In-situ electrochemical and piezogravimetric studies on the application of macrocyclic resorcinarene tetramer in the development of chemically-modified heavy metals ions detection platform in aqueous media

The new application of C-dec-9-enylcalix4]resorcinarene (R₁), as an ionophore to detect heavy metals (HMs) cations (Cd²⁺, Hg²⁺, Cu²⁺, and Pb²⁺) in the aqueous media has been investigated through the preparation of an effective mass-sensitive sensor via the exploitation of a flow-type QCM-I technique. By adjusting the ions’ amounts in model solutions over a wide range of concentrations, acquired changes in the oscillating frequency related to the loading of metal ions on the sensor’s surface were gained, and thus favorable metrological parameters displaying the lowest detection limit (LOD) associated with copper ions (10 ppb). Simultaneously, a novel voltammetric sensor was prepared by modifying gold screen-printed electrodes (SPEs) with R₁. Electrochemical characterization employing CV, SWV, and EIS was carried out, showing the success of the electrode modification. Then, the experimental conditions of supporting electrolyte, pH, accumulation time, and accumulation potential were optimized to achieve an enhanced detection. The R₁@SPE sensor simultaneously detected the HMs (Cd²⁺, Hg²⁺, Cu²⁺, Pb²⁺), and the lowest LOD was associated with Pb²⁺ (0.19 ppb). The selectivity evaluation of the electrochemical sensor was performed by studying the effect of interferences majorly present in water sources (Mg²⁺, Ni²⁺, Zn²⁺, Al³⁺, and K⁺) on the SWV detection signals, and it was revealed that the interfering ions did not affect the simultaneous detection of the studied HMs (RSD less than 5%), the voltammetric sensors also presented excellent repeatability and reproducibility (RSD less than 5%).