Compact program resolves overlapping voltammetric peaks

A simple self-contained program designed to separate overlapping peaks from electrochemical analyses is presented. Combining an original interactive way to define initial parameter estimates with nonlinear curve fitting based on the simplex method of optimization, it allows the user to resolve voltammograms consisting of 2 to 5 analytical peaks raised on a straight base line. The program provides highly intuitive interface, easy operation, and straightforward result documentation. A free package including the program, three data files and user instructions is available on request.     

Spline wavelet in the resolution of overlapping voltammetric peaks

Spline wavelet transform is used to resolve overlapping voltammetric peaks. A suitable resolving factor is chosen to multiply the filters of spline wavelet and make it a peak resoluter. Simulated overlapping voltammetric peaks are processed by the peak resoluter and satisfactory results are obtained. Base-line separation can be achieved, the relative errors of peak position are less than 3.0%, and the relative errors of peak area are less than 5.0%. The effect of different resolving factors and spline wavelet basis are discussed. To test the procedure, two systems, cadmium (Ⅱ)-indium (Ⅲ) and lead (Ⅱ)-thallium (Ⅰ), are used.     

Calculation of voltammetric peaks by the transformed Heyrovsky-Ilkovi? equation

Summary Calculating real polarographic or voltammetric peaks is rather difficult. A new possibility to compute such peaks is the use of the transformed Heyrovsky-Ilkovi equation. The calculation allows to simulate polarograms or voltammograms by computer. Furthermore, it is possible to smooth voltammetric peaks without loss of peak height or separation of overlapping peaks.     

Multivariate curve resolution of overlapping voltammetric peaks: quantitative analysis of binary and quaternary metal mixtures

The application of multivariate curve resolution-alternating least squares (MCR-ALS) to the quantitative analysis of different metal ion mixtures using voltammetric data is described. The performance of MCR-ALS was evaluated in the resolution and quantitation of overlapped voltammetric peaks obtained in the analysis of binary and quaternary mixtures of Cd(II), In(III), Pb(II) and Tl(I) metal ions by anodic stripping voltammetry. Quality assessment of qualitative and quantitative determinations was evaluated considering the effects of different constraints and of initial estimations. MCR-ALS results were validated and compared with those obtained by applying other well-established multivariate calibration methods, such as partial least squares (PLS) and direct classical least squares (DCLS) methods.     

A generalized lateral interactions function to fit voltammetric peaks of self-assembled monolayers

From the generalized lateral interactions model and via a few mathematical approximations, a suitable regression function has been developed in order to fit voltammetric peak of redox responsive SAM for extracting the characteristic parameters. The efficiency of the generalized lateral interactions function was tested on simulated and raw data.     

Continuous wavelet transform and its application to resolving and quantifying the overlapped voltammetric peaks

In order to resolve and quantify the overlapped peaks of voltammetry that can be described by sech²-function, continuous wavelet transform (CWT) is employed. Through CWT by using Marr wavelet, qualitative and quantitative analysis for the mixed solution of Cd(II) and In(III) can be performed from unresolved square wave voltammogram (SWV) and relevant theoretical basis is provided. A new method to construct the baseline for quantitative determination is also proposed. The results of analysis indicate that the overlapped voltammogram can be resolved and quantified effectively, conveniently and satisfactorily via CWT.     

Soft modelling for the resolution of highly overlapped voltammetric peaks: application to some Pb-phytochelatin systems

A differential pulse polarographic (DPP) study of the Pb²⁺/Cys-Gly, Pb²⁺/γ-Glu-Cys, Pb²⁺/PC₂ and Pb²⁺/PC₃ systems is performed, being PC₂ and PC₃ the phytochelatins of general structure (γ-Glu-Cys)_n-Gly, with n = 2 and 3, respectively. Analysis of DPP data is assisted by multivariate curve resolution with alternating least squares (MCR-ALS) method in order to establish the complexes formation sequence and their final stoichiometries. DPP signals of these systems present, besides overlapping of peaks due to free metal ion and metal complexes, interference of mercury anodic signals. Despite these complications, MCR-ALS allows us to propose a model of complexation for each system, and some tentative structures for the complexes.     

Application of surfactants in voltammetric analysis

The possibilities of applying surfactants to the voltammetry of various biologically active compounds are generalized. Attention is focused on micellar solutions and surfactant-modified electrodes in the determination of a number of organic compounds, including antioxidants. It is demonstrated that the use of surfactants makes it possible to improve analytical characteristics and, in some cases, to simultaneously determine different analytes.     

Spline wavelet analysis for voltammetric signals

Application of wavelet multifrequency channel decomposition (WMCD) in electroanalytical chemistry is presented in this paper. A new approach on this digital processing technique, to extract useful information from high noise signals in voltammetry, is described in detail. The method of constructing a model of B-spline WMCD and its application with 2nd, 3rd and 4th order B-spline in the linear scan voltammetry are thoroughly discussed and several results obtained. If the suitable optimal wavelet basis and frequency scale value are selected, the absolute values of the peak relative errors are less than 2% when the signal-to-noise ratio (S/N) is greater than 0.2, and the absolute values of the peak potential relative errors are less than 12% when S/N is greater than 0.3. The processed results of experimental data with high noise are also satisfactory. The whole computation is simple and needs shorter time than other signal processing methods.     

Critical evaluation of voltammetric analysis of fat-soluble vitamins

High precision, sensitivity, reliability, and specificity, coupled with simplicity, are essential requirements for a good quantitative analytical technique. With these parameters in mind recent developments have been incorporated into voltammetric methods for the quantification of fat-soluble vitamins.     

Multivariate analysis of non-homogeneous peaks in liquid chromatography

Summary The effects of concentration, separation and spectral similarity as factors influencing the accuracy of iterative target testing factor analysis (ITT-FA) are investigated for three component systems by the application of analysis of variance (ANOVAR). ANOVAR is applied over a range of peak separations to map the changing effects of the three factors with increasing overlap. Two error responses were measured and analysed, (a) Relative cluster error (RCE) a measure of the error over all peaks in a cluster and (b) Relative peak error (RPE) the error of an individual peak. Multicomponent analysis (MCA) a method requiringa priori spectral information, is used as a referee method for ITT-FA.     

Ultra-sensitive voltammetric sensor for trace analysis of carbamazepine

A multi-walled carbon nanotubes (MWCNTs) film-coated glassy carbon electrode (GCE) was used for the voltammetric determination of carbamazepine (CBZ). The results showed that this simple modified electrode exhibited excellent electrocatalytic activity towards the oxidation of CBZ. The voltammetric response of CBZ at this film-modified electrode increased significantly when compared with that at a bare glassy carbon electrode and the sensor response was reproducible. The proposed method was applied to the quantification of CBZ in wastewater samples, collected in a municipal wastewater treatment plant, and in pharmaceutical formulations. The developed methodology yields results in accord with those obtained by chromatographic techniques commonly used in the quantification of pharmaceutical compounds in real samples. Good recoveries have been obtained and the limits of detection and quantification (40 and 140 nM, respectively) are among the lowest that have been reported to date for this pharmaceutical compound using voltammetric techniques.     

Kinetic analysis of simple irreversible non-homogeneous reactions

Simple non-homogeneous irreversible reactions between a mobile reactant A, and immobile reactive groups R, in a solid yielding immobile product B, are considered. The possibilities are discussed of analysing such reactions when they are partially rate-controlled by the diffusion of A. It is shown that the effect of diffusion can be approximately described by a single parameter (“kinetic modulus”) up to a fairly marked degree of diffusion control; so that methods of kinetic analysis analogous to those used for reactions where the solid acts merely as a catalyst can be applied. The “effective reaction constant” previously defined for use as a kinetic modulus (analogous to the “Thiele modulus” of heterogeneous catalytic reactions) is considered further here. An improved, experimentally measurable kinetic modulus, based on the distribution of B across the solid, is also defined and studied.     

Applications of stripping voltammetric techniques in food analysis

Stripping voltammetric techniques are powerful analytical tools that are becoming widely used in various chemical analysis fields. Hence, the objective of this survey is to give a general overview on the scope of the applicability of stripping voltammetric methods in food industries. The applications discussed include recent studies on the utilization of these electroanalytical methods in determination of food contaminants (toxic metals, pesticide, fertilizers and veterinary drugs residuals), trace essential elements, food additive dyes and other organic compounds of biological significance. Tables that give method summaries referenced to the original work are provided.     

Background-current subtraction in voltammetric detection for flow-injection analysis

A new approach for background-current subtraction for flow-injection systems using potential-scanning voltammetric detection is described. The method is based on recording voltamperograms while the sample and carrier solutions flow through the cell, and taking the difference as the net response for the sample. Background currents due to hydrogen evolution, oxygen reduction, solvent oxidation or surface processes are thus compensated, and detection limits at submicromolar levels can be obtained. The compensation for oxygen reduction current means that samples do not need to be deaerated. The method has been evaluated for reproducibility, concentration dependence, detection limit, etc. A flow-cell with a stationary disk electrode, a 200-mul sample volume, and rapid differential pulse scanning are used. At a flow-rate of 0.3 ml min about 15 samples can be assayed per hour. Chlorpromazine, phenol, acetaminophen, norepinephrine, lead, cadmium, bismuth and zinc were used as test species.     

A new micro-cell for continuous-flow pulsed voltammetric analysis

The effect of p-toluenesulfonate and trifluoromethanesulfonate supporting electrolytes on the polarographic reduction of some alkaline earth and transition metal ions in N,N-dimethylformamide and acetonitrile has been investigated. Trifluoromethanesulfonate behaved similarly to perchlorate in dimethylformamide, while the half-wave potentials in p-toluenesulfonate supporting electrolyte shift to more negative potentials than those in perchlorate. in acetonitrile, the half-wave potentials shift to more negative potentials in trifluoromethanesulfonate than in perchlorate. The effect of the supporting electrolyte on the shift of the half-wave potential can be explained as the ion-pair formation between the divalent cation to be reduced and the supporting electrolyte anion.