Probe nanoelectrospray ionization mass spectrometry (PESI-MS) is practically desirable for rapid and ultra-sensitive analysis of trace contaminants in environment, but limited with the stable and selective probe coating. Herein, we show the design and preparation of irreversible fluorine-based covalent organic framework (TFPPA-F₄) covalently bonded probe to couple with ESI-MS (TFPPA-F₄-PESI-MS) for direct and rapid determination of perfluoroalkyl carboxylic acids (PFCAs) in environmental water. Chemical bonding coating of irreversible crystalline TFPPA-F₄ not only improved stability of the probe, but also offered accessible multiple interactions including hydrophobic, hydrogen bonding and F-F interactions to promote the kinetics and selectivity for PFCAs. The proposed TFPPA-F₄-PESI-MS realized rapid determination of PFCAs (about 4 min) with low limits of detection of 0.06–0.88 ng L⁻¹ and wide linear range of 1–5000 ng L^–1 (R² of 0.9982–0.9998). Recoveries for the spiked lake and pond water were 85.9–111.1 %. TFPPA-F₄ based probe can maintain the extraction performance after 100 times of extraction. This work shows the great potential of the irreversible covalent organic framework based PESI-MS in rapid and ultra-sensitive determination of contaminants in environmental samples.

探针纳米电喷雾电离质谱法(PESI-MS) 实际上是对环境中痕量污染物进行快速和超灵敏分析的理想方法，但受到稳定和选择性探针涂层的限制。在此，我们展示了不可逆氟基共价有机骨架 (TFPPA-F ₄ ) 共价键合探针与 ESI-MS (TFPPA-F ₄ -PESI-MS) 偶联的设计和制备，用于直接快速测定全氟烷基羧酸(PFCAs) 在环境水中。_{不可逆结晶TFPPA-F 4}的化学结合涂层不仅提高了探针的稳定性，而且还提供了可访问的多重相互作用，包括疏水、氢键和 FF 相互作用，以促进 PFCA 的动力学和选择性。拟议的 TFPPA-F ₄ -PESI-MS 实现了 PFCA 的快速测定（约 4 分钟），检测限低至 0.06–0.88 ng L ⁻¹，线性范围宽 1–5000 ng L ^–1（R ²为 0.9982 –0.9998）。加标湖水和池塘水的回收率为 85.9–111.1%。TFPPA-F ₄基探针在萃取100次后仍能保持萃取性能。这项工作展示了基于不可逆共价有机框架的 PESI-MS 在快速和超灵敏地测定环境样品中的污染物方面的巨大潜力。