PMID- 35366498 OWN - NLM STAT- MEDLINE DCOM- 20220413 LR - 20220413 IS - 1873-3778 (Electronic) IS - 0021-9673 (Linking) VI - 1670 DP - 2022 May 10 TI - Design and synthesis of amphiphilic carboxyl-functionalized magnetic polymer microspheres for fast determination of paraquat and its four metabolites in human urine samples prior to ultra-high performance liquid chromatography-high resolution mass spectrometry. PG - 462998 LID - S0021-9673(22)00196-0 [pii] LID - 10.1016/j.chroma.2022.462998 [doi] AB - In cases of low concentration paraquat (PQ) poisoning, as the disease progresses over a long period of time, the prototype PQ may not be detected in the urine, which has a significant negative impact on the precise treatment of the poisoning. But PQ poisoning can also be confirmed by the detection of specific metabolites of PQ in the urine samples. In the present study, core-shell amphiphilic carboxyl-functionalized magnetic polymer microsphere (Amphiphilic-MPs-COOH) was prepared, and the as-prepared Amphiphilic-MPs-COOH was characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetry and differential thermogravimetry analyses (TG-DTG). Then, the Amphiphilic-MPs-COOH was employed as a magnetic solid-phase extraction (MSPE) adsorbent for pretreatment and rapid determination of PQ and its four metabolites from urine samples prior to ultra-high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). The extraction-elution conditions of Amphiphilic-MPs-COOH towards PQ and its metabolites were optimized in spiking urine samples to obtain the best MSPE efficiency. The adsorption mechanism of PQ and its metabolites by Amphiphilic-MPs-COOH involves electrostatic attraction and pi-pi stacking interactions. Moreover, the effect of different ratios of hydrophilic monomer NVP and functional monomer 4-VBA on the extraction and purification performance of PQ and its metabolites in urine samples. And the results revealed that both hydrophilic monomer and functional monomer were important for the adsorption of PQ and its metabolites, and the addition of the appropriate amount of the hydrophilic monomer NVP can improve the compatibility of the adsorbent with the urine substrate. In addition, this study compared the matrix effect of the Amphiphilic-MPs-COOH based MSPE method and the commercial Waters Oasis WCX SPE method. The results showed that the Amphiphilic-MPs-COOH based MSPE method developed in this paper had better resistance to matrix interference. Under optimal conditions, the recoveries of PQ and its metabolites were ranging from 84.5 to 103%, with relative standard deviations (RSDs) of 1.1-6.3%. While the limits of detection (LODs, S/N >/= 3) and limits of quantification (LOQs, S/N >/= 9) of the method were in range of 0.1-1.6 mug/L and 0.3-4.8 mug/L, respectively. Finally, the established MSPE-UPLC-HRMS method in this study was used to confirm PQ poisoning not only based on detecting PQ prototype, but also on its four metabolites, providing strong technical support for clinical precision treatment. CI - Copyright (c) 2022. Published by Elsevier B.V. FAU - Pan, Shengdong AU - Pan S AD - Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province, Ningbo Municipal Center for Disease Control and Prevention, Ningbo, Zhejiang 315010, China. Electronic address: panshengdong0714@163.com. FAU - Huang, Zhiping AU - Huang Z AD - Beilun District People's Hospital, Ningbo, Zhejiang 315800, China. FAU - Shang, Chunqing AU - Shang C AD - Enriching Biotechnology (Shanghai) Co. Ltd, 1688 North Guoquan Road, Shanghai 200438, China. FAU - Wang, Li AU - Wang L AD - Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province, Ningbo Municipal Center for Disease Control and Prevention, Ningbo, Zhejiang 315010, China. FAU - Qiu, Qiaoli AU - Qiu Q AD - Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province, Ningbo Municipal Center for Disease Control and Prevention, Ningbo, Zhejiang 315010, China. FAU - Xu, Zemin AU - Xu Z AD - Ningbo Kangning Hospital, Ningbo, Zhejiang 315201, China. FAU - Zhang, Dandan AU - Zhang D AD - Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province, Ningbo Municipal Center for Disease Control and Prevention, Ningbo, Zhejiang 315010, China. Electronic address: 317569725@qq.com. LA - eng PT - Journal Article DEP - 20220326 PL - Netherlands TA - J Chromatogr A JT - Journal of chromatography. A JID - 9318488 RN - 0 (Polymers) RN - PLG39H7695 (Paraquat) SB - IM MH - Chromatography, High Pressure Liquid MH - Humans MH - Limit of Detection MH - Magnetic Phenomena MH - Microspheres MH - *Paraquat MH - *Polymers MH - Solid Phase Extraction MH - Tandem Mass Spectrometry OTO - NOTNLM OT - Amphiphilic carboxyl-functionalized magnetic polymer microspheres (Amphiphilic-MPs-COOH) OT - Magnetic-phase extraction (MSPE) OT - Metabolites OT - Paraquat OT - UPLC-HRMS OT - Urine sample COIS- Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. EDAT- 2022/04/03 06:00 MHDA- 2022/04/14 06:00 CRDT- 2022/04/02 20:07 PHST- 2022/02/08 00:00 [received] PHST- 2022/03/21 00:00 [revised] PHST- 2022/03/24 00:00 [accepted] PHST- 2022/04/03 06:00 [pubmed] PHST- 2022/04/14 06:00 [medline] PHST- 2022/04/02 20:07 [entrez] AID - S0021-9673(22)00196-0 [pii] AID - 10.1016/j.chroma.2022.462998 [doi] PST - ppublish SO - J Chromatogr A. 2022 May 10;1670:462998. doi: 10.1016/j.chroma.2022.462998. Epub 2022 Mar 26.