Synthesis, oxygenation and catalytic performance of manganese complex with p-aminomethyl benzoic acid Schiffbase

The amino acid Schiff base complex (Sal-AMBA-Mn) was prepared with p-amino-methylbenzoic acid, salicylaldehyde and Mn(OAc)2·4H2O. Its structures was characterized with IR and UV spectra. Oxygenation mechanism of the complex in N, N-dimethylformamide solution was investigated. The results show that lower temperature is in favor of the oxygenation, and energy, enthalpy and entropy are -3.8 kJ/mol, -4.2 J/mol and -161.44 J/(mol·K), respectively. In the presence of the manganese complex, dehydroepiandrosterone acetate is effectively oxidized by molecular oxygen and the corresponding enone 7-ketodehydroepiandrosterone acetate is obtained. The yield is 62.1% when the oxidation is carried out under the reaction conditions of 60 ℃, 2 MPa of O2 pressure, C5H5N as a solvent and molar ratio of the substrate to the complex of 1:10.     

Study on solubility of Nb2O5 in KOH solution and alkali leaching of niobite

Solubility of Nb₂O₅ and leaching behaviors of Nb and Ta from niobite in KOH solution have been investigated in order to develop an alkali hydrothermal leaching process of Nb and Ta. The solubility of Nb₂O₅ was measured in the range of 40 °C to 200 °C at various molar ratios of K₂O to Nb₂O₅(n(K₂O)/n(Nb₂O₅)). It has been found that Nb₂O₅ shows the maximum solubility at the solution composition of n(K₂O)/n(Nb₂O₅)=4/3 at a given temperature; the rise of temperature increases the solubility of Nb₂O₅ below 120 °C, but decreases it above 120 °C. The leaching behaviors of Nb and Ta were studied in the range of 150 °C to 250 °C and 0.1 MPa to 5 MPa. With the rise of temperature, the leaching degree increases when the leaching temperature is below 200 °C, but it decreases when the leaching temperature is above 200 °C. The maximum leaching degree is about 90% at 200 °C. It was proved that the alkali hydrothermal leaching process is effective for the recovery of Nb and Ta from niobite concentrate. Foundation item: The Key Project of Science and Technology Agency of Japan, 1994 Biography of the first author: ZHOU Kang-gen, doctor of engineering, professor, born in 1963, majoring in extractive metallurgy of rare metals and application of membrane separation technology.     

Synthesis of lanthanum tris (mono- i -octyl phthalate) and its thermal stability for polyvinyl chloride

A novel type of thermal stabilizer—lanthanum tris (mono-i-octyl phthalate) (LTMP) was synthesized by double-decomposition reaction of sodium mono-i-octyl phthalate with lanthanum chloride at 60 °C. Sodium mono-i-octyl phthalate was prepared by sodium hydrate and mono-i-octyl phthalate prepared by reaction of isooctyl alcohol and phthalic anhydride in the presence of sulfuric acid catalyst at 110 °C. The yield of lanthanum tris (mono-i-octyl phthalate) is about 84.5%. Its thermal stabilities were measured by heat-ageing oven test when incorporated into PVC. The experimental results show that the heat stability time is about 40min at 190 °C when adding 3phr (per hundred resin) to PVC. The thermal stability of this product is better than that of Ca-Zn complex and basic lead salt stabilizers, and equal to that of dibutyltin diaurate. Foundation item: The Key Program of 9^th Five-Year Plan of China(No. 96-119-04-03-05) Biography of the first author: LIU You-nian, associate professor, born in Oct. 1964, majoring in fine chemical engineering & separation processes.     

Identification and fermentation optimization of protopectinase-overproducing strain Aspergillus niger CD-01 for pectin production

In order to solve the citrus peel resource waste problem and minimize the drawbacks of chemical extraction of pectin, a protopectinase-overproducing strain CD-01 for pectin production was isolated from a pit soil dumped with perished orange in Changde City, Hunan Province of China. The strain CD-01 had the same morphology and 28S rRNA gene sequence (FJ184995) as that of Aspergillus niger (ATCC 64028). It was thus identified and named as Aspergillus niger CD-01. The fermentation condition was optimized based on L₉(3⁴) orthogonal experimental design and the variances analyses. The results show that the optimal condition for producing pectin is as follows: time 36 h, temperature 35 °C, pH 5, and urea as the nitrogen source. Under this condition, the pectin yield can reach up to 24.5%. This shows a great potential of Aspergillus niger CD-01 in pectin extraction from citrus. Foundation item: Projects(50621063, 50674101) supported by the National Natural Science Foundation of China     

Synthesis and characterization of high-voltage cathode material LiNi0.5Mn1.5O4 by one-step solid-state reaction

LiNi_0.5Mn_1.5O₄ was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry (XRD), scanning electron microscopy (SEM) and electrochemical measurement. XRD patterns show that LiNi_0.5Mn_1.5O₄ synthesized under various conditions has cubic spinel structure. SEM images exhibit that the particle size increases with increasing calcination temperature and time. Electrochemical test shows that the LiNi_0.5Mn_1.5O₄ calcined at 700 °C for 24 h delivers up to 143 mA · h/g, and the capacity retains 132 mA · h/g after 30 cycles. Foundation item: Project (76600) supported by Postdoctoral Science Foundation of Central South University     

Purification and characterization of extracellular chitinase from a novel strain Aspergillus fumigatus CS-01

Twelve samples derived from different locations in south central area of China are treated by enrichment and spread-plate technique for initial screening. Seven chitinase-producing strains are isolated. The chitinase present in the culture supernatant of strain CS-01 possesses the maximum activity of 0.118 U/mL. Analysis of the morphological feature and the ITS rDNA sequence reveals that strain CS-01 belongs to Aspergillus fumigatus. Production of the chitinase is regulated by a inducible way and the maximum activity appears at 36 h in colloidal chitin culture. Purification of the chitinase is carried out by salting out, gel filtrate chromatography and anion exchange chromatography sequentially. Native-PAGE and SDS-PAGE indicate that the chitinase from A. fumigatus CS-01 is a monomer with the relative molecular mass estimated to be 4.50×10⁴. Its maximum activity appears at pH 5 and 55 °C. The chitinase is stable at pH 4.0–7.5 and below 45 °C. Foundation item: Projects(50621063, 50674101) supported by the National Natural Science Foundation of China     

Production and characterization of alkaline extracellular lipase from newly isolated strain Aspergillus awamori HB-03

A strain HB-03 to produce alkaline extracellular lipase was isolated from oil-rich soil samples and identified as Aspergillus awamori.The growth conditions and nutritional factors for lipase production by strain HB-03 were optimized,and the maximum lipase production of (45.9±2.3) U/mL was obtained at 30 °C and pH 7.0 after 36 h using olive oil (1%) and sucrose (0.5%) as carbon sources and combination of peptone (2%),yeast extract (0.5%) and ammonium sulfate (0.1%) as nitrogen sources.The lipase was purified...     

The Effect of Bi2O3 on the Structure and Microwave Dielectric Properties of Ba6-3xNd8＋2xTi18O54 System（x=2/3）

The structures and dielectric properties of Ba6-3xNd8＋2xTi18O54 system（x=2/3） doped with different contents of Bi2O3, whose final molecular formula is Ba6-3x（Nd1-yBiy）8＋2xTi18O54 were investigated. It is indicated that the dielectric constant increases greatly whereas Q value（f0=4 GHz） decreases with the increase of Bi2O3 content. However, the temperature coefficient could be controlled below 0±30×10^-6/℃ in the experiment. These phenomena are related to the appearance of a new phase, Bi4Ti3O12, which has high dielectric constant. Also, that Bi^3＋（0.13 nm） substitutes for Nd^3＋（0.099 5 nm） will increase the unit cell volume, which will lead to the enlargement of the octahedron B site occupied by Ti^4＋. So the spontaneous polarization of Ti^4＋ ions will be strengthened. Besides, Bi^3＋ will fill up some vacancies which Ba^2＋ or Nd^3＋ ions leave in two A1 sites and four A2 sites. More positive ions polarize, which also contributes to higher dielectric constant. The samples got with the optimium properties are sintered at 1 200 ℃ for 4 h, when y=0.25, ε≈110, Q≈5 400（f0=4 GHz）, TCC=-4.7×10^-6/℃; When y=0.3, ε≈120, Q≈5 000（f0=4 GHz）, TCC=-24×10^-6/℃.     

Isolation and characterization of YNTC-1, a novel Alicyclobacillus sendaiensis strain

A heterotrophic acidothermophilic bacterial strain, YNTC-1, was isolated from an acidic hot spring in Tengchong, Yunan, China. YNTC-1 grows at pH value of 1.5-8.0 and temperature of 40-70 ℃, with optimal pH and temperature at 3.0 and 55 ℃, respectively. The cells of the strain are in shape of short rod, with 1.0-1.2 μm in length and 0.7-0.8 μm in diameter, and with distinct spores at both poles of each cell. The predominant fatty acids in cellular membrane of the strain are C18：1 ω7c. 16s rRNA gene analysis reveals that this strain is closely related to Alicyclobacillus sendaiensis, with over 99% sequence similarity. Based on phenotypic and genotypic analyses, YNTC-1 is identified as a member ofA. sendaiensis. Considering some important morphological and biochemical differences between strain YNTC-1 and A. sendaiensis ATCC 27009T, YNTC-1 may be proposed to be a novel subspecies of A. sendaiensis. However, this viewpoint has to be confirmed by further studies. Co-bioleaching of pyrite and chalcopyrite with strain YN22, Sulfobacillus thermosulfidooxidans, shows that strain YNTC-1 has no evident influence on bioleaching rates of these two sulphide minerals.     

Adsorption characteristics of thiobacillus ferrooxidans on surface of sulfide minerals

By using thiobacillus ferroxidans (T. f) from Qixiashan, Hubei Province, China, the adsorption characteristics of T. f on surface of sulfide mineral were studied. The influences of adsorption time, pH value, temperature, initial inoculated concentration of bacteria, concentration of sulfide mineral powder, and variety of minerals on the adsorption characteristics were firstly investigated by using the ninhydrin colorimetric method, and the changes of contact angles and Zeta potentials of mineral surface during the bacterial adsorption were then determined. The results show that when the leaching experiments are performed for a long time from several days to a month, the maximal quantity of adsorption of T f on the surface of pyrite is obtained under the following conditions: leaching for 20 d, pH value in range of 1–2 and temperature at 30 °C, respectively; when the bio-leaching experiments are performed for a shorter leaching time, the maximal quantity of adsorption is obtained under the conditions: bio-leaching for 2 h, at 2.4×10⁷ cell/mL of initial inoculated bacteria concentration, and at 10% of mineral powder concentration; and the adsorption quantities are different from one sulfide mineral to another, and the adsorption of T. f on the surface of sulfide minerals includes three phases: increasing phase, stationary phase and decreasing phase. Foundation item: Project(50321402) supported by the National Natural Science Foundation of China; project (2004CB619204) supported by the National Key Fundamental Research and Development Program of China     

Chemieal Synthesis and Magnetie Properties of Nanocrystalline （La0.67-XGdx）Sr0.33MnO3 Using Amorphous Molecular Alloy as Precursors

A new route to synthesize nanosized crystalline of （La0.67-xGdx）Sr0.33MnO3 （X=0.05, 0.10, 0.15, 0.20） perovskite-type complex oxides at calcination temperature of 600-1000℃ using the amorphous molecular alloy as precursors was reported. The precursor could be completely decomposed into complex oxide at temperature below 500℃ according to the TGA and DTA results. XRD demonstrates that the decomposed species is composed of perovskite-type structure at calcination temperature of 600℃ for 2 h. The particle size that depends on the calcination temperature of the precursor is in a range of 30-120 nm as determined by transmission electron microscopy （TEM）. This method is effective and can be easily quantitatively controlled to synthesize nanosized perovskite-type complex oxides. The magnetic properties of （La0.67 xGdx）Sr0.33MnO3 nanocrystalline were preliminary studied.     

Sintering of the NiFe2O4-10NiO/xNi Cermet

The sintering behavior of NiFe2 O4-10NiO/xNi cermet which was used as the most prospective inert anode materials for aluminum electrolysis was studied by examining the effects of raw powder particle size, sintering temperature, and the contents of Ni. The results show that fine particle size enables the powder to have high driving force for sintering. High temperature is beneficial to densification, but the ultra-high temperature does harm to the improvement of the density. The samples of NiFe2O4-10NiO/SNi has the highest relative density of 97.28 % when it is sintered at 1 350 ℃, but it decreases to 95.23 % when sintered at 1 400 ℃. Low addition of Ni has a great help to the sintering of NiFe2 O4-10NiO matrix. When the samples are sintered at 1 350 ℃ and the mass fraction of Ni is 5%, the highest relative density is gained, but the density decreases with the further increase of Ni contents. The low density of the sintered samples of NiFe2 O4-10NiO/17Ni is attributed to the high volume fraction of pores.     

Synthesis of γ-Al2O3 nanoparticles by chemical precipitation method

Highly pure active γ-Al₂O₃ nanoparticles were synthesized from aluminum nitrate and ammonium carbonate with a little surfactant by chemical precipitation method. The factors affecting the synthesis process were studied. The properties of γ-Al₂O₃ nanoparticles were characterized by DTA, XRD, BET, TEM, laser granularity analysis and impurity content analysis. The results show that the amorphous precursor Al(OH)₃ sols are produced by using 0.1 mol/L Al(NO₃)₃ · 9H₂O and 0.16 mol/L (NH₄)₂CO₃ · H₂O reaction solutions, according to the volume ratio 1.33, adding 0.024% (volume fraction) surfactant PEG600, and reacting at 40 °C, 1 000 r/min stirring rate for 15 min. Then, after stabilizing for 24 h, the precursors were extracted and filtrated by vacuum, washed thoroughly with deionized water and dehydrated ethanol, dried in vacuum at 80°C for 8 h, final calcined at 800 °C for 1 h in the air, and high purity active γ-Al₂O₃ nanoparticles can be prepared with cubic in crystal system, O _H ⁷ -FD3M in space group, about 9 nm in crystal grain size, about 20 nm in particle size and uniform size distribution, 131. 35 m²/g in BET specific surface area, 7 – 11 nm in pore diameter, and not lower than 99.93% in purity. Foundation item: Project(03JJY3015) supported by the Natural Science Foundation of Hunan Province     

Pressureless sintered 3Y-TZP/20%Al2O3 composite ceramic

Nanometer 3Y-TZP/20%Al₂O₃ (mass fraction) composite powders prepared by the chemical coprecipitation method were pressureless sintered at 1550 °C for 2 h. Effects of calcining temperatures at 800 °C, 1 000 °C, and 1 200 °C on phase structure, relative density, and Vicker’s hardness of the sintered bodies were studied. The results show that 1 000 °C was the optimal calcining temperature, and the powder calcined was composed of tetragonal zirconia with the Scherrer crystalline size of 6.3nm. The relative density was up to 98.5% under pressureless sintering, and the sintered body was t-ZrO₂ (without m-ZrO₂)+α-Al₂O₃ with the average size of 0.4 μm. Foundation item: State Key Laboratory for Powder Metallurgy(No.9706-36) Biography of the first author: YIN Bang-yao, born in 1966, majoring in advanced ceramic materials.     

Effects of temperature and initial molar ratio of Na2O to Al2O3 on agglomeration of fine Al（OH）3 seed in synthetic Bayer solution

Fine Al（OH）3 crystals were aggregated from supersaturated aluminate solution in the batch reaction tanks. By means of laser particle size analyzer and scanning electron microscopy, the influences of temperature and initial molar ratio of Na2O to Al2O3 （aK） on agglomeration of fine seed in Bayer process were investigated. The results show that agglomeration is almost finished in 8 h, and seeds with size less than 2 μm are easily aggregated together, and almost disappear in 8 h under the optimal process conditions. In the aluminate solution with the same moderate initial aK, when the reaction temperature reaches 75 ℃, the secondary nucleation does not occur, and the effect of agglomeration is better. And at the same reaction temperature, when the initial aK is 1.62, the initial supersaturation of aluminate solution is moderate, the binders on the surfaces of the seed are enough to maintain the agglomeration process, and the agglomeration degree is better. From SEM images, agglomeration mainly occurs in the fine particles, the combinations among the fine particles are loose and the new formed coarse crystal shapes are irregular.     

Electrochemical mechanism of rusticyanin （Rus.） isolated from A. ferrooxidans measured by Rus.-ZnS-QDs/L-Cys/Au electrode

Electrochimcal behaviors of rusticyanin (Rus.) isolated from Acidithiobacillus ferrooxidans were investigated through Rus.-ZnS-QDs/L-Cys/Au electrode.The cyclic voltammetric results indicate that rusticyanin immobilized on the surface of Rus.-ZnS-QDs/L-Cys/Au electrode can undergo a direct quasi-reversible electrochemical reaction.The immobilized rusticyanin is not denatured and still retains its activity in the temperature range of 19-43 °C.The reduction ability of the protein increases and its oxidation a...     

Effect of thermal crosslink conditions on dynamic mechanical behaviors of flexible epoxy

The dynamic mechanical behavior of a new kind of flexible epoxy FE-1,which was crosslinked under four different thermal crosslink conditions,was studied.Dynamic mechanical measurement was carried out from 10 ℃ to 120 ℃,and loss factor,tan δ and the storagemodulus as functions of temperature were presented under five different frequencies of 0.1 Hz, 1 Hz,5 Hz,50 Hz and 100 Hz. The experimental results show that temperature has dramatic effects on the dynamic mechanical behavior of flexible epoxy. Compared with other common available epoxy, the flexible epoxy has higher loss factor over broad frequency and common temperature range. Activation energy corresponding to glass transition process of FE-1 was calculated from the temperature corresponding to tan 8 rna~ values, obtained at different measurement frequencies. The maximum value of loss factor is 0.75 and the Tg varies from 6 ℃ to 50 ℃, indicating the flexible epoxy can be used as damping polymer materials at common temperature or frequency range.     

Flux pinning effect of cubic equiaxed morphology and its Ti stabilizing in Nb<Subscript>3</Subscript>Sn superconductors

Two sets of internal-Sn Nb3Sn superconducting strands were fabricated through RRP method, one with 2 wt% of Ti alloyed in Sn core and the other just pure Sn. Four reaction temperatures of 650℃, 675℃, 700℃ and 725℃ and 128 h duration were applied for A15 phase formation heat treatment after Cu-Sn alloying procedure of 210℃/50 h + 340℃/25 h. For the heat-treated coil samples, transport non-Cu JC was examined through standard 4-probe technique and phase microstructure was observed by means of Field Emission Sc...     

Correlations between the Optical Properties and the Microstructure of TiO2 Thin Films Prepared by Reactive Electron-beam Evaporation

High refractive index TiO₂ thin films were deposited on BK7 glass by reactive electron—beam (REB) evaporation at pressure of 2×10⁻² Pa, deposition rate of 0.2 nm/s and at various substrate temperatures from 120°C to 300°C. The refractive index and the thickness of the films were measured by visible spectroscopic ellipsometry (SE) and determined from transmission spectra. Optical properties and structure features were characterized by UV-VIS, SEM and XRD, respectively. The measurement and analysis on transmission spectra of all samples show that with the substrate temperature increasing from 120°C to 300°C, the refractive indices of thin films increase from 1.7 to 2.1 and the films after heat treatment have higher refractive indices due to its crystallizing. The XRD analysis results indicate that the structure of TiO₂ thin films deposited on BK7 glass at substrate temperatures of 120°C, 200°C and 300°C is amorphous, after post-annealing under air condition at 400°C for 1 hour, the amorphous structure is crystallized, the crystal phase is of 100% anatase with strong preferred orientation (004) and the grain size of crystalline is within 3.6–8.1 nm, which is consistent with results from SEM observation. WANG Xue-hua: Born in 1976. Funded by the Youth Project Foundation of Hubei Provincial Education Department (No. 2003B00)     

Low temperature properties of organic-inorganic Ag/ p -CuPc/ n -GaAs/Ag photoelectric sensor

A thin organic film of p-type semiconducting copper phthalocynanine (CuPc) was deposited by vacuum evaporation on an n-type GaAs single-crystal semiconductor substrate. The fabricated Ag/p-CuPc/n-GaAs/Ag sensor was carried through an ageing process to stabilize the parameters. Voltage-current characteristics and photoelectrical response of the sensor were investigated at a wide temperature range of 82 to 350 K. Photoelectric characteristics were measured under nonmodulated filament-lamp illumination. It was observed that such sensor parameters as rectification ratio, threshold voltage, junction, shunt and series resistances, open-circuit voltage and short circuit current are temperature-dependent. It was found that wide-range voltage-current characteristics of the sensor may be described similarly to that of a Schottky barrier diode. Using the experimental data on voltage-current characteristics and absorbance of the CuPc films, the energy-band diagram of the p-CuPc/n-GaAs heterojunction was developed. It was shown that data obtained from simulation of an equivalent circuit of photoelectric sensor agreed with experimental results. Supported by the National Engineering and Scientific Commission of Pakistan