Interação de compostos organossulfurados derivados do alho com o citocromo-c: um estudo eletroquímico

Organosulfur compounds present in garlic and onion have been evaluated as inhibitors of chemical carcinogenesis. Among them diallylsulfide was mainly investigated and studies demonstrated its metabolization to the corresponding sulfoxide and sulfone. In this work, we report the investigation of the interaction between the diallylsulfide and its oxidized derivatives, through cyclic voltammetry, with horse heart cytocrome-c (on a modified electrode with 4-mercaptopyridine). Our results suggest that there is a reversible interaction between cytocrome-c and diallylsulfide and diallylsulfone and an irreversible interaction with the diallylsulfoxide.

Aplicação de técnicas eletroquímicas no estudo da dissolução oxidativa da covelita (CuS) por Thiobacillus ferrooxidans

Among the copper sulphides, chalcopyrite (CuFeS2), covellite (CuS) and chalcocite (Cu2S) are the most important source of minerals for copper mining industry. The acknowledge of behaviour of these sulphides related with bacterial leaching process are essential for optimization procedures. Despite of its importance, covellite has not deserved much interest of researchers regarding this matter. In this work it was studied the oxidation of covellite by the chemolithotrophic bacterium Thiobacillus ferrooxidans by using electrochemical techniques, such as open circuit potentials with the time and cyclic voltammetry. The experiments were carried out in acid medium (pH 1.8), containing or not Fe2+ as additional energy source, and in different periods of incubation; chemical controls were run in parallel. The results showed that a sulphur layer is formed spontaneously due the acid attack, covering the sulphide in the initial phase of incubation, blocking the sulphide oxidation. However, the bacterium was capable to oxidize this sulphur layer. In the presence of Fe2+ as supplemental energy source, the corrosion process was facilitated, because ocurred an indirect oxidation of covellite by Fe3+, which was produced by T. ferrooxidans oxidation of the Fe2+ added in the medium.

Mechanism of 3,4-dihydroxybenzaldehyde electropolymerization at carbon paste electrodes: catalytic detection of NADH

Cyclic voltammetry was used to study 3,4-dihydroxybenzaldehyde (3,4-DHB) electropolymerization processes on carbon paste electrodes. The characteristics of the electropolymerized films were highly dependent on pH, anodic switching potential, scan rate, 3,4-DHB concentrations and number of cycles. Film stability was determined in citrate/phosphate buffer solutions at the same pH used during the electropolymerization process. The best conditions to prepare carbon paste modified electrodes were pH 7.8; 0.0 <= Eapl <= 0.25 V; 10 mV s-1; 0.25 mmol L-1 3,4-DHB and 10 scans. These carbon paste modified electrodes were used for NADH catalytic detection at 0.23 V in the range 0.015 <= [NADH] <= 0.21 mmol L-1. Experimental data were used to propose a mechanism for the 3,4--DHB electropolymerization processes, which involves initial phenoxyl radical formation.

Métodos de baixo custo para purificação de reagentes e controle da contaminação para a determinação de metais traços em águas naturais

Probably one of the most difficult and challenging aspects of measuring trace metals in natural waters is to avoid contamination during sampling, manipulation and analysis. This work discusses how to avoid contamination using simple procedures, and considers alternative methods to purify deionised water and low grade reagents to enable accurate determination of trace metals in natural waters in a common laboratory. Measurements were performed by cathodic stripping voltammetry and copper was used as a model metal to test the procedures. It was possible to evaluate copper speciation in natural waters even when total dissolved copper concentration was as low as 1.5 nmol L-1. The methods' accuracy was confirmed by analysis of certified seawater.

Voltametria de onda quadrada. Primeira parte: aspectos teóricos

The theoretical aspects of square wave voltammetry were discussed. Reversible, irreversible and quase-reversible electrode reactions were analyzed and the correlations between parameters like frequency, period, square wave potential and amplitude were showed. In this way, diagnostic relationships allow to characterize the electrode process. The analytical applications were discussed in base of the increment in the analytical response (current) due to the characteristics of the developed equations and the unique mode of collecting the electrode response, i.e., the direct and reverse signals. Finally, recent advances in the basic theory, as the applications to the hydrodynamic electrode and the ultramicroelectrode were also analyzed, and the multiple pulses square wave voltammetry was also introduced.

Estudo eletroanalítico do herbicida paraquat em soluções aquosas por voltametria de onda quadrada utilizando ultramicroeletrodos

The electrochemical behavior of paraquat on Pt, Au and carbon fiber ultramicroelectrodes were studied in laboratory samples by square wave voltammetry at high frequencies. The results showed two reversible peaks for paraquat reduction, in agreement to the literature data. The first peak was associated to the reduction of paraquat molecule in solution, with the further adsorption of the intermediate on the electrode surface. This adsorbed species undergoes to electroreduction in a reaction associated to the second voltammetric peak. The variation in pH and square wave parameters showed the best conditions to reduce paraquat as pH 5.0, frequency as high as 1000 s-1, scan increment of 2 mV and square wave amplitude of 50 mV. At such conditions, a variation of paraquat concentrations from 4.3 x 10-6 to 1.66 x 10-4 mol L-1 presented values for the detection limit equal to 3.9, 6.2 and 20.3 ppb on Pt, Au and carbon, respectively, at 1000 s-1. These values are quite below17 the allowed limit of paraquat in drinking water.

Aplicações eletroanalíticas com eletrodos de prata confeccionados a partir de CDs graváveis

This paper presents a new way for the construction of silver electrodes utilizing recordable CDs. The new electrodes were explored for the quantification of chloride (by potentiometry/FIA), cyanide (by amperometry/FIA) and for lead analysis (by square wave voltammetry). For the flowing measurements, a digital multimeter, connected to a microcomputer (via RS 232 interface) was used to collect directly the potential signal (for Cl- measurements) or to take the output signal from a potentiostat (for CN- measurements). The square wave voltammetry analysis was performed in a commercial instrument. The results shown good performance of the new electrodes and the detection limit (s/n = 3) attained for these three analytes were: 0.2, 50, and 200 µg L-1 for Pb2+, Cl-, and CN- respectively.

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.

Preparação e caracterização do complexo cobaloxima e sua utilização na construção de um eletrodo modificado: um experimento eletroquímico no curso de graduação

The present experiment describes the preparation, characterization of n-butyl(pyridil)cobaloxime complex and its electrochemical property. The infrared and uv-visible absorption spectra were used to characterize the complex obtained. The infrared spectrum of the compound showed characteristics bands that indicated the formation of the Co-C chemical bond formation. The electronic absorption spectrum in acetonitrile showed transition bands attributed to p-p*, metal-to-ligand charge transfer, d-d transitions and charge transfer Co-C. The electrochemical property was investigated by the pulse differential voltammetry technique. Two oxidation processes: Co(I)/Co(II) at -423 mV and Co(II)/Co(III) at 752 mV were observed.

Especiação analítica de compostos de arsênio empregando métodos voltamétricos e polarográficos: uma revisão comparativa de suas principais vantagens e aplicações

This paper provides a review on voltammetric and polarographic methods for the speciation analysis of inorganic and organic arsenic compounds in different matrices. A discussion on the main advantages of electroanalytical methods in comparison with other analytical methods employed for arsenic speciation is presented. The mechanistic aspects of the most relevant techniques employing cathodic and anodic stripping voltammetry as well as polarographic methods published in the last twenty five years are summarized and discussed. The bibliographic references cited in this work were selected from the Web of Science (published by the ISI) and the main journals of analytical chemistry.

Determinação eletroanalítica de corante reativo presente como contaminante em proteínas purificadas por cromatografia de afinidade

Procion Green HE-4BD is a reactive dye currently used in affinity purification, and commonly present as a contaminant in the final biological preparation. An assay method is described to determine trace amounts of the dye in the presence of human serum albumin(HSA) and leakage from agarose as affinity sorbent by cathodic stripping voltammetry. The proposed method is based on the reductive peak at -0.55V in B-R buffer pH 3 (E=0V and t= 240s), obtained when samples of HSA 2% (m/v) containing dye concentrations in sodium hydroxide pH 12 are submitted to a heating time of 330 min at 80 ºC. Linear calibration curves can be obtained for RG19 dye concentrations from 5x10-9 mol L-1 to 8 x10-8 mol L-1. The detection limit (3sigma) is 1x10-9 mol L-1.

Otimização da preparação de eletrodo de pasta de carbono contendo riboflavina imobilizada em suporte inorgânico

The aim of this work was to optimize the preparation of electrodes with riboflavin (RF) immobilized on a silica surface modified with niobium oxide and carbon paste. Electrode preparation was optimized employing a factorial design consisting of two levels and three factors. The electrochemical properties of immobilized RF were investigated by cyclic voltammetry. The factorial analysis was carried out analysing the current intensity (Ipa). It was possible to optimize the electrode to get the best reversibility in the redox process, i. e. the lowest separation between anodic and cathodic peak potentials and a current ratio close to unity. The concentration of supporting electrolyte has a small effect. The proportion has the highest effect and the interaction factor between proportion and mixture has also a significant effect on the current intensity.

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 Eletroquímicos e Métodos Eletroanalíticos - 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.

Quantificação do pesticida diclorvos por voltametria de onda quadrada em águas puras e naturais

This work reports the use of square wave voltammetry (SWV) to analyse the electrochemical reduction of dichlorvos (2, 2-dichlorovinyl-dimethylphosphate) in spiked pure and natural waters. SWV measurements were carried out in 0.5 mol L-1 Na2SO4 aqueous solutions at pH 5, prepared with water originated from three different sources, namely, one sample of purified water and others from two urban creeks in São Carlos County. In all cases, two reduction peaks were observed, at potentials of -0.15 and -1.05 V vs Ag/AgCl, with both current and potential being dependent on pesticide concentration. This allowed the calculation of the following detection limits: 1.0, 2.5 and 3.0x10-8 mol L-1 for purified, Gregorio creek and Monjolinho creek waters, respectively, in a working range between 2.0x10-7 and 1.4x10-6 mol L-1. Recovery measurements found values higher than 80% in all cases, for an added concentration of 4.0 x 10-7 mol L-1 of dichlorvos in each solution. All analytical experiments were performed in triplicate and showed a standard deviation always less than 3%.

Determinação eletroquímica da capacidade antioxidante para avaliação do exercício físico

Physical training can adapt or cause injury to skeletal muscles implicating metabolic alterations, which can be detected by biochemical analysis. Apparently the increase in the production of reactive oxygen species (ROS) is involved in both processes. Enzymatic and low molecular weight antioxidants (LMWA) minimize ROS's deleterious action through redox reactions. Cyclic voltammetry (CV) has been suggested as a tool to quantify the antioxidant capacity conferred by LMWA. The use of CV to evaluate the modulation of the antioxidant capacity conferred by LMWA in response to physical exercise is discussed here.