Eu3+/Tb3+ supramolecular assembly hybrids for ultrasensitive and ratiometric detection of anthrax spore biomarker in water solution and actual spore samples.

Rare earth (RE) complexes have found a variety of applications in materials science and biomedicine because of their unique luminescence properties. However, the poor stability and solubility in water of multicomponent RE assemblies significantly limit their practical applications. We rationally designed and developed a novel Eu3+/Tb3+ supramolecular assembly hybrids (Eu/Tb-SAH) by supramolecular host-guest recognition and coordination recognition with the excellent characteristics of water dispersion stability, biocompatibility and luminous properties. As anthrax spore biomarker, 2,6-pyridinedicarboxylic acid (DPA) can coordinate with Tb3+ and sensitize Tb3+, resulting in a proportional change of fluorescence intensity and lifetime on the ms timescales, thereby realizing rapid and sensitive detection of DPA in water media or actual spores. To confirm our prediction, accurate and selective detection of DPA was achieved with Eu/Tb-SAH as a nanoprobe through steady-state ratiometric fluorescence and time-resolved technology, of which the limit of detection (LOD) are 27.3 nM and 1.06 nM, respectively. This was obviously lower than the amount of anthrax spores infecting the human body (60 μM). Besides, the filter paper was used to carry out visual detection of DPA and read the corresponding data through smart phones. This work paves a new way to fabricate luminescent RE nanomaterials and provides new ideas for the design of ratiometic lifetime imaging biosensors in the meantime.