We studied the reaction kinetics of dismutation for superoxide ion by copper (Ⅱ) complex of macrocycllc dioxotetramine ligand 12- ( 4' - nitro )- benzyl-1,4,7,10- tetraazacy-clotridecane-11,13-dionato copper (Ⅱ)...We studied the reaction kinetics of dismutation for superoxide ion by copper (Ⅱ) complex of macrocycllc dioxotetramine ligand 12- ( 4' - nitro )- benzyl-1,4,7,10- tetraazacy-clotridecane-11,13-dionato copper (Ⅱ) by using pulse radiolysis. The rate constants of dismutation kcat's were measured to be 1. 78×106 mor-1 . L.s-1(at pH 7. 0) and 1. 06×106 mol-1. L. s-1(at pH 7. 8). The reaction mechanism is similar to that catalyzed by super-oxide dismutase.展开更多
The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·C...The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·ClO4·0. 5HCIO4·1. 5H2O was determined. Crystallographic data: Mr = 639.22,orthorhombic, space group Pcnb with a=11.743(4),b=16.446(2),c=29.611 (4) A,Z=8,V=5726(3) A3, Dc=1.482 g·cm-3, F(000)=1344,μ=9. 64 cm-1,R=0.063,and Rw=0.067 for 2386 reflections with I≥3σ(I). The structure shows an unusual configuration in which two carboxyl groups were bonded to two neighboring nitrogen atoms of the macrocycle, N1 and N4, and six methyl substituents occur on one side of the macrocycle, while two carboxyl groups on the other side, and central copper(Ⅱ) ion forms a five-coordinated geometry.展开更多
Two macrocyclic zinc(Ⅱ) complexes {[ZnL(VO3)2]·0.33H2O}n(1) and [ZnL(H2O)2][Ni(CN)4](2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been obtained from the reactions of [Z...Two macrocyclic zinc(Ⅱ) complexes {[ZnL(VO3)2]·0.33H2O}n(1) and [ZnL(H2O)2][Ni(CN)4](2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been obtained from the reactions of [ZnL](ClO4)2 with NH4VO3 and K2[Ni(CN)4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn(Ⅱ) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2+, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL(H2O)2]2+ and [Ni(CN)4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.展开更多
The reactions of chiral four-coordinated nickel(Ⅱ) complex [Ni(RR-L)](ClO4)2/[Ni(SS- L)](ClO4)2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni(RR-L)(β-d-HPhe)]...The reactions of chiral four-coordinated nickel(Ⅱ) complex [Ni(RR-L)](ClO4)2/[Ni(SS- L)](ClO4)2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni(RR-L)(β-d-HPhe)](ClO4)2(1) and [Ni(SS-L)(β-l-HPhe)](ClO4)2(2), respectively(L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine). Single-crystal X-ray diffraction analyses revealed that the nickel(Ⅱ) atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni(RR-L)(β-d-HPhe)]2+ and [Ni(SS-L)(β-l-HPhe)]2+ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.展开更多
The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO4)2(L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO...The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO4)2(L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O(1), [CuL]3[V(10)O(28)]·8H2O(2) and [Cu L]3[V6O(18)]·8H2O(3). Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O(18)]6- ring, [V(10)O(28)]6- cluster, and [V(12)O(35)]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2+ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O(18)]^6- rings in 1 and [V(12)O(35)]^10- rings in 3 into three-dimensional frameworks, respectively.展开更多
A new bicadmium(??) complex [Cd2L](ClO4)2?1.25H2O (C28H35Cd2Cl4N6O13.25) was synthesized and characterized by X-ray diffraction and ES mass spectral analyses. It crystallizes in the triclinic system, space gro...A new bicadmium(??) complex [Cd2L](ClO4)2?1.25H2O (C28H35Cd2Cl4N6O13.25) was synthesized and characterized by X-ray diffraction and ES mass spectral analyses. It crystallizes in the triclinic system, space group P1 with a = 15.630(3), b = 15.990(3), c = 16.330(3) ?, α = 89.90(3), β = 68.87(3), γ = 87.94(3)o, V = 3804.1(13) ?3, Mr = 1034.22, Z = 4, F(000) = 2060, Dc = 1.806 g/cm3, T = 293(2) K, μ = 1.468 mm-1 and λ = 0.71073 ?. The structure was refined to R = 0.0779 and wR = 0.1960 for 7034 observed reflections with I > 2σ(I).展开更多
Two complexes with formulas [Ni L][(Ni L)(IPA)2]·8H2O(1) and [(Ni L)(H2O)2] [(Ni L)(PMA)]·4H2O(2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane,IPA2– = isophthalic anion,P...Two complexes with formulas [Ni L][(Ni L)(IPA)2]·8H2O(1) and [(Ni L)(H2O)2] [(Ni L)(PMA)]·4H2O(2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane,IPA2– = isophthalic anion,PMA4– = 1,2,4,5-benzenetetracarboxylic anion) were synthesized and characterized by elemental analyses and IR spectra.The crystal structures were determined by X-ray diffraction.In complex 1,the [Ni L]^2+ bridged IPA^2– to give [(Ni L)(IPA)2]^2– monomer,and the [Ni L]^2+ bridged PMA4– to form a one-dimensional chain [(Ni L)(PMA)]n^2n– in complex 2.The [Ni L]^2+ and [(Ni L)(IPA)2]^2–/[(Ni L)(PMA)]^2– are connected through intermolecular hydrogen bonding to generate three-dimensional supramolecular structures.展开更多
A series of new macrocyclic dioxo 13 aneN 4 bearing various functional pendants, 2 methylfuran (LF), 2 methylthiophene (LT), 2 methylpyridine (LP), have been synthesized and characterized, where dioxo 13 aneN ...A series of new macrocyclic dioxo 13 aneN 4 bearing various functional pendants, 2 methylfuran (LF), 2 methylthiophene (LT), 2 methylpyridine (LP), have been synthesized and characterized, where dioxo 13 aneN 4 is 1,4,7,10 tetraazacyclotridecane 11,13 dione. The solution behaviours of the nickel(Ⅱ) complexes have been studied by Uv vis, cyclic voltammetric techniques. The red shifts were observed for the absorption band maxima of the electronic spectra from NiLR 1 to NiLR 2 (R=2 methylfuran, 2 methylthiophene, 2 methylpyridine). The value of E 1/2 of the NiLR 2 is less than NiLR 1 and both of them are lower than that of the nickel(Ⅱ) complex of the unsubstituted ligand, and these reasons are discussed.展开更多
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
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 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 copper(Ⅱ) complex [Cu2(MNA)2(2,2‘-bipy)2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid(MNA) and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It ...A new copper(Ⅱ) complex [Cu2(MNA)2(2,2‘-bipy)2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid(MNA) and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191(11),b = 12.8883(13),c = 16.1114(16) A,α = 70.8090(10),β = 80.568(2),γ = 77.440(2)o,V = 1984.3(4) A^3,Dc = 1.551 g/cm^3,Z = 2,F(000) = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η^1:η^0 3-carboxylate groups of MNA^2-.The coordination environment of Cu(Ⅱ) ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.展开更多
A novel copper(II) complex with the reduced Schiff base, [Cu(L)2]·H2O (I, HL = N-(4-hydroxybenzyl)-L-serine), was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ...A novel copper(II) complex with the reduced Schiff base, [Cu(L)2]·H2O (I, HL = N-(4-hydroxybenzyl)-L-serine), was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a = 8.9040(18), b = 9.1530(18), c = 24.891(5)A^°, V = 2028.6(7) A^°3, Z = 4, C20H26CuN2O9, Mr = 501.97, Dc = 1.644g·cm^3, μ = 1.135 mm^-1, F(000) = 1044, GOOF = 1.194, the final R = 0.0484 and wR = 0.1420 for 6186 observed reflections (I 〉 2σ(I)). In I, two L^- anions are coordinated to the copper ion in tridentate and bidentate chelating modes, respectively, resulting in the coordinated geometry of copper ion to be a distorted square pyramid. The intermolecular hydrogen bonds between the complexes, complexes and lattice water molecules lead to a 2D supramolecular network. The bioactivity of the complex as a potential PTPs inhibitory agent in vitro was investigated, displaying potent inhibition against PTP1B (IC50, 0.27 μM) and TCPTP (IC50, 0.57 μM) with a moderate selectivity.展开更多
A new dinuclear copper(II) complex [Cu2(L)2(phen)2]·5H2O (1) with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid (H2L) and 1,10-phenanthroline (phen) as ligands has been synthesized in the mixed sol...A new dinuclear copper(II) complex [Cu2(L)2(phen)2]·5H2O (1) with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid (H2L) and 1,10-phenanthroline (phen) as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925(4), b = 19.908(4), c = 11.235(2) A, β = 97.65(3)°, V= 3973.4(14) A3, Dc = 1.552 g/cm^3, Z = 8, F(000) = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 :η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.展开更多
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 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 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
文摘We studied the reaction kinetics of dismutation for superoxide ion by copper (Ⅱ) complex of macrocycllc dioxotetramine ligand 12- ( 4' - nitro )- benzyl-1,4,7,10- tetraazacy-clotridecane-11,13-dionato copper (Ⅱ) by using pulse radiolysis. The rate constants of dismutation kcat's were measured to be 1. 78×106 mor-1 . L.s-1(at pH 7. 0) and 1. 06×106 mol-1. L. s-1(at pH 7. 8). The reaction mechanism is similar to that catalyzed by super-oxide dismutase.
文摘The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·ClO4·0. 5HCIO4·1. 5H2O was determined. Crystallographic data: Mr = 639.22,orthorhombic, space group Pcnb with a=11.743(4),b=16.446(2),c=29.611 (4) A,Z=8,V=5726(3) A3, Dc=1.482 g·cm-3, F(000)=1344,μ=9. 64 cm-1,R=0.063,and Rw=0.067 for 2386 reflections with I≥3σ(I). The structure shows an unusual configuration in which two carboxyl groups were bonded to two neighboring nitrogen atoms of the macrocycle, N1 and N4, and six methyl substituents occur on one side of the macrocycle, while two carboxyl groups on the other side, and central copper(Ⅱ) ion forms a five-coordinated geometry.
基金supported by the Project for Undergraduate Research Study and Innovative Experiment of Hunan Provincial(2013-191)National Undergraduate Training Programs for Innovation and Entrepreneurship(201310551158)+4 种基金the Scientific Research Fund of Hunan Provincial Education Department(13B029,13A030)the Key Laboratory of Functional Organometallic Materials of Hunan Province College(13K09,13K10)the Program for Excellent Talents in Hunan University of Science and Engineeringthe Construct Program of the Key Discipline in Hunan Province(2011-76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province(2012-318)
文摘Two macrocyclic zinc(Ⅱ) complexes {[ZnL(VO3)2]·0.33H2O}n(1) and [ZnL(H2O)2][Ni(CN)4](2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been obtained from the reactions of [ZnL](ClO4)2 with NH4VO3 and K2[Ni(CN)4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn(Ⅱ) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2+, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL(H2O)2]2+ and [Ni(CN)4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.
基金Supported by the Scientific Research Fund of Hunan Provincial Education Department(13B029,13A030,13CY029)the Program for Excellent Talents in Hunan University of Science and Engineering(2013)+2 种基金the Construct Program of the Key Discipline in Hunan Province(2011-76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province(2012-318)NSF of Hunan(11JJ2009)
文摘The reactions of chiral four-coordinated nickel(Ⅱ) complex [Ni(RR-L)](ClO4)2/[Ni(SS- L)](ClO4)2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni(RR-L)(β-d-HPhe)](ClO4)2(1) and [Ni(SS-L)(β-l-HPhe)](ClO4)2(2), respectively(L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine). Single-crystal X-ray diffraction analyses revealed that the nickel(Ⅱ) atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni(RR-L)(β-d-HPhe)]2+ and [Ni(SS-L)(β-l-HPhe)]2+ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.
基金Supported by the Opening Project of Key Laboratory of Comprehensive Utilization of Advantage Plants Resources in Hunan South(XNZW14C08)the NSF of Hunan Province(2015JJ2072)+2 种基金the Construct Program of the Key Discipline in Hunan Provincethe Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Provincethe Project for Undergraduate Research Study and Innovative Experiment of Hunan Provincial(2016-283)
文摘The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO4)2(L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O(1), [CuL]3[V(10)O(28)]·8H2O(2) and [Cu L]3[V6O(18)]·8H2O(3). Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O(18)]6- ring, [V(10)O(28)]6- cluster, and [V(12)O(35)]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2+ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O(18)]^6- rings in 1 and [V(12)O(35)]^10- rings in 3 into three-dimensional frameworks, respectively.
基金This project was supported by the National Natural Science Foundation of China(No.50372028)
文摘A new bicadmium(??) complex [Cd2L](ClO4)2?1.25H2O (C28H35Cd2Cl4N6O13.25) was synthesized and characterized by X-ray diffraction and ES mass spectral analyses. It crystallizes in the triclinic system, space group P1 with a = 15.630(3), b = 15.990(3), c = 16.330(3) ?, α = 89.90(3), β = 68.87(3), γ = 87.94(3)o, V = 3804.1(13) ?3, Mr = 1034.22, Z = 4, F(000) = 2060, Dc = 1.806 g/cm3, T = 293(2) K, μ = 1.468 mm-1 and λ = 0.71073 ?. The structure was refined to R = 0.0779 and wR = 0.1960 for 7034 observed reflections with I > 2σ(I).
基金supported by the Natural Science Foundation of Hunan Province(2015JJ2072)the Key Laboratory of Comprehensive Utilization of Advantage Plants Resources in Hunan South(XNZW14C08)+1 种基金the Construct Program of the Key Discipline in Hunan Province(2011-76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province(2012-318)
文摘Two complexes with formulas [Ni L][(Ni L)(IPA)2]·8H2O(1) and [(Ni L)(H2O)2] [(Ni L)(PMA)]·4H2O(2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane,IPA2– = isophthalic anion,PMA4– = 1,2,4,5-benzenetetracarboxylic anion) were synthesized and characterized by elemental analyses and IR spectra.The crystal structures were determined by X-ray diffraction.In complex 1,the [Ni L]^2+ bridged IPA^2– to give [(Ni L)(IPA)2]^2– monomer,and the [Ni L]^2+ bridged PMA4– to form a one-dimensional chain [(Ni L)(PMA)]n^2n– in complex 2.The [Ni L]^2+ and [(Ni L)(IPA)2]^2–/[(Ni L)(PMA)]^2– are connected through intermolecular hydrogen bonding to generate three-dimensional supramolecular structures.
文摘A series of new macrocyclic dioxo 13 aneN 4 bearing various functional pendants, 2 methylfuran (LF), 2 methylthiophene (LT), 2 methylpyridine (LP), have been synthesized and characterized, where dioxo 13 aneN 4 is 1,4,7,10 tetraazacyclotridecane 11,13 dione. The solution behaviours of the nickel(Ⅱ) complexes have been studied by Uv vis, cyclic voltammetric techniques. The red shifts were observed for the absorption band maxima of the electronic spectra from NiLR 1 to NiLR 2 (R=2 methylfuran, 2 methylthiophene, 2 methylpyridine). The value of E 1/2 of the NiLR 2 is less than NiLR 1 and both of them are lower than that of the nickel(Ⅱ) complex of the unsubstituted ligand, and these reasons are discussed.
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 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 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 Natural Science Foundation of Hunan Province(No.11JJ9006)Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)the Construct Program of the Key Discipline in Hunan Province
文摘A new copper(Ⅱ) complex [Cu2(MNA)2(2,2‘-bipy)2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid(MNA) and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191(11),b = 12.8883(13),c = 16.1114(16) A,α = 70.8090(10),β = 80.568(2),γ = 77.440(2)o,V = 1984.3(4) A^3,Dc = 1.551 g/cm^3,Z = 2,F(000) = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η^1:η^0 3-carboxylate groups of MNA^2-.The coordination environment of Cu(Ⅱ) ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.
基金Supported by NNSFC(Nos.21271121,21471092,21571118)
文摘A novel copper(II) complex with the reduced Schiff base, [Cu(L)2]·H2O (I, HL = N-(4-hydroxybenzyl)-L-serine), was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a = 8.9040(18), b = 9.1530(18), c = 24.891(5)A^°, V = 2028.6(7) A^°3, Z = 4, C20H26CuN2O9, Mr = 501.97, Dc = 1.644g·cm^3, μ = 1.135 mm^-1, F(000) = 1044, GOOF = 1.194, the final R = 0.0484 and wR = 0.1420 for 6186 observed reflections (I 〉 2σ(I)). In I, two L^- anions are coordinated to the copper ion in tridentate and bidentate chelating modes, respectively, resulting in the coordinated geometry of copper ion to be a distorted square pyramid. The intermolecular hydrogen bonds between the complexes, complexes and lattice water molecules lead to a 2D supramolecular network. The bioactivity of the complex as a potential PTPs inhibitory agent in vitro was investigated, displaying potent inhibition against PTP1B (IC50, 0.27 μM) and TCPTP (IC50, 0.57 μM) with a moderate selectivity.
基金Supported by the Construct Program of the Key Discipline in Hunan Province and Key Project of Production Plan of Hengyang City(2013)
文摘A new dinuclear copper(II) complex [Cu2(L)2(phen)2]·5H2O (1) with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid (H2L) and 1,10-phenanthroline (phen) as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925(4), b = 19.908(4), c = 11.235(2) A, β = 97.65(3)°, V= 3973.4(14) A3, Dc = 1.552 g/cm^3, Z = 8, F(000) = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 :η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.
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.