β-cyclodextrin-modulated ratiometric supramolecular BODIPY fluoroprobe for highly selective and sensitive detection of thiophenol

• Published in: Journal of hazardous materials 2024-11, Vol.479, p.135751, Article 135751
• Main Authors: Wu, Di, Wang, Yuxin, Wu, Niu, Li, Tong, Shen, Yueyi, Liu, Hongli, Yarmamat, Mubarak, Wang, Mingpeng, Li, Lijie, Jian, Ningge
• Format: Article
• Language: English
• Subjects: Animals; beta-Cyclodextrins - chemistry; Bioimaging; Boron Compounds - chemistry; Fluorescent Dyes - chemistry; Fluorescent probe; Humans; Hydrogel; Limit of Detection; Phenols - analysis; Phenols - chemistry; Sulfhydryl Compounds - analysis; Sulfhydryl Compounds - chemistry; Supramolecular probe; Thiophenol; Water Pollutants, Chemical - analysis; Water Pollutants, Chemical - chemistry; Zebrafish
• ISSN: 0304-3894; 1873-3336; 1873-3336
• DOI: 10.1016/j.jhazmat.2024.135751

Thiophenol (PhSH) is an important industrial intermediate but displays significant toxicity towards environmental and biological systems. Here, we introduce a supramolecular system based on β-cyclodextrin (β-CD) and boron dipyrromethene (BODIPY) as a ratiometric fluorescence probe to discriminate PhSH in environmental water samples, cells, and in vivo. In aqueous solutions, BODIPY shows extremely weak fluorescence intensity due to its aggregation into nanometer-sized clusters, which prevents its interaction with thiols. However, within a β-CD environment, it can selectively and sensitively detect PhSH. Also, the stability of the probe was significantly improved. The mechanism studies based on stoichiometry, NMR spectroscopy, and theoretical calculation revealed distinct intermolecular interactions between β-CD and BODIPY, including host-guest interactions and hydrogen bonds. Low limit of detection (10.7 nM) and rapid response time (5 min) have been achieved, and the practicality of the supramolecular system (BODIPY@β-CD) has been verified by actual sample analysis. Furthermore, the first hydrogel-based sensing system for portable PhSH detection has been developed, facilitating rapid and on-site colorimetric visualization across both liquid and gas phases. Most importantly, using a low amount of the probe, early stages of low-dose exposure to PhSH can be visualized in living cells and zebrafish. Therefore, BODIPY@β-CD is a robust new monitoring tool for the detection of PhSH in various scenarios, indicating the promising application value of the host-guest supramolecular probe in detecting highly toxic substances. [Display omitted] •A novel supramolecular probe system was established based on the host-guest interactions between β-CD and BODIPY.•The BODIPY@β‐CD probe system could detect PhSH selectivity and sensitivity in water, cells, and in vivo.•The mechanisms of the formation of the supramolecular complex and the fluorescent response were thoroughly investigated.•A portable hydrogel sensing platform was constructed to sense PhSH in both solution and gaseous state.