分子印迹聚合物应用研究进展

综述了分子印迹技术的基本原理及其在分析传感技术领域和其它应用领域的最新进展,分析了分子印迹技术存在的问题,并指出了该技术的产业化潜力。     

分子印迹技术及其在痕量分析的应用

分子印迹技术是近年来集高分子合成、分子设计、分子识别、仿生生物工程等众多学科优势发展起来的一门边缘学科分支，分子印迹聚合物由于具有与天然抗体同样的识别性能力和与高分子同样的抗腐蚀性能的双重优点，因而广泛应用于生物工程、临床医学、环境监测、食品工业等众多领域．介绍了分子印迹技术的基本原理，对分子印迹聚合物合成研究的最新进展进行了综述，主要介绍了它在痕量分析中的应用．     

淫羊藿苷分子印迹聚合物吸附性能研究

以沉淀聚合法制备了淫羊藿苷分子印迹聚合物(MIPs).并用动态吸附、静态吸附和选择性吸附实验研究了制备的分子印迹聚合物对模板分子淫羊藿苷的吸附性能.结果表明制备的淫羊藿苷分子印迹聚合物对模板分子淫羊藿苷具有较好的吸附能力和识别能力,可以作为固相萃取材料来分离提取中草药淫羊藿中的淫羊藿苷.     

原儿茶酸分子印迹聚合物的色谱识别性能

应用非共价法在四氢呋喃溶剂中合成了原儿茶酸印迹聚合物.通过静态平衡吸附实验和高效液相色谱分析,评价了分子印迹聚合物对模板及其类似物的键合行为.结果表明：由于分子印迹聚合物基体存在大量多空的识别位点,并且这些位点的大小和形状与模板分子十分匹配,因此,分子印迹聚合物对模板分子具有高的吸附能力和选择性.Scatchard分析表明印迹聚合物表面有2类不同性能的键合位点.流动相及其流速对分析物的保留行为有较大影响.     

Template-imprinted nanostructured surfaces for protein recognition

Synthetic materials capable of selectively recognizing proteins are important in separations, biosensors and the development of biomedical materials. The technique of molecular imprinting creates specific recognition sites in polymers by using template molecules. Molecular recognition is attributed to binding sites that complement molecules in size, shape and chemical functionality. But attempts to imprint proteins have met with only limited success. Here we report a method for imprinting surfaces with protein-recognition sites. We use radio-frequency glow-discharge plasma deposition to form polymeric thin films around proteins coated with disaccharide molecules. The disaccharides become covalently attached to the polymer film, creating polysaccharide-like cavities that exhibit highly selective recognition for a variety of template proteins, including albumin, immunoglobulin G, lysozyme, ribonuclease and streptavidin. Direct imaging of template recognition is achieved by patterning a surface at the micrometre scale with imprinted regions.     

安石榴甙分子印迹聚合物微球的制备及识别性能

以安石榴甙为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁腈(AIBN)为引发剂,乙腈为溶剂,使用沉淀聚合方法,制备分子印迹聚合物,得到纳米级微球。等温吸附实验研究表明,印迹聚合物与空白聚合物相比,对目标分子具有更好的吸附性能,在研究浓度范围内,印迹聚合物对目标分子的最大吸附量为32.6μmol/g;Scatchard分析表明,印迹聚合物具有两种不同性能的结合位点,空白聚合物有一种结合位点,印迹聚合物的最大表观结合量为243μmol/g,空白聚合物的最大表观结合量为25.3μmol/g;底物选择实验表明分子印迹聚合物对安石榴甙具有更高的选择性能。     

表面分子印迹技术研究进展

分子印迹技术是制备对目标分子具有特异识别性能的高分子聚合物的技术,表面分子印迹是目前分子印迹技术领域的研究重点之一.本文概述了表面分子印迹材料的制备方法,主要包括牺牲载体法、聚合加膜法和化学接技法,以及近年来表面分子印迹技术的研究进展.     

水相中奎宁分子印迹聚合物的制备、表征及识别性质的研究

以奎宁分子为模板,甲基丙烯酸为功能单体,在亲水体系中,利用两步种子溶胀和微乳液聚合的分子印迹技术,通过条件优化,成功制备得到一种单分散性好的球形分子印迹聚合物.用红外光谱、热重分析、电镜扫描、粒度分析等技术对聚合物进行了表征.通过聚合物在不同溶剂中的吸附量的变化,揭示采用酸性的功能单体MAA制得的聚合物可与带胺基的模板分子通过氢键、离子键(静电)相互作用,且识别机理随溶剂类型改变而改变.对不同底物的选择性实验表明该聚合物对模板分子具有良好的识别能力和选择性.     

石墨烯掺杂对分子印迹电化学传感器的增敏作用

分别以掺杂氧化石墨烯和石墨烯的壳聚糖为功能基体,尿酸为模板分子,采用恒电位技术于玻碳电极表面制备氧化石墨烯-壳聚糖和石墨烯-壳聚糖的分子印迹电化学传感器.同时,利用电化学与波谱技术研究了不同石墨烯掺杂对制备出的传感器灵敏度的影响.表征结果表明:石墨烯的sp2共轭结构的完整性及其在界面的存在形态是导致不同电化学增敏效果的原因.     

邻香兰素分子模板聚合物结合作用及选择性研究

 以邻香兰素为烙印分子,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,采用分子烙印技术合成了1类新的分子烙印聚合物.研究了它们的吸附特性及选择性识别能力.结果表明,与组成相同的非模板聚合物相比,模板聚合物有一定的吸附性能和选择性.     

天麻素分子印迹聚合物的吸附和识别性能研究

采用分子印迹技术,以天麻素为模板,合成了对天麻素具有选择性吸附效果的分子印迹聚合物(MIPs)。扫描电镜和平衡吸附实验表明,与空白印迹聚合物(NIPs)相比,MIPs表面粗糙多孔并且有较多的结合位点和较高的吸附容量。在吸附动力学实验中,MIPs在30 min即可吸附最大吸附量的88.38%。在选择性实验中,MIPs对天麻素的吸附量远大于对其结构类似物葡萄糖的吸附量,体现了良好的选择性。研究结果表明,本材料有作为选择性填料来提取分离天麻素的潜能。     

表面分子印迹法制备棉酚印迹聚合物及其性能检测

分子印迹技术是高聚合物质对特定目标分子进行选择性识别和分离的技术,可以对目标分子进行高灵敏的检测和分离,因而得到广泛应用。制备了一种基于氧化硅的表面分子印迹聚合物,提高了传统印迹聚合物的结合率。在对表面分子印迹聚合物结合率和特异性的实验中,可知以甲基丙烯酸为单体,氯仿为致孔剂制备的表面分子印迹聚合物结合率和特异性最好,其k值和k’值分别为3.2和2.791。同时,该方法与高效液相色谱(high-performance liquid chromatography-ultraviolet HPLC-UV)进行了比较,发现表面分子印迹聚合物(I值为3.85)对棉酚的检测优于HPLC-UV(I值为2.28)。     

亲水性尿苷分子印迹聚合物的制备及分子选择性识别

研究亲水性核-壳结构分子印迹聚合物的制备并考察其吸附、分离性能.以尿苷为模板分子,通过回流沉淀聚合方法(DPP)制备亲水性的核-壳结构分子印迹聚合物微球.研究了模板分子UR与功能单体MMA之间的相互作用,考察了分子印迹聚合物对模板分子的吸附动力学、吸附平衡以及吸附选择性,评价了该分子印迹聚合物作为高效液相色谱柱填料时对尿苷及其类似物的分离能力.UR分子印迹聚合物对UR的吸附符合准一级动力学方程;Freund lich等温方程能更好地拟合分子印迹聚合物对印迹分子尿苷的等温吸附数据;UR分子印迹色谱柱能够实现UR及其类似物的分离,对尿苷具有选择性识别性能.     

苯并三氮唑分子印迹聚合物识别特性的研究

用芩并三氮唑作为模板分子，运用分子印迹技术合成了分子印迹聚合物，Seatchard模型研究其结合特性，测定了结合位点的离解常数，并讨沦溶剂的极性对识别特性的影响．     

分子印迹技术研究的新进展

分子印迹技术是制备对特定分子具有特异性识别能力的高分子聚合物的一种技术,本文就近些年来分子印迹技术在合成单体、合成方法以及应用领域等方面取得的新进展进行了综述.     

Molecular imprinting of bulk, microporous silica

Molecular imprinting aims to create solid materials containing chemical functionalities that are spatially organized by covalent or non-covalent interactions with imprint (or template) molecules during the synthesis process. Subsequent removal of the imprint molecules leaves behind designed sites for the recognition of small molecules, making the material ideally suited for applications such as separations, chemical sensing and catalysis. Until now, the molecular imprinting of bulk polymers and polymer and silica surfaces has been reported, but the extension of these methods to a wider range of materials remains problematic. For example, the formation of substrate-specific cavities within bulk silica, while conceptually straightforward, has been difficult to accomplish experimentally. Here we describe the imprinting of bulk amorphous silicas with single aromatic rings carrying up to three 3-aminopropyltriethoxysilane side groups; this generates and occupies microporosity and attaches functional organic groups to the pore walls in a controlled fashion. The triethoxysilane part of the molecules' side groups is incorporated into the silica framework during sol-gel synthesis, and subsequent removal of the aromatic core creates a cavity with spatially organized aminopropyl groups covalently anchored to the pore walls. We find that the imprinted silicas act as shape-selective base catalysts. Our strategy can be extended to imprint other functional groups, which should give access to a wide range of functionalized materials.     

Chiral separation of racemic drugs using molecular imprinting

Molecularly imprinted polymers (MIPs) of (S)-ketoprofen and (S)-naproxen are prepared using non-covalent imprinting in the presence of template molecules. The prepared MIPs are used as the chiral stationary phase to separate ramemic naproxen and ketoprofen. The results show that racemic naproxen and ketoprofen are efficiently resolved on MIPs. The effect of concentration of acetic acid in the mobile phase is studied, and the data are analyzed using the affinity chromatography model, and the close agreement is achieved between the simulated and experimental curves. The results suggest that the affinity chromatography mechanism controls the retention in this system. Moreover, the affinity chromatography equilibrium constants on (S)-naproxen and (S)-ketoprofen are estimated.     

Synthetic hosts by monomolecular imprinting inside dendrimers

Synthetic host systems capable of selectively binding guest molecules are of interest for applications ranging from separations and chemical or biological sensing to the development of biomedical materials. Such host systems can be efficiently prepared by 'imprinting' polymers or inorganic materials with template molecules, which, upon removal, leave behind spatially arranged functional groups that act as recognition sites. However, molecularly imprinted polymers have limitations, including incomplete template removal, broad guest affinities and selectivities, and slow mass transfer. An alternative strategy for moulding desired recognition sites uses combinatorial libraries of assemblies that are made of a relatively small number of molecules, interconverting in dynamic equilibrium; upon addition of a target molecule, the library equilibrium shifts towards the best hosts. Here we describe the dynamic imprinting of dendritic macromolecules with porphyrin templates to yield synthetic host molecules containing one binding site each. The process is based on our general strategy to prepare cored dendrimers, and involves covalent attachment of dendrons to a porphyrin core, cross-linking of the end-groups of the dendrons, and removal of the porphyrin template by hydrolysis. In contrast to more traditional polymer imprinting, our approach ensures nearly homogeneous binding sites and quantitative template removal. Moreover, the hosts are soluble in common organic solvents and amenable to the incorporation of other functional groups, which should facilitate further development of this system for novel applications.     

吡嘧磺隆分子印迹聚合物的合成及吸附性能研究

以吡嘧磺隆为模板分子，α-甲基丙烯酸为功能单体，偶氮二异丁腈为引发剂，三甲氧基丙烷三甲基丙烯酸酯为交联剂，合成了吡嘧磺隆分子印迹聚合物；并比较了3种不同致孔剂和致孔剂体积对所合成的聚合物吸附量和颗粒度的影响。结果表明，采用二氯甲烷为致孔剂制备的吡嘧磺隆印迹聚合物的吸附量均高于采用正己烷和正己烷/二氯甲烷（体积比为1∶1）为致孔剂的，致孔剂的用量对聚合物吸附量的影响不明显，但对聚合物的粒径影响比较明显；以36mL二氯甲烷为致孔剂制备的聚合物的颗粒度最大，D₅₀为5.36μm相似文献   

微囊藻毒素分子印迹聚合物的制备及性能研究

以微囊藻毒素MC-LR为模板,采用本体聚合法制备微囊藻毒素分子印迹聚合物,优化制备过程.通过电子显微镜、孔隙度分析、红外吸收等对其进行表征,并研究其反应机理和吸附性能.结果表明,单体∶模板∶交联剂配比为0.9×106∶1∶1.2×106,洗脱时间25 min时为优选条件,最大吸附量为153.7μg/g,此分子印迹聚合物对MC-LR具有显著的特异性吸附作用.