应用介孔分子印迹聚合物萃取粮食中的乙酰甲胺磷
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摘要
以乙酰甲胺磷为模板分子,3-氨基丙基三乙氧基硅烷(APTES)为功能单体,表面活性剂正十二烷胺(DDA)为介孔模板剂,正硅酸乙酯为交联剂,采用溶胶凝胶技术制备乙酰甲胺磷介孔分子印迹聚合物(MIP),并对其进行了表征。Scatchard分析表明,该聚合物对乙酰甲胺磷有两种结合方式,最大表观结合量Q_(max1)=47.03 mg/g,Q_(max2)=90.31 mg/g;平衡解离常数k_(d1)=57.14 mg/L,k_(d2)=188.68 mg/L。吸附动力学测定结果显示,其对乙酰甲胺磷的吸附符合准二级动力学模型;吸附热力学测定结果显示其吸附为放热过程。将该聚合物用于基质固相分散萃取(MSPD)粮食中乙酰甲胺磷,最佳条件为:聚合物与样品的质量比为1∶1,研磨时间为8 min,淋洗剂为乙醇-水(2∶1,体积比),洗脱剂为乙腈-乙酸溶液(19∶1,体积比)。所得洗脱液采用高效液相色谱法检测,测得乙酰甲胺磷的线性范围为0.03～0.3μg/g,检出限为0.015μg/g,回收率为92.5%～97.1%,相对标准偏差为2.9%～3.7%。该方法兼具介孔分子印迹技术的高选择性如和MSPD技术的快速分离性,为乙酰甲胺磷残留分析提供了新思路。
An acephate mesoporous molecularly imprinted polymer(MIP) was prepared by sol-gel technique using acephate as template molecule,3-aminopropyl propyl triethoxysilane(APTES) as functional monomer,surfactant dodecylamine(DDA) as mesoporous template and tetraethoxysilane as coupling agent.And it was characterized.Results of Scatchard analysis showed that there existed two kinds of binding sites.The values of apparent maximum absorption capacity were calculated as follows:Q_(max1)=47.03 mg/g and Q_(max2)=90.31 mg/g,and the dissociation constants:k_(d1)=57.14 mg/L and k_(d2)=188.68 mg/L.The adsorptive dynamics results showed that the adsorption of the polymer toward acephate accorded with quasi-secondary dynamics model.The results of adsorption thermodynamics showed that the adsorption process was exothermic.The prepared polymer was used for matrix solid-phase dispersion(MSPD) extraction of acephate in grains.The optimum experimental conditions were as follows:the ratio of polymer to sample:1 ∶1,grinding time:8 minutes,the washing solvent:ethanol-water(2 ∶1,by volume),the eluent:acetonitrile-acetic acid(19 ∶1,by volume).The final eluent was detected by high performance liquid chromatography,and the calibration curve of acephate was linear in the range of 0.03-0.3 μg/g with a detection limit of 0.015 μg/g.Recoveries for acephate were between 92.5%and 97.1%with relative standard deviations(RSD) of 2.9%-3.7%.With the advantages of high selectivity of mesoporous molecularly imprinting technique and the rapid separation of matrix solid-phase dispersion extraction,this method provides a new idea for the residue analysis of acephate.
An acephate mesoporous molecularly imprinted polymer(MIP) was prepared by sol-gel technique using acephate as template molecule,3-aminopropyl propyl triethoxysilane(APTES) as functional monomer,surfactant dodecylamine(DDA) as mesoporous template and tetraethoxysilane as coupling agent.And it was characterized.Results of Scatchard analysis showed that there existed two kinds of binding sites.The values of apparent maximum absorption capacity were calculated as follows:Q_(max1)=47.03 mg/g and Q_(max2)=90.31 mg/g,and the dissociation constants:k_(d1)=57.14 mg/L and k_(d2)=188.68 mg/L.The adsorptive dynamics results showed that the adsorption of the polymer toward acephate accorded with quasi-secondary dynamics model.The results of adsorption thermodynamics showed that the adsorption process was exothermic.The prepared polymer was used for matrix solid-phase dispersion(MSPD) extraction of acephate in grains.The optimum experimental conditions were as follows:the ratio of polymer to sample:1 ∶1,grinding time:8 minutes,the washing solvent:ethanol-water(2 ∶1,by volume),the eluent:acetonitrile-acetic acid(19 ∶1,by volume).The final eluent was detected by high performance liquid chromatography,and the calibration curve of acephate was linear in the range of 0.03-0.3 μg/g with a detection limit of 0.015 μg/g.Recoveries for acephate were between 92.5%and 97.1%with relative standard deviations(RSD) of 2.9%-3.7%.With the advantages of high selectivity of mesoporous molecularly imprinting technique and the rapid separation of matrix solid-phase dispersion extraction,this method provides a new idea for the residue analysis of acephate.
引文
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[16] GB 14872-94.Maximum Residue Limits of Acephate in Foods.National Standards of the People?s Republic of China(食品中乙酰甲胺磷最大残留限量标准.中华人民共和国国家标准).
[2] Tang Q R,Yan D Y.Pestic.Market Inf.(唐秋荣,严大禹.农药市场信息),2018,15(2):6-10.
[3] He M,Tie B Q,Dai R C,Chen L,Yu P Z.Agrochemicals(贺敏,铁柏清,戴荣彩,陈莉,余平中.农药),2008,47(2):122-124.
[4] Liu L,Yuan M A,Yu B,Ma J Y,Yang D Y.J.Agric.Catastrophol.(刘莉,袁名安,虞冰,马婧妤,杨德毅.农业灾害研究),2015,5(7):11-13.
[5] Wu M,Fan Y J,Gou Y P,Xie L W.Chin.J.Pestic.Sci.(吴茂,范亚军,郭亚平,谢连武.农药学学报),2018,20(6):689-703.
[6] Ma X B.Preparation of Flavonoids and Matrine Molecularly Imprinted Polymers and Their Application in High Efficiency Recognition and Separation of Tibetan Medicines.Lanzhou:Gansu Agricultural University(马兴斌.黄酮类与苦参碱类分子印迹聚合物合成及其在藏药中的高效识别及分离应用研究.兰州:甘肃农业大学),2018.
[7] He M Y,Ye Y F,Liu Y,Li Z Z,Jiao B N,Zeng S M,Su X S.J.Instrum.Anal.(贺美艳,叶玉凤,刘炎,李珍柱,焦必宁,曾绍梅,苏学素.分析测试学报),2017,36(3):325-330.
[8] Dang M.Structure Control and Biomedical Properties of Mesoporous Organic Silica Nanoparticles.Nanjing:Nanjing University of Posts and Telecommunications(党萌.介孔有机氧化硅纳米颗粒结构调控及其生物医学性质研究.南京:南京邮电大学),2018.
[9] Zheng Y.Preparation and Absorption Properties of Molecular Imprinted Materials Based on HMS Mesoporous Materials.Harbin:Harbin Institute of Technology(郑毅.基于介孔材料HMS的分子印迹材料制备及其吸附性能.哈尔滨:哈尔滨工业大学),2010.
[10] Yan S L.Syntheesis,Characterization and Application of Molecularly Imprinted Mesoporous Silica and Restricted Access Materials.Baoding:Hebei University(闫帅磊.分子印迹介孔硅胶材料与限进材料的合成、评价及应用.保定:河北大学),2012.
[11] Zhao H,Huang L H,Fan L.Ion Exch.Adsorpt.(赵华,黄丽华,范磊.离子交换与吸附),2018,34(3):238-246.
[12] Zang S P,Lü Y H,Miao W K,Chen H,Liu G Y,Chen L G.Sci.Technol.Food Ind.(臧顺平,吕云辉,苗文凯,陈浩,刘国一,陈立钢.食品工业科技),2016,37(16):67-75.
[13] Su L Q,Zou X Y,Teng Y.J.Anal.Sci.(苏立强,邹雪莹,滕跃.分析科学学报),2018,34(6):757-761.
[14] Xin J H.Determination of Multi-organophosphate Pesticide Residues in Vegetables through Moleculary Imprinted Solid-phase Extraction Couple to Gas Chromatography.Tai'an:Shandong Agricultural University(辛军红.分子印迹固相萃取与气相色谱联用检测蔬菜中有机磷农药多残留的研究.泰安:山东农业大学),2012.
[15] Chen T,Jiang H,Deng C H,Liu M Z,Chen L G.Sci.Technol.Food Ind.(陈逃,姜涵,邓晨辉,刘孟昭,陈立钢.食品工业科技),2014,35(19):312-315.
[16] GB 14872-94.Maximum Residue Limits of Acephate in Foods.National Standards of the People?s Republic of China(食品中乙酰甲胺磷最大残留限量标准.中华人民共和国国家标准).