In this study, novel benzenesulfonic acid groups modified magnetic microspheres (Fe3O4@SiO2@poly(4-VB)) were synthesized and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectrometry (FTIR), and vibrating sample magnetometer (VSM). The as-prepared Fe3O4@SiO2@poly(4-VB) was employed as a magnetic-phase extraction (MSPE) adsorbent for rapid determination of paraquat (PQ) and diquat (DQ) in human urine samples coupled with ultra-high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). Moreover, this paper had expounded systematically the mass spectrum cracking mechanisms of PQ and DQ. And a zwitterionic functionalized SIELC Obelisc R column was employed for separation and retention of the above two polar herbicides using 50 mmol/L ammonium formate (pH = 3.7)-acetonitrile as the mobile phase. Besides, the adsorption and desorption conditions of Fe3O4@SiO2@poly(4-VB) toward PQ and DQ were optimized in spiking urine samples to obtain the best adsorption and desorption efficiencies. And the adsorption mechanisms of Fe3O4@SiO2@poly(4-VB) toward PQ and DQ referred to synergetic effect of electrostatic attraction and π-π interaction. Under the optimal conditions, the inter-day and intra-day spiking recoveries of the proposed method were in the range of 86.7-109.9% with RSDs less than 10%. The limits of detection (LODs) were obtained by spiking in blank urine samples at a series of low concentrations and were found to be 0.12 μg/L and 0.14 μg/L for PQ and DQ, respectively, which were lower than the comparing literatures. The developed analytical method was proven to be simple, rapid, sensitive, and accurate for clinical poisoning analysis.

中文翻译：

---

苯磺酸基修饰的磁性微球的制备作为MSPE吸附剂，结合UPLC-HRMS快速测定人尿中的百草枯和敌草快。

在这项研究中，合成了新型的苯磺酸基修饰的磁性微球（Fe3O4 @ SiO2 @ poly（4-VB）），并通过扫描电子显微镜（SEM），透射电子显微镜（TEM），傅里叶变换红外光谱（FTIR）进行了表征。 ，以及振动样品磁力计（VSM）。制备的Fe3O4 @ SiO2 @ poly（4-VB）用作磁相萃取（MSPE）吸附剂，用于快速测定人尿液样品中的百草枯（PQ）和敌草快（DQ）（DQ），并配有超高性能液体色谱-高分辨率质谱法（UPLC-HRMS）。此外，本文系统地阐述了PQ和DQ的质谱裂解机理。用两性离子官能化的SIELC Obelisc R色谱柱，以50 mmol / L甲酸铵（pH = 3.7）-乙腈为流动相，分离和保留上述两种极性除草剂。此外，优化了Fe3O4 @ SiO2 @ poly（4-VB）对PQ和DQ的吸附和解吸条件，以加标尿样以获得最佳的吸附和解吸效率。Fe3O4 @ SiO2 @ poly（4-VB）对PQ和DQ的吸附机理是静电吸引和π-π相互作用的协同效应。在最佳条件下，该方法的日间和日内加标回收率在86.7-109.9％范围内，RSD小于10％。通过将一系列低浓度的空白尿样加标获得检测限（LOD），结果为0。PQ和DQ分别为12μg/ L和0.14μg/ L，低于比较文献。实践证明，所开发的分析方法简单，快速，灵敏且准确，可用于临床中毒分析。