Silver nanoparticles from orange peel extract: Colorimetric detection of Pb²⁺ and Cd²⁺ ions with a chemometric...

Green silver nanoparticles (AgNPs@OPE) were obtained by using orange (citrus sinensis) peel water extract (OPE) that acts as a reducing and capping agent. This procedure permits the valorisation of waste as orange peel, and lowers the environmental impact of the process, with respect to the conventional synthetic procedure. The OPE extract reduced Ag(I) to Ag(0) in alkaline conditions, and stabilised the produced nanoparticles as a capping agent. The AgNPs@OPE were deeply characterized by UV-Vis spectroscopy, FT-IR, SEM analysis and DLS analysis and successively used as colorimetric sensors for different metals in aqueous solution. The colourimetric assay showed that AgNPs@OPE were able to detect Pb²⁺ and Cd²⁺, as demonstrated by the splits of surface plasmon resonance (SPR) band accompanied by the formation of a second new band; these spectral modification resulted in a colour change, from pristine nanoparticles' yellow to brown, due to the aggregation process. For the quantification of each of the two target cations, a calibration was performed by using the univariate linear regression, within the linearity ranges, exploiting the absorbance ratio between the main SPR band and the new band relative to the aggregate formation. Then a multivariate approach was followed to perform both Cd²⁺ and Pb²⁺ quantification by means of Partial Least Square regression (PLS) and target cations distinction by Linear Discriminant Analysis (LDA) applied on Principal Components Analysis (PCA) outputs, in both cases using the entire UV-Vis spectra (350-800 nm) as input data. Finally, the ability to quantify and distinguish between Cd²⁺ and Pb²⁺ was tested in tap water samples spiked with the two cations in order to confirm the application of the AgNPs@OPE as selective sensor in real samples.