A near-infrared-emission aza-BODIPY-based fluorescent probe for fast, selective, and "turn-on" detection of HClO/ClO.

A novel near-infrared-emitting aza-BODIPY-based fluorescent probe with two tellurium atoms at two upper benzyl rings has been prepared and explored for its fluorescent sensing properties towards hypochlorous acid/hypochorite (HClO/ClO-), which showed high selectivity and absolutely fluorescent "turn-on" phenomenon at 738 nm. The fluorescence of this probe was sufficiently quenched due to photoindued electron transfer by two tellurium atoms. Upon exposure to HClO/ClO-, a strong near-infrared emission at 738 nm appeared with fluorescence quantum yields changing from 0 to 0.11. This remarkable fluorescence change was ascribed to the oxidation of both electron-rich tellurium atoms. The detection limit of this probe towards HClO/ClO- was calculated to 0.09 µM in acetonitrile aqueous solution by the linear fluorescence change at 738 nm in the HClO/ClO--concentration range of 0-30 µM. Interestingly, this probe was found to be applicable in a broad pH range (2-10). Meanwhile, the oxidized probe could be further responsive to biothiols with substantial fluorescence disappearance. The bioimaging experiments in RAW264.7 cells showed the appearance of intracellular near-infrared fluorescence after addition of HClO/ClO- and PMA, and the fluorescence could also be reversed to be silenced by further introduction of GSH, confirming its potential application for exogenous and endogenous detection of HClO/ClO- in living cells.

A novel near-infrared-emitting aza-boron-dipyrromethene-based remarkable fluorescent probe for Hg2+ in living cells.

A new near-infrared (NIR)-emitting aza-boron-dipyrromethene dye with two electron-donating amino groups at 1- and 7-positions has been prepared via several steps of reactions. This probe showed a NIR absorption at 748 nm with an obvious shoulder peak at 634 nm in CH3CN/H2O. Interestingly, a NIR fluorescence emission at 843 nm was observed with a large Stokes shift of 95 nm. This novel NIR-emitting aza-boron-dipyrromethene dye was further investigated as a Hg2+-sensing fluorescent probe, which selectively bound to Hg2+, showing a blue-shifted and sharp absorption band at 695 nm with the disappearance of the shoulder peak at 634 nm. Correspondingly, the color change could be easily seen from blue to green. Interestingly, the emission exhibited an absolutely "turn-on" peak at 725 nm with a significant blue shift by 118 nm (from 843 to 725 nm), due to the efficient inhibition of the intramolecular-charge-transfer process arising from two amino groups. This probe was finally introduced to Hela cells, showing a "OFF-ON" NIR emission upon exposure to Hg2+. The overall results confirmed that this novel NIR-emitting aza-boron-dipyrromethene fluorescent probe with a large Stokes shift could serve as a colorimetric and fluorescent "turn-on" sensor for Hg2+ in both solutions and living cells.