The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was det...The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.展开更多
Tourmaline from Altai mine in China＇s Sinkiang was used to remove lead （II）, copper （II） from aqueous solution. The results demonstrate that tourmaline contains Na（Mg,V）3AI6（BO3）3Si6Ols （OH）4, NaFe3AI6（BO3...Tourmaline from Altai mine in China＇s Sinkiang was used to remove lead （II）, copper （II） from aqueous solution. The results demonstrate that tourmaline contains Na（Mg,V）3AI6（BO3）3Si6Ols （OH）4, NaFe3AI6（BO3）3Si6Ols（OH）4. The data show that Tourmaline from Altai mine in China＇s Sinkiang can be used natural adsorbent for lead （II）, copper （II）.It is observed that the adsorption data fitted to the Langmuir isotherm. Furthermore, both Pb （II） and Cu （II） absorbed by tourmaline and tourmaline were characterized by X-ray diffraction, Laser Raman Spectrum, Fourier transform infrared spectroscopy, X-ray energy dispersive spectrometer, Transmission electron microscopy and Zeta potential.展开更多
The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H1...The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?展开更多
A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffracti...A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffraction study and IR spectroscopy. The crystal is monoclinic, space group: P2 1/n, with unit cell parameters: a=8.2952(2), b=18.4633(3), c=10.5049(2) . β=108.965(1)°, V=1521.56(5) 3, Z=2, C 22 H 30 N 8O 10 Cl 2Cu 2, M r =764.52, D c =1.669 Mg/m 3, F(000)=780, μ (Mo Kα )=8.60, T =293(2)K, final R=0.0623, wR =0.1536 for 2660 observed reflections with I>2.0σ(I ). The centrosymmetric complex Cu 2(CH 3O) 2(C 5H 6N 2) 4(ClO 4) 2 comprises a pair of Cu(II) atoms bridged by two methanoxo and N coordination 2 aminopyridine. The Cu(II)…Cu(II) distance is 3\^002(1).展开更多
Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the elec...Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the electrochemical method has been widely used due to its mild reaction condition and high reaction efficiency.In the electrochemical reduction system,the CO2 electrocatalyst is the most important part.Although many CO2 electrocatalysts have been developed,efficient catalysts with high activity,selectivity and stability are still lacking.Copper sulfide compound,as a low-toxicity and emerging material,has broad prospects in the field of CO2 reduction due to its unique structural and electrochemical properties.Much progress has been achieved with copper sulfide nanocrystalline and the field is rapidly developing.This paper summarizes the preparation,recent progress in development,and factors affecting the electrocatalytic CO2 reduction performance with copper sulfide compound as a catalyst.Prospects for future development are also outlined,with the aim of using copper sulfide compound as a highly active and stable electrocatalyst for CO2 reduction.展开更多
In this study, the adsorption behavior of copper(II) ions from aqueous solutions onto sesame husk (SH) was investigated. The effect of different parameters such as pH, contact time, adsorbent dosage, adsorbate concent...In this study, the adsorption behavior of copper(II) ions from aqueous solutions onto sesame husk (SH) was investigated. The effect of different parameters such as pH, contact time, adsorbent dosage, adsorbate concentration, temperature and agitation speed was studied. Thermodynamic parameters, equilibrium isotherms and kinetic data have been evaluated. The functional groups and surface morphology of SH adsorbent were characterized by FTIR and SEM. Adsorption equilibrium isotherms were expressed by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) adsorption models and it was found that Langmuir adsorption model fits the experimental data better than Freundlich and D-R models. The adsorption can be best described by the pseudo second-order kinetic model.展开更多
The complex [Cu2（apo）4Cl4]·2H2O （apo=2-aminopyridine N-oxide） was obtained. A single- crystal X-ray study shows that the complex is a binuclear compound （Cu2C20H28Cl4N8O6）. The coordination geometry about e...The complex [Cu2（apo）4Cl4]·2H2O （apo=2-aminopyridine N-oxide） was obtained. A single- crystal X-ray study shows that the complex is a binuclear compound （Cu2C20H28Cl4N8O6）. The coordination geometry about each copper atom is best described as a distorted square pyramid. The compound [Cu2（apo）4Cl4]·2H2O belongs to the triclinic system with space group P, lattice constants: a = 7.8550（7）, b = 8.5378（7）, c = 12.082（1） ?, α = 72.807（1）, β = 77.641（1）, γ = 70.800（1）(, V =724.85（11） ?3, Z=1, Mr =745.38, Dc=1.708 g/cm3, μ =1.886mm-1, F（000） =378, R=0.0359, wR2=0.0884 for 2220 reflections with I >2σ（I）. The distances between Cu（II） and O atoms are in the range from 1.934（2） to 2.042（2）?. The distance between two copper atoms Cu-Cu（A） is 3.2978（8） ?. The distances of Cu-Cl（1） and Cu-Cl（2） are 2.2322（9）, 2.5095（10） ?, respectively. There is no evident hydrogen bond between N and Cl.展开更多
Functionalization of shape-persistent aromatic oligoamides still represents a difficult task nowadays. A crescent aromatic oligothioamide was synthesized by simple thionation of the corresponding oligoamide with the L...Functionalization of shape-persistent aromatic oligoamides still represents a difficult task nowadays. A crescent aromatic oligothioamide was synthesized by simple thionation of the corresponding oligoamide with the Lawesson＇s reagent. The results from UV-vis spectra of the molecule upon metal ion complexation demonstrated its higher selectivity in recognizing Cu2~ ions compared to the oligoamide precursor. The stoichiometry of the complex formed between the thioamide and Cu2＋ was found to be 1：1 with a binding constant of （4.3 ± 0.9） × 104 mol/L.展开更多
Two new compounds,1（[Cu（IDB_）2]Cl_2·2CH_3CH_2OH·2H_2O（IDB = N,N-di（2-benzimidazolylmethyl）imine]） and 2（[Cu（EDTB）]·2[C_6H_4（OH）COO]·6H_2O（EDTB = N,N,N＇,N＇-tetrakis-[（2-benzimidazoly...Two new compounds,1（[Cu（IDB_）2]Cl_2·2CH_3CH_2OH·2H_2O（IDB = N,N-di（2-benzimidazolylmethyl）imine]） and 2（[Cu（EDTB）]·2[C_6H_4（OH）COO]·6H_2O（EDTB = N,N,N＇,N＇-tetrakis-[（2-benzimidazolyl）methyl]-1,2-ethanediamine]）,have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system,space group P1 with a = 9.565（2）,b = 9.863（2）,c = 10.252（3） ？,α = 81.915,β = 88.330,γ = 87.347°,V = 956.28（40） ？3,Z = 1,F（000） = 427,D_c = 1.419 g/cm3,Mr = 817.27 and μ（MoKα） = 0.764 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0505,wR = 0.1417; R indices（all data）： R = 0.0591,wR = 0.1525. Crystal 2 is of triclinic system,space group P1 with a = 11.487（3）,b = 13.396（4）,c = 17.977（5） ？,α = 73.899（5）,β = 86.629（5）,γ = 65.018（4）°,V = 2403.8（12） ？3,Z = 2,F（000） = 1072,D3c = 1.417 g/cm,Mr = 1025.54,μ（MoKα） = 0.528 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0769,w R = 0.163 2; R indices（all data）： R = 0.0769,wR = 0.1632. The two compounds exhibit mononuclear structures. The copper（Ⅱ） atom of crystal 1 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand IDB to adopt a distorted octahedral coordination geometry. The copper（Ⅱ） atom of crystal 2 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand EDTB to show a distorted octahedral coordination geometry. Particularly,the two compounds exhibit fluorescent properties at room temperature in ethanol.展开更多
Based on poly(vinyl chloride) membranes, a novel miniaturized screen-printed all-solid-state copper(II)-selective electrode has been developed for applications in environmental monitoring. Performance and applicabilit...Based on poly(vinyl chloride) membranes, a novel miniaturized screen-printed all-solid-state copper(II)-selective electrode has been developed for applications in environmental monitoring. Performance and applicability of the ion-selective electrode (ISE) have been proved by potentiometric investigations. Conducting polymers were used as intermediate layers and as solid contacts between the ion-selective membrane and the graphite transducer. The ion-complexing reagent 2-mercapto-benzoxazole was incorporated into poly(vinyl chloride) membranes. In the concentration range 10<sup>-6</sup> - 10<sup>-2</sup> mol/L, the ISE exhibited a linear Nernstian potential response to copper(II) with an average slope value of 28 mV/decade. The detection limit was 3 × 10<sup>-7</sup> mol/L. The electrode exhibits a short response time (<10 s) and can be used in the range of pH = 3 - 7. Selectivity coefficents against certain interfering ions are investigated. The life time of the electrode under laboratory conditions was approximately 12-month. The electrode was applied in the investigation of different aqueous environmental samples and the electrode characteristics were described. The copper(II) ASS electrode has also successfully been used in potentiometric, complexometric titrations with ethylenediaminetetraacetic acid.展开更多
Copper (II) complex derived from 2, 2'-pyridil ligand has been, demonstrated to cleave efficiently DNA at micromolar concentrations at room temperature and pH 7.25.
t-Butyldimethylsilyl (TBDMS) ether can be cleaved upon refluxing in acetone/H2O (95 : 5) in the presence of a catalytic amount of copper (II) chloride dihydrate (5 mmol %).
Using Cu(II) as the template, a complex {[Cu2L2(H2O)2]·4H2O}n (L = N-acetoxyl- picolinamide) has been successfully synthesized and characterized by single-crystal X-ray diffrac- tion. The crystal is of monoclin...Using Cu(II) as the template, a complex {[Cu2L2(H2O)2]·4H2O}n (L = N-acetoxyl- picolinamide) has been successfully synthesized and characterized by single-crystal X-ray diffrac- tion. The crystal is of monoclinic, space group C2/c, with a = 24.144(5), b = 7.1622(14), c = 17.283(4) ?, C16H24Cu2N4O12, Mr = 591.47, β = 131.73(3)o, V = 2230.3(8) ?3, Z = 4, Dc = 1.761 g/cm3, F(000) = 1208, μ = 1.978 mm?1, R = 0.0400 and wR = 0.1099. The copper (II) ion is five- coordinated with a distorted square pyramidal geometry. The complex can be viewed as a one- dimensional chain structure by carboxylic bridges among copper atoms. In the complex there exist hydrogen bonding interactions to stabilize the structure.展开更多
Two homochiral metallosalen complexes, Ni（salen） （salen = （1R,2R）-（-）-diamino- cyclohexane-N,N′-bis（3-tert-butyl-5-（4′-benzoic acid）-salicylidene） 1 and Cu（salen） 2, have been synthesized and characteri...Two homochiral metallosalen complexes, Ni（salen） （salen = （1R,2R）-（-）-diamino- cyclohexane-N,N′-bis（3-tert-butyl-5-（4′-benzoic acid）-salicylidene） 1 and Cu（salen） 2, have been synthesized and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 4. For 1, a = 12.082（2）, b = 15.447（3）, c = 18.784（4）A^°, V= 3505.7（12）A^°3, Mr = 731.50, Dc = 1.386 g/cm^3, μ = 0.606 mm^-1, F（000） = 1544, the final GOOF = 1.043, R = 0.0496 and wR = 0.1248 for 4791 observed reflections with I 〉 2σ（I）. For 2, a = 12.181（2）, b = 15.501（3）, c = 18.877（4） A^°, V = 3564.3（12）A^°3, Mr = 736.33, Dc = 1.372 g/cm^3, μ = 0.665 mm^-1, F（000） = 1548, the final GOOF = 1.062, R = 0.0575 and wR = 0.1508 for 4562 observed reflections with I 〉 2σ（I）. The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions.展开更多
A mononuclear copper(II) complex CuL with a Schiff-base L (H2L = N,N(- cyclohexanebis(3-formyl-5-tert-butyl-salicylaldimine)) has been synthesized and characterized. X-ray diffraction analysis at room temperature indi...A mononuclear copper(II) complex CuL with a Schiff-base L (H2L = N,N(- cyclohexanebis(3-formyl-5-tert-butyl-salicylaldimine)) has been synthesized and characterized. X-ray diffraction analysis at room temperature indicates that the complex (Cu C30H36N2O4, Mr = 552.15) crystallizes in tetrahedral system, space group P41 with a = 13.4685(6), c = 31.326(2) ?, V = 5682.5(5) ?3, Z = 8, Dc = 1.291 g/cm3, F(000) = 4656, μ(MoK() = 0.805 mm-1. The final R and Rw factors are 0.0421 and 0.0815, respectively with 4435 observed reflections. The title complex is a neutral molecule in which the ligand is doubly deprotonated, forming a four-coordinated Cu(II) complex by nitrogen and oxygen donors of the ligand and the coordination geometry of Cu(II) could be considered as an approximately planar configuration. There are two independent molecules, having a transoid arrangement in this structure.展开更多
A chloro-bridged dinuclear copper（H） complex with ligand 2-pyridylme-thylene- furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase...A chloro-bridged dinuclear copper（H） complex with ligand 2-pyridylme-thylene- furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase （XO） was also evaluated. It crystallizes in the triclinic system, space group P 1 with a = 8.0441（16）, b = 8.5663（17）, c = 10.060（2）A, α = 77.52（3）, β = 72.04（3）, γ = 70.12（3）°, V = 615.3（2）A^3, Z = 1, Dc = 1.731 g/cm^3, F（000） = 322, the final R = 0.0401 and wR = 0.0934 for 1971 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Cu（II） cation is five-coordinated by two N atoms of Schiff base and three Cl anions. The C-H…Cl intermolecular and intramolecular hydrogen bonds connect the molecules to form a three-dimensional network. This copper（II） complex shows more potent inhibitory activity against XO with IC50 = 3.48μM than the standard inhibitor allopurinol.展开更多
A complex polymer [Cu2(oxen)(pic)(H20)]n(Clo4)·2nHH2O, there oxen and pic are N.N' -bis(2aminoethyt )oxamide and Pyridine-4-carboxytate, respectivety, was synthesized. It crystallizes in the monoctinic space ...A complex polymer [Cu2(oxen)(pic)(H20)]n(Clo4)·2nHH2O, there oxen and pic are N.N' -bis(2aminoethyt )oxamide and Pyridine-4-carboxytate, respectivety, was synthesized. It crystallizes in the monoctinic space group P21/c, with a=10.420(2) A. b=13. 118(2) A, c=14 .863(5) A. β=93.05(2)°, and z=4. The structure of this complex consists of 2D network of copper(II) ions bridged by bis-tridentate oxen in transconformation, and by pyridine-4-carboxylate in which the pyridine ring acts as a monodentate group whereas the carboxylate as a tridentate group and bonds to three different copper centres in a novel fashion. The repeating asymmetric unit is a binuclear copper(II) fragment with one of the copper centre locating in a lengthening octahedrat environment, whereas the other in a distorted tetragonal pyramid geometry.展开更多
Thermodynamic data were determined for the reversible binding of O 2 to two compounds of dicobalt(II) di(meso tetra phenyl)porphyrin derivatives with different lengths of diamidoaliphatic bridge (abbreviated to Co ...Thermodynamic data were determined for the reversible binding of O 2 to two compounds of dicobalt(II) di(meso tetra phenyl)porphyrin derivatives with different lengths of diamidoaliphatic bridge (abbreviated to Co 2PP 8 and Co 2PP 4) in N,N dimethylformamide at room temperature. The partial pressure of dioxygen necessary for half oxygenation ( P 1/2 ) and Hill coefficient ( n ) at 298 K were determined as follows: P 1/2 =54.2 kPa, n =2.0 for Co 2PP 8 and P 1/2 =6.8 kPa, n =1.8 for Co 2PP 4,respectively. The rate equations of reversible oxygen binding by Co 2PP 8 were determined and the reaction path was proposed. The results of thermodynamic and kinetic studies indicate that there exists strong cooperative effect during oxygenation of the compounds. The ESR observation reveals that the dioxygen complexes formed in the solutions are of superoxo (Co O - 2) type.展开更多
The present study is aimed to examine the adsorption characteristics of Cu(II) by using the novel cellulose acetate composite and to apply it for the removal of Cu(II) from real wastewater samples. In order to achieve...The present study is aimed to examine the adsorption characteristics of Cu(II) by using the novel cellulose acetate composite and to apply it for the removal of Cu(II) from real wastewater samples. In order to achieve this objective, ethylenediamine, diethylenetriamine, triethylenetetramine and te-traethylenepentanene were used for immobilization of grafted cellulose acetate-nanoscale manganese dioxide. Cellulose was extracted from mangrove species Avicennia marina and converted to cellulose acetate then it was formed composite with nano-manganese dioxide via precipitation of nano-manganese dioxide on it. The composite was grafted with acrylamide monomer before immobilization. The synthesized compounds were used for adsorption of Cu(II) and characterized by FT-IR, TGA and SEM. The adsorption characteristics of synthesized sorbents were optimized. Langmuir and Freundlich models were used to establish sorption equilibria. The analytical applications of these modified materials were applied successfully for the removal of Cu(II).展开更多
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
基金This work was supported by the National Natural Science Foundation of China (20001007 20131020)+1 种基金and Natural Science Foundation of Fujian Province (2003I031 A0420002)
文摘The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.
基金supported by the National Natural Science Foundation of China (No. 51004066)the Opening Project of the Key Laboratory for Advanced Building Materials of Sichuan Province (No. (No.09ZXXK09)Research Fund of Mianyang Normal University (No. 2011C03)
文摘Tourmaline from Altai mine in China＇s Sinkiang was used to remove lead （II）, copper （II） from aqueous solution. The results demonstrate that tourmaline contains Na（Mg,V）3AI6（BO3）3Si6Ols （OH）4, NaFe3AI6（BO3）3Si6Ols（OH）4. The data show that Tourmaline from Altai mine in China＇s Sinkiang can be used natural adsorbent for lead （II）, copper （II）.It is observed that the adsorption data fitted to the Langmuir isotherm. Furthermore, both Pb （II） and Cu （II） absorbed by tourmaline and tourmaline were characterized by X-ray diffraction, Laser Raman Spectrum, Fourier transform infrared spectroscopy, X-ray energy dispersive spectrometer, Transmission electron microscopy and Zeta potential.
基金This work was supported by the foundation of Natural Science Research of Jiangsu Education Department (02KJB150007)
文摘The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?
文摘A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffraction study and IR spectroscopy. The crystal is monoclinic, space group: P2 1/n, with unit cell parameters: a=8.2952(2), b=18.4633(3), c=10.5049(2) . β=108.965(1)°, V=1521.56(5) 3, Z=2, C 22 H 30 N 8O 10 Cl 2Cu 2, M r =764.52, D c =1.669 Mg/m 3, F(000)=780, μ (Mo Kα )=8.60, T =293(2)K, final R=0.0623, wR =0.1536 for 2660 observed reflections with I>2.0σ(I ). The centrosymmetric complex Cu 2(CH 3O) 2(C 5H 6N 2) 4(ClO 4) 2 comprises a pair of Cu(II) atoms bridged by two methanoxo and N coordination 2 aminopyridine. The Cu(II)…Cu(II) distance is 3\^002(1).
基金the National Postdoctoral Program for Innovative Talents of China,Postdoctoral Science Foundation of China(Grant No.2018M640759)Natural Science Foundation of China(Grant No.21872174 and U1932148)+4 种基金Project of Innovation-Driven Plan in Central South University(Grant No.20180018050001)State Key Laboratory of Powder Metallurgy,International Science and Technology Cooperation Program(Grant No.2017YFE0127800)Hunan Provincial Science and Technology Program(2017XK2026)Shenzhen Science and Technology Innovation Project(Grant No.JCYJ20180307151313532)Thousand Youth Talents Plan of China and Hundred Youth Talents Program of Hunan.
文摘Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the electrochemical method has been widely used due to its mild reaction condition and high reaction efficiency.In the electrochemical reduction system,the CO2 electrocatalyst is the most important part.Although many CO2 electrocatalysts have been developed,efficient catalysts with high activity,selectivity and stability are still lacking.Copper sulfide compound,as a low-toxicity and emerging material,has broad prospects in the field of CO2 reduction due to its unique structural and electrochemical properties.Much progress has been achieved with copper sulfide nanocrystalline and the field is rapidly developing.This paper summarizes the preparation,recent progress in development,and factors affecting the electrocatalytic CO2 reduction performance with copper sulfide compound as a catalyst.Prospects for future development are also outlined,with the aim of using copper sulfide compound as a highly active and stable electrocatalyst for CO2 reduction.
文摘In this study, the adsorption behavior of copper(II) ions from aqueous solutions onto sesame husk (SH) was investigated. The effect of different parameters such as pH, contact time, adsorbent dosage, adsorbate concentration, temperature and agitation speed was studied. Thermodynamic parameters, equilibrium isotherms and kinetic data have been evaluated. The functional groups and surface morphology of SH adsorbent were characterized by FTIR and SEM. Adsorption equilibrium isotherms were expressed by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) adsorption models and it was found that Langmuir adsorption model fits the experimental data better than Freundlich and D-R models. The adsorption can be best described by the pseudo second-order kinetic model.
文摘The complex [Cu2（apo）4Cl4]·2H2O （apo=2-aminopyridine N-oxide） was obtained. A single- crystal X-ray study shows that the complex is a binuclear compound （Cu2C20H28Cl4N8O6）. The coordination geometry about each copper atom is best described as a distorted square pyramid. The compound [Cu2（apo）4Cl4]·2H2O belongs to the triclinic system with space group P, lattice constants: a = 7.8550（7）, b = 8.5378（7）, c = 12.082（1） ?, α = 72.807（1）, β = 77.641（1）, γ = 70.800（1）(, V =724.85（11） ?3, Z=1, Mr =745.38, Dc=1.708 g/cm3, μ =1.886mm-1, F（000） =378, R=0.0359, wR2=0.0884 for 2220 reflections with I >2σ（I）. The distances between Cu（II） and O atoms are in the range from 1.934（2） to 2.042（2）?. The distance between two copper atoms Cu-Cu（A） is 3.2978（8） ?. The distances of Cu-Cl（1） and Cu-Cl（2） are 2.2322（9）, 2.5095（10） ?, respectively. There is no evident hydrogen bond between N and Cl.
基金supported by the National Natural Science Foundation(No.21172158)NSAF(No.11076018)+2 种基金Sichuan Province Science and Technology Support Programme(No.2011FZ0048)the National Fund of China for Fostering Talents in Basic Science(No.J1210004)Open Project of Key Laboratory for Radiation Physics and Technology of Ministry of Education(No.2010-08)
文摘Functionalization of shape-persistent aromatic oligoamides still represents a difficult task nowadays. A crescent aromatic oligothioamide was synthesized by simple thionation of the corresponding oligoamide with the Lawesson＇s reagent. The results from UV-vis spectra of the molecule upon metal ion complexation demonstrated its higher selectivity in recognizing Cu2~ ions compared to the oligoamide precursor. The stoichiometry of the complex formed between the thioamide and Cu2＋ was found to be 1：1 with a binding constant of （4.3 ± 0.9） × 104 mol/L.
基金supported by Research Fund for the Doctor Program of Hubei University of Technology(No.BSQD12139)Ministry of Science and Technology Small and Medium-sized Enterprise Venture Funds(No.12C26214204453)+1 种基金Natural Foundation of Hubei Province(No.2010CDA020)the Key Foundation of Industry-University-Research Cooperation of Education Department,Hubei Province(No.CXY2009A010)
文摘Two new compounds,1（[Cu（IDB_）2]Cl_2·2CH_3CH_2OH·2H_2O（IDB = N,N-di（2-benzimidazolylmethyl）imine]） and 2（[Cu（EDTB）]·2[C_6H_4（OH）COO]·6H_2O（EDTB = N,N,N＇,N＇-tetrakis-[（2-benzimidazolyl）methyl]-1,2-ethanediamine]）,have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system,space group P1 with a = 9.565（2）,b = 9.863（2）,c = 10.252（3） ？,α = 81.915,β = 88.330,γ = 87.347°,V = 956.28（40） ？3,Z = 1,F（000） = 427,D_c = 1.419 g/cm3,Mr = 817.27 and μ（MoKα） = 0.764 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0505,wR = 0.1417; R indices（all data）： R = 0.0591,wR = 0.1525. Crystal 2 is of triclinic system,space group P1 with a = 11.487（3）,b = 13.396（4）,c = 17.977（5） ？,α = 73.899（5）,β = 86.629（5）,γ = 65.018（4）°,V = 2403.8（12） ？3,Z = 2,F（000） = 1072,D3c = 1.417 g/cm,Mr = 1025.54,μ（MoKα） = 0.528 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0769,w R = 0.163 2; R indices（all data）： R = 0.0769,wR = 0.1632. The two compounds exhibit mononuclear structures. The copper（Ⅱ） atom of crystal 1 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand IDB to adopt a distorted octahedral coordination geometry. The copper（Ⅱ） atom of crystal 2 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand EDTB to show a distorted octahedral coordination geometry. Particularly,the two compounds exhibit fluorescent properties at room temperature in ethanol.
文摘Based on poly(vinyl chloride) membranes, a novel miniaturized screen-printed all-solid-state copper(II)-selective electrode has been developed for applications in environmental monitoring. Performance and applicability of the ion-selective electrode (ISE) have been proved by potentiometric investigations. Conducting polymers were used as intermediate layers and as solid contacts between the ion-selective membrane and the graphite transducer. The ion-complexing reagent 2-mercapto-benzoxazole was incorporated into poly(vinyl chloride) membranes. In the concentration range 10<sup>-6</sup> - 10<sup>-2</sup> mol/L, the ISE exhibited a linear Nernstian potential response to copper(II) with an average slope value of 28 mV/decade. The detection limit was 3 × 10<sup>-7</sup> mol/L. The electrode exhibits a short response time (<10 s) and can be used in the range of pH = 3 - 7. Selectivity coefficents against certain interfering ions are investigated. The life time of the electrode under laboratory conditions was approximately 12-month. The electrode was applied in the investigation of different aqueous environmental samples and the electrode characteristics were described. The copper(II) ASS electrode has also successfully been used in potentiometric, complexometric titrations with ethylenediaminetetraacetic acid.
基金Young Science Foundation of Shanxi Province (No.20001005).
文摘Copper (II) complex derived from 2, 2'-pyridil ligand has been, demonstrated to cleave efficiently DNA at micromolar concentrations at room temperature and pH 7.25.
基金Financial support by National Natural Science Foundation of China !(Grant No. 29972002) isgreatly acknowledged.
文摘t-Butyldimethylsilyl (TBDMS) ether can be cleaved upon refluxing in acetone/H2O (95 : 5) in the presence of a catalytic amount of copper (II) chloride dihydrate (5 mmol %).
文摘Using Cu(II) as the template, a complex {[Cu2L2(H2O)2]·4H2O}n (L = N-acetoxyl- picolinamide) has been successfully synthesized and characterized by single-crystal X-ray diffrac- tion. The crystal is of monoclinic, space group C2/c, with a = 24.144(5), b = 7.1622(14), c = 17.283(4) ?, C16H24Cu2N4O12, Mr = 591.47, β = 131.73(3)o, V = 2230.3(8) ?3, Z = 4, Dc = 1.761 g/cm3, F(000) = 1208, μ = 1.978 mm?1, R = 0.0400 and wR = 0.1099. The copper (II) ion is five- coordinated with a distorted square pyramidal geometry. The complex can be viewed as a one- dimensional chain structure by carboxylic bridges among copper atoms. In the complex there exist hydrogen bonding interactions to stabilize the structure.
基金supported by the Natural Science Foundation of Anhui Province (No. KJ2008B166)
文摘Two homochiral metallosalen complexes, Ni（salen） （salen = （1R,2R）-（-）-diamino- cyclohexane-N,N′-bis（3-tert-butyl-5-（4′-benzoic acid）-salicylidene） 1 and Cu（salen） 2, have been synthesized and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 4. For 1, a = 12.082（2）, b = 15.447（3）, c = 18.784（4）A^°, V= 3505.7（12）A^°3, Mr = 731.50, Dc = 1.386 g/cm^3, μ = 0.606 mm^-1, F（000） = 1544, the final GOOF = 1.043, R = 0.0496 and wR = 0.1248 for 4791 observed reflections with I 〉 2σ（I）. For 2, a = 12.181（2）, b = 15.501（3）, c = 18.877（4） A^°, V = 3564.3（12）A^°3, Mr = 736.33, Dc = 1.372 g/cm^3, μ = 0.665 mm^-1, F（000） = 1548, the final GOOF = 1.062, R = 0.0575 and wR = 0.1508 for 4562 observed reflections with I 〉 2σ（I）. The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions.
基金the National Natural Science Foundation of China (No. 29871018) and the foundation of Open Laboratory for Chiral Technology of H
文摘A mononuclear copper(II) complex CuL with a Schiff-base L (H2L = N,N(- cyclohexanebis(3-formyl-5-tert-butyl-salicylaldimine)) has been synthesized and characterized. X-ray diffraction analysis at room temperature indicates that the complex (Cu C30H36N2O4, Mr = 552.15) crystallizes in tetrahedral system, space group P41 with a = 13.4685(6), c = 31.326(2) ?, V = 5682.5(5) ?3, Z = 8, Dc = 1.291 g/cm3, F(000) = 4656, μ(MoK() = 0.805 mm-1. The final R and Rw factors are 0.0421 and 0.0815, respectively with 4435 observed reflections. The title complex is a neutral molecule in which the ligand is doubly deprotonated, forming a four-coordinated Cu(II) complex by nitrogen and oxygen donors of the ligand and the coordination geometry of Cu(II) could be considered as an approximately planar configuration. There are two independent molecules, having a transoid arrangement in this structure.
基金the National Natural Science Foundation of China (No. 649620)
文摘A chloro-bridged dinuclear copper（H） complex with ligand 2-pyridylme-thylene- furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase （XO） was also evaluated. It crystallizes in the triclinic system, space group P 1 with a = 8.0441（16）, b = 8.5663（17）, c = 10.060（2）A, α = 77.52（3）, β = 72.04（3）, γ = 70.12（3）°, V = 615.3（2）A^3, Z = 1, Dc = 1.731 g/cm^3, F（000） = 322, the final R = 0.0401 and wR = 0.0934 for 1971 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Cu（II） cation is five-coordinated by two N atoms of Schiff base and three Cl anions. The C-H…Cl intermolecular and intramolecular hydrogen bonds connect the molecules to form a three-dimensional network. This copper（II） complex shows more potent inhibitory activity against XO with IC50 = 3.48μM than the standard inhibitor allopurinol.
文摘A complex polymer [Cu2(oxen)(pic)(H20)]n(Clo4)·2nHH2O, there oxen and pic are N.N' -bis(2aminoethyt )oxamide and Pyridine-4-carboxytate, respectivety, was synthesized. It crystallizes in the monoctinic space group P21/c, with a=10.420(2) A. b=13. 118(2) A, c=14 .863(5) A. β=93.05(2)°, and z=4. The structure of this complex consists of 2D network of copper(II) ions bridged by bis-tridentate oxen in transconformation, and by pyridine-4-carboxylate in which the pyridine ring acts as a monodentate group whereas the carboxylate as a tridentate group and bonds to three different copper centres in a novel fashion. The repeating asymmetric unit is a binuclear copper(II) fragment with one of the copper centre locating in a lengthening octahedrat environment, whereas the other in a distorted tetragonal pyramid geometry.
文摘Thermodynamic data were determined for the reversible binding of O 2 to two compounds of dicobalt(II) di(meso tetra phenyl)porphyrin derivatives with different lengths of diamidoaliphatic bridge (abbreviated to Co 2PP 8 and Co 2PP 4) in N,N dimethylformamide at room temperature. The partial pressure of dioxygen necessary for half oxygenation ( P 1/2 ) and Hill coefficient ( n ) at 298 K were determined as follows: P 1/2 =54.2 kPa, n =2.0 for Co 2PP 8 and P 1/2 =6.8 kPa, n =1.8 for Co 2PP 4,respectively. The rate equations of reversible oxygen binding by Co 2PP 8 were determined and the reaction path was proposed. The results of thermodynamic and kinetic studies indicate that there exists strong cooperative effect during oxygenation of the compounds. The ESR observation reveals that the dioxygen complexes formed in the solutions are of superoxo (Co O - 2) type.
文摘The present study is aimed to examine the adsorption characteristics of Cu(II) by using the novel cellulose acetate composite and to apply it for the removal of Cu(II) from real wastewater samples. In order to achieve this objective, ethylenediamine, diethylenetriamine, triethylenetetramine and te-traethylenepentanene were used for immobilization of grafted cellulose acetate-nanoscale manganese dioxide. Cellulose was extracted from mangrove species Avicennia marina and converted to cellulose acetate then it was formed composite with nano-manganese dioxide via precipitation of nano-manganese dioxide on it. The composite was grafted with acrylamide monomer before immobilization. The synthesized compounds were used for adsorption of Cu(II) and characterized by FT-IR, TGA and SEM. The adsorption characteristics of synthesized sorbents were optimized. Langmuir and Freundlich models were used to establish sorption equilibria. The analytical applications of these modified materials were applied successfully for the removal of Cu(II).
