Development of a highly efficient in‐tube solid‐phase microextraction system coupled with UHPLC‐MS/MS for analyzing trace hydroxyl polycyclic aromatic hydrocarbons in biological samples

Abstract Hydroxyl polycyclic aromatic hydrocarbons are considered active mutagenic and carcinogenic substances and are found in extremely low levels (ng/g) in biological samples. As a result, their determination in urine and blood samples is challenging, and a sensitive and effective method for the analysis of trace hydroxyl polycyclic aromatic hydrocarbons in complex biological matrices is required. In this work, a novel macroporous in‐tube solid‐phase microextraction monolith was prepared via a thiol‐yne click reaction, and a highly efficient analytical method based on in‐tube solid‐phase microextraction coupled with UHPLC‐MS/MS was developed to determine hydroxyl polycyclic aromatic hydrocarbons with low detection limits of 0.137–11.0 ng/L in complex biological samples. Four hydroxyl polycyclic aromatic hydrocarbons, namely, 2‐hydroxyanthraquinone, 1‐hydroxypyrene, 1,8‐dihydroxyanthraquinone, and 6‐hydroxychrysene, were determined in the urine samples of smokers, non‐smokers, and whole blood samples of mice. Satisfactory recoveries were achieved in the range of 83.1–113% with relative standard deviations of 3.2–9.7%. It was found that implementation of the macroporous monolith gave a highly efficient approach for enriching trace hydroxyl polycyclic aromatic hydrocarbons in biological samples.