Aim To study the effects of binuclear copper （Ⅱ） threonine complex （Cu2 （Thr）4） as analogue of superoxide dismutase （SOD） on blood glucose, blood lipids and vessels of hearts and kidneys in diabetic mice. Met...Aim To study the effects of binuclear copper （Ⅱ） threonine complex （Cu2 （Thr）4） as analogue of superoxide dismutase （SOD） on blood glucose, blood lipids and vessels of hearts and kidneys in diabetic mice. Methods Diabetic mouse model was established by intraperitioneal injection of alloxan. Low, middle, and high doses of Cu2（Thr）4 at 0.002%, 0.02% and 0.1% were given respectively to diabetic mice following lavage. The fasting blood glucose was determined after the diabetic mice were given Cu2 （Thr）4 for 0, 30, and 45 d. The diabetic mice were killed on the 45th day. Then glycosylated hemoglobin （HbAlc） and blood lipids were assayed, and pathologic changes in hearts and kidneys stained with HE were observed. Results Compared with the control group in which the diabetic mice were given distilled water, the value of blood glucose reduced significantly in middle dose group （P 〈 0.01 ）, followed by that in low dose group （P 〈 0.05）. TC level reduced markedly and HDL level increased significantly in all three treatment groups （P 〈 0.05）. Especially in middle dose group, cardiac muscle fibers were neatly arranged, nucleus and cytoplasm well distributed, glomeruli showing normal structure, cells well distributed and staining being normal. Conclusion Cu2 （Thr）4 reduces blood glucose, regulates blood lipids, and play protective action on the vessels of hearts and kidneys in diabetic mice. The effects of it in middle dose were better than those of other doses.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 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
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 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 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 flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 ...A flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 and [Cu（H2O）3 L].2Cl.H2O 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1： triclinic, space group PT, a = 5.253（2）, b = 7.406（3）, c = 14.792（5） A, α = 84.195（5）, β = 80.014（5）, γ = 78.053（5）°, V= 553.2（3）A^3, Z = 1, F（000） = 293, Dc = 1.717 g/cm^3, the final R = 0.0385 and wR = 0.1079 for 1883 observed reflections （I 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 10.222（3）, b = 25.287（7）, c = 9.277（3）A, β = 93.572（5）°, V = 2393.2（12）A^3, Z = 4, F（000） = 1140, Dc = 1.540 g/cm^3, the final R = 0.0472 and wR = 0.0956 for 3204 observed reflections （I 〉2o（/））.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 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
A new binuclear copper（Ⅱ） complex [Cu2（Hpt）2（TNCA）2（H2O）2]·4 H2O（1） has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid（TNCA） and 3-（pyridin-2-yl）-1,2,4-...A new binuclear copper（Ⅱ） complex [Cu2（Hpt）2（TNCA）2（H2O）2]·4 H2O（1） has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid（TNCA） and 3-（pyridin-2-yl）-1,2,4-triazole（Hpt）. It crystallizes in the triclinic space group P-1, with a = 8.8199（18）, b = 14.278（3）, c = 15.269（3） A, α = 76.21（3）o, β = 81.07（3）o, γ = 76.07（3）o, V = 1802.7（6） A3, Dc = 1.636 g/cm3, Z = 2, F（000） = 916, the final GOOF = 1.051, R = 0.0556 and wR = 0.1388. The whole molecule consists of two copper ions bridged by two μ2-η^1：η^0-3-（pyridin-2-yl）-1,2,4-triazole anions. The coordination environment of the Cu（1） ion is CuO2N3, giving a distorted square pyramidal geometry. 1 exhibits antiferromagnetic interaction between Cu（Ⅱ） ions, the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 440 K.展开更多
A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the tricl...A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.展开更多
A new dinuclear copper（Ⅱ） complex [Cu（CH3COO）（C7H5N4）（H2O）]2·3.5H2 O has been hydrothermally synthesized with copper acetate, o-acetamidobenzoic acid and 3-（pyridin-2-yl）-1,2,4-triazole. It crystallize...A new dinuclear copper（Ⅱ） complex [Cu（CH3COO）（C7H5N4）（H2O）]2·3.5H2 O has been hydrothermally synthesized with copper acetate, o-acetamidobenzoic acid and 3-（pyridin-2-yl）-1,2,4-triazole. It crystallizes in the monoclinic space group P21/c, with a = 12.0188（7）, b = 13.7993（8）, c = 8.7488（5） A, β = 101.7350（10）o, V = 1420.67（14） A3, D3 c = 1.568 g/cm, Z = 1, F（000） = 690, the final GOOF = 1.145, R = 0.0437, and w R = 0.1097. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ2-η1：η0 3-（pyridin-2-yl）-1,2,4-triazole anions. The coordination environment of Cu（Ⅱ） ion is Cu O2N3, giving a distorted square pyramidal geometry. The thermal stability and magnetic properties of the complex were investigated.展开更多
A new asymmetric bidentate copper（Ⅱ） complex,CuL 2（HL=2-（（E）-（4-bromophenylimino）methyl）-6-bromo-4-chlorophenol）,has been synthesized and characterized by elemental analyses and single-crystal X-ray diffrac...A new asymmetric bidentate copper（Ⅱ） complex,CuL 2（HL=2-（（E）-（4-bromophenylimino）methyl）-6-bromo-4-chlorophenol）,has been synthesized and characterized by elemental analyses and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic space group P2 1 /c with a=11.218（3）,b=9.355（3）,c=13.449（4）,β=108.722（4）°,V=1336.8（6）3,Z=2,Dc=2.008 g/cm 3,μ（MoKα）=7.024 mm-1,F（000）=806,S=0.999,the final R=0.0342 and wR=0.0641for2611observed reflections （I〉2σ（I））.The central copper（Ⅱ） is four-coordinate and bonds to two nitrogen and two oxygen atoms from two Schiff base ligands.The complex is linked into a two-dimensional supramolecular structure by weak intermolecular interactions.In addition,DNA-binding properties of the metal complex were investigated using spectrometric titrations and viscosity measurements.The results show that the complex binds with calf-thymus DNA（CT-DNA）,presumably via a partial intercalative mode.The intrinsic binding constant of the Cu（Ⅱ） complex with DNA is 7.335×10 3 M-1.展开更多
Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same stru...Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same structure with different geometric parameters. The α form crystallizes in the P2(1)/c space group and the β form in the P1 space group. Both the crystal structures consist of centrosymmetric monomeric molecules of Cu(OC_6H_4CNOH)_2. The IR spectra are in agreement with the structural data.展开更多
The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at ...The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.展开更多
The reaction of N-tosylatirdine with 1,2-diaminopropane in dry benzene solution yields an intermediate H2L, N,N,N＇,N＇-tetrakis（2-（p-tolylsulfonyl）aminoethyl） propane-1,2-diamine. The mononuclear copper（Ⅱ） com...The reaction of N-tosylatirdine with 1,2-diaminopropane in dry benzene solution yields an intermediate H2L, N,N,N＇,N＇-tetrakis（2-（p-tolylsulfonyl）aminoethyl） propane-1,2-diamine. The mononuclear copper（Ⅱ） complex, [CuLH2O]·H2O, was synthesized by the reaction between the intermediate and copper（Ⅱ） in absolute methanol. The complex has been characterized by IR, UV-vis and X-ray diffraction technology, and its crystal crystallizes in the orthorhombic system, space group Pbca with a = 15.589（1）, b = 21.897（2）, c = 27.645（2） A, V = 9436.4（1）A^3, Dc = 1.352 g/cm^3, Z = 8, Mr = 960.68, F（000） = 4040, μ（MoKa） = 0.698 mm-1, S = 0.98, R = 0.0537 and wR = 0.1180 for 5804 observed reflections （I 〉 2σ（I））. In the crystal structure, a one-dimensional chain is formed by abundant hydrogen bond interactions. The interaction of the complex with DNA was monitored using agarose gel electrophoresis. The result shows that the complex can transform the supercoiled to nicked and liner forms, and has a concentration-dependent cleavage activity.展开更多
A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ioniza...A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.展开更多
文摘Aim To study the effects of binuclear copper （Ⅱ） threonine complex （Cu2 （Thr）4） as analogue of superoxide dismutase （SOD） on blood glucose, blood lipids and vessels of hearts and kidneys in diabetic mice. Methods Diabetic mouse model was established by intraperitioneal injection of alloxan. Low, middle, and high doses of Cu2（Thr）4 at 0.002%, 0.02% and 0.1% were given respectively to diabetic mice following lavage. The fasting blood glucose was determined after the diabetic mice were given Cu2 （Thr）4 for 0, 30, and 45 d. The diabetic mice were killed on the 45th day. Then glycosylated hemoglobin （HbAlc） and blood lipids were assayed, and pathologic changes in hearts and kidneys stained with HE were observed. Results Compared with the control group in which the diabetic mice were given distilled water, the value of blood glucose reduced significantly in middle dose group （P 〈 0.01 ）, followed by that in low dose group （P 〈 0.05）. TC level reduced markedly and HDL level increased significantly in all three treatment groups （P 〈 0.05）. Especially in middle dose group, cardiac muscle fibers were neatly arranged, nucleus and cytoplasm well distributed, glomeruli showing normal structure, cells well distributed and staining being normal. Conclusion Cu2 （Thr）4 reduces blood glucose, regulates blood lipids, and play protective action on the vessels of hearts and kidneys in diabetic mice. The effects of it in middle dose were better than those of other doses.
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 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 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 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This work was financially supported by Liuhui Center for Applied Mathematics, Nankai and Tianjin Universities (No. H10114)
文摘A flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 and [Cu（H2O）3 L].2Cl.H2O 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1： triclinic, space group PT, a = 5.253（2）, b = 7.406（3）, c = 14.792（5） A, α = 84.195（5）, β = 80.014（5）, γ = 78.053（5）°, V= 553.2（3）A^3, Z = 1, F（000） = 293, Dc = 1.717 g/cm^3, the final R = 0.0385 and wR = 0.1079 for 1883 observed reflections （I 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 10.222（3）, b = 25.287（7）, c = 9.277（3）A, β = 93.572（5）°, V = 2393.2（12）A^3, Z = 4, F（000） = 1140, Dc = 1.540 g/cm^3, the final R = 0.0472 and wR = 0.0956 for 3204 observed reflections （I 〉2o（/））.
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 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 ℃.
基金Supported by the Scientific Research Found of Hunan Provincial Education Department of China(17A049,17C0226)Industry and Research Key Project of Hengyang City(2017KJ155,2017KJ193)Doctoral Scientific Research Foundation of Hengyang Normal University(17D01)
文摘A new binuclear copper（Ⅱ） complex [Cu2（Hpt）2（TNCA）2（H2O）2]·4 H2O（1） has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid（TNCA） and 3-（pyridin-2-yl）-1,2,4-triazole（Hpt）. It crystallizes in the triclinic space group P-1, with a = 8.8199（18）, b = 14.278（3）, c = 15.269（3） A, α = 76.21（3）o, β = 81.07（3）o, γ = 76.07（3）o, V = 1802.7（6） A3, Dc = 1.636 g/cm3, Z = 2, F（000） = 916, the final GOOF = 1.051, R = 0.0556 and wR = 0.1388. The whole molecule consists of two copper ions bridged by two μ2-η^1：η^0-3-（pyridin-2-yl）-1,2,4-triazole anions. The coordination environment of the Cu（1） ion is CuO2N3, giving a distorted square pyramidal geometry. 1 exhibits antiferromagnetic interaction between Cu（Ⅱ） ions, the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 440 K.
基金the Natural Science Foundation of Guangdong Province,China(No. 04105986)
文摘A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.
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 [Cu（CH3COO）（C7H5N4）（H2O）]2·3.5H2 O has been hydrothermally synthesized with copper acetate, o-acetamidobenzoic acid and 3-（pyridin-2-yl）-1,2,4-triazole. It crystallizes in the monoclinic space group P21/c, with a = 12.0188（7）, b = 13.7993（8）, c = 8.7488（5） A, β = 101.7350（10）o, V = 1420.67（14） A3, D3 c = 1.568 g/cm, Z = 1, F（000） = 690, the final GOOF = 1.145, R = 0.0437, and w R = 0.1097. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ2-η1：η0 3-（pyridin-2-yl）-1,2,4-triazole anions. The coordination environment of Cu（Ⅱ） ion is Cu O2N3, giving a distorted square pyramidal geometry. The thermal stability and magnetic properties of the complex were investigated.
文摘A new asymmetric bidentate copper（Ⅱ） complex,CuL 2（HL=2-（（E）-（4-bromophenylimino）methyl）-6-bromo-4-chlorophenol）,has been synthesized and characterized by elemental analyses and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic space group P2 1 /c with a=11.218（3）,b=9.355（3）,c=13.449（4）,β=108.722（4）°,V=1336.8（6）3,Z=2,Dc=2.008 g/cm 3,μ（MoKα）=7.024 mm-1,F（000）=806,S=0.999,the final R=0.0342 and wR=0.0641for2611observed reflections （I〉2σ（I））.The central copper（Ⅱ） is four-coordinate and bonds to two nitrogen and two oxygen atoms from two Schiff base ligands.The complex is linked into a two-dimensional supramolecular structure by weak intermolecular interactions.In addition,DNA-binding properties of the metal complex were investigated using spectrometric titrations and viscosity measurements.The results show that the complex binds with calf-thymus DNA（CT-DNA）,presumably via a partial intercalative mode.The intrinsic binding constant of the Cu（Ⅱ） complex with DNA is 7.335×10 3 M-1.
文摘Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same structure with different geometric parameters. The α form crystallizes in the P2(1)/c space group and the β form in the P1 space group. Both the crystal structures consist of centrosymmetric monomeric molecules of Cu(OC_6H_4CNOH)_2. The IR spectra are in agreement with the structural data.
基金Supported by the Education Department of Jiangxi Province (No 2007-125)the Initial Fund for Doctors from Jiangxi Normal University
文摘The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.
基金Supported by the National Natural Science Foundation of China (No. 20871097)the Foundation of the Innovative Group of the Education Department of Hubei Province (No. T200802)the Natural Science Foundation of the Science & Technology Department of Hubei Province (No. 2008CDB022)
文摘The reaction of N-tosylatirdine with 1,2-diaminopropane in dry benzene solution yields an intermediate H2L, N,N,N＇,N＇-tetrakis（2-（p-tolylsulfonyl）aminoethyl） propane-1,2-diamine. The mononuclear copper（Ⅱ） complex, [CuLH2O]·H2O, was synthesized by the reaction between the intermediate and copper（Ⅱ） in absolute methanol. The complex has been characterized by IR, UV-vis and X-ray diffraction technology, and its crystal crystallizes in the orthorhombic system, space group Pbca with a = 15.589（1）, b = 21.897（2）, c = 27.645（2） A, V = 9436.4（1）A^3, Dc = 1.352 g/cm^3, Z = 8, Mr = 960.68, F（000） = 4040, μ（MoKa） = 0.698 mm-1, S = 0.98, R = 0.0537 and wR = 0.1180 for 5804 observed reflections （I 〉 2σ（I））. In the crystal structure, a one-dimensional chain is formed by abundant hydrogen bond interactions. The interaction of the complex with DNA was monitored using agarose gel electrophoresis. The result shows that the complex can transform the supercoiled to nicked and liner forms, and has a concentration-dependent cleavage activity.
基金supported by the National Basic Research Program of China(No.2014CB643401)the National Natural Science Foundation of China(Nos.51134007 and 51474256)
文摘A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.
