Abstract The study on the catalysis of ionic liquids for alkylation of benzene with 1-octadecene to synthesize LAB （linear alkylbenzenes） was performed. The results showed that the most important factor that governe...Abstract The study on the catalysis of ionic liquids for alkylation of benzene with 1-octadecene to synthesize LAB （linear alkylbenzenes） was performed. The results showed that the most important factor that governed the conversion of olefin and selectivity of LAB was reaction temperature. Moreover, the effects of different ionic liquids and molar ratio of benzene to 1-octadecene on the conversion and selectivity were obviously in different degrees. The reaction temperature, molar ratio of benzene to 1-octadecene and the amount of catalyst were lower, compared with the traditional reaction technologies. The experimental results demonstrated that the ionic liquid had higher activity at 30℃, with over 98% selectivity of monoalkylbenzene and 100% conversion of the olefin at the molar ratio 0.08 of FeCl3 in ionic liquid to 1-octadecene and 10 for benzene to 1-octadecene.展开更多
Up to now the mechanism of Priedel-Crafts reactions catalyzed by ionic liquidhave not been fully understood, while carbocation mechanism was assumed. It was found that thesource of H^+ and the route of reaction initia...Up to now the mechanism of Priedel-Crafts reactions catalyzed by ionic liquidhave not been fully understood, while carbocation mechanism was assumed. It was found that thesource of H^+ and the route of reaction initiated the alkylation of benzene with ethylene catalyzedby [bmim]Cl/FeCl_3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity forthe alkylation of benzene with ethylene suggests that there exists a new catalytic route. Thedistinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR analysis of[bmim]Cl after titration with water free KOH in alcohol solution. In addition, the chemical shiftsof proton on the [bmim]Cl ring, especially 2-H, are sensitive to the change of FeCl_3 content andshifted downfield when FeCl_3 was added into [bmim]Cl to form ionic liquid. Thus 2-H was easy to bedisengaged from imidazolium ring with formation of H^+ to initiate the reaction. Theisotope-substituted method was employed to prove this mechanism, through the GC-MS analysis ofalkylation products of deuterated benzene with ethylene. The route of alkylation catalyzed by FeCl_3ionic liquid was found to follow the carbocation mechanism, the resource of H^+ was presented andproved using HNMR analysis of ionic liquid to inspect the intensity change of 2-H. It was found thatthe intensity of 2-H reduced 23% after reaction showing that the H^+ arising from alkylationreaction was supplied by 2-H on the imidazole ring.展开更多
The solid-liquid equilibria of musk ketone + musk xylene, musk xylene +l,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are measured by differential scanning calorimeter (DSC), these systems are proved to be simple eutec...The solid-liquid equilibria of musk ketone + musk xylene, musk xylene +l,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are measured by differential scanning calorimeter (DSC), these systems are proved to be simple eutectics. Moreover the melting points and the fusion enthalpies of musk ketone, musk xylene and 1,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are also measured by the DSC. These solid-liquid equilibrium data and the heats of fusion are reported for the first time. Then UNIFAC model is used to correlate the sofid-liquid equilibrium data. It is shown that the solid-liquid equilibria of musk systems can be predicted by the UNIFAC model.展开更多
A novel coordination polymer, [Co3（bta）2（dpe）3（H2O）2]·2H2O （1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di（pyridin-4-yl）ethene）, has been hydrothermally prepared and characterized by IR spect...A novel coordination polymer, [Co3（bta）2（dpe）3（H2O）2]·2H2O （1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di（pyridin-4-yl）ethene）, has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group P , with a = 9.5687（15）, b = 11.2470（17）, c = 13.686（2） , α = 78.262（3）, β = 89.271（4）, γ = 81.292（3）°, V = 1425.2（4） 3, C60H56N6O16Co3, Mr = 1293.90, Dc = 1.508 g/cm3, F（000） = 667, μ = 0.940 mm-1 and Z = 1. The final R = 0.0707 and wR = 0.1413 for 4950 observed reflections （I 2σ（I））. In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into lamellar frameworks which are further interlinked by the dpe ligands to generate a trinodal （3,4,6）-connected （4.62）2（42.68.83.102）（64.82） net.展开更多
One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characte...One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860（5）, b = 13.8246（6）, c = 19.0140（8） A, β = 104.3870（1）°, V = 3128.2（2） A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F（000） = 1444 and μ（Mo Kα） = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ（I） and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni（OTP）]n chain and the 2D [Ni2（bib）3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.展开更多
The title compound, 1,4-dimethyl-2,5-di { [2′-（3-pyridylmethylaminoformyl）phenoxyl]- methyl}benzene perchlorate （C36H36Cl2N4O12, Mr = 787.59）, has been synthesized and structurally determined by single-crystal X-...The title compound, 1,4-dimethyl-2,5-di { [2′-（3-pyridylmethylaminoformyl）phenoxyl]- methyl}benzene perchlorate （C36H36Cl2N4O12, Mr = 787.59）, has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 14.366（4）, b = 15.159（4）, c = 16.443（5）A, V = 3580.9（17）/A3 Z = 4, De = 1.461 g/cm^3, /t = 0.253 mm^-1, F（000） = 1640, R = 0.0618 and wR = 0.1525 for 1615 observed reflections （I 〉 2σ（I））. In the structure of the title compound, a two-dimensional supramolecular layer is formed via intermolecular hydrogen bonding interactions.展开更多
By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, ha...By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, have been investigated. The results show that there are some side reactions between BBr3 and benzene： （1） BBr3 as an electron-deficient molecule reacts with benzene at room temperature; （2） below 100℃, substitution of Br atom for H atom of benzene（ring-H） dominates in BBr3/benzene solution; （3） cracking of benzene ring occurs at a temperature above 100℃; （4） decomposition of benzene molecules and formation of long-chain aliphatic compounds feature the spectra of BBr3/benzene solution collected at above 160℃, They are unfavor for BN to form when BBr3 is excessive in the synthesis of BN by benzene-thermal route. On the basis of the experimental results, a coordination reaction mechanism via a η^2-C6H6 binding mode in BBr3/benzene solution is suggested.展开更多
The steady-state kinetics for complete oxidation of benzene over has been investigated by the external recycling reactor. The kinetics equation was described by the L-H model of adsorption of benzene and oxygen with t...The steady-state kinetics for complete oxidation of benzene over has been investigated by the external recycling reactor. The kinetics equation was described by the L-H model of adsorption of benzene and oxygen with the inhibition of carbon dioxide. The parameters of the kinetics model were estimated by the method of orthogonal design. The heats of adsorption of benzene, oxygen and carbon dioxide were determined by the method of gas-adsorption chromatography. The details of oscillations of complete oxidation of benzene were investigated.展开更多
The Influence of ultrasonic treatment on the coking amount of a nickel-based catalyst （Ni/γ-Al2O3） for the reaction of reforming with carbon dioxide of Benzene was investigated. The results show that ultrasonic tre...The Influence of ultrasonic treatment on the coking amount of a nickel-based catalyst （Ni/γ-Al2O3） for the reaction of reforming with carbon dioxide of Benzene was investigated. The results show that ultrasonic treatment modify the pore size distribution of the catalysts significantly and also reduce the amount of coke formed on the catalyst. The reduction in the coking amount is not sensitive to the power output of the ultrasonic treatment device in the power range tested （120 W and 500 W）.展开更多
A new three-dimensional（3D） chiral metal-organic coordination polymer, [Zn（dpb）（hfipbb）]n, was obtained under hydrothermal conditions by 1,3-di（pyridineyl）benzene（dpb） and 4,4-（Hexafluoroisopropylidene）bis...A new three-dimensional（3D） chiral metal-organic coordination polymer, [Zn（dpb）（hfipbb）]n, was obtained under hydrothermal conditions by 1,3-di（pyridineyl）benzene（dpb） and 4,4-（Hexafluoroisopropylidene）bis（benzoic acid）（H2hfipbb）. The as-prepared sample was characterized by single-crystal X-ray diffraction, PXRD, elemental analysis, IR spectroscopy and TGA analysis. The title coordination polymer crystallizes in orthorhombic, space group P21212, with a=21.923（4）, b=23.594（4）, c=7.3042（13） , V=3778.1（12） 3, Dc=1.209 g/cm3, Mr=687.90, F（000）=1328, μ=0.713 mm（-1） and Z=4. The compound contains two types of helical chains [Zn（hfipbb）]n and [Zn（dpb）]n which are linked with each other to generate a 3D framework by sharing the same Zn（Ⅱ） cations. It displays a 4-fold interpenetrated 3D framework. In addition, the luminescence, fluorescence lifetime and the second harmonic generation（SHG） efficiency properties in the solid state have been studied.展开更多
3-Methylthio-5-hydroxy-1,2,4-triazine(1c)reacted with substituted benzenesulfonyl chloride to give 3-methylthio-5-oxy-1,2,4-triazin-6-yl pyridinium betaine(4)in anhydrous pyridine.But when NaOH/H_2O/CH_3COCH_3 or NaOH...3-Methylthio-5-hydroxy-1,2,4-triazine(1c)reacted with substituted benzenesulfonyl chloride to give 3-methylthio-5-oxy-1,2,4-triazin-6-yl pyridinium betaine(4)in anhydrous pyridine.But when NaOH/H_2O/CH_3COCH_3 or NaOH/CH_3OH were used as reactant and solvent,3-methylthio-4-substituted benzenesulfonyl-5-oxo-6-hydroxy-1,4,5,6-tetrahydro-1,2,4-triazine(6)or 1-tosyl-3-methylthio-5-oxo-6-methyloxy-1,4,5,6-tetrahydro-1,2,4-triazine(7)was obtained respectively.The above reactions show anomalous properties of nucleophilic attack on 6-carbon in 1,2,4-triazine ring.展开更多
Benzene dimer （bz2） is the simplest prototype of the π-π interactions. Such interactions are ubiquitous in diverse areas of science and molecular engineering. In the present work, we have made assessment on some m...Benzene dimer （bz2） is the simplest prototype of the π-π interactions. Such interactions are ubiquitous in diverse areas of science and molecular engineering. In the present work, we have made assessment on some modern density functional methods including B97-D, BLYP-D3, M06-2X, XYG3, and force field models including CHARMM, AMBER, MM3, AMOEBA on six important interaction modes of bz2. Our results not only highlight the usefulness of these cost-effective methods, which can be used as economic substitutes of the expensive CCSD（T） for complex real-world systems, but also indicate their weakness in the description of the π-π interactions, which points to the future direction for further improvements.展开更多
White organic light-emitting diodes （WOLEDs） with a structure of indium-tin-oxide （ITO）/N,N＇-bis- （1-naphthyl）-N,N＇-diphenyl- （1, 1＇-biphenyl）-4,4＇-diamine （NPB）/1,2,3,4,5,6-hexakis（9,9-diethyl-9H-fluor...White organic light-emitting diodes （WOLEDs） with a structure of indium-tin-oxide （ITO）/N,N＇-bis- （1-naphthyl）-N,N＇-diphenyl- （1, 1＇-biphenyl）-4,4＇-diamine （NPB）/1,2,3,4,5,6-hexakis（9,9-diethyl-9H-fluoren-2- yl）benzene （HKEthFLYPh）/5,6,11,12-tetraphenylnaphtacene （rubrene）/tris（8-hydroxyquinoline） aluminum （Alq3）/Mg：Ag were fabricated by vacuum deposition method, in which a novel star-shaped hexafluorenyl- benzene HKEthFLYPh was used as an energy transfer layer, and an ultrathin layer of rubrene was inserted between HKEthFLYPh and Alq3 layers as a yellow light-emitting layer instead of using a time-consuming doping process. A fairly pure WOLED with Commissions Internationale De L＇Eclairage （CIE） coordinates of （0.32, 0.33） was obtained when the thickness of rubrene was 0.3 nm, and the spectrum was insensitive to the applied voltage. The device yielded a maximum luminance of 4816 cd/m2 at 18 V.展开更多
目的:了解职业苯接触及慢性苯中毒工人外周血中T细胞特异性转录因子T-bet和GATA-3mRNA表达情况。方法:利用SYBR Green I实时荧光定量PCR分别检测20例正常人、25例职业苯接触工人和27例慢性苯中毒工人外周血单个核细胞T-bet和GATA-3 mRN...目的:了解职业苯接触及慢性苯中毒工人外周血中T细胞特异性转录因子T-bet和GATA-3mRNA表达情况。方法:利用SYBR Green I实时荧光定量PCR分别检测20例正常人、25例职业苯接触工人和27例慢性苯中毒工人外周血单个核细胞T-bet和GATA-3 mRNA表达情况。结果:在职业接触苯工人组及慢性苯中毒工人组,多数样本表现为GATA-3表达上升和T-bet表达下降,而少数病人则表现为相反的模式。GATA-3在正常人的表达水平为0.39±0.22,与正常组对照比较职业接触苯工人组中有19例GATA-3表达水平呈上升趋势(0.57±0.54),慢性苯中毒工人组中则有20例GATA-3表达水平呈上升趋势(0.52±0.50)。此外,在职业接触苯工人组中发现6例GATA-3表达水平显著下降(0.15±0.12,P<0.05),同样在慢性苯中毒工人组中也有7例GATA-3表达水平显著下降(0.07±0.06,P<0.05)。T-bet在正常人的表达水平为2.15±1.45,与正常组对照比较职业接触苯工人组中有19例T-bet表达水平呈下降趋势(1.91±1.49),慢性苯中毒工人组中T-bet表达水平均呈下降趋势(1.52±0.56)。此外,在职业接触苯工人组中也可发现6例T-bet表达水平显著上升(3.19±2.10,P<0.05)。结论:职业苯接触及慢性苯中毒影响工人外周血中T细胞特异性转录因子T-bet和GATA-3mRNA表达水平。展开更多
基金Supported by the National Natural Science Foundation of China （No.20276038） and Beijing Natural Science Foundation （No.2052010）.
文摘Abstract The study on the catalysis of ionic liquids for alkylation of benzene with 1-octadecene to synthesize LAB （linear alkylbenzenes） was performed. The results showed that the most important factor that governed the conversion of olefin and selectivity of LAB was reaction temperature. Moreover, the effects of different ionic liquids and molar ratio of benzene to 1-octadecene on the conversion and selectivity were obviously in different degrees. The reaction temperature, molar ratio of benzene to 1-octadecene and the amount of catalyst were lower, compared with the traditional reaction technologies. The experimental results demonstrated that the ionic liquid had higher activity at 30℃, with over 98% selectivity of monoalkylbenzene and 100% conversion of the olefin at the molar ratio 0.08 of FeCl3 in ionic liquid to 1-octadecene and 10 for benzene to 1-octadecene.
文摘Up to now the mechanism of Priedel-Crafts reactions catalyzed by ionic liquidhave not been fully understood, while carbocation mechanism was assumed. It was found that thesource of H^+ and the route of reaction initiated the alkylation of benzene with ethylene catalyzedby [bmim]Cl/FeCl_3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity forthe alkylation of benzene with ethylene suggests that there exists a new catalytic route. Thedistinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR analysis of[bmim]Cl after titration with water free KOH in alcohol solution. In addition, the chemical shiftsof proton on the [bmim]Cl ring, especially 2-H, are sensitive to the change of FeCl_3 content andshifted downfield when FeCl_3 was added into [bmim]Cl to form ionic liquid. Thus 2-H was easy to bedisengaged from imidazolium ring with formation of H^+ to initiate the reaction. Theisotope-substituted method was employed to prove this mechanism, through the GC-MS analysis ofalkylation products of deuterated benzene with ethylene. The route of alkylation catalyzed by FeCl_3ionic liquid was found to follow the carbocation mechanism, the resource of H^+ was presented andproved using HNMR analysis of ionic liquid to inspect the intensity change of 2-H. It was found thatthe intensity of 2-H reduced 23% after reaction showing that the H^+ arising from alkylationreaction was supplied by 2-H on the imidazole ring.
文摘The solid-liquid equilibria of musk ketone + musk xylene, musk xylene +l,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are measured by differential scanning calorimeter (DSC), these systems are proved to be simple eutectics. Moreover the melting points and the fusion enthalpies of musk ketone, musk xylene and 1,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are also measured by the DSC. These solid-liquid equilibrium data and the heats of fusion are reported for the first time. Then UNIFAC model is used to correlate the sofid-liquid equilibrium data. It is shown that the solid-liquid equilibria of musk systems can be predicted by the UNIFAC model.
基金supported by the National Natural Science Foundation of China (No. 20971004)the Natural Science Foundation of Anhui Province (No. 11040606M45)
文摘A novel coordination polymer, [Co3（bta）2（dpe）3（H2O）2]·2H2O （1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di（pyridin-4-yl）ethene）, has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group P , with a = 9.5687（15）, b = 11.2470（17）, c = 13.686（2） , α = 78.262（3）, β = 89.271（4）, γ = 81.292（3）°, V = 1425.2（4） 3, C60H56N6O16Co3, Mr = 1293.90, Dc = 1.508 g/cm3, F（000） = 667, μ = 0.940 mm-1 and Z = 1. The final R = 0.0707 and wR = 0.1413 for 4950 observed reflections （I 2σ（I））. In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into lamellar frameworks which are further interlinked by the dpe ligands to generate a trinodal （3,4,6）-connected （4.62）2（42.68.83.102）（64.82） net.
基金supported by the Natural Science Foundation of Shandong Province(ZR2011BL020,ZR2012CM019)National Natural Science Foundation of China(21451001)Key Discipline and Innovation Team of Qilu Normal University
文摘One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860（5）, b = 13.8246（6）, c = 19.0140（8） A, β = 104.3870（1）°, V = 3128.2（2） A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F（000） = 1444 and μ（Mo Kα） = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ（I） and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni（OTP）]n chain and the 2D [Ni2（bib）3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.
基金supported by the National Natural Science Foundation of China (No. 20401008)
文摘The title compound, 1,4-dimethyl-2,5-di { [2′-（3-pyridylmethylaminoformyl）phenoxyl]- methyl}benzene perchlorate （C36H36Cl2N4O12, Mr = 787.59）, has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 14.366（4）, b = 15.159（4）, c = 16.443（5）A, V = 3580.9（17）/A3 Z = 4, De = 1.461 g/cm^3, /t = 0.253 mm^-1, F（000） = 1640, R = 0.0618 and wR = 0.1525 for 1615 observed reflections （I 〉 2σ（I））. In the structure of the title compound, a two-dimensional supramolecular layer is formed via intermolecular hydrogen bonding interactions.
基金Supported by the National Natural Science Foundation of China(No.50672048)the Program of Shandong Science & Technology Council,China(No.2006GG2202039)
文摘By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, have been investigated. The results show that there are some side reactions between BBr3 and benzene： （1） BBr3 as an electron-deficient molecule reacts with benzene at room temperature; （2） below 100℃, substitution of Br atom for H atom of benzene（ring-H） dominates in BBr3/benzene solution; （3） cracking of benzene ring occurs at a temperature above 100℃; （4） decomposition of benzene molecules and formation of long-chain aliphatic compounds feature the spectra of BBr3/benzene solution collected at above 160℃, They are unfavor for BN to form when BBr3 is excessive in the synthesis of BN by benzene-thermal route. On the basis of the experimental results, a coordination reaction mechanism via a η^2-C6H6 binding mode in BBr3/benzene solution is suggested.
基金Supported by the National Sciences Fundation of China.
文摘The steady-state kinetics for complete oxidation of benzene over has been investigated by the external recycling reactor. The kinetics equation was described by the L-H model of adsorption of benzene and oxygen with the inhibition of carbon dioxide. The parameters of the kinetics model were estimated by the method of orthogonal design. The heats of adsorption of benzene, oxygen and carbon dioxide were determined by the method of gas-adsorption chromatography. The details of oscillations of complete oxidation of benzene were investigated.
基金Supported by National ＂211＂ Key Discipline Development Program, Natural Science Foundation of Hubei Province（2006AB 192）, Science Foundation of Wuhan（20066002064）, China.
文摘The Influence of ultrasonic treatment on the coking amount of a nickel-based catalyst （Ni/γ-Al2O3） for the reaction of reforming with carbon dioxide of Benzene was investigated. The results show that ultrasonic treatment modify the pore size distribution of the catalysts significantly and also reduce the amount of coke formed on the catalyst. The reduction in the coking amount is not sensitive to the power output of the ultrasonic treatment device in the power range tested （120 W and 500 W）.
基金supported by the National Natural Science Foundation of China(No.21501002)China Postdoctoral Science Foundation Funded Project(2016M592031)+1 种基金Open Fund of State Key Laboratory of Coordination Chemistry(SKLCC1604)Young and Middle-aged Academic Backbone Training Project of Anhui University of Science and Technology
文摘A new three-dimensional（3D） chiral metal-organic coordination polymer, [Zn（dpb）（hfipbb）]n, was obtained under hydrothermal conditions by 1,3-di（pyridineyl）benzene（dpb） and 4,4-（Hexafluoroisopropylidene）bis（benzoic acid）（H2hfipbb）. The as-prepared sample was characterized by single-crystal X-ray diffraction, PXRD, elemental analysis, IR spectroscopy and TGA analysis. The title coordination polymer crystallizes in orthorhombic, space group P21212, with a=21.923（4）, b=23.594（4）, c=7.3042（13） , V=3778.1（12） 3, Dc=1.209 g/cm3, Mr=687.90, F（000）=1328, μ=0.713 mm（-1） and Z=4. The compound contains two types of helical chains [Zn（hfipbb）]n and [Zn（dpb）]n which are linked with each other to generate a 3D framework by sharing the same Zn（Ⅱ） cations. It displays a 4-fold interpenetrated 3D framework. In addition, the luminescence, fluorescence lifetime and the second harmonic generation（SHG） efficiency properties in the solid state have been studied.
基金Director of the project supported by National Natural Science foundation of China.
文摘3-Methylthio-5-hydroxy-1,2,4-triazine(1c)reacted with substituted benzenesulfonyl chloride to give 3-methylthio-5-oxy-1,2,4-triazin-6-yl pyridinium betaine(4)in anhydrous pyridine.But when NaOH/H_2O/CH_3COCH_3 or NaOH/CH_3OH were used as reactant and solvent,3-methylthio-4-substituted benzenesulfonyl-5-oxo-6-hydroxy-1,4,5,6-tetrahydro-1,2,4-triazine(6)or 1-tosyl-3-methylthio-5-oxo-6-methyloxy-1,4,5,6-tetrahydro-1,2,4-triazine(7)was obtained respectively.The above reactions show anomalous properties of nucleophilic attack on 6-carbon in 1,2,4-triazine ring.
基金Acknowledgments： This work was supported by the National Natural Science Foundation of China （No.91027044） and the Ministry of Science and Technology （No.2011CB808505）.
文摘Benzene dimer （bz2） is the simplest prototype of the π-π interactions. Such interactions are ubiquitous in diverse areas of science and molecular engineering. In the present work, we have made assessment on some modern density functional methods including B97-D, BLYP-D3, M06-2X, XYG3, and force field models including CHARMM, AMBER, MM3, AMOEBA on six important interaction modes of bz2. Our results not only highlight the usefulness of these cost-effective methods, which can be used as economic substitutes of the expensive CCSD（T） for complex real-world systems, but also indicate their weakness in the description of the π-π interactions, which points to the future direction for further improvements.
基金This work was supported by the National Natural Science Foundation of China （No.60425101 and No.20674049）, the Program for New Century Excellent Talents in University （No.NCET-06-0812）, and the Young Talent Project at University of Electronic Science and Technology of China （No.060206）.
文摘White organic light-emitting diodes （WOLEDs） with a structure of indium-tin-oxide （ITO）/N,N＇-bis- （1-naphthyl）-N,N＇-diphenyl- （1, 1＇-biphenyl）-4,4＇-diamine （NPB）/1,2,3,4,5,6-hexakis（9,9-diethyl-9H-fluoren-2- yl）benzene （HKEthFLYPh）/5,6,11,12-tetraphenylnaphtacene （rubrene）/tris（8-hydroxyquinoline） aluminum （Alq3）/Mg：Ag were fabricated by vacuum deposition method, in which a novel star-shaped hexafluorenyl- benzene HKEthFLYPh was used as an energy transfer layer, and an ultrathin layer of rubrene was inserted between HKEthFLYPh and Alq3 layers as a yellow light-emitting layer instead of using a time-consuming doping process. A fairly pure WOLED with Commissions Internationale De L＇Eclairage （CIE） coordinates of （0.32, 0.33） was obtained when the thickness of rubrene was 0.3 nm, and the spectrum was insensitive to the applied voltage. The device yielded a maximum luminance of 4816 cd/m2 at 18 V.
文摘目的:了解职业苯接触及慢性苯中毒工人外周血中T细胞特异性转录因子T-bet和GATA-3mRNA表达情况。方法:利用SYBR Green I实时荧光定量PCR分别检测20例正常人、25例职业苯接触工人和27例慢性苯中毒工人外周血单个核细胞T-bet和GATA-3 mRNA表达情况。结果:在职业接触苯工人组及慢性苯中毒工人组,多数样本表现为GATA-3表达上升和T-bet表达下降,而少数病人则表现为相反的模式。GATA-3在正常人的表达水平为0.39±0.22,与正常组对照比较职业接触苯工人组中有19例GATA-3表达水平呈上升趋势(0.57±0.54),慢性苯中毒工人组中则有20例GATA-3表达水平呈上升趋势(0.52±0.50)。此外,在职业接触苯工人组中发现6例GATA-3表达水平显著下降(0.15±0.12,P<0.05),同样在慢性苯中毒工人组中也有7例GATA-3表达水平显著下降(0.07±0.06,P<0.05)。T-bet在正常人的表达水平为2.15±1.45,与正常组对照比较职业接触苯工人组中有19例T-bet表达水平呈下降趋势(1.91±1.49),慢性苯中毒工人组中T-bet表达水平均呈下降趋势(1.52±0.56)。此外,在职业接触苯工人组中也可发现6例T-bet表达水平显著上升(3.19±2.10,P<0.05)。结论:职业苯接触及慢性苯中毒影响工人外周血中T细胞特异性转录因子T-bet和GATA-3mRNA表达水平。
