Ratiometric colorimetric detection of fluoride ions using a schiff base sensor: enhancing selectivity and sensitivity for naked-eye analysis.

ABSTRACT

A Schiff base receptor with an active -NH group was designed and synthesized for the selective and sensitive colorimetric detection of inorganic fluoride (F-) ions in an aqueous medium. The sensitivity of the receptor for F- ions was enhanced by the influence of two electron-withdrawing -NO2 groups at ortho and para positions which result in a vivid color change. The receptor underwent a remarkable color change from light yellow to violet, enabling naked-eye detection of F- ions without the need for spectroscopic equipment. To ensure the structural integrity of the synthesized receptors, prominent spectroscopic techniques such as 1H NMR, FTIR, and GCMS analysis were used for characterization. With a limit of detection (LoD) of 0.0996 ppm, a 1 2 stoichiometric binding ratio was observed for receptor and F- ions. The binding mechanism confirmed the deprotonation of the -NH group followed by the formation of -HF2, resulting in an intramolecular charge transfer (ICT) transition, which correlates with UV-vis and 1H NMR titration results. In addition, the proposed binding mechanism of F- ion interaction with the receptor was theoretically validated using DFT and TDDFT calculations. Furthermore, as a real-life implementation of the receptor, quantification of the F- ions present in a commercially available mouthwash was demonstrated. To assess the sensitivity performance, a paper-based dip sensor and a solid substrate sensor by functionalizing the receptor on diatomaceous earth were demonstrated. Finally, sensors were built into smartphones that could recognize the red, green, and blue percentages (RGB%) where each parameter defines the intensity of the color, which could also be used as a supplement to the colorimetric investigations.