3,4-二巯基甲苯衍生化法结合SPME/GC-MS技术分析尿样中超痕量氯乙烯基胂酸  

Determination of Ultra-trace 2-Chlorovinylarsonic Acid in Urine by SPME/GC-MS after Derivatization with 3,4-Dimercaptotoluene

作　　者：吴姬娜 刘石磊[1,2] 杨旸[1,2] 梁龙辉[1] 刘景全[1,2] 

机构地区：[1]防化研究院分析测试中心,北京102205 [2]国民核生化灾害防护国家重点实验室,北京102205

出　　处：《分析测试学报》2016年第8期999-1004,共6页Journal of Instrumental Analysis

摘　　要：选取氯乙烯基胂酸(CVAOA)为生物标志物,建立了路易氏剂染毒尿样中超痕量CVAOA的分析方法。采用正交试验,优化了CVAOA的巯基化衍生方法,选取3,4-二巯基甲苯(DMT)作为衍生试剂,CVAOA与DMT的用量摩尔比为1∶1 000,常温衍生5 min,可达到最高的衍生效率;之后在优化的顶空-固相微萃取(HS-SPME)条件下富集纯化衍生产物CVAOA-DMT;使用气相色谱-质谱/选择离子监测模式(GC-MS/SIM)进行定性定量分析。该方法在50.0 pg/m L^500 ng/m L浓度范围内呈良好的线性(r2=0.998 5),相对标准偏差(RSD)小于10%,检出限可达7.6 pg/m L,定量下限为23 pg/m L。对低、中、高3种浓度的路易氏剂染毒尿样进行检测,回收率为97.6%~105%,RSD为4.4%~7.1%。该方法分析灵敏度高,具有良好的准确度、精密度和普及性,可被广泛推广和使用。Selecting 2-chlorovinylarsonic acid（CVAOA） as the biomarker, a determination method of ultra-trace CVAOA in human urine specific to lewisite exposure was developed. The conditions for derivatization were optimized by orthogonal experiments, and the results were as follows： thiolation by a 1 ： 1 000 mole ratio of CVAOA to 3, 4-dimercaptotoluene （DMT） for 5 rain at room tempera- ture. Enrichment and purification of the derivative product（ CVAOA -DMT） based on the optimum headspace- solid phase microextraction（ HS- SPME） conditions, and then analysis of the derivative by gas chromatography- mass spectrometry in selective ion monitoring（GC -MS- SIM）. The linear calibration range was from 50. 0 pg/mL to 500 ng/mL（ r2 = 0. 998 5 ）, and the relative standard devi- ations（RSDs） were less than 10%. The limit of detection was 7.6 pg/mL and the limit of quantita- tion was 23 pg/mL. The recoveries of lewisite exposed urine samples at the low, middle and high concentration levels ranged from 97.6% to 105% with the RSDs of 4.4% - 7. 1% . The method exhibited a satisfactory universality with its high sensitivity, precision and accuracy, and could be applied in different laboratories.

关 键 词：氯乙烯基胂酸 路易氏剂 尿样 超痕量 固相微萃取(SPME) 气相色谱-质谱(GC-MS) 

分 类 号：O657.63[理学—分析化学] O611.63[理学—化学]