Perfluoroalkyl functionalized-Au nanoparticle sensor: Employing rate of spectrum shifting for highly selective and sensitive detection of per- and polyfluoroalkyl substances (PFASs) in aqueous environments

Abstract

Per- and polyfluoroalkyl substances (PFASs) are emerging contaminants detected ubiquitously and have negative impacts on human health and ecosystem; thus, developing in-situ sensing technique is important to ensure safety. Herein, we report a novel colorimetric-based sensor with perfluoroalkyl receptor attached to citrate coated gold nanoparticles (Citrate-Au NPs) that can detect several PFASs including perfluorocarboxylates with different chain lengths (PFHxA, PFOA, PFNA, PFDA), perfluorooctanoic sulfonate (PFOS), and perfluorooctanoic phosphonate (PFOPA). The sensor detects PFASs utilizing fluorous interaction between PFASs and the perfluoroalkyl receptor of Citrate-Au NPs in a solution at a fixed salt concentration, inducing changes in nanoparticle dispersity and the solution color. The rate of spectrum shift was linearly dependent on PFASs concentrations. Citrate-Au NPs with size between 29 – 109 nm were synthesized by adjusting citrate/Au molar ratios, and 78 nm showed the best sensitivity to PFOA concentration (with level of detection of 4.96 µM). Citrate-Au NPs only interacted with PFASs with perfluoroalkyl length > 4 and not with non-fluorinated alkyl compound (nonanoic acid). The performance of Citrate-Au NP based sensor was strongly dependent on the chain length of the perfluoroalkyl group and the head functional group; higher sensitivity was observed with longer chain over shorter chain, and with sulfonate functional group over carboxylate and phosphonate. The sensor was tested using real water samples (i.e., tap water, filtered river water), and it was found that the sensor is capable of detecting PFASs in these conditions if calibrated with the corresponding water matrix. While further optimization is needed, this study demonstrated new capability of Citrate-Au NPs based sensor for detection of PFASs in water.