Synthesis of stable and efficient amide-based covalent organic frameworks fiber coatings for the improved solid-phase microextraction of polar aromatic amines

Developing facile and general functionalization strategies to improve the durability of covalent organic framework (COF) coatings and their affinity for polar targets is of great significance for solid-phase microextraction (SPME) technology. In this work, a facile and general amidation strategy was developed for conversion from reversible (imine) to irreversible (amide) linkages in COF coatings. After the amidation, the durability of the obtained amide-linked covalent organic framework (Am-P-COF) coating was greatly improved, and the adsorption efficiency for polar aromatic amines (AAs) was also significantly increased. Moreover, this strategy is also applicable to the amidation of other two COF coatings, showing good general applicability. The obtained Am-P-COF coated fiber was used for SPME, and then coupled with gas chromatography tandem mass spectrometry (GC-MS/MS) to detect AAs. Under the optimal SPME conditions (extraction temperature: 50 °C, extraction time: 30 min, stirring rate: 600 rpm, pH: 8, NaCl concentration: 5.0 mg mL−1, desorption temperature: 290 °C and desorption time: 10 min), a detection method for trace AAs was established. The established method possess wide linear ranges (0.5–500.0 ng L−1), good correlation coefficients (0.9986–0.9993) and low detection limits (0.1–0.5 ng L−1). Moreover, the established method had also been successfully applied to detection of trace AAs in bottled tea beverage and plastic bags packed tea with satisfactory recoveries (83.5 %–116.8 %). This research provides a facile and general pathway for increasing the durability of COF coatings and affinity to the polar AAs. The detection method based on the obtained fibers possesses high sensitivity, satisfactory reproducibility and good precision.