A novel approach was developed for the determination of ultratrace amounts of copper in water samples by using electrothermal atomic absorption spectrometry （ETAAS） after cloud point extraction （ CPE ）. 1-（ 2-Pyr...A novel approach was developed for the determination of ultratrace amounts of copper in water samples by using electrothermal atomic absorption spectrometry （ETAAS） after cloud point extraction （ CPE ）. 1-（ 2-Pyridylazo ） -2- naphthol was used as the chelating reagent and Triton X-114 as the mieellar-forming surfactant. CPE was conducted in a pH 8. 0 medium at 40 ℃ for 10 rain. After the separation of the phases by contrifugafion, the surfactant-rieh phase was diluted with 1 mL of a methanol solution of 0. 1 mol/L HNO3. Then 20μL of the diluted surfactant-rieh phase was injected into the graphite furnace for atomization in the absence of any matrix modifier. Various experimental conditions that affect the extraction and atomization processes were optimized. A detection limit of 5 ng/L was obtained after preconeentration. The linear dynamic range of the copper mass concentration was found to be 0-2.0 ng/mL, and the relative standard deviation was found to be less than 3. 1% for a sample containing 1.0 ng/mL Cu （ Ⅱ ）. This developed method was successfully applied to the determination of uhratraee amounts of Cu in drinking water, tap water, and seawater samples.展开更多
Copper（ Ⅱ ） resercyiic acid（CuRes） nanoparticles were synthesized by using reactive precipitation method with resorcylic acid and blue copperas as the raw material in a rotating packed bed. The sample obtained wa...Copper（ Ⅱ ） resercyiic acid（CuRes） nanoparticles were synthesized by using reactive precipitation method with resorcylic acid and blue copperas as the raw material in a rotating packed bed. The sample obtained was characterized by using X-ray diffraction（XRD）, transmission electron micrescopy（TEM）, Fourier transform infrared spectroscopy （FTIR）, thermo-gravimetric analyses （TG）, and element analysis. In addition, the catalytic activity of CuRes nanoparticles on the thermal decomposition of nitrocellulose-nitroglycerine（NC-NG） was also determined via DSC. The results show that the spherical nanoparticles with a diameter of 20 nm were obtained in ethanol solution. The peak temperature of the thermal decomposition of NC-NG-CuRes decreases by 3℃ compared with that of normal CuRes, and the decomposition enthalpy is increased by 735 J/g, and therefore, it is reasonable to assume that CuRes nanoparticles have a better catalytic activity.展开更多
One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR a...One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.展开更多
A novel chromogenic reaction involving copper（Ⅱ） and bromosulphonazo Ⅲ （Br-SAZⅢ） in hexamethylenetetramine- hydrochloric buffer solution was investigated. The results showed that a blue complex of copper（Ⅱ） ...A novel chromogenic reaction involving copper（Ⅱ） and bromosulphonazo Ⅲ （Br-SAZⅢ） in hexamethylenetetramine- hydrochloric buffer solution was investigated. The results showed that a blue complex of copper（Ⅱ） and bromosulphonazo Ⅲ was formed with a molar ratio of 1：1. The apparent molar absorptivity was 3.3×10^5Lmol-1cm-1 and the maximum absorption peak was at 616.8 nm. The proposed procedure was used for quantitative estimation of Cu（II） in the concentration range of 0-1.024μg/mL with the detection limit （3σ） of 7.03 × 10^-4 μg/mL （n = 20）. The relative standard deviations （RSDs） were 0.56-4.68%. Under the optimized conditions, total copper in the vegetables and tea was successfully determined. 2007 Li Yuan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
A new copper(Ⅱ)coordination polymer[Cu5(Hpt)5(H2O)2(2,3-PCA)2]n·12nH2O(1)has been successfully synthesized under hydrothermal conditions with copper hydroxide,3-(pyridin-2-yl)-1,2,4-triazole(Hpt)and 2,3-pyridine...A new copper(Ⅱ)coordination polymer[Cu5(Hpt)5(H2O)2(2,3-PCA)2]n·12nH2O(1)has been successfully synthesized under hydrothermal conditions with copper hydroxide,3-(pyridin-2-yl)-1,2,4-triazole(Hpt)and 2,3-pyridinedi-carboxylic acid(2,3-PCA).The structure of the title compound was determined by X-ray diffraction analyses,elemental analyses and IR spectrum.The architecture of 1 consists of one-dimensional sandwich-like chains which are connected by extensive hydrogen bonding interactions.The solid-state photoluminescence displays an obvious emission band at 384 nm upon excitation at 340 nm.In addition,electrochemistry property has also been studied.展开更多
A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At ...A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.展开更多
Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terp...Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.展开更多
One-dimensional chain copper（Ⅱ） coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4＇-bipyridine and copper perchlorate.It is of ...One-dimensional chain copper（Ⅱ） coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4＇-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756（10）,b= 1.57756（10）,c=2.1438（3）nm,V=5.3352（8） nm^3,Dc=1.524 g/cm^3,Z=4,F（000）=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper（1） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry; the copper（2） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.展开更多
A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and st...A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.展开更多
The thermal behavior and kinetic parameters of the major exothermic decomposition reaction of the title compound in a temperature-programmed mode were studied by means of TG-DTG and DSC. The critical temperature of th...The thermal behavior and kinetic parameters of the major exothermic decomposition reaction of the title compound in a temperature-programmed mode were studied by means of TG-DTG and DSC. The critical temperature of thermal explosion was calculated. The effect of the title compound on the combustion characteristic of composition modifier double base propellant containing RDX was explored with a strand burner. The results show that the kinetic model function in differential forms, the apparent activation energy(E a) and the pre-exponential factor(A) of the major exothermic decomposition reaction are 3(1-α)[-ln(1-α)] 2/3, 190.56 kJ/mol and 10 13.39 s -1, respectively. The critical temperature of thermal explosion of the compound is 353.08 ℃. The kinetic equation of the major exothermic decomposition process of the title compound at 0.1 MPa could be expressed as dα/dT=10 14.65(1-α)[-ln(1-α)] 2/3 e -2.2920×104/T. As an auxiliary catalyzer, the title compound can help the main catalyzer of lead salt of 4-hydroxy-3,5-dinitropyridine to accelerate the burning rate and reduce the pressure exponent of RDX-CMDB propellant.展开更多
A novel copper（Ⅱ） complex derived from 1,4,7-triazacyclononane[CuL]_2（PF_6）_3×MeCN×H_2 O was synthesized and crystallographically characterized {L = 1,4-bis（2-carbamoylethyl）-7-benzimidazole-2-yl-meth...A novel copper（Ⅱ） complex derived from 1,4,7-triazacyclononane[CuL]_2（PF_6）_3×MeCN×H_2 O was synthesized and crystallographically characterized {L = 1,4-bis（2-carbamoylethyl）-7-benzimidazole-2-yl-methyl-1,4,7-triazacyclononane}. It crystallizes in triclinic, space group P1, with a = 13.2425（13）, b = 14.0807（15）, c = 17.6798（18）, α = 86.296（2）, β = 72.773（2）, γ= 68.905（2）o, V = 2934.5（5）A^3, Z = 2, D_c = 1.611 g/m^3, F（000） = 1456, M_r = 1423.09, m = 0.920 mm^-1. The final R = 0.0671 and wR = 0.1874 for 6501 observed reflections with I 〉 2σ（I）. The structural analysis shows that the complex cation（[CuL]_2^3＋） was formed by two complex cations, namely（[CuL^3]^2＋） and [CuL_（-H）~3]~＋） through a hydrogen bond. In each complex cation, the Cu（Ⅱ） lies in a distorted square pyramidal geometry. The redox behavior was studied by cyclic voltammetry（CV） in aqueous solution which indicates a reversible one electron redox reaction. The result of UV absorption, ethidium bromide（EB） fluorescence spectra indicated that the complex binds to CT-DNA in an intercalative mode. Superoxide dismutase（SOD） activity of the complex was determined by photoreduction of NBT, and the value of IC_（50） is 5.22 μmol·L^-1.展开更多
A ternary adduct Cu[S2P（OCH2CH2Ph）2]2·bipy（bipy=α,α＇-bipyridine） was syn-thesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The crystal belongs to the triclinic system...A ternary adduct Cu[S2P（OCH2CH2Ph）2]2·bipy（bipy=α,α＇-bipyridine） was syn-thesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P1 with a=10.2320（2）,b=11.5249（3）,c=18.0916（3）,α=98.95（1）,β =103.601（1）,γ=91.272（2）°,V=2044.49（7）3,Z=2,Dc=1.453 g/cm3,T=153（2） K,C42H44CuN2O4P2S4,Mr=894.51,λ（MoKα）=0.71073,μ=0.86 mm-1,S=0.999,（△/σ）max=0.002,the final R=0.0243 and wR=0.0704.A total of 9221 unique reflections were collected,of which 8573 with Ⅰ 〉2σ（Ⅰ） were observed.The Cu（Ⅱ） atom is five-coordinated in a rather distorted trigonal bipyramidal geometry（τ value=0.537）.The Cu-S distances range from 2.3491（4） to 2.4829（4） ,and the Cu-N distances are 1.9987（12） and 2.0584（11） ,respectively.An interesting feature of this adduct resides in its two-dimensional（2D） open framework constructing through hydrogen bonding and π-π interactions.展开更多
A new copper（Ⅱ） complex [Cu2（MNA）2（2,2‘-bipy）2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid（MNA） and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It ...A new copper（Ⅱ） complex [Cu2（MNA）2（2,2‘-bipy）2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid（MNA） and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191（11）,b = 12.8883（13）,c = 16.1114（16） A,α = 70.8090（10）,β = 80.568（2）,γ = 77.440（2）o,V = 1984.3（4） A^3,Dc = 1.551 g/cm^3,Z = 2,F（000） = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η^1：η^0 3-carboxylate groups of MNA^2-.The coordination environment of Cu（Ⅱ） ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.展开更多
A novel copper（II） complex with the reduced Schiff base, [Cu（L）2]·H2O （I, HL = N-（4-hydroxybenzyl）-L-serine）, was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ...A novel copper（II） complex with the reduced Schiff base, [Cu（L）2]·H2O （I, HL = N-（4-hydroxybenzyl）-L-serine）, was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a = 8.9040（18）, b = 9.1530（18）, c = 24.891（5）A^°, V = 2028.6（7） A^°3, Z = 4, C20H26CuN2O9, Mr = 501.97, Dc = 1.644g·cm^3, μ = 1.135 mm^-1, F（000） = 1044, GOOF = 1.194, the final R = 0.0484 and wR = 0.1420 for 6186 observed reflections （I 〉 2σ（I））. In I, two L^- anions are coordinated to the copper ion in tridentate and bidentate chelating modes, respectively, resulting in the coordinated geometry of copper ion to be a distorted square pyramid. The intermolecular hydrogen bonds between the complexes, complexes and lattice water molecules lead to a 2D supramolecular network. The bioactivity of the complex as a potential PTPs inhibitory agent in vitro was investigated, displaying potent inhibition against PTP1B （IC50, 0.27 μM） and TCPTP （IC50, 0.57 μM） with a moderate selectivity.展开更多
A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed sol...A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925（4）, b = 19.908（4）, c = 11.235（2） A, β = 97.65（3）°, V= 3973.4（14） A3, Dc = 1.552 g/cm^3, Z = 8, F（000） = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 ：η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.展开更多
基金the Analysis and Testing Foundation of Zhejiang Province(No 04045)
文摘A novel approach was developed for the determination of ultratrace amounts of copper in water samples by using electrothermal atomic absorption spectrometry （ETAAS） after cloud point extraction （ CPE ）. 1-（ 2-Pyridylazo ） -2- naphthol was used as the chelating reagent and Triton X-114 as the mieellar-forming surfactant. CPE was conducted in a pH 8. 0 medium at 40 ℃ for 10 rain. After the separation of the phases by contrifugafion, the surfactant-rieh phase was diluted with 1 mL of a methanol solution of 0. 1 mol/L HNO3. Then 20μL of the diluted surfactant-rieh phase was injected into the graphite furnace for atomization in the absence of any matrix modifier. Various experimental conditions that affect the extraction and atomization processes were optimized. A detection limit of 5 ng/L was obtained after preconeentration. The linear dynamic range of the copper mass concentration was found to be 0-2.0 ng/mL, and the relative standard deviation was found to be less than 3. 1% for a sample containing 1.0 ng/mL Cu （ Ⅱ ）. This developed method was successfully applied to the determination of uhratraee amounts of Cu in drinking water, tap water, and seawater samples.
基金the National Natural Science Foundation of China(No 20576128)partially supported by the Natural ScienceFoundation of Shanxi Province(No 20051015)
文摘Copper（ Ⅱ ） resercyiic acid（CuRes） nanoparticles were synthesized by using reactive precipitation method with resorcylic acid and blue copperas as the raw material in a rotating packed bed. The sample obtained was characterized by using X-ray diffraction（XRD）, transmission electron micrescopy（TEM）, Fourier transform infrared spectroscopy （FTIR）, thermo-gravimetric analyses （TG）, and element analysis. In addition, the catalytic activity of CuRes nanoparticles on the thermal decomposition of nitrocellulose-nitroglycerine（NC-NG） was also determined via DSC. The results show that the spherical nanoparticles with a diameter of 20 nm were obtained in ethanol solution. The peak temperature of the thermal decomposition of NC-NG-CuRes decreases by 3℃ compared with that of normal CuRes, and the decomposition enthalpy is increased by 735 J/g, and therefore, it is reasonable to assume that CuRes nanoparticles have a better catalytic activity.
基金Supported by the Hunan Provincial Department of Science and Technology Project (2009FJ3101)
文摘One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.
文摘A novel chromogenic reaction involving copper（Ⅱ） and bromosulphonazo Ⅲ （Br-SAZⅢ） in hexamethylenetetramine- hydrochloric buffer solution was investigated. The results showed that a blue complex of copper（Ⅱ） and bromosulphonazo Ⅲ was formed with a molar ratio of 1：1. The apparent molar absorptivity was 3.3×10^5Lmol-1cm-1 and the maximum absorption peak was at 616.8 nm. The proposed procedure was used for quantitative estimation of Cu（II） in the concentration range of 0-1.024μg/mL with the detection limit （3σ） of 7.03 × 10^-4 μg/mL （n = 20）. The relative standard deviations （RSDs） were 0.56-4.68%. Under the optimized conditions, total copper in the vegetables and tea was successfully determined. 2007 Li Yuan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金Supported by the Natural Science Foundation of Hunan Province(2019JJ60021,2019JJ50013)the Scientific Research Found of Education Department of Hunan Province(17A049)Industry and Research Key Project of Hengyang City(2018KJ016,HXKJ201942,2017KJ193)
文摘A new copper(Ⅱ)coordination polymer[Cu5(Hpt)5(H2O)2(2,3-PCA)2]n·12nH2O(1)has been successfully synthesized under hydrothermal conditions with copper hydroxide,3-(pyridin-2-yl)-1,2,4-triazole(Hpt)and 2,3-pyridinedi-carboxylic acid(2,3-PCA).The structure of the title compound was determined by X-ray diffraction analyses,elemental analyses and IR spectrum.The architecture of 1 consists of one-dimensional sandwich-like chains which are connected by extensive hydrogen bonding interactions.The solid-state photoluminescence displays an obvious emission band at 384 nm upon excitation at 340 nm.In addition,electrochemistry property has also been studied.
文摘A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.
基金Supported by the Program for New Century Excellent Talents in University(NCET-10-0176)the Natural Science Foundation of Jilin Province(No.20130521019JH)the fund of Jilin Provincial Education Department of China(No.2014154)
文摘Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
文摘One-dimensional chain copper（Ⅱ） coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4＇-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756（10）,b= 1.57756（10）,c=2.1438（3）nm,V=5.3352（8） nm^3,Dc=1.524 g/cm^3,Z=4,F（000）=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper（1） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry; the copper（2） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.
基金Supported by the National Natural Science Foundation of China (No. 60978059)the Key Project of Chinese Ministry of Education (No. 210053)the Natural Science Foundation of Jilin Province (No. 20090527)
文摘A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.
文摘The thermal behavior and kinetic parameters of the major exothermic decomposition reaction of the title compound in a temperature-programmed mode were studied by means of TG-DTG and DSC. The critical temperature of thermal explosion was calculated. The effect of the title compound on the combustion characteristic of composition modifier double base propellant containing RDX was explored with a strand burner. The results show that the kinetic model function in differential forms, the apparent activation energy(E a) and the pre-exponential factor(A) of the major exothermic decomposition reaction are 3(1-α)[-ln(1-α)] 2/3, 190.56 kJ/mol and 10 13.39 s -1, respectively. The critical temperature of thermal explosion of the compound is 353.08 ℃. The kinetic equation of the major exothermic decomposition process of the title compound at 0.1 MPa could be expressed as dα/dT=10 14.65(1-α)[-ln(1-α)] 2/3 e -2.2920×104/T. As an auxiliary catalyzer, the title compound can help the main catalyzer of lead salt of 4-hydroxy-3,5-dinitropyridine to accelerate the burning rate and reduce the pressure exponent of RDX-CMDB propellant.
基金supported by the Natural Science Foundation of Hubei Province(2014CFB410)
文摘A novel copper（Ⅱ） complex derived from 1,4,7-triazacyclononane[CuL]_2（PF_6）_3×MeCN×H_2 O was synthesized and crystallographically characterized {L = 1,4-bis（2-carbamoylethyl）-7-benzimidazole-2-yl-methyl-1,4,7-triazacyclononane}. It crystallizes in triclinic, space group P1, with a = 13.2425（13）, b = 14.0807（15）, c = 17.6798（18）, α = 86.296（2）, β = 72.773（2）, γ= 68.905（2）o, V = 2934.5（5）A^3, Z = 2, D_c = 1.611 g/m^3, F（000） = 1456, M_r = 1423.09, m = 0.920 mm^-1. The final R = 0.0671 and wR = 0.1874 for 6501 observed reflections with I 〉 2σ（I）. The structural analysis shows that the complex cation（[CuL]_2^3＋） was formed by two complex cations, namely（[CuL^3]^2＋） and [CuL_（-H）~3]~＋） through a hydrogen bond. In each complex cation, the Cu（Ⅱ） lies in a distorted square pyramidal geometry. The redox behavior was studied by cyclic voltammetry（CV） in aqueous solution which indicates a reversible one electron redox reaction. The result of UV absorption, ethidium bromide（EB） fluorescence spectra indicated that the complex binds to CT-DNA in an intercalative mode. Superoxide dismutase（SOD） activity of the complex was determined by photoreduction of NBT, and the value of IC_（50） is 5.22 μmol·L^-1.
基金supported by the Education Committee of Sichuan Province (No.09ZA057)Department of Science and Technology of Sichuan Province (No. 2009JY0071 and 2010GZ0130)+1 种基金Science and Technology Office of Zigong City (No. 08X01)Key Laboratory of Material Corrosion and Protection of Sichuan Colleges and Universities (No. 2008CL04)
文摘A ternary adduct Cu[S2P（OCH2CH2Ph）2]2·bipy（bipy=α,α＇-bipyridine） was syn-thesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P1 with a=10.2320（2）,b=11.5249（3）,c=18.0916（3）,α=98.95（1）,β =103.601（1）,γ=91.272（2）°,V=2044.49（7）3,Z=2,Dc=1.453 g/cm3,T=153（2） K,C42H44CuN2O4P2S4,Mr=894.51,λ（MoKα）=0.71073,μ=0.86 mm-1,S=0.999,（△/σ）max=0.002,the final R=0.0243 and wR=0.0704.A total of 9221 unique reflections were collected,of which 8573 with Ⅰ 〉2σ（Ⅰ） were observed.The Cu（Ⅱ） atom is five-coordinated in a rather distorted trigonal bipyramidal geometry（τ value=0.537）.The Cu-S distances range from 2.3491（4） to 2.4829（4） ,and the Cu-N distances are 1.9987（12） and 2.0584（11） ,respectively.An interesting feature of this adduct resides in its two-dimensional（2D） open framework constructing through hydrogen bonding and π-π interactions.
基金Supported by the Natural Science Foundation of Hunan Province(No.11JJ9006)Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)the Construct Program of the Key Discipline in Hunan Province
文摘A new copper（Ⅱ） complex [Cu2（MNA）2（2,2‘-bipy）2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid（MNA） and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191（11）,b = 12.8883（13）,c = 16.1114（16） A,α = 70.8090（10）,β = 80.568（2）,γ = 77.440（2）o,V = 1984.3（4） A^3,Dc = 1.551 g/cm^3,Z = 2,F（000） = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η^1：η^0 3-carboxylate groups of MNA^2-.The coordination environment of Cu（Ⅱ） ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.
基金Supported by NNSFC(Nos.21271121,21471092,21571118)
文摘A novel copper（II） complex with the reduced Schiff base, [Cu（L）2]·H2O （I, HL = N-（4-hydroxybenzyl）-L-serine）, was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a = 8.9040（18）, b = 9.1530（18）, c = 24.891（5）A^°, V = 2028.6（7） A^°3, Z = 4, C20H26CuN2O9, Mr = 501.97, Dc = 1.644g·cm^3, μ = 1.135 mm^-1, F（000） = 1044, GOOF = 1.194, the final R = 0.0484 and wR = 0.1420 for 6186 observed reflections （I 〉 2σ（I））. In I, two L^- anions are coordinated to the copper ion in tridentate and bidentate chelating modes, respectively, resulting in the coordinated geometry of copper ion to be a distorted square pyramid. The intermolecular hydrogen bonds between the complexes, complexes and lattice water molecules lead to a 2D supramolecular network. The bioactivity of the complex as a potential PTPs inhibitory agent in vitro was investigated, displaying potent inhibition against PTP1B （IC50, 0.27 μM） and TCPTP （IC50, 0.57 μM） with a moderate selectivity.
基金Supported by the Construct Program of the Key Discipline in Hunan Province and Key Project of Production Plan of Hengyang City(2013)
文摘A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925（4）, b = 19.908（4）, c = 11.235（2） A, β = 97.65（3）°, V= 3973.4（14） A3, Dc = 1.552 g/cm^3, Z = 8, F（000） = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 ：η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.
