Determination of 2, 6-dipicolinic acid as an Anthrax biomarker based on the enhancement of copper nanocluster fluorescence by reversible aggregation-induced emission.

The weak fluorescence efficiency of copper nanoclusters (Cu NCs) limits their wide applications in biosensing and bioimaging areas, while the aggregation-induced emission (AIE) effect is anticipated to increase their luminescence intensity. Herein, the weak red emission of Cu NCs is increased considerably by the addition of lanthanide Tb3+, ascribed to the AIE effect. Monitoring of spores contamination can be carried out by determining the level of 2, 6-dipicolinic acid (DPA), which is a marker of spores. Due to the stronger synergy between DPA and Tb3+ for its clamped configuration of adjacent pyridine nitrogen group with the carboxylic acid group, the addition of DPA leads Tb3+ to be taken away from Cu NCs through a stronger coordination effect, causing Cu NCs to return to the dispersed state and weakened fluorescence. Based on this, an "off-on-off" fluorescent probe for DPA sensing was built, in which Tb3+ was used as a bridge to achieve AIE enhanced fluorescence effect on Cu NCs as well as a specific recognizer of DPA. The detection range for DPA was 0.1-60 μM and the detection limit was 0.06 μM, which was much lower than the infectious dose of anthrax spores. Since DPA is a unique biomarker for bacterial spores, the method was applied to the detection of actual bacterial spores and satisfactory results were obtained with a detection limit of 4.9*103 CFU mL-1.