Time-Resolved Terbium-Based Probe for the Detection of Zinc(II) Ions: Investigation of the Formation of a Luminescent Ternary Complex.

Because of their unique photochemical and photophysical properties, luminescent lanthanide-based complexes have long captivated chemists. In recent years, the number of reports of luminescent lanthanide complex-based probes for monitoring of biological and environmental processes has dramatically increased, namely, because of their selectivity for particular analytes, lower limits of detection, and the fact that they allow monitoring of analytes in real time. Lanthanide-based probes need to be paired with an appropriate antenna/sensitizer to allow maximum energy transfer, with the antenna typically covalently attached to the stable lanthanide chelate. We have recently investigated "dark" lanthanide-based probes where the sensitizer is not covalently linked to the lanthanide chelate. Herein we report the use of a luminescent lanthanide-based probe system for the detection of Zn ions based on the formation of a ternary complex between a "dark" terbium complex, lumazine, and Zn. The terbium(III)-based probe incorporates a 1,4,7,10-tetraazacyclododecane-1,4,7,10-triacetic acid macrocyclic chelator covalently attached to a cyclen moiety, which is the Zn ion binding group. In the presence of Zn ions and lumazine (a strongly UV-absorbing sensitizer), a 1:1:1 ternary complex forms. The resulting complex is highly luminescent and selective for Zn ions over other cations of environmental significance. Furthermore, with a limit of detection of 1.2 μM, this probe can detect the level of chronic zinc(II) concentrations denoted by the U.S. Environmental Protection Agency.