

A series of cobalt-nitrogen modified catalysts were prepared and applied to the degradation of phenol. The Mott Schottky catalyst (CoO/NGr@C) with high pyridine nitrogen content was designed to activate potassium peroxodisulfate (PDS) to generate active free radicals for phenol degradation. The structural properties of the materials are analyzed by XPS, TEM and then the charge density calculation is performed by DFT, which proves the existence of the highly active interface effect. Co-N-CMCM-41 can only degrade phenol into benzoquinone and it is difficult to achieve further degradation of benzoquinone, while the modified CoO/NGr@C can achieve deep mineralization of the intermediate benzoquinone through UV spectrum. EPR was used to prove that both hydroxyl radicals and sulfate radicals exist in the degradation process of phenol. Through the DFT simulation calculation of the material, it is proved that the existence of carbon activated by nitrogen and the electron rearrangement between cobalt and nitrogen-rich carbon lead to the catalytic activity of the material. The degradation conditions of phenol were optimized and the reaction kinetics of further phenol degradation were studied. The activation energy of phenol degradation on CoO/NGr@C is calculated to be 34.38 kJ mol-1.

[Clinical features and genetic analysis of a Chinese pedigree affected with X-linked adrenoleukodystrophy].

OBJECTIVE: To analyze the clinical features and variants of ABCD1 gene in a Chinese pedigree affected with X-linked adrenoleukodystrophy. METHODS: Clinical data of the proband were collected and analyzed. Potential variant of the ABCD1 gene were analyzed by PCR and Sanger sequencing of the proband, his parents and 100 unrelated healthy individuals. RESULTS: The prominent features of the proband included cerebellar and brainstem lesions, along with increased serum level of very-long chain fatty acids. He was found to harbor a hemizygous c.1509delG (p.L504Sfs*54) variant of the ABCD1 gene, for which his mother was heterozygous. The same variant was not detected in his father and 100 healthy controls. CONCLUSION: X-linked adrenoleukodystrophy has a variety of clinical manifestations. Discovery of the c.1509delG (p.L504Sfs*54), as a novel pathogenic variant of the ABCD1 gene, has enabled diagnosis and genetic counseling for this pedigree.

Psoralen inhibits the inflammatory response and mucus production in allergic rhinitis by inhibiting the activator protein 1 pathway and the downstream expression of cystatin­SN.

Psoralen (PSO) exerts anti­inflammatory pharmacological effects and plays an important role in a variety of inflammatory diseases. However, the effects of PSO with allergic rhinitis (AR) are yet to be reported. In the present study, an in vitro AR model was generated by inducing JME/CF15 human nasal epithelial cells with IL­13, after which MTT was used to assess the cytotoxicity of PSO. The expression levels of inflammatory cytokines (granulocyte­macrophage colony­stimulating factor and Eotaxin) were determined by ELISA. Furthermore, the expression of inflammatory IL­6 and ­8, as well as mucin 5AC, was assessed by reverse transcription­quantitative PCR and western blotting, and cellular reactive oxygen species were detected using a 2',7'­dichlorodihydrofluorescein diacetate fluorescent probe. Western blotting was also used to detect the expression and phosphorylation of c­Fos and c­Jun in the activator protein 1 (AP­1) pathway, as well as the expression of cystatin­SN (CST1). PSO inhibited the inflammatory response and mucus production in IL­13­induced JME/CF15 cells. Furthermore, the levels of c­Fos and c­Jun phosphorylation in the AP­1 pathway were decreased in IL­13­induced JME/CF15 cells following PSO treatment. The expression of pathway proteins was activated by the addition of PMA, an AP­1 pathway activator, which concurrently reversed the inhibitory effects of PSO on the inflammatory response and mucus formation. The addition of an AP­1 inhibitor (SP600125) further inhibited pathway activity, and IL­13­induced inflammation and mucus formation was restored. In conclusion, PSO regulates the expression of CST1 by inhibiting the AP­1 pathway, thus suppressing the IL­13­induced inflammatory response and mucus production in nasal mucosal epithelial cells.

Oxidative esterification of renewable furfural on cobalt dispersed on ordered porous nitrogen-doped carbon.

A series of highly dispersed cobalt-based catalysts on N-doped ordered porous carbon (Co-NOPC) were synthesized using the sacrificial-template method. MCM-41, ZSM-5 and SBA-15 were employed as hard templates with 2,2'-bipyridine as the ligand. The physical and chemical properties of the Co-NOPC catalyst were characterized by Raman, XRD, SEM, TEM, EDX, ICP, BET, XPS. Co-NOPC had been proven to be a highly efficient catalyst for oxidative esterification of furfural (FUR) to methyl 2-furoate without alkaline additives. Catalytic performance was correlated to the dispersed cobalt, porous structure and specific surface area. The relationship between oxygen activation and the strong interaction of cobalt and pyridine nitrogen were confirmed by XPS. Catalytic performance enhancement mechanisms were correlated with the redistribution of electrons at the interface between carbon material and cobalt atoms through the molecular dynamics method and a reaction mechanism was also proposed. The optimized catalysts showed outstanding catalytic activity and stability and no obvious decrease in activity was found after 6 cycles with 99.6% FUR conversion and 96% methyl 2-furoate selectivity.

Pollution characteristics and sources of polybrominated diphenyl ethers in indoor air and dustfall measured in university laboratories in Hangzhou, China.

Laboratories at Zhejiang University of Technology in Hangzhou were selected to ascertain the pollution status of polybrominated diphenyl ethers (PBDEs) in indoor city air. Air and dustfall samples were collected during 2015 and analysed using gas chromatography. This study provides important information on the typical indoor pollution of brominated flame retardants in urban areas in China, particularly in university laboratories. The annual geometric mean concentration of PBDEs of passive air samples in the university laboratories was 545.64pg/m3, corresponding to a medium level of air pollution. The highest level was recorded in winter and the lowest in summer. The average concentration of PBDEs in dustfall was 8198.69ng/g, generally higher than that reported in other studies. The annual geometric mean of deposition fluxes of PBDEs was 121.96ng/(m2d). BDE-209 was the main congener of PBDEs in all areas studied, and BDE-47, BDE-66, and BDE-99 also made a significant contribution to the total concentration of PBDEs·The detection rates were 100% for BDE-17, -28, and -66 in air samples, while the detection rates of BDE-17, -28, -71 and -66 were all 100% in dustfall samples. PBDE concentrations and deposition fluxes were unevenly distributed and showed sampling point differences, mainly attributed to differences in the materials used for indoor furnishings, the function of the room, the ventilation systems and the surrounding environment. Seasonal variations of PBDE concentrations in air samples ranged as winter>autumn>spring>summer, while seasonal variations in dustfall samples were winter>summer>autumn>spring. Two significant positive linear relationship were found between the total quantity of electronic equipment (r=0.722, p<0.05) and the quantity of plywood desktop (r=0.745, p<0.05) with the deposition fluxes of PBDEs.

Quantifying long-term responses of crop yield and nitrate leaching in an intensive farmland using agro-eco-environmental model.

Quantitatively ascertaining and analyzing long-term responses of crop yield and nitrate leaching on varying irrigation and fertilization treatments are focal points for guaranteeing crop yield and reducing nitrogen loss. The calibrated agricultural-hydrological RZWQM2 model was used to explore the long-term (2003-2013) transport processes of water and nitrogen and the nitrate leaching amount into groundwater in summer maize and winter wheat rotation field in typical intensive plant area in the North China Plain, Daxing district of Beijing. Simulation results showed that application rates of irrigation and nitrogen fertilizer have couple effects on crop yields and nitrogen leaching of root zone. When both the irrigation and fertilizer for summer maize and winter wheat were 400mm and 400kgNha-1, respectively, nitrate leaching into groundwater accounted for 47.9% of application amount of nitrogen fertilizer. When application amount of irrigation is 200mm and fertilization is 200kgNha-1, NUPE (nitrogen uptake efficiency), NUE (nitrogen use efficiency), NPFP (nitrogen partial factor productivity), and Wpi (irrigation water productive efficiency) were in general higher than that under other irrigation and fertilization condition (irrigation from 104-400mm, fertilizer 104-400kgNha-1). Irrigation bigger than 200mm could shorten the response time of nitrate leaching in deeper soil layer in different irrigation treatment.

[PBDEs Levels in House Dust and Human Exposure to PBDEs via Dust Ingestion in Hangzhou].

In order to evaluate the pollution degree of the dust in Hangzhou City, the indoor dust samples of 19 offices, families and students' dormitories were collected from August to March in 2013 at Hangzhou for evaluating the pollution level of polybrominated diphenyl ethers (PBDEs), to analyze concentrations of 14 PBDEs congeners and congener distribution as well as the possible influencing factors, and to estimate the PBDEs exposure levels of adults and children through the dust intake. The results showed that the average ∑14PBDEs of office was 9.28×102 ng·g-1, and the median was 1.03×103 ng·g-1; the average ∑14PBDEs of family was 7.83×102 ng·g-1, and the median was 9.11×102 ng·g-1; the average ∑14PBDEs of student dormitory was 4.07×102 ng·g-1, and the median was 4.03×102 ng·g-1. The pollution level of the office was higher than that of the living environment. BDE-209 was the largest monomer, and its contribution was 75.48%, followed by BDE-190, BDE-154 and BDE-71.PBDEs exposure levels of adults and children by dust intake were 13.12-32.63 ng·d-1 and 32.40-54.54 ng·d-1, respectively. Children's PBDEs exposure in the dust was higher than that of the adults, mainly because the average dust intake of children was higher than that of adults. The analysis showed that the PBDEs from indoor dust intake was a potential health hazard, and the biggest potential harm to children.