Primary amide-functionalized cyclotricatechylene covalent organic frameworks membrane for efficient enrichment of melamine and its derivatives in migration solution of food contact materials

A highly chemically stable primary amide-functionalized cyclotricatechylene covalent organic framework was synthesized by an irreversible reaction and a post-synthetic modification. It possessed a rod-like morphology and exhibited strong solvent stability owing to the polyether bonds. The material showed good adsorption performance for melamine and its derivatives and adsorption mechanism was investigated by molecular simulations. The adsorbent was coated on the nylon-66 membrane to prepare the enrichment membrane. Under optimized conditions, an in-syringe membrane-based extraction method, combined with ultra-high performance liquid chromatography-tandem mass spectrometry was developed for the analysis of melamine and six melamine derivatives in the migration solution. A good linearity was obtained with correlation coefficients ranging from 0.9924 to 0.9995. The limits of detection were 1-200 ng/L and the limits of quantification were 3-500 ng/L. This method was successfully applied to the migration solution of sushi bamboo rolling mats with spiked recoveries of 73.2%-115% and relative standard deviations of 0.9%-9.9%. This work shows a practical and perspective approach for the efficient enrichment of food contact material hazards.