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1.
Xishi Tai  Na Wei  Donghao Wang 《Materials》2012,5(4):558-565
A new complex [Mg(L)2(phen)(H2O)2](phen)(H2O)2 [L= N-benzenesulphonyl-L-leucine] was synthesized by the reaction of magnesium chloride hexahydrate with N-benzenesulphonyl-L-leucine and 1,10-phenanthroline in the CH3CH2OH/H2O (v:v = 5:1). It was characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The crystal of the title complex [Mg(L)2(phen)(H2O)2](phen)(H2O)2 belongs to triclinic, space group P-1 with a = 0.72772(15) nm, b = 1.4279(3) nm, c = 1.4418(3) nm, α = 63.53(3)°, β = 79.75(3)°, γ = 81.83(3)°, V = 1.3163(5) nm3, Z =1, Dc= 1.258 μg·m−3, μ = 0.177 mm−1, F(000) = 526, and final R1 = 0.0506, ωR2 = 0.1328. The complex comprises a six-coordinated magnesium(II) center, with a N2O4 distorted octahedron coordination environment. The molecules are connected by hydrogen bonds and π-π stacking to form one dimensional chain structure. The luminescent property of the Mg(II) complex has been investigated in solid.  相似文献   

2.
Benzene alkylation with propylene was studied in the gas phase using a catalytic membrane reactor and a fixed-bed reactor in the temperature range of 200–300 °C and with a weight hourly space velocity (WHSV) of 51 h−1. β-zeolite was prepared by hydrothermal synthesis using silica, aluminum metal and TEAOH as precursors. The membrane’s XRD patterns showed good crystallinity for the β-zeolite film, while scanning electron microscopy SEM results indicated that its random polycrystalline film was approximately 1 μm thick. The powders’ specific area was determined to be 400 m2·g−1 by N2 adsorption/desorption, and the TPD results indicated an overall acidity of 3.4 mmol NH3·g−1. Relative to the powdered catalyst, the catalytic membrane showed good activity and product selectivity for cumene.  相似文献   

3.
Xishi Tai  Jinhe Jiang 《Materials》2012,5(9):1626-1634
A new trinuclear Cd (II) complex [Cd3(L)6(2,2-bipyridine)3] [L = N-phenylsulfonyl-L-leucinato] has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The results show that the complex belongs to the orthorhombic, space group P212121 with a = 16.877(3) Å, b = 22.875(5) Å, c = 29.495(6) Å, α = β = γ = 90°, V = 11387(4) Å3, Z = 4, Dc= 1.416 μg·m−3, μ = 0.737 mm−1, F (000) = 4992, and final R1 = 0.0390, ωR2 = 0.0989. The complex comprises two seven-coordinated Cd (II) atoms, with a N2O5 distorted pengonal bipyramidal coordination environment and a six-coordinated Cd (II) atom, with a N2O4 distorted octahedral coordination environment. The molecules form one dimensional chain structure by the interaction of bridged carboxylato groups, hydrogen bonds and π-π interaction of 2,2-bipyridine. The luminescent properties of the Cd (II) complex and N-Benzenesulphonyl-L-leucine in solid and in CH3OH solution also have been investigated.  相似文献   

4.
The paper analyzes the surface structure and phase state of Ti49.4Ni50.6 (at%) hydrogenated at 295 K in normal saline (0.9% NaCl aqueous solution with pH = 5.7) at 20 A/m2 for 0.5–6 h. The analysis shows that the average hydrogen concentration in the alloy increases with the hydrogenation time tH as follows: slowly to 50 ppm at tH = 0.5–1.5 h, steeply to 150 ppm at tH = 1.2–2 h, and linearly to 300 ppm at tH = 2–6 h. According to Bragg–Brentano X-ray diffraction data (θ–2 θ, 2 θ ≤ 50°, CoKα radiation), the alloy in its scanned surface layer of thickness ~5.6 µm reveals a TiNiHx phase with x = 0.64 and x = 0.54 after hydrogenation for 4 and 6 h, respectively. The structure of this phase is identifiable as an orthorhombic hydride similar to β1–TiFeH0.94 (space group Pmcm), rather than as a tetragonal TiNiHx hydride with x = 0.30–1.0 (space group I4/mmm). Time curves are presented to trace the lattice parameters and volume change during the formation of such an orthorhombic phase from the initial cubic B2 phase in Ti49.4Ni50.6 (at%).  相似文献   

5.
The catalytic activity of ruthenium(III) acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II) species is formed in situ from the reduction of ruthenium(III) and characterized using UV-Visible, Fourier transform infrared (FTIR), 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II) species is mer-[Ru(N2Me4)3(acac)H]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac)3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II) catalyst formed from the reduction of ruthenium(III) acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.  相似文献   

6.
An artificially prepared nanocrystalline iron sample with bimodal crystallite size distribution was nitrided and denitrided in the NH3/H2 atmosphere at 350 °C and 400 °C. The sample was a 1:1 mass ratio mixture of two iron samples with mean crystallite sizes of 48 nm and 21 nm. Phase transformations between α-Fe, γ’-Fe4N and ε-Fe3-2N were observed by the in situ X-ray powder diffraction method. At selected steps of nitriding or denitriding, phase transformations paused at 50% of mass conversion and resumed after prominent variation of the nitriding atmosphere. This effect was attributed to the separation of phase transformations occurring between sets of iron crystallites of 48 nm and 21 nm, respectively. This was due to the Gibbs–Thomson effect, which establishes the dependence of phase transformation conditions on crystallite sizes.  相似文献   

7.
Yields of β-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates, in particles formed from OH radical-initiated reactions of C9-C15 2-methyl-1-alkenes in the presence of NOx were measured by using a thermal desorption particle beam mass spectrometer coupled to a high-performance liquid chromatograph with a UV-visible (UV-vis) detector. Yields of β-hydroxynitrates and dihydroxynitrates increased with carbon number primarily due to enhanced gas-to-particle partitioning before reaching plateaus at ≈C14-C15, where the compounds were essentially entirely in the particle phase. Plateau yields of β-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates were 0.183 ± 0.005, 0.045 ± 0.005, and 0.034 ± 0.005, and, after normalization for OH radical addition to the C = C double bond, were 0.225 ± 0.007, 0.055 ± 0.006, and 0.042 ± 0.006. The fractions of 1-hydroxy and 2-hydroxy β-hydroxynitrate isomers were 0.90/0.10. Yields measured here and in our previous study of reactions of linear internal alkenes and linear 1-alkenes indicate that, for these alkene classes, the relative branching ratios for forming tertiary, secondary, and primary β-hydroxyalkyl radicals by OH radical addition to the C = C double bond are 4.3/1.9/1.0, and the branching ratios for forming β-hydroxynitrates from reactions of tertiary, secondary, and primary β-hydroxyperoxy radicals with NO are 0.25, 0.15, and 0.12. The effects of H2O vapor and NH3 on yields were also explored.  相似文献   

8.
9.
AIM: To study the uptake of bacterial lipopolysaccharides (LPS) and expression of tumor necrosis factor α-mRNA (TNF-α-mRNA) with cultured rat intrahepatic bile duct epithelial cells.METHODS: By using fluorescent, immunohistochemical and in situ hybridization techniques, the uptake of Escherichia coli LPS and expression of TNF-α-mRNA with isolated rat intrahepatic bile duct epithelial cells were observed with confocal laser scanning microscopy.RESULTS: Positive reactions to LPS were found in the cytoplasm of isolated intrahepatic bile duct epithelial cells after incubation with LPS for 15 min and the FITC fluorescent intensity against LPS was significantly higher than that of the controls (121.45 μFI/μm2 ± 15.62 μFI/μm2 vs 32.12 μFI/μm2 ± 9.64 μFI/μm2, P < 0.01). After incubation with LPS for 3 h, fluorescein isocyanate (FITC) fluorescent intensities of the expression of TNF-α-mRNA with fluorescent in situ hybridization in the cytoplasm and nuclei of the cultured bile duct epithelial cells were significantly higher than those of the controls (189.15 μFI/μm2 ± 21.33 μFI/μm2 vs 10.00 μFI/μm2 ± 8.99 μFI/μm2, 64.85 μFI/μm2 ± 14.99 μFI/μm2 vs 21.20 μFI/μm2 ± 2.04 μFI/μm2, respectively (P < 0.01)). The increase of FITC fluorescent intensity of TNF-α-mRNA expression in the cytoplasm peaked at 6 h after incubation (221.38 μFI/μm2 ± 22.99 μFI/μm2). At various time points after incubation with LPS, the increase of fluorescent intensities of TNF-α-mRNA in the cytoplasm were much higher than those in the nuclei (P < 0.01).CONCLUSION: LPS can act on and enter into isolated intrahepatic bile duct epithelial cells and stimulate the expression of TNF-α-mRNA.  相似文献   

10.
Spodumene concentrate from the Pilbara region in Western Australia was characterized by X-ray diffraction (XRD), Scanning Electron Microscope Energy Dispersive Spectroscopy (SEM-EDS) and Mineral Liberation Analysis (MLA) to identify and quantify major minerals in the concentrate. Particle diameters ranged from 10 to 200 microns and the degree of liberation of major minerals was found to be more than 90%. The thermal behavior of spodumene and the concentration of its polymorphs were studied by heat treatments in the range of 900 to 1050 °C. All three polymorphs of the mineral (α, γ and β) were identified. Full transformation of the α-phase was achieved at 975 °C and 1000 °C after 240 and 60 min treatments, respectively. SEM images of thermally treated concentrate revealed fracturing of spodumene grains, producing minor cracks initially which became more prominent with increasing temperature. Material disintegration, melting and agglomeration with gangue minerals were also observed at higher temperatures. The metastable γ-phase achieved a peak concentration of 23% after 120 min at 975 °C. We suggest 1050 °C to be the threshold temperature for the process where even a short residence time causes appreciable transformation, however, 1000 °C may be the ideal temperature for processing the concentrate due to the degree of material disintegration and α-phase transformation observed. The application of a first-order kinetic model yields kinetic parameters which fit the experimental data well. The resultant apparent activation energies of 655 and 731 kJ mol−1 obtained for α- and γ-decay, respectively, confirm the strong temperature dependence for the spodumene polymorph transformations.  相似文献   

11.
In this study, silicon nitride (SiNx) thin films were deposited on polyimide (PI) substrates as barrier layers by a plasma enhanced chemical vapor deposition (PECVD) system. The gallium-doped zinc oxide (GZO) thin films were deposited on PI and SiNx/PI substrates at room temperature (RT), 100 and 200 °C by radio frequency (RF) magnetron sputtering. The thicknesses of the GZO and SiNx thin films were controlled at around 160 ± 12 nm and 150 ± 10 nm, respectively. The optimal deposition parameters for the SiNx thin films were a working pressure of 800 × 10−3 Torr, a deposition power of 20 W, a deposition temperature of 200 °C, and gas flowing rates of SiH4 = 20 sccm and NH3 = 210 sccm, respectively. For the GZO/PI and GZO-SiNx/PI structures we had found that the GZO thin films deposited at 100 and 200 °C had higher crystallinity, higher electron mobility, larger carrier concentration, smaller resistivity, and higher optical transmittance ratio. For that, the GZO thin films deposited at 100 and 200 °C on PI and SiNx/PI substrates with thickness of ~000 nm were used to fabricate p-i-n hydrogenated amorphous silicon (α-Si) thin film solar cells. 0.5% HCl solution was used to etch the surfaces of the GZO/PI and GZO-SiNx/PI substrates. Finally, PECVD system was used to deposit α-Si thin film onto the etched surfaces of the GZO/PI and GZO-SiNx/PI substrates to fabricate α-Si thin film solar cells, and the solar cells’ properties were also investigated. We had found that substrates to get the optimally solar cells’ efficiency were 200 °C-deposited GZO-SiNx/PI.  相似文献   

12.
Two-phase TC21 titanium alloy samples were solution-treated at 990 °C (β phase zone) and cooled by furnace cooling (FC), air cooling (AC), and water quenching (WQ), respectively. The second solution stage treatment was carried out at 900 °C (α + β phase zone), then aging treatment was performed at 590 °C. The influence of the size and quantity of the α phase on the properties of the sample were studied. The experimental results showed as the cooling rate increased after the first solution stage treatment, wherein the thickness of primary layer α gradually decreased, and the tensile strength and yield strength gradually increased. After the second solution stage treatment, the tensile properties of samples increased due to the quantity of layers α increased. The aging treatment promoted the precipitation of the dispersed α phase and further improved the tensile strength. After the third solution stage treatments, the FC samples with more β-phase had the best comprehensive mechanical properties.  相似文献   

13.
Endoglucanases are key enzymes applied to the conversion of biomass aiming for second generation biofuel production. In the present study we obtained the small angle X-ray scattering (SAXS) structure of the G. trabeum endo-1,4-β-glucanase Cel12A and investigated the influence of an important parameter, temperature, on both secondary and tertiary structure of the enzyme and its activity. The CD analysis for GtCel12A revealed that changes in the CD spectra starts at 55 °C and the Tm calculated from the experimental CD sigmoid curve using the Boltzmann function was 60.2 ± 0.6 °C. SAXS data showed that GtCel12A forms monomers in solution and has an elongated form with a maximum diameter of 60 ± 5 Å and a gyration radius of 19.4 ± 0.1 Å as calculated from the distance distribution function. Kratky analysis revealed that 60 °C is the critical temperature above which we observed clear indications of denaturation. Our results showed the influence of temperature on the stability and activity of enzymes and revealed novel structural features of GtCel12A.  相似文献   

14.
Ultrafine MgH2 nanocrystalline powders were prepared by reactive ball milling of elemental Mg powders after 200 h of high-energy ball milling under a hydrogen gas pressure of 50 bar. The as-prepared metal hydride powders were contaminated with 2.2 wt. % of FeCr-stainless steel that was introduced to the powders upon using stainless steel milling tools made of the same alloy. The as-synthesized MgH2 was doped with previously prepared TiC nanopowders, which were contaminated with 2.4 wt. % FeCr (materials of the milling media), and then ball milled under hydrogen gas atmosphere for 50 h. The results related to the morphological examinations of the fabricated nanocomposite powders beyond the micro-and nano-levels showed excellent distributions of 5.2 wt. % TiC/4.6 wt. % FeCr dispersoids embedded into the fine host matrix of MgH2 powders. The as-fabricated nanocomposite MgH2/5.2 wt. % TiC/4.6 wt. % FeCr powders possessed superior hydrogenation/dehydrogenation characteristics, suggested by the low value of the activation energy (97.74 kJ/mol), and the short time required for achieving a complete absorption (6.6 min) and desorption (8.4 min) of 5.51 wt. % H2 at a moderate temperature of 275 °C under a hydrogen gas pressure ranging from 100 mbar to 8 bar. van’t Hoff approach was used to calculate the enthalpy (∆H) and entropy (∆S) of hydrogenation for MgH2, which was found to be −72.74 kJ/mol and 112.79 J/mol H2/K, respectively. Moreover, van’t Hoff method was employed to calculate the ΔH and ΔS of dehydrogenation, which was found to be 76.76 kJ/mol and 119.15 J/mol H2/K, respectively. This new nanocomposite system possessed excellent absorption/desorption cyclability of 696 complete cycles, achieved in a cyclic-life-time of 682 h.  相似文献   

15.
The impact of age and 24‐h ambulatory blood pressure (ABPM) on arterial stiffness and carotid intima‐media thickness (cIMT) in ischemic stroke patients younger than 60 years of age is poorly explored. A total of 385 acute ischemic stroke patients (aged 49.6±9.7 years, 68% men) were prospectively included and grouped in younger (15–44 years, n = 93) and middle‐aged (45–60 years, n = 292). Arterial stiffness was measured by carotid‐femoral pulse wave velocity (PWV), and cIMT by carotid ultrasound. 24‐h ABPM was recorded. The middle‐aged stroke patients had higher prevalence of smoking, hypertension, diabetes mellitus, metabolic syndrome and hypercholesterolemia, and had higher PWV and cIMT (all p < .05). In multivariable linear regression analyses adjusted for sex, BMI, smoking, diabetes mellitus, total cholesterol, high‐density lipoprotein cholesterol, triglycerides, eGFR, systolic BP and concomitant antihypertensive treatment, 1SD (4.4 years) higher age was associated with higher PWV (β = 0.44,R= 0.46, p < .001) in the younger group, and with higher mean cIMT (β = 0.16, R= 0.21, p = .01) in the middle‐aged group. In the middle‐aged group, 24‐h pulse pressure had a significant association with PWV (β = 0.18, R= 0.19, p = .009), while the association with cIMT was attenuated (β = 0.13, R= 0.16, p = .065). 24‐h diastolic BP was associated with higher cIMT in the middle‐aged group (β = 0.24, p < .001, R= 0.23), but not with PWV in either age groups. Among ischemic stroke patients < 60 years, higher age was associated with increased arterial stiffness for patients up to age 44 years, and with cIMT in middle‐aged patients. 24‐h pulse pressure was associated with arterial stiffness, and 24‐h diastolic BP was associated with cIMT only in middle‐aged patients.  相似文献   

16.
Thin-layer spectroelectrochemical methods have been employed to measure the reduction potentials of the blue copper in Polyporus versicolor laccase (EC 1.10.3.2) between 7°C and 41°C (0.2 M sodium phosphate, pH 5.4). Thermodynamic parameters are: ΔS° = -13.9 ± 2 cal/mol-K; ΔH° = -22.1 ± 0.5 kcal/mol; E° (25°C) = 780 ± 3 mV vs. the normal hydrogen electrode. Comparison of the ΔS° and ΔH° values with those for single-site proteins suggests that the high potential of the blue copper in fungal laccase is attributable mainly to stabilization of the copper (I) center by enhanced ligand binding interactions and that protein solvation effects play a lesser role.  相似文献   

17.
Two lytic phages, vB_SenM-PA13076 (PA13076) and vB_SenM-PC2184 (PC2184), were isolated from chicken sewage and characterized with host strains Salmonella Enteritidis (SE) ATCC13076 and CVCC2184, respectively. Transmission electron microscopy revealed that they belonged to the family Myoviridae. The lytic abilities of these two phages in liquid culture showed 104 multiplicity of infection (MOI) was the best in inhibiting bacteria, with PC2184 exhibiting more activity than PA13076. The two phages exhibited broad host range within the genus Salmonella. Phage PA13076 and PC2184 had a lytic effect on 222 (71.4%) and 298 (95.8%) of the 311 epidemic Salmonella isolates, respectively. We tested the effectiveness of phage PA13076 and PC2184 as well as a cocktail combination of both in three different foods (chicken breast, pasteurized whole milk and Chinese cabbage) contaminated with SE. Samples were spiked with 1 × 104 CFU individual SE or a mixture of strains (ATCC13076 and CVCC2184), then treated with 1 × 108 PFU individual phage or a two phage cocktail, and incubated at 4 °C or 25 °C for 5 h. In general, the inhibitory effect of phage and phage cocktail was better at 4 °C than that at 25 °C, whereas the opposite result was observed in Chinese cabbage, and phage cocktail was better than either single phage. A significant reduction in bacterial numbers (1.5–4 log CFU/sample, p < 0.05) was observed in all tested foods. The two phages on the three food samples were relatively stable, especially at 4 °C, with the phages exhibiting the greatest stability in milk. Our research shows that our phages have potential effectiveness as a bio-control agent of Salmonella in foods.  相似文献   

18.
19.
This study aimed to modify an EQUIA coat (EC; GC, Japan) by incorporating 1 and 2 wt.% of zinc oxide (ZnO; EC-Z1 and EC-Z2) and titanium dioxide (TiO2; EC-T1 and EC-T2) nanoparticles, whereby structural and phase analyses were assessed using Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD), respectively. Thermogravimetric analysis/differential scanning calorimetry, micro-hardness, and water absorption analyses were conducted, and the microstructure was studied by scanning electron microscopy/energy-dispersive spectroscopy. FTIR spectra showed a reduction in peak heights of amide (1521 cm−1) and carbonyl (1716 cm−1) groups. XRD showed peaks of ZnO (2θ ~ 31.3°, 34.0°, 35.8°, 47.1°, 56.2°, 62.5°, 67.6°, and 68.7°) and TiO2 (2θ ~ 25.3°, 37.8°, 47.9, 54.5°, 62.8°, 69.5°, and 75.1°) corresponding to a hexagonal phase with a wurtzite structure and an anatase phase, respectively. Thermal stability was improved in newly modified materials in comparison to the control group. The sequence of obtained glass transitions was EC-T2 (111 °C), EC-T1 (102 °C), EC-Z2 (98 °C), EC-Z1 (92 °C), and EC-C (90 °C). EC-T2 and EC-T1 showed the highest (43.76 ± 2.78) and lowest (29.58 ± 3.2) micro-hardness values. EC showed the maximum water absorption (1.6%) at day 7 followed by EC-T1 (0.82%) and EC-Z1 (0.61%). These results suggest that EC with ZnO and TiO2 nanoparticles has the potential to be used clinically as a coating material.  相似文献   

20.
A series of strontium titanates-vanadates (STVN) with nominal cation composition Sr1-xTi1-y-zVyNizO3-δ (x = 0–0.04, y = 0.20–0.40 and z = 0.02–0.12) were prepared by a solid-state reaction route in 10% H2–N2 atmosphere and characterized under reducing conditions as potential fuel electrode materials for solid oxide fuel cells. Detailed phase evolution studies using XRD and SEM/EDS demonstrated that firing at temperatures as high as 1200 °C is required to eliminate undesirable secondary phases. Under such conditions, nickel tends to segregate as a metallic phase and is unlikely to incorporate into the perovskite lattice. Ceramic samples sintered at 1500 °C exhibited temperature-activated electrical conductivity that showed a weak p(O2) dependence and increased with vanadium content, reaching a maximum of ~17 S/cm at 1000 °C. STVN ceramics showed moderate thermal expansion coefficients (12.5–14.3 ppm/K at 25–1100 °C) compatible with that of yttria-stabilized zirconia (8YSZ). Porous STVN electrodes on 8YSZ solid electrolytes were fabricated at 1100 °C and studied using electrochemical impedance spectroscopy at 700–900 °C in an atmosphere of diluted humidified H2 under zero DC conditions. As-prepared STVN electrodes demonstrated comparatively poor electrochemical performance, which was attributed to insufficient intrinsic electrocatalytic activity and agglomeration of metallic nickel during the high-temperature synthetic procedure. Incorporation of an oxygen-ion-conducting Ce0.9Gd0.1O2-δ phase (20–30 wt.%) and nano-sized Ni as electrocatalyst (≥1 wt.%) into the porous electrode structure via infiltration resulted in a substantial improvement in electrochemical activity and reduction of electrode polarization resistance by 6–8 times at 900 °C and ≥ one order of magnitude at 800 °C.  相似文献   

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