二乙基（3-甲基脲）（苯基）甲基磷酸酯（DEP）分子印迹聚合物的制备及其性能评价
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摘要
分子印迹聚合物(MIPs)由于对模板分子具有“记忆”识别功能,具有专一性,且由于制备简单、低造价、稳定性好、可重复使用的优点,它在有机磷农药的残留检测上具有广阔的应用前景。
当前在MIPs的制备和评价技术上存在着模板泄露这一问题。本文通过合成二乙基(3-甲基脲)(苯基)甲基磷酸酯(DEP),以此为假模板采用沉淀聚合法来制备MIPs,考察了其特异吸附性能及作为假模板对结构类似有机磷的保留识别性能。
1、通过Material studio软件进行计算机模拟筛选出了几个较优功能单体和交联剂。
2、在计算机模拟的基础上通过一系列的吸附和核磁实验,选出了一个最优印迹条件:甲基丙烯酸(MAA)为功能单体,交联剂为乙二醇二甲基丙烯酸酯(EDMA),所用比例为DEP:MAA:EDMA=1:9:45,溶剂为三氯甲烷。
3、等温吸附实验表明MIPs对DEP的吸附量大约是空白聚合物(NIPs)的两倍。Scatchard数据拟合发现MIPs主要存在两种不同亲和力的作用位点,高亲和力位点的最大表观结合常数Q_(max_=1.31/μmol/g,离解常数K_d=0.5 mmol/L,低亲和力位点的最大表观结合常数Q_(max)=2.41/μmol/g,离解常数K_d=26 mmol/L。
4、印迹材料对其结构类似物的选择吸附效果表明,与其它的农药分子相比较,含有N-H基团的有机磷小分子农药甲胺磷和乙酰甲胺磷有较好的印迹效果。
5、色谱保留实验表明,在DEP与8种农药(包括6种有机磷农药)中,对含有N-H基团的甲胺磷和乙酰甲胺磷有较大的保留能力。可以为将来更好地将MIPs材料用作液相色谱或固相萃取填料来对含有N-H基团的有机磷农药进行分离和富集提供了很好的理论基础和实践经验,从而提高分析鉴定的准确性。
6、通过物性表征发现MIPs、NIPs都具有良好的热稳定性,分解温度都高于210℃;电镜扫描显示,印迹聚合物呈微球状颗粒,其粒径在1.8 um～2.5 um,可以将此MIPs印迹微球用作高效液相色谱中快速分离的一种吸附材料。
Molecularly-Imprinted Polymers(MIPs) is the material which has the function of remembrance and recognition for template,and it has the merits of simple in preparation, cheaply making,steady in performance and also repeated use.Therefore,MIPs can be widely used in detection the organophosphorus pesticides residues.
Recently,MIPs mostly be synthesized by using the targete molecules as template, and the template can happen leak out of the polymer and interferes in the following analysis.In this paper,by synthesis diethyl(3-methylureido)(phenyl) methylphosphonate(DEP),we prapared the MIPs by precipitation polymerization using DEP as dummy template to study it's specific affinity and also the ability to recognize a series of pesticides,which are the structural analogues of DEP and mostly belong to organophosphorus pesticides.
1、Based on the computer simulation and by doing series NMR and adsorb experiments,we selected a best imprinting condition:DEP as dummy template, methacrylic acid(MAA),ethyleneglycol dimethacrylate(EDMA) and chloroform as functional monomer,cross-linker and porogen,respectively,and the ratios of the DEP:MAA:EDMA=1:9:45.
2、Equilibrium rebinding experiments indicated that the adsorption capacity of MIPs for DEP is two times of control polymer(NIPs).Scatchard plot of analysis revealed that there was two classes binding sites populated in the imprinted polymer with dissociation constants of 0.5mmol/L for high affinity sites and 26 mmol/L for low affinity sites,an apparent maximum binding constant of 1.31μmol/g for high affinity sites and 2.41μmol/g for low affinity sites.
3、Binding selectivity shows that MIPs exhibited better selectivity and recognizability for methamidophos and orthene which contain N-H group compared with other pesticides.
4、Liquid chromatographic analysis of the DEP and eight pesticides(including six organophosphorus pesticides) indicated that MIPs showed better reserved capability for methamidophos and orthene which contain N-H group compared with other pesticides.It is hoped that such MIPs material would be used as stuff being packed in liquid chromatographic column and solid phase extrated column.And it will improve the veracity of test results.
5、The thermal properties were studied by TG and their thermal decomposition temperatures were above 210℃;The SEM showed that the MIPs are microspheres and the diameters are about 1.8um～2.5um which may be used as affinity material for high speed separation in HPLC.
当前在MIPs的制备和评价技术上存在着模板泄露这一问题。本文通过合成二乙基(3-甲基脲)(苯基)甲基磷酸酯(DEP),以此为假模板采用沉淀聚合法来制备MIPs,考察了其特异吸附性能及作为假模板对结构类似有机磷的保留识别性能。
1、通过Material studio软件进行计算机模拟筛选出了几个较优功能单体和交联剂。
2、在计算机模拟的基础上通过一系列的吸附和核磁实验,选出了一个最优印迹条件:甲基丙烯酸(MAA)为功能单体,交联剂为乙二醇二甲基丙烯酸酯(EDMA),所用比例为DEP:MAA:EDMA=1:9:45,溶剂为三氯甲烷。
3、等温吸附实验表明MIPs对DEP的吸附量大约是空白聚合物(NIPs)的两倍。Scatchard数据拟合发现MIPs主要存在两种不同亲和力的作用位点,高亲和力位点的最大表观结合常数Q_(max_=1.31/μmol/g,离解常数K_d=0.5 mmol/L,低亲和力位点的最大表观结合常数Q_(max)=2.41/μmol/g,离解常数K_d=26 mmol/L。
4、印迹材料对其结构类似物的选择吸附效果表明,与其它的农药分子相比较,含有N-H基团的有机磷小分子农药甲胺磷和乙酰甲胺磷有较好的印迹效果。
5、色谱保留实验表明,在DEP与8种农药(包括6种有机磷农药)中,对含有N-H基团的甲胺磷和乙酰甲胺磷有较大的保留能力。可以为将来更好地将MIPs材料用作液相色谱或固相萃取填料来对含有N-H基团的有机磷农药进行分离和富集提供了很好的理论基础和实践经验,从而提高分析鉴定的准确性。
6、通过物性表征发现MIPs、NIPs都具有良好的热稳定性,分解温度都高于210℃;电镜扫描显示,印迹聚合物呈微球状颗粒,其粒径在1.8 um～2.5 um,可以将此MIPs印迹微球用作高效液相色谱中快速分离的一种吸附材料。
Molecularly-Imprinted Polymers(MIPs) is the material which has the function of remembrance and recognition for template,and it has the merits of simple in preparation, cheaply making,steady in performance and also repeated use.Therefore,MIPs can be widely used in detection the organophosphorus pesticides residues.
Recently,MIPs mostly be synthesized by using the targete molecules as template, and the template can happen leak out of the polymer and interferes in the following analysis.In this paper,by synthesis diethyl(3-methylureido)(phenyl) methylphosphonate(DEP),we prapared the MIPs by precipitation polymerization using DEP as dummy template to study it's specific affinity and also the ability to recognize a series of pesticides,which are the structural analogues of DEP and mostly belong to organophosphorus pesticides.
1、Based on the computer simulation and by doing series NMR and adsorb experiments,we selected a best imprinting condition:DEP as dummy template, methacrylic acid(MAA),ethyleneglycol dimethacrylate(EDMA) and chloroform as functional monomer,cross-linker and porogen,respectively,and the ratios of the DEP:MAA:EDMA=1:9:45.
2、Equilibrium rebinding experiments indicated that the adsorption capacity of MIPs for DEP is two times of control polymer(NIPs).Scatchard plot of analysis revealed that there was two classes binding sites populated in the imprinted polymer with dissociation constants of 0.5mmol/L for high affinity sites and 26 mmol/L for low affinity sites,an apparent maximum binding constant of 1.31μmol/g for high affinity sites and 2.41μmol/g for low affinity sites.
3、Binding selectivity shows that MIPs exhibited better selectivity and recognizability for methamidophos and orthene which contain N-H group compared with other pesticides.
4、Liquid chromatographic analysis of the DEP and eight pesticides(including six organophosphorus pesticides) indicated that MIPs showed better reserved capability for methamidophos and orthene which contain N-H group compared with other pesticides.It is hoped that such MIPs material would be used as stuff being packed in liquid chromatographic column and solid phase extrated column.And it will improve the veracity of test results.
5、The thermal properties were studied by TG and their thermal decomposition temperatures were above 210℃;The SEM showed that the MIPs are microspheres and the diameters are about 1.8um～2.5um which may be used as affinity material for high speed separation in HPLC.
引文
[1].马玉哲,张俊杰,李红霞,分子印迹聚合物的合成进展.河北理工大学学报,2008,30(4):96-99.
[2].王丽.高效液相色谱法测定大豆中的维生素E含量及其与粗脂肪含量的线性回归分析.大豆科学,2006,25(2):113-117.
[3].王宁,董襄朝,张学炜,吕宪禹,侯剑峰,范志金.单嘧磺隆除草剂分子印迹聚合物的识别特性研究.分析测试学报,2004,23(4):13-17.
[4].王加多,胡祥娜,周向阳,等.蔬菜农药残留快速检测技术-胆碱酯酶速测卡法.食品科学,2003,24(6):109-113.
[5].刘敏敏.分子印迹聚合物的分子设计及优化.河北化工,2008,31(7):20-22.
[6].刘俊秋,罗贵民.分子印迹聚合物及其应用.功能高分子学报,1998,11(4):561-565.
[7].刘亚强,王大伟,李先文.现代化学概论.陕西师范大学出版社,2001,11:91.
[8].刘和清,汪风珍,袁天佑,等.聚硅酸锌絮凝剂的电镜特征和絮凝效果[J].环境化学,2001,20(2):179-185.
[9].朱晓兰,杨俊,苏庆德,蔡继宝,高芸.久效磷分子印迹聚合物分子识别特性的光谱研究,光谱学与光谱分析,2006,26(10):1817-1820.
[10].张学炜,孙慧,董襄朝,吕宪禹.分子印迹技术及其应用研究进展.天津农学院学报,2002,9(3):23-28.
[11].张立永,成国祥,陆书来.悬浮法制备西咪替丁印迹聚合物微球的分子选择性.分析化学,2003,31(6):655-658.
[12].张秋越,孟子晖,肖小兵,倪伟,周智明,吴玉凯,温鸿亮.用分子烙印聚合物吸附溶液中的TNT.火炸药学报,2007,30(1):64-66.
[13].余建新,吴采樱.生物标志物用于污染物的快速检测及毒性评价.分析化学,2002,30(1):107-113.
[14].孟子晖,张秋越,陈小平,周智明,吴玉凯,温宏量.分子烙印固相萃取技术在环境样品分析中的应用.分析化学,2006,24(6):551-554.
[15].孟子晖,周永新,冯建林,刘荫棠,怀榴红,阮金秀.分子烙印聚合物吸附有机磷毒剂的研究.分析化学,2000,28(4):432-435.
[16].姚伟,高志贤,房彦军,程义勇.沉淀聚合法制备咖啡因分子印迹聚合物微球.化工进展,2007,26(6):869-877.
[17].高志刚,周杰,曲详金.植物激素吲哚酸分子模板聚合物的分子识别特性.分析化学,2003,31(10):1173-1177.
[18].凌云,马明科,陈万义,a-(3-莰-2'-基脲基)苄基膦酸酯的合成及生物活性.农药学学报,2002,4(2):29-34.
[19].徐磊,韩泾鸿,梁卫国.光寻址电位式传感器在有机磷检测上得应用.传感器技术,2003,22(10):42-44.
[20].黄智明.转入HPT1基因的油菜种子中维生素E含量的提高.植物生理学通讯,2006,42(5):888-890.
[21].黄梓平,王建宁.鲁米诺过氧化氢体系对敌敌畏得检测分析.农药,2002,43(9):19-21.
[22].赖家平,何锡文,郭洪声,梁宏.分子印迹技术的回顾、现状与展望.分析化学,2001,29(7):836-844.
[23].游静,劳文剑,黄悯嘉.分子烙印聚合物作为超临界流体萃取后处理用固体吸附剂.分析化学,2002,30(5):518-521.
[24].樊明涛.维生素E测定方法的研究进展.江苏大学学报,2002,23(1):53-57.
[25].潘元海,金军,蒋可.高效液相色谱P大气压化学电离质谱快速分析水中痕量有机磷农药.分析化学.2000,28(6):666-671.
[26].Axel Scebach,Andreas Seidel-Morgenstero.Enantioseparation on molecularly imprinted monoliths-Preparation and adsorption isotherms[J].Analytica Chimica Acta,2007,591(1):57-62.
[27].Dickey F.H.A new stategyforthe generation of catalytic antibodies[J].Proc.Natl.Acad.Sci.USA.1949,35:227-229.
[28].Dhal P K,Arnold F H.Template-mediated synthesis of metal-complexing polymers for molecular recognition J.Am.Chem.Soc,1991,113(19):7417-7418.
[29].Esther T,Antonio M.E,Pilar F,et al.Molecular recognition in a propazine-imprinted polymer and its application to the determination of triazines in environmental samples.Anal Chem,2001,73(21):5133-5141.
[30].Fujii Y,Matsutani K,Kikuchi K.J.Formation of a Specific Co-ordination Cavity for a Chiral Amino Acid by Template Synthesis of a Polymer Schiff Base Cobalt(ⅲ) Complex.Chem.Soc,Chem.Common,1985,7:415-417.
[31].Gang Chen,Jianhua Li,Song QIl,et al.Low temperature bonding of poly (methylmethacrylate)electrophorcsis micrechips by in aim polymerization[J].Journal of Chromatography A,2005,1094(1-2):138-147.
[32].Jenkins AL,Yin R,Jensen JL.Molecularly imprinted polymer sensors for pesticide and insecticide detection in water.Analyst,2001,126:798-802.
[33].Kempe M.,Mosbach K.,Ficher L.Chiral separation using molecularing imprinted heteroaromatic polymers.J Mol Recognit,1993,6(1):25-29.
[34].Keiichi Yoshimatsu,Kristina Reimhult,Anatol Krozer,Klaus Mosbacha,Koji Sode,Lei Ye.Uniform molecularly imprinted microspheres and nanoparticles prepared by precipitation polymerization:The control of particle size suitable for different analytical applications.Analytica Chimica Acta,2007,584:112-121.
[35].Kuo-Chuan Ho,Wei-Ming Yeh,Tsai-Shih Tung,Jung-Yu Liao,Amperometric detection of morphine based on poly(3,4-ethylenedioxythiophene) immobilized molecularly imprinted polymer particles prepared by precipitation polymerization.Analytica Chimica Acta,2005,542:90-96.
[36].Kawaguchi M,Hayatsu Y,Nakata H,et al.Molecularly imprinted solid phase extraction using stable isotope labeled compounds as template and liquid chromatography-mass spectrometryfor trace analysis of bisphenol A in water sample.Analytica Chimica Acta,2005,539:83-89.
[37].Lin J M,Nakagama T,Uchiyama K,Hobo T.Temperature Effect on Chiral Recognition of Some Amino Acids with Molecularly Imprinted Polymer Filled Capillary Electrochromatography Biomed.Chromatogy,1997,11(5):298-302.
[38].MosbachK,ViatakisG,MullerR,et al.Drug assay using antibody mimics made by molecular imprinting[J].Nature,1993,361:645-647.
[39].Matsui J,Doblhoff-Dier O,Takeuchi T.2-(Trifluoromethyl) acrylic acid:a novel functional monomer in non-covalent molecular imprinting.Anal Chim Acta,1997,343(12):1-4.
[40].Milojkovic S.S.,Kostoski D,Comor J.J.Radiation induced synthesis of molecularly imprinted polymers.Polymer,1997,38(11):2853-2855.
[41].Malitesta C,Losiuto I,Zambonin P.G.Molecularly imprinted electrosynthesized polymers:New materials for biomimetic sensors.Anal Chem,1999,71(7):1366-1370.
[42] .Marx S, Zaltsman A, Turyan I, et al. Parathion sensor based on molecularly imprinted sol-gel films [J] .Anal Chem, 2004, 76:120-126.
[43].Mark S, Williams D H. The cost of conformational order: entropy changes in molecular associations. J. Am. Chem. Soc, 1992,114(27): 10690-10697.
[44].Mark S, Williams D H. Ute Gerhard Partitioning of free energy contributions in the estimation of binding constants: residual motions and consequences for amide-amide hydrogen bond strengths. J.Am. Chem. Soc, 1992,114(27): 10697-10704.
[45].Mallat E, Barcelo D, Barzen C, et al. Immonosensors for pesticide determination in natural waters. Trends Anal Chem, 2001, 20 (3) : 1242-1247.
[46].Matsui J, Miyoshi Y, Doblhoff-Dier O, Takerchi T. A molecularly imprinted synthetic polymer receptor selective for atrazine. Anal .Chem, 1995, 67: 4404-4408.
[47].Mayes A. G, Mobach K, molecular imprinted polymer beads: suspension polymerization using a liquid perfluorocarbon as the dispersing phase.Anal. Chem, 1996, 68: 3769-3774.
[48].Matsui J, Doblhoff-Dier O, Takeuchi T. 2-(Trifluoromethyl)acrylic acid: a novel functional monomer in non-covalent molecular imprinting.Anal Chim Acta, 1997, 343(1): 1-9.
[49].Nicholls I A. Thermodynamic Considerations for the Design of and Ligand Recognition by Molecularly Imprinted Polymers. Chem. Lett, 1995,11:1035-1036.
[50].Naka K, Kaetsu I, Yamamoto Y. Preparation of microphere by radiation-induced polymerization. I. Mechanism for the formation of monodisperse poly (diethylene glycol dimethacrylate) miceosphere.J Polym Sci, Part A: Polym Chem, 1991, 29(6): 1197-1202.
[51].Pauling, L. Am J. Chem.Soc. A Theory of the Structure and Process of Formation of Antibodies.Am. Chem. Soc, 1940, 62: 26-43.
[52].Panling L. Drug assay using antibedy mimics made by molecular imprinting [J]. Am. Chem. Soc, 1940, 62: 2643-2657.
[53].Sellergren B, Andersson L. Molecular recognition in macroporous polymer prepared by a substrate analogue imprinting strategy.J Org Chem, 1990, 55: 3381-3383.
[54].Sellergren B, Shea KJ. J. Chromatogr Correlation between solute retention and a theoreticalion-exchange model using imprinted polymers. J Org Chem. 1993, 654: 17-28.
[55].Sellergren B, Ekberg B, Mosbach K. J. Demonstration of substrate and enantio-selectivity by chromatographic resolution of racemic mixtures of amino. Chromatogr, 1985, 347: 1-10.
[56].Sellergren B, Shea KJ. Origin of peak asymmetry and the effect of temperature on solute retention in enantiomer separations on imprinted chiral stationary phases. J. Chromatogr, 1995, 690: 29-39.
[57].Sajonz P, Kele M, Zhong GM, Sellergren B, Guiochon G. Study of the thermodynamics and mass transfer kinetics of two enantiomers on a polymeric imprinted stationary phase . J. Chromatogr. A, 1998, 810: 1-17.
[58] .Sellergren B, Dauwe C, Schneider T. Self-diffusivity in block copolymer solutions.2.A_2B simple grafts. Macromolecules, 1997, 30(8): 2454-2459.
[59].Schweitz L, Andersson L. I, Nilsson S. Capillary electrochromatography with molecular imprint-based selectivity for enantiomer separation of local anaesthetics. J. Chromatogr A., 1997, 792(1): 401-409.
[60].Schweitz L, Andersson L. I, Nilsson S. Molecular imprint-based stationary phases for capillary electrochromatography. J. Chromatogr A, 1998, 87(1): 5-13.
[61].Tanabe, K, Takeuchi, T, matsui, J, et al. Recognition of Barbiturates in Molecularly Imprinted Copolymers using Multiple Hydrogen Bonding . J. Chem.soc.Chem. Commun. 1995, 2303.
[62].Wulff, Sarhan A. Enzyme-Analogue Built Polymers and Their Use for The Resolution of Racemates [J]. Tetrahedron Lett, 1973, 4329-4332.
[63].Whitombe M. J, Rodriguez M. E, Vulfson E. N. A new method for introduction of recognition site functionality into polymers prepared by polymer imprinting synthesis and characterization of polymeric receptors for cholesterol. J Am Chem Soc, 1995, 117: 7105 -7111.
[64] .Wang Chenghuang, Li Chunya, Xu Xiuling, Li Ting, Wang Changfa. Electrochemical Investigation of Parathion Imprinted Sensor and Its Application. Chinese Journal of Applied Chemistry, 2006. 23(4): 404-408.
[65].Wulff G. Molecular Recognition in Polymers Prepared by Imprinting with Template .ACS Sympo sium Series, 1986, 308: 1862-1869.
[66].Yiguang, Tan, Zhiling Zhou, Peng wang. A study of a bio-mimetic recognition material for the BAW sensor by molecular imprinting and its application for the determination of paracetamol in the human serum and urine. Talanta, 2001, 55: 337.
[67].Yoshida M, Uezu K, Nakashio F. Spacer effect of novel bifunctional organophosphorus monomers in metal-imprinted polymers prepared by surface template polymerization. Journal of Polymer Science Part a-Polymer Chemistry, 1998, 36(15): 2727-2734.
[68].Yan Shoulei, Gao Zhixian, Fang Yanjun, Preparation and affinity assessment of monocrotophos moleculary imprinted polymers.Acta Polymerica Sinica, 2006(1): 160-163.
[69].Zhu QZ, Haupt K, Knopp D, et al. Molecularly imprinted polymer formet sulfuron2methyl and its binding charaterictics for sulfonylurea herbicides. Anal Chim Acta, 2002, 468: 217-227.
[2].王丽.高效液相色谱法测定大豆中的维生素E含量及其与粗脂肪含量的线性回归分析.大豆科学,2006,25(2):113-117.
[3].王宁,董襄朝,张学炜,吕宪禹,侯剑峰,范志金.单嘧磺隆除草剂分子印迹聚合物的识别特性研究.分析测试学报,2004,23(4):13-17.
[4].王加多,胡祥娜,周向阳,等.蔬菜农药残留快速检测技术-胆碱酯酶速测卡法.食品科学,2003,24(6):109-113.
[5].刘敏敏.分子印迹聚合物的分子设计及优化.河北化工,2008,31(7):20-22.
[6].刘俊秋,罗贵民.分子印迹聚合物及其应用.功能高分子学报,1998,11(4):561-565.
[7].刘亚强,王大伟,李先文.现代化学概论.陕西师范大学出版社,2001,11:91.
[8].刘和清,汪风珍,袁天佑,等.聚硅酸锌絮凝剂的电镜特征和絮凝效果[J].环境化学,2001,20(2):179-185.
[9].朱晓兰,杨俊,苏庆德,蔡继宝,高芸.久效磷分子印迹聚合物分子识别特性的光谱研究,光谱学与光谱分析,2006,26(10):1817-1820.
[10].张学炜,孙慧,董襄朝,吕宪禹.分子印迹技术及其应用研究进展.天津农学院学报,2002,9(3):23-28.
[11].张立永,成国祥,陆书来.悬浮法制备西咪替丁印迹聚合物微球的分子选择性.分析化学,2003,31(6):655-658.
[12].张秋越,孟子晖,肖小兵,倪伟,周智明,吴玉凯,温鸿亮.用分子烙印聚合物吸附溶液中的TNT.火炸药学报,2007,30(1):64-66.
[13].余建新,吴采樱.生物标志物用于污染物的快速检测及毒性评价.分析化学,2002,30(1):107-113.
[14].孟子晖,张秋越,陈小平,周智明,吴玉凯,温宏量.分子烙印固相萃取技术在环境样品分析中的应用.分析化学,2006,24(6):551-554.
[15].孟子晖,周永新,冯建林,刘荫棠,怀榴红,阮金秀.分子烙印聚合物吸附有机磷毒剂的研究.分析化学,2000,28(4):432-435.
[16].姚伟,高志贤,房彦军,程义勇.沉淀聚合法制备咖啡因分子印迹聚合物微球.化工进展,2007,26(6):869-877.
[17].高志刚,周杰,曲详金.植物激素吲哚酸分子模板聚合物的分子识别特性.分析化学,2003,31(10):1173-1177.
[18].凌云,马明科,陈万义,a-(3-莰-2'-基脲基)苄基膦酸酯的合成及生物活性.农药学学报,2002,4(2):29-34.
[19].徐磊,韩泾鸿,梁卫国.光寻址电位式传感器在有机磷检测上得应用.传感器技术,2003,22(10):42-44.
[20].黄智明.转入HPT1基因的油菜种子中维生素E含量的提高.植物生理学通讯,2006,42(5):888-890.
[21].黄梓平,王建宁.鲁米诺过氧化氢体系对敌敌畏得检测分析.农药,2002,43(9):19-21.
[22].赖家平,何锡文,郭洪声,梁宏.分子印迹技术的回顾、现状与展望.分析化学,2001,29(7):836-844.
[23].游静,劳文剑,黄悯嘉.分子烙印聚合物作为超临界流体萃取后处理用固体吸附剂.分析化学,2002,30(5):518-521.
[24].樊明涛.维生素E测定方法的研究进展.江苏大学学报,2002,23(1):53-57.
[25].潘元海,金军,蒋可.高效液相色谱P大气压化学电离质谱快速分析水中痕量有机磷农药.分析化学.2000,28(6):666-671.
[26].Axel Scebach,Andreas Seidel-Morgenstero.Enantioseparation on molecularly imprinted monoliths-Preparation and adsorption isotherms[J].Analytica Chimica Acta,2007,591(1):57-62.
[27].Dickey F.H.A new stategyforthe generation of catalytic antibodies[J].Proc.Natl.Acad.Sci.USA.1949,35:227-229.
[28].Dhal P K,Arnold F H.Template-mediated synthesis of metal-complexing polymers for molecular recognition J.Am.Chem.Soc,1991,113(19):7417-7418.
[29].Esther T,Antonio M.E,Pilar F,et al.Molecular recognition in a propazine-imprinted polymer and its application to the determination of triazines in environmental samples.Anal Chem,2001,73(21):5133-5141.
[30].Fujii Y,Matsutani K,Kikuchi K.J.Formation of a Specific Co-ordination Cavity for a Chiral Amino Acid by Template Synthesis of a Polymer Schiff Base Cobalt(ⅲ) Complex.Chem.Soc,Chem.Common,1985,7:415-417.
[31].Gang Chen,Jianhua Li,Song QIl,et al.Low temperature bonding of poly (methylmethacrylate)electrophorcsis micrechips by in aim polymerization[J].Journal of Chromatography A,2005,1094(1-2):138-147.
[32].Jenkins AL,Yin R,Jensen JL.Molecularly imprinted polymer sensors for pesticide and insecticide detection in water.Analyst,2001,126:798-802.
[33].Kempe M.,Mosbach K.,Ficher L.Chiral separation using molecularing imprinted heteroaromatic polymers.J Mol Recognit,1993,6(1):25-29.
[34].Keiichi Yoshimatsu,Kristina Reimhult,Anatol Krozer,Klaus Mosbacha,Koji Sode,Lei Ye.Uniform molecularly imprinted microspheres and nanoparticles prepared by precipitation polymerization:The control of particle size suitable for different analytical applications.Analytica Chimica Acta,2007,584:112-121.
[35].Kuo-Chuan Ho,Wei-Ming Yeh,Tsai-Shih Tung,Jung-Yu Liao,Amperometric detection of morphine based on poly(3,4-ethylenedioxythiophene) immobilized molecularly imprinted polymer particles prepared by precipitation polymerization.Analytica Chimica Acta,2005,542:90-96.
[36].Kawaguchi M,Hayatsu Y,Nakata H,et al.Molecularly imprinted solid phase extraction using stable isotope labeled compounds as template and liquid chromatography-mass spectrometryfor trace analysis of bisphenol A in water sample.Analytica Chimica Acta,2005,539:83-89.
[37].Lin J M,Nakagama T,Uchiyama K,Hobo T.Temperature Effect on Chiral Recognition of Some Amino Acids with Molecularly Imprinted Polymer Filled Capillary Electrochromatography Biomed.Chromatogy,1997,11(5):298-302.
[38].MosbachK,ViatakisG,MullerR,et al.Drug assay using antibody mimics made by molecular imprinting[J].Nature,1993,361:645-647.
[39].Matsui J,Doblhoff-Dier O,Takeuchi T.2-(Trifluoromethyl) acrylic acid:a novel functional monomer in non-covalent molecular imprinting.Anal Chim Acta,1997,343(12):1-4.
[40].Milojkovic S.S.,Kostoski D,Comor J.J.Radiation induced synthesis of molecularly imprinted polymers.Polymer,1997,38(11):2853-2855.
[41].Malitesta C,Losiuto I,Zambonin P.G.Molecularly imprinted electrosynthesized polymers:New materials for biomimetic sensors.Anal Chem,1999,71(7):1366-1370.
[42] .Marx S, Zaltsman A, Turyan I, et al. Parathion sensor based on molecularly imprinted sol-gel films [J] .Anal Chem, 2004, 76:120-126.
[43].Mark S, Williams D H. The cost of conformational order: entropy changes in molecular associations. J. Am. Chem. Soc, 1992,114(27): 10690-10697.
[44].Mark S, Williams D H. Ute Gerhard Partitioning of free energy contributions in the estimation of binding constants: residual motions and consequences for amide-amide hydrogen bond strengths. J.Am. Chem. Soc, 1992,114(27): 10697-10704.
[45].Mallat E, Barcelo D, Barzen C, et al. Immonosensors for pesticide determination in natural waters. Trends Anal Chem, 2001, 20 (3) : 1242-1247.
[46].Matsui J, Miyoshi Y, Doblhoff-Dier O, Takerchi T. A molecularly imprinted synthetic polymer receptor selective for atrazine. Anal .Chem, 1995, 67: 4404-4408.
[47].Mayes A. G, Mobach K, molecular imprinted polymer beads: suspension polymerization using a liquid perfluorocarbon as the dispersing phase.Anal. Chem, 1996, 68: 3769-3774.
[48].Matsui J, Doblhoff-Dier O, Takeuchi T. 2-(Trifluoromethyl)acrylic acid: a novel functional monomer in non-covalent molecular imprinting.Anal Chim Acta, 1997, 343(1): 1-9.
[49].Nicholls I A. Thermodynamic Considerations for the Design of and Ligand Recognition by Molecularly Imprinted Polymers. Chem. Lett, 1995,11:1035-1036.
[50].Naka K, Kaetsu I, Yamamoto Y. Preparation of microphere by radiation-induced polymerization. I. Mechanism for the formation of monodisperse poly (diethylene glycol dimethacrylate) miceosphere.J Polym Sci, Part A: Polym Chem, 1991, 29(6): 1197-1202.
[51].Pauling, L. Am J. Chem.Soc. A Theory of the Structure and Process of Formation of Antibodies.Am. Chem. Soc, 1940, 62: 26-43.
[52].Panling L. Drug assay using antibedy mimics made by molecular imprinting [J]. Am. Chem. Soc, 1940, 62: 2643-2657.
[53].Sellergren B, Andersson L. Molecular recognition in macroporous polymer prepared by a substrate analogue imprinting strategy.J Org Chem, 1990, 55: 3381-3383.
[54].Sellergren B, Shea KJ. J. Chromatogr Correlation between solute retention and a theoreticalion-exchange model using imprinted polymers. J Org Chem. 1993, 654: 17-28.
[55].Sellergren B, Ekberg B, Mosbach K. J. Demonstration of substrate and enantio-selectivity by chromatographic resolution of racemic mixtures of amino. Chromatogr, 1985, 347: 1-10.
[56].Sellergren B, Shea KJ. Origin of peak asymmetry and the effect of temperature on solute retention in enantiomer separations on imprinted chiral stationary phases. J. Chromatogr, 1995, 690: 29-39.
[57].Sajonz P, Kele M, Zhong GM, Sellergren B, Guiochon G. Study of the thermodynamics and mass transfer kinetics of two enantiomers on a polymeric imprinted stationary phase . J. Chromatogr. A, 1998, 810: 1-17.
[58] .Sellergren B, Dauwe C, Schneider T. Self-diffusivity in block copolymer solutions.2.A_2B simple grafts. Macromolecules, 1997, 30(8): 2454-2459.
[59].Schweitz L, Andersson L. I, Nilsson S. Capillary electrochromatography with molecular imprint-based selectivity for enantiomer separation of local anaesthetics. J. Chromatogr A., 1997, 792(1): 401-409.
[60].Schweitz L, Andersson L. I, Nilsson S. Molecular imprint-based stationary phases for capillary electrochromatography. J. Chromatogr A, 1998, 87(1): 5-13.
[61].Tanabe, K, Takeuchi, T, matsui, J, et al. Recognition of Barbiturates in Molecularly Imprinted Copolymers using Multiple Hydrogen Bonding . J. Chem.soc.Chem. Commun. 1995, 2303.
[62].Wulff, Sarhan A. Enzyme-Analogue Built Polymers and Their Use for The Resolution of Racemates [J]. Tetrahedron Lett, 1973, 4329-4332.
[63].Whitombe M. J, Rodriguez M. E, Vulfson E. N. A new method for introduction of recognition site functionality into polymers prepared by polymer imprinting synthesis and characterization of polymeric receptors for cholesterol. J Am Chem Soc, 1995, 117: 7105 -7111.
[64] .Wang Chenghuang, Li Chunya, Xu Xiuling, Li Ting, Wang Changfa. Electrochemical Investigation of Parathion Imprinted Sensor and Its Application. Chinese Journal of Applied Chemistry, 2006. 23(4): 404-408.
[65].Wulff G. Molecular Recognition in Polymers Prepared by Imprinting with Template .ACS Sympo sium Series, 1986, 308: 1862-1869.
[66].Yiguang, Tan, Zhiling Zhou, Peng wang. A study of a bio-mimetic recognition material for the BAW sensor by molecular imprinting and its application for the determination of paracetamol in the human serum and urine. Talanta, 2001, 55: 337.
[67].Yoshida M, Uezu K, Nakashio F. Spacer effect of novel bifunctional organophosphorus monomers in metal-imprinted polymers prepared by surface template polymerization. Journal of Polymer Science Part a-Polymer Chemistry, 1998, 36(15): 2727-2734.
[68].Yan Shoulei, Gao Zhixian, Fang Yanjun, Preparation and affinity assessment of monocrotophos moleculary imprinted polymers.Acta Polymerica Sinica, 2006(1): 160-163.
[69].Zhu QZ, Haupt K, Knopp D, et al. Molecularly imprinted polymer formet sulfuron2methyl and its binding charaterictics for sulfonylurea herbicides. Anal Chim Acta, 2002, 468: 217-227.