A near-infrared colorimetric and fluorescent dual-channel probe for cyanide detection based on dicyanomethylene-4H-pyran

A novel dicyanomethylene-4H-pyran-based sensor bearing 2-thiophenecarbonyl as a masking group was established for the detection of cyanide anions. Upon the addition of cyanide, sensor 1 manifested a near-infrared emission band at 717 nm, with an extremely large red-shift (similar to 180 nm) in the absorption spectrum. It also showed an obvious color change from yellow to green. Sensor 1 was used to sensitively measure CN- with low detection limit of 1.44 mu M. The stoichiometric ratio between probe and CN- were determined as 1:1, with the association constant of 7.87 x 10(2) M-1. The reaction mechanism was investigated by ESI-MS, H-1 NMR, HPLC, and density functional theory methods. Results indicate that the nucleophilicity of the cyanide catalyzes the elimination of 2-thiophenecarbonyl, which strengthens the intramolecular charge transfer effect of the dicyanomethylene-4H-pyran fluorophore. Furthermore, sensor 1 was found to be efficient in detecting cyanide in the intracellular region of MCF-7 cells.