Discrimination of beers by cyclic voltammetry using a single carbon screen-printed electrode

A fast, simple and costless methodology without sample pre-treatment is proposed for the discrimination of beers. It is based on cyclic voltammetry (CV) using commercial carbon screen-printed electrodes (SPCE) and includes a correction of the signals measured with different SPCE units. Data are submitted to partial least squares discriminant analysis (PLS-DA) and support vector machine discriminant analysis (SVM-DA), which allow a reasonable classification of the beers. Also, CV data from beers can be used to predict their alcoholic degree by partial least squares (PLS) and artificial neural networks (ANN). In general, non-linear methods provide better results than linear ones

A chemometric survey about the ability of voltammetry to discriminate pharmaceutical products from the evolution of signals as a function of pH.

Many pharmaceutical products are electroactive and, therefore, can be determined by voltammetry. However, most of these substances produce signals in the same region of oxidative potentials, which makes it difficult to identify them. In this work, chemometric tools are applied to extract characteristic information not only from the peak potential of differential pulse voltammograms (DPV), but also from their evolution as a function of pH. The chemometric approach is based on principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA) and support vector machine discriminant analysis (SVM-DA) yielding promising results for the future discrimination of pharmaceutical products in water samples

Screen-printed electrodes for the voltammetric sensing of benzotriazoles in water

Benzotriazoles (BZTs) are high production volume industrial chemicals that are used in various applications such as corrosion inhibitors, antifreeze agents, and UV radiation stabilizers. Given their potential ecotoxicological implications for different ecosystems and in human health, as well as their poor biodegradability, they are of increasing concern. In this study, a new voltammetric method using commercial screen-printed electrodes (SPEs) has been developed for the sensing of BZTs in water samples to help in their environmental monitoring. To this end, different types of SPEs based on carbon nanoallotropes and copper were tested under several experimental conditions to determine the two BZTs most frequently detected in the environment: 1H-benzotriazole (BZT) and 5-methyl-1H-benzotriazole (Me-BZT, tolyltriazole) as model compounds for BZTs. Carbon nanofibers electrodes exhibited the best performance, allowing detection limits as low as 0.4 mg L-1 for both BZTs, with repeatability and reproducibility of ca. 5%. The applicability of the method was tested through the determination of BZT in spiked drinking water samples, suggesting its suitability for the sensing of samples heavily polluted with BZTs

Multivariate standard addition for the analysis of overlapping voltammetric signals in the presence of matrix effects: Application to the simultaneous determination of hydroquinone and catechol

A multivariate version of the classical univariate standard addition method is tested as a proof of concept for the voltammetric analysis of complex samples generating overlapped signals in the presence of significant matrix effects. The proposed strategy applies a multivariate calibration method such as partial least squares (PLS) to the full voltammograms measured for the sample alone and after combined additions of a series of standard solutions (one for every analyte). Then, a calibration model is built and further applied to the prediction of the concentration added to a blank, i.e., a full voltammetric signal measured in the absence of analytes. The absolute value of such predicted concentration is taken as the concentration of the analyte in the sample. The method has been successfully tested in different natural water samples spiked with hydroquinone and catechol and appears to be a promising tool for the analysis of overlapped signals in complex matrices

Mercury films on commercial carbon screen-printed devices for the analysis of heavy metal ions: a critical evaluation

The suitability of mercury films on commercial screen-printed electrodes for the analysis of heavy metal ions is critically tested for the particular case of Pb(II)-ions. Although determination is possible by anodic stripping voltammetry with a reasonable detection limit (8.9 µg L-1), important drawbacks are noticed as a consequence of the heterogeneous deposition of mercury on the rough surface of screen-printed devices

A chemically-bound glutathione sensor bioinspired by the defense of organisms against heavy metal contamination: Optimization of the immobilization conditions

The influence of the experimental conditions (glutathione concentration and incubation time and temperature) concerning the covalent immobilization of glutathione via carbodiimide coupling on the behavior of a glutathione modified screen-printed carbon electrode obtained by electrografting is evaluated. The optimized parameters fasten the modification process and improve the performance of the sensor as compared to the usual procedure. This suggests the convenience of a tailored preparation of metal sensors based on metal-binding biomolecules such as glutathione

Glutathione modified screen-printed carbon nanofiber electrode for the voltammetric determination of metal ions in natural samples

This work reports the development of a glutathione modified electrode via electrografting on a screen-printed carbon nanofiber substrate (GSH-SPCNFE). GSH-SPCNFE was compared to a classical screen-printed carbon electrode modified with glutathione (GSH-SPCE) for the simultaneous voltammetric determination of Cd(II) and Pb(II). Their electrochemical characterization and analytical performance suggest that SPCNFE could be a much better support for GSH immobilization. The applicability of GSH-SPCNFE for the determination of low concentration levels of Pb(II) and Cd(II) ions in environmental samples was successfully tested in a certified wastewater reference material by means of stripping voltammetry with a very high reproducibility and good trueness

A screen-printed voltammetric electronic tongue for the analysis of complex mixtures of metal ions

A voltammetric electronic tongue was constituted by four screen-printed modified electrodes: a carbon nanofiber modified electrode, an ex-situ antimony film electrode prepared from carbon nanofiber modified electrode, and two carbon nanofiber electrodes chemically modified withCys and GSH. The tongue was successfully applied to the analysis of a complex mixture of metal ions (4 analytes and 2 interferences) by differential pulse anodic stripping voltammetry. Each sensor was firstly studied for the determination of each metal separately confirming that all electrodes showed differentiated response for the metals. The obtained voltammetric signals provided by the sensor array were processed by Partial Least Squares regression (PLS) to resolve the overlapped nature of the obtained multimetal stripping measurements. This PLS model was built considering a hierarchical model in order to reduce the large amount of data. The method was applied to synthetic mixtures of Cd(II), Pb(II), Tl(I), and Bi(III) in the presence of Zn(II) and In(III) at the levels of μg L-1 and successfully validated with correlation coefficients of both calibration and prediction higher than 0.9 obtained from predicted vs. expected concentration graphs. Moreover, the simultaneous determination of Cd(II), Pb(II), Tl(I), and Bi(III) in the presence of Zn(II) and In(III) in a spiked tap water was also satisfactory achieved, providing comparable results to those obtained by ICP-MS

Simultaneous determination of Tl(I) and In(III) using a voltammetric sensor array

A sensor array consisting of a chemically modified sensor in which 4-carboxybenzo-18-crown-6 was immobilized onto a screen-printed carbon nanofiber-modified electrode (crown-6-SPCNFE) and an ex-situ antimony film deposited on a screen-printed carbon nanofiber-modified electrode (ex-situ-SbSPCNFE) was applied for the resolution of the strong overlapped signals resulting from the simultaneous determination of Tl(I) and In(III) by stripping voltammetry. A Partial Least Squares model was constructed and good calibration curves of predicted vs. expected concentrations of the considered metal ions, with correlation coefficients higher than 0.98 for both training and test sets, were obtained. These results provided by the sensor array were compared with those obtained by a single electrode. Moreover, this sensor array was successfully applied for the voltammetric determination of both Tl(I) and In(III) in tap water, providing comparable results to those obtained by ICP-MS measurements

New approaches to antimony film screen-printed electrodes using carbon-based nanomaterials substrates

Three different commercial carbon nanomaterial-modified screen-printed electrodes based on graphene, carbon nanotubes and carbon nanofibers were pioneeringly tested as electrode platforms for the plating with Sb film. They were microscopically and analytically compared to each other and to the most conventional unmodified carbon screen-printed electrode (SPCE). The obtained detection and quantification limits suggest that the in-situ antimony film electrode prepared from carbon nanofibers modified screen-printed electrode (SbSPCE-CNF) produces a better analytical performance as compared to the classical SPCE modified with antimony for Pb(II) and Cd(II) determination, approving its appropriateness for measuring low μg L(-1) levels of the considered metals. In-situ SbSPCE-CNF was successfully used for the simultaneous determination of Pb(II) and Cd(II) ions, by means of differential pulse anodic stripping voltammetry, in a certified reference estuarine water sample with a very high reproducibility and good trueness