Amino-Functionalized Laponite Clay Material as a Sensor Modifier for the Electrochemical Detection of Quercetin

In this work, an electrode modified with an amino-functionalized clay mineral was used for the electrochemical analysis and quantification of quercetin (QCT). The resulting amine laponite (LaNH₂) was used as modifier for a glassy carbon electrode (GCE). The organic-inorganic hybrid material was structurally characterized using X-ray diffraction, Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and CHN elemental analysis. The covalent grafting of the organosilane to the clay backbone was confirmed. The charge on the aminated laponite, both without and with the protonation of NH₂ groups, was evaluated via cyclic voltammetry. On the protonated amine (LaNH₃⁺)-modified GCE, the cyclic voltammograms for QCT showed two oxidation peaks and one reduction peak in the range of -0.2 V to 1.2 V in a phosphate buffer-ethanol mixture at pH 3. By using the differential pulse voltammetry (DPV), the modification showed an increase in the electrode performance and a strong pH dependence. The experimental conditions were optimized, with the results showing that the peak current intensity of the DPV increased linearly with the QCT concentration in the range from 2 × 10^-7 M to 2 × 10^-6 M, leading to a detection limit of 2.63 × 10^-8 M (S/N 3). The sensor selectivity was also evaluated in the presence of interfering species. Finally, the proposed aminated organoclay-modified electrode was successfully applied for the detection of QCT in human urine. The accuracy of the results achieved with the sensor was evaluated by comparing the results obtained using UV-visible spectrometry.