典型有机磷酸酯在小鼠组织内的特异性分布

The tissue accumulation and distribution of typical organophosphate flame retardants (OPFRs) in mice

基于气相色谱质谱(GC-MS/MS)联用建立了生物体内典型有机磷酸酯(OPFRs)的高效提取和仪器分析方法,并探讨了其在小鼠组织中的积累分布特征.本研究通过对样品提取、净化和仪器定性定量等环节的条件优化,建立了高效测定机体中典型OPFRs的超声辅助萃取-无乙二胺-N-丙基硅烷(PSA)柱净化-气相色谱质谱分析方法.结果显示,在最优条件下加标样品中氘代磷酸三丁酯TnBP-d27和氘代磷酸三苯酯TPhP-d15的回收率分别为104.86%和102.12%.暴露实验采用昆明(KM)小鼠单次尾静脉注射OPFRs标记物的方式,分时间段取样,获得实际样品.使用本文建立的方法对实际样品进行定量分析,TnBP-d27和TPhP-d15的线性范围在1—200μg·L^-1之间,r2>0.99,检出限为0.02—1.08μg·L^-1,定量限为0.06—3.61μg·L^-1;平均回收率为54.04%—130.29%,相对标准偏差(RSDs)为9.58%—18.21%;TnBP-d27主要在脾脏(36 h)和肾脏(24 h)富集,分别为(8.55±1.00)ng·g^-1和(20.34±6.60)ng·g^-1;TPhP-d15主要在肾脏(12 h)富集,为(29.86±11.90)ng·g^-1.

In this study,an optimized method of solid-phase extraction and GC-MS/MS was applied to characterize and analyze the tissue distribution of typical organophosphate flame retardants(OPFRs)in KM mice.The procedures of extraction and purification,as well as chromatographic and mass spectrometric parameters were optimized.An effective method for determination of typical OPFRs in organism by GC-MS/MS with ultrasonic-assisted solvent extraction and non-primary secondary amine(PSA)purification was developed.Under the optimized conditions,our results showed that recoveries of TnBP-d27 and TPhP-d15 were 104.86%and 102.12%,respectively,showing a suitable extraction method.The tissue samples were obtained from mice after tail intravenous injection with different time points.The calibration curves showed good linearity in 1—200μg·L^-1 with correlation coefficients of r2>0.99.The limits of detection were 0.02—1.08μg·L^-1 and the limits of quantification were 0.06—3.61μg·L^-1.The average spiked recoveries were 54.04%—130.29%with relative standard deviation(RSDs)of 9.58%—18.21%.Spleen and kidney were the most obvious tissues for TnBP-d27 bioaccumulation with the concentration of(8.55±1.00)ng·g^-1 in spleen after the 36 h exposure,and(20.34±6.60)ng·g^-1 in kidney after the 24 h exposure.The highest concentration of TPhP-d15 was(29.86±11.90)ng·g^-1 in kidney after exposure of 24 h.