THE POTENTIALITIES OF USING A GRAPHITE-SILICONE RUBBER COMPOSITE ELECTRODE IN THE DETERMINATION OF PROPRANOLOL

A graphite silicone-rubber composite electrode (GSR) was used for the determination of propranolol in drug formulation. Cyclic voltammetry (CV) at the GSR presented an irreversible oxidation peak at + 0.8V vs. SCE, in Britton Robinson (B-R) buffer pH 7.4. The quantitative determination was carried out using differential pulse voltammetry (DPV). Under optimized parameters a linear dynamic range from 5.0 to 80.6 mu mol L(-1) with a detection limit of 1.1 mu mol L(-1) was observed. A repeatability of 4.5 +/- 0.1 mu A (n = 10) peak current was found after 10 successive DPV voltammograms of propranolol in the same solution after surface renovations. Using the proposed electrode, propranolol was quantified in a pharmaceutical formulation with results that agreed within 95% confidence level (t-test) with those from an official method.

Analytical Potentialities of Carbon Nanotube/Silicone Rubber Composite Electrodes: Determination of Propranolol

A new composite electrode based on multiwall carbon nanotubes (MWCNT) and silicone-rubber (SR) was developed and applied to the determination of propranolol in pharmaceutical formulations. The effect of using MWCNT/graphite mixtures in different proportions was also investigated. Cyclic voltammetry and electrochemical impedance spectroscopy were used for electrochemical characterization of different electrode compositions. Propranolol was determined using MWCNT/SR 70% (m/m) electrodes with linear dynamic ranges up to 7.0 mu molL(-1) by differential pulse and up to 5.4 mu molL(-1) by square wave voltammetry, with LODs of 0.12 and 0.078 mu molL(-1), respectively. Analysis of commercial samples agreed with that obtained by the official spectrophotometric method. The electrode is mechanically robust and presented reproducible results and a long useful life.

Electrochemical Behavior of Verapamil at Graphite-Polyurethane Composite Electrodes: Determination of Release Profiles in Pharmaceutical Samples

A solid graphite-polyurethane composite electrode has been used to determine release profiles of verapamil, a calcium-channel blocker. The electro-oxidation process was characterized by cyclic voltammetry and electrochemical impedance spectroscopy and showed no adsorption of analyte or oxidation products, unlike at other carbon-based electrodes. Quantification gave linear ranges up to 40molL-1 with cyclic voltammetry and detection limits of 0.7molL-1 by differential pulse and square-wave voltammetry. Commercial product samples were successfully analyzed with results equal to those from spectrophotometry. Because no electrode surface renewal is needed, this electrode material has many advantages.

Simultaneous voltammetric determination of paracetamol and caffeine in pharmaceutical formulations using a boron-doped diamond electrode

A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-doped diamond (BDD) electrode using square wave voltammetry (SWV) or differential Pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials Of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 x 10(-7) mol L(-1) to 8.3 x 10(-7) mol L(-1) for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 x 10(-7) mol L-1 and 3.5 x 10(-8) mol L(-1), respectively. The proposed method Was Successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level). (C) 2008 Elsevier BY. All rights reserved.

Trace metal speciation in the Pieman River catchment, western Tasmania

The Pieman River catchment has seen continuous mining of economic deposits of gold, silver, lead, copper, zinc and tin since the 1870’s. Tributaries of this river which receive mining effluent, either directly or from acid mine drainage (AMID), have total metal concentrations considerably above background levels and are of regulatory concern. The lower Pieman River is however classified as a State Reserve in which recreational fishing and tourism are the major activities. It is therefore important that water entering the lower Pieman River from upstream hydroelectric impoundments is of high quality. Metals in natural waters exist in a variety of dissolved, colloidal and particulate forms. The bioavailability and hence toxicity of heavy metal pollutants is very dependant on their physico form. Knowledge of the speciation of a metal in natural aquatic environments is therefore necessary for understanding its geochemical behaviour and biological availability. Complexation of metal ions by natural ligands in aquatic systems is believed to play a significant role in controlling their chemical speciation. This study has investigated temporal and spatial variation in complexation of metal ions in the Pieman River. The influence of pH, temperature, organic matter, salinity, ionic strength and time has been investigated in a series of field studies and in laboratory-based experiments which simulated natural and anthropogenic disturbances. Labile metals were measured using two techniques in various freshwater and estuarine environments. Diffusive gradients in thin-films (DGT) allowed in situ measurement of solution speciation whilst differential pulse anodic stripping voltammetry (DPASV) was used to measure labile metal species in water samples collected from the catchment. Organic complexation was found to be a significant regulating mechanism for copper speciation and the copper-binding ligand concentration usually exceeded the total copper concentration in the river water. Complexation was highly dependent on pH and at the river-seawater interface was also regulated by salinity, probably as a result of competitive complexation by major ions in seawater (eg. Ca 2+ ions). Zinc complexation was also evident, however total zinc concentrations in the water column often far exceeded the potential binding capacity of available ligands. In addition to organic complexation, Zn speciation may also be associated with adsorption by flocculated or resuspended colloidal Mn and/or Fe oxyhydroxides. Metal ion complexation and hence speciation was found to be highly variable within the Pieman River catchment. This presents major difficulties for environmental managers, as it is therefore not possible to make catchment-wide assumptions about the bioavailability of these metals. These results emphasise the importance of site-specific sampling protocols and speciation testing, ideally incorporating continuous, in situ monitoring.

One-pot facile synthesis of platinum nanoparticle decorated reduced graphene oxide composites and their application in electrochemical detection of rutin

We report on the synthesis of platinum nanoparticle-reduced graphene oxide (PtNP-rGO) composites and their application as a novel architecture in electrochemical detection of rutin. PtNPs anchored over rGO are synthesized through a facile one-pot synthesis method, where the reduction of GO and in situ generation of PtNPs occurred concurrently. The characterization results of transmission electron microscopy (TEM) demonstrate that PtNPs with small particle sizes are dispersed on the rGO matrix. Electrochemical measurements reveal that a PtNP-rGO modified glass carbon electrode (GCE) directly catalyzes rutin oxidation and displays an enhanced current response compared with a bare GCE. Under the optimal experimental conditions, the peak current was linear with rutin concentration in the range of 5 × 10^-8 to 1 × 10^-5 M with the detection limit of 1 × 10^-8 M (S/N = 3) by differential pulse voltammetry. The proposed method was successfully applied to determine rutin in tablet samples with satisfactory results. This journal is

An electroanalytical application of 2-aminothiazole-modified silica gel after adsorption and separation of Hg(II) from heavy metals in aqueous solution

2-Aminothiazole covalently attached to a silica gel surface was prepared in order to obtain an adsorbent for Hg(II) ions having the following characteristics: good sorption capacity, chemical stability under conditions of use, and, especially, high selectivity. The accumulation voltammetry of mercury(II) was investigated at a carbon paste electrode chemically modified with silica gel functionalized with 2-aminothiazole (SIAMT-CPE). The repetitive cyclic voltammogram of mercury(II) solution in the potential range -0.2 to + 0.6 V versus Ag/AgCl (0.02 mol L-1 KNO3; V = 20 mV s(-1)) show two peaks one at about 0.1 V and other at 0.205 V. The anodic wave peak at 0.205 V is well defined and does not change during the cycles and it was therefore further investigated for analytical purposes using differential pulse anodic stripping voltammetry in differents supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. The precision for six determinations (n = 6) of 0.02 and 0.20 mg L-1 Hg(II) was 4.1 and 3.5% (relative standard deviation), respectively. The detection limit was estimated as 0.10 mu g L-1 mercury(II) by means of 3:1 current-to-noise ratio in connection with the optimization of the various parameters involved and using the highest-possible analyser sensitivity. (c) 2006 Elsevier Ltd. All rights reserved.

Stripping voltammetry of mercury(II) with a chemically modified carbon paste electrode containing silica gel functionalized with 2,5-dimercapto-1,3,4-thiadiazole

The accumulation voltammetry of mercury(II) was investigated at a carbon paste electrode chemically modified with silica gel functionalized with 2,5-dimercapto-1,3,4-thiadiazole (DTTPSG-CPE). The repetitive cyclic voltammogram of mercury(II) solution in the potential range -0.2 to +0.8 V (vs. Ag/AgCl), (0.02 mol L-1 KNO3; nu=20 mV s(-1)) show two peaks one at about 0.0 V and other at 0.31 V. However, the cathodic wave peak, around 0.0 V, is irregular and changes its form in each cycle. This peak at about 0.0 V is the reduction current for mercury(II) accumulated in the DTTPSG-CPE. The anodic wave peak at 0.31 V is well-defined and does not change during the cycles. The resultant material was characterized by cyclic and differential pulse anodic stripping voltammetry performed with the electrode in differents supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. The precision for six determinations (n=6) of 0.05 and 0.20 mg (L)-(1) Hg(II) was 2.8 and 2.2% (relative standard deviation), respectively. The method was satisfactory and used to determine the concentration of mercury(II) in natural waters contaminated by this metal.

Aplicação da técnica eletroanalítica de pulso diferencial usando o eletrodo de carbono vítreo modificado com cisteína para monitorar a degradação eletroquímica de ácido oxálico

In this paper, the technique of differential pulse voltammetry (DPV) has been studied for monitoring the concentration of oxalic acid (OA) during their electrochemical oxidation (EO) in acidic medium using platinum anode supported on titanium (Ti / Pt). The DPV was standardized and optimized using a glassy carbon electrode modified with cysteine. The modification with cysteine was developed electrochemically, forming a polymeric film on the surface of the glassy carbon electrode. The formation of the polymer film was confirmed by analysis of scanning electron microscope and atomic force microscope, confirming the modification of the electrode. The electrochemical degradation was developed using different current densities 10, 20 30 and 40 mA cm -2 electrode with Ti / Pt observing the degradation of oxalic acid, and monitored using the method of KMnO4 titration. However, the analyzes with DPV showed the same behavior elimination of oxalic acid titration. Compared with the titration method classical observed and DPV could be a good fit, confidence limits of detection and confirming the applicability of the technique electroanalytical for monitoring the degradation of oxalic acid

Aplicação das técnicas eletroanalíticas (voltametria cíclica e de pulso diferencial) usando o eletrodo de diamante dopado com boro para o estudo da isoniazida, etambutol, rifampicina e pirazinamida

In this work a study was done using electrochemical cyclic voltammetry and differential pulse voltammetry for isoniazida (INH), ethambutol (EMB), rifampicina (RIF) and pyrazinamide (PZA) using the electrode boron-doped diamond (BDD) as working electrode. It also verified the applicability of the technique of differential pulse voltammetry in the quantification of the active compounds used in the treatment of tuberculosis, subsequently applying in samples of pharmaceutical formulation. Among the four active compounds studied, isoniazid showed the best results for the detection and quantification using differential pulse voltammetry. At pH 4 and pH 8, for the calibration curves to INH showed good linearity, with quantification limits of 6.15 mmol L-1 (0,844 ppm) and 4.08 mmol L-1 (0.560 ppm) for the respective pH. The proposed method can be used to determine drug isoniazid, for recovery values were obtained in approximately 100%

Aplicabilidade da voltametria de pulso diferencial na quantificação de ácido fólico e ácido oxálico: um método comparativo

The development of more selective and sensitive analytical methods is of great importance in different areas of knowledge, covering, for example, food, biotechnological, environmental and pharmaceutical sectors. The study aimed to employ the technique electroanalytical differential pulse voltammetry (DPV) as an innovative and promising alternative for identification and quantification of organic compounds. The organic compounds were investigated in this study oxalic acid (OA) and folic acid (FA). The electrochemical oxidation of oxalic acid has been extensively studied as a model reaction in the boundary between the organic and inorganic electrochemistry. Since the AF, an essential vitamin for cell multiplication in all tissues, which is essential for DNA synthesis. The AF has been investigated using analytical techniques, liquid chromatography and molecular absorption spectrophotometry. The results obtained during the experimental procedure indicated that the process of electrochemical oxidation of oxalic acid is strongly dependent on the nature of the anode material and the oxidation mechanism, which affects their detection. Efficient removal was observed in Ti/PbO2 anodes, graphite, BDD and Pt 90, 85, 80 and 78% respectively. It was also shown that the DPV employing glassy carbon electrode offers a fast, simple, reliable and economical way to determine the AO during the process of electrochemical oxidation. Furthermore, electroanalytical methods are more expensive than commonly used chromatographic analysis and other instrumental methods involving toxic reagents and higher cost. Compared with the classical method of titration and DPV could be a good fit, confidence intervals and detection limits confirming the applicability of electroanalytical technique for monitoring the degradation of oxalic acid. For the study of AF was investigated the electrocatalytic activity of the carbon paste electrode for identification and quantification in pharmaceutical formulations by applying the DPV. The results obtained during the experimental procedure showed an irreversible oxidation peak at 9.1 V characteristic of FA. The carbon paste sensor showed low detection limit of 5.683×10−8 mol L-1 reducing matrix effects. The spectrophotometric analysis showed lower concentrations of HF compared with those obtained by HPLC and DPV. The levels of AF were obtained according to the methodology proposed by the Brazilian Pharmacopoeia. The electroanalytical method (DPV) proposed is cheaper than GC analysis commonly used by the pharmaceutical industry. The results demonstrated the potential of these electroanalytical techniques for future applications in environmental, chemical and biological sensors

Electrochemical Redox Behavior of Omeprazole Using a Glassy Carbon Electrode

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

SOLID STATE ELECTROCHEMICAL BEHAVIOR of USNIC ACID AT A GLASSY CARBON ELECTRODE

The electrochemical redox behavior of usnic acid, mainly known for its antibiotic activity, has been investigated using cyclic, differential pulse and square wave voltammetry in aqueous electrolyte. These studies were carried out by solid state voltammetry with the solid mechanically attached on the surface of a glassy carbon electrode and at different pH values. Usnic acid did not present any reduction reaction. The pH-dependent electrochemical oxidation occurs in three steps, one electron and one proton irreversible processes, assigned to each of the hydroxyl groups in the molecule. Adsorption of the non-electroactive oxidation product was also observed, blocking the electrode surface. An oxidation mechanism was proposed and electroanalytical methodology was developed to determine usnic acid.

Poly(glutamic acid) nanofibre modified glassy carbon electrode: Characterization by atomic force microscopy, voltammetry and electrochemical impedance

Glassy carbon electrodes (GCE) were modified with poly(glutamic acid) acid films prepared using three different procedures: glutamic acid monomer electropolymerization (MONO), evaporation of poly(glutamic acid) (PAG) and evaporation of a mixture of poly(glutamic acid)/glutaraldehyde (PAG/GLU). All three films showed good adherence to the electrode surface. The performance of the modified GCE was investigated by cyclic voltammetry and differential pulse voltammetry, and the films were characterized by atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). The three poly(glutamic acid) modified GCEs were tested using the electrochemical oxidation of ascorbic acid and a decrease of the overpotential and the improvement of the oxidation peak current was observed. The PAG modified electrode surfaces gave the best results. AFM morphological images showed a polymeric network film formed by well-defined nanofibres that may undergo extensive swelling in solution, allowing an easier electron transfer and higher oxidation peaks. (C) 2007 Elsevier Ltd. All rights reserved.