Selective Detection of Hg2+ Ions with Boron Dipyrromethene-Based Fluorescent Probes Appended with a Bis(1,2,3-triazole)amino Receptor

Abstract

By using a copper-promoted alkyne-azide cycloaddition reaction, two boron dipyrromethene (BODIPY) derivatives bearing a bis(1,2,3-triazole)amino receptor at the meso position were prepared and characterized. For the analogue with two terminal triethylene glycol chains, the fluorescence emission at 509 nm responded selectively toward Hg²⁺ ions, which greatly increased the fluorescence quantum yield from 0.003 to 0.25 as a result of inhibition of the photoinduced electron transfer (PET) process. By introducing two additional rhodamine moieties at the termini, the resulting conjugate could also detect Hg²⁺ ions in a highly selective manner. Upon excitation at the BODIPY core, the fluorescence emission of rhodamine at 580 nm was observed and the intensity increased substantially upon addition of Hg²⁺ ions due to inhibition of the PET process followed by highly efficient fluorescence resonance energy transfer (FRET) from the BODIPY core to the rhodamine moieties. The Hg²⁺ -responsive fluorescence change of these two probes could be easily seen with the naked eye. The binding stoichiometry between the probes and Hg²⁺ ions in CH₃ CN was determined to be 1:2 by Job's plot analysis and ¹ H NMR titration, and the binding constants were found to be (1.2±0.1)×10¹¹ m^-2 and (1.3±0.3)×10¹⁰ m^-2 , respectively. The overall results suggest that these two BODIPY derivatives can serve as highly selective fluorescent probes for Hg²⁺ ions. The rhodamine derivative makes use of a combined PET-FRET sensing mechanism which can greatly increase the sensitivity of detection.

Keywords: boron dipyrromethene; fluorescence resonance energy transfer; mercury sensors; photoinduced electron transfer; rhodamine.