Self-Aggregative Recognition and Extraction of Perfluorooctanesulfonate with Flexible Cationic Water-Soluble Deep Cavitands
Ria Lian, Yu‐Dong Yang, José Luis Fernández Moreno, Becky L. Eggimann, Junyi Chen, Lucas J. Gibson-Elias, Christopher Williams, Peixi Jiang, Andrew Lee, Leonard J. Mueller, J.L. Sessler, J. Ilja Siepmann, Darren W. Johnson, Richard J. Hooley
Abstract
Cationic water-soluble deep cavitands enable hierarchical assembly-based recognition, optical detection, and extraction of perfluoroalkyl substances (PFAS) in aqueous solution. Recognition of PFAS occurs at the lower rim crown of the cavitand, which triggers self-aggregation of a PFAS-cavitand complex, allowing extraction from water. In addition, when paired with an indicator dye that can be bound in the cavity of the host molecule, the PFAS-cavitand association causes a significant (>20-fold at micromolar [PFAS]) enhancement of dye fluorescence due to conformational rearrangement of the fluxional cavitand AMI, allowing optical detection of PFAS. The cavitands are water-soluble, and the detection and recognition occur in purely aqueous solution. The association is most effective for long-chain sulfonate PFAS, and as such, selective optical detection of perfluorooctanesulfonate is possible, with a LOD = 130 nM in buffered water and 530 nM in real-world samples such as polluted canal water. By pairing the AMI host with multiple dyes in an array-based format, full discrimination of five other PFAS can be achieved at micromolar concentrations via differential sensing. In addition, the aggregation process allows extraction of PFAS from solution, and a 99% reduction of PFOS concentration in water is possible with a single treatment of an equimolar concentration of AMI cavitand. The hierarchical nature of the cavitand recognition system allows both selective, sensitive optical detection and extraction of PFAS from water with a single scaffold.