高效液相色谱-串联质谱法检测婴幼儿血清中4种双酚类环境激素残留

引用本文: 刘芳, 孟桃于, 陈练, 吴雅君, 熊顺, 丁利. 高效液相色谱-串联质谱法检测婴幼儿血清中4种双酚类环境激素残留[J]. 色谱, 2020, 38(12): 1381-1387. doi: 10.3724/SP.J.1123.2020.03024 shu

Citation: LIU Fang, MENG Taoyu, CHEN Lian, WU Yajun, XIONG Shun, DING Li. Determination of four bisphenol environmental hormone residues in infant serum by liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(12): 1381-1387. doi: 10.3724/SP.J.1123.2020.03024 shu

高效液相色谱-串联质谱法检测婴幼儿血清中4种双酚类环境激素残留

刘芳 ^1,2, ,
孟桃于 ^2, ,
陈练 ^3, ,
吴雅君 ^2, ,
熊顺 ^2, ,
丁利 ^{1,
,}

1.
长沙理工大学化学与食品工程学院, 湖南长沙 410014;
2.
长沙和合医学检验实验室有限公司, 湖南长沙 410000;
3.
长沙海关技术中心, 湖南长沙 410004

通讯作者: 丁利, E-mail:5284530@qq.com

基金项目:
国家重点研发计划（2016YFF0103800，2016YFF0203701）；湖南省创新平台与人才计划（2017RS3055）；长株潭国家自主创新示范区专项（2018XK2006-1）.

摘要: 目前，双酚类化合物是重要的工业原料，常用来制造塑料（奶）瓶、幼儿用吸口杯、食品和饮料（奶粉）罐内侧涂层，其具有类似雌激素的作用，摄入低剂量的双酚类物质便会引起机体尤其婴幼儿体内激素水平的调节。建立了一种同时测定婴幼儿血清中双酚A（BPA）、双酚B（BPB）、双酚F（BPF）、双酚S（BPS）4种双酚类环境激素的高效液相色谱-串联质谱法（HPLC-MS/MS）。以甲基叔丁基醚（MTBE）为提取溶剂，采用液液萃取的方法进行样品处理，同时对影响4种双酚类环境激素提取效率的提取溶剂、提取时间、提取溶剂体积等影响因素进行了优化。100 μL血清样本在40℃下经400 μL MTBE提取15 min后，采用Waters ACQUITY UPLC BEH C18柱（50 mm×2.1 mm，1.7 μm）进行分离，以超纯水和含0.5 mmol/L乙酸铵的甲醇溶液为流动相进行梯度洗脱，流速为0.2 mL/min，采用电喷雾电离、负离子模式扫描，在多反应监测（MRM）模式下测定。BPA、BPB、BPS在0.25~100 μg/L范围内线性关系良好，BPF在1~00 μg/L范围内线性关系良好，相关系数为0.9929~0.9959；方法的检出限分别为0.05、0.05、0.05、0.5 μg/L；在3个添加水平（5、20、100 μg/L）下，4种目标化合物的回收率为84.56%~104.43%，相对标准偏差小于10%。应用该方法对150例婴幼儿血清样品进行检测，结果表明：BPA、BPF、BPS在男童和女童血清中的检出率分别为90.67%和89.33%、6.67%和1.33%、5.33%和16.00%，BPB未被检出。该方法操作简单，回收率好，精密度高，适用于婴幼儿血清中4种双酚类环境激素的同时测定。

关键词:

English

Determination of four bisphenol environmental hormone residues in infant serum by liquid chromatography-tandem mass spectrometry

LIU Fang ^1,2, ,
MENG Taoyu ^2, ,
CHEN Lian ^3, ,
WU Yajun ^2, ,
XIONG Shun ^2, ,
DING Li ^{1,
,}

1.
College of Chemistry and Food Engineering, Changsha University of Science and Technology, Changsha 410014, China;
2.
Changsha Harmony Health Medical Laboratory Co., Ltd., Changsha 410000, China;
3.
Technology Center of Changsha Customs, Changsha 410004, China

Corresponding author: DING Li, 5284530@qq.com

Received Date: 26 March 2020
Fund Project:
National Key Research and Development Plan Project (Nos. 2016YFF0103800, 2016YFF0203701)

Abstract: Bisphenols are important industrial raw materials that are widely used to produce plastic bottles (feeding bottles), infant cups, and food and beverage (milk powder) cans. Because of the estrogen-like effect of bisphenols, even low-dose intake of these compounds by trace migration affects normal hormone levels in the human body. Therefore, it is imperative to develop a rapid, accurate, and highly sensitive method for the determination of bisphenols in serum. In this study, methyl tert-butyl ether (MTBE) was used as the extraction solvent, and the liquid-liquid extraction pretreatment method was used for sample processing. A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was established for the simultaneous determination of bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF), and bisphenol S (BPS) at trace levels in infant serum. The important parameters affecting the extraction efficiency, such as the extraction solvent, extraction time, and extraction solvent volume for the four bisphenol environmental hormones were optimized. Serum samples were extracted by MTBE at 40℃ for 15 min. The target compounds were separated on a Waters ACQUITY UPLC BEH C18 column (50 mm×2.1 mm, 1.7 μm) using ultrapure water and methanol solution containing 0.5 mmol/L ammonium acetate as the mobile phases, with gradient elution at a flow rate of 0.2 mL/min. Finally, the analytes were analyzed by HPLC-MS/MS in the negative ion mode. BPA, BPB, and BPS showed good linearity in the range of 0.25-100 μg/L, while BPF showed good linearity in the range of 1-100 μg/L. The correlation coefficients were 0.9929-0.9959, and the limits of detection for BPA, BPB, BPS, and BPF were 0.05, 0.05, 0.05, 0.5 μg/L, respectively. At the three spiked levels (5, 20, 100 μg/L), the average recoveries of BPA, BPB, BPS, and BPF ranged from 84.56% to 104.43%, and the relative standard deviations were less than 10%. The proposed method was successfully applied to the determination of bisphenol contents in 150 infant serum samples. BPA was detected in most serum samples, and the detection rates in the serum of boys and girls were 90.67% and 89.33%, respectively. The detection rates of BPF in the serum of boys and girls were 6.67% and 1.33%, respectively; the corresponding values for BPS were 5.33% and 16.00%. BPB was not detected. The proposed method has the advantages of simple operation, good recovery, and high precision, and it is suitable for the simultaneous determination of the four bisphenol environmental hormones in infant serum.

Key words:

high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)
/ liquid-liquid extraction
/ environmental hormones
/ infant serum

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沈阳化工大学材料科学与工程学院沈阳 110142

高效液相色谱-串联质谱法检测婴幼儿血清中4种双酚类环境激素残留

通讯作者: 丁利, E-mail:5284530@qq.com

English

Determination of four bisphenol environmental hormone residues in infant serum by liquid chromatography-tandem mass spectrometry

Corresponding author: DING Li, 5284530@qq.com

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中国化学会秘书处

高效液相色谱-串联质谱法检测婴幼儿血清中4种双酚类环境激素残留

通讯作者: 丁利, E-mail:5284530@qq.com

English

Determination of four bisphenol environmental hormone residues in infant serum by liquid chromatography-tandem mass spectrometry

Corresponding author: DING Li, 5284530@qq.com

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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