Ratiometric Fluorescence and Chromogenic Probe for Trace Detection of Selected Transition Metals

Abstract

The design and development of a fluorescence sensor aimed at detecting and quantifying trace amounts of toxic transition metal ions within environmental, biological, and aquatic samples has garnered significant attention from diagnostic and testing laboratories, driven by the imperative to mitigate the health risks associated with these contaminants. In this context, we present the utilization of a heterocyclic symmetrical Schiff Base derivative for the purpose of fluorogenic and chromogenic detection of Co²⁺, Cu²⁺ and Hg²⁺ ions. The characterization of the ligand involved a comprehensive array of techniques, including physical assessments, optical analyses, NMR, FT-IR, and mass spectrometric examinations. The mechanism of ligand-metal complexation was elucidated through the utilization of photophysical parameters and FT-IR spectroscopic analysis, both before and after the interaction between the ligand and the metal salt solution. The pronounced alterations observed in absorption and fluorescence spectra, along with the distinctive chromogenic changes, following treatment with Co²⁺, Cu²⁺ and Hg²⁺, affirm the successful formation of complexes between the ligands and the treated metal ions. Notably, the receptor's complexation response exhibited selectivity towards Co(II), Cu(II), and Hg(II), with no observed chromogenic changes, spectral variations, or band shifts for the various tested metal ions, including Na⁺, Ag⁺, Ni²⁺, Mn²⁺, Pd²⁺, Pb²⁺, Cd²⁺, Zn²⁺, Sn²⁺, Fe²⁺, Fe³⁺, Cr³⁺ and Al³⁺. This absence of interaction between these metal ions and the ligand could be attributed to their compact or inadequately conducive conduction bands for complexation with the ligand's structural composition. To quantify the sensor's efficacy, fluorescence titration spectra were employed to determine the detection limits for Co²⁺, Cu²⁺ and Hg²⁺, yielding values of 2.92 × 10^-8, 8.91 × 10^-8, and 4.39 × 10^-3 M, respectively. The Benesi-Hildebrand plots provided association constant values for the ligand-cobalt, ligand-copper, and ligand-mercury complexes as 0.74, 2.52, and 13.89 M^-1, respectively.

Keywords: Chromogenic; Complexation; Detection; Fluorescence; Sensor; Transition metals.