The authors report on an energy transfer based fluorometric approach for the detection of nitroaromatic pollutants. This is achieved using 4-mercaptobenzoic acid (4-MBA)-capped CaF2:Tb3+ nanocrystals that were synthesized by a microwave procedure. 4-MBA acts as both a capping agent and a sensitizer for the Tb3+ ions in CaF2 host matrix. This approach is different from the earlier studies where Ce3+ is generally used as the sensitizer for the Ln3+ ions. The use of capping ligand as sensitizer has the feature that binding of nitroaromatics directly to the sensitizer can alter the energy transfer efficiency between the sensitizer and the Tb3+ ions. The fluorescent nanocrystal probe doped with 2% of Tb3+ displays green emission with a peak at 542 nm if photoexcited at 311 nm. The emission is quenched if the nanocrystals are exposed to nitroaromatic compounds such as 4-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol (picric acid), 4-nitrotoluene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene. These analytes also cause a (longwave/shortwave) shift in the excitation maxima which helps in identifying the individual nitroaromatic compound using single nanoprobe. The respective detection limits (by applying the 3σ/K criterion) are 0.86 μM, 0.83 μM, 0.78 μM, 0.36 μM, 1.5 μM, and 1.96 μM. Graphical abstract Schematic illustration of the use of 4-mercaptobenzoic acid (MBA)-capped CaF2:Tb3+ nanocrystals as a fluorescent nanoprobe for the detection of nitroaromatic analytes. The Tb3+ ions show strong green fluorescence via 4-MBA-induced ligand sensitization. The specific π interaction between 4-MBA capped CaF2 nanocrystals and nitroaromatics leads to reduction in the fluorescence intensity by inhibiting the energy transfer from 4-MBA to Tb3+ ion in CaF2 nanocrystals.
Keywords: Energy transfer; Hydrogen bonding and π interactions; Lanthanide; Ligand sensitization; Luminescence; Nanocrystals; Quenching; Solvatochromic effect.