Extraction of copper(II) ions from aqueous solutions with a methimazole-based ionic liquid

The recently synthesized ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf2], has been used for the extraction of copper(II) from aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu]+, which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of sparingly soluble water in [mimSBu][NTf2] also is required in solvent extraction studies to promote the incorporation of Cu(II) into the [mimSBu][NTf2] ionic liquid phase. The labile copper(II) system formed by interacting with both the water and the IL cation component has been characterized by cyclic voltammetry as well as UV−vis, Raman, and 1H, 13C, and 15N NMR spectroscopies. The extraction process does not require the addition of a complexing agent or pH control of the aqueous phase. [mimSBu][NTf2] can be recovered from the labile copper−water−IL interacting system by washing with a strong acid. High selectivity of copper(II) extraction is achieved relative to that of other divalent cobalt(II), iron(II), and nickel(II) transition-metal cations. The course of microextraction of Cu2+ from aqueous media into the [mimSBu][NTf2] IL phase was monitored in situ by cyclic voltammetry using a well-defined process in which specific interaction with copper is believed to switch from the ionic liquid cation component, [mimSBu], to the [NTf2] anion during the course of electrochemical reduction from Cu(II) to Cu(I). The microextraction−voltammetry technique provides a fast and convenient method to determine whether an IL is able to extract electroactive metal ions from an aqueous solution.

Adsorption of Cu(II) and Co(II) complexes on a silica gel surface chemically modified with 2-mercaptoimidazole

The isotherms of adsorption of MeX2 (Me = Cu2+, Co2+; X = Cl-, Br-, ClO4-) by silica gel chemically modified with 2-mercaptoimidazole (SiMI) were studied in acetone and ethanol solutions, at 25 degrees C. Covalently attached 2-mercaptoimidazole molecule to silica gel surface adsorbs MeX2 from solvent by forming a surface complex. The metal is bonded to the surface through the nitrogen atom of attached 2-mercaptoimidazole. At low loading, the electronic and ESR spectral parameters indicated that the Cu2+ complexes are in a distorted-tetragonal symmetry field. The d-d electronic transition spectra showed that for Cu(ClO4)(2) complex, the peak of absorption did not change for any degree of metal loading and for Cl- and Br- complexes, the peak maxima shifted to higher energy with lower metal loading. The CoX2(X = Cl-, Br-, ClO4-) analogues possess a distorted-tetrahedral field.

Estudo da mistura comercial dolomita-quartzo, dopada com Hg(I), Cd(II) e Cr(III), para adsorção de H2S

The present work was to carry out a study on the adsorption of hydrogen sulfide (H2S) in arrays synthesized from a commercial clay mineral formed by a mixture of dolomite and quartz. To produce the ion exchange matrix were made using aqueous solutions of salts of cobalt II chloride hexahydrate (CoCl2.6H2O) II cadmium nitrate tetrahydrate (Cd (NO3)2.4H2O) I mercuric chloride (HgCl) nitrate and chromium III pentahydrate (Cr (NO3)3.5H2O). The arrays were subjected to hydrogen sulphide gas passage for one hour. To check the amount of gas adsorbed was used gravimetric process. The best result was in the adsorption matrix doped with cadmium and the solution retained for a longer time than the largest amount of H2S was the cobalt matrix. The matrix unmodified exhibited poor adsorption capacity. The characterization of the matrices were used XRD, XRF and IV. Mother with cadmium showed a high capacity in ion exchange, because the percentage of cadmium increased from 0% to 81.38% by replacing atoms of calcium and silicon which increased from 96.54% to 17.56% and 15, 72% to 0.32%, respectively, but also the best performance in adsorption of H2S adsorbing 11.89507 mg per gram of matrix

Equilibrium, Thermoanalytical and Spectroscopic Studies to Characterize Phytic Acid Complexes with Mn(II) and Co(II)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis, Characterization and Biological Activities of a Bidentate Schiff Base Ligand: N,N '-Bis(1-phenylethylidene)ethane-1,2-diamine and its Transition Metals (II) Complexes

Schiff base ligand: N,N'-bis(1-phenylethylidene)ethane-1,2-diamine (L), was derived from acetophenone and ethylenediamine by condensation and its complexes (1-5) were prepared with Pb2+, Ni2+, Co2+, Cu2+ and Cd2+ metal ions. Their structures were characterized by FAB-MS, IR spectra, elemental analyses and molar conductance. The octahedral geometry of the complexes was proposed by electronic spectra and magnetic moment data. The conductivity data showed that the complexes have non-electrolytic nature. The complexes (1-5) have higher in vitro antimicrobial activity than the Schiff base ligand (L). In the nuclease activity, the complexes cleave DNA as compared to control DNA in the presence of H2O2.

Polímeros de coordenação à base de cobalto(II) e N,N'-bis(4-piridil)-1,4,5,8-naftaleno diimida como ligante e suas propriedade estruturais, espectroscópicas e fotoelétricas

Polímeros de coordenação têm atraído a atenção de pesquisadores na última década por conta de sua incrível versatilidade e virtualmente infinito número de possibilidades de combinação de ligantes orgânicos e centros metálicos. Estes compostos normalmente herdam as características magnéticas, eletrônicas e espectroscópicas de seus componentes base. Entretanto, apesar do crescente número de trabalhos na área, ainda são raros os polímeros de coordenação que apresentem condutividade elétrica. Para este fim, utilizou-se a N,N\'-bis(4-piridil)-1,4,5,8-naftaleno diimida, ou NDI-py, que pertence a uma classe de compostos rígidos, planares, quimicamente e termicamente estáveis e que já foram extensamente estudados por suas propriedades fotoeletroquímicas e semicondução do tipo n. O primeiro polímero de coordenação sintetizado, MOF-CoNDI-py-1, indicou ser um polímero linear, de estrutura 1D. O segundo, MOF-CoNDI-py-2, que conta com ácido tereftálico como ligante suporte, é um sólido cristalino com cela unitária monoclínica pertencente ao grupo espacial C2/c, determinado por difração de raios-X de monocristal. A rede apresenta um arranjo trinuclear de íons Co(II) alto spin com coordenados em uma geometria de octaedro distorcido, enquanto os ligantes NDI-py se encontram em um arranjo paralelo na estrutura, em distâncias apropriadas para transferência eletrônica. Com o auxílio de cálculo teóricos a nível de DFT, foi realizado um estudo aprofundado dos espectros eletrônicos e vibracionais, com atribuição das transições observadas, tanto para o MOF-CoNDI-py-2 quanto para o ligante NDI-py livre. A rede de coordenação absorve em toda a região do espectro eletrônico analisada, de 200 nm a 2500 nm, além de apresentar luminescência com característica do ligante. Dispositivos eletrônicos fabricados com um cristal do MOF-CoNDI-py-2 revelaram condutividades da ordem de 7,9 10-3 S cm -1, a maior já observada para um MOF. Além de elevada, a condutividade elétrica dos cristais demonstrou-se altamente anisotrópica, sendo significativamente menos condutor em algumas direções. Os perfis de corrente versus voltagem foram analisados em termos de mecanismos de condutividade, sendo melhores descritos por um mecanismo limitado pelo eletrodo to tipo Space-Charge Limited Current, concordando com a proposta de condutividade através dos planos de NDI-py na rede. A condutividade dos cristais também é fortemente dependente de luz, apresentando fotocondução quando irradiado por um laser vermelho, de 632 nm, enquanto apresenta um comportamento fotorresistivo frente a uma fonte de luz branca. Estes resultados, combinados, trazem um MOF em uma estrutura incomum e com elevada condutividade elétrica, modulada por luz, em medidas diretas de corrente. Não existem exemplos conhecidos de MOFs na literatura com estas características.

Towards improved precision in the quantification of surface-enhanced Raman scattering (SERS) enhancement factors: A renewed approach

This paper demonstrates a renewed procedure for the quantification of surface-enhanced Raman scattering (SERS) enhancement factors with improved precision. The principle of this method relies on deducting the resonance Raman scattering (RRS) contribution from surface-enhanced resonance Raman scattering (SERRS) to end up with the surface enhancement (SERS) effect alone. We employed 1,8,15,22-tetraaminophthalocyanato-cobalt(II) (4α-CoIITAPc), a resonance Raman- and electrochemically redox-active chromophore, as a probe molecule for RRS and SERRS experiments. The number of 4α-CoIITAPc molecules contributing to RRS and SERRS phenomena on plasmon inactive glassy carbon (GC) and plasmon active GC/Au surfaces, respectively, has been precisely estimated by cyclic voltammetry experiments. Furthermore, the SERS substrate enhancement factor (SSEF) quantified by our approach is compared with the traditionally employed methods. We also demonstrate that the present approach of SSEF quantification can be applied for any kind of different SERS substrates by choosing an appropriate laser line and probe molecule.

Late Transition Metal and Aluminum Complexes for the Polymerization of Ethene and Acrylates

Polyethene, polyacrylates and polymethyl acrylates are versatile materials that find wide variety of applications in several areas. Therefore, polymerization of ethene, acrylates and methacrylates has achieved a lot attention during past years. Numbers of metal catalysts have been introduced in order to control the polymerization and to produce tailored polymer structures. Herein an overview on the possible polymerization pathways for ethene, acrylates and methacrylates is presented. In this thesis iron(II) and cobalt(II) complexes bearing tri- and tetradentate nitrogen ligands were synthesized and studied in the polymerization of tertbutyl acrylate (tBA) and methyl methacrylate (MMA). Complexes are activated with methylaluminoxane (MAO) before they form active combinations for polymerization reactions. The effect of reaction conditions, i.e. monomer concentration, reaction time, temperature, MAO to metal ratio, on activity and polymer properties were investigated. The described polymerization system enables mild reaction conditions, the possibility to tailor molar mass of the produced polymers and provides good control over the polymerization. Moreover, the polymerization of MMA in the presence of iron(II) complex with tetradentate nitrogen ligands under conditions of atom transfer radical polymerization (ATRP) was studied. Several manganese(II) complexes were studied in the ethene polymerization with combinatorial methods and new active catalysts were found. These complexes were also studied in acrylate and methacrylate polymerizations after MAO activation and converted into the corresponding alkyl (methyl or benzyl) derivatives. Combinatorial methods were introduced to discover aluminum alkyl complexes for the polymerization of acrylates and methacrylates. Various combinations of aluminum alkyls and ligands, including phosphines, salicylaldimines and nitrogen donor ligands, were prepared in situ and utilized to initiate the polymerization of tBA. Phosphine ligands were found to be the most active and the polymerization MMA was studied with these active combinations. In addition, a plausible polymerization mechanism for MMA based on ESI-MS, 1H and 13C NMR is proposed.

Schiff Base Complexes and their Assemblies on Surfaces

Schiff bases and their transition metal complexes are of significant current interest even though they have been prepared for decades. They have been used in various applications such as catalysis, corrosion protection, and molecular sensors. In this study, N-aryl Schiff base ketimine ligands as well as numerous new, differently substituted salen and salophen-type ligands and their cobalt(II), copper(II), iron(II), manganese(II), and nickel(II) complexes were synthesised. New solid state structures of the above compounds and the dioxygen coordination properties of cobalt(II) complexes and catalytic properties of three synthesised binuclear complexes were examined. The prepared complexes were applied in the formation of self-assembled layers on a polycrystalline gold surface and liquid-graphite interface. The effect of metal ion and ligand structure on the as-formed patterns was studied. When studying gold surfaces, a unique thiol-assisted dissolution of elemental gold was observed and a new thin gold foil preparation method was introduced. In the summary, synthesis, structures, and properties of Schiff base ligands and their transition metal complexes are described in detail and the applications of these reviewed. Assemblies of other complexes on a liquid-graphite interface and on a gold surface are also presented, and the surface characterisation methods and surfaces employed are described.

Epitaxial growth of Co3O4 films by low temperature, low pressure chemical vapour deposition

The growth of strongly oriented or epitaxial thin films of metal oxides generally requires relatively high growth temperatures or infusion of energy to the growth surface through means such as ion bombardment. We have grown high quality epitaxial thin films of Co3O4 on different substrates at a temperature as low as 400 degreesC by low-pressure metalorganic chemical vapour deposition (MOCVD) using cobalt(II) acetylacetonate as the precursor. With oxygen as the reactant gas, polycrystalline Co3O4 films are formed on glass and Si (100) in the temperature range 400-550 degreesC. Under similar conditions of growth. highly oriented films of Co3O4 are formed on SrTiO3 (100) and LaAlO3 (100). The activation energy for the growth of polycrystalline films on glass is significantly higher than that for epitaxial growth on SrTiO3 (100). The film on LaAlO3 (100) grown at 450 degreesC shows a rocking curve FWHM of 1.61 degrees, which reduces to 1.32 degrees when it is annealed in oxygen at 725 degreesC. The film on SrTiO3 (100) has a FWHM of 0.33 degrees (as deposited) and 0.29 (after annealing at 725 degreesC). The phi -scan analysis shows cube-on-cube epitaxy on both these substrates. The quality of epitaxy on SrTiO3 (100) is comparable to the best of the perovskite-based oxide thin films grown at significantly higher temperatures. A plausible mechanism is proposed for the observed low temperature epitaxy. (C) 2001 Published by Elsevier Science B.V.

On the existence of hydrotalcite-like phases in the absence of trivalent cations

alpha-Hydroxides of nickel(II) and cobalt(II) are hydrotalcite-like phases, possessing a layered double hydroxide (LDH) structure even though there are no trivalent cations in the lattice. While the LDHs acquire a positive charge on the hydroxide layers by the incorporation of trivalent cations, we suggest that the alpha-hydroxides acquire a positive charge by partial protonation of the hydroxyl ions according to the equation M(OH)(2)+xH(+) --> [M(OH)(2-x)(H2O)(x)](x+). As in the LDHs, charge balance is restored by the incorporation of anions in the interlayer region. (C) 1997 Academic Press.

Epitaxial Growth of Co3O4 Films by Low Temperature, Low Pressure Chemical Vapor Deposition

The growth of strongly oriented or epitaxial thin films of metal oxides generally requires relatively high growth temperatures or infusion of energy to the growth surface through means such as ion bombardment. We have grown high quality epitaxial thin films of Co3O4 on different substrates at a temperature as low as 450°C by low-pressure metal-organic chemical vapor deposition (MOCVD) using cobalt(II) acetylacetonate as the precursor. With oxygen as the reactant gas, polycrystalline Co3O4 films are formed on glass and Si(100) in the temperature range 350-550°C. Under similar conditions of growth, highly oriented films of Co3O4 are formed on SrTiO3(100) and LaAlO3(100). The film on LaAlO3(100) grown at 450°C show a rocking curve FWHM of 1.61°, which reduces to 1.32° when it is annealed in oxygen at 725°C. The film on SrTiO3(100) has a FWHM of 0.330 (as deposited) and 0.29° (after annealing at 725°C). The ø-scan analysis shows cube-on-cube epitaxy on both these substrates. The quality of epitaxy on SrTiO3(100) is comparable to the best of the pervoskite-based oxide thin films grown at significantly higher temperatures.

Ligational behaviour of (E)-2-amino-N ` -1-(2-hydroxyphenyl) ethylidene]benzohydrazide towards later 3d metal ions: X-ray crystal structure of nickel(IV) complex

Ligational behaviour of (E)-2-amino-N'-1-(2-hydroxyphenyl)ethylidene]benzohydrazide (Aheb) towards later 3d metal ionscopper(II), cobalt(II), manganese(II), zinc(II), cadmium(II) and nickel(IV)] has been studied. Their structures have been elucidated on the basis of spectral (IR, H-1 NMR, UV-Vis, EPR and FAB-mass), elemental analyses, conductance measurements, magnetic moments, and thermal studies. During complexation Ni(II) ion has got oxidized to Ni(IV). The changes in the bond parameters of the ligand on complexation has been discussed by comparing the crystal structure of the ligand with that of its Ni(IV) complex. The X-ray single crystal analysis of Ni(aheb)(2)]Cl-2 center dot 4H(2)O has confirmed an octahedral geometry around the metal ion. EPR spectra of the Cu(II) complex in polycrystalline state at room (300 K) and liquid nitrogen temperature (77 K) were recorded and their salient features are reported. (C) 2014 Elsevier B.V. All rights reserved.

Copurification of the Lac repressor with polyhistidine-tagged proteins in immobilized metal affinity chromatography.

One of the commonly used resins for immobilized metal affinity purification of polyhistidine-tagged recombinant proteins is TALON resin, a cobalt (II)--carboxymethylaspartate-based matrix linked to Sepharose CL-6B. Here, we show that TALON resin efficiently purifies the native form of Lac repressor, which represents the major contaminant when (His)(6)-tagged proteins are isolated from Escherichia coli host cells carrying the lacI(q) gene. Inspection of the crystal structure of the repressor suggests that three His residues (residues 163, 173, and 202) in each subunit of the tetramer are optimally spaced on an exposed face of the protein to allow interaction with Co(II). In addition to establishing a more efficient procedure for purification of the Lac repressor, these studies indicate that non-lacI(q)-based expression systems yield significantly purer preparations of recombinant polyhistidine-tagged proteins.

A tale of two cobalts

There are important problems to overcome if solar energy or other renewable energy sources are to be used effectively on a global scale. Solar photons must not only be harvested and converted into a usable form, but they must also be efficiently stored so that energy is available for use on cloudy days and at night. In this work, both the energy conversion and energy storage problems are addressed. Specifically, two cobalt complexes were designed and their reactivity probed for applications in energy conversion and storage. The first chapter describes a cobalt complex that is the first example of a dimeric cobalt compound with two singly proton-bridged cobaloxime units linked by a central BO4--bridge. Using electrochemical methods, the redox properties of the dimer were evaluated and it was found to be an electrocatalyst for proton reduction in acetonitrile.

Because hydrogen gas is difficult to handle and store, the hydrogenation of CO2 and later dehydrogenation of the liquid product, formic acid, has been proposed as a hydrogen storage system. Thus, a second complex, described in chapter two, supported by a triphosphine ligand framework was used as a catalyst precursor for this key dehydrogenation step. The studies here demonstrate the efficacy of the complex as a precatalyst for the desired reaction, with good conversion of starting formic acid to CO2 and H2. In order to better understand the properties of the triphosphine cobalt complex, a synthetic procedure for substituting electron donating groups (e.g., methoxy groups) onto the ligand was investigated, yielding a novel diphosphine cobalt(II) complex.