Integrating molecular imprinting into flexible covalent organic frameworks for selective recognition and efficient extraction of aflatoxins

Abstract

Covalent organic frameworks (COFs) are promising adsorbents for extraction, but their selectivity for molecular recognition remains a challenging issue due to the very limited structural design with rigid structure. Herein, we report an elegant strategy for the design and synthesis of molecularly imprinted flexible COFs (MI-FCOFs) via one-pot reaction between the flexible building block of 2,4,6-tris(4-formylphenoxy)− 1,3,5-triazine and linear 4-phenylenediamine for selective extraction of aflatoxins. The flexible chain structure enabled the developed MI-FCOF to adjust the shape and conformation of frameworks to suit the template molecule, giving high selectivity for aflatoxins recognition. Moreover, MI-FCOF with abundant imprinted sites and function groups exhibited an exceptional adsorption capacity of 258.4 mg g−1 for dummy template which is 3 times that of no-imprinted FCOF (NI-FCOF). Coupling MI-FCOF based solid-phase extraction with high-performance liquid chromatography gave low detection limits of 0.003–0.09 ng mL−1 and good precision with relative standard deviations ≤ 6.7% for the determination of aflatoxins. Recoveries for the spiked rice, corn, wheat and peanut samples were in the range of 85.4%− 105.4%. The high selectivity of the developed MI-FCOF allows matrix-free determination of AFTs in food samples. This work offers a new way to the design of MI-FCOF for selective molecular recognition.