Journal
NANOSCALE
Volume 9, Issue 4, Pages 1599-1606Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6nr07545b
Keywords
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Funding
- National Basic Research Program of China [2015CB932002]
- China-Singapore Joint Project [2015DFG92510]
- Science and National Natural Science Foundation of China [21507134, 21371174, 21671052]
- Natural Science Foundation of Anhui Province [1408085QB29, 1508085QB29]
- Scientific Research Foundation of Anhui Agricultural University [yj2016-06]
- Youth Research Foundation of Anhui Agricultural University [2015zr007]
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Chemical sensing for the convenient detection of trace aqueous fluoride ions (F-) has been widely explored with the use of various sensing materials and techniques. It still remains a challenge to achieve ultrasensitive but simple, rapid, and inexpensive detection of F-for environmental monitoring and protection. Here we reported a novel surface-enhanced Raman scattering (SERS) nanosensor, fluorescein phenylboronic acid covalently linked to 1,4-dimercapto-2,3-butanediol modified Au@Ag NPs by a cyclic boronate ester (Flu-PBA-Diol-Au@Ag NPs), for the rapid and ultrasensitive detection of F-. Once the Flu-PBA approached the surface of Au@Ag NPs, the Raman signals of Flu-PBA were remarkably enhanced due to the strong SERS effect. However, the presence of F- will induce the cleavage reaction of the cyclic boronate ester into the trifluoroborate anion (3F-Flu-PBA) and diol. The 3F-Flu-PBA molecules exfoliated from the surface of Au@Ag NPs, and the SERS signals of the nanosensor were quenched. Following the sensing mechanism, a silica-based SERS chip has been fabricated by the assembly of Flu-PBA-Diol-Au@Ag NPs on a piece of silicon wafer. The silica-based SERS chips showed high sensitivity for aqueous F-, and the limit of detection (LOD) could reach as low as 0.1 nM. Each test using the SERS chip only needs a droplet of 20 mu L sample and is accomplished within similar to 10 min. The silica-based SERS chip has also been applied to the quantification of F-in tap water and lake water.
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