Zirconium-Directed Supramolecular Self-Assembly of Coenzyme A@GNCs with Enhanced Phosphorescence for Developing Ultrasensitive Tracer Probe of Dipicolinic Acid, a Biomarker of Bacterial Spores

Luminescent gold nanoclusters (GNCs) are a class of attractive quantum-sized nanomaterials bridging the gap between organogold complexes and gold nanocrystals. They typically have a core-shell structure consisting of a Au(I)-organoligand shell-encapsulated few-atom Au(0) core. Their luminescent properties are greatly affected by their Au(I)-organoligand shell, which also supports the aggregation-induced emission (AIE) effect. However, so far, the luminescent Au nanoclusters encapsulated with the organoligands containing phosphoryl moiety have rarely been reported, not to mention their AIE. In this study, coenzyme A (CoA), an adenosine diphosphate (ADP) analogue that is composed of a bulky 5-phosphoribonucleotide adenosine moiety connected to a long branch of vitamin B5 (pantetheine) via a diphosphate ester linkage and ubiquitous in all living organisms, has been used to synthesize phosphorescent GNCs for the first time. Interestingly, the synthesized phosphorescent CoA@GNCs could be further induced to generate AIE via the PO₃^2- and Zr⁴⁺ interactions, and the observed AIE was found to be highly specific to Zr⁴⁺ ions. In addition, the enhanced phosphorescent emission could be quickly turned down by dipicolinic acid (DPA), a universal and specific component and also a biomarker of bacterial spores. Therefore, a Zr⁴⁺-CoA@GNCs-based DPA biosensor for quick, facile, and highly sensitive detection of possible spore contamination has been developed, showing a linear concentration range from 0.5 to 20 μM with a limit of detection of 10 nM. This study has demonstrated a promising future for various organic molecules containing phosphoryl moiety for the preparation of AIE-active metal nanoclusters.