Advances in synthesis methods and applications of microporous organic networks for sample preparation

Sample pretreatment is an essential step in chromatographic analysis. Solid phase extraction (SPE) is a widely used sample pretreatment method. In SPE, the quality of the adsorbent directly affects the adsorption and enrichment efficiency of the target compounds as well as the sensitivity and selectivity of the pretreatment and subsequent analysis. Therefore, the selection and development of adsorbents has become a research hotspot. Microporous organic networks (MONs) are a novel type of covalent organic materials that are synthesized by the Sonogashira reaction of aromatic alkynes and aromatic halides. These networks have the advantages of modifiable structures, large specific surface areas, high porosity, and simple synthesis methods. This paper reviews the synthesis and functional modification methods of MONs, with an emphasis on their applications in sample pretreatment. Future development trends are also prospected. In terms of synthesis, the preparation methods for MON-based materials have progressed from reflux and solvothermal synthesis to room-temperature synthesis, the conditions of which tend to be milder and more efficient. In terms of functional modification, the introduction of macromolecules and active groups (including amino, hydroxyl, and carboxylic groups) can increase the selectivity and active sites of MON-based materials. The combination of MONs with Fe3O4, SiO2, and metal organic frameworks yields core-shell-structured MONs. Furtherly, they can be calcined and etched to form porous carbon structures or hollow multilayer materials. Functionalized MONs and their composite materials have multiple interaction mechanisms (e. g., hydrogen bonding, hydrophobic, electrostatic, and pi-pi interactions) with various target compounds, thereby realizing their efficient extraction. MONs can be used as adsorbent materials in SPE, Solid phase microextraction, dispersed solid phase extraction, magnetic solid phase extraction, and other pretreatment methods. When combined with chromatography and chromatography-mass spectrometry, MONs achieve good adsorption effects and high sensitivity, demonstrating the application potential of these materials in sample pretreatment.