A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]py...A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.展开更多
Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron...Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.展开更多
The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
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
Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal s...Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.展开更多
The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The resul...The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40℃, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60℃, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80℃, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar-quartz-copper-iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar-quartz-copper-iron colloid.展开更多
In the present investigation, the novel copper Schiff base complex was synthesized and its catalytic activity was evaluated for the ring-opening polymerization （ROP） of lactide and block polymerization of poly（lact...In the present investigation, the novel copper Schiff base complex was synthesized and its catalytic activity was evaluated for the ring-opening polymerization （ROP） of lactide and block polymerization of poly（lactide） with po/y（ethylene glycol）methyl ether,展开更多
A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in ...A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 21.680(4), b = 20.680(4), c = 26.120(5) ?, V = 11711(4) ?3, Dc = 3.972 g/cm3, Z = 8, μ(MoKa) = 24.661 mm?1, F(000) = 12440, the final R = 0.0527 and wR = 0.1416 for 11527 observed reflec- tions with I > 2σ(I). The crystal structure is composed of [{Cu(en)2}HPW12O40]2? anions, discrete [Cu(en)2H2O]+ complex cations and crystal water molecules, which are held together into a three- dimensional network through hydrogen-bonding interactions. The anionic [{Cu(en)2}HPW12O40]2? is formed by the mixed valance {HPWVI11WVO40}3? Keggin unit covalently linked by a {Cu(en)2}+ group.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 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
Introduction Nucleases which catalyze the hydrolytic cleavage of the phosphodiester backbone of DNA and RN A play animportant role in the molecular genetics and genetic engineering.The development of reagents which hy...Introduction Nucleases which catalyze the hydrolytic cleavage of the phosphodiester backbone of DNA and RN A play animportant role in the molecular genetics and genetic engineering.The development of reagents which hydrolytically cleave nucleic acids under mild conditions has currently been attracting great interest in the field of artificial nucleases"",for example,the small metal complexes that promote the hydrolysis of DNA and RNA are useful not only in molecular biology and drug design but also in elucidating the role of metal ions in enzyme catalysis.展开更多
Heavy metals and ammonia are difficult to remove from wastewater,as they easily combine into refractory complexes.The struvite formation method（SFM） was applied for the complex decomposition and simultaneous removal...Heavy metals and ammonia are difficult to remove from wastewater,as they easily combine into refractory complexes.The struvite formation method（SFM） was applied for the complex decomposition and simultaneous removal of heavy metal and ammonia.The results indicated that ammonia deprivation by SFM was the key factor leading to the decomposition of the copper-ammonia complex ion.Ammonia was separated from solution as crystalline struvite,and the copper mainly co-precipitated as copper hydroxide together with struvite.Hydrogen bonding and electrostatic attraction were considered to be the main surface interactions between struvite and copper hydroxide.Hydrogen bonding was concluded to be the key factor leading to the co-precipitation.In addition,incorporation of copper ions into the struvite crystal also occurred during the treatment process.展开更多
The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic ...The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic parameters: a = 7.4161(2), b = 8.1754(3), c = 10.7545(4) ? a = 92.958(2), b = 109.978(1), g = 93.369(2)? V = 609.96(4) ?, C20H20N10CuO8, Mr = 592.00, Dc = 1.612 g/cm3, m(MoKa) = 0.964 mm-1, F(000) = 303, Z = 1, the final R = 0.0494 and wR = 0.1269 for 1945 observed reflections (I > 2s(I)). X-ray analysis reveals that the Cu atom adopts a distorted octahedral (4 + 2) coordination. The four closer donor atoms include two N atoms of 3,3?azpy and two O atoms of the coordination aqua with the CuN and CuO distances of 2.014(3) and 1.974(3) ? respectively. Two longer out-of-plane CuO bonds (2.450(3) ? from nitrate complete the strongly distorted octahedral coordination of the Cu atom. Hydrogen bonds are formed through H atoms of each coordination aqua with the remaining N atoms of 3,3?azpy and O atoms of nitrate. A two-dimensional network is constructed by hydrogen bonds and p-p interactions.展开更多
The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been s...The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.展开更多
An unusual inorganic-organic hybrid hexatungstate complex [Cu（phen）3][W6O19] 1 （C36H24 CuN6O19W6, Mr= 2011.20） was hydrothermally synthesized and characterized by singlecrystal X-ray diffraction, IR spectrum, UV-V...An unusual inorganic-organic hybrid hexatungstate complex [Cu（phen）3][W6O19] 1 （C36H24 CuN6O19W6, Mr= 2011.20） was hydrothermally synthesized and characterized by singlecrystal X-ray diffraction, IR spectrum, UV-VIS spectrum and elemental analyses. This compound crystallizes in the monoclinic system, space group C2/c with a = 19.1005（11）, b = 11.2585（11）, c = 20.2867（15） A, β= 102.177（2）°, V= 4264.4 A^ 3, μ（MoKa） = 16.691 mm^-1, Dc = 3.133 g/cm^3, Z = 4, F（000） = 3628, the final R = 0.0338 and wR = 0.0798 for 4090 observed reflections with I 〉 2σ（I）. The result of structure determination shows that the crystal structure is constructed from [W6O19]^2- cluster anions and [Cu（phen）3]^2＋ complex fragments, which are held together into a three-dimensional network through hydrogen-bonding interactions.展开更多
A new ternary copper（Ⅱ） complex, [C43H27Cu2N7O5][C14H6CuN2O8]＇6.5H2O, has been synthesized by the reaction of copper sulfate, 2,6-pyridinedicarboxylic acid and 1,10- phenanthroline （phen）, and characterized by e...A new ternary copper（Ⅱ） complex, [C43H27Cu2N7O5][C14H6CuN2O8]＇6.5H2O, has been synthesized by the reaction of copper sulfate, 2,6-pyridinedicarboxylic acid and 1,10- phenanthroline （phen）, and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. It crystallizes in triclinic, space group P1, with a = 14.379（5）, b = 15.510（5）, c = 15.835（6） A, a = 78.567（6）, β = 63.594（6）, y = 81.287（6）°, V= 3092.1（19） A3, C57H46Cn3N9O19.5, Mr = 1359.54, Z = 2, Dc = 1.446 Mg/m3, λ（MoKa） = 0.71073 A,μ = 1.101 mm^-1, F（000） = 1362, S = 1.071, the final R = 0.0718 and wR = 0.11960 for 10705 observer reflections （I 〉 2σ（I））. The structure unit of the title complex consisfs of a mononuclear part and a di-nuclear part, and the three copper ions show three coordination modes. Each 6-coordinated geometry of the Cu atom is a distorted octahedral coordination geometry. The 3D supramolecular system is formed by the hydrogen bond O-H-O and π-π stacking interaction between neighboring single cells. The antibacterial activity of the title complex is also studied.展开更多
The chelate complex of Cu2＋ with 2-hydroxy-（4-methylthio）butanoate（MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA） is an e...The chelate complex of Cu2＋ with 2-hydroxy-（4-methylthio）butanoate（MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA） is an efficient, bioavailable trace mineral additive for animal feeding. The structure of MHA-H copper chelate was investigated by single-crystal X-ray diffraction. The crystal structure（C10H18Cu O6S2, 1, monoclinic, space group P21/c, Z = 2, a = 16.158（4）, b = 4.9733（12）, c = 9.159（2） ？, β = 104.786（4）°） exhibits that two MHA-H ligands coordinate with a CuII ion to form a square-planar environment completed to an octahedron through interaction with carbonyl oxygens of neighboring molecules, which expand to constitute a two-dimensional sheet coordination network. And a separation between the hydrophilic and lipophilic moieties like micelles was found in the packing structure. X-ray powder diffraction and thermogravimetric analysis were used to study the phase purity of the bulk sample and thermostability of complex 1, respectively.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 new copper complex { [Cu（CH3COO）2（bbtz）]（H2O）2 }, 1 （bbtz = 1,4-bis（ 1,2,4- triazol-1-ylmethyl）benzene） was synthesized and the structure was determined by single-crystal X-ray diffraction. Crystal data...The new copper complex { [Cu（CH3COO）2（bbtz）]（H2O）2 }, 1 （bbtz = 1,4-bis（ 1,2,4- triazol-1-ylmethyl）benzene） was synthesized and the structure was determined by single-crystal X-ray diffraction. Crystal data： C16H22CuN6O6, monoclinic, space group P21/n, a = 12.589（5）, b = 6.455（2）, c = 12.677（5） A, β= 98.748（9）°, V= 1018.2（7） A^3, Mr = 457.95, Z = 2, Dc= 1.494 g/cm^3, F（000） = 474, μ = 1.118 mm^-1, R = 0.0463 and wR = 0.0939 for 1971 observed reflections with I 〉 2σ（I）. The crystal structure of 1 is a one-dimensional chain via the bridging flexible ligand bbtz.展开更多
文摘A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.
文摘Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
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.
文摘Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.
基金Project(U1608254) supported by the Special Fund for the National Natural Science Foundation of ChinaProjects(ZJKY2017(B)KFJJ01,ZJKY2017(B)KFJJ02) supported by Zijin Mining Group Co.,Ltd.,China
文摘The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40℃, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60℃, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80℃, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar-quartz-copper-iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar-quartz-copper-iron colloid.
文摘In the present investigation, the novel copper Schiff base complex was synthesized and its catalytic activity was evaluated for the ring-opening polymerization （ROP） of lactide and block polymerization of poly（lactide） with po/y（ethylene glycol）methyl ether,
基金This work was supported by the Natural Science Foundation of Fujian Province (No. E0420001) and the Science Foundation of Huaqiao University (No. 03HZR9)
文摘A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 21.680(4), b = 20.680(4), c = 26.120(5) ?, V = 11711(4) ?3, Dc = 3.972 g/cm3, Z = 8, μ(MoKa) = 24.661 mm?1, F(000) = 12440, the final R = 0.0527 and wR = 0.1416 for 11527 observed reflec- tions with I > 2σ(I). The crystal structure is composed of [{Cu(en)2}HPW12O40]2? anions, discrete [Cu(en)2H2O]+ complex cations and crystal water molecules, which are held together into a three- dimensional network through hydrogen-bonding interactions. The anionic [{Cu(en)2}HPW12O40]2? is formed by the mixed valance {HPWVI11WVO40}3? Keggin unit covalently linked by a {Cu(en)2}+ group.
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.
文摘Introduction Nucleases which catalyze the hydrolytic cleavage of the phosphodiester backbone of DNA and RN A play animportant role in the molecular genetics and genetic engineering.The development of reagents which hydrolytically cleave nucleic acids under mild conditions has currently been attracting great interest in the field of artificial nucleases"",for example,the small metal complexes that promote the hydrolysis of DNA and RNA are useful not only in molecular biology and drug design but also in elucidating the role of metal ions in enzyme catalysis.
基金supported by the National Natural Science Foundation of China(No.51204213)the Key Project of Science and Technology of Hunan Province(No.2013WK2007)the Innovation Stimulating Program of Central South University(No.2015CX001)
文摘Heavy metals and ammonia are difficult to remove from wastewater,as they easily combine into refractory complexes.The struvite formation method（SFM） was applied for the complex decomposition and simultaneous removal of heavy metal and ammonia.The results indicated that ammonia deprivation by SFM was the key factor leading to the decomposition of the copper-ammonia complex ion.Ammonia was separated from solution as crystalline struvite,and the copper mainly co-precipitated as copper hydroxide together with struvite.Hydrogen bonding and electrostatic attraction were considered to be the main surface interactions between struvite and copper hydroxide.Hydrogen bonding was concluded to be the key factor leading to the co-precipitation.In addition,incorporation of copper ions into the struvite crystal also occurred during the treatment process.
基金the funds of the Key Laboratory of Organic Syntheses of Jiansu province, and the funds of the State Key Laboratory of Structural Chemistry
文摘The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic parameters: a = 7.4161(2), b = 8.1754(3), c = 10.7545(4) ? a = 92.958(2), b = 109.978(1), g = 93.369(2)? V = 609.96(4) ?, C20H20N10CuO8, Mr = 592.00, Dc = 1.612 g/cm3, m(MoKa) = 0.964 mm-1, F(000) = 303, Z = 1, the final R = 0.0494 and wR = 0.1269 for 1945 observed reflections (I > 2s(I)). X-ray analysis reveals that the Cu atom adopts a distorted octahedral (4 + 2) coordination. The four closer donor atoms include two N atoms of 3,3?azpy and two O atoms of the coordination aqua with the CuN and CuO distances of 2.014(3) and 1.974(3) ? respectively. Two longer out-of-plane CuO bonds (2.450(3) ? from nitrate complete the strongly distorted octahedral coordination of the Cu atom. Hydrogen bonds are formed through H atoms of each coordination aqua with the remaining N atoms of 3,3?azpy and O atoms of nitrate. A two-dimensional network is constructed by hydrogen bonds and p-p interactions.
基金This work was supported by the Scientific Research Common Program of Beijing Municipal Commission of Education (KM20051028005)
文摘The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.
文摘An unusual inorganic-organic hybrid hexatungstate complex [Cu（phen）3][W6O19] 1 （C36H24 CuN6O19W6, Mr= 2011.20） was hydrothermally synthesized and characterized by singlecrystal X-ray diffraction, IR spectrum, UV-VIS spectrum and elemental analyses. This compound crystallizes in the monoclinic system, space group C2/c with a = 19.1005（11）, b = 11.2585（11）, c = 20.2867（15） A, β= 102.177（2）°, V= 4264.4 A^ 3, μ（MoKa） = 16.691 mm^-1, Dc = 3.133 g/cm^3, Z = 4, F（000） = 3628, the final R = 0.0338 and wR = 0.0798 for 4090 observed reflections with I 〉 2σ（I）. The result of structure determination shows that the crystal structure is constructed from [W6O19]^2- cluster anions and [Cu（phen）3]^2＋ complex fragments, which are held together into a three-dimensional network through hydrogen-bonding interactions.
文摘A new ternary copper（Ⅱ） complex, [C43H27Cu2N7O5][C14H6CuN2O8]＇6.5H2O, has been synthesized by the reaction of copper sulfate, 2,6-pyridinedicarboxylic acid and 1,10- phenanthroline （phen）, and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. It crystallizes in triclinic, space group P1, with a = 14.379（5）, b = 15.510（5）, c = 15.835（6） A, a = 78.567（6）, β = 63.594（6）, y = 81.287（6）°, V= 3092.1（19） A3, C57H46Cn3N9O19.5, Mr = 1359.54, Z = 2, Dc = 1.446 Mg/m3, λ（MoKa） = 0.71073 A,μ = 1.101 mm^-1, F（000） = 1362, S = 1.071, the final R = 0.0718 and wR = 0.11960 for 10705 observer reflections （I 〉 2σ（I））. The structure unit of the title complex consisfs of a mononuclear part and a di-nuclear part, and the three copper ions show three coordination modes. Each 6-coordinated geometry of the Cu atom is a distorted octahedral coordination geometry. The 3D supramolecular system is formed by the hydrogen bond O-H-O and π-π stacking interaction between neighboring single cells. The antibacterial activity of the title complex is also studied.
基金supported by the National Natural Science Foundation of China (No. 21301139,21373158,21103135,51304158)Scientific Research Program Funded by Shaanxi Provincial Education Department (No. 2013JK0651)+1 种基金the Scientific Research Cultivating Fund (No. 201221)the Doctoral Starting Fund (No. 2014QDJ004) from Xi'an University of Science and Technology
文摘The chelate complex of Cu2＋ with 2-hydroxy-（4-methylthio）butanoate（MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA） is an efficient, bioavailable trace mineral additive for animal feeding. The structure of MHA-H copper chelate was investigated by single-crystal X-ray diffraction. The crystal structure（C10H18Cu O6S2, 1, monoclinic, space group P21/c, Z = 2, a = 16.158（4）, b = 4.9733（12）, c = 9.159（2） ？, β = 104.786（4）°） exhibits that two MHA-H ligands coordinate with a CuII ion to form a square-planar environment completed to an octahedron through interaction with carbonyl oxygens of neighboring molecules, which expand to constitute a two-dimensional sheet coordination network. And a separation between the hydrophilic and lipophilic moieties like micelles was found in the packing structure. X-ray powder diffraction and thermogravimetric analysis were used to study the phase purity of the bulk sample and thermostability of complex 1, respectively.
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 supported by the Natural Science Foundation of Universities of Jiangsu Province (No. 03KJB150118) ② Corresponding author. Fax: +86-512-65224783, E-mail: blli1965@pub.sz.jsinfo.net
文摘The new copper complex { [Cu（CH3COO）2（bbtz）]（H2O）2 }, 1 （bbtz = 1,4-bis（ 1,2,4- triazol-1-ylmethyl）benzene） was synthesized and the structure was determined by single-crystal X-ray diffraction. Crystal data： C16H22CuN6O6, monoclinic, space group P21/n, a = 12.589（5）, b = 6.455（2）, c = 12.677（5） A, β= 98.748（9）°, V= 1018.2（7） A^3, Mr = 457.95, Z = 2, Dc= 1.494 g/cm^3, F（000） = 474, μ = 1.118 mm^-1, R = 0.0463 and wR = 0.0939 for 1971 observed reflections with I 〉 2σ（I）. The crystal structure of 1 is a one-dimensional chain via the bridging flexible ligand bbtz.
