Carboxyl-functionalized covalent organic frameworks for the efficient adsorption of foodborne heterocyclic aromatic amines

Abstract

The development of sorbents with high sensitivity and specificity for the effective extraction and assessment of carcinogenic heterocyclic aromatic amines (HAAs) in thermally processed foods is of utmost significance for food safety monitoring. Herein, we report the design and synthesis of a carboxyl-functionalized covalent organic framework (COF), TpPa-(COOH)2, through the regulation of carboxyl modification and crystallinity. The resulting flower-like TpPa-(COOH)2 exhibited excellent crystallinity and microporosity in an eclipsed stacking structure. Compared to TpPa, the introduction of carboxyl moieties in TpPa-(COOH)2 provided additional binding sites and significantly enhanced adsorption affinity for the 16 target analytes, despite having a smaller BET surface area. The adsorption of HAAs by TpPa-(COOH)2 followed the pseudo-second-order model and exhibited rapid kinetics (10–30 min). The experimental data demonstrated a strong fit with the Freundlich isotherm model, resulting in a maximum adsorption capacity of HAAs ranging from 1.8 to 155.8 mg/g. Additionally, the presence of interfering compounds only caused a slight reduction in both the equilibrium adsorption capacity and HAAs recovery. Notably, TpPa-(COOH)2 maintained its effective adsorption performance even after three adsorption–desorption cycles. Theoretical calculations indicated that the rapid binding of HAAs to TpPa-(COOH)2 could be attributed to the joint effects of electrostatic interaction, π–π interaction, C–H–π interaction, lone pair–π interaction, and hydrogen bonding. This adsorbent exhibits a notable enhancement in both adsorption capacity and mass transfer rates for the adsorption of HAAs, surpassing the performance of the reported adsorbents. This highlights its substantial potential for the precise detection of HAAs within food systems.