A novel aptamer-based online magnetic solid phase extraction method for simultaneous determination of urinary 8-hydroxy-2′-deoxyguanosine and monohydroxylated polycyclic aromatic hydrocarbons

In this work, an innovative aptamer-based magnetic adsorbent (Fe3O4 @PDA-aptamer MNPs) was prepared by hydrothermal synthesis method followed by the surface functionalization of nanoparticles. After fixing in a steel stainless tube as sorbent of magnetic solid phase extraction (MSPE), an online magnetic solid phase extraction-high performance liquid chromatography-mass spectrometry (online-MSPE-HPLC-MS) method was developed and applied for the determination of 8-hydroxy-2'-deoxyguanosine (8-OHdG) and monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) simultaneously in urine. The synthesized sorbent presented outstanding features, including large specific surface area, high enrichment capacity and excellent stability. High throughput analysis can be achieved by affinity-specific adsorption of 8-OHdG and non-specific adsorption of OH-PAHs at the same time. In addition, online MSPE can greatly simplify the analysis process, reduce human errors and enhance the sensitivity. When compared with offline MSPE, a sensitivity enhancement of 30-400 times was obtained for the online method. Some experimental parameters such as the amount of the sorbent, sampling flow rate and sample volume, were optimized systematically. Under the optimal conditions, the limits of detection (LOD) were in the range of 0.028-0.114 ng mL(-1), and the correlation coefficients (R-2) were higher than 0.9962. The relative standard deviations (RSDs) were less than 16.1% (n = 5) and the recoveries ranged from 71% to 116%. The above results show that the rapid, sensitive and automated online-MSPE-HPLC-MS method has potential application in the simultaneous determination of 8-OHdG and PAHs in complex sample matrix to assess the environmental exposure level.