Rhodamine 6G-PAH probes for heavy metal: Fluorescence detection, bioimaging, and solid-phase sensing application

Four rhodamine 6G-PAH probes with pyrene (R6G-Pyr), anthracene (R6G-Ant), acenaphthene (R6G-Acp) or phenanthrene (R6G-PA) as fluorophore were designed and synthesized for Hg(II) detection. Probe R6G-PA, which had the lowest detection limit of 0.84 nmol/L, displayed the best fluorescence performance as compared to the other three probes. This type of probe had good anti-interference properties against most common metal ions except Cu(II). Metal Cu(II) had a certain quenching effect on the fluorescence generated by Hg(II), with a minimum detection limit of 0.31 nmol/L (for R6G-Acp), indicating its potential practicability for Cu(II) detection. The structure-fluorescence relationship was discussed based on density functional theory (DFT) calculations, and R6G-PA + Hg(II), which had the minimum dihedral angle between polycyclic aromatic rings and rhodamine spiro ring, produced the strongest π-π accumulation and provided the brightest fluorescence. Probe R6G-PA was successfully employed for fluorescence detection of Hg(II) in biological samples. Its solid-phase sensor PS@R6G-PA was developed by immobilizing R6G-PA on PS microspheres for the determination of Hg(II) in water and food samples, with excellent reproducibility and fluorescence "on/off" response. The relative error of the spiked recovery rate was less than 10 %.