Voltammetric determination of isoprenaline in pharmaceutical preparations using a copper(II) hexacyanoferrate(III) modified carbon paste electrode

The electroanalytical determination of isoprenaline in pharmaceutical preparations of a homemade carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) was studied by cyclic voltammetry. Several parameters were studied for the optimization of the sensor such as electrode composition, electrolytic solution, pH effect, potential scan rate and interferences in potential. The optimum conditions were found in an electrode composition (in mass) of 15% CuHCF, 60% graphite and 25% mineral oil in 0.5 mol l(-1) acetate buffer solution at pH 6.0. The analytical curve for isoprenaline was linear in the concentration range from 1.96 x 10(-4) to 1.07 x 10(-3) mol l(-1) with a detection limit of 8.0 x 10(-5) mol l(-1). The relative standard deviation was 1.2% for 1.96 x 10(-4) mol l(-1) isoprenaline solution (n=5). The procedure was successfully applied to the determination of isoprenaline in pharmaceutical preparations; the CuHCF modified carbon paste electrode gave comparable results to those results obtained using a UV spectrophotometric method. (C) 2004 Elsevier B.V. All rights reserved.

Determination of Analgesics (Dipyrone and Acetaminophen) in Pharmaceutical Preparations by Cyclic Voltammetry at a Copper(II) Hexacyanoferrate(III) Modified Carbon Paste Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Study of the Electrochemical Behavior of Histamine Using a Nafion (R)-Copper(II) Hexacyanoferrate Film-Modified Electrode.

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

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.

Voltammetric determination of isoprenaline in pharmaceutical preparations using a copper(II) hexacyanoferrate(III) modified carbon paste electrode

The electroanalytical determination of isoprenaline in pharmaceutical preparations of a homemade carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) was studied by cyclic voltammetry. Several parameters were studied for the optimization of the sensor such as electrode composition, electrolytic solution, pH effect, potential scan rate and interferences in potential. The optimum conditions were found in an electrode composition (in mass) of 15% CuHCF, 60% graphite and 25% mineral oil in 0.5 mol l(-1) acetate buffer solution at pH 6.0. The analytical curve for isoprenaline was linear in the concentration range from 1.96 x 10(-4) to 1.07 x 10(-3) mol l(-1) with a detection limit of 8.0 x 10(-5) mol l(-1). The relative standard deviation was 1.2% for 1.96 x 10(-4) mol l(-1) isoprenaline solution (n=5). The procedure was successfully applied to the determination of isoprenaline in pharmaceutical preparations; the CuHCF modified carbon paste electrode gave comparable results to those results obtained using a UV spectrophotometric method. (C) 2004 Elsevier B.V. All rights reserved.

Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

Bacterial Diversity Assessment In Soil Of An Active Brazilian Copper Mine Using High-throughput Sequencing Of 16s Rdna Amplicons.

Mining activities pose severe environmental risks worldwide, generating extreme pH conditions and high concentrations of heavy metals, which can have major impacts on the survival of organisms. In this work, pyrosequencing of the V3 region of the 16S rDNA was used to analyze the bacterial communities in soil samples from a Brazilian copper mine. For the analysis, soil samples were collected from the slopes (geotechnical structures) and the surrounding drainage of the Sossego mine (comprising the Sossego and Sequeirinho deposits). The results revealed complex bacterial diversity, and there was no influence of deposit geographic location on the composition of the communities. However, the environment type played an important role in bacterial community divergence; the composition and frequency of OTUs in the slope samples were different from those of the surrounding drainage samples, and Acidobacteria, Chloroflexi, Firmicutes, and Gammaproteobacteria were responsible for the observed difference. Chemical analysis indicated that both types of sample presented a high metal content, while the amounts of organic matter and water were higher in the surrounding drainage samples. Non-metric multidimensional scaling (N-MDS) analysis identified organic matter and water as important distinguishing factors between the bacterial communities from the two types of mine environment. Although habitat-specific OTUs were found in both environments, they were more abundant in the surrounding drainage samples (around 50 %), and contributed to the higher bacterial diversity found in this habitat. The slope samples were dominated by a smaller number of phyla, especially Firmicutes. The bacterial communities from the slope and surrounding drainage samples were different in structure and composition, and the organic matter and water present in these environments contributed to the observed differences.

Bile And Liver Metallothionein Behavior In Copper-exposed Fish.

The present study analyzed metallothionein (MT) excretion from liver to bile in Nile Tilapia (Oreochromis niloticus) exposed to sub-lethal copper concentrations (2mgL(-1)) in a laboratory setting. MTs in liver and bile were quantified by spectrophotometry after thermal incubation and MT metal-binding profiles were characterized by size exclusion high performance liquid chromatography coupled to ICP-MS (SEC-HPLC-ICP-MS). Results show that liver MT is present in approximately 250-fold higher concentrations than bile MT in non-exposed fish. Differences between the MT profiles from the control and exposed group were observed for both matrices, indicating differential metal-binding behavior when comparing liver and bile MT. This is novel data regarding intra-organ MT comparisons, since differences between organs are usually present only with regard to quantification, not metal-binding behavior. Bile MT showed statistically significant differences between the control and exposed group, while the same did not occur with liver MT. This indicates that MTs synthesized in the liver accumulate more slowly than MTs excreted from liver to bile, since the same fish presented significantly higher MT levels in liver when compared to bile. We postulate that bile, although excreted in the intestine and partially reabsorbed by the same returning to the liver, may also release MT-bound metals more rapidly and efficiently, which may indicate an efficient detoxification route. Thus, we propose that the analysis of bile MTs to observe recent metal exposure may be more adequate than the analysis of liver MTs, since organism responses to metals are more quickly observed in bile, although further studies are necessary.

Weight Variation In Users Of Depot-medroxyprogesterone Acetate, The Levonorgestrel-releasing Intrauterine System And A Copper Intrauterine Device For Up To Ten Years Of Use.

Data on record regarding weight variation in depot-medroxyprogesterone acetate (DMPA) and levonorgestrel-releasing intrauterine system (LNG-IUS) users are controversial. To date, no studies have yet evaluated weight variation in DMPA and LNG-IUS users in up to ten years of use compared to non-hormonal contraceptive users. A retrospective study analysed weight variations in 2138 women using uninterruptedly DMPA (150 mg intramuscularly, three-monthly; n = 714), the LNG-IUS (n = 701) or a copper-intrauterine device (Cu-IUD; n = 723). At the end of the first year of use, there was a mean weight increase of 1.3 kg, 0.7 kg and 0.2 kg among the DMPA-, LNG-IUS- and Cu-IUD users, respectively, compared to weight at baseline (p < 0.0001). After ten years of use, the mean weight had risen by 6.6 kg, 4.0 and 4.9 kg among the DMPA-, LNG-IUS- and Cu-IUD users, respectively. DMPA-users had gained more weight than LNG-IUS- (p = 0.0197) and than Cu-IUD users (p = 0.0294), with the latter two groups not differing significantly from each other in this respect (p = 0.5532). Users of hormonal and non-hormonal contraceptive methods gained a significant amount of weight over the years. DMPA users gained more weight over the treatment period of up to ten years than women fitted with either a LNG-IUS or a Cu-IUD.

EPR and magnetic studies of a carboxylate-bridged dinuclear copper(II) compound: [cu2(flu)4(dmf)2]

We report magnetic and EPR (electron paramagnetic resonance) spectroscopy studies of [Cu2(flu)4(dmf)2] (flu = flufenamate and dmf = dimethylformamide), which has CuII ions in tetracarboxylate "paddle wheel" dinuclear units. Susceptibility measurements at 10 < T < 275 K allowed the evaluation of an antiferromagnetic intradinuclear exchange coupling J0 = -294 ± 5 cm-1 between CuII ions (Hex = "J0 S1·S2). EPR experiments at 300 K in powder and single-crystals at 9.5 and 34.4 GHz indicated g// = 2.373, g⊥ = 2.073 and zero field splitting parameters D = (-0.334 ± 0.001) cm"1 and E ca. 0. EPR signal intensity measurements at X-band in the range 4 < T < 295 K indicated that J0 = "283 ± 5 cm"1. A higher limit |J´| < 5×10-3 cm-1 for the interdinuclear exchange coupling between neighbor units at ca.14.24 Å was estimated from the angular variation of the single crystal spectra around the magic angles. The results are discussed in terms of the structure of the dinuclear unit and the bridges connecting CuII ions and compared with values reported for similar compounds.

Metallochlorophylls of magnesium, copper and zinc: evaluation of the influence of the first coordination sphere on their solvatochromism and aggregation properties

In this study the role of different metal centers (magnesium, zinc and copper) on the enhancement of the hydrophilic character of metallochlorophylls, was evaluated. The solvatochromism as well as the aggregation process for these compounds in water/ethanol mixtures at different volume ratios were evaluated using Fluorescence, and Resonant Light Scattering (RLS) measurements, aiming to characterize the behavior of these compounds. Independently on the studied metallochlorophyll, the presence of at least 60% of water results in a considerable increase in the fluorescence emission, probably a direct consequence of a lower aggregation of these compounds, which is confirmed by the results from RLS measurements. Additionally, the results suggest that magnesium and zinc chlorophyll should be promising phototherapeutic agents for Photodynamic Therapy.

Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

Herein, the immobilization of some Schiff base-copper(II) complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

Predictive values of aspartate aminotransferase and gamma-glutamyl transferase for the hepatic accumulation of copper in cattle and buffalo

Ten cattle and 10 buffalo were divided into 2 groups (control [n = 8] and experimental [n = 12]) that received daily administration of copper. Three hepatic biopsies and blood samples were performed on days 0, 45, and 105. The concentration of hepatic copper was determined by spectrophotometric atomic absorption, and the activities of aspartate aminotransferase (AST) and gamma-glutamyl transferase (GGT) were analyzed. Regression analyses were done to verify the possible existing relationship between enzymatic activity and concentration of hepatic copper. Sensitivity, specificity, accuracy, and positive and negative predictive values were determined. The serum activities of AST and GGT had coefficients of determination that were excellent predictive indicators of hepatic copper accumulation in cattle, while only GGT serum activity was predictive of hepatic copper accumulation in buffalo. Elevated serum GGT activity may be indicative of increased concentrations of hepatic copper even in cattle and buffalo that appear to be clinically healthy. Thus, prophylactic measures can be implemented to prevent the onset of a hemolytic crisis that is characteristic of copper intoxication.

cis-Bis[1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureato-kappa(2)O,S]copper(II)

In the title compound, [Cu(C(20)H(17)N(2)O(2)S)(2)], the Cu(II) atom is coordinated by the S and O atoms of two 1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureate ligands in a distorted square-planar geometry. The two O and two S atoms are mutually cis to each other. The Cu-S and Cu-O bond lengths lie within the ranges of those found in related structures. The dihedral angle between the planes of the two chelating rings is 26.15 (6)degrees.