Eu³⁺@metal-organic frameworks encapsulating carbon dots as ratiometric fluorescent probes for rapid recognition of anthrax spore biomarker

Anthrax spores pose a serious threat to human well-being and life, so it is highly desirable to develop a rapid, sensitive, and selective quantitative assay of calcium pyridine dicarboxylate (CaDPA) as a biomarker of anthrax spores. Herein, carbon dots (CDs) chelated Eu³⁺@metal-organic framework (Eu-MOFs) as dual-emissive ratiometric fluorescent (RF) probe was successfully fabricated by a simple one-pot in situ selective self-assembly synthetic strategy. The developed RF probe has an effective self-calibration function, which performs a highly sensitive and selective recognition of CaDPA in water and human serum sample. The blue-emitting CDs was employed as an effective fluorescence reference, while the Eu-MOFs exhibited enhanced red fluorescence signal through the coordination interaction with CaDPA chromophore. The sensing mechanism is attributed to that CaDPA can sensitize Eu³⁺ intrinsic luminescence due to the energy transfer from CaDPA to Eu³⁺. What's more interesting is that with the continuous drop of CaDPA, the emission color of CDs@Eu-MOF changes from blue to red. The results revealed that CDs@Eu-MOFs RF probe can detect CaDPA effectively in the range of 8-170 μg/L with good linear relationship, and exhibited a remarkable selectivity for CaDPA. More interestingly, a paper-based probe has also been devised for on-site detection of CaDPA. In addition, CaDPA is used as input signal to construct an IHIBITION logic gate device which performs the "off-on" mode. The constructed CDs@Eu-MOF probe can achieve exceptionally rapid, highly sensitive and selective detection of CaDPA, which can further expand the application prospects in environmental and biological analysis.