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Microporous organic polymers (MOPs) are an emerging class of functional porous materials for diverse potential applications. Typically, tailored microporous structures of MOPs are generated by linkages of organic polymerizable monomer building blocks, providing high permanent porosity and excellent stability. Herein, we reported the first example of the application of organic building block based MOPs (OBB-MOPs) as efficient enrichment media for sample preparation. A novel multilayer interbridging strategy was proposed to fabricate OBB-MOP coatings, and hereby SNW-1 (a kind of OBB-MOPs) was coated on silica substrate with well-controlled thickness. Strong covalent bonds throughout the network and interlayer bridging improved the durability of the coating significantly. Outstanding chemical stability was observed in diverse solvents as well as solutions with a wide range of pH or high ionic strength and even under extremely harsh conditions like boiling water. The SNW-1 coating possessed a microporous network structure constructed of conjugated and nitrogen-rich building blocks. Thus, the coating exhibited a superior enrichment performance of polycyclic aromatic hydrocarbons and volatile fatty acids (VFAs) over commercial coatings based on interactions including π-π affinity and acid-base interaction. For further application, this coating was combined with gas chromatography/mass spectrometry for the noninvasive analysis of VFAs from tea leaf and tobacco shred samples. The low detection limits of 0.014-0.026 μg/L were achieved with the relative standard deviations (RSDs) between 4.3 and 9.0%. Consequently, trace original VFAs from the samples were detected. Good recoveries were obtained in the range of 90-129% and 77-118% with the corresponding RSDs (n = 3) of 2.6-9.3% and 1.9-10%, respectively.

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