Enhanced selective enrichment of hydroxylated polycyclic aromatic hydrocarbons from biological samples using 4-carboxy-3-fluorophenylboronic acid-functionalized magnetic sorbents with UHPLC-MS/MS detection

A novel magnetic nanocomposite (FPB@PEI@PDA@Fe 3 O 4 ) was synthesized for selective enrichment of HPAHs. • The MSPE-UHPLC-MS/MS method was developed to quantify nine trace HPAHs in urine and serum. • The Langmuir model governs adsorption, involving π–π, hydrogen bonding, electrostatic, and boronate affinity interactions. Hydroxylated polycyclic aromatic hydrocarbons (HPAHs) are bioaccumulative and environmentally persistent contaminants, recognized for their significant carcinogenic potential. However, accurate analysis remains challenging due to the inherent complexity of biological matrices (e.g., high protein content and numerous interfering compounds) and the ultra-trace concentrations (ng/L or pg/L levels) at which HPAHs typically occur. The efficient isolation of these analytes therefore requires a specially designed sorbent capable of strong interactions with HPAHs. To address this challenge, we designed and synthesized a novel magnetic adsorbent, 4-carboxy-3-fluorophenylboronic acid-functionalized polyethylenimine-coated polydopamine@Fe 3 O 4 (FPB@PEI@PDA@Fe 3 O 4 ), for use in magnetic solid-phase extraction (MSPE). Leveraging the properties of this novel material, an efficient MSPE-ultra-high pressure liquid chromatography-mass spectrometry method was developed to isolate and quantify nine HPAHs in urine and serum, with high sensitivity and selectivity, a wide linear range (0.0050–10 μg/L), and low detection limits (1.5–40 ng/L). To validate its applicability for human biomonitoring, urine and serum samples were analyzed, and four HPAHs, 1-naphthol, 9-phenanthrol, 1-phenanthrol, and 4-phenanthrol, were identified and quantified. The method exhibited satisfactory accuracy and precision, with recoveries of 80.3%–114% and relative standard deviations of 2.4%–13%. These results enable further understanding of the distribution and potential risks of HPAHs, and the method facilitates more accurate human health assessment and environmental monitoring. Download: Download high-res image (135KB) Download: Download full-size image