An AIRE-active far-red ratiometric fluorescent chemosensor for specifically sensing Zn2+ and resultant Zn2+ complex for subsequent pyrophosphate detection in almost pure aqueous media.

Abstract A simple Schiff-base fluorescent chemosensor (1) was synthesized by the reaction of 3-amino-pyrazine-2-carbohydrazide and 7-diethylamino-3-formylcoumarin; the sensor 1 displayed a notable green emission at 524 nm in DMSO and an aggregation-induced ratiometric emission (AIRE) at 555 nm in an almost buffered aqueous media (0.5% DMSO content). The AIRE of 1 was quenched following binding to Zn2+ ions, while the fluorescence emission in the far-red region was evidently enhanced at 628 nm. Notably, the ratiometric signal output could be utilized to specifically distinguish Zn2+ among various metal ions. Moreover, the 1-Zn2+ complex was effectively employed as a fluorescent ratiometric chemosensor for pyrophosphate (PPi) detection. The detection limit was 3.52 μM and 2.45 μM for Zn2+ and PPi, respectively. The binding mechanism was evaluated by 1H NMR, ESI-MS, single-crystal X-ray diffraction, TEM, time-resolved fluorescence spectrophotometry, and density functional theory studies. Overall, owing to its sensitive fluorescence behavior, cell imaging studies demonstrated that this sensor is capable of sensing Zn2+ and PPi in living cells.