Using foxtail millet (Setaria italica (L.) Beauv.) male-sterile line 1066A as female parent and Yugu 1 primary trisomic series (1 - 7) and tetrasomics 8, 9 as male parents, chromosome location of gene for male-sterili...Using foxtail millet (Setaria italica (L.) Beauv.) male-sterile line 1066A as female parent and Yugu 1 primary trisomic series (1 - 7) and tetrasomics 8, 9 as male parents, chromosome location of gene for male-sterility and yellow seedling in line 1066A was studied by primary trisomic analysis. The plants of F-1 generation of trisomics 2 - 9 were obtained by crossing with a great many plants of 1066A. F-1 generation of trisomics was similar to their male parent in morphologic characters, the color of their seedling was green, and pollen was partially fertile. The segregation ratio of fertility to sterility is 3:1 in F-2 generation of trisomics 2, 3, 4, 5, 7, 8 and 9; and 14:1 only in F-2 generation of trisomic 6 (chi(0.05)(2) = 0.012). The segregation ratio of green seedling to yellow seedling is 12:1 only in F-2 generation of trisomic 7 (chi(0.05)(2) = 0.31), but in other cases, this ratio is 3:1. The results indicated that the male-sterility gene was located on chromosome 6, and the gene for yellow seedling was monogenic recessive and located on chromosome 7. The rate of trisomics transmission by pollen was tested, trisomics 8 and 9 were the highest in rates of trisomics transmission and followed by trisomics 6 and 4.展开更多
Aim To quantitatively determine five nucleosides and nucleobases, including cytidine, uridine, guanosine, adenosine and uracil in different parts of Panax notoginseng. Methods Separation was performed on a Zorbax SB-A...Aim To quantitatively determine five nucleosides and nucleobases, including cytidine, uridine, guanosine, adenosine and uracil in different parts of Panax notoginseng. Methods Separation was performed on a Zorbax SB-Aq column using a gradient elution with mobile phase of 8 mmol^L-1 ammonium acetate aqueous solution (A) and methanol (B). The assay was carried out at a flow rate of 1 mL·min^-1 at 25 ℃ with the diode-array detection at 260 nm. Results Cytidine, uridine, guanosine, adenosine and uracil had good linearity in the ranges of 1.79 - 57.40 μg·mL^-1 (r^2 = 1.0000), 3.30 - 105.60 μg·mL^-1 (r^2 = 1.0000), 3.09 - 98.80 μg·mL^ -1(r^2 = 0.9999), 2.77 - 88.60 μg·mL^-1 (r^2 = 1.0000) and 0.38 - 12.30 μg·mL ^-1 (r^2 = 1.0000) with average recoveries of 93.9%, 96.5%, 92.7%, 93.2% and 98.8%, respectively. The content of cytidine, uridine, guanosine, adenosine and uracil in different parts of P. notogingeng were significantly different. Conclusion This is the first report on quantitative determination of nucleosides and nucleobases in P notoginseng.展开更多
The interaction between pile and soft soil of the passive pile group subjected to soil movement was analyzed with three-dimensional finite element model by using ANSYS software. The soil was assumed to be elastic-plas...The interaction between pile and soft soil of the passive pile group subjected to soil movement was analyzed with three-dimensional finite element model by using ANSYS software. The soil was assumed to be elastic-plastic complying with the Drucker-Prager yield criterion in the analysis. The large displacement of soil was considered and contact elements were used to evaluate the interaction between pile and soil. The influences of soil depth of layer and number of piles on the lateral pressure of the pile were investigated, and the lateral pressure distributions on the (2×1) pile group and on the (2×2) pile group were compared. The results show that the adjacent surcharge may result in significant lateral movement of the soft soil and considerable pressure on the pile. The pressure acting on the row near the surcharge is higher than that on the other row, due to the "barrier" and arching effects in pile groups. The passive load and its distribution should be taken into account in the design of the passive piles.展开更多
Synthesis of ZnO nanoparticles by hydrothermal technique in presence of cetyltrimethylammonium bromide (CTAB) as surfactant was carried out by statistically designed experiments based on Box Behnken method. The mean...Synthesis of ZnO nanoparticles by hydrothermal technique in presence of cetyltrimethylammonium bromide (CTAB) as surfactant was carried out by statistically designed experiments based on Box Behnken method. The mean parameters, surfactant concentration, time and temperature have been studied to show their effect on ZnO particle size and morphology. The results of experimental design indicate that the surfactant concentration, reaction time and temperature were significant. ZnO particles were investigated using XRD and SEM and the findings show that ZnO nanoparticles were formed at 100 ℃ and their crystallinity were improved with temperature rise from 100 to 200 ℃. Particle size of ZnO in the range of 39-76 nm is achieved using this technique.展开更多
Based on the functional theory, catastrophe theory, simultaneity principle and the idea of strength reduction method (SRM), the bearing capacity functional anti SRM of pile group foundation were established, and the...Based on the functional theory, catastrophe theory, simultaneity principle and the idea of strength reduction method (SRM), the bearing capacity functional anti SRM of pile group foundation were established, and the criteria of ultimate load and the concept of safety storage coefficient (Css) were advanced. The inclined ultimate loads by the static loading test, load increment method (LIM) and SRM are compared. Theoretically, the ultimate load of piles does not change with the loading levels when it is calculated by SRM. When the one strength reduction parameter is applied in the calculation boundary, there are calculating errors because the bearing capacity action of soils happened in the finite zone. The inclined 10adings are 108, 132 and 144 kN, and SSC are 1.07, 0.94 and 0.79, respectively, so the calculation values of ultimate loads are about 115.56, 124.08 and 113.76 kN, respectively. The error between calculations and observation values is less than 6%. But .the error between calculations of LIM and observations is 20%. Because of the effect of inclined loading, the push-rotation phenomenon of screw pile group appears. Under this testing, the ultimate bearing capacity of piles is mostly determined by the horizontal ultimate bearing capacity, and the effect of the vertical component of inclined load should also be considered.展开更多
Fe-based ionic liquid (Fe-IL) was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigate...Fe-based ionic liquid (Fe-IL) was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigated to construct a ternary desulfurization solution for wet flue gas desulfurization. The effects of flow rate and concentration of SO2, reaction temperature, pH and Fe-IL fraction in aqueous desulfurization solution on the desulfiariza- tion efficiency were investigated. The results shows that the best composition of ternary desulfurization solution of Fe-IL, ethanol and water is 1 : 1.5 : 3 by volume ratio, and pH should be controlled at 2.0. Under such conditions, a desulfurization rate greater than 90% could be obtained. The product of sulfuric acid had inhibition effect on the wet desulfurization process. With applying this new ternary desulfurization solution, not only the catalyst Fe-IL can be recycled and reused, but also the product sulfuric acid can be separated directly from the ternary desulfurization system.展开更多
The complexation of BDHTD (4-benzylidenamino-4,5-dihydro-lH-l,2,4-triazol-5-one derivatives) by divalent doubly charged metal ions M2+ (M = Mg, Ca, Fe and Cu) has been investigated using the density functional me...The complexation of BDHTD (4-benzylidenamino-4,5-dihydro-lH-l,2,4-triazol-5-one derivatives) by divalent doubly charged metal ions M2+ (M = Mg, Ca, Fe and Cu) has been investigated using the density functional method B3LYP. Two distinct coordination modes (k2-O,O and k2-O,N) have been taken into account. Geometry optimizations have been performed in gas-phase and solution-phase: acetonitrile and DMF (N,N-dimethylformamide) with the basis set 6-31G(d,p). The B3LYP method was also used to calculate the stability and free energies of the 24 complexes of BDHTD with metal ions M2+ (M = Mg, Ca, Fe and Cu) respectively in gas-phase and solution-phase: acetonitrile and DMF. Results indicate that k2-O,N structures are most stable in gas-phase. The influence of substitution on the stability is sensitive in solution-phase. The interaction energies of complexation process in various media have been calculated at B3LYP/6-31G(d,p) and CCSD(T) level. The MIA (metal ion affinity) of BDHTD with M2+ (M = Mg, Ca, Fe and Cu) in various media has been explored. The results show that the M1A highly varies with the coordination mode and substitution effect. From the calculated Gibb energies of complexation in various media, it is revealed that the complexation is possible in gas in acetonitrile. The ligand's affinity toward individual cation M2+ (M = Mg, Ca, Fe and Cu) has been analysed. A significant reduce of BDEs observed confirms the decrease of the antioxidant activity by the metal chelation. The charge transfer induced by metal chelation is examined using the NBO analysis.展开更多
Research at home and abroad shows that the simulation of ground motion using the 3D finite-difference method might be accurate and feasible. Based on related theories and methods,and using the wave velocity and densit...Research at home and abroad shows that the simulation of ground motion using the 3D finite-difference method might be accurate and feasible. Based on related theories and methods,and using the wave velocity and density model of the crust in the Yanqing-Huailai Basin,this paper makes a simulation of ground motion at Guanting Reservoir Dam based on the scenario earthquake in the Yanqing-Huailai Basin. Comparative analysis shows that the results of 3D finite-difference simulation accord with those of the empirical formula. The parameters such as the velocity-time series of ground motion,PGV and frequency might be referred to for the analysis of seismic protection design of the dam's structure.展开更多
A rapid, precise, sensitive and simple method has been developed for the extraction and determination of TPT (triphenyltin), DPT (diphenyltin) and MPT (monophenyltin) in seawater samples. The procedure is based ...A rapid, precise, sensitive and simple method has been developed for the extraction and determination of TPT (triphenyltin), DPT (diphenyltin) and MPT (monophenyltin) in seawater samples. The procedure is based on the use of the dual functionalization of mesoporous silica with diol and Cl6 alkane groups for the collection of TPT and its derivatives, DPT and MPT, from seawater samples, followed by ethylation of the target matrices using sodium tetraethylborate (NaBEt4) and quantification by gas chromatography with pulsed flame photometric detection. The modified extraction method replaces conventional solid- and liquid-phase extraction with solid dispersion of silica nanoparticles. The partitioning of the analyte between a carefully size-selected silica nanoparticles (solid phase) and a liquid phase occurs as the solid moves through the sample as a colloidal sol. By tailoring the size of the particles to approximately 250 nm in diameter, they can be easily dispersed in aqueous solution, without the need for any mechanical or hand shaking and the solid can then be readily recovered, together with the analytes, by simple filtration or centrifugation. Recoveries of TPT, DPT and MPT chloride spiked matrices rang from 87.3±1.1 to 98.1±1.3 in seawater samples (n = I 1 samples). The limit of detection obtained was typically in the range of 0.1-3 ng Sn/L. The proposed method shows excellent linearity in the range of 0.5-2 ng Sn/L and good repeatability (RSD 〈 5% at 0.02 ng TPT (as Sn)/L). The method performance is demonstrated with real seawater samples.展开更多
Fluvoxamine maleate is an excellent antidepressive drug. In the literatures, it was synthesized by the use of 4-(trifluoromethyl) aniline or 4-(trifluoromethyl) benzonitrile as starting materials and 5-methoxy-4'...Fluvoxamine maleate is an excellent antidepressive drug. In the literatures, it was synthesized by the use of 4-(trifluoromethyl) aniline or 4-(trifluoromethyl) benzonitrile as starting materials and 5-methoxy-4'-(trifluoromethyl-phenyl) valerophenone as a key intermediate. However, the methods in literatures have some disadvantages, such as the use of expensive materials, heavy pollution of environment, long reaction time and low yield of the product (only 30-40% overall yield). We herein report an environmentally friendly synthetic method of fluvoxamine maleate, which used 4-(trifluoromethyl) benzoic acid and tetrahydrofuran as starting materials and FeCI3 as catalyst for the coupling of acid chloride with Grignard reagent. The fluvoxamine maleate was synthesized in 46% overall yield, through the oximation, etheration and salification of the intermediate successively.This method has some advantages, such as the use of commercially available materials, low cost, short production period (12-14 h), high yield and light pollution.展开更多
A Cu(II) complex [CuCl(C19H20N4O)]ClO4 1 containing hydroxymethyl substituted TPA (TPA = tris(2-pyridylmethyl)amine) was prepared. It crystallizes in monoclinic, space group P21/c with a = 11.7628(2), b = 13.0083(3), ...A Cu(II) complex [CuCl(C19H20N4O)]ClO4 1 containing hydroxymethyl substituted TPA (TPA = tris(2-pyridylmethyl)amine) was prepared. It crystallizes in monoclinic, space group P21/c with a = 11.7628(2), b = 13.0083(3), c = 15.11280(10) ?, β = 108.724(2)°, V = 2190.09(7) ?3, Mr = 518.83, Z = 4, T = 293(2) K, Dc = 1.574 g/cm3, μ = 1.280 mm-1, F(000) = 1060 and S = 1.085. The final R = 0.0543 and wR = 0.1433 for 2693 observed reflections with I >2σ(I). The penta- coordinated copper (II) complex assumes an approximate square pyramidal geometry. Cyclic volta- mmetry measurement of the complex showed a quasi-reversible CuII/CuI redox couple with E1/2 = –0.467 v and ?E = 68 mv.展开更多
It is investigated the interaction of Ge(IV) with bis(2,3,4-trigodroksifenolazo) benzidine (R) in the presence of KSAS (cationic surface active substances)-CPCl (cetylpyridinium chloride), CPBr (cetylpyridi...It is investigated the interaction of Ge(IV) with bis(2,3,4-trigodroksifenolazo) benzidine (R) in the presence of KSAS (cationic surface active substances)-CPCl (cetylpyridinium chloride), CPBr (cetylpyridinium bromide) and CTMABr (cetyltrimethylammonium bromide). It is studied the effect pH, time on the formation of ternary complexes. It is determinated of molar absorption coefficients and stability constants of germanium. Binary (Ge-R) and triple (Ge-R-CPCI, Ge-R-CPBr, Ge-R-CTMaBr) complex form at pH 4 and pH 1, respectively. The composition proportion of binar system is 1:2 and the composition proportion triple complex is 1:1:2. The concentration interval of germanium which obeying beer low in the Ge-R 0.12-2.92 mkq/mL, in the Ge-R-CPCI is 0.04-1.46 mkq/mL, in the Ge-R-CPBr is 0.00-1.00 mkq/mL and in the Ge-R-CTMaBr is 0.00-1.00 mkq/mL. Molar absorbtivities of complexes are 45,000, 57,000, 59,000 and 60,000, respectively. The effect of interfering ions and masking agents has been learned. Stability constants of complexes have been determined: lgKl = 7.21 + 0.06 (Ge-R),' lgK1 = 12.08 _+ 0.05 (Ge-R-CPCI), lgK1 = 12.12 + 0.07 (Ge-R-CPBr) and lgK1 = 12.85 + 0.06 (Ge-R-CTMaBr). It is developed highly selective method of photometric determination of trace amounts of Ge(IV) in petroleum coke.展开更多
We present an efficient spherical parameterization approach aimed at simultaneously reducing area and angle dis-tortions. We generate the final spherical mapping by independently establishing two hemisphere parameteri...We present an efficient spherical parameterization approach aimed at simultaneously reducing area and angle dis-tortions. We generate the final spherical mapping by independently establishing two hemisphere parameterizations. The essence of the approach is to reduce spherical parameterization to a planar problem using symmetry analysis of 3D meshes. Experiments and comparisons were undertaken with various non-trivial 3D models, which revealed that our approach is efficient and robust. In particular, our method produces almost isometric parameterizations for the objects close to the sphere.展开更多
Protic ionic liquid (PIL) triethylammonium acetate was prepared by mixing equimolar amounts of acetic acid and triethylamine, and then studied using the combination of the Attenuated Total Reflection Fourier Transform...Protic ionic liquid (PIL) triethylammonium acetate was prepared by mixing equimolar amounts of acetic acid and triethylamine, and then studied using the combination of the Attenuated Total Reflection Fourier Transform Infrared spectroscopy, in-situ infrared spectroscopy, pH, and conductivity titration measurements. It was found that the equimolar synthesized triethylammonium acetate was separated into two layers, which suggesting that there were both chemical and phase equilibrium in this solution. Molecular species could be directly observed in the IR spectra over the range of 1200-1800 cm-1 and also checked by 1H NMR. Based on analysis, the upper layer was rich in amine with little acid and PIL, and the down layer was rich in PIL with residual acetic acid and amine. And single PIL-rich layer could be separated into two layers again when the mole ratio of newly added triethyamine to the theoretical produced triethylammonium acetate reached 0.12.展开更多
The design of hollow mesoporous nanostructures for cascade catalytic reactions can inject new vitality into the development of nanostructures. In this study, we report a versatile cooperative template-directed coating...The design of hollow mesoporous nanostructures for cascade catalytic reactions can inject new vitality into the development of nanostructures. In this study, we report a versatile cooperative template-directed coating method for the synthesis of hollow and yolk-shell mesoporous zirconium titanium oxide nanospheres with varying compositions (ZrO2 content from 0 to 100%), high surface areas (465 m2·g-1) and uniform mesopores. In particular, the hexadecylamine (HDA) used in the coating procedure serves as a soft template for silica@mesostructured metal oxide core-shell nanosphere formation. By a facile solvothermal treatment route with an ammonia solution and calcination in air, the silica@mesostructured zirconium titanium oxide spheres can be converted into highly uniform hollow zirconium titanium oxide spheres. By simply replacing hard template silica nanospheres with core-shell silica nanocomposites, the synthesis approach can be further used to prepare yolk-shell mesoporous structures through the coating and etching process. The approach is similar to the preparation of mesoporous silica nanocomposites from the self-assembly of the core, the soft template cetyltrimethylammonium bromide (CTAB) and a silica precursor and can be extended as a general method to coat mesoporous zirconium titanium oxide on other commonly used hard templates (e.g., mesoporous silica spheres, mesoporous organosilica ellipsoids, polymer spheres, and carbon nanospheres). The presence of highly permeable mesoporous channels in the zirconium titanium oxide shells has been demonstrated by the reduction of 4-nitrophenol with yolk-shell Au@mesoporous zirconium titanium oxide as the catalyst. Moreover, a cascade catalytic reaction including an acid catalyzed step and a catalytic hydrogenation to afford benzimidazole derivatives can be carried out very effectively by using the accessible acidity of the yolk-shell structured mesoporous zirconium titanium oxide spheres containing a Pd core as a bifunctional catalyst, which makes the hollow zirconium titanium oxide spheres a practicable candidate for advanced catalytic systems.展开更多
文摘Using foxtail millet (Setaria italica (L.) Beauv.) male-sterile line 1066A as female parent and Yugu 1 primary trisomic series (1 - 7) and tetrasomics 8, 9 as male parents, chromosome location of gene for male-sterility and yellow seedling in line 1066A was studied by primary trisomic analysis. The plants of F-1 generation of trisomics 2 - 9 were obtained by crossing with a great many plants of 1066A. F-1 generation of trisomics was similar to their male parent in morphologic characters, the color of their seedling was green, and pollen was partially fertile. The segregation ratio of fertility to sterility is 3:1 in F-2 generation of trisomics 2, 3, 4, 5, 7, 8 and 9; and 14:1 only in F-2 generation of trisomic 6 (chi(0.05)(2) = 0.012). The segregation ratio of green seedling to yellow seedling is 12:1 only in F-2 generation of trisomic 7 (chi(0.05)(2) = 0.31), but in other cases, this ratio is 3:1. The results indicated that the male-sterility gene was located on chromosome 6, and the gene for yellow seedling was monogenic recessive and located on chromosome 7. The rate of trisomics transmission by pollen was tested, trisomics 8 and 9 were the highest in rates of trisomics transmission and followed by trisomics 6 and 4.
文摘Aim To quantitatively determine five nucleosides and nucleobases, including cytidine, uridine, guanosine, adenosine and uracil in different parts of Panax notoginseng. Methods Separation was performed on a Zorbax SB-Aq column using a gradient elution with mobile phase of 8 mmol^L-1 ammonium acetate aqueous solution (A) and methanol (B). The assay was carried out at a flow rate of 1 mL·min^-1 at 25 ℃ with the diode-array detection at 260 nm. Results Cytidine, uridine, guanosine, adenosine and uracil had good linearity in the ranges of 1.79 - 57.40 μg·mL^-1 (r^2 = 1.0000), 3.30 - 105.60 μg·mL^-1 (r^2 = 1.0000), 3.09 - 98.80 μg·mL^ -1(r^2 = 0.9999), 2.77 - 88.60 μg·mL^-1 (r^2 = 1.0000) and 0.38 - 12.30 μg·mL ^-1 (r^2 = 1.0000) with average recoveries of 93.9%, 96.5%, 92.7%, 93.2% and 98.8%, respectively. The content of cytidine, uridine, guanosine, adenosine and uracil in different parts of P. notogingeng were significantly different. Conclusion This is the first report on quantitative determination of nucleosides and nucleobases in P notoginseng.
基金Project(50378036) supported by the National Natural Science Foundation of China
文摘The interaction between pile and soft soil of the passive pile group subjected to soil movement was analyzed with three-dimensional finite element model by using ANSYS software. The soil was assumed to be elastic-plastic complying with the Drucker-Prager yield criterion in the analysis. The large displacement of soil was considered and contact elements were used to evaluate the interaction between pile and soil. The influences of soil depth of layer and number of piles on the lateral pressure of the pile were investigated, and the lateral pressure distributions on the (2×1) pile group and on the (2×2) pile group were compared. The results show that the adjacent surcharge may result in significant lateral movement of the soft soil and considerable pressure on the pile. The pressure acting on the row near the surcharge is higher than that on the other row, due to the "barrier" and arching effects in pile groups. The passive load and its distribution should be taken into account in the design of the passive piles.
文摘Synthesis of ZnO nanoparticles by hydrothermal technique in presence of cetyltrimethylammonium bromide (CTAB) as surfactant was carried out by statistically designed experiments based on Box Behnken method. The mean parameters, surfactant concentration, time and temperature have been studied to show their effect on ZnO particle size and morphology. The results of experimental design indicate that the surfactant concentration, reaction time and temperature were significant. ZnO particles were investigated using XRD and SEM and the findings show that ZnO nanoparticles were formed at 100 ℃ and their crystallinity were improved with temperature rise from 100 to 200 ℃. Particle size of ZnO in the range of 39-76 nm is achieved using this technique.
基金Project(51178457) supported by the National Natural Science Foundation of ChinaProject(cstc2012jjys0001) supported by the Natural Science Foundation of Chongqing,ChinaProject(L2011231) supported by the Liaoning Education Department,China
文摘Based on the functional theory, catastrophe theory, simultaneity principle and the idea of strength reduction method (SRM), the bearing capacity functional anti SRM of pile group foundation were established, and the criteria of ultimate load and the concept of safety storage coefficient (Css) were advanced. The inclined ultimate loads by the static loading test, load increment method (LIM) and SRM are compared. Theoretically, the ultimate load of piles does not change with the loading levels when it is calculated by SRM. When the one strength reduction parameter is applied in the calculation boundary, there are calculating errors because the bearing capacity action of soils happened in the finite zone. The inclined 10adings are 108, 132 and 144 kN, and SSC are 1.07, 0.94 and 0.79, respectively, so the calculation values of ultimate loads are about 115.56, 124.08 and 113.76 kN, respectively. The error between calculations and observation values is less than 6%. But .the error between calculations of LIM and observations is 20%. Because of the effect of inclined loading, the push-rotation phenomenon of screw pile group appears. Under this testing, the ultimate bearing capacity of piles is mostly determined by the horizontal ultimate bearing capacity, and the effect of the vertical component of inclined load should also be considered.
基金Supported by the National Natural Science Foundation of China (21076019,90610007)the National High Technology Research and Development Program of China (2007AA06Z115)+1 种基金the Ph.D. Programs Foundation of Ministry of Education of China (20090010110003)the Fundamental Research Funds for the Central Universities (ZD1001)
文摘Fe-based ionic liquid (Fe-IL) was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigated to construct a ternary desulfurization solution for wet flue gas desulfurization. The effects of flow rate and concentration of SO2, reaction temperature, pH and Fe-IL fraction in aqueous desulfurization solution on the desulfiariza- tion efficiency were investigated. The results shows that the best composition of ternary desulfurization solution of Fe-IL, ethanol and water is 1 : 1.5 : 3 by volume ratio, and pH should be controlled at 2.0. Under such conditions, a desulfurization rate greater than 90% could be obtained. The product of sulfuric acid had inhibition effect on the wet desulfurization process. With applying this new ternary desulfurization solution, not only the catalyst Fe-IL can be recycled and reused, but also the product sulfuric acid can be separated directly from the ternary desulfurization system.
文摘The complexation of BDHTD (4-benzylidenamino-4,5-dihydro-lH-l,2,4-triazol-5-one derivatives) by divalent doubly charged metal ions M2+ (M = Mg, Ca, Fe and Cu) has been investigated using the density functional method B3LYP. Two distinct coordination modes (k2-O,O and k2-O,N) have been taken into account. Geometry optimizations have been performed in gas-phase and solution-phase: acetonitrile and DMF (N,N-dimethylformamide) with the basis set 6-31G(d,p). The B3LYP method was also used to calculate the stability and free energies of the 24 complexes of BDHTD with metal ions M2+ (M = Mg, Ca, Fe and Cu) respectively in gas-phase and solution-phase: acetonitrile and DMF. Results indicate that k2-O,N structures are most stable in gas-phase. The influence of substitution on the stability is sensitive in solution-phase. The interaction energies of complexation process in various media have been calculated at B3LYP/6-31G(d,p) and CCSD(T) level. The MIA (metal ion affinity) of BDHTD with M2+ (M = Mg, Ca, Fe and Cu) in various media has been explored. The results show that the M1A highly varies with the coordination mode and substitution effect. From the calculated Gibb energies of complexation in various media, it is revealed that the complexation is possible in gas in acetonitrile. The ligand's affinity toward individual cation M2+ (M = Mg, Ca, Fe and Cu) has been analysed. A significant reduce of BDEs observed confirms the decrease of the antioxidant activity by the metal chelation. The charge transfer induced by metal chelation is examined using the NBO analysis.
基金sponsored by the key lab.program of Shaanxi Province (08JZ04)the key discipline fund for scientific research program of Baoji University of Arts and Science (ZK0796)the key discipline fund for natural geography of Shaanxi Province in Baoji University of Arts and Science
文摘Research at home and abroad shows that the simulation of ground motion using the 3D finite-difference method might be accurate and feasible. Based on related theories and methods,and using the wave velocity and density model of the crust in the Yanqing-Huailai Basin,this paper makes a simulation of ground motion at Guanting Reservoir Dam based on the scenario earthquake in the Yanqing-Huailai Basin. Comparative analysis shows that the results of 3D finite-difference simulation accord with those of the empirical formula. The parameters such as the velocity-time series of ground motion,PGV and frequency might be referred to for the analysis of seismic protection design of the dam's structure.
文摘A rapid, precise, sensitive and simple method has been developed for the extraction and determination of TPT (triphenyltin), DPT (diphenyltin) and MPT (monophenyltin) in seawater samples. The procedure is based on the use of the dual functionalization of mesoporous silica with diol and Cl6 alkane groups for the collection of TPT and its derivatives, DPT and MPT, from seawater samples, followed by ethylation of the target matrices using sodium tetraethylborate (NaBEt4) and quantification by gas chromatography with pulsed flame photometric detection. The modified extraction method replaces conventional solid- and liquid-phase extraction with solid dispersion of silica nanoparticles. The partitioning of the analyte between a carefully size-selected silica nanoparticles (solid phase) and a liquid phase occurs as the solid moves through the sample as a colloidal sol. By tailoring the size of the particles to approximately 250 nm in diameter, they can be easily dispersed in aqueous solution, without the need for any mechanical or hand shaking and the solid can then be readily recovered, together with the analytes, by simple filtration or centrifugation. Recoveries of TPT, DPT and MPT chloride spiked matrices rang from 87.3±1.1 to 98.1±1.3 in seawater samples (n = I 1 samples). The limit of detection obtained was typically in the range of 0.1-3 ng Sn/L. The proposed method shows excellent linearity in the range of 0.5-2 ng Sn/L and good repeatability (RSD 〈 5% at 0.02 ng TPT (as Sn)/L). The method performance is demonstrated with real seawater samples.
文摘Fluvoxamine maleate is an excellent antidepressive drug. In the literatures, it was synthesized by the use of 4-(trifluoromethyl) aniline or 4-(trifluoromethyl) benzonitrile as starting materials and 5-methoxy-4'-(trifluoromethyl-phenyl) valerophenone as a key intermediate. However, the methods in literatures have some disadvantages, such as the use of expensive materials, heavy pollution of environment, long reaction time and low yield of the product (only 30-40% overall yield). We herein report an environmentally friendly synthetic method of fluvoxamine maleate, which used 4-(trifluoromethyl) benzoic acid and tetrahydrofuran as starting materials and FeCI3 as catalyst for the coupling of acid chloride with Grignard reagent. The fluvoxamine maleate was synthesized in 46% overall yield, through the oximation, etheration and salification of the intermediate successively.This method has some advantages, such as the use of commercially available materials, low cost, short production period (12-14 h), high yield and light pollution.
基金This project was supported by "973" program of the Ministry of Science and Technology ofChina and National Natural Science Foundation of China (20376010 20128005)
文摘A Cu(II) complex [CuCl(C19H20N4O)]ClO4 1 containing hydroxymethyl substituted TPA (TPA = tris(2-pyridylmethyl)amine) was prepared. It crystallizes in monoclinic, space group P21/c with a = 11.7628(2), b = 13.0083(3), c = 15.11280(10) ?, β = 108.724(2)°, V = 2190.09(7) ?3, Mr = 518.83, Z = 4, T = 293(2) K, Dc = 1.574 g/cm3, μ = 1.280 mm-1, F(000) = 1060 and S = 1.085. The final R = 0.0543 and wR = 0.1433 for 2693 observed reflections with I >2σ(I). The penta- coordinated copper (II) complex assumes an approximate square pyramidal geometry. Cyclic volta- mmetry measurement of the complex showed a quasi-reversible CuII/CuI redox couple with E1/2 = –0.467 v and ?E = 68 mv.
文摘It is investigated the interaction of Ge(IV) with bis(2,3,4-trigodroksifenolazo) benzidine (R) in the presence of KSAS (cationic surface active substances)-CPCl (cetylpyridinium chloride), CPBr (cetylpyridinium bromide) and CTMABr (cetyltrimethylammonium bromide). It is studied the effect pH, time on the formation of ternary complexes. It is determinated of molar absorption coefficients and stability constants of germanium. Binary (Ge-R) and triple (Ge-R-CPCI, Ge-R-CPBr, Ge-R-CTMaBr) complex form at pH 4 and pH 1, respectively. The composition proportion of binar system is 1:2 and the composition proportion triple complex is 1:1:2. The concentration interval of germanium which obeying beer low in the Ge-R 0.12-2.92 mkq/mL, in the Ge-R-CPCI is 0.04-1.46 mkq/mL, in the Ge-R-CPBr is 0.00-1.00 mkq/mL and in the Ge-R-CTMaBr is 0.00-1.00 mkq/mL. Molar absorbtivities of complexes are 45,000, 57,000, 59,000 and 60,000, respectively. The effect of interfering ions and masking agents has been learned. Stability constants of complexes have been determined: lgKl = 7.21 + 0.06 (Ge-R),' lgK1 = 12.08 _+ 0.05 (Ge-R-CPCI), lgK1 = 12.12 + 0.07 (Ge-R-CPBr) and lgK1 = 12.85 + 0.06 (Ge-R-CTMaBr). It is developed highly selective method of photometric determination of trace amounts of Ge(IV) in petroleum coke.
基金Project supported by the National Natural Science Foundation of China (Nos. 60673006 and 60533060)the Program for New Century Excellent Talents in University (No. NCET-05-0275), Chinathe IDeA Network of Biomedical Research Excellence Grant (No. 5P20RR01647206) from National Institutes of Health (NIH), USA
文摘We present an efficient spherical parameterization approach aimed at simultaneously reducing area and angle dis-tortions. We generate the final spherical mapping by independently establishing two hemisphere parameterizations. The essence of the approach is to reduce spherical parameterization to a planar problem using symmetry analysis of 3D meshes. Experiments and comparisons were undertaken with various non-trivial 3D models, which revealed that our approach is efficient and robust. In particular, our method produces almost isometric parameterizations for the objects close to the sphere.
基金supported by the National Natural Science Foundation of China (20990221, 20976151)
文摘Protic ionic liquid (PIL) triethylammonium acetate was prepared by mixing equimolar amounts of acetic acid and triethylamine, and then studied using the combination of the Attenuated Total Reflection Fourier Transform Infrared spectroscopy, in-situ infrared spectroscopy, pH, and conductivity titration measurements. It was found that the equimolar synthesized triethylammonium acetate was separated into two layers, which suggesting that there were both chemical and phase equilibrium in this solution. Molecular species could be directly observed in the IR spectra over the range of 1200-1800 cm-1 and also checked by 1H NMR. Based on analysis, the upper layer was rich in amine with little acid and PIL, and the down layer was rich in PIL with residual acetic acid and amine. And single PIL-rich layer could be separated into two layers again when the mole ratio of newly added triethyamine to the theoretical produced triethylammonium acetate reached 0.12.
基金This work was supported by the National Natural Science Foundation of China (Grant Nos. 21171064 and 21071059).
文摘The design of hollow mesoporous nanostructures for cascade catalytic reactions can inject new vitality into the development of nanostructures. In this study, we report a versatile cooperative template-directed coating method for the synthesis of hollow and yolk-shell mesoporous zirconium titanium oxide nanospheres with varying compositions (ZrO2 content from 0 to 100%), high surface areas (465 m2·g-1) and uniform mesopores. In particular, the hexadecylamine (HDA) used in the coating procedure serves as a soft template for silica@mesostructured metal oxide core-shell nanosphere formation. By a facile solvothermal treatment route with an ammonia solution and calcination in air, the silica@mesostructured zirconium titanium oxide spheres can be converted into highly uniform hollow zirconium titanium oxide spheres. By simply replacing hard template silica nanospheres with core-shell silica nanocomposites, the synthesis approach can be further used to prepare yolk-shell mesoporous structures through the coating and etching process. The approach is similar to the preparation of mesoporous silica nanocomposites from the self-assembly of the core, the soft template cetyltrimethylammonium bromide (CTAB) and a silica precursor and can be extended as a general method to coat mesoporous zirconium titanium oxide on other commonly used hard templates (e.g., mesoporous silica spheres, mesoporous organosilica ellipsoids, polymer spheres, and carbon nanospheres). The presence of highly permeable mesoporous channels in the zirconium titanium oxide shells has been demonstrated by the reduction of 4-nitrophenol with yolk-shell Au@mesoporous zirconium titanium oxide as the catalyst. Moreover, a cascade catalytic reaction including an acid catalyzed step and a catalytic hydrogenation to afford benzimidazole derivatives can be carried out very effectively by using the accessible acidity of the yolk-shell structured mesoporous zirconium titanium oxide spheres containing a Pd core as a bifunctional catalyst, which makes the hollow zirconium titanium oxide spheres a practicable candidate for advanced catalytic systems.