An Interference-Free Voltammetric Method for the Detection of Sulfur Dioxide in Wine Based on a Boron-Doped Diamond Electrode and Reaction Electrochemistry.

This paper describes a new, simple, and highly selective analytical technique for the detection of sulfur dioxide in wine, as a real sample with a relatively complicated matrix. The detection of the above analyte was based on the electrogeneration of iodine from iodide on a boron-doped diamond electrode, without modifications, in the presence of 0.1 mol dm-3 HClO4 as a supporting electrolyte. The electrogenerated iodine reacted with sulfur dioxide, forming iodide ions and sulfuric acid (i.e., a Bunsen reaction). The product of this reaction, the iodide ion, diffused back to the surface of the boron-doped diamond electrode and oxidized itself again. This chemical redox cycling enhanced the voltammetric response of the boron-doped diamond electrode. The selectivity of the determination was assured using NaOH and formaldehyde during sample preparation, and a blank was also measured and taken into account. The detection limit was estimated to be 10-6-10-7 mol dm-3. However, the content of sulfur dioxide in wine is significantly higher, which can lead to more accurate and reliable results.

A Review of Analytical Techniques for the Determination and Separation of Silver Ions and Its Nanoparticles.

Many articles have already been published dealing with silver ions and its nanoparticles, but mostly from the environmental and toxicological point of view. This article is a review focused on the various analytical techniques and detection platforms used in the separation and determination of mentioned above species, especially on the trace concentration level. Commonly used are optical methods because of their high sensitivity and easy automation. The separation methods are mainly used for the separation and preconcentration of silver particles. Their combination with other analytical techniques, mainly inductively coupled plasma mass spectrometry (ICP-MS) leads to very low detection limits of analysis. The electrochemical methods are also powerful and perspective mainly because of the fabrication of new sensors designed for silver determination. All methods may be combined with each other to achieve a synergistic improvement of analytical parameters with an impact on sensitivity, selectivity and reliability. The paper comprises a review of all three types of analytical methods on the determination of trace quantities of silver ions and its nanoparticles.

Electroanalytical Techniques for the Detection of Selenium as a Biologically and Environmentally Significant Analyte-A Short Review.

This short review deals with the properties and significance of the determination of selenium, which is in trace amounts an essential element for animals and humans, but toxic at high concentrations. It may cause oxidative stress in cells, which leads to the chronic disease called selenosis. Several analytical techniques have been developed for its detection, but electroanalytical methods are advantageous due to simple sample preparation, speed of analysis and high sensitivity of measurements, especially in the case of stripping voltammetry very low detection limits even in picomoles per liter can be reached. A variety of working electrodes based on mercury, carbon, silver, platinum and gold materials were applied to the analysis of selenium in various samples. Only selenium in oxidation state + IV is electroactive therefore the most of voltammetric determinations are devoted to it. However, it is possible to detect also other forms of selenium by indirect electrochemistry approach.

Voltammetric detection of antimony in natural water on cathodically pretreated microcrystalline boron doped diamond electrode: A possibility how to eliminate interference of arsenic without surface modification.

Very simple and fast electroanalytical method for the detection Sb(III) on chemically unmodified boron-doped diamond electrode (BDDE) has been developed. Voltammetric behavior of antimony was investigated in various acidic supporting electrolytes and the most suitable medium for the determination of Sb(III) on bare BDDE has been 6molL-1 HClO4 solution. The analytical performance was studied with differential pulse anodic stripping voltammetry (DPASV) with optimized conditions (deposition potential -1V vs. Ag/ AgCl and deposition time 240s). An analysis of possible effects due to the presence of other metal ions (especially As(III)) in the solution was eliminated using NaH2PO4 as supporting electrolyte with addition EDTA as selective complexing agent for Sb(III). Speciation of antimony was also investigated. The detection limit of this analytical strategy achieved value of 1.08 × 10-7molL-1. The proposed method was validated and applied for natural water from former antimony mines as real samples.

Microelectrode arrays with overlapped diffusion layers as electroanalytical detectors: theory and basic applications.

This contribution contains a survey of basic literature dealing with arrays of microelectrodes with overlapping diffusion layers as prospective tools in contemporary electrochemistry. Photolithographic thin layer technology allows the fabrication of sensors of micrometric dimensions separated with a very small gap. This fact allows the diffusion layers of single microelectrodes to overlap as members of the array. Various basic types of microelectrode arrays with interacting diffusion layers are described and their analytical abilities are accented. Theoretical approaches to diffusion layer overlapping and the consequences of close constitution effects such as collection efficiency and redox cycling are discussed. Examples of basis applications in electroanalytical chemistry such as amperometric detectors in HPLC and substitutional stripping voltammetry are also given.

Voltammetric determination of caffeine in beverage samples on bare boron-doped diamond electrode.

A sensitive and selective electrochemical method for the caffeine determination using bare boron-doped diamond electrode was developed. It was found that caffeine provided highly reproducible and well-defined irreversible oxidation peak at very positive potential. The effects of supporting electrolyte, pH and scan rate on the voltammetric response of caffeine oxidation were studied to select the optimum experimental conditions. Linear response of peak current on the concentration in the range from 4×10(-7) to 2.5×10(-5)M, good repeatability (RSD of 2.1%) and detection limit of 1.5×10(-7)M without any chemical modifications and electrochemical surface pretreatment were evaluated. The effect of possible interferents appeared to be negligible which evidently proved very good selectivity. The proposed method was successfully applied for the caffeine determination in commercially available beverage samples, with results in a close statistical agreement to those declared by manufacturer and HPLC used as independent method.

Voltammetric determination of penicillin V in pharmaceutical formulations and human urine using a boron-doped diamond electrode.

Simple, sensitive and selective differential pulse voltammetric method for determination of penicillin V on a bare (unmodified) boron-doped diamond electrode has been developed. Penicillin V provided highly reproducible and well-defined irreversible oxidation peak at very positive potential of +1.6V (vs. Ag/AgCl). The optimum experimental conditions for oxidation of penicillin V were achieved in acetate buffer solution (pH 4.0). The modulation amplitude of 0.1V, modulation time of 0.05s and scan rate of 0.05Vs(-1) were selected as optimum instrumental parameters for differential pulse voltammetry. Linear response of peak current on the concentration in the range from 0.5 to 40µM with coefficient of determination of 0.999, good repeatability (RSD of 1.5%) and detection limit of 0.25µM were observed without any chemical modifications and electrochemical surface pretreatment. The effect of possible interferents such as stearic acid, glucose, urea, uric acid and ascorbic acid appeared to be negligible which evidently proved the good selectivity of method. The practical analytical utility of proposed method was demonstrated by determination of penicillin V in pharmaceutical formulations (tablets) and human urine samples with satisfactory recoveries (from 98 to 101% for tablets and 97 to 103% for human urine).

A hyaluronic acid dispersed carbon nanotube electrode used for a mediatorless NADH sensing and biosensing.

A biocompatible nanocomposite consisting of single-walled carbon nanotubes (CNTs) dispersed in a hyaluronic acid (HA) was investigated as a sensing platform for a mediatorless electrochemical detection of NADH. The device was characterised by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and extensively by electrochemistry. CNT-HA bionanocomposite showed more reversible electrochemistry, higher short-term stability of NADH sensing and higher selectivity of NADH detection compared to frequently used CNT-CHI (chitosan) modified GCE. Finally the performance of the sensor modified by CNT-HA was tested in a batch and flow injection analysis (FIA) mode of operation with basic characteristics revealed. The NADH sensor exhibits a good long-term operational stability (95% of the original sensitivity after 22 h of continuous operation). Subsequently a d-sorbitol biosensor based on such a nanoscale built interface was prepared and characterised with a d-sorbitol dehydrogenase used as a biocatalyst.

Indirect voltammetric detection of fluoride ions in toothpaste on a comb-shaped interdigitated microelectrode array.

A novel technique based on dynamic electrochemistry for the detection of fluoride ions was developed. It is based on its strong complexation with ferric ion. Formed fluoroferric complex is cathodically inactive at the potential of the reduction of free ferric aquo ion. The voltammetric and amperometric response of platinum comb-shaped interdigitated microelectrode array is decreased after fluoride addition. This decrease serves for the quantification of fluoride ions added to the solution. The detection limit of 4.5×10(-5) mol dm(-3) was achieved when one of the segments of interdigitated microelectrode array (IDA) was used as an indicating electrode. The detection limit is about one order of magnitude lower than in the case of conventional platinum macroelectrode. In comparison with ISE electrodes this method is faster and also avoiding large error resulting from the antilogarithmization of ISE Nerstian response. The method was applied to the analysis of toothpaste.

The ammonia-free partial reduction of substituted pyridinium salts.

This paper reports a study into the partial reduction of N-alkylpyridinium salts together with subsequent elaboration of the intermediates thus produced. Activation of a pyridinium salt by placing an ester group at C-2, allows the addition of two electrons to give a synthetically versatile enolate intermediate which can be trapped with a variety of electrophiles. Furthermore, the presence of a 4-methoxy substituent on the pyridine nucleus enhances the stability of the enolate reaction products, and hydrolysis in situ gives stable dihydropyridone derivatives in good yields. These versatile compounds are prepared in just three steps from picolinic acid and can be derivatised at any position on the ring, including nitrogen when a p-methoxybenzyl group is used as the N-activating group on the pyridinium salt. This publication describes our exploration of the optimum reducing conditions, the most appropriate N-alkyl protecting group, as well as the best position on the ring for the methoxy group. Electrochemical techniques which mimic the synthetic reducing conditions are utilised and they give clear support for our proposed mechanism of reduction in which there is a stepwise addition of two electrons to the heterocycle, mediated by di-tert-butylbiphenyl (DBB). Moreover, there is a correlation between the viability of reduction of a given heterocycle under synthetic conditions and its electrochemical response; this offers the potential for use of electrochemistry in predicting the outcome of such reactions.

The detection of formaldehyde in textiles using interdigitated microelectrode array diffusion layer titration with electrogenerated hypobromite.

An interdigitated microelectrode array (IDA) was applied to the determination of formaldehyde released from textiles produced in industry. The proposed method is based on formaldehyde reaction with hypobromite which is formed in weakly basic media by control current electrooxidation of bromide on the generator segment of the IDA array. The unreacted hypobromite diffuses through the gap between individually polarisable IDA segments and it is amperometrically detected on the collector segment of the IDA. The efficiency of this nonconvective transfer process in the absence of formaldehyde was substantially higher (78%) in comparison with that when using the rotating ring disc electrode. The influence of the added formaldehyde on the transfer process can be utilised to develop a simple and sensitive analytical procedure for formaldehyde detection with a detection limit of 4 x 10(-6) mol dm(-3).

Manganese detection in marine sediments: anodic vs. cathodic stripping voltammetry.

Three different electroanalytical techniques for the detection of manganese in marine sediments are evaluated. The anodic stripping voltammetry of manganese at an in situ bismuth-film-modified boron-doped diamond electrode and cathodic stripping voltammetry at a carbon paste electrode are shown to lack the required sensitivity and reproducibility whereas cathodic stripping voltammetry at a bare boron-doped diamond electrode is shown to be reliable and selective with a limit of detection, from applying a 60s accumulation period of 7.4 x 10(-7)M and a sensitivity of 0.24AM(-1). The method was used to evaluate the manganese content of marine sediments taken from Sibenik, Croatia.

A self-catalytic carbon paste electrode for the detection of vitamin B12.

A simple, sensitive, and selective method for the detection of vitamin B12 (cyanocobalamin) is presented. A carbon paste electrode has been constructed with trans-1,2-dibromocyclohexane (DBCH) acting as both the paste binder and a reactive material facilitating the electrocatalytic detection of the target. The latter reaction is based on the electroreduction of the Co(III) center in vitamin B12 to Co(I), which specifically reacts with DBCH to produce electrocatalytic currents with the regeneration of Co (II); a detection limit of 8.5 x 10(-10) mol dm(-3) (based on 3sigma) was found. The electrode has been successfully used for the quantification of vitamin B12 in pharmaceutical products and biological matrix media.

Cadmium detection via boron-doped diamond electrodes: surfactant inhibited stripping voltammetry.

The deposition of cadmium on boron-doped diamond is investigated with square-wave anodic stripping voltammetry. The system was investigated in quiescent conditions, in the presence of an acoustic field and then in the presence of the neutral surfactant Triton((R)) X-100. The effect of optimised insonation was to increase the sensitivity from 0.63 (under silent conditions) to 3.78muAmuM(-1) and to reduce the limit of detection by an order of magnitude from 10(-8) to 10(-9)M. Measurements with or without insonation were found to deteriorate in the presence of the surfactant. Studies using AFM and chronoamperometry showed that this was due to inhibition of the deposition of the metal. Comparative data obtained for analogous measurements for copper on glassy carbon in the presence of industrial effluent, which also leads to signal deterioration under silent but not insonated conditions, showed that for this case also it was the nucleation of copper rather than the metal dissolution which was adversely affected.