On-off-on relay fluorescence recognition of ferric and fluoride ions based on indicator displacement in living cells

摘要： A new boronic acid derivative functionalized with a 4-(3-(4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl)-1,2,4-oxadiazol-5-yl)phenyl (IOP) moiety was synthesized for use as a sequential “on-off-on”-type relay fluorescence probe for Fe3+ ions and F? ions with high selectivity and sensitivity under physiological conditions. The introduction of Fe3+ to IOP boronic acid (IOPBA) formed an Fe3+-IOPBA complex, which led to quenching of the blue fluorescence intensity at 458 nm. The lowest-energy conformation of IOPBA was theoretically predicted to adopt an extended structure, and the Fe3+ ion in the Fe3+-IOPBA complex was coordinated to two phenyl groups to form a p-complex. Upon addition of F? to the Fe3+-IOPBA complex, the original fluorescence was recovered due to formation of [FeF6]3?, resulting in “on-off-on”-type sensor behavior. IOPBA showed high selectivity towards Fe3+ among other cations. Moreover, the Fe3+-IOPBA complex showed specific selectivity towards F?, with other cations and anions not interfering with detection. Both sensing processes showed 1:1 stoichiometry with binding constants of 6.87 × 106 and 4.49 × 106 mol–1 L for Fe3+ with IOPBA and F? with Fe3+-IOPBA, respectively. The limits of detection for Fe3+ and F? were 10 and 1 nM, respectively. The proposed method was successfully applied in real water samples. Furthermore, the probe had low cytotoxicity and was successfully used as a bioimaging reagent to detect intracellular Fe3+ and F? in living HeLa cells.