Engineering of molecularly imprinted cavity within 3D covalent organic frameworks: an innovation for enhanced extraction and removal of microcystins

The scarcity of selective adsorbents for efficient extraction and removal of microcystins (MCs) from complex samples greatly limits the precise detection and effective control of MCs. Three-dimensional covalent organic frameworks (3D COFs), characterized by their large specific surface areas and highly ordered rigid structure, are promising candidates, but suffer from lack of specific recognition. Herein, we design to engineer molecularly imprinted cavities within 3D COFs via molecularly imprinted technology, creating a novel adsorbent with exceptional selectivity, kinetics and capacity for the efficient extraction and removal of MCs. As proof-of-concept, a new C=C bond-containing 3D COF, designated JNU-7, is designed and prepared for copolymerization with methacrylic acid, the pseudo template L-arginine and ethylene dimethacrylate to yield the JNU-7 based molecularly imprinted polymer (JNU-7-MIP). The JNU-7-MIP exhibits a great adsorption capacity (156mgg-1) for L-arginine. Subsequently, the JNU-7-MIP based solid-phase extraction coupled with high performance liquid chromatography-mass spectrometry achieves low detection limit of 0.008ngmL-1, wide linear range of 0.025-100ngmL-1, high enrichment factor of 186, rapid extraction of 10min, and good recoveries of 92.4%-106.5% for MC-LR. Moreover, the JNU-7-MIP can rapidly remove the MC-LR from 1mgL-1 to levels (0.26-0.35μgL-1) lower than the WHO recommended limit for drinking water (1μgL-1). This work reveals the considerable potential of 3D COF based MIPs as promising adsorbents for the extraction and removal of contaminants in complex real samples. Environmental Implication Global warming and man-made eutrophication have greatly raised the hazardous exposure levels of microcystins (MCs) in environment. The scarcity of selective adsorbents capable of efficiently extracting and removing MCs from complex samples severely limits the precise detection and effective control of MCs. Here, a new molecularly imprinted three-dimensional covalent organic framework was designed and prepared as novel adsorbent for the efficient extraction and remove of MCs in real environmental samples.