Rapid and in-situ preparation COFs coated capillary by adsorption method for the separation and determination of phthalate ester using CEC

As a novel class of stationary phase materials, covalent organic frameworks (COFs) have shown great promise in open-tubular capillary electrochromatography. However, the current preparation of COFs coating capillaries heavily relies on tedious and time-consuming covalent bond methods. In this work, a novel, simple and rapid adsorption method was developed for fabrication of TPB-DMTP COF (fabricated from 1,3,5-tris(4-aminophenyl) benzene (TPB) and 2,5-dimethoxyterephthalaldehyde (DMTP)) coated capillary. Due to the crystallization process of the COF is greatly shortened because pre-modification capillary does not require silane coupling agent, this method enables the rapid preparation of COFs-coated capillaries. The organic molecular building units only need 25 min to form a stable COFs coating on the inner wall of a capillary by this method. To our knowledge, this is the shortest method for preparing COFs coated capillary up to now. The performance of the TPB-DMTP COF coated capillary was evaluated by using phthalate esters as model analytes. The results demonstrated that the TPB-DMTP COF coated capillary has excellent repeatability and stability. The relative standard deviations (RSDs) of the analyte's retention time of intra-day, inter-day and column-to-column were in the range of 0.05 %-0.27 %, 0.31 %-0.63 % and 0.31 %-0.88 %, respectively. And, no significant changes were observed in separation efficiency and retention time after over 200 runs. Finally, the TPB-DMTP COF coated capillary was applied for the determination of phthalates in marketed plastic bag and the recovery ranged from 88.0 % to 114.0 %.