辛基功能化离子液体键合硅胶固相萃取海水中贝类毒素的方法研究  

Research on Octyl-functionalized Ionic Liquid Bonding Silica Gel for Solid Phase Extraction of Shellfish Toxins in Seawater

作　　者：孙晓杰[1] 丁海燕[1] 谭杰[1,2] 邢钧 郭萌萌[1] 邢丽红[1] 李兆新[1] 翟毓秀[1] SUN Xiao-Jie;DING Hai-Yan;TAN Jie;XING Jun;GUO Meng-Meng;XING Li-Hong;LI Zhao-Xin;ZHAI Yu-Xiu(Key Laboratory of Testing and Evaluation for Aquatic Product Safety and Quality,Ministry of Agriculture and Rural Affairs,Yellow Sea Fisheries Research Institute,Chinese Academy of Fishery Sciences,Qingdao 266071,China;Qingdao National Laboratory for Marine Science and Technology,Qingdao 266000,China;Key Laboratory of Analytical Chemistry for Biology and Medicine(Ministry of Education),College of Chemistry and Molecular Sciences,Wuhan University,Wuhan 430072,China)

机构地区：[1]农业农村部水产品质量安全检测与评价重点实验室,中国水产科学研究院黄海水产研究所,青岛266071 [2]青岛海洋科学与技术国家实验室,青岛266000 [3]武汉大学化学与分子科学学院,生物医学分析化学教育部重点实验室,武汉430072

出　　处：《分析化学》2020年第1期104-112,共9页Chinese Journal of Analytical Chemistry

基　　金：国家重点研发计划项目(No.2017YFC1600705);中国水产科学研究院黄海水产研究所基本科研业务费项目(Nos.20603022016007,20603022017015);国家自然科学基金项目(No.21207162)资助~~

摘　　要：贝类毒素(Shellfish toxins)是重点监控的海洋污染物。本研究通过将辛基功能化离子液体接枝到硅胶表面,制备了一种混合模式的共价键合硅胶材料(Silica-[SOIM][PF 6]),利用红外光谱、核磁共振和元素分析进行了表征。采用自制材料填制固相萃取柱,通过固相萃取-液相色谱-质谱联用(SPE-LC-MS/MS)技术对海水中贝类毒素(大田软海绵酸毒素(OA)、鳍藻毒素-1(DTX-1)和鳍藻毒素-2(DTX-2))进行富集检测。研究发现,此固相萃取材料与目标贝类毒素可能存在疏水作用和离子交换作用等多重相互作用。分别对进样溶液的体积和pH值、淋洗剂和洗脱剂的种类、用量以及pH值范围等因素进行了优化。结果表明,此固相萃取材料对海水中3种贝类毒素具有良好的萃取效果,优于或与商用化萃取材料性能相当,检出限(LOD)为0.01μg/L,定量限(LOQ)为0.05μg/L,在0.02~2.50μg/L范围内线性关系良好(R 2>0.995),回收率在93.0%~116%之间。同时,材料具有良好的重现性,批内和批间的相对标准偏差均小于15%。本方法准确、灵敏、简便、可靠,可用于实际样品中贝类毒素的萃取检测。Shellfish toxins are a kind of important marine pollutant.In this study,a novel ionic liquid bonded silica gel material(silica-[SOIM][PF 6])was prepared by grafting octyl-functionalized ionic liquid onto silica gel,which was characterized and analyzed by infrared spectroscopy(IR),nuclear magnetic resonance(NMR),and elemental analysis.Solid phase extraction cartridge of silica-[SOIM][PF 6],coupled with LC-MS/MS technique was used to extract and determine the concentration of shellfish toxins[Okadaic acid(OA),Dinophysistoxin-1(DTX-1)and Dinophysistoxin-2(DTX-2)]in seawater for the first time.It was found that the solid phase extraction material silica-[SOIM][PF 6]had multiple interactions with the 3 kinds of shellfish toxins,such as hydrophobic and ion-exchange.The method was optimized in aspects of volume and pH of the loaded sample solution,as well as the usage of rinsing and eluting reagents.Results indicated that the silica-[SOIM][PF 6]had good extraction effect on target shellfish toxins in seawater,which was better than or equivalent to the performance of commercial extraction materials.The method had a good linearity(R 2>0.995)in the concentration range of shellfish toxins from 0.02μg/L to 2.50μg/L,with limit of detection(LOD)of 0.01μg/L and limit of quantification(LOQ)of 0.05μg/L.The average recoveries for 3 kinds of shellfish toxins were 93.0%-116.0%at different spiking levels in blank seawater.Simultaneously,the material had good reproducibility,with the relative standard deviation(RSD)of less than 15%intra-and inter-batch.This method was accurate,sensitive,simple and reliable,and could be used for the extraction and detection of shellfish toxins in actual samples.

关 键 词：离子液体 固相萃取 混合模式 贝类毒素 海水 

分 类 号：R28[医药卫生—中药学]