以功能化的Fe3O4纳米粒子为磁芯,啶虫脒为模板分子、α-甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,制备了具有特异性识别能力的磁性分子印迹聚合物材料,用于饮用水中啶虫脒的高选择性快速分离。用傅里叶红外光谱、透射电镜、X-射线衍射和振动样品磁强计对材料进行表征,通过等温吸附和动力学吸附实验对材料的吸附性能进行考察。结果表明,磁性分子印迹聚合物在60 min内对啶虫脒达到吸附平衡,且饱和吸附量为43.50 mg/g,吸附过程符合准二级动力学方程(R2=0.993 9)。将聚合物材料作为磁性固相萃取吸附剂,结合高效液相色谱-紫外(high performance liquid chromatography-ultraviolet,HPLC-UV)技术对饮用水中啶虫脒进行检测,啶虫脒在10~800 μg/kg有良好的线性关系,线性相关系数(r)大于0.998 7,啶虫脒的检出限和定量限分别为3.50和10.78 μg/kg,回收率为82.21%~96.20%,相对标准偏差(relative standard deviation,RSD)为1.07%~8.25%(n=6)。与传统方法相比,该方法在外加磁场的作用下即可实现目标物与样品基质的分离,操作简单、绿色经济、选择性高,为复杂基质中痕量啶虫脒残留的分析提供依据。
The magnetic molecularly imprinted polymers (MMIPs) nanoparticles were synthesized using Fe3O4 nanoparticles as the carrier material, acetamiprid as template molecule, methacrylic acid (MAA) as functional monomer and ethylene glycol dimethyl acrylate as a crosslinking agent. The structures of molecularly imprinted polymer were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, X-ray diffraction, and vibrating sample magnetometer. The results showed that the particle size of the material obtained spherical magnetic MIPs was about 320 nm and had good monodispersity. The maximum saturation magnetization of this composite was 3.08 emu/g which was lower than the saturation magnetization Fe3O4 (74.30 emu/g), but it was still sufficient for the requirements of magnetic solid phase extraction (MSPE). The adsorption performance of the material was investigated through isothermal adsorption and kinetic adsorption experiments. Experimental results showed that the fast mass transfer rate (60min) and the maximum adsorption capacity of the magnetic molecularly imprinted microspheres for acetamiprid was 43.50 mg/g. The kinetic experimental data were correlated with the second-order kinetic model (R2＞0.993 9). Using MMIPs as magnetic solid-phase extraction adsorbents, combined with high performance liquid chromatography-ultraviolet detection (HPLC-UV) to detect acetamiprid in water samples. Various parameters such as limits of detection (LOD), limits of quantification (LOQ) were calculated to evaluate the accuracy and accuracy of the method. The method showed good linearity in the range of 10-800 μg/L (r＞0.998 7), LOD and LOQ were 3.50 and 10.78 μg/kg respectively, the recoveries range from 82.21%-96.20% with relative standard deviations (RSD) range of 1.07%-8.25% (n=6). Compared with the traditional method, this method could realize the separation of the target substance and the sample matrix under the action of an external magnetic field. It is simple to operate, green and economical, and has high selectivity. It provides analysis of trace acetamiprid residues in complex matrices.
[1] WATANABE E.Review of sample preparation methods for chromatographic analysis of neonicotinoids in agricultural and environmental matrices:From classical to state-of-the-art methods[J].Journal of Chromatography A,2021,1 643:462042.
[2] ZHANG Y Y,LI G L,WU D,et al.Recent advances in emerging nanomaterials based food sample pretreatment methods for food safety screening[J].TrAC Trends in Analytical Chemistry,2019,121:115669.
[3] 贺艳,邓月华.水环境中新烟碱类农药去除技术研究进展[J].环境化学,2020,39(7):1 963-1 976.
HE Y,DENG Y H.A review on the removal technologies of neonicotinoid pesticides from aquatic environment[J].Environmental Chemistry,2020,39(7):1 963-1 976.
[4] CASTILLO DIAZ J M,MARTIN-LAURENT F,BEGUET J,et al.Fate and effect of imidacloprid on vermicompost-amended soils under dissimilar conditions:Risk for soil functions,structure,and bacterial abundance[J].Science of the Total Environment,2017,579:1 111-1 119.
[5] ATL ŞEKERO$\ddot{G}$LU Z,ŞEKEROĞLU V,UÇGUN E,et al.Cytotoxicity and genotoxicity of clothianidin in human lymphocytes with or without metabolic activation system[J].Drug and Chemical Toxicology,2019,42(4):364-370.
[6] GOLGE O,CINPOLAT S,KABAK B.Quantification of pesticide residues in gherkins by liquid and gas chromatography coupled to tandem mass spectrometry[J].Journal of Food Composition and Analysis,2021,96:103755.
[7] CARBONELL-ROZAS L,LARA F J,DEL O I M,et al.A novel approach based on capillary liquid chromatography for the simultaneous determination of neonicotinoid residues in cereal samples[J].Microchemical Journal,2021,161:1-7.
[8] SAMSIDAR A,SIDDIQUEE S,SHAARANI S M.A review of extraction,analytical and advanced methods for determination of pesticides in environment and foodstuffs[J].Trends in Food Science & Technology,2018,71:188-201.
[9] ZHANG Y,ZHANG Q,LI S,et al.Simultaneous determination of neonicotinoids and fipronils in tea using a modifiedQuEChERS method and liquid chromatography-high resolution mass spectrometry[J].Food Chemistry,2020,329:1-8.
[10] ZHOU W L,YUE M,LIU Q,et al.Measuring urinary concentrations of neonicotinoid insecticides by modified solid-phase extraction-ultrahigh performance liquid chromatography-tandem mass spectrometry:Application to human exposure and risk assessment[J].Chemosphere,2021,273:129714.
[11] KHANEHZAR H,FARAJI M,NEZHADALI A,et al.Combining of modified QuEChERS and dispersive liquid-liquid microextraction as an efficient sample preparation method for extraction of acetamiprid and imidacloprid from pistachio samples[J].Journal of the Iranian Chemical Society,2021,18(3):641-649.
[12] 高强,冯钰锜.磁性微纳米材料的功能化及其在食物样品前处理中的应用进展[J].色谱,2014,32(10):1 043-1 051.
GAO Q,FENG Y Q.Magnetic micro-/nano-materials:Functionalization and their applications in pretreatment for food samples[J].Chinese Journal of Chromatography,2014,32(10):1 043-1 051.
[13] CHEN L X,WANG X Y,LU W H,et al.Molecular imprinting:Perspectives and applications[J].Chemical Society Reviews,2016,45(8):2 137-2 211.
[14] MALIK M I,SHAIKH H,MUSTAFA G,et al.Recent applications of molecularly imprinted polymers in analytical chemistry[J].Separation & Purification Reviews,2019,48(3):179-219.
[15] DINALI L A F,DE OLIVEIRA H L,TEIXEIRA L S,et al.Efficient development of a magnetic molecularly imprinted polymer for selective determination of trimethoprim and sulfamethoxazole in milk[J].Microchemical Journal,2020,154:104648.
[16] XU Y,TANG Y H,ZHAO Y Y,et al.Bifunctional monomer magnetic imprinted nanomaterials for selective separation of tetracyclines directly from milk samples[J].Journal of Colloid and Interface Science,2018,515:18-26.
[17] HE Y Y,WU P,XIAO W,et al.Efficient removal of Pb(II) from aqueous solution by a novel ion imprinted magnetic biosorbent:Adsorption kinetics and mechanisms[J].PLoS One,2019,14(3):e0213377.
[18] CHENG Y,NIE J Y,LIU H D,et al.Synthesis and characterization of magnetic molecularly imprinted polymers for effective extraction and determination of kaempferol from apple samples[J].Journal of Chromatography A,2020,1630:461531.
[19] SUN H,LI Y,YANG J,et al.Preparation of dummy-imprinted polymers by Pickering emulsion polymerization for the selective determination of seven bisphenols from sediment samples[J].Journal of Separation Science,2016,39(11):2 188-2 195.
[20] 陈静钰,黄鑫,王力,等.同时脱除吡虫啉和啶虫脒农残的虚拟模板表面分子印迹的制备和应用[J].食品与发酵工业,2020,46(5):91-97.
CHEN J Y,HUANG X,WANG L,et al.Synthesis of molecularly imprinted polymers of virtual template surface and its application on simultaneously remove imidacloprid and acetamiprid[J].Food and Fermentation Industries,2020,46(5):91-97.
[21] 丁青青,张文敏,张兰.磁性纳米材料在样品前处理中的应用进展与展望[J].色谱,2020,38(1):14-21.
DING Q Q,ZHANG W M,ZHANG L.Advances in magnetic nanomaterials for sample pretreatment and future prospects[J].Chinese Journal of Chromatography,2020,38(1):14-21.
[22] YU Q R,HE C X,LI Q,et al.Fluorometric determination of acetamiprid using molecularly imprinted upconversion nanoparticles[J].Microchimica Acta,2020,187(4):1-10.
[23] KUMAR N,NARAYANAN N,GUPTA S.Application of magnetic molecularly imprinted polymers for extraction of imidacloprid from eggplant and honey[J].Food Chemistry,2018,255:81-88.
[24] ZHANG M,ZHAO H T,YANG X,et al.Preparation and characterization of surface molecularly imprinted film coated on a magnetic nanocore for the fast and selective recognition of the new neonicotinoid insecticidepaichongding (IPP)[J].RSC Advances,2016,6(5):3 714-3 722.
[25] DENG H,LI X L,PENG Q,et al.Monodisperse magnetic single-crystal ferrite microspheres[J].Angewandte Chemie,2005,117(18):2 842-2 845.
[26] FU H,XU W,WANG H X,et al.Preparation of magnetic molecularly imprinted polymer for selective identification of patulin in juice[J].Journal of Chromatography B,2020,1 145:122101.
[27] 陈静钰.表面分子印迹聚合物的制备及其对茶多酚中吡虫啉和啶虫脒脱出的研究[D].无锡:江南大学,2019.
CHEN J Y.Preparation of surface molecularlyimprinted polymer and its application in the removal of imidacloprid and acetamiprid from tea polyphenols[D].Wuxi:Jiangnan University,2019.
