Simultaneous determination of aluminium,aluminium fluoride complexes and iron in groundwater samples by new HPLC–UVVIS method

The paper presents the application of the new HPLC–UVVIS method used in speciation analysis of aluminium form Al³⁺, aluminium complexes with fluorides and iron in groundwater samples. Based on the obtained results of groundwater samples analysis, the separation of iron in the retention time ≈ 3.7, was obtained. The conditions of the occurrence of particular aluminium forms based on the speciation analysis and modeling in the Mineql program were presented and confirmed. The influence of pH and ligand concentration on forming complexes was shown. The preliminary study of aluminium complexes with sulfates based on model solutions did not allow for the separation of the above complexes in presented analytical system. The paper presents the possible types of transformation of aluminium hydroxy forms and aluminium sulfate complexes by the reaction of the sample with mobile phase. An indirect method for the determination of aluminium in the form of aluminium sulfate was proposed. The new method was successfully applied in the determination of the following aluminium forms: Al³⁺, AlF₂⁺, AlF₃⁰, AlF₄^?, AlF²⁺ and Fe³⁺.     

Paramagnetic aluminium β-diketiminate

The β-diketiminate ligand framework is shown to undergo reduction to form a neutral main group radical stabilized by spiroconjugation of the unpaired electron over the group 13 element centre. The synthesized paramagnetic complex was characterized by EPR spectroscopy and computational chemistry.     

Interconversion of copper(II) to copper(I): synthesis,characterization of copper(II) and copper(I) 2,2′-biquinoline complexes and their microbiological activity

The complexes [Cu(biq)₂]Cl₂ and [Cu(biq)₂]BF₄·biq (biq?=?2,2′-biquinoline) have been prepared and characterized. The interconversion to copper(I) complex [Cu(biq)₂]BF₄·biq, from [Cu(biq)₂]Cl₂ has been established. The new complexes have been characterized by elemental analysis, conductivity and magnetic measurements, IR, UV-vis and ¹H- and ¹³C-NMR spectroscopy. The X-ray analysis of the complex [Cu(biq)₂]BF₄·biq supports the assumption of the interconversion of copper(II) to copper(I) in this case. The crystal structure shows that geometry around the metal is severely distorted from T_d, and displays many supramolecular motifs incorporating both hydrophobic (aryl···aryl) and hydrophilic (C–H···F) intermolecular interactions. The microbiological activity of the complexes against bacteria and fungi was found to be high against Candida albicans, and slight to moderate against bacteria. The antimicrobial activity of [Cu(biq)₂]BF₄·biq was slightly better than that observed for [Cu(biq)₂]Cl₂ against both bacteria and fungi.     

International comparability of determination of mass fractions of chromium, copper, iron, manganese and zinc in aluminium alloy: Comité Consultatif pour la Quantité de Matière key comparison K42

The degree of equivalence within the participating national metrology institutes for the measurement results of the mass fractions of the analytes Cr, Cu, Fe, Mn and Zn in an aluminium alloy was assessed. This interlaboratory comité consultatif pour la quantité de matière key comparison (CCQM-K42) was organised as an activity of the Inorganic Analytical Working Group of CCQM. In total seven laboratories participated, six of them for all analytes. Measurands were the mass fractions of the analytes in a range of 0.05 and 0.2%. As an outcome the consistency of the results for all elements investigated was acceptable, hence satisfactory comparability was established. An aluminium based certified reference material—undisclosed to the analysts which one it was—was used as test sample. For the purpose of this study homogeneity was tested at BAM. Each laboratory was free to choose any analytical method they wanted to use for the analysis. Consequently various methods of measurement were employed: instrumental neutron activation analysis, X-ray fluorescence spectrometry (XRF) using fused cast-bead method combined with reconstitution technique, inductively coupled plasma optical emission spectrometry (ICP OES) and inductively coupled plasma mass spectrometry. Metrological traceability of the measurement results to the SI unit had to be demonstrated. Therefore, methods such as spark OES or XRF (without fused cast-bead technique)—both of them being most important methods for the analysis of metals and alloys in industrial laboratories—could not be used in the frame of the key comparison.     

Synthesis,structure and properties of an imidazolate bridged copper,zinc binuclear complex

A new imidazolate bridged Cu~(2+),Zn~(2+)binuclear complex[(dtma) CulmZn (dtma)]ClO_4·2.5H_2O taken as active site model for Cu,Zn-SOD has been synthesized and its crystal structuredetermined.All the bond lengths, bond angles and the distance between Cu and Zn atoms in Cu-Im-Zn core of the model complex are close to those in Cu,Zn-SOD.ESR parameters of the modelcomplex as a function of pH show that the imidazolate bridge is stable in pH range 10—12,and isbroken on Zn side at pH～9.With decreasing pH,the imidazole is released at pH～4 and the dtmaligand dissociates from the Cu containing fragment at pH～2.4.     

Vinyl copper derivatives 30 reactivity of γ-silylated vinyl copper reagents

γ-silylated vinyl copper reagents react with electrophiles with total retention of configuration of the CC double bond. Oxidation, allylation, vinylation and acylation lead to fonctionalized dienes with a given geometry.     

Syntheses,crystal structures and magnetic properties of two cyano-bridged copper(I)–copper(II) mixed-valence complexes

Two cyano-bridged copper(II)–copper(I) mixed-valence assemblies, Cu(EAM)₂[Cu(CN)₂]₂ 1 (EAM?=?ethanolamine) and Cu(DETA)[Cu(CN)₂]₂·0.5H₂O 2 (DETA?=?diethylenetriamine), have been prepared and structurally and magnetically characterized. IR spectra indicate the presence of bridging cyano groups in both 1 and 2, confirmed by structure analyses; Cu(I)–CN–Cu(II), Cu(I)–CN–Cu(I) and Cu(I)–Cu(I) metal bond linkages are evident. In the lattice, a 3D network is formed by two [Cu(CN)₂]?^? units and one [Cu(EAM)₂]²⁺unit for 1. Variable temperature magnetic susceptibilities, measured in the 5–300?K range, indicate weak antiferromagnetic exchange interactions in complex 1.     

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.     

Kinetics of iron–copper sulphides oxidation in relation to protohistoric copper smelting

This article deals with one specific step of the copper extractive metallurgy process: the roasting of iron–copper sulphides. It aims at shedding light on an archaeological issue: the reconstruction of the copper extractive metallurgy processes during protohistory (IV^e–II^e millennium BC). Experimental simulations are performed at laboratory scale by modelizing the conditions of protohistoric furnaces. Kinetic of roasting is studied by thermogravimetry combined with the physico-chemical analysis of synthetic products. The influence of two parameters is studied: (i) the temperature (773, 973 and 1173 K) and (ii) the granularity of the roasted ores (1 mm and 100 μm). In each case, the chemical mechanism governing the oxidation of iron copper sulphide is proposed. Apart from one extreme case (∅ = 1 mm; T = 773 K), it is showed that kinetic is controlled by the transport of molecular oxygen (O₂) from the gas to the grain surface. Moreover, we prove that, in some cases where the diffusivity of gaseous oxygen is low, roasting can be accelerated by the presence of an oxide, which constitute an in-situ source of oxygen. Theses experiments support the hypothesis that such a technique could have allowed a roasting process where iron and sulfur were removed by the solid oxygen instead of the gaseous oxygen. These results allow to validate a one-step copper smelting process starting from sulphidic ores, and to identify the experimental parameters of this process.     

A theoretical study of the copper–cysteine bond in blue copper proteins

 The accuracy of theoretical calculations on models of the blue copper proteins is investigated using density functional theory (DFT) Becke's three-parameter hybrid method with the Lee–Yang–Parr correlation functional (B3LYP) and medium-sized basis sets. Increasing the basis set to triple-zeta quality with f-type functions on all heavy atoms and enlarging the model [up to Cu(imidazole-CH₃)₂(SC₂H₅) (CH₃SC₂H₅)^0/+] has only a limited influence on geometries and relative energies. Comparative calculations with more accurate wave-function–based methods (second-order M?ller–Plesset perturbation theory, complete-active-space second-order perturbation theory, coupled-cluster method, including single and double replacement amplitudes and in addition triple replacement perturbatively) and a variety of basis sets on smaller models indicate that the DFT/B3LYP approach gives reliable results with only a small basis set dependence, whereas the former methods strongly depend on the size of the basis sets. The effect of performing the geometry optimizations in a continuum solvent is quite small, except for the flexible Cu-S_Met bond. The results of this study confirm the earlier results that neither the oxidized nor the reduced copper site in the blue proteins is strained to any significant degree (in energy terms) by the protein surrounding. Received: 7 July 2000 / Accepted: 17 November 2000 / Published online: 21 March 2001     

Uniform copper nanoparticles as an inexpensive and efficient catalyst for synthesis of novel β-carbonyl-1, 2, 3-triazoles in water medium

Copper nanoparticles as an efficient, inexpensive catalyst were prepared via ball milling for synthesis of β-carbonyl 1, 2, 3-triazoles from azido alcohol by click reaction in water. An extensive range of raw materials such as sodium azide, phenacyl bromide, epichlorohydrin, and terminal alkynes were used. Complete reduction of CuO in presence of NaBH₄ was done via ball milling with a ball-to-powder weight ratio of 50:1 under air atmosphere at room temperature. The final copper nanoparticles (Cu NPs) were characterized by SEM, EDX, XRD and FT-IR. The Cu NPs catalyzed one-pot three component synthesis of β-carbonyl 1, 2, 3-triazoles at room temperature with short reaction time and high product yields. The catalyst could be easily recovered and reused in several successive runs.

     

Synthesis,characterization, crystal structure,and DNA binding of two copper(II)–hydrazone complexes

Two new Cu(II)–hydrazone complexes, [Cu(L)(Hbpe)ClO₄]·ClO₄·[Cu(L)Cl] (1) and [Cu(HL)₂]·1.5ClO₄·0.5OH (2) (where HL?=?(E)-N′-(1-(pyridine-2-yl)ethylidene)benzohydrazide and bpe = trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene), have been synthesized and characterized by physicochemical methods. The structures of the complexes have been established by single-crystal X-ray diffraction direct methods, which reveal that the metal ions have distorted square-pyramidal and square-planar geometries in 1, and a distorted octahedral geometry in 2. DNA binding of HL, 1, and 2, performed by UV–vis titration in tris-buffer medium, yielded binding constants, which are 9.5 × 10³, 1.88 × 10⁴, and 4.66 × 10⁴ M^?1, respectively. Viscosity measurements suggest a surface or groove-binding mode of interaction between CT-DNA with HL, 1, and 2.     

Vinyl copper derivatives n° 29: Addition of α-silylated organocopper reagents to alkynes,access to γ-silylated vinyl copper reagents

α silylated organocopper reagents add regio- and stereoselectively to alkynes. Experimental procedures (temperature, solvent, ligands, main group metal salts) are highly dependent on the structure of the various simple or functionalized alkynes.     

A calorimetric investigation into copper–arginine and copper–alanine solid state interactions

Complexes of formula CuCl₂ · 2arg and CuCl₂ · 4ala (arg = arginine; ala = alanine) were prepared at room temperature by a solid state route. The metal–amino acid solid state interactions were studied by i.r. spectroscopy and solution calorimetry. For both complexes, participation of the carboxylate group as well as nitrogen in coordination are inferred, based on the i.r. data. For the copper–arginine compound, the calculated thermochemical parameters are: _rH_m = –114.9 ± 1.42 and _fH_m = –1608.3 ± 11.6 kJ mol^–1. For copper–alanine compound, a complete set of thermochemical parameters were calculated: _rH_m = –18.0 ± 0.9; _fH_m = –2490.4 ± 4.3; _DH_m = 597.2 ± 17.7; _MH_m = 771.9 ± 18.7; _gH_m = 627.1 ± 22.3 and D (Cu–L) = 156.8 ± 5.7 kJ mol^–1. Based on _rH_m and dissolution enthalpy values, a stronger intermolecular solid state interaction can be inferred for the arginine complex, than for the alanine one complex, probably due to the formation of intermolecular hydrogen bonds in the former.     

Synthesis and structural features of copper(II) complexes of N,N,N′,N′-tetramethylethylenediamine with 2-chlorobenzoate1− and 2-hydroxybenzoate1−

Abstract

Two copper(II) coordination complexes, formulated as [Cu(tmen)(Clba)₂] (1) and [Cu(tmen)(Hsal)₂·H₂O] (2) (where tmen?=?N,N,N′,N′-tetramethyl ethylenediamine (C₆H₁₆N₂), Clba^1? = 2-chlorobenzoate (C₇H₄ClO₂^1?), and Hsal^1? (C₇H₅O₃^1? = monoanion of o-hydroxybenzoic acid (salicylic acid)), have been synthesized and characterized by elemental combustion analysis, spectroscopic techniques, thermal studies, and single crystal X-ray analyses. Complex 1 consists of two distinct monomeric units in which the coordination environment around the central copper(II) ion is a distorted octahedron with a CuN₂O₄ chromophore, constituted by a chelating tmen molecule, and two 2-chlorobenzoate^1? anions coordinated through their carboxylate-O atoms in an asymmetrical bidentate fashion. Complex 2 is also a monomer and consists of an CuN₂O₃ chromophore, in which tmen is coordinated to Cu(II) through its two N atoms in a chelating bidentate fashion, and an aqua-O and the two o-hydroxybenzoate^1? (HSal^1?) anions are coordinated through one of their carboxylate-O atoms in a monodentate mode, forming a square pyramidal structure. Hydrogen bonding interactions especially of O–H…O, N–H…O, and C–H…Cl types interweave monomeric units and stabilize the overall crystal structures in both complexes. Thermal analysis and antibacterial activities of 1 and 2 against various bacterial strains were also investigated.     

Characteristics of copper sulfide nanoparticles obtained in the copper sulfate–sodium thiosulfate system

Stable hydrosols of copper sulfide nanoparticles are synthesized by heating aqueous solutions with different ratios of sodium thiosulfate and copper sulfate in the presence of polyvinylpyrrolidone and studied by a number of physicochemical methods in situ (optical spectroscopy, dynamic light scattering) and ex situ (transmission electron microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy). The main product is CuS covellite nanoparticles with some impurities of other phases (Cu₂S, Cu_1,8S, Cu₇S₄). With an increase in the initial molar ratio S₂O ^2?₃ / Cu from 0.2 to 5 the nanoparticle size increases from 1-5 nm to 30-50 nm and then decreases to 4 nm at a ratio of 10. A substantial increase in the intensity of plasmon absorption within 800-1500 nm is observed during the formation of planar nanoparticles with a lateral size of about 30 nm at S₂O ^2?₃:Cu = 5. A band gap obtained from both direct and indirect optical absorption spectra of sulfides (2.6 eV and 1.7 eV respectively) remains constant for all particles.     

Nickel(II) and copper(II) – l-cysteine,l-methionine,l-tryptophan-nucleotide ternary complexes

Four new ternary complexes of Cu^II with l-methionine and the nucleotides 5AMP (adenosine 5-phosphate), 5GMP (guanosine 5-phosphate) and 5IMP (inosine 5-phosphate), and with l-tryptophan and 5AMP, were synthesized and characterized by elemental analysis and i.r. spectroscopy. One ternary complex of N^II with l-cysteine and 5IMP was also prepared and characterized. The study of the three ternary compounds of Cu^II, of general formulae Cu-5NMP-l-methionine, indicates coordination of the phosphate group and of N(7) of the purinic ring. l-Methionine is bound by the carboxylic and amino groups. The ternary complex obtained from a mixture of Cu-5AMP and l-tryptophan is a dimer in which the nucleotide bridges the two copper atoms. In the complex of Ni-5IMP and l-cysteine, the nucleotide seems to bind the metal through the N(7) of the heterocyclic ring, and the l-cysteine is coordinated as a bidentate chelate by the carboxyl and thiol groups. E.s.r. spectra of the copper complexes are in good agreement with the low symmetry structure proposed. The one-electron reduction potentials E_c(Fc⁺/Fc) (V) of Cu^II to Cu^I were established for the four copper complexes from cyclic voltammetry studies. The one-electron oxidation potential E_a(Fc⁺/Fc⁺) (V) of Ni^II to Ni^III was also measured for the nickel complex.     

Pyridoxylidene aminoguanidine and its copper(II) complexes – Syntheses,structure, and DFT calculations

Two nitrate salts of the well-known, and due to its significant biological activity very important, compound pyridoxylidene aminoguanidine (PLAG) were obtained in the form of single crystals. Thus this ligand is structurally characterized for the first time. In addition, the first data on the structure of a Schiff base of aminoguanidine with the active form of vitamin B₆, i.e. pyridoxal-phosphate, of the formula PLPAG·HCl·2H₂O, are presented. Two new square-pyramidal Cu(II) complexes of PLAG were synthesized and their physicochemical and structural properties analyzed. In these complexes, PLAG is coordinated as a zwitter-ion, in a tridentate ONN manner, via the oxygen atom of the deprotonated phenolic OH-group and nitrogen atoms of the azomethine and imino group of the aminoguanidine moiety. For the first time it was possible to make a comparative analysis of the structural properties of ligand salts and the coordinated ligand, so the effects of coordination could be unequivocally pointed out. Common fragments encountered in ligand structures were compared by half-normal probability plots. Density functional theory calculations have been conducted in order to gain insight into reactive properties of the investigated molecules. Molecular electrostatic potential, average local ionization energy surfaces, and Fukui functions have been calculated in order to obtain further information on the reactive properties.     

What determines the inhibition effectiveness of ATA, BTAH, and BTAOH corrosion inhibitors on copper?

Three corrosion inhibitors for copper-3-amino-1,2,4-triazole (ATA), benzotriazole (BTAH), and 1-hydroxybenzotriazole (BTAOH)-were investigated by corrosion experiments and atomistic computer simulations. The trend of corrosion inhibition effectiveness of the three inhibitors on copper in near-neutral chloride solution is determined experimentally as BTAH ? ATA ? BTAOH. A careful analysis of the results of computer simulations based on density functional theory allowed to pinpoint the superior inhibiting action of BTAH and ATA as a result of their ability to form strong N-Cu chemical bonds in deprotonated form. While these bonds are not as strong as the Cl-Cu bonds, the presence of solvent favors the adsorption of inhibitor molecules onto the surface due to stronger solvation of the Cl(-) anions. Moreover, benzotriazole displays the largest affinity among the three inhibitors to form intermolecular aggregates, such as [BTA-Cu](n) polymeric complex. This is another factor contributing to the stability of the protective inhibitor film on the surface, thus making benzotriazole an outstanding corrosion inhibitor for copper. These findings cannot be anticipated on the basis of inhibitors' molecular electronic properties alone, thus emphasizing the importance of a rigorous modeling of the interactions between the components of the corrosion system in corrosion inhibition studies.     

Extraction of cadmium,lead, cobalt,copper, and zinc ions from aqueous solutions into hydrophilic–hydrophobic ionic liquids

Extraction of cadmium(II), lead(II), cobalt(II), copper(II), and zinc(II) into ionic liquids tetraoctylammonium N-lauroyl sarcosinate and trioctylmethylammonium salicylate is studied. Cadmium(II), lead(II), copper(II) in tetraoctylammonium N-lauroyl sarcosinate and copper(II) in trioctylmethylammonium salicylate are quantitatively extracted from neutral and weakly alkaline solutions in the absence of additional reagents. The effect of the composition of aqueous and organic phases, as well as the contact time, on metal extraction is investigated.