A highly selective two-photon fluorescent probe for detection of cadmium(II) based on intramolecular electron transfer and its imaging in living cells

Abstract

A new quinoline-based probe was designed that shows one-photon ratiometric and two-photon off-on changes upon detecting Cd(2+) . It exhibits fluorescence emission at 407 nm originating from quinoline groups in Tris-HCl (25 mM, pH 7.40), H2 O/EtOH (8:2, v/v). Coordination with Cd(2+) causes quenching of the emission at 407 nm and simultaneously yields a remarkable redshift of the emission maximum to 500 nm with an isoemissive point at 439 nm owing to an intramolecular charge-transfer mechanism. Thus, dual-emission ratiometric measurement with a large redshift (Δλ=93 nm) and significant changes in the ratio (F500 /F439 ) of the emission intensity (R/R0 up to 27) is established. Moreover, the sensor H2 L displays excellent selectivity response, high sensitive fluorescence enhancement, and strong binding ability to Cd(2+). Coordination properties of H2 L towards Cd(2+) were fully investigated by absorption/fluorescence spectroscopy, which indicated the formation of a 2:1 H2 L/Cd(2+) complex. All complexes were characterized by X-ray crystallography, and TD-DFT calculations were performed to understand the origin of optical selectivity shown by H2 L. Two-photon fluorescence microscopy experiments have demonstrated that H2 L could be used in live cells for the detection of Cd(2+).

Keywords: cadmium; fluorescence; intramolecular electron transfer; ratiometry; semirigid structures.