Preparation of Metal Nanocluster Supraparticles for Ultrasensitive Sensing of Tetracycline Based on Multiple Interactions between a Target and Sensor

J Agric Food Chem. 2024 Nov 18. doi: 10.1021/acs.jafc.4c09194. Online ahead of print.

Abstract

New strategies for enhancing the fluorescence emission of metal nanoclusters (MNCs) are very crucial for the highly sensitive sensing of food hazards. In this work, we prepared MNC supraparticles (Sc-CB/AuNCs) by simultaneously introducing cucurbit[7]uril (CB[7]) and Sc3+ ions into ATT-AuNCs for the first time. The obtained supraparticles exhibited strong emission enhancement due to synergistic aggregation-induced emission enhancement and restriction of intramolecular motion effects. Notably, the fluorescence of ATT-AuNCs was enhanced by 24-fold due to the combination of CB[7] and Sc3+ ions, and the quantum yield reached 69.1%. Moreover, we found that tetracycline (TC) could bind to the Sc-CB/AuNCs through simultaneous host-guest recognition and ionic complexation, which effectively quenched the Sc-CB/AuNCs through the synergy of photoinduced electron transfer and inner filter effect. Based on the above multiple interactions between TC and Sc-CB/AuNCs, an ultrasensitive sensing method for TC was constructed with an LOD of 0.3 nM. Furthermore, a portable fluorescent gel sensor was constructed and successfully used for TC detection in honey samples. The test took only 2 min. This work not only provided a simple and effective fluorescence enhancement strategy for MNCs but also offered a novel sensing strategy, which may largely extend the potential of host-guest recognition-based sensors for food and environmental hazards.

Keywords: dual recognition; fluorescence enhancement; metal nanoclusters; supraparticles; tetracycline.