Electrometric monitoring of water adsorption by porous glass modified with copper(II) oxide

Modification of porous glass with copper(II) oxide with planar structure does not change the run of the water-adsorption isotherm, whereas in the case when nanoparticles are formed from the supported oxide, a cluster-type adsorption mechanism is operative when a relative pressure p/p ₀ > 0.5 is reached. These specific features are reflected in the different dependences of the electrical resistance of the samples on humidity. It was shown that a porous glass with distributed copper(II)oxide planar layer can be used as a sensitive element of a resistive humidity sensor.     

Synthesis of copper(II) oxide hydrosols

A procedure is developed for the synthesis of copper(II) oxide hydrosols. It is shown that the main parameters that govern the reproducibility of the synthesis results and the aggregation stability of synthesized hydrosols are the temperature of copper(II) nitrate hydrolysis and the concentration of a peptizing agent. Dispersed phase particles are shown to have a cylindrical shape with a prevailing length-to-diameter ratio of approximately 2.7.     

Emission quenching of binuclear pyrophosphito platinum(II) complexes in aqueous solution by sulphur dioxide. Spectroscopic measurements on sulphur dioxide addition and chromous ion reduction

The emission intensity at 517 nm from Pt₂(pop)₄⁴⁻ (pop = P₂O₅H₂²⁻) is quenched by the addition of sulphur dioxide. The sulphur dioxide coordinates at the axial platinum(II) sites by a η¹-SO₂ bond. This coordination is supported by ³¹p NMR and Raman spectroscopy of aqueous solutions. The electronic spectrum of a sulphur dioxide saturated solution of Pt₂(pop)₄⁴⁻ shows an absorption at 428.5nm ( = 4.1 × 10⁴). From the decrease in the chromophore for uncomplexed Pt₂(pop)₄⁴⁻ the equilibrium constant for SO₂ binding is estimated to be 1.74 M₂l⁻². The effect of adding different quenchers to aqueous solutions of Pt_2(pop)4⁴⁻ is discussed. The compound Pt₂(pop)₄⁴⁻ will undergo 2-electron reduction with chromous ion.     

Extraction of lead(II) and copper(II) from salicylate media by tributylphosphine oxide.

Tributylphosphine oxide (TBPO) is proposed as an extractant for the extraction of lead(II) and copper(II) from salicylate media. The optimum conditions were evaluated by varying the experimental parameters, such as the pH, sodium salicylate concentration, tributylphosphine oxide (TBPO) concentration, shaking period and various diluents. The probable extracted species, deduced from log-log plots were Pb(HSal)2.2TBPO and Cu(HSal)2.2TBPO. The extraction took place through a solvation mechanism. The method permits the binary separation of lead(II) and copper(II) from commonly associated elements as well as the mutual separation of lead(II) and copper(II). The method is applicable to the determination of lead(II) and copper(II) in various alloys as well as environmental and pharmaceutical samples.     

Direct asymmetric aldol reactions catalyzed by nanocrystalline copper(II) oxide

The direct asymmetric aldol reactions of aromatic and heteroaromatic aldehydes with acetone to afford chiral β-hydroxy carbonyl compounds in good yields and good to moderate enantioselectivities are realized using nanocrystalline copper(II) oxide in the presence of (1S,2S)-(−)-1,2-diphenylethylenediamine at −30 °C. The catalyst can be reused for four cycles with consistent activity and enantioselectivity.     

Nitric oxide reduction of copper(II) complexes: spectroscopic evidence of copper(II)-nitrosyl intermediate

Two copper(II) complexes, 1 and 2 with L(1) and L(2) [L(1) = 2- aminomethyl pyridine; L(2) = bis-(2-aminoethyl)amine], respectively, in degassed acetonitrile solvent, on exposure to NO gas, were found to form a thermally unstable [Cu(II)-NO] intermediate which then resulted in the reduction of the copper(II) centers. The formation of the [Cu(II)-NO] intermediate was evidenced by UV-visible, FT-IR, and EPR spectroscopic studies. The reduction of the copper(II) centers by nitric oxide afforded ligand transformation through diazotization at the primary amine coordination site, in both cases. The modified ligands, in each case, were isolated and characterized.     

Thermal decomposition kinetics of diethyl dithiocarbamate complexes of copper(II) and nickel(II)

Thermogravimetric (TG), derivative thermogravimetric (DTG) and differential thermal analysis (DTA) curves of CuL₂ and NiL₂ (L^?=diethyl dithiocarbamate anion) in air are studied. The main decomposition temperature ranges are: For CuL₂, DTG 250–350°, DTA 300–320° and for NiL₂, DTG 290–390°, DTA 360–400°. Mass loss considerations at the main decomposition stages indicate conversion of the complex to sulphides. Mathematical analysis of TG data shows that first order kinetics are applicable in both cases. Kinetic parameters (energy and entropy of activation and preexponential factor) are reported.

     

Direct nitric oxide detection in aqueous solution by copper(II) fluorescein complexes

A series of FL(n) (n = 1-5) ligands, where FL(n) is a fluorescein modified with a functionalized 8-aminoquinoline group as a copper-binding moiety, were synthesized, and the chemical and photophysical properties of the free ligands and their copper complexes were investigated. UV-visible spectroscopy revealed a 1:1 binding stoichiometry for the Cu(II) complexes of FL(1), FL(3), and FL(5) in pH 7.0 buffered aqueous solutions. The reactions of FL(2) or FL(4) with CuCl(2), however, appear to produce a mixture of 1:1 and 1:2 complexes, as suggested by Job's plots. These binding modes were modeled by the synthesis and X-ray crystal structure determination of Cu(II) complexes of 2-[(quinolin-8-ylamino)methyl]phenol (modL), employed as a surrogate of the FL(n) ligand family. Two kinds of crystals, [Cu(modL)(2)](BF(4))(2) and [Cu(2)(modL')(2)(CH(3)OH)](BF(4))(2) (modL' = 2-[(quinolin-8-ylamino)methyl]phenolate), were obtained. The structures suggest that one oxygen and two nitrogen atoms of the FL(n) ligands most likely bind to Cu(II). Introduction of nitric oxide (NO) to pH 7.0 buffered aqueous solutions of Cu(FL(n)) (1 microM CuCl(2) and 1 microM FL(n)) at 37 degrees C induces an increase in fluorescence. The fluorescence response of Cu(FL(n)) to NO is direct and specific, which is a significant improvement over commercially available small molecule-based probes that are capable of detecting NO only indirectly. The NO-triggered fluorescence increase of Cu(FL(5)) occurs by reduction of Cu(II) to Cu(I) with concomitant dissociation of the N-nitrosated fluorophore ligand from copper. Spectroscopic and product analyses of the reaction of the FL(5) copper complex with NO indicated that the N-nitrosated fluorescein ligand (FL(5)-NO) is the species responsible for fluorescence turn-on. Density functional theory (DFT) calculations of FL(5) versus FL(5)-NO reveal how N-nitrosation of the fluorophore ligand brings about the fluorescence increase. The copper-based probes described in the present work form the basis for real-time detection of nitric oxide production in living cells.     

Thermal decomposition kinetics of Schiff base complexes of copper(II) and palladium(II)

Thermogravimetric (TG), derivative thermogravimetric (DTG) and differential thermal analysis (DTA) curves of CuL₂ and Pd(LH)₂Cl₂ (LH=salicylidene-2-aminofluorene and 2-hydroxy-1-naphthalidene-2-aminofluorene) in air are studied. Mass loss considerations at the main decomposition stages indicate conversion of the complex to oxides. Mathematical analysis of TG data shows that first order kinetics are applicable in all cases. Kinetic parameters (energy and entropy of activation and preexponential factor) are reported.     

Simulation of the effect of hydroxyethylidenediphosphonic acid on the kinetics of copper(II) oxide dissolution in sulfuric acid

The effect of hydroxyethylidenediphosphonic acid (HEDP) on the kinetics of copper(II) oxide dissolution in aqueous sulfuric acid was studied. The addition of HEDP in acidic media decreases the CuO dissolution rate. The simulation of these processes showed that the inhibiting effect is due to the decrease in the concentration of the intermediate compound (CuOH⁺), which restricts the dissolution of Cu²⁺ ions, due to adsorption of the HEDP ions (H₄Y^?) on the oxide surface.     

Complexes of chromium(III), cobalt(II) and copper(II) with sulphur or oxygen and nitrogen donors

Summary The synthesis and characterization of 4-acetyl-pyridinesemicarbazone (4-apsc) and 4-acetylpyridine-thiosemicarbazone (4-aptsc) and their complexes with CrCl₃, CoCl₂ and CuCl₂ are reported. These compounds were characterized on the basis of elemental analyses, electronic and i.r. spectra, magnetic moments and conductivities measurements. The compounds are nonconductors in dimethylformamide. Tentative structures for the complexes are suggested.     

Effect of incorporation of sodium into copper(II) oxide

Copper(II) oxide containing different amounts of sodium has been prepared. Thermo-analytical studies reveal differences in behaviour between sodium-incorporated samples and the control sample. A strong esr signal withg=2.1 is explained by assuming a square planar configuration around the Cu²⁺ ion. The spin concentration is found to vary linearly with the sodium content, each sodium decoupling the spins of 40 Cu²⁺ ions in CuO. The signal is found to be present even in a reduced sample. The origin of such species is explained on the basis of antiferromagnetic decoupling of spins.The authors are grateful to Mr. A. N. Dutta for carrying out the DTA and TG experiments, to Dr. P. C. Srivastava for sodium analysis and to Dr. S. K. Ghosh, M. L. Kundu and G. Sengupta for helpful discussions.     

Manganese(II) and copper(II) complexes of some nitrogenoxygen and nitrogensulphur donor ligands

Manganese(II) and copper(II) complexes of the type M(ligandH)₂ with some nitrogenoxygen and nitrogensulphur donor ligands (HL) viz. phenylpyruvic acid semicarbazone (ppysc), 4-methylphenylpyruvic acid semicarbazone (4-mppysc), phenylpyruvic acid thiosemicarbazone (ppytsc) and 4-methylphenyl pyruvic acid thiosemicarbazone (4-ppytsc), have been synthesised. All the complexes have been characterised by magnetic moment measurements, IR electronic and electron spin resonance special studies. All the ligands behave as tridentate.     

Studies of the effects of copper, copper(II) oxide and copper(II) chloride on the thermal degradation of poly(vinyl chloride)

Investigations of the pyrolysis of poly(vinyl chloride) (PVC) in the presence of copper metal (Cu), copper(II) oxide (CuO) and copper(II) chloride (CuCl₂) are of potential importance because of the likelihood of the formation of these copper compounds during the thermal degradation of PVC-coated copper wires, a step in the recovery of copper from waste. The presence of Cu, CuO and CuCl₂ (i) retards the thermal degradation of PVC in air and in nitrogen and (ii) decreases the percentages of volatile products produced at both stages of the decomposition. These effects are greatest for PVC-CuO. The presence of copper, CuO or CuCl₂ in PVC has a major effect on the nature of the gaseous emissions of the thermal decomposition in air and in nitrogen. The concentrations of total chlorine, aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons and soot particulates are all affected relative to an equivalent amount of PVC. These changes are greatest for the PVC-CuO system for which total chlorine emissions in air and nitrogen are reduced by 40% in air and 20% in nitrogen, benzene emissions are reduced by greater than 90% in air and nitrogen, other aromatic and chloroaromatic emissions are reduced, and soot particulate emissions are reduced by more than 50% as the concentrations of aliphatic compounds are increased. These changes are consistent with the presence of copper or its compounds permitting more efficient combustion of the carbon content of the PVC and particularly in the case of PVC-CuO with the removal of chlorine during pyrolysis in the inorganic phase.     

Electron-transfer kinetics of copper(II/I) tripodal ligand complexes

The electron-transfer kinetics for each of three copper(II/I) tripodal ligand complexes reacting with multiple reducing and oxidizing counter reagents have been examined in aqueous solution at 25 degrees C, mu = 0.10 M. For all of the ligands studied, an amine nitrogen serves as the bridgehead atom. Two of the ligands (PMMEA and PEMEA) contain two thioether sulfurs and one pyridyl nitrogen as donor atoms on the appended legs while the third ligand (BPEMEA) has two pyridyl nitrogens and one thioether sulfur. Very limited kinetic studies were also conducted on two additional closely related tripodal ligand complexes. The results are compared to our previous kinetic study on a Cu(II/I) system involving a tripodal ligand (TMMEA) with thioether sulfur donor atoms on all three legs. In all systems, the Cu(II/I) electron self-exchange rate constants (k(11)) are surprisingly small, ranging approximately 0.03-50 M(-)(1) s(-)(1). The results are consistent with earlier studies reported by Yandell involving the reduction of Cu(II) complexes with four similar tripodal ligand systems, and it is concluded that the dominant reaction pathway involves a metastable Cu(II)L intermediate species (designated as pathway B). Since crystal structures suggest that the ligand reorganization accompanying electron transfer is relatively small compared to our earlier studies on macrocyclic ligand complexes of Cu(II/I), it is unclear why the k(11) values for the tripodal ligand systems are of such small magnitude.     

Effect of copper(II) ions on kinetics of ascorbic acid oxidation by methylene blue

A kinetic scheme is proposed for the reduction of methylene blue by ascorbic acid in the presence of copper(II) ions. The introduction of copper(II) ions increases the reaction rate, owing to the increased concentration of ascorbic acid radicals in the solution. It is shown that the inhibition of the reaction that is observed with low concentrations of copper(II) is a result of redox reactions proceeding in the system, involving oxygen dissolved in the water.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 5, pp. 277–282, September–October, 1994.     

A magnetic copper(II)-imprinted polymer for the selective enrichment of trace copper(II) ions in environmental water

We have developed a convenient, selective and reliable method for the rapid enrichment of trace quantities of Cu(II) by using a magnetic Cu(II) ion-imprinted polymer. This is followed by their determination by FAAS. The imprints were prepared by using (a) Cu(II) ions as the template, (b) 3-aminopropyltriethoxysilane as both the functional monomer and the crosslinking agent, and (c) Fe₃O₄ as the magnetic component. Enrichment is carried out in a single step, and adsorbed copper ions can be separated from the sample solution by applying a strong magnet. The effects of pH, elution condition, amount of imprint, and of potentially interfering ions were evaluated. Under the optimal conditions, the detection limit and enrichment factor are 0.3?μg L^?1 and 100, respectively, and the recovery is >95?%. The procedure was successfully applied in the enrichment and detection of trace copper ions in environmental water.

Dissolution of copper oxide by the ethanolamine and ammonium fluoride in aqueous solution

Dissolution properties of copper oxide in aqueous solutions containing ethanolamine and/or ammonium fluoride have been evaluated at various pH ranges. The dissolution rate was strongly affected by the pH of the solution. The solution of ammonium fluoride showed good properties for the dissolution of copper oxide in the range of acidic conditions, whereas the solution containing ethanolamine showed a dissolution property within the basic condition. A mixture solution of ethanolamine and ammonium fluoride displayed enhanced dissolution property of copper oxide at acidic and basic conditions only. An expected synergy effect on the dissolution rate and selectivity could not be produced through a mixture of ethanolamine and ammonium fluoride in an aqueous solution. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of sulphur in petroleum products after sulphur dioxide generation and of sulphur dioxide in air by chemiluminescent flame emission

The determination of sulphur in petroleum products by combustion, concentration of the sulphur dioxide in sodium tetrachtoromercurate solutions and cool flame molecular emission is described. Improvements in burner design and optimization of analytical conditions result in a minimum detectable amount of 6 ng of sulphur. The absorption of sulphur dioxide from air samples and its determination by a similar method gives a detection limit of 1.3 μg SO₂ m^-3.