Amine-functionalized MIL-53(Al)-coated stainless steel fiber for efficient solid-phase microextraction of synthetic musks and organochlorine pesticides in water samples

The fiber coating is the key part of the solid-phase microextraction (SPME) technique, and it determines the sensitivity, selectivity, and repeatability of the analytical method. In this work, amine (NH2)-functionalized material of Institute Lavoisier (MIL)-53(Al) nanoparticles were successfully synthesized, characterized, and applied as the SPME fiber coating for efficient sample pretreatment owing to their unique structures and excellent adsorption properties. Under optimized conditions, the NH2-MIL-53(Al)-coated fiber showed good precision, low limits of detection (LODs) [0.025-0.83 ng L-1 for synthetic musks (SMs) and 0.051-0.97 ng L-1 for organochlorine pesticides (OCPs)], and good linearity. Experimental results showed that the NH2-MIL-53(Al) SPME coating was solvent resistant and thermostable. In addition, the extraction efficiencies of the NH2-MIL-53(Al) coating for SMs and OCPs were higher than those of commercially available SPME fiber coatings such as polydimethylsiloxane, polydimethylsiloxane-divinylbenzene, and polyacrylate. The reasons may be that the analytes are adsorbed on NH2-MIL-53(Al) primarily through pi-pi interactions, electron donor-electron acceptor interactions, and hydrogen bonds between the analytes and organic linkers of the material. Direct immersion (DI) SPME-gas chromatography-mass spectrometry methods based on NH2-MIL-53(Al) were successfully applied for the analysis of tap and river water samples. The recoveries were 80.3-115% for SMs and 77.4-117% for OCPs. These results indicate that the NH2-MIL-53(Al) coating may be a promising alternative to SPME coatings for the enrichment of SMs and OCPs.