光度法研究聚乙二醇-硫酸铵-邻苯三酚红体系中铋(Ⅲ), 铁(Ⅲ), 铜(Ⅱ), 镍(Ⅱ), 钴(Ⅱ), 铅(Ⅱ)的萃取分离

本文研究了在聚乙二醇(PEG)-硫酸铵[(NH_4)_2SO_4]-邻苯三酚红(PR)体系中Bi(Ⅲ),Fe(Ⅲ),Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Pb(Ⅱ)的萃取行为。实验结果表明,Bi(Ⅲ)在pH3.5～6.5及Fe(Ⅲ)在pH4.0～7.0范围内可以被PEG相几乎完全萃取,而Cu(Ⅱ),Co(Ⅱ)在pH1.0～7.0,Pb(Ⅱ)在pH2.0～7.0,Ni(Ⅱ)在pH1.0～4.5则不被萃取。从而实现了将Bi(Ⅲ)(pH3.5),Fe(Ⅲ)(pH5.0)与Cu(Ⅱ),Co(Ⅱ),Pb(Ⅱ),Ni(Ⅱ)混合离子的定量分离。同时探讨了PEG相的萃取机理。     

Adsorbate interactions of Cu(II) in Cu(II)-exchanged K-L gallosilicate studied by CW and Pulsed electron spin resonance

The interactions of Cu(II) in Cu(II)-exchanged K-L gallosilicate with adsorbates containing coordinative nitrogens in ammonia, pyridine, aniline, acetonitrile and hydrazine, and with the adsorbates carbon monoxide, benzene, propanol and dimethyl sulfoxide are investigated by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies. These results are compared with those in Cu(II)-exchanged K-L aluminosilicate and the differences are discussed. Adsorption of ammonia produces a complex containing four molecules of ammonia based on resolved nitrogen superhyperfine interaction. Upon equilibrium with pyridine, Cu(II) forms a complex containing four molecules of pyridine in CuK-L gallosilicate and a complex containing only three molecules of pyridine in CuK-L aluminosilicate based on resolved nitrogen superhyperfine. Upon adsorption of aniline and acetonitrile, Cu(II) forms complexes containing two molecules of each in CuK-L gallosilicate based on resolved nitrogen superhyperfine. However, no resolved nitrogen superhyperfine between hydrazine and Cu(II) is seen. Adsorption of carbon monoxide, benzene, propanol and dimethyl sulfoxide causes changes in the ESR spectrum of Cu(II), indicating migration of Cu(II) into cation positions in the main channels where adsorbate coordination can occur. Cu(II) forms complexes with one molecule of benzene and two molecules of propanol based on ESEM data in both K-L gallosilicate and K-L aluminosilicate. However, Cu(II) interacts directly with one dimethyl sulfoxide in K-L aluminosilicate but only indirectly at a longer distance with one dimethyl sulfoxide in K-L gallosilicate based on ESEM data.     

High oxygen pressures and the stabilization of a new mixed valence Cu(III)/Cu(IV)

Abstract

The Cu(III) oxides were investigated first for the unusual copper oxidation state and then for the high-Tc superconductivity. In the last case this property is observed when a mixed copper valence is stabilized : Cu(I)/Cu(II) or Cu(II)/Cu(III). A new mixed valence Cu(III)/Cu(IV) has been stabilized in the three dimensional lattice of the perovskite-type oxide Lal_-xSr_xCuO₃ (0 ≥ ′ ≥ 0,25). Chemical analysis and XPS study confirm the mixed valence. This compound shows metallic properties with an broadening of the conduction band compared to LaCu0₃. Such a behaviour can be explained either by the increase of the covalence of the average Cu-0 bond or by the decrease of the structural distortion induced by the substitution of Sr(II) for La(III). No superconducting property has been detected down to 4K.     

Positronium interactions with Cu(II) Ions in water

Summary Positronium reactions with Cu(II) ions in aqueous solution were investigated by measuring the concentration dependence of lifetime spectra and of 1D-ACAR curves for the following Cu (II) complexes: [Cu(H₂O)₆[²⁺, [Cu(NH₃)₄ (H₂O)₂]²⁺ and [Cu(EDTA)(H₂O)]²⁻. The combined analysis of lifetime and ACAR data shows that Cu(II) ions:a) reduce the formation of positronium (inhibition effect),b) promote both ortho ⇌ para conversion and redox reactions. It was also found that inhibition and reaction rate constants are affected by the ligand type.     

Spectroscopic Study of Cu(II) Ion Doped in Bis-Glycine Sodium Nitrate

Single-crystal Electron Paramagnetic Resonance (EPR) and optical absorption studies were performed at room temperature on Cu(II)-ion–doped bis-glycine sodium nitrate, a semiorganic nonlinear optical material (NLO). Spin-Hamiltonian parameters, obtained from single-crystal EPR spectra, recorded in three mutually orthogonal planes, revealed the presence of two magnetically inequivalent Cu(II) sites. Molecular orbital parameters were also evaluated. The optical absorption spectrum at room temperature exhibits the lowering of octahedral symmetry to an axially elongated tetragonal of Cu(II) ion in NLO.     

Adsorption of Hydrogels Based on Cellulose for Cu(II) and Ni(II): Behaviors and Mechanisms

Hydrogels based on cellulose-graft-poly (acrylic acid) copolymers (C-g-AA) were synthesized by graft copolymerization in a phosphoric acid solvent. Fourier transform infrared (FT-IR) spectra confirmed the structure of the C-g-AA. The adsorption behaviors of the hydrogels for Cu(II) and Ni(II) were investigated. The results showed that their adsorption capacity increased as the initial concentrations of metal ions and the pH value of the solution increased. Freundlich and Langmuir isotherm models were employed to analyze the data from batch adsorption experiments. The results indicated that there were very good correlation coefficients for their linearized equations. The maximum adsorption amounts of the hydrogels for the metal ions, based on the Langmuir model, were 182 and 200 mg/g for Cu(II) and Ni(II), respectively. When the initial concentration of metal ions was 1000 mg/g the actual adsorption amounts of the hydrogels for Cu(II) and Ni(II) were 181 and 183 mg/g, respectively.     

荧光光谱法研究肌红蛋白活性中心铁卟啉与铜离子的相互作用

首次应用荧光光谱法研究了肌红蛋白 (FePP Mb)的活性中心铁卟啉与铜离子的相互作用 ,结果表明在水溶液中肌红蛋白中的铁可被铜离子取代 ,形成铜卟啉化合物 (CuPP Mb) ,并且随着体系中铜离子量的增加 ,其相互作用增强。本课题从蛋白质的角度研究了金属离子同生物大分子相互作用的现象并探讨了作用机理 ,可以为进一步研究有害重金属在人体内作用及毒害机理提供一定的理论依据。同时 ,本文采用的荧光光谱法与常规的UV和CD法相比有较高的灵敏度。     

Adsorption and thermodynamic studies of Cu(II) and Zn(II) on organofunctionalized-kaolinite

Kaolinite-bearing clay samples from Perus, São Paulo state, Brazil, were used for chemical modification process with dimethyl sulfoxide and organofunctionalized with the silyating agent (RO)₃Si(CH₂)₃NH(CH₂)₂NH₂ in the present study. The resulting material and natural kaolinite were subjected adsorpion process with Cu(II) and Zn(II) from aqueous solution at pH 6.0 and controlated temperature of 298 K. The Langmuir adsorption isotherm model has been applied to fit the experimental data. The results showed that the chemical modification process increases the basal spacing of the natural kaolinite from 0.711 to 0.955 nm. The energetic effects caused by Cu(II) and Zn(II) interactions were determined through calorimetric titration at the solid–liquid interface and gave a net thermal effect that enabled the calculation of the exothermic values and the equilibrium constant.     

Fluorescence sensor for Cu(II) based on R6G derivatives modified silicon nanowires

A fluorescence sensor for selective detection of Cu(II) is realized by covalently immobilizing derivatives of rhodamine6G (R6G) on the surface of silicon nanowires (SiNWs). It features the release of R6G from the SiNWs in the presence of Cu(II), which causes a significant enhancement of the fluorescence over other metal ions. The present Cu(II) sensor has good selectivity and sensitivity, and exhibits a linear response in the range of 0.0-7.0 μM Cu(II). Different from conventional Cu(II) sensor with fluorescence quenching, the present sensor based on fluorescence enhancement facilitates the practical application. Especially, the release of the R6G from SiNWs could be utilized as fluorescent labeling for Cu(II) in microenvironment.     

Vibrational spectra of clioquinol and its Cu(II) complex

The infrared and Raman spectra of 5‐chloro‐7‐iodo‐8‐hydroxyquinoline (clioquinol, CQ) and that of its Cu(II) complex of stoichiometry [Cu(CQ)₂] were recorded and briefly discussed. Some comparisons were made with related complexes. The interest of the investigated systems in relation to Alzheimer's disease is briefly commented. Copyright © 2006 John Wiley & Sons, Ltd.     

A Rhodamine-Based Dual Chemosensor for Cu(II) and Fe(III)

An “off-on” rhodamine-based fluorescence probe for the selective signaling of Cu(II) and Fe(III) has been designed and synthesized. The optical properties of this compound have been investigated in acetonitrile-water (1:1) binary solution. Very interestingly, this compound showed sensitivity and selectivity towards Cu(II) during absorption process and towards Fe(III) during emission process. So this is a nice example of an excellent dual chemosensor for two biologically/physiologically very important transition metal ions using only the two very different techniques (absorption and emission); both cases displayed only intensity enhancement.     

Catalytically Active Cu(II)-Pybox Complexes: Insights by EPR Spectroscopy and DFT Computations

This paper addresses the geometry of the catalytic Cu(II) complexes formed in the course of stereoselective Diels–Alder reaction. The parent catalyst is [Cu(II)-isopropyl-pybox](OTf)₂. Ethyl glyoxylate serves as dienophile and it reacts with 1,3-cyclohexadiene. The reaction is followed by CW EPR, HYSCORE, and (pulsed) ENDOR spectroscopy and the experimental results are supported by DFT computations. It is shown that during the catalytic process, the Cu(II) complex is pentacoordinated and one of the triflate counterions is coordinated to the Cu(II) center in axial position.     

Calix Receptor Edifice; Scrupulous Turn Off Fluorescent Sensor for Fe(III), Co(II) and Cu(II)

Novel Supramolecular fluorescence receptor derived from calix-system i.e. calix[4]resorcinarene bearing dansylchloride as fluorophore was designed and synthesized. The compound was purified by column chromatography and characterized by elemental analysis, NMR and Mass spectroscopy. Tetradansylated calix[4] resorcinarene (TDCR) shows a boat conformation with C₂v symmetry. The complexation behaviour of metal cations [Ag(I), Cd(II), Co(II), Fe(III), Hg(II), Cu(II), Pb(II), Zn(II), U(VI) (1?×?10^-4?M)] with tetra dansylated calix[4]resorcinarene (1?×?10^-6?M) was studied by spectophotometry and spectrofluorometry. Red shift in the absorption spectra led us to conclude that there is strong complexation Fe(III), Co(II) and Cu(II) with TDCR. These metal cations also produce quenching with red shifts in the emission spectra. The maximum quenching in emission intensity was observed in the case of Fe(III) and its binding constant was also found to be significantly higher than that of Co(II) and Cu(II). Quantum yield of metal complexes of Fe(III) was found to be lower in comparison with Co(II) and Cu(II) complexes. Stern Volmer analysis indicates that the mechanism of fluorescence quenching is either purely dynamic, or purely static.     

Na2Cu5Shi4·4H2O配合物的合成、结构及性质研究

合成了Na2Cu5Shi4·4H2O配合物,经元素分析,IR,UV,NMR,荧光及分子力学计算等表征了配合物的结构.2D 1HNMR谱及磁矩等测定表明,配合物中水杨酰肟酸π电子分布有大的改变,最大吸收峰红移25 nm,芳环d质子表现出烷烃质子性质;铜离子之间有强的磁相互作用,基态S为1/2.     

Cu(II) content in the structures of the peripheral nervous system at their damage

Employing electron paramagnetic resonance with diethyldithiocarbamate as a spin trap it was shown that after the transection of the rat sciatic nerve the Cu(II) content increased in the proximal stump and did not change in the distal stump. No changes of the Cu(II) content in dorsal root ganglia L4-L5 containing sensory neurons with their peripheral processes in the damaged nerve were registered.     

Cu(Ⅱ)离子对多巴色素作用的紫外-可见光谱研究

采用紫外 可见光谱法研究了在pH 6 5的缓冲溶液中Cu(Ⅱ )离子对多巴色素的催化作用。在通氮除氧的体系中 ,Cu(Ⅱ )离子显著加快多巴色素 (DC)于 4 75nm波长的褪色速度 ,并同时出现在 30 0～ 80 0nm波长范围内的全程吸收。实验结果表明 :Cu(Ⅱ )离子催化重排多巴色素生成的主要产物为 5 ,6 二羟基吲哚 2 羧酸 (DHICA) ,其反应前期对于DC为动力学一级反应 ;而且Cu(Ⅱ )离子可进一步催化 5 ,6 二羟基吲哚(DHI)和DHICA形成吲哚醌 (即吲哚 5 ,6 醌和吲哚 5 ,6 醌 2 羧酸 )的反应 ,吲哚醌一经生成 ,立即聚合形成黑色素。     

ESR study of some solvent effects of the Cu(II)-aspirinate complex

Powder ESR spectra of the [Cu₂(Asp)₄](H₂O)₂ complex show the existence of Cu(II) acetate like dimers characterized by a strong antiferromagnetic exchange interaction (J=?288 cm^?1). In pyridine-dimethylformamide solutions the monomeric species prevail. Two different monomeric species, the Cu(DMF)₄ of planar-distorted tetrahedral (T_d) symmetry and the Cu(Asp)₂(DMF)₂ with elongated tetrahedral-octahedral symmetry were evidenced in DMF solution adsorbed on NaY zeolite. In 40 % Py+60 % DMF solution two monomeric species were also identified. These are Cu(Asp)₂(DMF)₂ and Cu(Asp)₂(Py)₂, the last species having a CuN₂O₂ chromophore in atrans squareplanar arrangement. In pyridine Cu(II)-aspirinate solution only the Cu(Py)₄ monomeric species of CuN₄ chromophore was evidenced.     

Spectrophotometric Studies and Analytical Applications of the Complexes of Fe(III), Ni(II) and Cu(II) with Some 4-Amino-Antipyrene Azo Derivatives

Extensive study of composition, stability constants and optimum conditions of Fe(III), Nl (II) and Cu(II) complexes with four azo compounds based on 4 - amlnoantlpyrene are done. The coloured complexes formed, at the optimum. conditions mentioned, can be successfully used In the mlcrodetermlnation of metal Ions In synthetic solutions as well as In Incoloy 800 alloy. The method described Is rapid, sensitive, highly accurate and reproducable.     

Infrared Studies on the Complexes of Zn(II), Cd(II), Hg(II), Pb(II), Cu(I) and Ag(I) with 5-Benzylthio-1,2,4.-triazole

Zn(II), Cd(II), Hg(II), Pb(II), Cu(I) and Ag(I) complexes of 5-benzylthio-1,2,4-triazole (BTT) have been prepared and characterised on the basis of analytical and IR data. Hg(II), Cd(II), Zn(II), and Pb(II) complexes are assigned tetrahedral structure with polymeric intermolecular linkages through S and N atoms while Ag(I) and Cu(I) are proposed to have polymeric linear structure     

New Bio-Based Cu(II) Complexes and Study of their Anti-Cancer Activities

Two new Cu(II) complexes with Picolinic acid and Tryptophan [Cu(II)(DPTR)(H₂O)₂](1:1) (1) and [Cu(II)(DPTR)(Phen)] (1:1:1) (2) were synthesized, characterized and studied their DNA binding, cleavage, docking and anti-cancer properties. The molecular modeling studies were carried out with energy minimized structures of metal complexes. CT-DNA binding studies revealed that the complexes bind through an intercalative mode and show good binding propensity. The docking study also confirms the intercalative mode of binding. The hydrolytic DNA cleavage activity of these complexes has been studied using gel electrophoresis. Complex 2 shows better efficiency than 1. Cell viability experiments indicated that the ligand, complexes show significant dose dependent cytotoxicity in selected cell lines.

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Graphical Abstract Two new Cu(II) complexes with Picolinic acid and Tryptophan, [Cu(II)(DPTR)(H₂O)₂](1:1) (1) and [Cu(II)(DPTR)(Phen)] (1:1:1) (2) were synthesized, characterized and studied their DNA binding, cleavage, docking and anti-cancer properties.