An On-Off-On Fluorescence Probe Based on Coumarin for Cu²⁺, Cysteine, and Histidine Detections

A simple coumarin-based Schiff base (probe L) was successfully developed. It showed strong green fluorescence emission at 527 nm with a 70.3% of fluorescence quantum efficiency (Φ_F). However, after the addition of common metal ions, probe L can only combine with Cu²⁺ ions and displayed significant fluorescence quenching of > 96.2% (Φ_F = 2.7%) due to the paramagnetic quenching action from Cu²⁺. Conversely, by the coordination action of cysteine (Cys) and histidine (His), the quenching fluorescence of the complex (L-Cu²⁺) between probe L and Cu²⁺ ions was recovered mostly because the Cys and His can usurp Cu²⁺ of L-Cu²⁺ and led to the liberation of probe L. Based on the fluorescence changes of probe L with the actions of Cu²⁺, Cys, and His, an on-off-on reversible fluorescence probe for sensitive and specific monitoring Cu²⁺, Cys, and His has been prepared. More importantly, the probe L and L-Cu²⁺ ensemble can be used, respectively, to test Cu²⁺ and Cys/His in live cells and human urine samples with great reliability.