Effects of binuclear copper(Ⅱ)threonine complex on blood glucose, lipids and protection of the hearts and kidneys in diabetic mice

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.

Crystal Structure and Molecular Structure of Binuclear Copper(Ⅱ) Complex, [Cu (C_5H_5NO) (C_6H_5COO)_2]_2

At room temperature, dibenzoyl peroxide and pyridine N-oxide reacted with metallic copper powder in a mixed solvent(dichloromethane, trichloromethane and tetrahydrofuran), resulting in a binuclear copper(Ⅱ) complex. [Cu (C_5H_5NO)-(C_6H_5COO)_2]_2. The structure of the complex was characterized by elemental analyses.IR spectra and X-ray single crystal analysis. The crystal is triclinic, space group P1,with cell parameters . a= 9. 262(4) ,b= 10. 697(2) , c=10. 881 (3 )A , a=59. 60( 2 ),β= 74. 83 ( 3 ) .Y = 72. 80 ( 2 )°. V= 880. 0 A￣3 . D_c = 1 . 5 20 g/cm￣3 . Z = 1 . μ= 1 2. 7 cm-1, R=0. 044 ,R_w=0. 048 for 3477 reflections with I>3σ(I), M_r=805. 78. Each copper(Ⅱ) atom is coordinated by four bridging bidentate benzoate ligands and one pyridine M-oxide.

Synthesis, Crystal Structure and Properties of a New Binuclear Copper(Ⅱ) Complex with 5-Oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic Acid(TNCA)

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.

Synthesis, Structure and Spectral Characterization of a Discrete Binuclear Copper (II) Complex

A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffraction study and IR spectroscopy. The crystal is monoclinic, space group: P2 1/n, with unit cell parameters: a=8.2952(2), b=18.4633(3), c=10.5049(2) . β=108.965(1)°, V=1521.56(5) 3, Z=2, C 22 H 30 N 8O 10 Cl 2Cu 2, M r =764.52, D c =1.669 Mg/m 3, F(000)=780, μ (Mo Kα )=8.60, T =293(2)K, final R=0.0623, wR =0.1536 for 2660 observed reflections with I>2.0σ(I ). The centrosymmetric complex Cu 2(CH 3O) 2(C 5H 6N 2) 4(ClO 4) 2 comprises a pair of Cu(II) atoms bridged by two methanoxo and N coordination 2 aminopyridine. The Cu(II)…Cu(II) distance is 3\^002(1).

Synthesis and Crystal Structure of Binuclear Copper (Ⅱ) Complex Containing (Dimethylaminomethyl)ferrocene

A binuclear complex including ferrocenyl, Cu2{Fe(C5H5)[C5H4CH2N(CH3)2]}2 (CH3COO)4, was synthesized and characterized by X-ray diffraction. The title complex crystallizes in triclinic, space group P with a = 8.2779(8), b = 9.4830(8), c = 12.262(1) ? = 81.079(5), b = 80.620(4), g = 78.960(4), V = 924.4(1) 3, Z = 1, C34H46Cu2Fe2N2O8, Mr = 849.51, Dc = 1.526 g/cm3, l(MoK) = 0.71073 ? ?= 1.954 mm-1, F(000) = 438, R = 0.0297 and wR = 0.0901. Both cyclopentadienyl rings in each dmaf (dmaf = (dimethylaminomethyl)ferrocene, Fe(C5H5)- [C5H4CH2N(CH3)2]) have an eclipsed conformation. The binuclear molecule has a crystallographic centrosymmetry; four acetates and two Cu atoms form a cage structure with the distance between two neighboring Cu atoms of 2.655(1) .

MAGNETIC PROPERTIES OF BINUCLEAR COPPER COMPLEX WITH PICOLINALDEHYDE N-OXIDE THIOSEMICARBAZONE

Recently there is great interest in the study of magnetic exchange interactions in polynuclear transition metal complexes, especially the magneto-structural correlations and exchange mechanism, because these studies may be helpful in understanding the electron transfer pathway in biological systems and the mechanism of oxidation-reduction reactions, and also in exploring the new magnetic materials.

Synthesis, Properties and Structureof a Novel Unsymmetrical Bis (phenoxo) BridgedBinuclear Copper (Ⅱ) Complex

A novel bis (phenoxo) bridged binuclear copper ( II) complex with dissimilar coordination environments was synthesized and characterized by spectroscopies and X-ray crystallography. It crystallized in the monoclinic system with space group C2/c, a=2. 241 1(2) nm, b=1. 834 2 (2) nm, c=1.877 9(2) nm, β=122.861(2)°, V=6.484 3(11) nm3, Z=8. Itconsistsof two unsymmetrical Cu (Ⅱ ) centers bridged by two phenolic oxygen atoms to yield a Cu2O2 core with the Cu-Cu separation of 0. 310 2 nm, in which Cul and Cu2 ions exhibit distorted N2O3 and N3O2 square pyramidal geometries, respectively.

Hydrothermal Synthesis and Crystal Structure of Binuclear Copper(Ⅱ) Complex Bridged by 1,2,4,5- Benzenetetracarboxylato Trivalent Anion

The title complex [(phen) 2Cu(Htcb)Cu(phen) 2]H 3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.

Syntheses of Binuclear Copper(I) Complexes Containing Benzimidazole

A binuclear copper（I） complex [Cu2（dppm）2（C7H6N2）2]（NO3）2 （C7H6N2 = benzimidazole, dppm = Ph2PCH2PPh2） has been synthesized and characterized by X-ray crystallography.The crystal belongs to monoclinic, space group C2/c with a = 14.167（3）, b = 21.209（4）, c =20.680（4）A°, β = 103.93（3）°, C32H28CuN3O3P2, Mr = 628.05, Z = 8, μ = 0.868 mm^-1, V = 6031 （2） ,A°^3,F（000） = 2592, De= 1.383 g/cm^3, R = 0.0593 and wR = 0.1736. A total of 5297 independent reflections were collected, of which 3503 were observed with 1 〉 2σ（/）. The central copper atom is tri-coordinated by phosphorus atoms from bridging dppm and nitrogen atom from benzimidazole. In the coordination sphere, the bond lengths of Cu-P（1） and Cu-P（2） are 2.2607（17） and 2.2503（16） A°,respectively and the P-Cu-P bond angle is 127.26（6）°.

Synthesis and Crystal Structure of Binuclear Complex of Copper(Ⅱ)Chloroacetate with Acetamine

The title complex, Cu 2(O 2CCH 2Cl) 4 OC(NH 2)CH 3 2, crystallizes in space group P2 1/a with a=7.616(4), b=18.665(5), c=7.949(5) , β=106.29(5)°. V=1084(1) 3, Z=2, M r=619.19, D c =1.896 g/cm 3; μ =25.05 cm -1 and F(000)=620.00, R =0.045 and R w =0.054 for 1807 observable reflections. X ray crystal structure analysis revealed that two Cu atoms are bridged by four chloroacetate groups, and the acetamine ligands are bonded by O(carboxide) to the terminal Cu atoms of each dimeric unit. The coordination geometry of Cu atom is a distorted octahedral configuration. The distance between the two Cu atoms is 2.648(1) .

DNA Cleavage of the Copper(II) Complexes with a Polyamine Ditopic Ligand

A new binuclear complex [Cu2L(OH)](ClO4)3·2H2O has been synthesized and characterized, where L=2,6-bis{[bis-(2-aminoethyl)amino]methyl}-benzene. In the presence of 0.5 mmol/L complex at pH 8.10 and 37°C, the complex can efficiently cleavage pBR322 DNA with a rate constant kobs of 1.35×10-4 s-1. The cleavage occurred by a non-oxidative mechanism showing activity to be dependent on pH.

Synthesis and Crystal Structure of Bridging Complex [Cu_2(bipy)_2·OAc·Cl·OH]·TsTausH·3H_2O

The title complex [Cu2(bipy)2OAcClOH]TsTausH3H2O(C31H37Cl- Cu2N5O11S2) has been synthesized by the reaction of 2,2?bipyridine(bipy), N-P-tolysulfony taurine (TsTausH) and copper acetate in water-ethanol solution, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to triclinic, space group P with a = 0.74485(14), b = 1.6094(3), c = 1.7472(3) nm, a = 114.662(4), b = 99.997(4), g = 93.218(4), V = 1.8551(6) nm3, Mr = 882.31, Z = 2, Dc = 1.580 g/cm3, m = 1.395 mm-1 and F(000) = 906. The complex is a binuclear copper compound, and the two copper ions nearly have the same coordination environment. There exists MM bond in the complex. The distance of Cu(1)Cu(2) is 0.29747(7) nm. The two ions form two distorted octahedral geometries.

Synthesis and Crystal Structure of Tetrabonzoato Bis （2－Aminothiazol） Dicopper（Ⅱ）

Reaction of Cu with dibenzovi peroxide, 2-aminothiazol gave a binuclear complex [Cu_2 (C_6H_5COO)_4(C_3H_4N_2S)_2]. Crystal of the title compound is monoclinic system space group P2_1/n , M_r = 807. 84 with cell parameters a= 10. 685 ( 1 ), b=19. 028(6), c=17. 046(9) , β=96. 49(33)￣°, Z=4, V=3443. 4, D_c=1. 565 g/cm￣-3, μ= 14. 078 cm￣-1, F(000)= 824. The final refinement with 3429 observed reflections is converged with R= 0. 046 and R_w=0. 053. X-ray crystal structure analysis revealed that each copper ion is coordinated by four bridging birfentate benzoate ligandsand one Zaminothiazol to form a binuclear molecule. In the crvstal, there are intramolecular hydrogen bonds N (1)- H ( 1 )-O(4) and N (3)- H (3)-O(1) with NO distance of 3. 005, N-H-O angle of 131. 9°.

Synthesis, structure and characterization of binuclear copper(Ⅱ) complexes

At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry.

Synthesis and magnetic properties of μ-phenolato copper (Ⅱ) binuclear complexes with different exogenous bridges

The syntheses and magnetic properties are reported for a series of copper(Ⅱ) complexes prepared from a pentadentate binucleating ligand 2,6-diformyl-4-methylphenol di(benzoyl-hydrazone) (H3L). These complexes incorporate different exogenous ions (X-) into a bridging position to form copper(Ⅱ) binuclear complexes of the formula [Cu2(H2L)X]2+, where X-= Br-(1), Cl-(2), HO-(3), C2H5O-(4) and C3H3N2- (5). The complexes have been characterized with variable temperature magnetic susceptibility (4.2-300 K) and the observed data were fit to those from a modified Bleaney-Bowers equation by least-squares method, giving the exchange integral 2J = -6.2 cm-1 for 1, -76.4 cm-1 for 2, -241.9 cm-1 for 3, -231.1 cm-1 for 4 and -343.8 cm-1 for 5. This suggested that there is an antiferromagnetic interaction between the Cu(Ⅱ) ions and the sequence of the effect of some exogenous bridging ligands on magnetic coupling is corresponding to that in spectrochemical series.

Synthesis and magnetic properties of copper(Ⅱ)-lanthanoid(Ⅲ) binuclear complexes with N,N'-bis(3-aminopropyl) oxamido ligand

Six novel u-oxamido binuclear complexes, namely Cu(oxpn)Ln(L)2(ClO4)3 (Ln: Eu, Gd, Tb, Nd, Ho, Er), where oxpn is N,N'-bis(3-aminopropyl) oxamido, L denotes 5-nitro-1,10-phenanthroline (abbreviated as NO2-phen), have been synthesized and characterized. The magnetic susceptibility of complexes Cu(oxpn)Gd(NO2-phen)2(ClO4)3.2H2O was measured over the 4-300 K and the observed data were successfully simulated by equation based on spin Hamil-tonian operator (H = -2JS1.S2), giving the exchange integral J(Cu-Gd)=-1.62 cm-1. This indicates a weak antiferromagnetic interaction between the Cu(Ⅱ) and Gd(Ⅲ) ions.

Synthesis, Structure and Magnetic Properties of a Diphenoxo-bridged Binuclear Copper(II) Complex

A mixed-ligand copper(Ⅱ) complex [Cu_2 (phen)_2 (HL^1 )_2]-(ClO_4)_2 (1) wassynthesized. X-ray analyses reveal that 1 has a bis (μ_2-phenoxo)-bridged dicopper(Ⅱ) structure.2D hydrogen-bonded network is formed utilizing the N―H, O―H and C―H groups of the (HL^1)^-ligands (H_2L^1 = N-(2-hydroxybenzyl) ethanolamine), the C―H groups of the phenan-throlines and theperchlorate anions. Variable temperature magnetic properties of 1 have shown comparatively weakanti-ferromagnetic interactions with respect to the bridge angles, which have been ascribed to theunfavorable overlaps of the magnetic orbitals for the highly distorted copper coordination polyhedraand the pyramidal distortions at the phenoxo oxygen atoms.

Exogenous bridge and tautomer effects on magnetic interaction of binuclear copper(II) complexes of μ-phenolato Schiff bases

<正> Four enol-form binuclear copper complexes with different exogenous bridges, [Cu2(L)(μ-Cl)] (1), [Cu(L)(μ-N3)]· DMF (2), [Cu2(L)(μ-OCH3)] (3) and [Cu2(L)(μ-C3H3N2)]· 1/2C2H5OH (4), where L is the trivalence anion of binucleating ligand 2,6-diformyl-4-methylphenol di(tenzoylhydrazone), have been synthesized and characterized. Crystal data for complex (3) are as follows: space group P1- , a=0.8294(1), 6=0.9333(3), c= 1.473 6(6) nm, α=79.51(3)°, β=80.93(2)°,γ=81.32(2)°, Z=1. The magnetic measurements indicated that the effect of exogenous bridging ligands on magnetic interaction is corresponding to that in spectrochemical series. The effect of enol- and keto-form tautomer on magnetic interaction was explained from the point of view of structural factors and electron effects by using molecular mechanks and quantum chemistry calculations.

SYNTHESIS, STRUCTURE AND MAGNETISM OF μ-OXAMIDO BINUCLEAR COPPER(Ⅱ) COMPLEXES

<正> Two new binuclear copper（Ⅱ） complexes, [Cu（oxpn）CuL]（ClO4）2, have been synthesizedand characterized, where oxpn is N,N’ bis（3-aminopropyl）oxamido and L is 1,10-phenan-throline （phen） or 5-nitro-1,10-phenanthroline （NO2-phen）. The crystal structure and vari-able-temperature magnetic susceptibility （4- 300 K） of the Complex （L=phen） have beendetermined. Crystal data: orthorhombic system, space group Pnma, with a = 10.433（1）, b11.458（2）, c = 21.999（2）A, z = 4. Every copper（Ⅱ） ion is in a square pyramidal environment.The two copper（Ⅱ） ions are linked by μ-oxamido bridge and the separation of them is 5.208A. The singlet-triplet energy gap J was found equal to -452.92cm-1, indicating that astrongantiferromagnetic spin-exchange interaction operates between the copper（Ⅱ） ions.

Solvothermal Synthesis, Crystal Structure and Characterization of a New Binuclear Copper(Ⅱ) Complex with K^(3):N^(1):N^(2):N^(4)-3-(Pyridin-2-yl)-1,2,4-triazole(HPT)

A new binuclear copper(Ⅱ)complex[Cu_(2)(MBBA)_(2)(HPT)_(2)(H_(2)O)_(2)]·2H_(2)O(1)was synthesized with copper acetate,2-(4-methylbenzoyl)benzoic acid(MBBA)and 3-(pyridin-2-yl)-1H-1,2,4-triazole(HPT).It crystallizes in the monoclinic space group P21/c with a=14.722(2),b=8.8907(12),c=18.5565(18)A,β=116.820(7)o,V=2167.6(5)A^(3),Mr=483.96,Dc=1.483 g/cm^(3),Z=4,μ(Mo Ka)=1.049 mm^(-1),F(000)=981,the final GOOF=0.952,R=0.0586 and w R=0.0823.The whole molecule consists of two copper ions bridged by two HPT molecules.The central Cu(Ⅱ)ion is coordinated by six atoms to give a distorted octahedral coordination geometry.The structure of 1 has been determined by X-ray diffraction,IR spectrum and thermal stability analysis.The solid-state fluorescence displays an obvious emission band at 412 nm upon excitation at 330 nm.Magnetic properties indicate that 1 exhibits antiferromagnetic properties.