固相萃取-超高效液相色谱-串联质谱法测定水体中4种解热镇痛类药物  

Determination of four antipyretic and analgesic drugs in water by solid-phase extraction coupled ultra-performance liquid chromatography-tandem mass spectrometry

作　　者：朱峰[1] 姚志建 霍宗利[1] 吉文亮[1] 刘华良[1] 周庆[2] 李爱民[2] 焦伟 谷静[1] ZHU Feng;YAO Zhijian;HUO Zongli;JI Wenliang;LIU Hualiang;ZHOU Qing;LI Aimin;JIAO Wei;GU Jing(Jiangsu Provincial Center for Disease Control and Prevention, Nanjing 210009, China;State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China;Jiangsu Guochuang Enviro-Protection Technology Co., Ltd., Nanjing 211100, China)

机构地区：[1]江苏省疾病预防控制中心,南京210009 [2]南京大学环境学院,污染控制与资源化研究国家重点实验室,南京210023 [3]江苏国创环保科技有限公司,南京211100

出　　处：《色谱》2020年第12期1465-1471,共7页Chinese Journal of Chromatography

基　　金：国家自然科学基金项目(51678290,51438008,51778281);江苏省预防医学项目(Y2018081).

摘　　要：近年来,环境水体中出现的药物及个人护理品污染物受到人们越来越多的关注,其中就包括解热镇痛类药物。传统的固相萃取材料对水体中解热镇痛类药物的富集效率较低。为此,开发了一种亲水亲脂型的双亲多孔吸附聚合物材料(Guochuang hydrophilic material, GCHM)。以N-乙烯基吡咯烷酮和二乙烯基苯为原料,利用乳液胶束-分步反应法成功制备出GCHM。基于自主研发的固相萃取柱,采用超高效液相色谱-串联质谱技术,建立了水体中4种解热镇痛类药物的检测方法。水样经GCHM固相萃取柱富集净化后上机检测,以0.1%(v/v)甲酸水溶液和乙腈作为流动相进行梯度洗脱,目标分析物在ACQUITY UPLC■ HSS T3色谱柱(100 mm×2.1 mm, 1.8μm)上实现分离,在电喷雾正离子模式下进行多反应监测(MRM),内标法定量。比较Oasis HLB、Bond Elut Plexa和GCHM 3种固相萃取柱的富集效率,结果表明GCHM固相萃取柱总体效果最优。在不同pH值下比较了GCHM固相萃取柱对目标分析物的富集效果,并对基质效应进行了评估。结果表明,当pH为7时,4种目标分析物在固相萃取柱上的富集效果最好;各物质的基质效应均在82.8%~102.2%之间,表明水样经GCHM固相萃取柱净化后,基质去除明显。4种目标分析物在1~100μg/L范围内线性关系良好,相关系数(r)均大于0.995,方法定量限(S/N=10)在1~5 ng/L之间,在3个加标水平下的回收率均在85.6%~106.4%之间,相对标准偏差(RSD)均低于5.6%。GCHM固相萃取柱成本低,效果好,适用于水体中4种解热镇痛类药物的检测,较商品化的进口固相萃取柱具有潜在的优势,值得推广应用。The widespread use of pharmaceutical and personal care products(PPCPs),including antipyretic and analgesic drugs,in the last two decades had led to the existence of PPCP residues in the environment,thus raising concerns about their pseudo-persistent nature and potential threat to human health.Generally,most of the detected contaminants are present at low levels(ranging from ng/L toμg/L)in environmental water.Therefore,advanced analytical methodologies are crucial to monitor the occurrence and distribution of antipyretic and analgesic drugs in environmental water.However,trace analysis of environmental pollutants is always challenging because it is necessary to extract analytes present in the sample at ultralow levels from complex environmental matrices.Therefore,an appropriate sample pretreatment is necessary to enrich the target compounds.Conventional solid-phase extraction materials show poor efficiency for the enrichment of antipyretic and analgesic drugs.We herein report a hydrophilic and lipophilic amphiphilic porous polymeric material GCHM(Guochuang hydrophilic material).GCHM was successfully prepared by a stepwise emulsification and micellization process using N-vinyl-2-pyrrolidone(NVP)and divinylbenzene(DVB)as raw materials.An ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)method was developed for the determination of four antipyretic and analgesic drugs in water using our solid-phase extraction(SPE)column.The water samples were extracted and purified by the GCHM solid-phase extraction column,and then analyzed by UPLC-MS/MS.Gradient elution was carried out with 0.1%formic acid aqueous solution and acetonitrile as the mobile phase.The target analytes were separated on an ACQUITY UPLC HSS T3 column(100 mm×2.1 mm,1.8μm),and multiple reaction monitoring(MRM)was conducted in the positive electrospray ionization mode.The isotope internal standard method was used for quantitative correction.Comparison of the enrichment efficiencies of Oasis HLB,Bond Elut Plexa,and GCHM revealed th

关 键 词：固相萃取 超高效液相色谱-串联质谱 解热镇痛类药物 水体 

分 类 号：O658[理学—分析化学]