PhIO-mediated Synthesis of Ketones from Alkynes and Alkenes

A facile and efficient method for the preparation of methyl ketones was developed in the reaction of alkynes and alkenes with PhIO-BF3·Et2O.The reaction features mild conditions,short time and metal-free catalyst.The possible mechanism for the formation of methyl ketones was proposed.H2O functions as both a nucleophile and an oxygen source.     

Synthesis of a Polymer—bound Sensitizer and its Application in the Photoisomeriz

A polymer-bound photosensitizer was synthesized by the reaetion of Merritield resin with 9-anthraeenemethanol in the presence of potassium hydride.The photoisomerization of trans-vitamin D3 to cis-vitamin D3 was earried out with this polymer-bound photosensitizer in ethanol and toluene solutions.The experiment results demonstrate that this solid photosensitizer is efficient for the photoismerization and easy for separation from the reaetion mixtures.     

Converting Thiophene in Simulated Coking Crude Benzene to N,N-Dimethyl-2-thiophenecarboxamide by Dimethylcarbamyl Chloride Under Mild Conditions

Since the content of thiophene in coking crude benzene is high, it is necessary to remove it from coking crude benzene for efficient utilization. In this study, an important intermediate, N,N-dimethyl-2-thiophenecarboxamide, was synthesized from thiophene and dimethylcarbamyl chloride. The influences of the dosages of dimethylcarbamyl chloride and ZnCl2 catalyst, reaction temperature and time on the removal rate were further explored based on the reaction kinetics.The structure of the target product was characterized by means of MS,NMR and 13C NMR.The removal rate of thiophene was 98.14% after the reaction for 2 h and thiophene was almost removed after the reaction for 3 h under the optimal reaction conditions [a molar ratio of n(thiophene):n(dimethylcarbamyl chioride):w(ZnCl2)=1:12:10,300 r/min, 318 K and 101.325 kPa].The acylation of thiophene with dimethylcarbamyl chloride was approximately in accord with the first order kinetic equation at 303-323K.The activation energy was 53.9850 kJ/mol and the pre-exponential factor was 1.4521×10^9 h^-1.     

氧化铝负载的银纳米颗粒高选择性催化合成亚胺(英)

The oxidative dehydrogenation of alcohols to aldehydes catalyzed by Ag nanoparticles supported on Al₂O₃ was studied.The catalyst promoted the direct formation of imines by tandem oxidative dehydrogenation and condensation of alcohols and amines.The reactions were performed under mild conditions and afforded the imines in high yield（up to 99%） without any byproducts other than H₂O.The highest activity was obtained over 5 wt%Ag/Al₂O₃ in toluene with air as oxidant.The reactions were also performed under oxidant-free conditions where the reaction was driven to the product side by the production of H₂ in the gas phase.The use of an efficient and selective Ag catalyst for the oxidative dehydrogenation of alcohol in the presence of amines gives a new green reaction protocol for imine synthesis.     

Framework nucleic acid-based confined enzyme cascade for efficient synergistic cancer therapy in vivo

Artificial enzyme cascade systems with confinement effect are highly important in synthetic biology and biomedicine.Herein,a framework nucleic acid-based confined enzyme cascade(FNA-CEC)for synergistic cancer therapy in vivo was developed.The FNA-CEC consisted of glucose oxidase and horseradish peroxidase precisely assembled on an addressable DNA tetrahedron scaffold within few nanometers.Glucose oxidase(GOx)can trigger efficient glucose depletion for tumor starvation therapy,and increase the local concentration of H₂O₂ in situ for enhanced downstream horseradish peroxidase(HRP)-activated prodrug therapy.Due to the spatial-confinement on DNA tetrahedron scaffold,the efficiency of intermediate metabolites transportation between the enzyme cascades was improved.Moreover,FNA-CEC was applied for efficient synergistic cancer therapy in vitro and in vivo.As a simple and efficient approach,the FNA-CEC is expected to expand the toolbox of technologies in synthetic biology and biomedicine.     

Rh/ZnO-Al2O3催化剂用于巴豆醛选择性加氢（英文）

Gas phase hydrogenation of crotonaldehyde was performed over 1 wt% Rh/ZnO-Al2O3 catalysts with various Zn/Rh atomic ratios. Monometallic Rh/Al2O3 was also prepared for comparison. The samples were prepared by the successive impregnation of Al2O3 with chlo-ride precursors of zinc and rhodium. The solids have been characterized by H2 chemisorption,temperature-programmed reduction,scanning electron microscopy,and cyclohexane dehydrogenation. Their catalytic behaviour in the gas phase crotonaldehyde hydrogenation reaction after reduction treatment in flowing hydrogen at 723 K was investigated. The relationship between catalytic activity,selectivity for crotyl alcohol,and physicochemical properties of the catalysts was examined. Results obtained showed that the presence of Zn clearly promotes the hydrogenation of the carbonyl bond. The catalyst with Zn/Rh atomic ratio of 5 displayed good catalytic stability and the highest selectivity for crotyl alcohol(70%) along with alloy formation.     

稻壳灰负载FeCl2·2H2O:一个温和高效的多相催化剂用于Friedlnder杂成环反应合成多取代喹啉（英文）

Rice husk ash was used as a new, green, and cheap adsorbent for FeCl3. Characterization of the obtained reagent showed that rice husk ash supported FeCl2·2H2O was formed. This reagent is efficient at catalyzing the synthesis of multisubstituted quinolines by the Friedl鋘der heteroannulation of o‐aminoaryl ketones with ketones or β‐diketones under mild reaction conditions. This methodology allows for the synthesis of a broad range of substituted quinolines in high yields and with excellent regioselectivity in the absence of a solvent.     

Synergistic impact of cocatalysts and hole scavenger for promoted photocatalytic H_2 evolution in mesoporous TiO_2–NiS_x hybrid

Photocatalytic solar energy conversion to hydrogen is sustainable and attractive for addressing the global energy and environmental issue. Herein, a novel photocatalytic system(NiS/Ni_3S_4 cocatalysts modified mesoporous TiO_2) with superior photocatalytic hydrogen evolution capability through the synergistic impact of NiS/Ni_3S_4(NiS_x) cocatalyst and efficient hole scavenger has been demonstrated. The photocatalytic hydrogen evolution of TiO_2–Ni Sxhybrids with the different content of Ni Sxand upon different organic hole scavengers was both investigated. The hybrid of TiO_2 decorated with 3%(mole ratio of Ni~(2+)) Ni Sxcocatalyst in methanol solution showed the optimal photocatalytic hydrogen evolution rate of 981.59 μmol h~(-1)g~(-1) which was about 20 times higher than that of bare mesoporous TiO2. Our results suggested that the boosted hydrogen production performance is attributed to both the improved photoinduced electrons migration between NiS and Ni_3S_4 in cocatalyst and the high hole captured efficiency by hole scavengers of methanol.     

一种新型高比表面积 TiO2载体在 NH3选择性催化还原反应中对 V2O5分散性的促进作用

A titania support with a large surface area was developed, which has a BET surface area of 380.5 m2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt%vanadia. A special heat treatment was used in the calcination to maintain the large sur‐face area and high dispersion of vanadium species. This catalyst was compared to a common V2O5‐TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new cata‐lyst has a surface area of 117.7 m2/g, which was 38%higher than the traditional V2O5‐TiO2 catalyst. The selective catalytic reduction (SCR) performance demonstrated that the new catalyst had a wid‐er temperature window and better N2 selectivity compared to the traditional one. The NO conver‐sion was>80%from 200 to 450 °C. The temperature window was 100 °C wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V‐O‐V linkages on the catalyst prepared by the traditional method. The amount of V‐O‐Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.     

Efficient oxidative degradation of 2-chlorophenol and 4-chlorophenol over supported CuO-based catalysts

A series of metal oxide catalysts for catalytic oxidative degradation of 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP) were prepared, and the supported CuO catalysts were studied particularly. The supported CuO catalysts were characterized by XRD and NH3-TPD techniques, in which CuO/γ-Al2O3 exhibited high degradation activity. The addition of Na2O or K2O into CuO/γ-Al2O3 improved the oxidative degradation of CPs remarkably, in which Na2O was more efficient than K2O. Over CuO/γ-Al2O3-Na2O, CPs were completely converted and the liberation of the inorganic chloride from 2-CP or 4-CP reached 97% or 100% respectively at 30 ?C for 2 h. The supported CuO catalysts with good dispersion of CuO particles and less acid sites were favorable for the efficient oxidative degradation of CPs. In addition, the initial pH of the reaction solution was found to be an important factor which influenced the catalytic oxidative degradation of CPs and the initial pH of 11.2 and 9.8 was preferred for the oxidative degradation of 2-CP and 4-CP respectively over CuO/γ-Al2O3 catalyst.     

四元交互体系Li^＋,K^＋／cL^—,CO^2—3—H2O在298K时相平？…

Zabuye Saline Lake, Tibet, China, is unrivalled in the world for its very high salinity, in particular, for the very high concentration of ions of lithium, potassium, and boron in the brine. It belongs to alkaline and carbonate-borate-type salt lake. As a part of the study on phase equilibrium of the 6component subsystem Li+, Na+, K+/C1-, CO2-3, B4O2-7-H2O of the brine system, a study on the reciprocal quaternary system Li+, K+/C1-, CO32-H2O at 298 K was done with isothermal dissolution equilibrium method in the present work. The phase equilibrium of the reciprocal quaternary system Li+,K+/C1, CO2-3-H2O at 298 K was studied with isothermal dissolution method in this work. The physicochemistry properties of the corresponding equilibrium solutions such as densities, viscosities, refractive index, conductivities and pH value were determined. The dried salt diagram of the system consists of four crystallization fields (KC1, Li2CO3, LiCI·H2O, K2CO3·3/2H2O) and five isothermal solubility curves.There are no double slat or solid solution found. Pitzer′s model of the electrolyte solution theory was used for parameterization from the results of solubility determination for subsystems and the prediction of solubilities for the reciprocal quaternary system was made. The solubility data of the experiment are in agreement with those calculated.     

Potassium dihydrogen phosphate catalyzed one-pot synthesis of 2,4,5-triaryl-1H-imidazoles

<正>A simple and efficient method has been developed;benzil/benzoin undergoes smooth condensation with various substituted aldehyde and ammonium acetate in the presence of potassium dihydrogen phosphate(KH_2PO_4) under mild reaction conditions to afford the corresponding trisubstituted imidazole in excellent yields.The method for synthesis of product,the reaction mixture was reflux in ethanol for 40-90 min.The present method is simple,efficient,and cost-effective.     

改性磁性壳聚糖微球对Cu2+、Cd2+和Ni2+的吸附性能

Fe3O4/ chitosan magnetic microspheres of 50 to 80 滋m were prepared using the inverse phase emulsion dispersion and chemical crosslinking technology, and then modified with ethylenediamine for use in the adsorption of heavy metal ions. The adsorption properties of the modified Fe3O4/chitosan toward Cu2+, Cd2+ and Ni2+ were investigated. It was found that the adsorption capacities of Cu2+ and Ni2+ increased with pH, and a maximum adsorption for Cd2+ occurred at pH=3. The saturated adsorption capacities calculated by Langmuir isotherms were 54.3 mg·g-1 for Cu2+, 20.4 mg·g-1 for Cd2+, and 12.4 mg·g-1 for Ni2+, respectively. The adsorption kinetics were well described by pseudo-second-order equation models. The experimental results showed that the Fe3O4/chitosan modified with ethylenediamine presented higher adsorption selectivity for Cu2+ than for Cd2+ and Ni2+ in all studied pH ranges.     

Palladium particles from oxime-derived palladacycle supported on Fe3O4/oleic acid as a catalyst forthe copper-free Sonogashira cross-coupling reaction

An oxime-derived palladacycle was synthesized using4-bromobenzoxime and pyridine in CHCl3, and characterized by FT-IR and1H NMR spectroscopy. This Pd complex was supported on Fe3O4/oleic acid and shown to be an efficient catalyst for the copper-free Sonogashira cross-coupling reaction of various aryl halides with phenylacetylene in air and in ethanol or mixed aqueous medium. The oxime-derived palladacycle gave highly active palladium nanoparticles for the organicsynthesis. The coupling products were obtained in high yields with low Pd loading and theheterogeneous catalyst can be separated by an external magnet andreused six times without loss of its activity. The characterization of the catalyst wascarried out by XRD, SEM and TEM. Both TEM and XRD revealed that the palladium nanoparticles were well dispersed with diameters from 5 to 10 nm and average size 9.97 nm.     

Application of Fe2O3/Al2O3 Composite Particles as Oxygen Carrier of Chemical Looping Combustion

Chemical looping combustion (CLC) of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process: in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction (XRD) analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis (TGA) reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy (SEM) test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.     

Low Temperature Solvent Evaporation-induced Crystallization Synthesis of Nanocrystalline TiO2 Photocatalyst

A novel and efficient methodology for obtaining highly active photocatalyst of bi-phase TiO2 with small particle size and high specific surface area was developed by solvent evaporation-in-duced crystallization (SEIC) method at low temperature. The prepared TiO2 powder was characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface areas. The photocatalyfic activity was evaluated by the photocatalyflc oxidation of acetone in air. The results showed that the photocatalytic activity of the TiO2 powder preDared by this method approached that of Degnssa P25. This may be atotributed to the fact that the predated TiO2 powder had larzer specific surface areas (265 m2. g- 1 ) and smaller crystallite size (about 5 nm), but relatively low crystallinity, as compared with Degussa P25.     

PURIFICATION AND KINETICS OF MOUSE LIVER FRUCTOSE 6-PHOSPHATE, 2-KINASE

The mouse liver fructose 6-phosphate, 2-kinase was purified by ultracentrifugation, polyethylene glycol precipitation, and subsequently by chromatography on DEAE-Sephadex, Blue-Sepharose and phasphocellulose columnS. Gel filtration and SDS polyacrylamide electrophorcsis showed that the enzyme has a molecular weight of 110,000 with two identical subunits. Mg~(2+) is essential for its activity. The activation of the enzyme by Mg~(2+) showed a positive cooperativity. The substrate saturation curve for fructose 6-phosphate was sigmoidal and for ATP was hyperbolic. The K_m's for ATP increased with decrease in concentrations of fructose 6-phosphate indicating that the sequence for the substrates binding was in an ordered mechanism with respect to fructose 6-phosphate prior to ATP. An ionizable residue at the active site with pKa 9.5 was essential for the ATP binding and the pKa shifted to 9.8 after the binding of ATP.     

Esterification and Chemoselective Synthesis of R-Tetrahydrothiazo-2-thione-4-carboxylic Esters Catalyzed by TiCl4

A series of esters of R-tetrahydrothiazo-2-thione-4-carboxylic acid[R-TTCA] was synthesized by direct esterification of R-TTCA with alcohols(CH3OH,C2H5OH,n-C3H7OH,i-C3H7OH,n-C4H9OH,sec-C4H9OH)in the presence of TiCl4 as the catalyst at room temperature without using any other solvent or dehydrant in high yields,91.6%-99.1% for primary alcohols and 55%- 80% for secondary alcohols.The catalyst has a strong chemoselective activity for the esterification of primary alcohols with R-TTCA in the presence of secondary alcohols.Owing to high yield,high chemoselectivity,and mild conditions used,this is an efficient method for the esterification of primary alcohols with R-TTCA.     

Double perovskite oxides Sr_2Mg_(1-x)Fe_xMoO(6-δ) for catalytic oxidation of methane

The double perovskite oxides Sr2Mg1-xF exMoO6-δ were investigated as catalysts for the methane oxidation.The structural properties of catalysts were characterized in detail by X-ray diffraction,X-ray photoelectron spectroscopy and X-ray absorption spectroscopy.The catalytic property was strongly influenced by the Fe substitution.The relation between catalytic performance and the degree of Fe substitution was examined with regard to the structure and surface characteristics of the mixed oxides.The Fe-containing catalysts exhibited higher activity attributable to the possible(Fe2+,Mo6+) and (Fe3+,Mo5+)valency pairs,and the highest activity was observed for Sr2Mg0.2Fe0.8MoO6-δ.The enhancement of the catalytic activity may be correlated with the Fe-relating surface lattice oxygen species and was discussed in view of the presence of oxygen vacancies.     

Construction of hierarchical photocatalysts by growing ZnIn2S4 nanosheets on Prussian blue analogue-derived bimetallic sulfides for solar co-production of H2 and organic chemicals

Exploring highly efficient bifunctional photocatalysts for simultaneous H2 evolution and organic chemical production in pure water represents a green route for sustainable solar energy storage and conversion.Herein,a facile strategy was explored for preparing a hierarchical porous heterostructure of Fe₄Ni₅S₈@ZnIn₂S₄(FNS@ZIS)by the in situ growth of ZIS nanosheets on Prussian blue analogue(PBA)-derived bimetallic FNS sulfides.A series of FNS@ZIS hierarchical structures were facilely prepared by adjusting the loading amount(n%)of FNS(n=19,26,and 32 for FNS@ZIS-1-3).These structures can efficiently drive the solar co-production of H₂ and organic chemicals.The optimal co-production was achieved with FNS@ZIS-2,affording a H₂ evolution rate of 10465μmol·g^-1·h^-1,along with high selectivity for the oxidation of benzyl alcohol to benzaldehyde(>99.9%).The performance was 22 and 31 times higher than that of FNS and ZIS,respectively,and even superior to the state-of-the-art results achieved using various sacrificial agents.Further mechanistic study indicated that the unique hierarchical core/shell architecture can facilitate interfacial charge separation,afford bimetallic synergy,abundant active sites and excellent photostability.This work highlights a simple and efficient method for preparing porous multimetallic hierarchical structures for the solar co-production of organic chemicals and H₂ fuel.