Preparation of a pyridyl covalent organic framework via Heck cross-coupling for solid-phase microextraction of perfluoropolyether carboxylic acids in food

Haoyue Han; Shangzhi Ding; Yanling Geng; Zhaoyu Qiao; Xuemei Li; Rongyu Wang; Xiqing Zhang; Wenhua Ji

doi:10.1016/j.foodchem.2022.134310

Preparation of a pyridyl covalent organic framework via Heck cross-coupling for solid-phase microextraction of perfluoropolyether carboxylic acids in food

Food Chem. 2023 Mar 1:403:134310. doi: 10.1016/j.foodchem.2022.134310. Epub 2022 Sep 19.

Authors

Haoyue Han¹, Shangzhi Ding², Yanling Geng², Zhaoyu Qiao¹, Xuemei Li¹, Rongyu Wang¹, Xiqing Zhang³, Wenhua Ji⁴

Affiliations

¹ Key Laboratory for Applied Technology of Sophisticated Analytical Instruments of Shandong Province, Shandong Analysis and Test Center, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China.
² Key Laboratory for Applied Technology of Sophisticated Analytical Instruments of Shandong Province, Shandong Analysis and Test Center, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China; School of Pharmaceutical Sciences, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China.
³ Shandong Jienuo Testing Service Co., Ltd, Yantai 265200, China; Yantai Longda Food Co., Ltd, Yantai 265200, China.
⁴ Key Laboratory for Applied Technology of Sophisticated Analytical Instruments of Shandong Province, Shandong Analysis and Test Center, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China; School of Pharmaceutical Sciences, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China. Electronic address: jwh519@163.com.

PMID: 36156398
DOI: 10.1016/j.foodchem.2022.134310

Abstract

The growing detection of emerging perfluoropolyether carboxylic acids (PFECAs) in food has raised considerable concerns about their high persistence, bioaccumulation, and toxicity. In this study, a pyridine-functionalized covalent organic framework (Py-COF) was synthesized by introducing basic pyridyl groups into Br-COF via Heck cross-coupling. According to density functional theory, PFECAs were adsorbed in the pore sites of Py-COF via O^-···HN⁺ interaction, which was the stable and predominant adsorption configuration. After systematic characterization, Py-COF was used as the coating for solid-phase microextraction combined with high-performance liquid chromatography-tandem mass spectrometry (SPME-HPLC-MS/MS) for the efficient determination of PFECAs in food. Under the optimum conditions, the method showed satisfactory linearity (R² ≥ 0.998), low limits of detection (0.001-0.004 ng g^-1), and good relative recoveries (82.5 %-112 %). The established method was satisfactorily used for the analysis of trace PFECAs in food samples.

Keywords: Covalent organic framework; Food; Heck reaction; Perfluoropolyether carboxylic acids; Solid-phase microextraction.

MeSH terms

Carboxylic Acids
Limit of Detection
Metal-Organic Frameworks* / chemistry
Solid Phase Microextraction* / methods
Tandem Mass Spectrometry

Substances

Metal-Organic Frameworks
perfluoropolyether
Carboxylic Acids