Enhanced fluorescence quenching for p-nitrophenol in imidazolium ionic liquids using a europium-based fluorescent probe

Abstract

p-Nitrophenol (PNP) is a toxic contaminant in water, the detection of which has attracted considerable attention. Since ionic liquids (ILs) have been widely used as popular solvents in both extraction and catalysts for PNP, the remediation of PNP is not limited to water and traditional organic solvents. Thus, it is significant to develop approaches for the detection of PNP in ILs. Accordingly, the present work is focused on the detection of PNP in a series of imidazolium-based ILs, 1-hexyl-3-methyl-imidazolium bromide ([Hmim]Br), 1-butyl-3-methyl-imidazolium tetrafluoroborate ([Bmim]BF₄), 1-butyl-3-methyl-imidazolium trifluoromesulfonate ([Bmim]TfO), 1-butyl-3-methyl-imidazolium trifluoroacetate ([Bmim]TA), and 1-butyl-3-methyl-imidazolium nitrate ([Bmim]NO₃), using a europium-based fluorescent probe, Na₃[Eu(DPA)₃] (DPA = 2, 6-pyridinedicarboxylic acid). This fluorescent probe showed excellent selectivity and sensitivity toward [Bmim]NO₃ in aqueous solution. Further studies showed that not only the fluorescence performance of the europium complex was enhanced in the other four ILs compared with that in water, but also the detecting capability for PNP was improved. The order of the quenching efficiency in different solvents was: [Bmim]BF₄ > [Bmim]TfO > [Hmim]Br > [Bmim]TA > water. The higher sensitivity for PNP in ILs was proven to be related to the efficient energy transfer of the europium complex and lower solvent polarity of the ILs. The quenching mechanism for the detection of PNP was established as being due to the ground state electrostatic interactions between the fluorescent probe and analyte, photoinduced electron transfer (PET) and inner filter effect (IFE).