A facile chemiluminescence strategy for copper(ii) ion detection utilizing azothiacalix[4]arene-functionalized carboxymethylcellulose polymeric ligand

Abstract

The main objective of the current work is to develop a luminol-based chemiluminescence (CL) system with the help of a reactive functional polymer of azothiacalix[4]arene-modified carboxymethyl cellulose (ACCMC) for the trace analysis of copper(II) ions. ACCMC was synthesized by linking water-soluble deoxy-azido carboxymethyl cellulose to monopropargyl-tetradiazothiacalix[4]arene through a [2+3] dipolar cycloaddition click reaction for the first time. The obtained materials were characterized by FT-IR, ¹H, and ¹³C NMR spectroscopies, TGA, and FE-SEM. Under optimal conditions, AC and ACCMC quenched the CL intensity of luminol and 1,2-dihydro-3,6-pyridazinedione through hydrogen peroxide-assisted oxidation in an alkaline solution, which was evaluated for the detection of copper(II) ions based on the enhancement effect of Cu(II). According to the CL spectra in the presence of Cu²⁺, the CL intensities of the luminol-H₂O₂, luminol-AC-H₂O₂, and luminol-ACCMC-H₂O₂ increased to about 2, 6.5, and 3-fold, respectively. The introduced systems provide luminescence in a wide range, with the advantage of analyzing or measuring analytes in the CL system. The prepared AC and ACCMC exhibited suitable figures of merit for copper(II) with linear calibration curves in the low levels of copper(II) ions ranging from 0.01 to 100 μM, with detection limits of 1.36 nM and 2.2 nM, and relative standard deviations (RSDs) of 5.41% and 4.82% in determining 0.1 μM Cu²⁺ using luminol-AC-H₂O₂ and luminol-ACCMC-H₂O₂ systems, respectively. The recovery values were in the range of 92–112% and RSDs were less than 5.3%.