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

Abstract

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.

Current progress in the environmental analysis of poly- and perfluoroalkyl substances (PFAS)

“…45 A direct injection (DI) approach followed by liquid chromatography tandem mass spectrometry (DI-LC-MS/MS) for targeted PFAS analysis of various water samples including drinking water, ground water, river water, lake water and wastewater reported with satisfactory sensitivity has been recently reported. 37 Jia et al introduced multiple interactions into the conventional SPME process via a dual-functional modification of MIL-101(Cr), 46 namely amination and subsequent fluorination, which was then used as an adsorbent for the efficient enrichment of PFAS prior to analysis by LC-MS/MS. Ultrasensitive quantitative analysis was achieved for nine selected PFASs with high linearities above 0.9941 in the ranges of 0.5–1500 ng L −1 , low limits of detection of 0.004–0.12 ng L −1 , and satisfactory repeatability and reproducibility with a relative standard deviation (RSD) <11.6%, as well as excellent performance in complicated water samples (recovery ratio of 76.2–108.6%).…”

Towards Solving the PFAS Problem: The Potential Role of Metal‐Organic Frameworks

“…A window of opportunity, therefore, lies in the flexibility of MOFs for chemical functionalization. Jia et al [78] used fluorinated diethylenetriamine (DETA)-functionalized MIL-101(Cr) (MIL-101-DETA-F) as a fiber coating for the SPME process that was combined with ultra-high-performance liquid chromatography-tandem MS to detect PFAS molecules. The MIL-101-DETA-F fiber demonstrated detection limits over the range of 0.004-0.12 ng L À 1 to PFAS molecules.…”

Advances with Metal Organic Framework based nanomaterials in 4th industrial revolution

“…Researchers have used a hydrothermal method to embed -MnO2 nanoparticles into a MIL-101 (Cr) matrix to prepare a -MnO2/ MIL-101 (Cr) composite. They reported that the abundant micropores and high surface area that resulted from this process improved the accessibility of the reactant to the catalytically active sites, thereby increasing oxygen reduction reaction (ORR) activity in alkaline electrolytes [33]. In addition, the robust interaction between the -MnO2 and the MOF maintained structural stability, which led to outstanding stability [34].…”