Selective extraction and determination of aromatic amine metabolites in urine samples by using magnetic covalent framework nanocomposites and HPLC-MS/MS

Purification and selective enrichment of ultra-low level metabolites in bio-samples is very important for HPLC-MS/MS analysis. A magnetic covalent organic framework (i.e. COFs) (TpPa-1) (i.e. 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde-p-phenylenediamine) material was synthesized and used for a magnetic solid phase extraction (MSPE) method in aromatic amine (AA) metabolites (i.e. 1-naphthylamine, 2-naphthylamine, 3-aminobiphenyl and 4-aminobiphenyl) in urine, and then HPLC-MS/MS was employed for analysis. The morphology, pore structure, surface area, chemical composition, magnetic properties, and thermal stability of the synthesized magnetic COFs were characterized with several analysis techniques, such as nitrogen adsorption–desorption isotherms, HRTEM, FTIR, XRD, and so on. MSPE conditions were optimized and analytical performance of the developed method was characterized. The limit of detection (LOD) and limit of quantification (LOQ) of four AAs ranged from 0.01 to 0.07 ng mL(−1) and 0.04 to 0.22 ng mL(−1), respectively. The recoveries of 1-NA, 2-NA, 3-ABP, 4-ABP were in the range of 81.9–105%, 87.8–102%, 101–120%, 88.3–117%, respectively. Good intra-day and inter-day precision were obtained with RSD of less than 5.8% and 9.9%, respectively. Furthermore, the synthesized magnetic COFs absorbent could be recycled in MSPE at least 5 times. Analytical results of AA metabolites in real urine samples with the developed method showed significant difference (p < 0.01) between smokers and nonsmokers. Thus, urinary AA metabolites could be exposure biomarkers for cigarette smoke.