A multivariate version of the classical univariate standard addition method is proposed for the analysis of samples generating overlapping signals in the presence of notorious matrix effects.Unlike previous versions based on multivariate calibration by partial least squares (PLS), the proposed strategy takes advantage of a self-modelling methodology: multivariate curve resolution by alternating least squares (MCR-ALS) enhanced with signal shape constraints based on parametric functions. In this way, there is no need for the full multivariate response of a blank solution and, in multianalyte determinations, the standard additions can be made with a solution containing all the analytes, which constitutes a clear advance as compared to PLS approach. The proposed method has been successfully tested in the voltammetric determination of hydroquinone and catechol in solutions of increasing complexity and appears to be a promising tool in the field of electroanalysis.
A two-dimensional (2D) Sb-modified screen-printed carbon nanofibers electrode (2D Sbexf-SPCNFE) was developed to improve the stripping voltammetric determination of Cd(II) and Pb(II), taking advantage of the synergistic effect between the two nanomaterials. The surface morphology of the 2D Sbexf-SPCNFE was investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy. The analytical performance of 2D Sbexf-SPCNFE was compared to those presented by screen-printed carbon electrodes modified with 2D Sbexf (2D Sbexf-SPCE) and the corresponding bare electrodes: screen-printed carbon nanofibers electrode (SPCNFEbare) and screen-printed carbon electrode (SPCEbare). After optimizing the experimental conditions, the 2D Sbexf-SPCNFE exhibited much better analytical parameters compared to the other assessed sensors. Analysis in 0.01 mol L−1 HCl (pH = 2) using 2D Sbexf-SPCNFE showed excellent linear behavior in the concentration range of 2.9 to 85.0 µg L−1 and 0.3 to 82.0 µg L−1 for Cd(II) and Pb(II), respectively. The limits of detection after 240 s deposition time for Cd(II) and Pb(II) were 0.9 and 0.1 µg L−1, and sensitivities between 1.5 and 3 times higher than those displayed by SPCEbare, SPCNFEbare, and 2D Sbexf-SPCE were obtained. Finally, the 2D Sbexf-SPCNFE was successfully applied to the determination of Cd(II) and Pb(II) traces in a certified estuarine water sample.
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