Construction of Donor–Acceptor Heteroporous Covalent Organic Frameworks as Photoregulated Oxidase-like Nanozymes for Sensing Signal Amplification

Nanomaterials with enzyme-like characteristics (called nanozymes) show their extreme potentials as alternatives to natural enzymes. Covalent organic frameworks (COFs) as metal-free nanozymes have attracted huge attention for catalytic applications due to their flexible molecular design and synthetic strategies and conjugated, porous, and chemically stable architectures. Designing high-performance two-dimensional (2D) porous COF materials embedded with functional building units for modulating nanozymes' catalytic activity is of immense importance in contemporary research. The proper combination of donor-acceptor (D-A) fragments within a porous COF skeleton is an effective strategy to decrease the band gap and provide a strong charge-transfer pathway for highly effective charge separation. Herein, two donor-acceptor heteroporous COFs using an electron-deficient 4,4'-(thiazolo[5,4-d]thiazole-2,5-diyl)dibenzaldehyde (Tz) unit or 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde (Td) unit and electron-rich tetrakis(4-aminophenyl)ethane (ETTA) linkers were presented. The resulting crystalline and heteroporous COFs showed outstanding oxidase-like activity under light irradiation, which can catalyze the oxidation of typical substrates and corresponding evolution in color and absorption. The light-activatable ETTA-Tz COF with prominent oxidase-like activity can serve as a colorimetric probe for quantitative detection of sulfide ions with a linear range of 1-50 μM and a detection limit of 0.27 μM within 3 min. The colorimetric approach could also be used for sulfide ion detection in human serum samples. The research demonstrated the future potential of D-A motifs within fully conjugated COFs to obtain excellent mimic enzyme activity.