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A simple and highly sensitive electrochemical sensor COOH−C4 derived from dicarboxyl‐calix[4]arene modified on a screen printed gold electrode (Au) was developed for the determination of lead ions in water samples. A 3‐mercaptopropionic acid (MPA) monolayer was used as a template on the gold electrode for the surface modification with dicarboxyl‐calixarene. The modified electrodes were surface‐characterized using Fourier Transform infrared spectroscopy (FTIR). The data obtained proved the confirmation of each stage of the electrode modification. The electrochemical analyses of the COOH−C4 electrode showed an enhanced electrocatalytic activity and higher current towards Pb2+ ions as compared to the bare Au and MPA/Au electrodes. Under optimum conditions, the differential pulse voltammetry response of COOH−C4 displayed a wide linear response ranging from 280–2500 μg/L for Pb2+ with a detection limit of 6.2 μg/L. In addition, the fabricated electrode showed a high selectivity and stability towards the Pb2+ ions in presence of possible interfering species. The present method was successfully applied to determine Pb2+ ions in real samples with satisfactory precision, with a relative standard deviation of 3.12 % and an acceptable recovery of 92 %, which demonstrated the potential application of dicarboxyl‐calix[4]arene modified on electrodes for heavy‐metal sensing.

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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.

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