Preparation of Ni(HCO_3)_2 and its catalytic performance in synthesis of benzoin ethyl ether

Ni（HCO3）2 with unique phase and high crystallinity was synthesized with urea hydrolysis. The as-prepared samples were well characterized in detail. N2 adsorption and desorption result manifests a high surface area of 99.03 m2/g with a pore size of 7.8 nm. Scanning electron microscopy （SEM） and particle size distribution reveal that the diameters of the formed pellets are uniform. Thermogravimetry （TG） analysis result shows that 500 ℃ could be the appropriate temperature for converting Ni（HCO3）2 precursors into NiO via a thermal decomposition process. CO2 and NH3 temperature-programmed desorption results show that Ni（HCO3）2 has explicit acid-base sites. Transmission electron microscopy （TEM） results vividly indicate that the pellets are aggregated by hexagonal platelets and possess porous structures. Ni（HCO3）2 can efficiently catalyze the one-step synthesis of benzoin ethyl ether from benzaldehyde and ethanol, with the conversion ofbenzaldehyde up to 57.5% and nearly 100% selectivity of benzoin ethyl ether.

胃肠动力药西沙比利对表达于HEK293细胞的人ether-a-go-go相关基因2通道的影响

目的：研究胃肠动力药西沙比利对于在 HEK293细胞异源性表达的人 ether-a-go-go 相关基因2（human ether-a-go-go related gene 2,hERG2）通道性质的影响。方法用 Lipofectamine 2000将 hERG2（AF311913）瞬时转染至 HEK293细胞,使其表达hERG2通道,利用全细胞膜片钳技术记录 hERG2电流。加入西沙比利（终浓度分别为0.001,0.01,0.1,1.0,10.0μmol/ L）,分别记录加药前和加药后2~8 min 的 hERG2电流,分析西沙比利浓度和作用时间对此通道电流的影响。结果西沙比利各浓度实验组中,hERG2时间依赖性电流和尾电流幅度均下降。在去极化电压为＋20 mV 时,随西沙比利浓度升高,电流抑制率逐渐增加。西沙比利的抑制作用随时间延长逐渐增强,西沙比利浓度为1μmol/ L 时,电流在8 min 内完全消失。结论西沙比利对HEK293细胞表达的 hERG2通道的时间依赖性电流和尾电流均有抑制作用,该抑制作用具有浓度依赖性和时间依赖性,即浓度越高,时间越长,抑制效果越明显,直至电流降低至稳态或消失。

Effects of ZrO_2 on the Performance of CuO-ZnO-Al_2O_3/HZSM-5 Catalyst for Dimethyl Ether Synthesis from CO_2 Hydrogenation

A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 （CuO/ZnO/Al2O3=3/6/1 by weight） component was prepared by a modified ＇two-step＇ co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.

Dimensional Gradient Structure of CoSe2@CNTs-MXene Anode Assisted by Ether for High-Capacity,Stable Sodium Storage

Recently,abundant resources,low-cost sodium-ion batteries are deemed to the new-generation battery in the field of largescale energy storage.Nevertheless,poor active reaction dynamics,dissolution of intermediates and electrolyte matching problems are significant challenges that need to be solved.Herein,dimensional gradient structure of sheet-tube-dots is constructed with CoSe2@CNTs-MXene.Gradient structure is conducive to fast migration of electrons and ions with the association of ether electrolyte.For half-cell,CoSe2@CNTs-MXene exhibits high initial coulomb efficiency(81.7%)and excellent cycling performance(400 mAh g^-1 cycling for 200 times in 2 Ag^−1).Phase transformation pathway from crystalline CoSe2-Na2Se with Co and then amorphous CoSe2 in the discharge/charge process is also explored by in situ X-ray diffraction.Density functional theory study discloses the CoSe2@CNTs-MXene in ether electrolyte system which contributes to stable sodium storage performance owing to the strong adsorption force from hierarchical structure and weak interaction between electrolyte and electrode interface.For full cell,CoSe2@CNTs-MXene//Na3V2(PO4)3/C full battery can also afford a competitively reversible capacity of 280 mAh g^−1 over 50 cycles.Concisely,profiting from dimensional gradient structure and matched electrolyte of CoSe2@CNTs-MXene hold great application potential for stable sodium storage.

Synthesis of nanocrystalline γ-Al_2O_3 by sol-gel and precipitation methods for methanol dehydration to dimethyl ether

The capability of sol-gel and conventional precipitation techniques for the synthesis of nanocrystalline γ-alumina was investigated. These catalysts were used for vapor-phase dehydration of methanol to dimethyl ether in a fixed-bed reactor under the same operating conditions （T = 300 ？C, P = 1 bar, LHSV = 2.8, 11.7, 26.1 h？1） and characterized by means of N2 adsorption-desorption, NH3-TPD, XRD, TGA and SEM techniques. According to the experimental results, the catalysts prepared using sol-gel method in non-aqueous medium showed better performance compared with those prepared by other methods.

Catalytic Oxidation of Dimethyl Ether to Dimethoxymethane over Cs Modified H_3PW_(12)O_(40)/SiO_2 Catalysts

The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40（40%）/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40（40%）/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40（40%）/SiO2.

Synthesis and antibacterial activity of brominated 2′(4′)-nitro-3-hydroxy diphenyl ethers

Eight new brominated 2＇（4＇）-nitro-3-hydroxy diphenyl ethers have been designed and synthesized. The structures of new compounds were confirmed by ^1H NMR, IR and HRMS. The bioactivity tests showed that these compounds possessed antibacterial activities against the tested bacteria. These new compounds cannot be transformed into dioxins when they were manufactured and used.

Partial oxidation of dimethyl ether to H_2/syngas over supported Pt catalyst

Dimethyl ether （DME） is a non-toxic fuel with high H/C ratio and high volumetric energy density, and could be served as an ideal source of H2/syngas production for application in solid oxide fuel cells （SOFC）. This study presents results of DME partial oxidation over a 1.5 wt% Pt/Ce0.4Zr0.6O2 catalyst under the condition of gas hourly space velocity （GHSV） of 15000-60000 ml/（g·h）, molar ratio of O2/DME of 0.5 and 500-700 ℃, and this temperature range was also the operation temperature range for intermediate temperature SOFC. The results indicated that the catalyst showed good activity for the selective partial oxidation of DME to H2/syngas. Under the working conditions investigated, DME was completely converted. Increase in reaction temperature enhanced the amount of syngas, but lowered the H2/CO ratio and yield of methane; while increase in reaction GHSV resulted in only slight variation in the distribution of products. The good catalytic activity of Pt supported on Ce0.4Zr0.6O2 for the partial oxidation of DME may be directly associated with the good oxygen storage capacity of the support, which is worth of further investigation to develop materials for application in SOFC.

2D-Cell Experiment on Methyl Tert-Butyl Ether Transport in Saturated Zone of Groundwater

As an additive of gasoline,methyl ten-butyl ether(MTBE)has a higher solubility in water,which is about 20 times as high as that of benzene.This characteristic results in MTBE dissolving out of the gasoline into the soil and groundwater.Due to relative unique physicochemical behavior of MTBE it would be an ideal candidate for use in environmental forensic investigations.In order to study the transport and distribution of MTBE in saturated zone of ground water,a two-dimensional experimental cell was setup to simulate the real environment of the groundwater flow.The effects of soil and groundwater flow velocity on the MTBE transport were investigated.The results show that the mobile distance of MTBE in vertical direction was smaller than that in horizontal direction paralleling with the groundwater flow.Because the main dynamics of groundwater flow direction was convection and dispersion,the movement of MTBE is also diffusion in the vertical direction.In addition,the transport of MTBE was more quick in high permeability porous media,and the increase of groundwater flow velocity can accelerate the MTBE plume development,but the irregularity and randomness of the plume are enhanced synchronously.These research results can give some helps for the investigation of MTBE movement in the groundwater,also can make some references for other petroleum contamination behavior.

Enhanced catalytic performance for direct synthesis of dimethyl ether from syngas over a La_2O_3 modified Cu-ZrO_2/γ-Al_2O_3 hybrid catalyst

A series of hybrid catalysts were made by physically mixing Cu-ZrO2 and γ-A12O3, for former it was modified with different loadings of La2O3 prepared by co-precipitation method. The catalysts were characterized by BET, XRD, N2O-adsorption, EXAFS, H2-TPR, NH3-TPD techniques and evaluated in the synthesis of dimethyl ether from syngas. The results show that La2O3 promoted catalysts displayed a significantly better catalytic performance compared with Cu-ZrO2#y-A12O3 catalyst in CO conversion and DME selectivity, and the optimum catalytic activity was obtained when the content of La2O3 was 12 wt%. The characterizations reveal that high copper dispersion, facile reducibility of copper particles and appropriate amount of acidic sites are responsible for the superior catalytic performance.

Solubilities of CO2 in some glycol ethers under high pressure by experimental determination and correlation

The binary vapor–liquid equilibrium data of CO_2 in diethylene glycol(monomethyl,monoethyl,monobutyl,dimethyl,diethyl,dibutyl)ether were determined from 288.15 to 318.15 K at pressure up to 6 MPa based on the constant-volume method.It was found by contrast that the ether group in solvents can promote the CO_2 absorption,but the hydroxyl group will inhibit the CO_2 absorption.Furthermore,the solubilities of CO_2 showed an upward trend with the increasing molecular lengths of absorbents.The experimental data were also correlated with a modified Patel–Teja equation of state(PT EOS)combined with the traditional van der Waals one-fluid mixing rules and the results showed a satisfactory agreement between the model and the experimental data.

Enhanced stability of Fe-modified CuO-ZnO-ZrO_(2)-Al_(2)O_(3)/HZSM-5 bifunctional catalysts for dimethyl ether synthesis from CO_(2)hydrogenation

A series of iron(Fe)modified CuO-ZnO-ZrO_(2)-Al_(2)O_(3)(CZZA)catalysts,with various Fe loadings,were prepared using a co-precipitation method.A bifunctional catalyst,consisting of Fe-modified CZZA and HZSM-5,was studied for dimethyl ether(DME)synthesis via CO_(2)hydrogenation.The effects of Fe loading,reaction temperature,reaction pressure,space velocity,and concentrations of precursor for the synthesis of the Fe-modified CZZA catalyst on the catalytic activity of DME synthesis were investigated.Long-term stability tests showed that Fe modification of the CZZA catalyst improved the catalyst stability for DME synthesis via CO_(2)hydrogenation.The activity loss,in terms of DME yield,was significantly reduced from 4.2%to 1.4%in a 100 h run of reaction,when the Fe loading amount was 0.5(molar ratio of Fe to Cu).An analysis of hydrogen temperature programmed reduction revealed that the introduction of Fe improved the reducibility of the catalysts,due to assisted adsorption of H2 on iron oxide.The good stability of Femodified CZZA catalysts in the DME formation was most likely attributed to oxygen spillover that was introduced by the addition of iron oxide.This could have inhibited the oxidation of the Cu surface and enhanced the thermal stability of copper during long-term reactions.

BF₃.OEt₂-Mediated Benzylation of Arenes and Heteroarenes with Benzyl Ether Derivatives

An efficient BF3.OEt2-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mild conditions via an easy work-up procedure.

2—甲苯缩水甘油醚协同提升环氧复合物韧性及刚性研究

电气及电子设备集成度的不断提高,对环氧复合物的热学与力学综合性能提出了更高需求。环氧复合物的耐热性能、刚性与韧性三者之间存在“跷跷板”现象,难以协同提升。该文提出将六氢邻苯二甲酸酐/四氢邻苯二甲酸酐/邻苯二甲酸酐3种固化剂复配提升环氧复合物热学性能,并采用2—甲苯缩水甘油醚协同提升环氧复合物韧性及刚性的方法。研究表明:固化剂复配的方法将环氧复合物的玻璃化转变温度Tg及热分解温度T5%分别提升了17.93%、7.72%;2—甲苯缩水甘油醚改性使得环氧复合物冲击强度和弯曲强度分别提升了123.03%、61.71%。采用分子动力学模拟,从分子角度揭示了2—甲苯缩水甘油醚提升环氧固化物性能的机理,其刚性苯环基团增强了环氧体系分子结构稳定性,柔性—C—O—C—链段改善了交联体系柔韧性。该研究提出一种不降低环氧复合物热学性能,并协同提升其韧性与刚性的可行方法,可为具备高综合热学与力学性能环氧复合物配方的设计提供新思路。

On an Expression of Extraction Constants without the Interfacial Equilibrium-Potential Differences for the Extraction of Univalent and Divalent Metal Picrates by Crown Ethers into 1,2-Dichloroethane and Nitrobenzene

An idea on interfacial equilibrium-potential differences () which are generated for the extraction of univalent metal picrate (MPic) and divalent ones (MPic2) by crown ethers (L) into high-polar diluents was improved. These potentials were clarified with some experimental extraction-data reported before on the M = Ag(I), Ca(II), Sr(II) and Ba(II) extraction with 18-crown-6 ether (18C6) and benzo-18C6 into 1,2-dichloroethane (DCE) and nitrobenzene (NB). Consequently, it was demonstrated that the? values from the extraction-experimentally obtained logKD,Pic ones are in agreement with or close to those calculated from charge balance equations in many cases, where the symbol, KD,Pic, denotes an individual distribution constant of Pic﹣ into the DCE or NB phase. Also, it was experimentally shown that extraction constants based on the overall extraction equilibria do not virtually contain the? terms in their functional expressions.

A Facile One-pot Method for the Synthesis of Vinyl Ethers from 2-Hydroxyalkyl Phenyl Selenides

A mild, one-pot procedure for the synthesis of vinyl ethers in good yields from 2-hydroxyalkyl phenyl selenides with primary or secondary organic halides has been developed.

Anthracylmethyl Benzoazacrown Ether as Selective Fluorescence Sensors for Zn^(2+)

A new benzoazacrown ether fluorescence sensor was synthesized with 9-anthrylmethyl chloride and benzoaza-15-crown-5 in CH3CN, which particularly shows a strong affinity for Zn2+. Its fluorescence quantum yield increase more than one order of magnitude and a red shift could be noticed when passing from the apolar to the polar solvent.

Regioselective Addition of Silyl Enolates to α, β-Unsaturated Aldehyde and its Acetal Catalyzed by MgI2 Etherate

Regioselective addition reactions of silyl enolates to a, b-unsaturated aldehyde and its acetal catalyzed by MgI2 etherate give aldol adducts (1, 2-addition) preferentially over Michael adducts (1, 4-addition). This unique regioselectivity is distinctly different with other Lewis acidic promoters and may be attributed to the high oxyphilicity of IMg+.

STUDIES ON RARE EARTH COMPLEXES WITH CROWN ETHERS ⅩⅧ——Synthesis,Characterization and Crystal Structure of[Sc(NO_3)_3(H_2O)_2]·(15-Crown-5)

The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.The new complex has been characterized by elemental analysis,IR spectra,solubility and molar conductance measurements.The structure of the complex is determined by single crystal X-ray diffraction analysis.

Production of Hydrogen: Photocatalytic Decomposition of Dimethyl Ether over Metal-Promoted TiO₂Catalysts

The photo-induced vapor-phase decomposition of dimethyl ether was investigated on Pt metals deposited on pure and N-doped TiO2. Infrared spectroscopic measurements revealed that adsorption of dimethyl ether on TiO2 samples underwent partial dissociation to methoxy species. Illumination of the (CH3)2O-TiO2 and (CH3)2O-M/TiO2 systems led to the conversion of methoxy into adsorbed formate. In the case of metal-promoted TiO2 catalysts, CO bonded to the metals was also detected. Pure titania exhibited a very little photoactivity. Deposition of Pt metals on TiO2 markedly enhanced the extent of photocatalytic decomposition of dimethyl ether to give H2 and CO2 as the major products. A small amount of CO and methyl formate was also identified in the products. The most active metal was the Rh followed by Pd, Ir, Pt and Ru. When the bandgap of TiO2 was lowered by N-doping, the photocatalytic activity of metal/TiO2 catalysts appreciably increased. The effect of metals was explained by a better separation of charge carriers induced by illumination and by enhanced electronic interaction between metal nanoparticles and TiO2.