色谱

色谱 ›› 2026, Vol. 44 ›› Issue (6): 682-693.DOI: 10.3724/SP.J.1123.2025.09019

• 技术与应用 • 上一篇    下一篇

超高效液相色谱-串联质谱法测定人体全血中22种有机磷酸酯及其代谢物和11种邻苯二甲酸酯类代谢物

石飞云1, 徐浩宇2, 黎俊宏1, 徐梦媛1,*()   

  1. 1.常州市疾病预防控制中心，江苏 常州 213022
    2.常州市中医医院，江苏 常州 213022
  • 收稿日期:2025-09-28 出版日期:2026-06-08 发布日期:2026-06-03
  • 通讯作者: *Tel：0519-86684627，E-mail：429330434@qq.com.
  • 基金资助:
    2024年常州市卫生健康委员会青年人才科技项目(QN202463);2024年常州市卫生健康委员会青年人才科技项目(QN202425);江苏省第六期“333高层次人才培养工程”第三层次培养对象［（2022）3-4-163］

Determination of 22 organophosphates and their metabolites and 11 phthalate metabolites in human whole blood by ultra performance liquid chromatography-tandem mass spectrometry

SHI Feiyun1, XU Haoyu2, LI Junhong1, XU Mengyuan1,*()   

  1. 1. Changzhou Center for Disease Control and Prevention，Changzhou 213022，China
    2. Changzhou Hospital of Traditional Chinese Medicine，Changzhou 213022，China
  • Received:2025-09-28 Online:2026-06-08 Published:2026-06-03
  • Supported by:
    Youth Talent Science and Technology Project of Changzhou Municipal Health Commission in 2024(QN202463);Youth Talent Science and Technology Project of Changzhou Municipal Health Commission in 2024(QN202425);The Third Level Training Objects of the Sixth “333 High Level Talent Training Project” in Jiangsu Province ［（2022） 3-4-163］

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摘要：

有机磷酸酯（organic phosphate esters， OPEs）和邻苯二甲酸酯（phthalate esters， PAEs）是两类人工合成的化合物，常作为阻燃剂和增塑剂以物理结合的方式被添加到各种工业和消费品中，二者均具有多脏器累积毒性。本研究采用超高效液相色谱-串联质谱（UPLC-MS/MS）建立了全血中22种OPEs及其二酯代谢物（mOPEs）和11种邻苯二甲酸酯类代谢物（mPAEs）的检测方法。全血样本采用HMR S-micro BIO 96孔固相萃取柱净化，使用Ghost Trap DS-HP色谱柱（30 mm×2.1 mm）作为背景鬼峰捕集柱，以ACQUITY UPLC® BEH C18色谱柱（150 mm×2.1 mm，1.7 μm）作为分析柱，采用0.5 mmol/L乙酸铵溶液和甲醇为流动相进行梯度洗脱，质谱采用电喷雾离子源（ESI）电离，以正负离子扫描、多反应监测（MRM）模式检测，同位素内标法定量。结果表明，33种目标化合物在15 min内均可实现基线分离，目标化合物在相应质量浓度范围内线性关系良好（r为0.993 3~0.999 8），检出限为0.003～0.31 ng/mL，定量限为0.01～1.02 ng/mL。全血样本加标回收率为60.5%～138.3%，相对标准偏差（RSD）为1.6%～11.0%。应用该方法对14个全血样本进行检测，在14份样本中均检出磷酸三（1-氯-2-丙基）酯、磷酸三苯酯（TPHP）、磷酸2-乙基己基二苯基酯、邻苯二甲酸单（2-乙基-5-羟己基）酯、邻苯二甲酸单正丁酯和邻苯二甲酸单正辛酯，且TPHP的检出量最高（10.04 ng/mL）。该方法具有操作简便、灵敏度高、准确性好、所需样品量少以及节约试剂等优点，适用于人体的生物监测，为人群有机磷酸酯和邻苯二甲酸酯类物质的监测提供了理论依据。

关键词: 有机磷酸酯, 邻苯二甲酸酯类代谢物, 全血, 超高效液相色谱-串联质谱法

Abstract:

Organic phosphate esters （OPEs） and phthalate esters （PAEs） are two classes of synthetic compounds widely incorporated into various industrial and consumer products as flame retardants and plasticizers. Both exhibit multi-organ cumulative toxicity. In this study， an ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） method was developed for the determination of 22 OPEs and their diester metabolites （mOPEs） and 11 phthalate ester metabolites （mPAEs） in whole blood. The whole blood samples were extracted with 0.1% formic acid-acetonitrile by liquid-liquid extraction for protein precipitation， and then purified by HMR S-micro BIO 96-well solid phase extraction column. The filtrate was blown to near dryness with nitrogen， and reconstituted with 0.1% formic acid-acetonitrile solution. The target compounds were detected by UPLC-MS/MS. A Ghost Trap DS-HP chromatographic column （30 mm×2.1 mm） was used as the background ghost peak trap column， and an ACQUITY UPLC® BEH C18 chromatographic column （150 mm×2.1 mm， 1.7 μm） was used as the analytical column. Methanol and 0.5 mmol/L ammonium acetate were used as mobile phase for gradient elution. Electrospray ionization （ESI） was used for MS detection， with both positive and negative ion scanning in the multiple reaction monitoring （MRM） mode. Isotope internal standard method was used for quantification. The results showed that 33 target compounds could be separated within 15 min， and good linear relationships were observed for all target compounds across their respective mass concentration ranges （r=0.993 3-0.999 8）. The limits of detection were 0.003-0.31 ng/mL and the limits of quantification were 0.01-1.02 ng/mL. The spiked recoveries of 33 targets in whole blood samples ranged from 60.5% to 138.3%， with relative standard deviations （RSDs） from 1.6% to 11.0%. The detection rates of tris-（2-chloroisopropyl）phosphate （TCiPP）， triphenyl phosphate （TPHP）， 2-ethylhexyl diphenyl （EHDPP）， mono（2-ethyl-5-hydroxyhexyl） phthalate （MEHHP）， mono-n-butyl phthalate （MNBP） and mono-n-octyl phthalate （MOP） were 100% in 14 whole blood samples， and the highest detection amount of TPHP was 10.04 ng/mL. The developed method is simple to operate， sensitive， accurate， requires small sample volumes， and is cost-effective on reagents. It is suitable for human biomonitoring， and provides a theoretical basis for monitoring organic phosphate and phthalic ester substances in the population.

Key words: organic phosphate esters, phthalate ester metabolites, whole blood, ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）

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