Highly Selective Luminescence Determination of Terbium at the Sub-ppb Level with Sulfonylcalix[4]arene-p-tetrasulfonate

The energy-transfer luminescence of complexes of Tb3+ with calix- (CAS), thiacalix- (TCAS), and sulfonylcalix[4]arene-p-tetrasulfonates (SO2CAS), in which four p-phenolsulfonates are jointed by –CH2–, –S–, and –SO2–, respectively, was applied to an ultratrace determination of the Tb3+ ion. Based on the complexation behavior of each calix ligand, a determination procedure was established. A time-resolved measurement was conveniently employed to separate the background fluorescence from the luminescence of the calix-Tb3+ complexes. An improved sensitivity was attained by sulfur-bridged calixes, TCAS and SO2CAS, as compared to CAS, owing to the photophysical properties of the Tb3+-complexes. The detection limits for Tb3+ ion by CAS, TCAS, and SO2CAS ligands were estimated to be 8.2×10−10 mol dm−3 (131 ppt), 2.0 × 10−10 mol dm−3 (32 ppt), and 2.3 × 10−10 mol dm−3 (37 ppt) at S/N = 3, respectively. In terms of the selectivity, the effect of diverse coexisting ions on the luminescence intensity of the Tb3+ comp...