新型salamo衍生物苦味酸铜(Ⅱ)配合物的合成与表征

以丙酮为溶剂,1,3-二胺氧丙烷双缩邻香草醛(H2L)与苦味酸铜反应,制备了一种新型salamo衍生物苦味酸铜(Ⅱ)配合物,其结构经元素分析,1HNMR,IR,TG-DTA及UV表征。结果表明,新型salamo衍生物是一种四齿配体,配合物的可能结构式为[Cu4L2(pic)4(H2O)2].2CH3COCH3.2H2O。     

Synthesis, structure and magnetism of a μ3-carbonato bridged nickel(II) complex with 2,2′,2″-tris(2-aminoethyl)amine ligand: a new coordination mode of carbonato bridge

A novel bridged Ni(II) complex with tris(2-aminoethyl)amine (tren), [Ni₃(tren)₃(H₂O)₂(μ₃-CO₃)](ClO₄)₄ · 2H₂O, was obtained by bubbling CO₂ into an aqueous solution of μ₂-OH bridged Ni(II) complex. The X-ray structure analysis of the title complex shows that the three nickel atoms are asymmetrically bridged by one tetradentate carbonato ligand, which presents a new bridge mode. The further magnetochemistry study exhibits a strong antiferromagnetic coupling between nickel(II) ions with J₁ = −11.03 cm⁻¹, J₂ = −80.27 cm⁻¹ in the title compound.     

Reactions of bis(3-aminopropyl)amine with formaldehyde in the presence of a metal ion: Preparation of a metal-free macropolycycle and a dinuclear copper(II) complex

The reaction of bis(3-aminopropyl)amine with excess formaldehyde in the presence of Ni²⁺ ion produces the macropentacyclic compound L¹(ClO₄)₂ (1) L¹ = 1,3,7,11,13,17- hexaazapentacyclo[15.3.1.1^3.7.1^7.13.1^13.17]tetracosane). The dinuclear complex [Cu₂(L²)₂(H₂O)₂](ClO₄)₂ (2) (HL¹ = 1-(3-aminopropyl)-3-(hydroxymethyl)-1,3-diazacyclohexane) as well as 1 can be prepared by the condensation reaction in the presence of Cu²⁺ ion. Interestingly, 2 · 2H₂O exhibits uncommon magnetic behavior.     

Polycarbonateurethane films containing complex of copper(II) catalyzed generation of nitric oxide

Nitric oxide (NO) is a well known potent antiplatelet agent, and its continuous release will effectively prevent the adhesion of platelets on artificial blood vessel walls. In this paper, polycarbonateurethane (PCU) with lipophilic Cu(II)‐complex (Cu(II)‐DTTCT) blending films were prepared and used as catalyst to generate NO from nitrite. The mechanical properties of PCU films blended with Cu(II)‐DTTCT were characterized by tensile strength measurement. The tensile stress and Young's modulus of PCU films blending with Cu(II)‐DTTCT increased, however, the elongation at break decreased compared with corresponding PCU films. The NO generation was investigated in vitro in the presence of NaNO₂ and ascorbic acid in PBS (pH = 7.4) at 37°C. The flux of NO generation was quantitatively measured by Griess assay. NO flux and velocity increased with the increase of NaNO₂ concentration, the concentration of ascorbic acid in PBS and the amount of Cu(II) in the films. The loss of Cu(II) from blending film surfaces was found during the in vitro NO generation experiments, which resulted in the decrease of NO flux in the second run. The PCU film could catalyze continually generation of NO for two days, which will provide a promising approach that enable endogenous NO generation on the surface of the medical devices. The generation of biologically active level of NO at the blood/polymer interface can reduce the risk of thrombosis on the implants. Polycarbonateurethane films with NO generation function may be used as high thromboresistant blood contacting materials or coating. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and structures of dinuclear copper(II) complex and μ-phenolatotetrazinc(II) complex with 1,3-diphenyl-4-(salicylidene hydrazone)-phenylethylene-pyrazolone-5

Novel dinuclear copper(II) complex and phenoxy-bridged tetranuclear zinc(II) complex with 1,3-diphenyl-4-(salicylidene hydrazone)-phenylethylene-pyrazolone-5 (DPPeP-SAH) have been synthesized and characterized by X-ray crystallography. The X-ray diffraction analyses of the complexes show that two Cu(II) centers are bonded with two tetradentated ligands and the geometries around the central ions are slightly distorted square planar, while in zinc(II) complex central metal ions are held together by four μ-phenoxo bridges that lead to the formation of the tetra-μ-phenolatotetrazinc(II) centers.     

A novel one-dimensional nickel(II) complex with a hydrogen-bond-link

A novel compound [Ni(L)(H₂O)₂]_0.5[Ni(L)(WO₄)₂]_0.5·4H₂O (1) (L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane) has been structurally and magnetically characterized. The nickel(II) ions are shown to be in distorted octahedral environments with secondary amines of macrocycles in which two trans water molecules and two trans tungstate ions are assembled around each metal center. Two nickel(II) complexes are connected into a one-dimensional chain via hydrogen bonds. The magnetic susceptibility measurement for 1 indicates weak antiferromagnetic interaction (J=−1.01(2) cm⁻¹; H=−JΣS_i·S_i+1) between the S=1 nickel(II) paramagnetic centers.     

Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I) complex [Cu(ABPQ)(DPEphos)]BF₄ [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h;3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF₄ are attributed to the ligand-centered π → π* transition and the metal-to-ligand charge transfer dπ(Cu) → π*(N–N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF₄ in CHCl₃ is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF₄.     

Immobilization of copper(II)-poly(N-vinylimidazole) complex on magnetic nanoparticles and its catalysis of oxidative polymerization of 2,6-dimethylphenol in water

Poly(N-vinylimidazole) (PVI) was grafted onto magnetic Fe₃O₄ nanoparticles through siloxane bonds to produce PVI-grafted Fe₃O₄ nanoparticles (shortened as Fe₃O₄-g-PVI). The amount of imidazolyl groups in Fe₃O₄-g-PVI was estimated to be 1.16 mmol/g by elemental analysis and thermal gravimetric analysis. The Fe₃O₄-g-PVI coordinated with Cu(II) to form the immobilized Cu(II)-PVI complex. The stoichiometric ratio between imidazolyl groups in Fe₃O₄-g-PVI and Cu(II) was found to be 4 and the complex formation constant (K) was calculated to be 5.6 × 10¹⁴ mol⁻⁴ L⁴. The immobilized Cu(II)-PVI complex was employed to catalyze the oxidative polymerization of 2,6-dimethylphenol (DMP) in water and showed excellent C O/C C selectivity to form PPO. After polymerization, the immobilized Cu(II)-PVI complex catalyst was collected by an external magnetic field and reused in the next run with additional immobilized catalyst and copper ions. After three runs of oxidative polymerization of DMP, the recovery rate of the immobilized Cu(II)-PVI catalyst was above 95% and the yield of PPO maintained as high as 79.2% with the addition of supplementary catalysts. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of a novel μ-acetate bridged dinuclear Cu(II) complex as model compound for the active site of tyrosinase: crystal structure, magnetic properties and catecholase activity

Reaction of the ligand N,N,N^′,N^′-bis[(2-hydroxybenzyl)(N-methylimidazolyl)]-2-ol-1,3-propendiamine (Hbhbmipo) with copper(II) perchlorate and sodium acetate in acetonitrile/ethanol leads to the assembly of a novel dinuclear copper(II) complex. The crystal structure, magnetic properties and its catecholase activity are reported. Both copper(II) ions are set in a distorted square pyramidal coordination sphere with a N₂O₃ donor set resulting in a CuCu distance of 3.382(5) Å. To our knowledge this is the first example of a dinuclear Cu(II) complex with square pyramidal coordination geometry in which the N₂O₃ donor set contains N-imidazol and O-phenol. The complex represents a structural model for a tyrosine intermediate in the proposed mechanism during hydroxylation of monophenols.     

The synthesis, structure, and magnetic properties of a novel copper(II) cluster with H-bonding directed 3D-structure comprised of interconnected double-stranded ladders

Reaction between 2,6-diformyl-4-methylphenol (DFMP) and tris(hydroxymethyl)aminomethane (THMAM) with copper(II) acetate and sodium azide formed the antiferromagnetically coupled, polymeric copper(II) coordination cluster {[(H₅L)Cu₂(μ-N₃)]₂[Cu(N₃)₄]·2CH₃OH}_n (1), with a novel double-stranded ladder like structure in which [Cu(N₃)₄]²⁻ anions link single-chains comprised of dinuclear subunits, forming a 3D-structure of interconnected ladders through H-bonding. The 3D-structure is the result of coordinatively driven and hydrogen-bonding directed self-assembly.     

Synthesis and characterization of resins with ligands containing guanidinine derivatives. Cu(II) sorption and coordination properties

A new modification direction of acrylonitrile, vinyl acetate and divinylbenzene terpolymers (A, B) are presented. The aminolysis of nitrile groups of the terpolymers using ethylenediamine or hydroxylamine hydrochloride was a first stage of the modification. The resulting amine groups reacted with dicyandiamide (DCDA), cyanamide (CA) and sodium dicyanimide (SDC) in order to obtain the biguanidyl, guanidyl or nitrilguanidyl derivatives in the polymer side chain, respectively. The properties of all obtained resin such as water regain, nitrogen content, amine and carboxyl group concentration and sorption properties towards Cu(II) from nitric acid solutions were determined. The studies of IR spectra of all the resins were performed. Structures of ligand complexes with Cu(II) were studied using electron paramagnetic resonance spectroscopy.     

Synthesis, characterization and luminescent property of a novel zinc(II) 1,2,3,4-tetra(4-pyridyl)thiophene metal–organic framework

A novel metal–organic framework (MOF) [Zn(TPT)(MPDCO)(H₂O)·H₂O]n (TPT = 1,2,3,4-tetra (4-pyridyl)thiophene, MPDCO = 6-methylpyridine-2,4-dicarboxylic acid N-oxide) (1) was obtained via hydrothermal synthesis and characterized by the elemental analysis, IR spectroscopy, TG analysis, luminescent spectroscopy and single-crystal X-ray diffraction analysis. Single-crystal structural analysis reveals that a one-dimensional (1-D) ladderlike MOF is constructed through the mixed ligands, and it is further connected by the intermolecular hydrogen bonds to form a 3-D supramolecular network. Complex 1 exhibits efficient blue luminescence at room temperature, and the framework is stable below 235 °C.     

Synthesis, structural characterization and microbial activities of mixed ligand copper(II) complexes of 2,2′-bipyridine and acetylacetonate

Two new mixed ligand complexes of copper(II) with acetylacetonate (acac) and 2,2′-bipyridine (bpy) belonging to the class of cytotoxic and antineoplastic compounds known as CASIOPEINAS® have been synthesized and characterized on the basis of analytical and spectroscopic data. Molecular structures of the complexes, [Cu(acac)(bpy)Cl][Cu(acac)(bpy)(H₂O]Cl.H₂O and [Cu(acac)(bpy)Br]H₂O, were established by single crystal X-ray study. The Cu(II) ion in both the complexes exhibited square pyramidal geometry with acac and bpy in the equatorial plane and halide/water in the axial position. Interestingly, for the complex with chloride anion, two types of complexes with chloride and water at the axial positions were derived from the same reaction and co-crystallized in the asymmetric unit with strong intermolecular interactions. Microbial property of these two complexes as antibacterial and antifungal agents has been investigated and some of the results are comparable to that of the standard drugs such as E. coli, P. aeruginosa, S. aureus, S. pyogenes, A. niger and C. albicans, used in this study.     

Formation of first gold(III) complex of an N(4)-disubstituted thiosemicarbazone derived from 2-benzoylpyridine: structural and spectral studies

The reaction between gold(III) chloride(AuCl₃) and 2-benzoylpyridine N(4), N(4)-(butane-1,4-diyl) thiosemicarbazone (HBpypTsc) leads to an unexpected formation of a first gold(III) complex from an N(4)-disubstituted thiosemicarbazone derived from 2-benzoylpyridine. The crystal structure, spectroscopic characterization, and preliminary biological activity of [Au(III)(Cl)(BpypTsc)][Au(I)Cl₂] complex are discussed herein.     

Synthesis, crystal structure and luminescent properties of a thiocyanato bridged two-dimensional heteronuclear polymeric complex of cadmium(II) and copper(II)

A novel heteronuclear polymeric complex Cd(SCN)₃Cu(en)₂NO₃ (1) (en = ethylenediamine) has been synthesized and structurally characterized. The Cd(II) atom is surrounded by three S atoms and three N atoms from four 1,3-μ-SCN⁻ and two 1,1,3-μ-SCN⁻ to attain a distorted octahedral coordination geometry. Six Cd(II) centers are linked by twelve thiocyanato bridges to form hexagonal metallocyclic unit [Cd₆(SCN)₁₂] and extend a 2D network. Moreover, a 1,1,3-μ-SCN⁻ links two cadmium and one copper metal atoms. The luminescent properties of 1 in the solid state were investigated.     

Bioaccumulation and biosorption of copper(II) and chromium(III) from aqueous solutions by Pichia stipitis yeast

BACKGROUND: Bioaccumulation and biosorption by Pichia stipitis yeast has not yet been explored. This paper evaluates, for the first time, the use of both viable and nonviable P. stipitis yeast to eliminate Cu(II) and Cr(III) from aqueous solutions. The effect of Cu(II) and Cr(III) ions on the growth and bioaccumulation properties of adapted and nonadapted biomass is investigated as a function of initial metal concentration. Binding capacity experiments using nonviable biomass are also performed as a function of temperature. RESULTS: The addition of Cu(II) and Cr(III) had a significant negative effect on the growth of yeast. Nonadapted cells could tolerate Cu(II) and Cr(III) ions up to a concentration of 75 ppm. The growth rate of nonadapted and adapted cells decreased with the increase in Cu(II) and Cr(III) concentration. Adapted P. stipitis biomass was capable of removing Cu(II) and Cr(III) with a maximum specific uptake capacity of 15.85 and 9.10 mg g⁻¹, respectively, at 100 ppm initial Cu(II) and Cr(III) concentration at pH 4.5. Adsorption data on nonviable cells were found to be well modeled by the Langmuir and Temkin isotherms. The maximum loading capacity of dry biomass predicted from Langmuir isotherm for Cu(II) and Cr(III) at 20 °C were 16.89 and 19.2 mg g⁻¹, respectively, at pH 4.5. Biosorptive capacities were dependent on temperature for Cu(II) and Cr(III) solutions. CONCLUSION: Cu(II)‐ and Cr(III)‐adapted cells grow and accumulate these ions at high ratios. On the other hand, nonviable P. stipitis was found to be an effective biosorbent for Cu(II) and Cr(III) biosorption. Copyright © 2008 Society of Chemical Industry     

配合物[Cu（L）2]ECu’（L）2]·CH3OH·3H2O的合成和结构表征

以邻氯蜷苯磺酸与吡啶-2-甲醛进行缩合得到席夫碱配体（KL）,然后与Cu（AeO）2．H20进行配位反应,得到了席夫碱配合物[Cu（L）2][Cu’（L】2】’CH3OH·3H2O,用面素分析、FT—IR和X-射线单晶衍射进行r表征。结果表明t配合物属]i单斜晶系,P21／c空间群。配合物的一一个独立单元由置个品格水分子、一个晶格甲醇分子和两个不同的单核铜单元构成。有趣的是,这两个荤核铜单元的组成完全相同但配位模式不同,它们均由一个铜离子和两个脱质子的席夫碱配体组成,其中一个瞥核铜单元中的两个磺酸基均参与了配位,另一个则只有一个磺酸基配位。     

Removal of Cu(II) and Zn(II) Using Lignocellulosic Fiber Derived from Citrus reticulata (Kinnow) Waste Biomass

Abstract

The biosorption of Cu(II) and Zn(II) using dried untreated and pretreated Citrus reticulata waste biomass were evaluated. The Cu(II) and Zn(II) sorption were found to be dependent on the solution pH, the biosorbent dose, the biosorbent particle size, the shaking speed, the temperature, the initial metal ions (800 mg/L), and the contact time. Twenty-eight physical and chemical pretreatments of Citrus reticulata waste biomass were evaluated for the sorption of Cu(II) and Zn(II) from aqueous solutions. The results indicated that biomass pretreated with sulphuric acid and EDTA had maximum Cu(II) and Zn(II) uptake capacity of 87.14 mg/g and 86.4 mg/g respectively. Moreover, the Langmuir isotherm model fitted well than the Freundlich model with R ² > 0.95 for both metal ions. The sorption of Cu(II) and Zn(II) occurred rapidly in the first 120 min and the equilibrium was reached in 240 min. FTIR and SEM studies were also carried out to investigate functional groups present in the biomass and the surface morphological changes of biomass.     

Terminal ligand effect on the structure variation of Copper(II) complexes

Two copper(II)–poly(pyrazolyl)methane complexes [Cu₂(bpm)₄(ta)](ClO₄) ₂ · 2H₂O 1 and {[Cu₂(tpm)₂(ta)₂] · H₂O}_n 2 (bpm = bis(3,5-dimethylpyrazolyl)methane, tpm = tris(pyrazolyl)methane, H₂ta = terephthalic acid) were synthesized and characterized by elemental analysis, FT-IR and UV–vis spectra. 1 is a binuclear complex, while 2 exhibits as a 1D zigzag coordination polymer.     

Introduction of Cu(II) complex into transparent synthetic resin and optical function of the resin as a near-infrared ray cutoff filter

A mole ratio method was conducted to determine a necessary condition to solubilize Cu(II) ion into an organic solvent. Copper benzoate anhydrous (CB) and acetone was used as a Cu(II) ion supplier and a solvent, respectively. Methacryloyloxy-ethyl phosphate (PMOE) and di(2-ethylhexyl) phosphate (DIEHP) were used asligands for solubilization. Cu(II) ion was solubilized with only two PMOE molecules, although six molecules were needed for DIEHP. PMOE formed an intermediate layer which surrounded the Cu(II) ion with two molecules between the ion and solvent and made it possible to solubilize Cu(II) ion into the organic solvent. In the case of DIEHP, however, six molecules were needed to form such a layer for solubilization. Furthermore, Cu(II) ion was introduced homogeneously into poly(methyl methacrylate) (PMMA) by copolymerization of PMOE with MMA, although the polymer was opaque in the case of DIEHP. The ligand having a methacryloyl group was considered to participate in the polymerization process, which avoided exclusion of the Cu(II) complex from polymer phase. The intermediate zone formed by PMOE was considered to keep compatibility of Cu(II) ion with the polymer matrix even after polymerization. The near-infrared ray cutting-off filter made of resin was realized by introducing Cu(II) ion at higher concentration through complexation with the proper ligand. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:903–912, 1998