We have synthesized novel coumarin-based fluorescent chemosensors for detection of fluoride ions in aqueous solution. The detection mechanism relied on a fluoride-mediated desilylation triggering fluorogenic reaction and a strong interaction between fluoride and the silicon center. In this work, the hydroxyl-decorated coumarins containing oxysilyl moiety have been synthesized through the aldehyde-functionalized coumarins. The optical responses toward fluoride, as well as aqueous stability studies of both aldehyde and hydroxyl functionalized coumarins, have been investigated. Due to the highest fluorescence enhancement upon the addition of fluoride and good stability in aqueous solution, the hydroxyl-decorated coumarin connected with the bulky tert-butyldiphenyloxysilyl group (-OSitBuPh₂) has been selected for further investigation of its potential as a fluoride sensor. This hydroxyl-decorated coumarin can selectively sense fluoride ions in aqueous media (contain 0.8% MeCN) with desirable response times (40 min). The limit of detection of this compound was determined as 0.043 ppm, satisfying the standard fluoride level (0.7 ppm) in drinking water recommended by U.S. Department of Health and Human Services. The application of this silyl-capped coumarin derivative for fluoride analysis in collected water samples displayed satisfactory analytical accuracy (<5% error). Finally, this compound was successfully employed in fluorescence bioimaging of fluoride ions in human liver cancer cells, indicating its excellent cell permeability, ability to retain inside the living cells, and good stability under physiological conditions.
Keywords: bioimaging; chemosensor; coumarin; fluorescence; fluoride.