Detection of Per- and Polyfluoroalkyl Substances (PFAS) by Interrupted Energy Transfer

The ubiquitous presence of per- and polyfluoroalkyl substances (PFAS) in aqueous environments has aroused societal concern. Nonetheless, effective sensing technologies for continuous monitoring of PFAS within water distribution infrastructures currently do not exist. Herein, we describe a ratiometric sensing approach to selectively detect aqueous perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) at concentrations of μg ⋅ L⁻¹. Our method relies on the excitonic transport in a highly fluorinated poly(p-phenylene ethynylene) to amplify a ratiometric emission signal modulated by an embedded fluorinated squaraine dye. The electronic coupling between the polymer and dye occurs through overlap of π-orbitals and is designed such that energy transfer is dominated by an electron-exchange (Dexter) mechanism. Exposure to aqueous solutions of PFAS perturbs the orbital interactions between the squaraine dye and the polymer backbone, thereby diminishing the efficiency of the energy transfer and producing a “polymer-ON/dye-OFF” response. These polymer/dye combinations were evaluated in spin-coated films and polymer nanoparticles and were able to selectively detect PFAS at concentrations of ca. 150 ppb and ca. 50 ppb, respectively. Both polymer films and nanoparticles are not affected by the type of water, and similar responses to PFAS were found in milliQ and well water.