Smart Colorimetric Chemosensors for Multi‐Analyte Signaling: Recognition of Heavy Metal Ions in an Aqueous Medium and DFT Studies

Abstract

A Schiff's base colorimetric chemosensors R1–R3 consist of carbohydrazide, and heterocyclic aldehydes have been designed and synthesized for sensing of heavy metal ions. Synthesized receptors were well characterized by various standard spectroscopic techniques. The receptor R1 exhibited multi‐ion selectivity for Cd2+, Hg2+, Pb2+, Cu2+ ions and showed lowest detection limit of 1.9 ppb, for Cd2+ & Hg2+ ions. The receptors R2 and R3 displayed dual ion selectivity (R2 for Hg2+, Cu2+, and R3 for Cu2+, AsO2– ions) in an aqueous medium at ppb levels. The UV–Vis and colorimetric studies confirmed the selectivity and sensitivity of chemosensors R1–R3 in the presence of other interfering metal ions. Further, using the B–H plot, FT‐IR, and mass analysis data, the binding modes, stoichiometric ratios of receptors R1–R3 with the metal ions were investigated. The estimated association constant values were found to be 104 to 105 M–1/M–2. The experimental results are well concordant with that of calculated theoretical DFT results. The receptors R1–R3 exhibited good sensitivity and selectivity compared to literature reports and successfully demonstrated for test strip applications.

Applications of Density Functional Theory on Heavy Metal Sensor and Hydrogen Evolution Reaction (HER)

“…The HOMO-LUMO band gap was reduced by 2.49 eV in the metal ion complexes. Carbohydrazide based colorimetric sensors for detection of multiple ions were reported by Tekuri et al [55] The receptors showed selectivity towards Cd 2+ , Hg 2+ , Pb 2+ , Cu 2+ and AsO 2 − ions with low detection limit. Using B3LYP functional and non-relativistic effective core potential (ECP) with LANL2DZ and 6-31 g(d,p) basis sets confirmed the binding of receptor with different metal ions as per hard and soft (Lewis) acids and bases (HSAB) theory.…”