Márcio F. Bergamini

Voltammetric determination of L-dopa using an electrode modified with trinuclear ruthenium ammine complex (Ru-red) supported on Y-type zeolite.

The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinsons disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH(3))(5)Ru(III)ORu(IV)(NH(3))(4)ORu(III)(NH(3))(5)](6+) (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2x10(-4) and 1.0x10(-2)moll(-1) (r=0.9988) with a detection limit of 8.5x10(-5)moll(-1). The variation coefficient for a 1.0x10(-3)moll(-1) L-dopa (n=10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa.

Voltammetric Determination of the Antioxidant Capacity in Wine Samples Using a Carbon Nanotube Modified Electrode

A direct determination of gallic acid was achieved at a carbon paste electrode modified with carbon nanotubes under differential pulse voltammetry conditions. The values obtained for gallic acid were used to estimate the antioxidant properties of the wine sample based on gallic acid oxidation. The proposed method is based on the gallic acid oxidation process at a modified carbon paste electrode (MCPE) containing 30% (m/m) of carbon nanotubes monitored at 0.35 V versus Ag/AgCl (KCl 3 mol L(-1)). Using the optimized experimental conditions, the calibration curve for gallic acid was linear in the concentration range from 5.0 × 10(-7) to 1.5 × 10(-5) mol L(-1) with a detection limit of 3.0 × 10(-7) mol L(-1). The MCPE was successfully applied for the determination of the antioxidant capacity for red and white wine samples without interference of glucose and ascorbic acid, and the obtained results were compared with the standard spectrophotometric method.

Evaluation of a carbon paste electrode modified with organofunctionalized amorphous silica in the cadmium determination in a differential pulse anodic stripping voltammetric procedure

The determination of cadmium using a carbon paste electrode modified with organofunctionalized amorphous silica with 2-benzothiazolethiol was investigated. The Cd(II) oxidation peak was observed around -0.80 V (vs. SCE) in phosphate buffer (pH 4.0) in differential pulse anodic stripping voltammetry. The best results were obtained under the following optimized conditions: 1 min accumulation time, 50 mV pulse amplitude, 20 mV s(-1) scan rate in phosphate buffer pH 4.0. Using such parameters a linear dynamic range from 5.6 x 10(-7) to 3.5 x 10(-5) mol l(-1) Cd(II) was observed with a sensitivity of 2.83 microA mol(-1) l, limit of detection 1.0 x 10(-7) mol l(-1). Cd(II) spiked in a natural water sample was determined with 99% mean recovery at 10(-7) mol l(-1) level. Interference were also evaluated.

Determination of isoniazid in human urine using screen-printed carbon electrode modified with poly-L-histidine.

A sensitive voltammetric method for trace measurements of isoniazid (INZ) in synthetic human urine sample is described. The method is based on its electroreduction at -0.98V vs. Ag/AgCl on screen-printed carbon electrode (SPCE) modified with poly-l-histidine (PH). A film of good adherence on SPCE and electrocatalytic properties was obtained coating the electrode by histidine monomer electropolymerization process (SPCE/EPH). The electrochemical behavior of the modified SPCE was investigated by cyclic, linear sweep (LSV), differential pulse (DPV), square-wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS). Limits of detection of 5.0x10(-7) mol L(-1), 1.7x10(-7) mol L(-1) and 2.5x10(-7) mol L(-1) were estimated from LSV, DPV and SWV determinations, respectively. The method was successfully applied to the determination of INZ in human urine samples.

Electrochemical determination of copper ions in spirit drinks using carbon paste electrode modified with biochar

This work describes for first time the use of biochar as electrode modifier in combination with differential pulse adsorptive stripping voltammetric (DPAdSV) techniques for preconcentration and determination of copper (II) ions in spirit drinks samples (Cachaça, Vodka, Gin and Tequila). Using the best set of the experimental conditions a linear response for copper ions in the concentration range of 1.5 × 10(-6) to 3.1 × 10(-5) mol L(-1) with a Limit of Detection (LOD) of 4.0 × 10(-7) mol L(-1). The repeatability of the proposed sensor using the same electrode surface was measured as 3.6% and 6.6% using different electrodes. The effect of foreign species on the voltammetric response was also evaluated. Determination of copper ions content in different samples of spirit drinks samples was also realized adopting inductively coupled plasma optical emission spectroscopy (ICP-OES) and the results achieved are in agreement at a 95% of confidence level.

An electroanalytical approach for evaluation of biochar adsorption characteristics and its application for lead and cadmium determination.

This work describes for first time the use of electroanalytical techniques for evaluation of adsorptive proprieties of biochar using it as electrode modifier and its application for preconcentration and determination of Lead(II) and Cadmium(II) under differential pulse adsorptive voltammetric conditions (DPAdSV). Samples of biochars were obtained from castor oil cake using a predefined set of experimental conditions varying the heating rate (V), final temperature (T) and warm-up period (P) and subsequently used for carbon paste modified electrode (CPME) preparation. The proposed method was applied for Lead(II) and Cadmium(II) determination in spiked simulated industrial effluents and the limit of detection obtained for both metals were adequated for determination of these evaluated ions taking into account the limits established by Brazilian legislation. For all samples analyzed, recoveries ranged from 95% to 104% were obtained and no significative interferences were observed for common cations in water samples.

Flow injection amperometric determination of dipyrone in pharmaceutical formulations using a carbon paste electrode

The behavior of a carbon paste electrode was investigated as an amperometric detector for the determination of dipyrone by flow injection analysis (FIA). The electrode presented low cost and easy construction by simple mixing of graphite powder and mineral oil. Initially, an electrochemical study of the dipyrone oxidation at a carbon paste electrode has been developed before its use in the FIA system. The oxidation currents monitored at +0.35 V versus Ag/AgCl, were proportional to the dipyrone concentrations. Experimental parameters, such as nature of supporting electrolyte, pH of the carrier solution, flow rate, sample volume injection and probable interferents were investigated. Under the best experimental conditions selected, the calibration curve for dipyrone was linear in the concentration range from 4.91 x 10(-6) to 2.50 x 10(-4) M l(-1) (I(anodic)/microA)=0.056+81.06 [dipyrone]) with a detection limit of 2.07 x 10(-6) M l(-1). Recoveries ranged from 93.8 to 100.8% and an analytical frequency of 130 h(-1) was achieved. The proposed flow procedure has been satisfactorily applied to the determination of dipyrone in several pharmaceutical formulations.

One material, multiple functions: graphene/Ni(OH)2 thin films applied in batteries, electrochromism and sensors

Different nanocomposites between reduced graphene oxide (rGO) and Ni(OH)2 nanoparticles were synthesized through modifications in the polyol method (starting from graphene oxide (GO) dispersion in ethylene glycol and nickel acetate), processed as thin films through the liquid-liquid interfacial route, homogeneously deposited over transparent electrodes and spectroscopically, microscopically and electrochemically characterized. The thin and transparent nanocomposite films (112 to 513 nm thickness, 62.6 to 19.9% transmittance at 550 nm) consist of α-Ni(OH)2 nanoparticles (mean diameter of 4.9 nm) homogeneously decorating the rGO sheets. As a control sample, neat Ni(OH)2 was prepared in the same way, consisting of porous nanoparticles with diameter ranging from 30 to 80 nm. The nanocomposite thin films present multifunctionality and they were applied as electrodes to alkaline batteries, as electrochromic material and as active component to electrochemical sensor to glycerol. In all the cases the nanocomposite films presented better performances when compared to the neat Ni(OH)2 nanoparticles, showing energy and power of 43.7 W h kg−1 and 4.8 kW kg−1 (8.24 A g−1) respectively, electrochromic efficiency reaching 70 cm2 C−1 and limit of detection as low as 15.4 ± 1.2 μmol L−1.

Sensitive voltammetric determination of lead released from ceramic dishes by using of bismuth nanostructures anchored on biochar

A simple and sensitive electroanalytical method was developed for determination of nanomolar levels of Pb(II) based on the voltammetric stripping response at a carbon paste electrode modified with biochar (a special charcoal) and bismuth nanostructures (nBi-BchCPE). The proposed methodology was based on spontaneous interactions between the highly functionalized biochar surface and Pb(II) ions followed by reduction of these ions into bismuth nanodots which promote an improvement on the stripping anodic current. The experimental procedure could be summarized in three steps: including an open circuit pre-concentration, reduction of accumulated lead ions at the electrode surface and stripping step under differential pulse voltammetric conditions (DPAdSV). SEM images revealed dimensions of bismuth nanodots ranging from 20 nm to 70 nm. The effects of main parameters related to biochar, bismuth and operational parameters were examined in detail. Under the optimal conditions, the proposed sensor has exhibited linear range from 5.0 to 1000 nmol L(-1) and detection limit of 1.41 nmol L(-1) for Pb(II). The optimized method was successfully applied for determination of Pb(II) released from overglaze-decorated ceramic dishes. Results obtained were compared with those given by inductively coupled plasma optical emission spectroscopy (ICP-OES) and they are in agreement at 99% of confidence level.

Preconcentration of Rutin at a Poly Glutamic Acid Modified Electrode and its Determination by Square Wave Voltammetry

Abstract The voltammetric determination of rutin in 0.04 mol l−1 B‐R buffer (pH 4.0) by square wave voltammograms (+0.41 V vs. Ag/AgCl(sat.)) at a poly glutamic acid modified glassy carbon electrode was found to be several orders of magnitude lower than that on a bare glassy carbon electrode. Rutin can be preconcentrated on the films of poly glutamic acid and presented linear relationship from concentration of 7×10−7 to 1×10−5 mol l−1 in 0.04 mol l−1 B‐R buffer pH 4.0. The method was successfully applied to the determination of rutin in pharmaceutical formulation without any pretreatment.