三硝基甲苯分子印迹微球的制备与应用
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摘要
以三硝基甲苯(TNT)为模板分子,丙烯酰胺(AM)为功能单体,采用沉淀聚合法制备分子印迹聚合物MIP。通过紫外光谱法研究TNT和AM之间的相互作用,结果表明TNT与AM之间作用力较强,有助于形成结构稳定、亲和性强的聚合物;利用扫描电镜观测不同制备条件下印迹聚合物的表观形貌,发现乙腈用量为100m L,缓慢的搅拌速率下制备的聚合物形貌较优异;利用红外光谱分析聚合物的结构特征,验证印迹聚合物的制备与模板分子的洗脱;平衡吸附实验表明,MIP对TNT的吸附存在两种作用位点并且吸附量随TNT初始浓度增加而增加;动力学吸附实验发现印迹聚合物对TNT的吸附速率远大于非印迹聚合物;选择性吸附实验中,MIP对TNT表现出较好的特异吸附性能,而对于TNT的结构类似物DNT、RDX吸附能力较差。
The molecularly imprinted polymers(MIP)were prepared by precipitation polymerization method using 2,4,6-trinitrotoluene(TNT)as the template molecule and acrylamide(AM)as the functional monomer. The interaction between TNT and AM was studied by UV spectroscopy. It was found that TNT and AM had a strong force,which could help to form MIP with stable structure and binding ability. The morphologies of the polymers were observed by scanning electron microscopy(SEM). It was found that the polymers prepared with 100 m L acetonitrile under slow stirring were better than others. The equilibrium adsorption experiments showed that there were two kinds of adsorption sites and the adsorption capacity increased with the increase of initial concentration of TNT. Kinetic adsorption experiments showed that the adsorption rate of MIP was much quicker than that of non-imprinted polymers(NIP). Meanwhile,the specific adsorption of MIP was also tested. The results showed that MIP had strong specific adsorption properties to TNT,while the adsorption to the structural analogues of TNT(DNT and RDX)was quite weak.
The molecularly imprinted polymers(MIP)were prepared by precipitation polymerization method using 2,4,6-trinitrotoluene(TNT)as the template molecule and acrylamide(AM)as the functional monomer. The interaction between TNT and AM was studied by UV spectroscopy. It was found that TNT and AM had a strong force,which could help to form MIP with stable structure and binding ability. The morphologies of the polymers were observed by scanning electron microscopy(SEM). It was found that the polymers prepared with 100 m L acetonitrile under slow stirring were better than others. The equilibrium adsorption experiments showed that there were two kinds of adsorption sites and the adsorption capacity increased with the increase of initial concentration of TNT. Kinetic adsorption experiments showed that the adsorption rate of MIP was much quicker than that of non-imprinted polymers(NIP). Meanwhile,the specific adsorption of MIP was also tested. The results showed that MIP had strong specific adsorption properties to TNT,while the adsorption to the structural analogues of TNT(DNT and RDX)was quite weak.
引文
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[19]杨卫海,严守雷,卫晨,等.沉淀聚合法制备三聚氰胺分子印迹聚合物微球[J].高分子学报,2010(10):1163-1169.YANG W H,YAN S L,WEI C,et al.Preparation of melamine molecularly imprinted polymer microspheres by precipitation polymerization[J].Acta Polymerica Sinica,2010(10):1163-1169.
[2]高大明.二氧化硅纳米粒子表面的分子印记识别和TNT的荧光探测[D].合肥:中国科学技术大学,2007.GAO D M.Molecule imprinting recognition and fluorescence detection for TNT at surface of silica[D].Hefei:University of Science and Technology of China,2007.
[3]CHEN L,LI B.Chem Inform abstract:application of magnetic molecularly imprinted polymers in analytical chemistry[J].Chem Inform,2012,43(44):2613-2621.
[4]GIUSEPPE V,DEL S R,LUCIA M,et al.Molecularly imprinted polymers:present and future prospective[J].International Journal of Molecular Sciences,2011,12(9):5908.
[5]LIU F,ZHANG S,WANG G,et al.A novel bifunctional molecularly imprinted polymer for determination of Congo red in food[J].RSC Advances,2015,5(29):22811-22817.
[6]肖淑娟,李红霞,于守武.分子印迹固相萃取法提取花生壳中木犀草素[J].化工进展,2010,29(2):293-296.XIAO S J,LI H X,YU S W.Solid-phase extraction of luteolin from peanut hull using molecular imprinted polymers[J].Chemical Industry and Engineering Progress,2010,29(2):293-296.
[7]OH J K,DRUMRIGHT R,SIEGWART D J,et al.The development of microgels/nanogels for drug delivery applications[J].Progress in Polymer Science,2008,33(4):448-477.
[8]栾崇林,李铭杰,李仲谨,等.分子印迹电化学传感器的研究进展[J].化工进展,2011,30(2):353-358.LUAN C L,LI M J,LI Z J,et al.Progress of molecularly imprinted electrochemical sensor[J].Chemical Industry and Engineering Progress,2011,30(2):353-358.
[9]MURATSUGU S,TADA M.Molecularly imprinted Ru complex catalysts integrated on oxide surfaces[J].Accounts of Chemical Research,2013,46(2):300.
[10]刘建明,李红红,熊振湖.核-壳表面磁性印迹聚合物的制备及其对水中双酚A的特异性去除[J].环境科学,2013,34(6):2240-2248.LIU J M,LI H H,XIONG Z H.Removal of bisphenol a in aqueous solutions by core-shell magnetic molecularly imprinted polymers[J].Environmental Science,2013,34(6):2240-2248.
[11]杜自卫,刘学涌,赵小东.TNT分子印迹聚合物微球的合成与性能研究[J].高分子学报,2010,1(3):360-365.DU Z W,LIU X Y,ZHAO X D.Preparation and properties of TNT imprinted polymer microspheres[J].Acta Polymerica Sinica,2010(3):360-365.
[12]谢成根.纳米结构TNT分子印迹探针及其仿生敏感性能研究[D].合肥:安徽大学,2007.XIE C G.Study on nanostructured TNT-imprinted probes and their biomimetic sensitivity properties[J].Hefei:Anhui University,2007.
[13]PARDESHI S,DHODAPKAR R,KUMAR A.Molecularly imprinted microspheres and nanoparticles prepared using precipitation polymerisation method for selective extraction of gallic acid from Emblica officinalis[J].Food Chemistry,2014,146(1):385-393.
[14]PARDESHI S,SINGH S K.Chem Inform abstract:precipitation polymerization:a versatile tool for preparing molecularly imprinted polymer beads for chromatography applications[J].RSC Advances,2016,47(17):23525-23536.
[15]WANG J F,CORMACK P A G,SHERRINGTON D C,et al.Synthesis and characterization of micrometer-sized molecularly imprinted spherical polymer particulates prepared via precipitation polymerization[J].Pure&Applied Chemistry,2007,79(9):1505-1519.
[16]姚伟,高志贤,房彦军,等.沉淀聚合法制备咖啡因分子印迹聚合物微球[J].化工进展,2007,26(6):869-872.YAO W,GAO Z X,FANG Y J,et al.Study on the synthesis and performance of caffeine molecularly imprinted polymer microspheres via precipitation polymerization[J].Chemical Industry and Engineering Progress,2007,26(6):869-872.
[17]庞思思,王兵.沉淀制备双酚Aπ-π堆积自组装印迹聚合物及其特异性识别机理研究[J].高分子学报,2014(1):49-55.PANG S S,WANG B.Synthesis of bisphenol Aπ-πstacking self-assembly imprinted polymer by precipitation polymerization and study on specificity recognition mechanism[J].Acta Polymerica Sinica,2014(1):49-55.
[18]GAO D,ZHANG Z,WU M,et al.A surface functional monomer-directing strategy for highly dense imprinting of TNT at surface of silica nanoparticles[J].Journal of the American Chemical Society,2007,129(25):7859.
[19]杨卫海,严守雷,卫晨,等.沉淀聚合法制备三聚氰胺分子印迹聚合物微球[J].高分子学报,2010(10):1163-1169.YANG W H,YAN S L,WEI C,et al.Preparation of melamine molecularly imprinted polymer microspheres by precipitation polymerization[J].Acta Polymerica Sinica,2010(10):1163-1169.