Abstract
To inform the design of polymer-based adsorbent materials for sequestration of per- and polyfluoroalkyl substances (PFAS) from aqueous solution, we report here on the critical aggregation concentration (CAC), shape, size, composition, and interactions of assemblies formed in water between perfluorooctanoic acid ammonium salt (PFOA) and the nonionic polymer poly(ethylene oxide) (PEO), obtained from complementary experiments (conductivity, surface tension, pyrene fluorescence, viscosity, and small-angle neutron scattering (SANS)) and atomistic molecular dynamics (MD) simulations. PEO–PFAS binding commences at concentrations lower than the PFOA critical micelle concentration (CMC) and is driven by PEO localizing on the micelle surface and shielding the fluorocarbon parts of PFOA from contact with water. PFOA + PEO mixed micelles have a 10% higher association number and are 40% more elongated compared to polymer-free PFOA micelles. This is the first investigation on the structure of polymer + fluorocarbon surfactant mixed micelles and contributes fundamental insights into the association of water-soluble polymers with PFAS surfactants.
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