固相萃取-超高效液相色谱-高分辨质谱法测定尿液中草甘膦  

Determination of glyphosate in urine by solid-phase extraction and ultra-performance liquid chromatography-high resolution mass spectrometry

作　　者：庄立 宋志军[3] 潘胜东[4,5] 蔡美强[3] 金米聪[4,5] ZHUANG Li;SONG Zhi -jun;PAN Sheng - dong;CAI Mei - qiang;JIN Mi - cong(The Central Blood Station of Ningbo, Ningbo, Zhejiang 315010, China)

机构地区：[1]宁波市中心血站,浙江宁波315010 [2]宁波市献血办公室,浙江宁波315010 [3]浙江工商大学环境科学与工程学院,浙江杭州310015 [4]宁波市疾病预防控制中心浙江省微量有毒化学物健康风险评估技术研究重点实验室,浙江宁波315010 [5]宁波市疾病预防控制中心宁波市毒物研究与控制重点实验室,浙江宁波315010

出　　处：《中国卫生检验杂志》2018年第7期774-777,781,共5页Chinese Journal of Health Laboratory Technology

基　　金：浙江省自然科学基金项目(LY17B050001);宁波市自然科学基金项目(2016A610178)

摘　　要：目的建立尿液中草甘膦的固相萃取-超高效液相色谱-高分辨质谱(UPLC-HRMS)分析方法。方法尿液样品采用0.1%(V/V)甲酸-乙腈沉淀蛋白后,利用MCX阳离子交换固相萃取小柱净化,采用Phenomenex Luna NH2柱(50 mm×4.6 mm,3μm)为分离柱,以乙腈/10 mmol/L乙酸铵-0.1%(V/V)氨水溶液为流动相进行梯度洗脱,采用电喷雾负离子源在选择离子监测模式(SIM)下检测,定量检测离子为m/z 168.006 7。结果尿液中草甘膦在1.0μg/L^100.0μg/L具有良好的线性关系,相关系数(r)为0.999 2,尿液中草甘膦的检出限(S/N=3)为0.3μg/L,定量检出限(S/N=10)为1.0μg/L,方法的回收率在92.0%~97.2%,低、中、高3个添加水平浓度的日内RSD为2.4%~4.4%,日间RSD为3.3%~6.9%。结论建立的方法准确、简便、灵敏,可用于中毒者尿液中草甘膦的检测。Objective To developed a method for the determination of glyphosate in urine by solid-phase extraction（SPE）and ultra-performance liquid chromatography-high resolution mass spectrometry（UPLC-HRMS）.Methods The urine sample was precipitated for protein by 0.1%（V/V）formic acid-acetonitrile,and cleaned-up by MCX cation exchange cartridge.The chromatographic separation was performed on a Phenomenex Luna NH2 column（50 mm × 4.6 mm,3 μm）with acetonitrile/10 mmol/L ammonium acetate-0.1%（V/V）ammonia solution as mobile phase in a gradient elution mode.The detection was carried out by HRMS using electrospray ionization in the negative selective ion monitoring（SIM）mode with the quantitative ion of m/z 168.006 7.Results The calibration curve was linear within the range of 1.0 μg/L-100.0 μg/L,with correlation coefficient（r）of 0.999 2.The limit of detection（LOD）was 0.3 μg/L（S/N = 3）,and the limit of quantitation（LOQ）was1.0 μg/L in urine sample（S/N = 10）.The extraction recoveries at the three spiked levels（low,medium and high）were within92.0%-97.2%,and the intra-day RSD was within 2.4%-4.4%,and the inter-day RSD was within 3.3%-6.9%.Conclusion The developed method is simple,accurate and high sensitive,and it can be used for the determination of glyphosate in the poisoned patients＇ urine.

关 键 词：超高效液相色谱-高分辨质谱法 固相萃取 草甘膦 尿 

分 类 号：O657.72[理学—分析化学]