Lúcia Codognoto

Electroanalytical determination of 4-nitrophenol by square wave voltammetry on diamond electrodes

The anodic voltammetric behavior of 4-Nitrophenol on a Boron-doped diamond electrode in aqueous solution has been studied using square wave voltammetry. After optimization of the experimental conditions, that model molecule was analyzed in pure water solutions using a Britton-Robinson buffer with pH 6.0 as the supporting electrolyte. Oxidation occurs at 1.0 V vs. Ag/AgCl in an irreversible two-electron process controlled by adsorption of the species. The detection limit (DL) obtained was 2.8 mg L-1. This result was comparable to that obtained from reduction of the molecule at -0.8 V vs. Ag/AgCl under the same experimental conditions (DL = 4.2 mg L-1). Both DL values are within the limits required by the legislation for drinking water (30 mg L-1). The combination of square wave voltammetry and diamond electrodes has proved to be an interesting and desirable alternative for the analytical determination of organic molecules.

Selective oxidation of pentachlorophenol on diamond electrodes

The influence of electrode potential on pentachlorophenol (PCP) oxidation on boron doped diamond (BDD) electrodes in a 0.1 mol L−1 Britton–Robinson buffer (pH 5.5) is described. Controlled potential electrolyses were carried at 0.9, 2.0 and 3.0 V vs Ag/AgCl and the solutions analysed by square wave voltammetry, high performance liquid chromatography, chloride ion selective electrode and spectroscopy in the ultraviolet–visible region. At low positive potential (0.9 V), the formation of an adherent film on the electrode surface involving the transference of 1 electron per PCP molecule was observed. The film was identified as the dimer 2,3,4,5,6-pentachloro-4-pentachlorophenoxy-2,5-cyclohexadienone and the current efficiency was as high as 90%. At potentials close to the onset of O2 evolution (2.0 V), the formation of the corresponding quinone (p-tetrachlorobenzoquinone) was detected at the beginning of the process. This was followed by further oxidation to the hydroxy-benzoquinone with a practically quantitative yield. Electrolyses carried out well into the region of oxygen evolution (3.0 V) lead to the electrochemical combustion of PCP to CO2 and H2O as well as to the release into solution of 5 Cl− ions per PCP molecule destroyed.

Voltametria de onda quadrada. Segunda parte: aplicações

The aim of this work is to discuss some selected applications of square wave voltammetry published in the last five years. The applications focused here cover several electroanalytical fields such as: determination of pesticides; molecules with biological activity; metals and other environmental pollutants. Special attention is given to the work developed in the Grupo de Materiais Eletroquimicos e Metodos Eletroanaliticos - IQSC - USP concerning the utilization of square wave voltammetry, with different kinds of electrodes, for the determination of pesticides in natural waters and active principles in pharmaceutical formulations. The new methodology is simple, fast and sensitive when compared with the traditional ones such as chromatography and spectrophotometry. The satisfactory results obtained provide alternative procedures for the quality control of drugs and the monitoring of pesticides in natural environments.

Carbon Surfaces for Electroanalytical Applications: A Comparative Study

Abstract Boron‐doped diamond (BDD), glassy carbon (GC), and pyrolytic graphite (PG) are distinct carbon surfaces that are widely used for electrochemical applications. The significant differences, either in morphological or electrical properties of such surfaces, result in charge‐transfer processes with totally distinct characteristics. In aqueous electrolyte, electrochemical impedance spectroscopy demonstrates that the BDD electrode presents lower capacitive currents and lower electron transfer resistance over the potential range studied compared with PG or GC. In this way, the BDD electrode is the best choice for several electroanalytical studies, as demonstrated by the electrochemical oxidation of 4‐nitrophenol in 0.1 mol L−1 BR buffer electrolyte (pH 6.0). We thank FAPESP (procs. 01/14320‐0, 03/00710‐6) and CNPq, Brazil, for the financial support. We also thank Eng. W. Haenni from CSEM, Switzerland, for providing the BDD electrode.

Determinação voltamétrica de 4-clorofenol sobre o eletrodo de diamante dopado com boro utilizando a voltametria de onda quadrada

The anodic voltammetric behavior of 4-chlorophenol (4-CF) in aqueous solution has been studied on a Boron-doped diamond electrode using square wave voltammetry (SWV). After optimization of the experimental conditions, 4-CF was analyzed in pure and natural waters using a Britton-Robinson buffer with pH = 6.0 as the supporting electrolyte. Oxidation occurs at 0.80 V vs Ag/AgCl in a two-electron process controlled by adsorption of the species. The detection limits obtained were 6.4 µg L-1 in pure water and 21.5 µg L-1 for polluted water taken from a local creek, respectively. The combination of square wave voltammetry and diamond electrodes is an interesting and desirable alternative for analytical determinations.

Electroanalytical Determination of the Herbicide Paraquat in Natural Water and Commercial Tea Samples with Gold Electrodes Obtained from Recordable Compact Disc

Abstract This work describes the application of gold electrodes constructed from recordable compact discs for the analytical determination of the herbicide paraquat in natural water samples using square wave voltammetry. The detection limit for pure water (laboratory samples) was 21 µg L−1, lower than the EPA limit for drinking water (100 µg L−1). The experimental quantification limit was determined as 73 µg L−1. In polluted creek water samples the detection limit rose to 76.4 µg L−1 and is shown to be dependent on BOD and COD values. Recovery measurements in tea and natural water samples were approximately 95%, which indicates that the methodology can be employed to analyze paraquat in such matrices. The authors acknowledge the financial support of FAPESP and CNPq.

Azure dyes as new photosensitizer prototypes to application in photodynamic therapy against Candida spp.

Infections caused by Candida albicans are of increasing concern, especially considering immunodepressed patients. The toxicity of most antifungal agents, the great number of cases with recidives, as well as the emergence of resistant samples has provoked the evaluation of new forms of therapy. In this context, the photodynamic therapy (PDT) presents auspicious antimicrobial properties, stimulating the development of trials employing several kinds of photosensitizers. In the present work, the application of different kind of Azure dyes as photosensitizer in PDT against C. albicans was evaluated through instrumental measurements of electronic spectroscopy. In fact, the values of optical density were a precise indicator of the growth inhibition of the microorganisms. Indeed, Azures are phenothiazinium derivatives that constitute a very relevant class of compounds with several biomedical applications, such as photoantimicrobial therapy against local bacterial infection, tuberculosis, trypanosomi- asis, malaria, Rickettsia, yeasts, viral infection n and cancer. Azure A, Azure B, Azure A thiocyanate, Azure B BF4 ,A zure A eosinate are the dyes tested against C. albicans. The results denoted completely distinct behaviors to the different types of Azure compound evaluated in this work. In fact, Azure A and Azure A eosinate presented significant results when irradiated with 56 J/cm 2 , since the growth inhibition of C. albicans reached approximately 60%. This Azure compounds have significant potential to be employed as photosensitizer (PS) in PDT, especially in cases of mucocutaneous candidosis. The spectroscopic evaluation was very effective to the detection of slight alterations in the growth of the microorganisms, denoting that this kind of analysis is an excellent alternative to determine growth inhibition of Candida albicans. The experimental data are discussed in details in agreement with recent results from literature.

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.