Dual fluorophores embedded in zeolitic imidazolate framework‑8 for ratiometric fluorescence sensing of a biomarker of anthrax spores

Abstract

The precise and selective monitoring of dipicolinic acid (DPA), a particular biomarker associated with anthrax spores, is crucial for the rapid detection and diagnosis of anthrax infection. A ratiometric fluorescence nanoprobe called AuNCs/GQDs@ZIF-8, has been designed by encapsulating gold nanoclusters (AuNCs) and graphene quantum dots (GQDs) into zeolitic imidazolate framework‑8 (ZIF-8) for sensing DPA. By leveraging enrichment effects of ZIF-8, embedded AuNCs restricts intramolecular movements and triggers aggregation-induced emission, further acquiring bright fluorescence. In the presence of europium ions (Eu3+), the fluorescence of AuNCs@ZIF-8 significantly decreases due to static quenching. However, Eu3+ are sequestered by DPA through strong coordination effects, causing fluorescence recovery of AuNCs@ZIF-8. Eu3+-mediated AuNCs@ZIF-8 therefore serve as response signals for DPA recognition. Integrating with stable reference signals of GQDs, a ratiometric fluorescence sensor exhibits the satisfactory linearity of 0.1–200 µM and detection limit of 32 nM. Furthermore, the smartphone-integrated visual mode can immediately identify fluorescence colors for assessing DPA. Compared to alternative nanoprobes, this ratiometric fluorescence sensor demonstrates higher sensitivity, lowering than DPA commonly released by infectious spores (60 µM). This study not only provides the promising sensor for DPA measurement during early anthrax diagnosis, but offers insights on designing ratiometric sensors with diverse fluorescence nanomaterials.