Propagació de la incertesa en laboratoris d'anàlisi

El document és una guia per al càlcul de la propagació de la incertesa en laboratoris d'anàlisi

Guia de xifres significatives

El document és una guia per a l'expressió de valors numèrics amb el nombre adequat de xifres significatives i el seu arrodoniment

Determination of trace levels of nickel(II) by adsorptive stripping voltammetry using a disposable and low-cost carbon screen-printed electrode

A commercial and disposable screen-printed carbon electrode (SPCE) has been proposed for a fast, simple and low-cost determination of Ni(II) at very low concentration levels by differential pulse adsorptive stripping voltammetry (DPAdSV) in the presence of dimethylglyoxime (DMG) as complexing agent. In contrast with previously proposed methods, the Ni(II)-DMG complex adsorbs directly on the screen-printed carbon surface, with no need of mercury, bismuth or antimony coatings. Well-defined stripping peaks and a linear dependence of the peak area on the concentration of Ni(II) was achieved in the range from 1.7 to 150 microg/L, with a limit of detection of 0.5 microg/L using a deposition time of 120 s. An excellent reproducibility and repeatability with 0.3% (n = 3) and 1.5% (n = 15) relative standard deviation, respectively, were obtained. In addition, the suitability of the SPCE as sensing unit has been successfully assessed in a wastewater certificated reference material with remarkable trueness and very good reproducibility

Crown ether-modified electrodes for the simultaneous stripping voltammetric determination of Cd(II), Pb(II) and Cu(II)

This work describes the immobilization of 4-carboxybenzo-18-crown-6 (CB-18-crown-6) and 4-carboxybenzo-15-crown-5 (CB-15-crown-5) assisted by lysine on aryl diazonium salt monolayers anchored to the surface of graphite-epoxy composite electrodes (GEC), and their use for the simultaneous determination of Cd(II), Pb(II) and Cu(II) by differential pulse anodic stripping voltammetry (DPASV). These modified electrodes display a good repeatability and reproducibility with detection and quantification limits at levels of µg L(-1) (ppb), confirming their suitability for the determination of Cd(II), Pb(II) and Cu(II) ions in environmental samples. The overlapped nature of the multimetal stripping measurements was resolved by employing the two-sensor array CB-15-crown-5-GEC and CB-18-crown-6-GEC, since the metal complex selectivity exhibited by the considered ligands could add some discrimination power. For the processing of the voltammograms, Discrete Wavelet Transform and Causal Index were selected as preprocessing tools for data compression coupled with an artificial neural network for the modeling of the obtained responses, allowing the resolution of mixtures of these metals with good prediction of their concentrations (correlation with expected values for an external test subset better than 0.942)

Crown ether-modified electrodes for the simultaneous stripping voltammetric determination of Cd(II), Pb(II) and Cu(II)

This work describes the immobilization of 4-carboxybenzo-18-crown-6 (CB-18-crown-6) and 4-carboxybenzo-15-crown-5 (CB-15-crown-5) assisted by lysine on aryl diazonium salt monolayers anchored to the surface of graphite-epoxy composite electrodes (GEC), and their use for the simultaneous determination of Cd(II), Pb(II) and Cu(II) by differential pulse anodic stripping voltammetry (DPASV). These modified electrodes display a good repeatability and reproducibility with detection and quantification limits at levels of µg L−1 (ppb), confirming their suitability for the determination of Cd(II), Pb(II) and Cu(II) ions in environmental samples. The overlapped nature of the multimetal stripping measurements was resolved by employing the two-sensor array CB-15-crown-5-GEC and CB-18-crown-6-GEC, since the metal complex selectivity exhibited by the considered ligands could add some discrimination power. For the processing of the voltammograms, Discrete Wavelet Transform and Causal Index were selected as preprocessing tools for data compression coupled with an artificial neural network for the modeling of the obtained responses, allowing the resolution of mixtures of these metals with good prediction of their concentrations (correlation with expected values for an external test subset better than 0.942)

A hybrid sensing system combining simultaneous optical and electrochemical measurements: application to beer discriminations

A hybrid sensing system, which combines simultaneous cyclic voltammetric (CV) and UV-vis absorbance measurements using a commercial carbon screen-printed electrode and a set of optical fibres in disposable cuvettes, is proposed. The hybrid system approach was applied to 27 samples of recognized beer brands, improving the classification power as compared to only voltammetric or only spectrophotometric measurements. The developed partial least squares discriminant analysis (PLS-DA) model was able to discriminate between five types of beer (lager, marzen, black/stout, alcohol-free and white/ale). The model was also successfully applied to 28 beer samples of white-label brands sold in local supermarkets, demonstrating their similarity to recognized brand beers

Authentication of soothing herbs by UV-vis spectroscopic and chromatographic data fusion strategy

A data fusion approach combining chromatographic and spectroscopic profiles is proposed for the discrimination and classification of soothing herbs in different types of herbal preparations. Particularly, chamomile, lavender, passionflower, and valerian were considered. The proposed data fusion approach revealed a higher clusterization ability than each analytical technique in a separate way, which was assessed through an exploratory analysis based on Principal Component Analysis (PCA) coupled to Silhouette analysis: percentage of samples with a negative Silhouette width were 19, 15 and 10 for chromatography, spectroscopy and data fusion, respectively. Furthermore, a Partial Least Squares - Discriminant Analysis (PLS-DA) model developed based on data fusion was able to perfectly discriminate samples of chamomile, passionflower, and valerian in a set of 20 samples, overcoming the difficulties related to dealing with different types of herbal preparations including pure herbs, infusions, tablets, capsules and herbal drops

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

New discrimination tools for harvest year and varieties of white wines based on hydrophilic interaction liquid chromatography with amperometric detection

A simple HPLC-EC method based on hydrophilic interaction liquid chromatography with amperometric detection through gold screen-printed electrodes has been developed and applied for the first time to the determination of aminothiols in white wines. Moreover, the coupling of the method with partial least squares discriminant analysis (PLS-DA) using the analysed aminothiols as biomarkers provides wine discrimination in terms of harvest year. White wine samples were directly injected and chromatographic areas, together with pH and redox potential values, allowed a successful discrimination of wines from different harvest years with a global classification rate of 97.8%. The developed HPLC-EC method also generated characteristic fingerprints that were combined with PLS-DA to classify wines according to three wine varieties, with a global classification rate of 95.3%