Molten-salt Synthesis and Properties of ZnS with Hexagonal Prism Morphology

ZnS with hexagonal prism morphology has been synthesized successfully by molten-salt method with ZnS nanoparticles as precursors, and the ZnS nanoparticles were prepared by one-step solid-state reaction of Zn（CH3COO）2·2H2O with Na2S·9H2O at ambient temperature. Crystal structure and morphology of the product were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and HRTEM. Ultraviolet-visible optical absorption spectrum of the ZnS hexagonal prism shows a distinct red shift from that of bulk ZnS crystals and photoluminescence spectrum exhibits strong emissions at 380 and 500 nm, respectively. Further experiments were designed and the formation mechanism of the ZnS hexagonal prism has been also discussed in brief.     

Synthesis of Benzo[α] phenoxazin—5—one Derivatives and Their Interactions with DNA

The spectroscopic properties of benzo[a] phenoxazin-5-one derivatives(3a-3m)including newly synthesized 3k-3m from 4-nitrosoaniline hydrochlorides and ethyl 1,3-dihydroxy-2-naphthoate were studied.Compound 31 was converted into a covalent product with DNA,which had a blue shift of the fluorescence maximum,Compounds 3a-3k were fornd to undergo interation with DNA and their complexes with DNA had a red shift of the fluorescence maximum and showed increasing melting temperature of DNA,compound 3m-DNA had a blue shift of the fluorescence maximum to 3m and showed decreasing melting temperature of DNA.     

Protein Flexibility and Multiple Docking in Ligand Docking and Virtual Screening to the BRAF (Type Ⅰ1/2) Inhibitors

BRAF has been recognized as a promising target for cancer therapy. A number of crystal structures have been published. Molecular docking is one of the most effective techniques in the field of computer-aided drug design(CADD). Appropriate protein conformation and docking method are essential for the successful virtual screening experiments. One approach considering protein flexibility and multiple docking methods was proposed in this study. Six DFG-in/αC-helix-out crystal structures of BRAF, three docking programs(Glide, GOLD and Ligand Fit) and 12 scoring functions were applied for the best combination by judging from the results of pose prediction and retrospective virtual screening(VS). The most accurate results(mean RMSD of about 0.6 ?) of pose prediction were obtained with two complex structures(PDB: 3 C4 C and 3 SKC) using Glide SP. From the retrospective VS, the most active compounds were identified by using the complex structure of 3 SKC, indicated by a ROC/AUC score of 0.998 and an EF of 20.6 at 5% of the database screen with Glide-SP. On the whole, PDB 3 SKC could achieve a higher rate of correct reproduction, a better enrichment and more diverse compounds. A comparison of 3 SKC and the other X-ray crystal structures led to a rationale for the docking results. PDB 3 SKC could achieve a broad range of sulfonamide substitutions through an expanded hydrophobic pocket formed by a further shift of the αC-helix. Our study emphasized the necessity and significance of protein flexibility and scoring functions in both ligand docking and virtual screening.     

球形Gd2O3∶Eu纳米发光材料的制备

Spherical nanometer Gd₂O₃∶Eu luminescent materials were prepared by homogeneous precipitation method, and the properties were studied also. TG, FTIR and XRD analysis showed that the precursor was carbonate, the cubic Gd₂O₃was obtained after calcination. TEM photographs indicated that the samples were spherical and well dispersed with nanometer and submicrometer size of 200～300 nm which is the nanoparticles’ aggregate. The mechanics of agglomerating growth is also discussed. ED photograph showed that the particle was crystalline. The PL analysis exhibited that CTB band of nanometer Gd₂O₃∶Eu was of 17 nm red shift to bulk materials, and the emission peak was broadened due to the surface and interface effect of nanocrystals.     

LB膜诱导Ba(NO3)2晶体取向生长

In this work, Ba(NO₃)₂ crystals with single crystal face were induced by using the the method of bio-mimetic mineralization and double LB films of behenic acid (BA) as the template. The crystals were characterized by Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD). The crystals were observed in regular square shape with uniform size about 5～8 μm by SEM, and they were found by XRD to grow along the (111) plane. From these experiments, we can conclude that the good selection of the (111) crystal face of Ba(NO₃)₂ is due to the electrostatic interactions , the match between this crystal face and the definite lattice structure of the LB films.     

Synthesis and characterization of magnetic and luminescent Fe_3O_4/CdTe nanocomposites using aspartic acid as linker

In this study,the preparation of a new kind of magnetic and luminescent Fe₃O₄/CdTe nanocomposites was demonstrated. Superparamagnetic Fe₃O₄ nanoparticles were first synthesized by hydrothermal coprecipitation of ferric and ferrous ions,followed by the modification of their surfaces with tetramethylammonium hydroxide（TMAOH） and the chemical activation with aspartic acid.The surface-modified Fe₃O₄ nanoparticles were then covalently coated with CdTe quantum dots（QDs）,which were modified with mercaptoacetic acid（MPA）,to form the Fe₃O₄/CdTe magnetic and luminescent nanocomposites through the coordination of the amino groups on the surfaces of Fe₃O₄ and the carboxyl groups on CdTe QDs.The structure and properties of as-synthesized nanocomposites were characterized.It was indicated that the nanocomposites possessed structure with an average diameter of 40- 50 nm,yellow-green emission feature and room temperature ferro-magnetism.Both the fluorescence and UV-vis absorption spectra of the nanocomposites showed a blue shift comparing with those of CdTe QDs.The mechanism of the blue shift was presented.The nanocomposites retained the ferromagnetic property with a saturation magnetization of 8.9 emu/g.     

Oxygen permeability and CO2-tolerance of Ce0.8Gd0.2O2-δ-Ln BaCo2O5+δ dual-phase membranes

A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% Ln Ba Co2O5+δ(CGO-LBCO, Ln = La, Pr, Nd,Sm, Gd and Y) were synthesized through a sol-gel route and effects of the Ln3+cations on their phase structure, oxygen permeability and chemical stability against CO2 were investigated systemically by XRD, SEM, TG-DSC and oxygen permeation experiments. XRD patterns reveal that the larger Ln3+cations(La3+, Pr3+and Nd3+) successfully stabilized the double-layered perovskite structure of sintered LBCO,while the smaller ones(Sm3+, Gd3+, and Y3+) resulted in the partial decomposition of LBCO with some impurities formed. CGO-PBCO yields the highest oxygen permeation flux, reaching 2.8×10-7mol s-1 cm-2at 925?C with 1 mm thickness under air/He gradient. The TG-DSC profiles in 20 mol% CO2/N2 and oxygen permeability experiments with CO2 as sweep gas show that CGO-YBCO demonstrates the best chemical stability against CO2, possibly due to its minimum basicity. The stable oxygen permeation flux of CGO-YBCO under CO2 atmosphere reveals its potential application in the oxy-fuel combustion route for CO2 capture.     

PHOTO-INDUCED INTERMOLECULAR AND INTRAMOLECULAR ELECTRON-TRANSFER REACTIONS BETWEEN XANTHENE DYES AND DONORS/ACCEPTORS

A number of electron donors, acceptors and diads containing xanthene dyes were sythesized. When the dyes were excited, the rate constants and the efficiencies of the intermolecular and intramolecular photo-induced electron transfer reactions were determined and calculated. It is found that the photo-induced electron transfer reactions occurred between xanthene dyes and many, including very weak donors or acceptors. The rate constants of intermolecular reactions were controlled by diffusion, and influenced by the reactant concentrations. The laser flash experiments showed that for low reactant concentrations, this kind of reactions took place mainly via the triplet excited state of the dyes. If different electric charges exist with dyes and donors/acceptors, there will be static quenching of the dyes' fluorescence. The intramolecular electron transfer reactions are independent of the solution concentrations, and they may directly proceed via the singlet excited state of the dyes effectively.     

Photocatalytic Synthesis of Hydrocarbon Oxygenates from C2H6 and CO2 over Pd-MoO3/SiO2 Catalyst

Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoOe/SiO2 has a significant effect on the photo absorbing performance of MoO3/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.     

溶胶凝胶法合成莫来石纳米带

Single-crystal mullite nanobelts were prepared by a simple sol-gel method using WO₃ as additive, and nanobelts were straight and uniform with width of 200 nm and length of 3~4 μm. The as-prepared products were characterized with XRD, SEM and TEM and the nanobelt formation mechanism was also discussed. The interphase of aluminium tungstate acted as seed crystals or epitaxial templates during the formation of nanobelts. The further experiments showed that there was a strong correlation between the formation of nanobelts and the presence of WO₃.     

低温固相反应法合成水分散性CdS纳米晶

A novel solid-state method for the preparation of the CdS nanoparticles at the room temperature has been developed. The nanoparticles were characterized with FT-IR, XRD, TEM, XPS and PL techniques. The results indicated that the surfaces of the CdS nanoparticles were modified with sodium thioglycollate and thus they were water-dispersive. The mean particle size was about 3～5 nm. A blue shift has been observed in the photoluminescence emission spectrum.     

NMR analysis of a pair of isomers

In this work,the structures of a pair of isomers were identified.And we showed the ability of the selective 1D version,performed the most common NMR experiments including the ID-HMBC and GOESY experiments,to determine the isomeric composition that were found in the production process of roflumilast.The experimental results proved that this method would be even more time saving and could get more reliable results.     

Discovery and synthesis of N2,N4-substitued-cycloalkyl[d]pyrimidine 2,4-diamine analogs： The first examples of small-molecular FGFR-1 activator

A series of novel, cycloalkyl-modified pazopanib analogs 2 and 3 were designed and synthesized. Their kinase modulatory effects on FGFR-1, VEGFR-2, PDGFR-β and c-KIT were evaluated by the caliper mobility shift assay. Introduction of cycloalkyl into the pyrimidine linker of pazopanib almost abolished the four kinases inhibitory potency of compounds 2 and 3, but surprisingly, resulted in good activation effects on FGFR-1. Compounds 3d and 3g showed double-digit, nanomolar, selective activation effects on FGFR-1, and could be classified as first-generation small molecular activators of FGFR-1 kinase.     

Catalytic activity and crystal structure modification of Pd/γ-Al_2O_3–TiO_2 catalysts with different Al_2O_3 contents

Pd/γ-Al_2O_3–TiO_2 catalysts containing various compositions of titania and alumina were prepared by sol–gel and wet-impregnation methods in attempt to study the particle size, nature of phases, morphology and structure of the composite samples. The ethanol oxidation experiments, N_2 adsorption–desorption,FTIR, XRD and XPS were conducted, and the effects of Al_2O_3 content on the surface area, phase transformation and structural properties of TiO_2 were investigated. The optimal value of ethanol conversion appeared on Pd/Al(0.05)–Ti and Pd/Al(0.90)–Ti catalysts irrespective of the ethanol oxidation temperature, and we call this as a double peaks phenomenon of catalytic activity. The XRD results reveal that the phase composition and crystallite size of the mixed oxides depend on Al_2O_3/TiO_2 ratio and calcination temperature. Al_2O_3 can effectively prevent the agglomeration of TiO_2 and this can be ascribed to the formation of Al–O–Ti chemical bonds in Al_2O_3–TiO_2 crystals. Binding energy and Pd surface concentration of the catalysts were modified apparently, which may also lead to catalyst activity changes.     

Substituent effects on direct arylation polycondensation and optical properties of alternating fluorene-thiophene copolymers

Four thiophene derivatives were prepared by replacing the 3,4 positions of thiophene by―OCH3, ―CH3―COOCH3 and ―CN, respectively. The polycondensations via direct arylation took place between the four thiophene derivatives and 2,7-dibromo-9,9-dioctylfluorene under six various catalytic conditions to investigate the substituent effects. The substituent can affect the electron cloud density of the active C―H bond, which can be monitored by the NMR chemical shift. The experimental results show that the reactivity decreases with increasing the chemical shift of active C―H bonds in the four thiophene derivatives, and thus can promote the direct arylation polycondensation. This phenomenon is explained by the electrophilic aromatic substitution(SEAr) mechanism. UV-Visible absorption and photoluminescence were studied to investigate the substituent effect on optical properties of the four copolymers. The results show that these alternating fluorene-thiophene copolymers with different substituents are good fluorescent materials and promising in PLED applications.     

Three-dimensionally ordered macro-porous Pt/TiO2 catalyst used for water-gas shift reaction

Three-dimensionally ordered macro-porous （3DOM） Pt/TiO2 catalysts were prepared by template and impregnation methods, and the resultant samples were characterized by using TG-DTA, XRD, SEM, TEM, and TPR techniques. The catalytic performance for water-gas shift （WGS） reaction was tested, and the influences of some conditions, such as reduction temperature of catalysts, the amount of Pt loadings and space velocity on catalytic performance were investigated. It was shown that Pt particles were homogeneously dispersed on 3DOM TiO2. The reduction of TiO2 surface was important for the catalytic performance. The activity test results showed that the 3DOM Pt/TiO2 catalysts exhibited very good catalytic performance for WGS reaction even at high space velocity, which was owing to the better mass transfer of 3DOM porous structure besides the high intrinsic activity of Pt/TiO2.     

Theoretical and Experimental Study on the Adsorption and Desorption of Methane by Granular Activated Carbon at 25 ℃

A theoretical and experimental study was conducted to accurately determine the amount of adsorption and desorption of methane by various Granular Activated Carbon(GAC)under different physical conditions.To carry out the experiments,the volumetric method was used up to 500 psia at constant temperature of 25℃.In these experiments,adsorption as well as desorption capacities of four different GAC in the adsorption of methane,the major constituent of natural gas,at various equilibrium pressures and a constant temperature were studied.Also,various adsorption isotherm models were used to model the experimental data collected from the experiments.The accuracy of the results obtained from the adsorption isotherm models was compared and the values for the regressed parameters were reported.The results shows that the physical characteristics of activated carbons such as BET surface area,micropore volume,packing density,and pore size distribution play an important role in the amount of methane to be adsorbed and desorbed.     

Two new ent-kaurane diterpenoids from the aerial parts of Isodon excisoides简

Two new ent-kaurane diterpenoids, ent-7a,14b-dihydroxykaur-16-en-15-one-20-oic acid(1) and 1,7a,12b,14b-tetrahydroxy-1,10-seco-ent-kaur-10,16-dien-15-one(2), together with six known ones(3–8), were isolated from the EtOAc extract of the aerial parts of Isodon excisoides. Their structures were elucidated on the basis of 1D NMR and 2D NMR analyses as well as HR-ESI-MS experiments.     

SYNTHESIS AND CHARACTERIZATION OF ORGANOMONTMORILLONITE AND POLYAMIDE 66/MONTMORILLONITE NANOCOMPOSITES

The montmorillonites (MMTs), layered, smectite-type silicates, were premodified by two different methods priorto the polymer melt intercalation. In one case MMTs were modified with cetyltrimethylammonium bromide (CTAB), andtermed as organomontmorillonites (OMMTs); in the other case MMTs were modified by nylon, and the products were calledmodified montmorillonites (MMMTs). The effects of CTAB and nylon on the MMTs were investigated by using TG andWAXD. The results show that interlayer spacings of CTAN and nylon modified MMTs are larger than that of sodium MMTs.Then, polyamide 66 (PA 66)/MMT nanocomposites were obtained through the method of melt intercalation of polymers. Thenanocomposites were characterized by WAXD, TEM and Molau experiments. The results indicate that the MMTs dispersehomogeneously in the PA 66 matrix. The mechanical properties of nanocomposites, such as tensile properties and flexuralproperties, were also measured and show a tendency to increase with increase of MMT content and reach the maximumvalues at 5phr MMT content. The heat distortion temperature (HDT) of the nanocomposites (7 phr) is about 32 K higher thanthat of pure PA 66.     

Influence of Gas Components on the Formation of Carbonyl Sulfide over Water-Gas Shift Catalyst B303Q

Water-gas shift reaction catalyst at lower temperature (200—400℃) may improve the conversion of carbon monoxide. But carbonyl sulfide was found to be present over the sulfided cobalt-molybdenum/alumina catalyst for water-gas shift reaction. The influences of temperature, space velocity, and gas components on the formation of carbonyl sulfide over sulfided cobalt-molybdenum/alumina catalyst B303Q at 200—400℃were studied in a tubular fixed-bed quartz-glass reactor under simulated water-gas shift conditions. The experimental results showed that the yield of carbonyl sulfide over B303Q catalyst reached a maximum at 220℃with the increase in temperature, sharply decreased with the increase in space velocity and the content of water vapor, increased with the increase in the content of carbon monoxide and carbon dioxide, and its yield increased and then reached a stable value with the increase in the content of hydrogen and hydrogen sulfide. The formation mechanism of carbonyl sulfide over B303Q catalyst at 200—400℃was discussed on the basis of how these factors influence the formation of COS. The yield of carbonyl sulfide over B303Q catalyst at 200-400℃was the combined result of two reactions, that is, COS was first produced by the reaction of carbon monoxide with hydrogen sulfide, and then the as-produced COS was converted to hydrogen sulfide and carbon dioxide by hydrolysis. The mechanism of COS formation is assumed as follows: sulfur atoms in the Co9S8-MOS2/Al2O3 crystal lattice were easily removed and formed carbonyl sulfide with CO, and then hydrogen sulfide in the water-gas shift gas reacted with the crystal lattice oxygen atoms in CoO-MoO3/Al2O3 to form Co9S8-MoS2/Al2O3. This mechanism for the formation of COS over water-gas shift catalyst B303Q is in accordance with the Mars-Van Krevelen's redox mechanism over metal sulfide.