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 6hydroxychrysene, were determined in the urine samples of smokers, nonsmokers, 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.

Nontarget Screening of Novel Urinary Biomarkers for Occupational Exposure to Toxic Chemicals from Coking Industry Using HPLC-QTOF-MS

“…The median levels were 0.12 ng/mL in the exposed group and 0.031 ng/mL in the control group. The OH-AntQ levels in the control group were consistent with an early study that reported comparable levels in smokers’ and nonsmokers’ urine samples (0.039 and 0.034 ng/mL, respectively) . However, the levels of OH-AntQ were higher in the exposed group than in smokers’ and nonsmokers’ groups.…”

“…The current work also unveiled several novel metabolites, including indoxyl (3-OH-Ind), 4-hydroxyindole (4-OH-Ind), quinolin-2-ol (2-OH-QNL), 2-hydroxydibenzofuran (2-OH-DBF) and its isomers, and hydroxyanthraquinone (OH-AntQ). These compounds were identified as metabolites of HPAHs incubated by human cells in vitro or via rat experiment. , In this study, 3- and 4-OH-Ind and 2-OH-QNL were detected in human urine for the first time, while 2-OH-DBF and OH-AntQ had only been reported in a handful of studies. , These compounds show potential as biomarkers for occupational exposure at coking sites. However, it is important to note that some of their parent compounds such as quinoline (QNL) and anthraquinone (AntQ) have been classified as possible human carcinogens by the International Agency for Research on Cancer, indicating that exposure to these pollutants could pose a potential health risk to humans.…”

“…The OH-AntQ levels in the control group were consistent with an early study that reported comparable levels in smokers' and nonsmokers' urine samples (0.039 and 0.034 ng/mL, respectively). 36 However, the levels of OH-AntQ were higher in the exposed group than in smokers' and nonsmokers' groups. Unlike PAHs, AntQ does not seem to be affected by smoking, and therefore, OH-AntQ could be a good candidate as a urinary biomarker for occupational exposure at coking sites.…”

Monitoring of hydroxylated polycyclic aromatic hydrocarbons in human tissues: Targeted and untargeted approaches using liquid chromatography‐high resolution mass spectrometry

“…To date, the determination of OH-PAHs in human samples has been widely addressed in urine [5][6][7][8][9][10]. Other human samples studied have included serum [11], hair [12], and fingernails [13].…”

A simple and green liquid chromatography method for the determination of ibuprofen in milk‐containing simulated gastrointestinal media for monitoring the dissolution studies of three‐dimensional‐printed formulations

“…A review on the electrochemical analysis of the analyte has been recently published [10]. UHPLC is another analytical technique that has gained popularity in recent years in the field of pharmaceutical, clinical and toxicological analysis [11][12][13]. Compared to the traditional HPLC technique, it can effectively contribute to the reduction of organic solvent consumption and analysis cost which complies with the principles of Green Analytical Chemistry [14,15].…”