Ultrasound-assisted synthesis of clover-shaped nano-titania functionalized covalent organic frameworks for the dispersive solid phase extraction of N-nitrosamines in drinking water

In this study, three batches of nano-titania functionalized covalent organic frameworks were acquired depending on different solvothermal reaction stages (24 h, 48 h and 72 h), which were named as single roll-up shaped nano-titania functionalized COFs (SSTF-COFs), double roll-up shaped nano-titania functionalized COFs (DSTF-COFs) and clover-shaped nano-titania functionalized covalent organic framework (CSTF-COFs), respectively. After comparing their extraction performances, the more efficient and stable CSTF-COFs were selected as sorbent for the dispersive solid phase extraction (dSPE) of eight target N-nitrosamines in drinking water, followed by the determination with liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS). Owing to the introduction of hydroxy groups, CSTF-COFs showed high extraction efficiency for N-nitrosamines with a wide range of polarities through hydrogen bonding interaction, hydrophobic interaction and hydrophilic interaction. Under optimum conditions, the developed method provided relatively low limits of detection (0.13-2.45 ng/L) and satisfactory recoveries (88.6-105.5%), with relative standard deviations (RSDs) less than 8.3%. Therefore, with the assistance of CSTF-COFs, trace levels of N-nitrosamines were quantitatively and sensitively determined in 31 out of 460 bottled drinking water samples in a sensitive and convenient way.