Novel ultra-sensitive and highly selective cyanine sensors based on solvent-free microwave synthesis for the detection of trace hypochlorite ions in drinking water

Nermeen S Hafez; Wael A Amer; Ehab A Okba; Mahmoud A S Sakr; Hussein H Alganzory; El-Zeiny M Ebeid

doi:10.1016/j.saa.2023.123116

Novel ultra-sensitive and highly selective cyanine sensors based on solvent-free microwave synthesis for the detection of trace hypochlorite ions in drinking water

Spectrochim Acta A Mol Biomol Spectrosc. 2023 Dec 15:303:123116. doi: 10.1016/j.saa.2023.123116. Epub 2023 Jul 11.

Authors

Nermeen S Hafez¹, Wael A Amer², Ehab A Okba³, Mahmoud A S Sakr⁴, Hussein H Alganzory⁵, El-Zeiny M Ebeid⁶

Affiliations

¹ Chemistry Department, Faculty of Science, Tanta University, Tanta 31527, Egypt. Electronic address: Nermin.Salah@science.tanta.edu.eg.
² Chemistry Department, Faculty of Science, Tanta University, Tanta 31527, Egypt; Department of Chemistry, College of Science, University of Bahrain, Sakhir 32038, Bahrain.
³ Chemistry Department, Faculty of Science, Tanta University, Tanta 31527, Egypt.
⁴ Center of Basic Science, Misr University for Science and Technology, 6(TH) of October City, Egypt.
⁵ Department of Chemistry, Faculty of Science, Benha University, Benha, Egypt.
⁶ Chemistry Department, Faculty of Science, Tanta University, Tanta 31527, Egypt; Center of Basic Science, Misr University for Science and Technology, 6(TH) of October City, Egypt.

PMID: 37459665
DOI: 10.1016/j.saa.2023.123116

Abstract

The adoption of chlorine in drinking water disinfection with the determination of residual chlorine in the form of hypochlorite ion (ClO^-) is in widespread demand. Several sensors including colorimetric, fluorometric, and electrochemical methods are currently in use, but detection limits and ease of application remain a challenge. In this work, two new cyanine derivatives-based ClO^- sensors, that were prepared by solvent-free microwave synthesis, are reported. The two sensors are highly sensitive and selective to ClO^-, exhibiting a noticeable color change visible to the naked eye. Additionally, the sensors can detect ClO^- without interference from other potential water pollutants, with low detection limits of 7.43 ppb and 0.917 ppb based on absorption performance. When using fluorometric methods, the sensors' detection limits are pushed down to 0.025 ppb and 0.598 ppb for sensors I and II, respectively. The sensors can be loaded with paper strips for field and domestic detection of ClO^- in tap water treatment installations. Using the quartz crystal microbalance (QCM) technique, these sensors showed strong detection sensitivity to ClO^-, with detection limits of 0.256 ppm and 0.09 ppm for sensors I and II, respectively. Quantum chemical studies using density functional theory (DFT) calculations, natural bond orbital (NBO) analysis, molecular electrostatic potential (MESP), and time-dependent density functional theory (TD-DFT) supported the findings. The sensing mechanism is rationalized in terms of radical cation formation upon ClO^- oxidation of cyanine sensors I and II.

Keywords: Colorimetric detection; Cyanine sensors; Fluorometric detection; Naked-eye detection; Quartz crystal microbalance; Solvent-free microwave synthesis; Tap water.