Preparation, characterization and electrochemical studies of dinuclear copper(II) complexes with pseudohalides and bidentate amines on platinum electrode in acetonitrile

The complexes: [Cu(N 3) 2(N,N-diEten)] 2, [Cu(N 3) 2(tmeen)] 2, [Cu(N 3)(NCO)(N,N-diEten)] 2, [Cu(N 3) 2(N,N′-diMeen)] 2 and [Cu(N 3)(NCO)(tmeen)] 2 were prepared, characterized and their electrochemical behavior was investigated by cyclic voltammetry and controlled potential electrolysis. Cyclic voltammograms for all complexes studied are similar and exhibit one pair of current peaks in the range of -0.65 to +0.0 V. The number of electrons obtained from controlled potential electrolysis at ca. -0.55 V for all compounds was 1.8 ≤ n ≤ 2.1, indicating that both copper(II) metallic centres in the molecule were reduced to copper (I). Comparing the peak potential values for these complexes one can observe that the redox process corresponding to copper(II)/copper(I) couple is slightly influenced by the σ-basicity of the ligands. © 1997 Soc. Bras. Química.

Minimization of lead and copper interferences on spectrophotometric determination of cadmium using electrolytic deposition and ion-exchange in multi-commutation flow system

A new strategy for minimization of Cu2+ and Pb2+ interferences on the spectrophotometric determination of Cd2+ by the Malachite green (MG)-iodide reaction using electrolytic deposition of interfering species and solid phase extraction of Cd2+ in flow system is proposed. The electrolytic cell comprises two coiled Pt electrodes concentrically assembled. When the sample solution is electrolyzed in a mixed solution containing 5% (v/v) HNO3, 0.1% (v/v) H2SO4 and 0.5 M NaCl, Cu2+ is deposited as Cu on the cathode, Pb2+ is deposited as PbO2 on the anode while Cd2+ is kept in solution. After electrolysis, the remaining solution passes through an AG1-X8 resin (chloride form) packed minicolumn in which Cd2+ is extracted as CdCl4/2-. Electrolyte compositions, flow rates, timing, applied current, and electrolysis time was investigated. With 60 s electrolysis time, 0.25 A applied current, Pb2+ and Cu2+ levels up to 50 and 250 mg 1-1, respectively, can be tolerated without interference. For 90 s resin loading time, a linear relationship between absorbance and analyte concentration in the 5.00-50.0 μg Cd 1-1 range (r2 = 0.9996) is obtained. A throughput of 20 samples per h is achieved, corresponding to about 0.7 mg MG and 500 mg KI and 5 ml sample consumed per determination. The detection limit is 0.23 μg Cd 1-1. The accuracy was checked for cadmium determination in standard reference materials, vegetables and tap water. Results were in agreement with certified values of standard reference materials and with those obtained by graphite furnace atomic absorption spectrometry at 95% confidence level. The R.S.D. for plant digests and water containing 13.0 μg Cd 1-1 was 3.85% (n = 12). The recoveries of analyte spikes added to the water and vegetable samples ranged from 94 to 104%. (C) 2000 Elsevier Science B.V.

Study of the electrochemical behavior of histamine using a Nafion®-copper (II) hexacyanoferrate film-modified electrode

A study on the electrochemical behavior of histamine species in aqueous medium is described. A glassy carbon electrode chemically modified with copper (II) hexacyanoferrate (CuHCFe) film and covered with Nafion® film was employed. The interaction between the analyte and the CuHCFe film can be demonstrated by a decrease in both the cathodic and anodic peak currents at 0.68V (vs. Ag/AgCl), attributed to the film and the appearance of new peak current at 0.47V. Cyclic voltammetric parameters obtained for histamine indicate the formation of stable complex between histamine adsorbed at the electrode surface. The dependence of peak currents on the concentration of the analyte is not linear in the employed work range, indicating the presence of a coupled chemical reaction in the electrodic process. © 2010 by ESG.

TiO2-Cu photocatalysts: A study on the long- and short-range chemical environment of the dopant

In this study, the short- and long-range chemical environments of Cu dopant in TiO2 photocatalyst have been investigated. The Cu-doped and undoped TiO2 specimens were prepared by the sol-gel approach employing CuSO4·5H2O and Ti(O-iPr)4 precursors and subjecting the dried gels to thermal treatment at 400 and 500 C. The photocatalytic activity, investigated by methylene blue degradation under sunlight irradiation, showed a significantly higher efficiency of Cu-doped samples than that of pure TiO2. The X-ray diffraction results showed the presence of anatase phase for samples prepared at 400 and 500 C. No crystalline CuSO4 phase was detected below 500 C. It was also found that doping decreases the crystallite size in the (004) and (101) directions. Infrared spectroscopy results indicated that the chemical environment of sulfate changes as a function of thermal treatment, and UV-vis spectra showed that the band gap decreases with thermal treatment and Cu doping, showing the lowest value for the 400 C sample. X-ray absorption fine structure measurements and analysis refinements revealed that even after thermal treatment and photocatalytic assays, the Cu2+ local order is similar to that of CuSO4, containing, however, oxygen vacancies. X-ray photoelectron spectroscopy data, limited to the near surface region of the catalyst, evidenced, besides CuSO4, the presence of Cu1+ and CuO phases, indicating the active role of Cu in the TiO2 lattice. © 2013 Springer Science+Business Media New York.

An alternative method for the simultaneous determination of copper and lead for quality control of sugar cane spirit using a nanotube-based sensor

The development of an electroanalytical method for simultaneous determination of copper and lead ions in sugar cane spirit (cachaça) using carbon paste electrode modified with ascorbic acid and carbon nanotubes (CPE-AaCNT) is described. Squarewave voltammetry (SWV) with anodic stripping was employed, and this technique was optimized with respect to the following parameters: frequency (50 Hz), amplitude (100 mV) and scan increment (9 mV). The analytical curves were linear in the range from 0.0900 to 7.00 mg L - 1 for lead and copper. The limits of detection were 48.5 and 23.9 µg L - 1 for lead and copper, respectively. The developed method was applied to the simultaneous determination of copper and lead in five commercial samples of sugar cane spirit. The results were in good agreement with those obtained by F AAS/GF AAS (flame atomic absorption spectrometry/graphite furnace atomic absorption spectrometry) and showed that CPE-AaCNT can be successfully employed in the simultaneous determination of these metals in real sugar cane spirit samples.

Determination of ethyl carbamate in cachaça produced from copper stills by HPLC

Ethyl carbamate (EC) is a common substance in fermented foods and drinks, and its quantification is important because of its carcinogenic nature and its usually presence in alcoholic beverages. The present work involved the development and validation of an analytical method for the evaluation of EC in cachaça by HPLC-FLD after previous derivatization with xanthydrol. The method presented a mean recovery of 94.88%, an intra-day precision of 4.19% (30.0 μg L−1) and 3.32% (75.0 μg L−1), a coefficient of determination (r2) equal to 0.9985, and limits of detection and quantification equal to 6.39 and 21.32 μg L−1, respectively. The results show that the analytical method is accurate, reproducible and linear over the concentration range from 5.0 to 160 μg of EC per litre. The method was applied to the analysis of EC in cachaça, the analyses being rapid and efficient.

Square-wave voltammetric determination of rutin in pharmaceutical formulations using a carbon composite electrode modified with copper (II) phosphate immobilized in polyester resin

Descreve-se um eletrodo de carbono modificado com fosfato de cobre (II) imobilizado em uma resina de poliéster (Cu₃(PO₄)₂-Poly) para a determinação de rutina em amostras farmacêuticas por voltametria de onda quadrada. O eletrodo modificado permite a determinação de rutina em potencial (0.20 V vs Ag / AgCl (3,0 mol L^-1 KCl)) menor que o observado em um eletrodo não modificado. Verificou-se que a corrente de pico foi linear com a concentração de rutina na faixa de 9,9 × 10^-8 a 2,5 × 10^-6 mol L^-1, com um limite de detecção de 1,2 × 10^-8 mol L^-1. A resposta do eletrodo foi estável, sem variação significativa dentro de várias horas de operação contínua. A morfologia da superfície do eletrodo modificado foi caracterizada por microscopia eletrônica de varredura (MEV) e pelo sistema de energia dispersiva de raios-X (EDX). Os resultados obtidos foram precisos e exatos. Ademais, estes resultados estão de acordo com aqueles obtidos pelo método cromatográfico a um nível de confiança de 95%.

Multivariate curve resolution analysis applied to time-resolved synchrotron X-ray Absorption Spectroscopy monitoring of the activation of copper alumina catalyst

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Kinetic role of a histidine residue in the T1 copper site of the laccase from Rigidoporus lignosus

Laccases (benzendiol:oxygen oxidoreductases; EC 1.10.3.2) catalyze the oxidation of a broad range of substrates, such as polyphenols, dyes and pollutants, and thus these enzymes are widely applied in industrial, biotechnological and environmental fields. In order to improve their biotechnological applications, a deep knowledge of structural factors involved in controlling their activity, in various experimental conditions and on different substrates, is required. In the present study, a laccase from the mushroom Rigidoporus lignosus was kinetically characterized. In particular, the stability, the effects of pH, ionic strength and fluoride ion concentration on the kinetic parameters were investigated, using three di-hydroxy-benzene isomers (1,2-dihydroxy-benzene, 1,3-dihydroxy-benzene and 1,4-dihydroxy-benzene) as substrates. The catalytic constant values of the laccase showed a bell-shaped pH profile, with the same optimum pH and pK(a) values for all tested substrates. This behavior appears to be due to the presence of an ionizable residue in the enzyme active site. To identify this residue, the enzyme was derivatized with diethylpyrocarbonate to modify accessible histidine residues, which, according to structural data, are present in the active site of this enzyme. The kinetic behavior of the derivatized laccase was compared with that of the native enzyme and the derivatized residues were identified by mass spectrometry. Mass spectrometry and kinetic results suggest the main role of His-457 in the control of the catalytic activity of laccase from R. lignosus. (C) 2013 Elsevier B.V. All rights reserved.

Hydroxyquinoline derived vanadium(IV and V) and copper(II) complexes as potential anti-tuberculosis and anti-tumor agents

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Voltammetric behaviour of a modified electrode with azide copper octa(3-aminopropyl)octasilsesquioxane composite in the oxidation of ascorbic acid

A novel nanostructured composite, azide copper octa (3-aminopropyl)octasilsesquioxane (ASCA) was incorporated into a graphite paste electrode and the electrochemical studies were conducted with cyclic voltammetry. The cyclic voltammogram of the modified graphite paste electrode with ASCA (GPE-ASCA), showed one redox couple with formal potential (E  ) = 0.30 V and an irreversible process at 1.1 V (vs Ag/AgCl; NaCl 1.0 mol L-1 ; v = 20 mV s-1 ). The redox couple with (E  ) = 0.30V presents an electrocatalytic response for determination of ascorbic acid. The modified electrode gives a linear range from 1.010-4 – 1.010-3 mol L-1 (r = 0.998) for the determination of ascorbic acid with detection limit of 6.910-5 mol L-1 and standard deviation of 2.3% for n = 3 . The amperometric sensitivity was 122.1 mA/mol L-1 for ascorbic acid. The application this electrode was tested and ascorbic acid in three commercial pharmaceutical product (Cebion, Cewin and Redoxon) have been determined.

Correlation between structural and catalytic properties of copper supported on porous alumina for the ethanol dehydrogenation reaction

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

An Alternative Method for the Simultaneous Determination of Copper and Lead for Quality Control of Sugar Cane Spirit using a Nanotube-Based Sensor

The development of an electroanalytical method for simultaneous determination of copper and lead ions in sugar cane spirit (cachaca) using carbon paste electrode modified with ascorbic acid and carbon nanotubes (CPE-AaCNT) is described. Squarewave voltammetry (SWV) with anodic stripping was employed, and this technique was optimized with respect to the following parameters: frequency (50 Hz), amplitude (100 mV) and scan increment (9 mV). The analytical curves were linear in the range from 0.0900 to 7.00 mg L-1 for lead and copper. The limits of detection were 48.5 and 23.9 mu g L-1 for lead and copper, respectively. The developed method was applied to the simultaneous determination of copper and lead in five commercial samples of sugar cane spirit. The results were in good agreement with those obtained by F AAS/GF AAS (flame atomic absorption spectrometry/graphite furnace atomic absorption spectrometry) and showed that CPE-AaCNT can be successfully employed in the simultaneous determination of these metals in real sugar cane spirit samples.

Flow injection analysis of free glycerol in biodiesel using a copper electrode as an amperometric detector

The main goal of this work was to develop a simple analytical method for quantification of glycerol based on the electrocatalytic oxidation of glycerol on the copper surface adapted in a flow injection system. Under optimal experimental conditions, the peak current response increases linearly with glycerol concentration over the range 60-3200 mg kg(-1) (equivalent to 3-160 mg L(-1) in solution). The repeatability of the electrode response in the flow injection analysis (FIA) configuration was evaluated as 5% (n = 10), and the detection limit of the method was estimated to be 5 mg kg(-1) in biodiesel (equivalent to 250 mu g L(-1) in solution) (S/N = 3). The sample throughput under optimised conditions was estimated to be 90 h(-1). Different types of biodiesel samples (B100), as in the types of vegetable oils or animal fats used to produce the fuels, were analysed (seven samples). The only sample pre-treatment used was an extraction of glycerol from the biodiesel sample containing a ratio of 5 mL of water to 250 mg of biodiesel. The proposed method improves the analytical parameters obtained by other electroanalytical methods for quantification of glycerol in biodiesel samples, and its accuracy was evaluated using a spike-and-recovery assay, where all the biodiesel samples used obtained admissible values according to the Association of Official Analytical Chemists. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.

Urinary copper excretion before and after oral intake of D-penicillamine in parents of patients with Wilson's disease

Background: Urinary copper excretion higher than 100 mu g/24 h is useful for diagnosing Wilson's disease. D-Penicillamine challenge test may produce higher levels than 1400 mu g/24 h, allowing for better diagnostic accuracy. This study investigated whether heterozygotes reach this value and compared copper serum levels, ceruloplasmin, and urinary copper excretion before and after administering D-penicillamine to the parents of Wilson's disease patients. Methods: Fifty parents of adult patients were enrolled to obtain copper serum levels and ceruloplasmin along with 24-h urinary copper excretion before and after administering 1 g D-penicillamine. Results: Serum ceruloplasmin and copper levels were significantly lower in fathers than in mothers (mean 21.8 x 27.8 mg%; 71.4 x 88.0 mu g%; p <= 0.001). The mean of basal 24-h urinary copper excretion was higher in fathers (26.2 x 18.7 mu g/24 h, p = 0.01), but did not differ between the genders after D-penicillamine (521.7 x 525.3, range 31.6-1085.1 mu g/24 h, p = 0.8). Conclusions: The mean values of serum copper, ceruloplasmin, and basal urinary copper excretion were different between males and females. The current diagnostic threshold of 24-h urinary copper excretion after D-penicillamine was not reached by heterozygotes. The increased urinary copper excretion after D-penicillamine challenge was much higher than fivefold the upper limit of normal urinary copper excretion in the majority of heterozygotes and should not be taken into account when diagnosing Wilson's disease. (C) 2011 Editrice Gastroenterologica Italiana S.r.l. Published by Elsevier Ltd. All rights reserved.