Facile preparation of a cationic COF functionalized magnetic nanoparticle and its use for the determination of nine hydroxylated polycyclic aromatic hydrocarbons in smokers’ urine

A novel dual-shell magnetic nanoparticle coated with a cationic covalent organic framework, containing ethidium bromide, is easily prepared, characterized and applied as an adsorbent for fast, simple and highly selective capture of nine hydroxylated polycyclic aromatic hydrocarbons in urine samples of non-smokers and smokers who smoked cigarettes with different tar yields. This is the first time that a cationic crystalline framework with high thermal and chemical stability was used for magnetic solid phase extraction. Multiple probes and quantum chemistry theory calculations were conducted to describe the versatile adsorption property directly and quantifiably. A method using high-performance liquid chromatography with a fluorescence detector based on the prepared magnetic adsorbent was established and used to investigate differences in the exposure levels of OH-PAHs in non-smokers and smokers smoking cigarettes with different tar yields. All the OH-PAH analyses present good linearities in the range of 0.1–100 ng mL−1, with R2 > 0.9965. The LOD for the 9 OH-PAHs ranged from 0.0030 to 0.0096 ng mL−1 and the LOQ ranged from 0.096 to 0.030 ng mL−1. The recoveries of the 9 OH-PAHs ranged from 93.3 to 121.3% with the RSD ranging from 0.47 to 3.53%. These results imply that the versatile EB-DS MNPs as adsorbents have great potential in the analysis of trace targets in samples with complex matrices.