Physicochemical and Ion-Sensing Properties of Benzofurazan-Appended Calix[4]arene in Solution and on Gold Nanoparticles: Spectroscopy, Microscopy, and DFT Computations in Support of the Species of Recognition

[Image: see text] A calix[4]arene conjugate (L) functionalized at the lower rim with a benzofurazan fluorophore (NBD) and at the upper rim with a thioether moiety has been synthesized and characterized by (1)H NMR, (13)C NMR, and mass spectrometry techniques. Both the absorption and emission spectral data for L in different solvents exhibited progressive changes with an increase in polarity. Ion recognition studies were performed by absorption and fluorescence spectroscopy using 10 different metal ions. Among these, Hg(2+) exhibited greater changes in these spectra, whereas Cu(2+) showed only significant changes and all other ions showed no change in the spectral features. Although the Hg(2+) has dominant influence on the spectral features and provides a detection limit of 56.0 ± 0.6 ppb, the selectivity was hampered because of the presence of the derivatizations present on both the rims of L for ion interaction in solution. Therefore, L was immobilized onto gold nanoparticles (AuNP(L)’s) so that the upper rim derivatizations anchor onto the gold surface through Au–S interactions, and this leaves out only the lower rim NBD derivatization for interaction with ions selectively. The AuNP(L)’s were characterized by transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS) analyses. The surface characteristics were analyzed by contact angle measurements. The AuNP(L)’s exhibit greater selectivity and enhanced sensitivity for Hg(2+) ions with a lowest detection limit of 48.0 ± 0.8 ppb. The immobilization of L onto AuNPs was reflected in the corresponding fluorescence lifetime values, and the addition of Hg(2+) to either L or AuNP(L) showed fluorescence quenching. The reversible recognition of Hg(2+) by L was demonstrated by titrating L or AuNP(L) with Hg(2+) followed by tetra-butyl ammonium iodide for several cycles. The structural features of Hg(2+)-bound species were demonstrated by density functional theory computations and were supported by the XPS data. The Hg(2+) induces aggregated fibrillar morphology into supramolecular L, as demonstrated by microscopy when Hg(2+) was added either to L or to AuNP(L), supporting aggregation-caused quenching.