Development of instrumentation for amperometric and coulometric detection using ultramicroelectrodes

In this work it is presented the development of a simple, portable and inexpensive instrumentation for amperometric and coulometric detection in different analytical instrumentation systems utilizing ultramicroelectrodes. The software, developed in LabVIEW 7.1TM, is capable to carry out three main detection techniques (amperometric, pulsed amperometric and coulometric detection) and a voltammetric technique (cyclic voltammetry). The instrumentation was successfully evaluated using the following systems: cyclic voltammograms of metallic electrodes in alkaline solutions, flow electrochemical detection of glucose and glycine and direct determination of herbicide glyphosate (electrochemical detection coupled to HPLC).

Caffeine Determination at a Carbon Fiber Ultramicroelectrodes by Fast-Scan Cyclic Voltammetry

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

Highly Sensitive Neurotransmitters Analysis at Platinum-Ultramicroelectrodes Arrays

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

Highly Sensitive Neurotransmitters Analysis at Platinum-Ultramicroelectrodes Arrays

An easy way to determine norepinephrine (NE) in biological fluid using a platinum ultramicroelectrode array (Pt-UMEAs) is described. Issues related to UME electrode surface treatment and characterizations are also addressed. At optimized experimental conditions the dynamic concentration range was 1.0 to 10.0 mu mol?L-1 with a detection limit of 40.5 nmol?L-1. The repeatability of current responses for injections of 5 mu mol?L-1 NE was evaluated to be 4.0?% (n=10). This approach obtained excellent sensitivity, a reliable calibration profile and stable electrochemical response for norepinephrine detection. The content of NE in urine samples without any preconcentration, purification, or pretreatment step, was successfully analyzed by the standard addition method using the Pt-UMEAs.

Caffeine Determination at a Carbon Fiber Ultramicroelectrodes by Fast-Scan Cyclic Voltammetry

Caffeine determination using a fast-scan voltammetric procedure at a carbon fiber ultramicroelectrode (CF-UME) is described. The CF-UME was submitted to electrochemical pretreatment. Parameters such as number of acquisition cycles, scan rate, potential window, and the electrochemical surface pretreatment were optimized. Using the optimized conditions, it was possible to achieve a LDR from 10.0 up to 200 mu mol L-1, with a LOD of 3.33 mu mol L-1. The method has been applied in the determination of caffeine in commercial samples, with errors of 1.0-3.5% in relation to the label values and recoveries of 97-114% within the linear range.

Caffeine determination at a carbon fiber ultramicroelectrodes by fast-scan cyclic voltammetry

Caffeine determination using a fast-scan voltammetric procedure at a carbon fiber ultramicroelectrode (CF-UME) is described. The CF-UME was submitted to electrochemical pretreatment. Parameters such as number of acquisition cycles, scan rate, potential window, and the electrochemical surface pretreatment were optimized. Using the optimized conditions, it was possible to achieve a LDR from 10.0 up to 200 μmol L-1, with a LOD of 3.33 μmol L-1. The method has been applied in the determination of caffeine in commercial samples, with errors of 1.0-3.5% in relation to the label values and recoveries of 97-114% within the linear range.

Altering the biochemical state of individual cultured cells and organelles with ultramicroelectrodes

We describe an efficient technique for the selective chemical and biological manipulation of the contents of individual cells. This technique is based on the electric-field-induced permeabilization (electroporation) in biological membranes using a low-voltage pulse generator and microelectrodes. A spatially highly focused electric field allows introduction of polar cell-impermeant solutes such as fluorescent dyes, fluorogenic reagents, and DNA into single cells. The high spatial resolution of the technique allows for design of, for example, cellular network constructions in which cells in close contact with each other can be made to possess different biochemical, biophysical, and morphological properties. Fluorescein, and fluo-3 (a calcium-sensitive fluorophore), are electroporated into the soma of cultured single progenitor cells derived from adult rat hippocampus. Fluo-3 also is introduced into individual submicrometer diameter processes of thapsigargin-treated progenitor cells, and a plasmid vector cDNA construct (pRAY 1), expressing the green fluorescent protein, is electroporated into cultured single COS 7 cells. At high electric field strengths, observations of dye-transfer into organelles are proposed.

Estudo da eletrocristalização de Ni e Ni-P sobre ultramicroeletrodo de platina

This work describes a comparative study of the electrocrystallization of Ni and Ni-P on Pt ultramicroelectrodes using chronoamperometric measurements. It was possible to confirm that in all cases a progressive nucleation was the predominant mechanism. Moreover, the application of the Atomistic Theory to the experimental rate of nuclei formation showed that the number of atoms in the critical nucleus was zero, except for Ni-P on Pt at low overpotentials were a value of one was observed. Furthermore, the physical characterisation of the different deposits on Pt by atomic force microscopy allowed observing the coalescence of the hemispherical nuclei of Ni and Ni-P at t max thus confirming the results obtained from the current-time analysis.

Análise potenciométrica de redissolução com ultramicroeletrodos: fundamentos e aplicações na determinação de metais traços

The Potentiometric Stripping Analysis (PSA) is described with emphasis on ultramicroelectrode applications with a laboratory developed computer based instrumentation. The technique potentialities as compared with the voltammetric approach are pointed out based on the current literature. Some results of trace metals analysis including zinc, cadmium, lead and copper in vinegar and canned food samples are presented. The mainly advantage found in our laboratory was the technique capability to analyse natural samples with minimum matrix interference and the low level of noise found in our determinations.

Ultramicroeletrodos. Parte II: construção e aplicações

This work describes the techniques of construction and several applications of ultramicroelectrodes in electrochemistry and electroanalytical chemistry. Disc shaped UME are produced by embedding metal wires on insulating materials such as glass or epoxy resin. In the field of electrochemistry, UME have been applied in studies of the hydrogen evolution reaction and the electrocrystallization of metals. The negligible values of sensibility for ohmic drop and the enhanced mass transport rate by spherical diffusion are the main advantages of UME in these applications. New important conclusions regarding the phenomena under study were drawn from the experimental results. The applications in electroanalytical chemistry involved the determination of contaminants such as heavy metals and nitrites in natural waters and food products. The use of UME requires little sample manipulation and, in general, no need for oxygen removal or the addition of supporting electrolytes.

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.

Utilização de técnicas eletroanalíticas na determinação de pesticidas em alimentos

The aim of this work is to discuss selected applications of electroanalytical techniques for the detection of pesticides in foods and beverages, published in the last ten years. The applications involved different working electrodes for the electroanalytical determination of pesticides, namely amperometric biosensors, cholinesterase-based biosensors, polymer-modified electrodes, ultramicroelectrodes and hanging mercury drop electrodes. They were used for several voltammetric and amperometric techniques in different analytical procedures for the detection and quantification of different classes of pesticides in different food matrices.

Estudo da eletrocristalização de Ni e Ni-P sobre ultramicroeletrodo de platina

This work describes a comparative study of the electrocrystallization of Ni and Ni-P on Pt ultramicroelectrodes using chronoamperometric measurements. It was possible to confirm that in all cases a progressive nucleation was the predominant mechanism. Moreover, the application of the Atomistic Theory to the experimental rate of nuclei formation showed that the number of atoms in the critical nucleus was zero, except for Ni-P on Pt at low overpotentials were a value of one was observed. Furthermore, the physical characterisation of the different deposits on Pt by atomic force microscopy allowed observing the coalescence of the hemispherical nuclei of Ni and Ni-P at t max thus confirming the results obtained from the current-time analysis.

Development of an Analytical Methodology for Quantification of Strong Acid in Diesel Oil

Many factors can affect the quality of diesel oil, in particular the degradation processes that are directly related to some organosulfur compounds. During the degradation process, these compounds are oxidized into their corresponding sulfonic acids, generating a strong acid content during the process. p-Toluene sulfonic acid analysis was performed using the linear sweep voltammetry technique with a platinum ultramicroelectrode in aqueous solution containing 3 mol L(-1) potassium chloride. An extraction step was introduced prior to the voltammetric detection in order to avoid the adsorption of organic molecules, which inhibit the electrochemical response. The extraction step promoted the transference of sulfonic acid from the diesel oil to an aqueous phase. The method was accurate and reproducible, with detection and quantification limits of 5 ppm and 15 ppm, respectively. Recovery of sulfonic acid was around 90%.

Carbon fiber microelectrodes for adsorptive stripping analysis of trace nucleic acids

Carbon fiber ultramicroelectrodes are shown to be suitable for adsorptive stripping potentiometric measurements of trace DNA and RNA. The origin of the carbon fiber has a profound effect upon its suitability for trace analysis of nucleic acids, with the 'Aesar' materials performing most favorably. The resulting ultramicroelectrodes offer effective adsorptive accumulation of DNA and RNA from unstirred microliter-volume solutions, and are shown to be useful in adsorptive stripping transfer experiments. The influence of the surface pretreatment and accumulation conditions is described, along with the analytical-performance characteristics. The detection limits are 6, 15 and 40 mu g/l tRNA, ssDNA and dsDNA, respectively (5 min accumulation). (C) 1998 Elsevier B.V. S.A.