磁性亲水亲脂平衡萃取材料辅助基质固相分散萃取-高效液相色谱-串联质谱法同时测定中药材中76种农药残留  

Simultaneous determination of 76 pesticide residues in the traditional Chinese medicine by magnetic hydrophilic-lipophilic-balanced materials assisted matrix solid phase dispersion extraction-high performance liquid chromatography-tandem mass spectrometry

作　　者：魏丹 国明 WEI Dan;GUO Ming(College of Bioscience and Engineering,Hebei University of Economics and Business,Shijiazhuang 050061,China;Zhejiang Chemical Production Quality Inspection Co.,Ltd,Hangzhou 310023,China)

机构地区：[1]河北经贸大学生物科学与工程学院,河北石家庄050061 [2]浙江省化工产品质量检验站有限公司,浙江杭州310023

出　　处：《色谱》2022年第4期313-322,共10页Chinese Journal of Chromatography

基　　金：国家自然科学基金(3210161286);河北省自然科学基金(B2021207002).

摘　　要：建立灵敏、可靠的中药材中农药多残留的检测方法对保证中药材的质量和安全十分重要。制备了磁性亲水亲脂平衡萃取材料Fe_(3)O_(4)@PLS,将其应用于农药多残留的磁性基质固相分散萃取中,并结合高效液相色谱-串联质谱法(HPLC-MS/MS)检测了金银花、菊花和三七块根(干)3种中药材中76种农药残留量。研究通过扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)和X-射线衍射仪(XRD)对磁性萃取材料Fe_(3)O_(4)@PLS进行表面形貌和结构的表征。同时考察了影响磁性基质固相分散萃取效率的主要因素,结果表明,磁性萃取材料Fe_(3)O_(4)@PLS的用量为10 mg、研磨分散吸附时间为5 min、淋洗液为10 mL 20%(v/v)甲醇水溶液、涡旋振荡清洗1 min、以0.5 mL 0.1%(v/v)甲酸乙腈为洗脱剂、涡旋振荡洗脱1 min,76种农药的萃取效果最佳。在实际应用中,76种农药在金银花、菊花、三七块根(干)3种中药材中的萃取回收率别为69.1%~112.2%、67.1%~102.8%和70.1%~105.1%,相对标准偏差分别为2.0%~12.4%、2.1%~13.2%和2.0%~13.5%。该方法利用Fe_(3)O_(4)@PLS良好的磁响应性和亲水亲脂通用吸附特性,可以同时萃取极性农药(如多菌灵等)和非极性农药(如敌瘟磷等),建立了测定中药材中76种农药残留的磁性基质固相分散萃取-高效液相色谱-串联质谱联用的分析方法,具有低消耗、操作简便、灵敏度高等优点,适用于非液态中药材基质中多种类农药残留的检测。Traditional Chinese medicine(TCM)is gaining popularity worldwide,but its quality is often affected by excessive pesticide residues during cultivation and production.A sensitive and reliable method for the simultaneous determination of multi-residue pesticides in TCMs is the key to guarantee the quality and safety of TCMs.In this study,broad-spectrum hydrophilic-lipophilic balanced magnetic adsorbents were prepared for the magnetic matrix solid phase dispersion(MMSPD)extraction of 76 pesticides from three different TCMs before their detection by high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS).Unlike the traditional matrix solid phase dispersion(MSPD),which required tedious SPE column packing,an external magnetic field was employed in our method for magnetic isolation and extraction from TCM samples,followed by grounding adsorption.First,broad-spectrum hydrophilic-lipophilic balanced magnetic adsorbents,Fe_(3)O_(4)@PLS,were successfully fabricated by the swelling polymerization of divinyl benzene(DVB)and N-vinyl pyrrolidone(NVP)on the surface of Fe_(3)O_(4)magnetic particles.The prepared materials were systematically characterized by scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FT-IR),and X-ray diffractometry(XRD)for their morphologies,chemical structure,and crystalline structure.Then,the obtained magnetic particles(Fe_(3)O_(4)@PLS)were applied to MMSPD for the simultaneous extraction and analysis of the 76 pesticides in honeysuckle,chrysanthemum,and pseudo-ginseng root(dry)prior to detection by HPLC-MS/MS.In order to establish the optimal extraction conditions,the key parameters affecting the MMSPD extraction efficiency were optimized,including the amount of magnetic materials Fe_(3)O_(4)@PLS(5,10,12,15,20 mg),volume fractions of methanol in water for matrix purification(0%,5%,10%,20%,25%),grinding adsorption time for dispersion(2,3,4,5,6 min),type(methanol,methanol containing 0.1%(v/v)formic acid,acetonitrile,acetonitrile containing 0.1%(v/v)formic acid)and

关 键 词：高效液相色谱-串联质谱 磁性基质固相分散萃取 磁性亲水亲脂平衡萃取材料 多农药残留 中药材 

分 类 号：O658[理学—分析化学]