On a Fluorescent Dye for Indicator Displacement From Cucurbit[7]uril-Based Molecular Recognition: A Joint...

The host-guest complexation of a new fluorescent probe called 7-(diethylamino)-4-hydroxyquinoline-2(1H)-one (QD) and its inclusion complex with the Cucurbit[7]uril (CB7) macrocycle were studied. QD was successfully synthesized, and an extensive characterization was performed for both the free probe and its corresponding QD•CB7 adduct. Spectroscopic measurements indicate that the complexation enhances and promotes the photophysical properties of the QD, increasing its quantum yield and resulting in a 4.6-fold increase in it. Aqueous QD and QD•CB7 were also investigated, combining density functional theory wavefunctions with quantum theory of atoms in molecules descriptors and a semiclassical molecular dynamics technique. The derived picture suggests that the spontaneous CB7-based molecular recognition mechanically hinders a light-driven free rotation-along a diethylamino substituent within the QD molecule-avoiding the formation of a nonemissive torsional intramolecular charge transfer state. Moreover, the addition of Tyramine (TA), a biogenic primary amine with a high affinity for CB7, resulting in a fluorescence switch-off response. These results demonstrate that the TA analyte effectively displaces the dye QD from the CB7 host-guest complex. This dye is then proposed as a fluorescent indicator-displacement assay for the detection and determination of the binding constants of biogenic amines.