Sensitive and selective urinary 1-hydroxypyrene detection by dinuclear terbium-sulfonylcalixarene complex

A new sulfonylcalix[4]arene-based dinuclear terbium molecular container (1) was conveniently synthesized and utilized as a fluorescence probe for the detection of a well-known biomarker 1-hydroxypyrene (1-OHP), which is used for the evaluation of polycyclic aromatic hydrocarbons (PAHs). The sulfonylcalix[4]arene ligand could not only serve as an efficient antenna ligand to promote the ligand-to-metal energy transfer but also provide a suitable cavity to accommodate 1-OHP. Promising fluorescence quenching effects were well established during the titration of the compound 1 with 1-OHP, and these effects were due to the enhancement in the host-guest intermolecular charge transfer and the decrease in the ligand-to-metal energy transfer after the formation of the stable host-guest complex. The fluorescence sensing mechanism was clearly understood through the titration experiments, and the data could be fit with the Benesi-Hildebrand and Stern-Volmer models. The TbIII-TBSC-based luminescent sensor exhibited quick response, high sensitivity, and specific selectivity to 1-OHP, even in the presence of other constituents in urine, thus providing a new sensing platform for the clinical diagnosis of human exposure to PAHs.