Lighting Up PFAS: Rapid Detection with Fluorescent Nanosensors

Atomically precise Ce(IV) clusters are identified as a novel class of fluorescent probes for rapid s

Atomically precise Ce(IV) clusters are identified as a novel class of fluorescent probes for rapid single step detection of carboxylated PFAS.

Scientific Achievement

CFN users collaborated with staff to demonstrate fluorescent nanosensors using hexanuclear Cerium-oxo clusters (Ce-Gly) for rapid, one-step detection of long-chain carboxylated per- and polyfluoroalkyl substances (PFAS) in environmental samples.

Significance and Impact

This method provides a cost-effective and efficient alternative for PFAS detection, which is critical due to the harmful effects of PFAS on health and the environment. The approach offers potential for widespread environmental monitoring.

Research Details

The presence of poly- and perfluoroalkyl substances (PFAS) in the environment is associated with adverse health effects but measuring PFAS is challenging due to the associated high cost and technical complexities of the analysis. Here, the reactivity of atomically precise metal-oxo clusters is reported and the foundation for their use is provided as fluorescent nanosensors for PFAS detection. The material comprises crystalline, water soluble, hexanuclear cerium-oxo clusters [Ce63-O)43-OH)4]12+ decorated with glycine molecules (Ce-Gly) characterized by fluorescence emission at 353 nm. The Ce-Gly fluorescence is found sensitive to long chain carboxylated PFAS of CF3–(CF2)n –, where n ≥ 6, such as perfluorooctanoic, perfluorononanoic and perfluorodecanoic acids. This unique reactivity leads to a change in the emission spectra in a concentration dependent manner, enabling PFAS detection through ligand exchange and aggregation-induced emission (AIE) enhancement. No significant cross-reactivity from potentially co-existing species, including sulfonated PFAS, octanoic and dodecanoic acids, humic acid, and inorganic ions is observed. With an optimal concentration of 3.3 µg mL−1 Ce-Gly, the method demonstrated detection limits of 0.24 ppb for PFOA and 0.4 ppb for PFNA. These findings highlight the potential of fluorescence-based detection strategies utilizing nanoscale probes such as Ce-Gly as fluorescent probes and nanosensors for PFAS.

Ce-Gly clusters exhibit aggregation-induced emission upon interacting with PFAS, leading to concentration-dependent fluorescence changes. The method demonstrated detection limits as low as 0.24 ppb for PFOA and 0.4 ppb for PFNA.

Publication Reference

MH Hassan, R Khan, D Andreescu, S Shrestha, M Cotlet, S Andreescu, Atomically Precise Hexanuclear Ce (IV) Clusters as Functional Fluorescent Nanosensors for Rapid One-Step Detection of PFAS, Advanced Functional Materials, 2403364, (2024).

DOI: https://doi.org/10.1002/adfm.202403364
OSTIhttps://www.osti.gov/pages/biblio/2372690-atomically-precise-hexanuclear-ce-iv-clusters-functional-fluorescent-nanosensors-rapid-one-step-detection-pfas

Acknowledgment of Support

This work was supported by grant NSF- 2141017 and the New York State Center of Excellence (CoE) in Healthy Water Solutions to SA. This research used the advanced optical facilities of the Center for Functional Nanomaterials (CFN), which is a U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

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