On-line clean-up by multidimensional liquid chromatography-electrospray ionization tandem mass spectrometry for high throughput quantification of primary and secondary phthalate metabolites in human urine
On-line clean-up by multidimensional liquid chromatography-electrospray ionization tandem mass spectrometry for high throughput quantification of primary and secondary phthalate metabolites in human urine
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DOI：
10.1016/s1570-0232(02)00785-7
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发表时间：
2003-01-25
影响因子：
3
通讯作者：
Angerer, J
中科院分区：
文献类型：
--
作者：
Koch, HM;Gonzalez-Reche, LM;Angerer, J
我们开发了一种新的快速多维在线HPLC方法，用于定量测定一般人群尿液样本中邻苯二甲酸二乙基己酯（DEHP）、5-羟基-单（2-乙基己基）-邻苯二甲酸酯（5 OH-MEHP）和5-氧代-单（2-乙基己基）-邻苯二甲酸酯（5 oxo-MEHP）的二级链氧化单酯代谢物。该方法还包括DEHP的简单单酯代谢产物邻苯二甲酸二辛酯（DOP）、邻苯二甲酸二丁酯（DBP）、邻苯二甲酸丁基苄酯（BBzP）和邻苯二甲酸二乙酯（DEP）。除了用于代谢物解偶联的酶水解外，无需进一步的样品预处理步骤。通过在限制进入材料（LiChrospher（R）ADS-8）预柱上在线提取，从尿液基质中分离邻苯二甲酸酯代谢物，以反冲洗模式转移，并通过反相HPLC进行色谱分离。洗脱代谢物通过ESI-串联质谱法在负离子模式下检测，并通过同位素稀释定量。在25分钟的总运行时间内，我们可以选择性地和灵敏地定量七种常见的邻苯二甲酸二酯的尿液代谢物，包括有争议的邻苯二甲酸二（2-乙基己基）酯（DEHP）。所有分析物的检测限均在低ppb范围内（0.5-2.0 mug/l尿液）。一个小的非暴露组（n = 8）的第一个结果范围为5 OH-MEHP 0.59 - 124 μ g/l，5 oxo-MEHP
We developed a new and fast multidimensional on-line HPLC-method for the quantitative determination of the secondary, chain oxidized monoester metabolites of diethylhexylphthalate (DEHP), 5-hydroxy-mono-(2-ethylhexyl)-phthalate (5OH-MEHP) and 5-oxo-mono-(2-ethylhexyl)-phthalate (5oxo-MEHP) in urine samples from the general population. Also included in the method were the simple monoester metabolites of DEHP, dioctylphthalate (DOP), dibutylphthalate (DBP), butylbenzylphthalate (BBzP) and diethylphthalate (DEP). Except for enzymatic hydrolysis for deconjugation of the metabolites no further sample pre-treatment step is necessary. The phthalate metabolites are stripped from urinary matrix by on-line extraction on a restricted access material (LiChrospher(R) ADS-8) precolumn, transferred in backflush-mode and chromatographically resolved by reversed-phase HPLC. Eluting metabolites are detected by ESI-tandem mass spectrometry in negative ionization mode and quantified by isotope dilution. Within a total run time of 25 min we can selectively and sensitively quantify seven urinary metabolites of six commonly occurring phthalate diesters including the controversial di(2-ethylhexyl)phthalate (DEHP). The detection limits for all analytes are in the low ppb range (0.5-2.0 mug/l urine). First results on a small non-exposed group (n = 8) ranged for 5OH-MEHP from 0.59 to 124 mug/l, for 5oxo-MEHP from