Dual-Functionalized MIL-101(Cr) for the Selective Enrichment and Ultrasensitive Analysis of Trace Per- and Poly-fluoroalkyl Substances.

The presence of per- and poly-fluoroalkyl substances (PFASs) even at trace levels poses a potential threat to ecological safety and human health. PFASs often require an extraction pretreatment for enrichment before detection and analysis, which is still challenged by the relatively low efficiency because of the limited specific interactions involved. Here, we deliberately introduced multiple interactions into the solid-phase microextraction (SPME) process via a dual-functional modification of MIL-101(Cr), i.e., amination and subsequent fluorination, which is then used as an adsorbent for the efficient enrichment of PFASs. In combination with ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), ultrasensitive quantitative analysis is available for nine selected PFASs with high linearities above 0.9941 in the ranges of 0.5-1500 ng/L, low limits of detection of 0.004-0.12 ng/L, satisfactory repeatability and reproducibility with a relative standard deviation (RSD) < 11.6%, as well as excellent performance in complicated real water samples (recovery ratio of 76.2-108.6%). This work represents a rational design of a solid extractant with the desired structure and functionality for the selective enrichment and analysis of PFASs at trace concentrations in real applications.