Synthesis and Characterization of the First Cyrhetrenyl-Appended Calix[4]Arene Macrocycle and Its Application as an Electrochemical Sensor for the Determination of Cu(Ii) in Bivalve Mollusks Using Square Wave Anodic Stripping Voltammetry

An electrochemical sensor for the determination of Cu(II) in bivalve mollusks using a glassy carbon electrode modified with p-tert-butylcalix [4]arene-bis-cyrhetrenylimine (Cy2(Calix [4])) by square wave anodic stripping voltammetry (SWASV) has been developed. The organometallic compound was synthesized from cyrhetrene-carboxaldehyde and 25,26-bis-(2-aminoethoxy)-26,28-dihydrocalix [4]arene through a condensation reaction. Metalloligand (Cy2(Calix [4])) was characterized by FT-IR and 1H-13C 2D NMR spectroscopies and monocrystal X-ray diffraction and was obtained as a single isolated isomer (E). The optimum chemical and electrochemical conditions for the modified electrode were optimized and the methodology was applied in different samples of bivalve mollusks with satisfactory results. A cooperative effect between the organometallic fragment and the calixarene macrocycle improves the preconcentration capacity of the electrochemical sensor, creating a new opportunity to perform rapid and sensitive analyses in the detection of copper in marine resources. © 2018 Elsevier B.V.