Two new complexes: [Cu(TBZ)(bipy)Cl]Cl[H2O (1) and [Cu(TBZ)(phen)CI]CloH20 (2) [TBZ=2-(4'-thiazolyl)- benzimidazole, phen = 1,10-phenanthroline and bipy =2,2'-bipyridine] have been synthesized and cha...Two new complexes: [Cu(TBZ)(bipy)Cl]Cl[H2O (1) and [Cu(TBZ)(phen)CI]CloH20 (2) [TBZ=2-(4'-thiazolyl)- benzimidazole, phen = 1,10-phenanthroline and bipy =2,2'-bipyridine] have been synthesized and characterized by elemental analysis, molar conductivity, IR, and UV-vis methods. Complex 2, structurally characterized by single-crystal X-ray crystallography, crystallizes in the monoclinic space group P21/c in a unit cell of a = 0.85257(12) nm, b=2.5358(4) nm, c=1.15151(13) nm, β=118.721(8)°, V=2.183.2(5) nm^3, Z=4, Dc=1.624 gocm 3, μ= 1.367 mm^-1. The complexes, free ligands and chloride copper(II) salt were each tested for their ability to inhibit the growth of two gram-positive (B. subtilis and S. aureus) and two gram-negative (Salmonella and E. coli) bacteria. The complexes showed good antibacterial activities against the microorganisms. The interaction between the com- plexes and calf thymus DNA in aqueous solution was investigated adopting electronic absorption spectroscopy, fluorescence spectroscopy, viscosity measurements and cyclic voltammetry. Results suggest that the two complexes can bind to DNA by intercalative mode. In addition, the result of agarose gel electrophoresis suggested that the complexes can cleave the plasmid DNA at physiological pH and room temperature. Mechanistic studies with different inhibiting reagents reveal that hydroxyl radicals, and a singlet oxygen-like copper-oxo species are all involved in the DNA scission process mediated by the complexes.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
The BLU (back light unit) is the core component of the LCD for notebook, mobile-phone, navigation, as well as large sized TV, PID (public information display), etc. In order to enhance optical efficiency of LCD, optic...The BLU (back light unit) is the core component of the LCD for notebook, mobile-phone, navigation, as well as large sized TV, PID (public information display), etc. In order to enhance optical efficiency of LCD, optical films with the uniform prism patterns have been used for BLU by stacking two films up orthogonally. In this case, light interference-phenomenon occurred such as Morie, wet-out, u-turning, etc. It caused several problems such as low brightness, spots and stripes in LCD. Recently, the high-luminance micro complex prism patterns are actively studied to avoid the light interference-phenomenon and enhance the optical efficiency. In this study, the roll master to manufacture complex micro prism pattern film was machined by using the high precision lathe. The machined patterns on the roll master were 50, 45, 40, 35, 30, 25, 20, 15, 10 and 5 μm in the pitch with 25.0, 22.5, 20.0, 17.5, 15.0, 12.5, 10.0, 7.5, 5.0 and 2.5 μm in the peak height, respectively. The roll was 2 000 mm in length and 320 mm in diameter. The electroplated roll by copper and the natural single crystal diamond tool was used for machining the patterns. The cutting force was measured and analyzed for each cutting condition by using the dynamometer. The chips and the surfaces after being machined were analyzed by SEM and microscope.展开更多
The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crysta...The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235(10),b=1.27935(18),c=1.28569(17) nm,α=112.633(2),β=102.971(3),γ=97.089(2)o,V=0.9673(2) nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ(MoKα)=3.356 mm 1,F(000)=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ(Ⅰ).In 1,two deprotonated 3,5-pyrazoledicarboxylic acids (pdc 3),one copper(Ⅱ) ion and one cadmium(Ⅱ) ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium(Ⅱ) ions through chelating carboxylate groups to construct the copper(Ⅱ)-cadmium(Ⅱ) heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional (3D) supramolecular framework.展开更多
The bimetallic ternary complex formation in the aqueous solution of La and Cu with alizarin fluorine blue (AFB) was studied by spectrophotometry.The ternary complex LaCu3(AFB)3 has maximum light absorption at 550nm.Th...The bimetallic ternary complex formation in the aqueous solution of La and Cu with alizarin fluorine blue (AFB) was studied by spectrophotometry.The ternary complex LaCu3(AFB)3 has maximum light absorption at 550nm.The colour reaction selectivity is fairly good and the method can be applied to the direct photometric determination of copper in lanthanum or some pure metals.A new mathematical approach to the treatment of spectrophotometric data for differentiation between mononuclear and polynuclear in solution is presented.The improvable fixed logarithm method is for complexes of the type MmBn(m=n) or MmBn(m=n).We report that La(Ⅲ) combines with AFB at pH 4.5 to form a single complex,withm=n=2,La2(AFB)2.展开更多
A novel thiocyanate-controlled copper(Ⅱ)-L-arginine complex with the formula of Cu(Arg)(SCN)2(1,Arg:L-arginine) has been obtained from aqueous solution and structurally characterized by single-crystal X-ray ...A novel thiocyanate-controlled copper(Ⅱ)-L-arginine complex with the formula of Cu(Arg)(SCN)2(1,Arg:L-arginine) has been obtained from aqueous solution and structurally characterized by single-crystal X-ray diffraction method.Crystal data:orthorhombic,space group P212121,a = 6.0156(5),b = 12.1905(11),c = 18.4203(16) A°,V = 1350.8(2) A°3,Z = 4,μ = 1.933mm^(-1),F(000) = 724,S = 1.084,the final R = 0.0410,wR = 0.0754 for 1893 observed reflections with I 〉 2σ(I),and R = 0.0559,wR = 0.0820 for all reflections.In addition,elemental analysis,IR,TG-DTG and magnetism characterization are presented.展开更多
Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'...Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1) and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methods and Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7), b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055 Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4), b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055, Rw=0.062.展开更多
A dinuclear copper complex [Cu2LCl2](ClO4)2 (L = 2,2'-(piperazine-1,4-diyl)bis- (N,N-bis(pyridine-2-ylmethyl)ethan-1-amine)) has been synthesized and structurally characterized. It crystallizes in triclinic...A dinuclear copper complex [Cu2LCl2](ClO4)2 (L = 2,2'-(piperazine-1,4-diyl)bis- (N,N-bis(pyridine-2-ylmethyl)ethan-1-amine)) has been synthesized and structurally characterized. It crystallizes in triclinic, space group Pī with α = 8.5707(9), b = 10.5083(12), c = 11.4878(13) A, α = 76.197(2), β = 88.271(2), γ = 87.855(2)o, V = 1003.81(19) A3, Z = 1, F(000) = 478, Dc = 1.544 Mg/m3, Mr = 933.60, μ = 1.383 mm^-1, the final R = 0.0669 and wR = 0.1486 for 3675 observed reflections with I 〉 2σ(I). Its catechol oxidase mimic activity was studied spectroscopically by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. The results showed that the kinetics of catechol catalyzed by the complex accorded with the Michaelis-Mentent equation, and the catechol oxidase catalytic activity of the complex increased with increasing the pH values.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
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
The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, spa...The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, space group P61 with a = 11.1870(4), c = 21.578(1) ? V = 2338.6(2) ?, Dc = 1.729 g/cm3, Z = 6, m(MoKa) = 1.583 mm-1 and F(000) = 1254. The final R and wR are 0.0253 and 0.0416 for 1458 observed reflections with I≥2s(I), respectively. It was revealed that the square pyramidal Cu(II) sites are linked through 4,4?bipyridine groups, forming infinite one-dimensional chains, with the sulfate anions and lattice water molecules occupying the inter-chain positions. During the electrostatic interactions, there exist O…O hydrogen bonds and p-p stacking interactions between the parallel aromatic bipy rings in the structure.展开更多
A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characteriz...A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data: C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420(2), b = 9.1070(2), c = 15.1140(6) A, a = 76.889(9), β = 81.332(11), γ = 74.844( 11)°, V = 1009.89(5) A^3, Z = 2, Dc = 1.605 g/cm^3, F(000) = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.展开更多
A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b =...A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.展开更多
The title complex of copper(Ⅱ) with m-chlorobenzoic acid, 1,10-phenanthroline (phen) and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for th...The title complex of copper(Ⅱ) with m-chlorobenzoic acid, 1,10-phenanthroline (phen) and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex: triclinic, space group PI^-, a = 1.06853(12), b = 1.30740(16), c = 1.49546(17) nm, α= 101.791(2),β = 103.413(2), γ = 105.815(2)°, V= 1.8736(4) nm^3, Mr = 904.67, Dc = 1.604 g/cm^3, Z = 2,/7(000) = 924,μ = 1.34 mm^-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three wate: molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.展开更多
A new copper(Ⅱ) complex with formula CuL(py), where L^2- is the dianion of 2,4-dihydroxybenzylidene benzoylhydrazone, has been synthesized and characterized by IR spectra and single-crystal X-ray diffraction meth...A new copper(Ⅱ) complex with formula CuL(py), where L^2- is the dianion of 2,4-dihydroxybenzylidene benzoylhydrazone, has been synthesized and characterized by IR spectra and single-crystal X-ray diffraction method. The crystal belongs to monoclinic, space group P2 1/c with a=0.9630(4), b=1.4808(6), c=1.2320(5) nm, β=104.969(6)°, V=1.6973(Ⅱ) nm^3, Z=4, Dc=1.553 g/cm^3,μ(MoKa)=1.311 mm^-1, F(000)=812, R=0.0694 and wR=0.1727 for 1511 observed reflections (I〉2σ(I)). The crystal structure analysis indicates that the copper(Ⅱ) ion lies in a distorted square-planar environment composed of two oxygen atoms, one nitrogen atom from the tridentate acylhydrazone Schiff base ligand L^2- and one nitrogen atom from the pyridine ligand. Two adjacent molecules are connected via weak Cu…O bonding interactions to form dimers, which are further linked to generate a two-dimensional layer structure via interdimeric hydrogen bonds.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
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
A planar transition metal complex Cu(L)2 (L = (E)-benzyl-2-(4-nitrobenzylidene)-hydrazinecarbodithioate) has been prepared and determined by X-ray single-crystal diffraction. The crystal belongs to the monocli...A planar transition metal complex Cu(L)2 (L = (E)-benzyl-2-(4-nitrobenzylidene)-hydrazinecarbodithioate) has been prepared and determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system,space group P21/c with a = 6.7101(11),b = 16.952(3),c = 13.962(3) ,β = 92.458(4)°,V = 1586.7(5) 3,Z = 4,Mr = 724.33,Dc = 1.516 g·m-3,μ = 0.998 mm-1,F(000) = 742,S = 1.021,R = 0.0634 and wR = 0.1077 for 813 observed reflections with Ⅰ〉 2σ(Ⅰ) and 205 parameters. In the molecular structure of the title complex,the copper atom exhibits a slightly distorted square-planar geometry in which the basal plane is defined by two N and two S atoms from two bidentate ligands. The complex was evaluated for its antitumor activity against two kinds of cell lines (MKN45 and HepG2) by MTT method. The preliminary bioassay indicates that the complex exhibits weak antitumor activity.展开更多
文摘Two new complexes: [Cu(TBZ)(bipy)Cl]Cl[H2O (1) and [Cu(TBZ)(phen)CI]CloH20 (2) [TBZ=2-(4'-thiazolyl)- benzimidazole, phen = 1,10-phenanthroline and bipy =2,2'-bipyridine] have been synthesized and characterized by elemental analysis, molar conductivity, IR, and UV-vis methods. Complex 2, structurally characterized by single-crystal X-ray crystallography, crystallizes in the monoclinic space group P21/c in a unit cell of a = 0.85257(12) nm, b=2.5358(4) nm, c=1.15151(13) nm, β=118.721(8)°, V=2.183.2(5) nm^3, Z=4, Dc=1.624 gocm 3, μ= 1.367 mm^-1. The complexes, free ligands and chloride copper(II) salt were each tested for their ability to inhibit the growth of two gram-positive (B. subtilis and S. aureus) and two gram-negative (Salmonella and E. coli) bacteria. The complexes showed good antibacterial activities against the microorganisms. The interaction between the com- plexes and calf thymus DNA in aqueous solution was investigated adopting electronic absorption spectroscopy, fluorescence spectroscopy, viscosity measurements and cyclic voltammetry. Results suggest that the two complexes can bind to DNA by intercalative mode. In addition, the result of agarose gel electrophoresis suggested that the complexes can cleave the plasmid DNA at physiological pH and room temperature. Mechanistic studies with different inhibiting reagents reveal that hydroxyl radicals, and a singlet oxygen-like copper-oxo species are all involved in the DNA scission process mediated by the complexes.
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Project(R15-2006-022-01001-0) supported by the National Core Research Center Program from MOST and KOSEF
文摘The BLU (back light unit) is the core component of the LCD for notebook, mobile-phone, navigation, as well as large sized TV, PID (public information display), etc. In order to enhance optical efficiency of LCD, optical films with the uniform prism patterns have been used for BLU by stacking two films up orthogonally. In this case, light interference-phenomenon occurred such as Morie, wet-out, u-turning, etc. It caused several problems such as low brightness, spots and stripes in LCD. Recently, the high-luminance micro complex prism patterns are actively studied to avoid the light interference-phenomenon and enhance the optical efficiency. In this study, the roll master to manufacture complex micro prism pattern film was machined by using the high precision lathe. The machined patterns on the roll master were 50, 45, 40, 35, 30, 25, 20, 15, 10 and 5 μm in the pitch with 25.0, 22.5, 20.0, 17.5, 15.0, 12.5, 10.0, 7.5, 5.0 and 2.5 μm in the peak height, respectively. The roll was 2 000 mm in length and 320 mm in diameter. The electroplated roll by copper and the natural single crystal diamond tool was used for machining the patterns. The cutting force was measured and analyzed for each cutting condition by using the dynamometer. The chips and the surfaces after being machined were analyzed by SEM and microscope.
基金Nanjing University of Posts and Telecommunications (No. NY209032)Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University),Ministry of Education,Science Foundation for Youths of Guangxi Province (No. 0991089)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235(10),b=1.27935(18),c=1.28569(17) nm,α=112.633(2),β=102.971(3),γ=97.089(2)o,V=0.9673(2) nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ(MoKα)=3.356 mm 1,F(000)=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ(Ⅰ).In 1,two deprotonated 3,5-pyrazoledicarboxylic acids (pdc 3),one copper(Ⅱ) ion and one cadmium(Ⅱ) ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium(Ⅱ) ions through chelating carboxylate groups to construct the copper(Ⅱ)-cadmium(Ⅱ) heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional (3D) supramolecular framework.
文摘The bimetallic ternary complex formation in the aqueous solution of La and Cu with alizarin fluorine blue (AFB) was studied by spectrophotometry.The ternary complex LaCu3(AFB)3 has maximum light absorption at 550nm.The colour reaction selectivity is fairly good and the method can be applied to the direct photometric determination of copper in lanthanum or some pure metals.A new mathematical approach to the treatment of spectrophotometric data for differentiation between mononuclear and polynuclear in solution is presented.The improvable fixed logarithm method is for complexes of the type MmBn(m=n) or MmBn(m=n).We report that La(Ⅲ) combines with AFB at pH 4.5 to form a single complex,withm=n=2,La2(AFB)2.
基金the National Natural Science Foundation of China(No.21203160)Education Department Foundation of Shaanxi Province(No.12JK0631)+1 种基金Natural Science Foundation of Shaanxi Province(No.2013JM2013)Special Research Fund of Xianyang Normal University(No.11XSYK204,11XSYK205)
文摘A novel thiocyanate-controlled copper(Ⅱ)-L-arginine complex with the formula of Cu(Arg)(SCN)2(1,Arg:L-arginine) has been obtained from aqueous solution and structurally characterized by single-crystal X-ray diffraction method.Crystal data:orthorhombic,space group P212121,a = 6.0156(5),b = 12.1905(11),c = 18.4203(16) A°,V = 1350.8(2) A°3,Z = 4,μ = 1.933mm^(-1),F(000) = 724,S = 1.084,the final R = 0.0410,wR = 0.0754 for 1893 observed reflections with I 〉 2σ(I),and R = 0.0559,wR = 0.0820 for all reflections.In addition,elemental analysis,IR,TG-DTG and magnetism characterization are presented.
文摘Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1) and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methods and Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7), b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055 Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4), b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055, Rw=0.062.
基金financially supported by the National Natural Science Foundation of China(51173060)
文摘A dinuclear copper complex [Cu2LCl2](ClO4)2 (L = 2,2'-(piperazine-1,4-diyl)bis- (N,N-bis(pyridine-2-ylmethyl)ethan-1-amine)) has been synthesized and structurally characterized. It crystallizes in triclinic, space group Pī with α = 8.5707(9), b = 10.5083(12), c = 11.4878(13) A, α = 76.197(2), β = 88.271(2), γ = 87.855(2)o, V = 1003.81(19) A3, Z = 1, F(000) = 478, Dc = 1.544 Mg/m3, Mr = 933.60, μ = 1.383 mm^-1, the final R = 0.0669 and wR = 0.1486 for 3675 observed reflections with I 〉 2σ(I). Its catechol oxidase mimic activity was studied spectroscopically by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. The results showed that the kinetics of catechol catalyzed by the complex accorded with the Michaelis-Mentent equation, and the catechol oxidase catalytic activity of the complex increased with increasing the pH values.
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 ℃.
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This work was financially supported by the Natural Science Foundation of Fujian province
文摘The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, space group P61 with a = 11.1870(4), c = 21.578(1) ? V = 2338.6(2) ?, Dc = 1.729 g/cm3, Z = 6, m(MoKa) = 1.583 mm-1 and F(000) = 1254. The final R and wR are 0.0253 and 0.0416 for 1458 observed reflections with I≥2s(I), respectively. It was revealed that the square pyramidal Cu(II) sites are linked through 4,4?bipyridine groups, forming infinite one-dimensional chains, with the sulfate anions and lattice water molecules occupying the inter-chain positions. During the electrostatic interactions, there exist O…O hydrogen bonds and p-p stacking interactions between the parallel aromatic bipy rings in the structure.
基金This work was supported by the NSF for Distinguished Young Scientist of China (20425104) and the NSF of Fujian Province (A0420002, 2005I017)
文摘A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data: C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420(2), b = 9.1070(2), c = 15.1140(6) A, a = 76.889(9), β = 81.332(11), γ = 74.844( 11)°, V = 1009.89(5) A^3, Z = 2, Dc = 1.605 g/cm^3, F(000) = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.
基金Project(21001118)supported by National Natural Science Foundation of ChinaProject(12JJ3016)supported by Natural Science Foundation of Hunan Province,China
文摘A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.
基金Project supported by the Foundation of Education Committee of Hunan Province (06C187), Fund for Distinguished Young Cadreman of Hengyang Normal University (2006) and Science and Technology Bureau Foundation of Hengyang (2005Cg10-23)
文摘The title complex of copper(Ⅱ) with m-chlorobenzoic acid, 1,10-phenanthroline (phen) and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex: triclinic, space group PI^-, a = 1.06853(12), b = 1.30740(16), c = 1.49546(17) nm, α= 101.791(2),β = 103.413(2), γ = 105.815(2)°, V= 1.8736(4) nm^3, Mr = 904.67, Dc = 1.604 g/cm^3, Z = 2,/7(000) = 924,μ = 1.34 mm^-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three wate: molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.
文摘A new copper(Ⅱ) complex with formula CuL(py), where L^2- is the dianion of 2,4-dihydroxybenzylidene benzoylhydrazone, has been synthesized and characterized by IR spectra and single-crystal X-ray diffraction method. The crystal belongs to monoclinic, space group P2 1/c with a=0.9630(4), b=1.4808(6), c=1.2320(5) nm, β=104.969(6)°, V=1.6973(Ⅱ) nm^3, Z=4, Dc=1.553 g/cm^3,μ(MoKa)=1.311 mm^-1, F(000)=812, R=0.0694 and wR=0.1727 for 1511 observed reflections (I〉2σ(I)). The crystal structure analysis indicates that the copper(Ⅱ) ion lies in a distorted square-planar environment composed of two oxygen atoms, one nitrogen atom from the tridentate acylhydrazone Schiff base ligand L^2- and one nitrogen atom from the pyridine ligand. Two adjacent molecules are connected via weak Cu…O bonding interactions to form dimers, which are further linked to generate a two-dimensional layer structure via interdimeric hydrogen bonds.
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.
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.
基金supported by the Education Office of Henan and Anhui Provinces (2009A150020 and KJ2008B178)
文摘A planar transition metal complex Cu(L)2 (L = (E)-benzyl-2-(4-nitrobenzylidene)-hydrazinecarbodithioate) has been prepared and determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system,space group P21/c with a = 6.7101(11),b = 16.952(3),c = 13.962(3) ,β = 92.458(4)°,V = 1586.7(5) 3,Z = 4,Mr = 724.33,Dc = 1.516 g·m-3,μ = 0.998 mm-1,F(000) = 742,S = 1.021,R = 0.0634 and wR = 0.1077 for 813 observed reflections with Ⅰ〉 2σ(Ⅰ) and 205 parameters. In the molecular structure of the title complex,the copper atom exhibits a slightly distorted square-planar geometry in which the basal plane is defined by two N and two S atoms from two bidentate ligands. The complex was evaluated for its antitumor activity against two kinds of cell lines (MKN45 and HepG2) by MTT method. The preliminary bioassay indicates that the complex exhibits weak antitumor activity.