Simultaneous HPLC-MS determination of 8-hydroxy-2-deoxyguanosine, 3-hydroxyphenanthrene and 1-hydroxypyrene after online in-tube solid phase microextraction using a graphene oxide/poly(3,4-ethylenedioxythiophene)/polypyrrole composite

The exploration of monohydroxy polycyclic aromatic hydrocarbons and 8-hydroxy-2-deoxyguanosine (8-OHdG) produced by oxidative stress and DNA damage is a powerful and non-invasive tool to study the health risk of exposure to polycyclic aromatic hydrocarbons (PAHs). A nanocomposite prepared from graphene oxide, poly(3,4-ethylenedioxythiophene) and polypyrrole was electrodeposited on the internal surface of a stainless-steel tube for online in-tube solid phase microextraction (IT-SPME) of 8-OHdG, 3-hydroxyphenanthrene and 1-hydroxypyrene from urine. The coating possesses excellent chemical and mechanical stability, high extraction efficiency, good resistance to matrix interference, and a long lifespan. An online IT-SPME-high performance liquid chromatography-mass spectrometry method was developed for the determination of these three metabolite biomarkers in human urine. Figures of merit include (a) enrichment factors of 30-48; (b) low limits of detection (4-41pgmL(-1) at S/N=3); (c) wide linear ranges (0.05-50ngmL(-1)); (d) good recoveries from spiked samples (71.6-109.5%); and (e) acceptable repeatability (2.3-14.6%). The method offers the advantages of low cost, simplicity, sensitivity, rapidity and automation.