液相色谱-质谱联用快速测定尿中游离1-羟基芘和1-羟基芘葡萄糖的研究

Simultaneous detection of the level of free 1-hydropyrene and 1-hydropyrene glucuronide in urine samples with high performance liquid chromatography mass spectrometry

目的建立以液质联用仪/离子阱(HPLC-MS/Trap)测定人尿中游离1-羟基芘(1-OHP)和1-羟基芘葡萄糖(1-OHP-G)的快速检测方法。方法尿样经过固相微萃取(SPE)法处理,二甲基亚砜复溶、离心取上清液分析;优化仪器的各种参数,10min内完成整个分析过程;1-OHP在m/z217.0～199.0离子对的跃迁和1-OHP-G在m/z413.3～301.2离子对的跃迁灵敏度最高。结果本方法能最低检测到8.4μg/L的游离1-OHP和12.5μg/L的1-OHP-G;尿样中的游离1-OHP和1-OHP-G含量:焦化工人分别为0.23和3.15μmol/molCr,普通居民分别为0.05和0.38μmol/molCr,接触组与对照组之间差异有显著性(P<0.05)。结论本方法分析时间短,HPLC-MS/Traps分析目标物受干扰少、特异性高,可作为一种评价多环芳香烃内负荷接触程度的有效方法。

Objective To develop a rapid analysis method using high performance liquid chromatography-electric spray ionization traps mass spectrometry for simultaneous detection of free 1-hydropyrene （1-OHP） and 1-hydropyrene glueuronide （1- OHP-G） in urine. Methods Prior to the supernatants were injected into the analysis instrument, authentic urine samples were processed by SPE cartridges and re-dissolved in 1 ml of DMSO. Only 10 minute was needed for the analysis while the parameters of the instrument were optimized. Mass transitions were monitored at m/z 217.0 - 199.0 for 1-OHP and m/z 413.3 - 301.2 for 1-OHP-G. Results The detection limits of the method were 8.4 μg/L for free 1-OHP and 12. 5 μg/L for 1-OHP-G. The levels of free 1-OHP and 1-OHP-G in coke workers were 0.23 and 3.15 μmol/molCr respectively,and the levels of free 1-OHP and 1- OHP-G in the residents were 0. 05 and 0.38 μmol/molCr respectively. There was a significant difference between the exposure groups and the control groups （ P 〈 0. 05）. Conclusion The developed method was successfully used to measure urinary PAH metabolites in coke workers and residents.