固相萃取净化/超高效液相色谱-串联质谱法测定养殖环境中地西泮及其代谢物  

Determination of Diazepam and Its Metabolites in Aquaculture Environment Samples by Solid Phase Extraction Cleanup and Ultra-performance Liquid Chromatography-Tandem Mass Spectrometry

作　　者：王旭峰[1] 王强[1] 张英侠 黄珂[1] WANG Xu-feng;WANG Qiang;ZHANG Ying-xia;HUANG Ke(South China Sea Fisheries Research Institute,Chinese Academy of Fishery Sciences,Fishery Environment and Aquatic Products Quality Inspection&Testing Center of the Ministry of Agriculture and Rural Affaires(Guangzhou),Guangzhou 510300,China)

机构地区：[1]农业农村部渔业环境及水产品质量监督检验测试中心(广州),中国水产科学研究院南海水产研究所,广东广州510300

出　　处：《分析测试学报》2023年第3期337-343,共7页Journal of Instrumental Analysis

基　　金：中国水产科学研究院南海水产研究所中央级公益性科研院所基本科研业务费专项资金(2021SD20);广东省现代农业产业技术体系创新团队建设专项资金(2023KJ151)。

摘　　要：建立了固相萃取净化/超高效液相色谱-串联质谱(SPE/UPLC-MS/MS)同时测定养殖水和沉积物样品中地西泮及其3种代谢物的分析方法。水样经0.45μm玻璃纤维膜过滤,沉积物采用1%氨水-乙酸乙酯提取后,均通过混合型阳离子交换固相萃取(MCX SPE)柱富集净化。目标物用5%氨水-乙腈溶液洗脱后吹干,1 mL 40%乙腈水溶液溶解残渣,UPLC-MS/MS测定。经Phenomenex Kinetex C_(18)(100 mm×2.1 mm,1.7μm)色谱柱分离,乙腈和0.1%甲酸水溶液为流动相进行梯度洗脱。采用电喷雾正离子电离,多反应监测(MRM)模式下测定,内标法定量。4种目标物在0.1~100μg/L范围内的线性关系良好,相关系数(r^(2))大于0.999。水体和沉积物中的方法检出限分别为1.0~2.0 ng/L和0.02~0.05μg/kg,定量下限分别为2.0~5.0 ng/L和0.05~0.1μg/kg;平均加标回收率为90.2%~115%,相对标准偏差(RSD,n=6)为2.1%~9.6%。该方法灵敏度高,实用性强,可满足养殖环境中地西泮及其代谢物的测定要求。A multi-residue analytical method was developed for the simultaneous determination of diazepam and its three metabolites in aquaculture water and sediment samples based on ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).Water samples were filtered through 0.45μm glass fiber membranes,and subsequently enriched with a mixed cation exchange solid phase extraction(MCX SPE)cartridge.Sediment samples were extracted with 1%ammonium hydroxide-ethyl acetate,and then cleaned up using a MCX SPE cartridge.The purified extracts were eluted with 5%ammonium hydroxide-acetonitrile solution,and then dried residues were redissolved with 1 mL 40%acetonitrile water solution for UPLC-MS/MS analysis.The chromatographic separation of four targeted analytes were performed on a Phenomenex Kinetex C_(18)(100 mm×2.1 mm,1.7μm)column by gradient elution,with acetonitrile and 0.1%formic acid solution as mobile phases.Targeted compounds were determined with positive electrospray ionization under multiple reaction monitoring(MRM)mode,and quantified by internal standard method.Good linear relationships for targeted analytes were obtained in the range of 0.1-100μg/L with correlation coefficients(r^(2))larger than 0.999.The detection limits of the method for aquaculture water samples and sediment samples were 1.0-2.0 ng/L and 0.02-0.05μg/kg,while the quantitation limits were 2.0-5.0 ng/L and 0.05-0.1μg/kg,respectively.The average recoveries for spiked negative aquaculture water and spiked sediment matrix ranged from 90.2%to 115%,with relative standard deviations(RSDs,n=6)between 2.1%and 9.6%.The proposed method is sensitive and accurate,and it is suitable for the residual determination of diazepam and its metabolites in real aquaculture water and sediment samples.

关 键 词：地西泮 代谢物 固相萃取(SPE) 超高效液相色谱-串联质谱(UPLC-MS/MS) 养殖环境 

分 类 号：O657.7[理学—分析化学] X132[理学—化学]