The binding interactions between aqueous copper (Cu(2+)) and lithium (Li(+)) ions and Langmuir monolayers and Langmuir-Blodgett (LB) multilayers have been investigated by studying surface pressure-area (Pi-A) isotherms and surface potential-area (DeltaV-A) behavior in order to find the effective dipole moment, mu(perpendicular), of the calixarene molecules in the uncomplexed and complexed states. The orientation of both calix[4]arenes, namely, 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene and 5,17-(9H-fluoren-2-yl)methyleneamino)-11,23-di-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene, is such that the plane of the calix ring is parallel with the plane of the water surface regardless of the ion content of the subphase. The Gibbs equation was used to interpret the adsorption of ions with both calix[4]arenes as a function of the concentration. Effective dipole moments have been calculated from surface potential values using the Helmholtz equation. In this work, new LB films have been prepared employing two novel amphiphilic calix[4]arene derivatives bearing different upper rim substituents. Thus, the effect of modifiying the upper rim has been observed. The results have shown that these calixarenes may be useful components of ion sensors.

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In this paper, we have reported an electrochemical detection of metal ions based on Calixarene-based sensor. In the sensing strategy, 3-aminopropylsilane (APTMS) was initially self-assembled on indium tin oxide (ITO) followed by functionalization of dicarboethoxycalix [4]arene (EtC4). The morphology and properties of electrodes were characterized by contact angle, atomic force microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. The electrochemical response characteristics of the modified electrodes (EtC4/APTMS/ITO) towards analyte ions; Zn(II), Cu(II), and Fe(II) ions were investigated by differential pulse voltammetry (DPV) under optimized conditions. It was found that the response of modified electrode towards the analytes was improved significantly as compared to the ITO electrode and resulted in limit of detections (LOD) of 9.88 pg/L, 8.33 μg/L and 1.15 μg/L, respectively. In addition, the detection limit of simultaneous detection quantification of Cu2 +, Zn2 + and Fe2 + ions could be achieved with the concentration 6.19 ng/L, 3.02 mg/L and 2.79 mg/L, respectively. It is worth to show that dicarboethoxy-calix [4]arene modified electrode is a promising candidate as electrochemical sensors for simultaneous and ultrasensitive heavy metal ions determination.