Highly crystalline polyimide covalent organic framework as electrochemical sensing platform for the ultrasensitive detection of purine bases in DNA

Abstract

It is of great significance to propose simple methods to detect DNA bases sensitively for biological analysis and medical diagnosis. Herein, a highly crystalline polyimide covalent organic framework (TAPM-COF) has been successfully synthesized via a solvothermal route using pyromellitic dianhydride (PMDA) and tris(4-aminophenyl) amine (TAPA), which possessed large specific surface area (2286 m² g⁻¹) and excellent thermal stability. Intriguingly, the crystallinity of the TAPM-COF improved significantly with the increase of water content in the reaction medium. To verify this phenomenon, we synthesized TPPM-COF with two pores by pyromellitic dianhydride (PMDA) and N,N,N′,N'-tetrakis(4-aminophenyl)-1,4-benzenediamine (TPDA), which bonding was similar to TAPM-COF. Furthermore, the prepared TAPM–COF–0.3 was used to construct a novel and independent electrochemical biosensor on glassy carbon electrode for simultaneously determination of adenine (A) and guanine (G) without other additives. However, to further improve signal of TAPM-COF in electrochemical sensing, the crystalline TAPM–COF–0.3 can be readily integrated with amino-functionalized multiwalled carbon nanotubes (NH₂-MWCNT) to form core-shell TAPM–COF–0.3@NH₂-MWCNT driven by a π–π stacking interaction for more sensitive electrochemical sensing toward purine bases. In comparison to TAPM-COF/GCE, the TAPM-COF@NH₂-MWCNT/GCE exhibited more favorable linear range and lower limit of detection. The work provided a new strategy for amplifying signal of COF in the field of electrochemical sensors.