Effect of Coordinate Bond in Molecular Recognition of Enrofloxacin with Imprinted Polymers

1 Results Molecular imprinting is a technique for the preparation of functional materials with molecular recognition properties.Molecular imprinted polymers (MIPs) have become an increasingly active field of study for the construction of new material capable of molecular recognition.In general,MIPs are synthesized by polymerization of cross-linking complexes of template molecules and functional monomers.After removing the template molecules from de polymers,binding sites are formed by functional monomer...     

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.     

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.     

敌百虫分子印迹聚合物的合成及其性能

采用分子印迹技术,以壳聚糖为聚合物基体.敌百虫为模板分子,制备在空间结构和结合位点上与敌百虫匹配的分子印迹聚合物.研究该聚合物的合成条件,包括壳聚糖与敌百虫的作用力.以及交联、洗脱条件.测定分子印迹聚合物对敌百虫的吸附和选择识别能力,并对其结构进行表征.结果表明,所合成的分子印迹聚合物对敌百虫具有良好的吸附和选择识别能力,其中对结构类似的氧化乐果的分离系数达到3.57.     

外消旋色氨酸印迹聚合物的制备及性能研究

以外消旋色氨酸(DL-Trp)为模板分子,β-环糊精(β-CD)及其衍生物为单体构建手性环境,改变印迹体系和聚合方法合成了14种印迹聚合物(MIP1~14).采用SEM和N2吸附试验表征优化印迹聚合物MIP14的结构,通过吸附动力学曲线和吸附等温线模型探讨其吸附特性,并结合HPLC分析聚合物对DL-Trp的手性拆分能力.结果表明:MIP14为孔径分布较为均一的中孔材料,主要存在两类结合位点,符合二级动力学模型.MIP14具有良好的手性拆分能力,在含有6种芳香族氨基酸的复杂体系中可特异性拆分DL-Trp,拆分因子1.477,表明以环糊精衍生物直接印迹外消旋混合物来制备手性印迹材料是一条简便而可行的合成路线.     

Molecular imprinted polymer with positively charged assistant recognition polymer chains for adsorption/enrichment of low content target protein

Here, we introduce a new type of molecular imprinted polymer （MIP） with immobilized assistant recognition polymer chains （ARPCs） to create effective recognition sites and with bacterial cloned protein as template for adsorbing the low content target protein from cell extract. In this work, cloned pig cyclophilin 18 （pCyP18）, a peptidyl-prolyl cis/trans-isomerase, was used as template. The template protein was selectively assembled with ARPCs from their library, which consists of numerous limited length polymer chains with randomly distributed recognition sites of positively charged amino groups and immobilizing sites. These assemblies were adsorbed by porous microsphers and immobilized on them. After removing the template, binding sites complementary to the target protein in size, shape and the position of recognition groups were exposed, and their confirmation was preserved by the cross-linked structure. The synthesized MIP was used to adsorb the cellular pCyP18, and its proportional content was enriched more than hundred times. The extended experiment on imprinting bovine serum albumin （BSA） with ARPCs shows that this method is also suitable for large protein.     

Understanding and tuning the epitaxy of large aromatic adsorbates by molecular design

If the rich functionality of organic molecules is to be exploited in devices such as light-emitting diodes or field-effect transistors, interface properties of organic materials with various (metallic and insulating) substrates must be tailored carefully. In many cases, this calls for well-ordered interfaces. Organic epitaxy-that is, the growth of molecular films with a commensurate structural relationship to their crystalline substrates--relies on successful recognition of preferred epitaxial sites. For some large pi-conjugated molecules ('molecular platelets') this works surprisingly well, even if the substrate exhibits no template structure into which the molecules can lock. Here we present an explanation for site recognition in non-templated organic epitaxy, and thus resolve a long-standing puzzle. We propose that this form of site recognition relies on the existence of a local molecular reaction centre in the extended pi-electron system of the molecule. Its activity can be controlled by appropriate side groups and--in a certain regime--may also be probed by molecularly sensitized scanning tunnelling microscopy. Our results open the possibility of engineering epitaxial interfaces, as well as other interfacial nanostructures for which specific site recognition is essential.     

用分子复制法制备具有分子识别功能的高分子膜

将分子复制法应用于功能性高分子膜的制备中，以1，3－二甲基黄嘌呤（茶碱，THO）为模板分子，含有成膜骨干残基和功能残基的丙烯腈－丙烯酸的共聚物为膜材料，用相转化沉淀法制备了具有THO分子识别功能的高分子膜，FT－IR及NMR测试结果表明：制备的高分子膜中，THO模板分子和膜中的丙烯酸功能残基存在着氢键键合作用。大量的极性醋酸水溶液可抽出膜中的模板分子。THO溶液和与模板分子具有相似结构的1，3，7－三甲基黄嘌呤(咖啡因，CAF）溶液的基质透过实验结果：进入膜结构中THO分子的量远大于CAF分子，这表明制备的高分子膜具有THO分子识别功能。实验结果还表明：进入膜结构中THO分子的量与相转化沉淀法制膜时乔膜液中模板分子的添加量成正比。     

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.     

香豆素分子印迹复合膜的制备与性能研究

在优化了载体膜种类、引发剂与交联剂用量以及载体膜在预聚合溶液中的浸泡时间基础上,以聚偏氟乙烯(PDVF)为载体膜,甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,固定模板、单体及交联剂的加入量比为1:4:8,在乙腈中用AIBN引发聚合反应,制备了一种对香豆素具有较高吸附容量(0.151 8 mmol/g)和理想印迹因子(2.09)的香豆素分子印迹复合膜.用红外光谱和扫描电镜表征了膜的结构与形貌,探讨了膜的传质机制及其渗透选择性.结果表明,在浓度差驱动下,该膜通过溶解-扩散机理进行传质,并在有干扰物存在时,对香豆素具有良好的分离选择性,从桂枝甲醇粗提液中提取分离香豆素的回收率达到了89.6%.     

EGCG分子印迹壳聚糖膜的制备及性能研究

利用分子印迹技术,以壳聚糖为功能基体,表没食子儿茶素没食子酸酯(EGCG)为模板分子,硫酸为交联剂,制备了EGCG分子印迹壳聚糖膜,并探讨了平衡吸附时间、pH值、温度及功能单体和模板分子的比例等因素对印迹膜吸附性能的影响.SEM和AFM测试结果表明印迹膜的表面形貌不同于非印迹膜;同时用红外光谱分析了印迹分子的洗脱情况.平衡结合法实验结果表明,印迹膜对EGCG具有较好的亲和性和选择性.Scatchard分析表明,印迹膜在识别EGCG的过程中存在1类结合位点,其平衡结合常数K为4.046,最大吸附量Qmax为49.52mg·g-1.     

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.     

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.     

香豆素分子印迹复合膜的制备与性能研究

 在优化了载体膜种类、引发剂与交联剂用量以及载体膜在预聚合溶液中的浸泡时间基础上,以聚偏氟乙烯（PDVF）为载体膜,甲基丙烯酸（MAA）为功能单体,乙二醇二甲基丙烯酸酯（EDMA）为交联剂,固定模板、单体及交联剂的加入量比为1∶〖KG-*2〗4∶〖KG-*2〗8,在乙腈中用AIBN引发聚合反应,制备了一种对香豆素具有较高吸附容量（0.1518mmol/g）和理想印迹因子（2.09）的香豆素分子印迹复合膜.用红外光谱和扫描电镜表征了膜的结构与形貌,探讨了膜的传质机制及其渗透选择性.结果表明,在浓度差驱动下,该膜通过溶解-扩散机理进行传质,并在有干扰物存在时,对香豆素具有良好的分离选择性,从桂枝甲醇粗提液中提取分离香豆素的回收率达到了89.6%.     

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.     

壬基酚分子印迹材料的制备与评价

以分子印迹技术与溶胶凝胶技术相结合、以3-氨基丙基三乙氧基硅烷为功能单体,四乙氧基硅烷为交联剂,以壬基酚为模板分子制备了壬基酚分子印迹材料,并对印迹材料的性能进行了分析研究。结果表明该材料在选择性分离和去除壬基酚具有较好的应用前景。     

环丙沙星印迹聚合物微球的合成及性能表征

以甲基丙烯酸为功能单体,环丙沙星为模板分子,采用悬浮聚合的方法制备了球形分子印迹聚合物,并用扫描电镜对聚合物进行了表征;通过平衡吸附法研究了聚合物对模板分子及其类似物的吸附行为和选择识别能力.结果表明,实验所研究的分子印迹聚合物,吸附4 h后基本接近最大吸附量,其中模板分子、MMA和交联剂物质的量比为1:6:20的MIPMs2最大表观吸附量为183.18 μmol/g, 印迹因子为1.58,效果最佳.吸附过程存在两类结合位点,一类为特异性印迹吸附,另一类为非特异性吸附;该分子印迹聚合物有很好的选择吸附性和再生性,可用于环丙沙星药物的分析和分离.     

结合适配体技术的磁性粒子表面蛋白分子印迹材料研制

本文将具有高度特异性的生物分子核酸适配体引入分子印迹技术,并结合磁性纳米粒子材料比表面积大、操作简便性和易于修饰性于一体,制备出了新型蛋白分子印迹材料.首先获得性能更好的硅烷化的磁性微球,之后加入功能单体、交联剂和衍生化适配体,以溶菌酶为模板分子,制备出磁性溶菌酶蛋白分子印迹适配体-纳米粒子.实验结果显示,不同材料的蛋白吸附能力顺序由高到低分别为结合适配体的蛋白印迹材料,结合适配体的非蛋白印记材料,蛋白印迹材料和无适配体的非蛋白分子印记材料.初步研究表明,适配体与磁性粒子的结合可以有效提高蛋白质分子印迹材料的印迹效果.     

毒死蜱分子印迹聚合物的制备与性能研究

分子印迹技术是近些年发展起来的一种新技术,因其具有构效预定性、特异识别性和广泛实用性等特点而被广泛应用于环境、生物医药等领域,其在食品安全检测中也有重要的研究潜力.以毒死蜱为模板分子,采用原位逐步聚合法制备了具有良好识别性能的分子印迹聚合物(MIPs),考察了毒死蜱、敌敌畏及甲胺磷在毒死蜱分子聚合物上的选择性分离富集特...     

杨小舟蛾MtroOBP1基因的克隆、序列分析及表达

【目的】气味结合蛋白(odorant binding proteins,OBPs)是一种嗅觉相关的蛋白,该蛋白参与大多数气味分子的识别过程,并与气味分子相结合。获得杨小舟蛾[Micromelalopha troglodyta (Graeser)]OBPs以明确其特性。【方法】选择羽化后健康的杨小舟蛾触角为模板,通过反转录聚合酶链反应(RT-PCR)技术克隆杨小舟蛾MtroOBP1基因,利用生物信息学分析软件研究其基因序列和蛋白结构,运用实时荧光定量PCR(qPCR)技术研究MtroOBP1的组织表达模式。【结果】利用RT-PCR技术从杨小舟蛾触角总RNA中扩增得到MtroOBP1基因(GenBank登录号:MN056510),序列分析表明,MtroOBP1开放阅读框为777 bp,一共编码了258个氨基酸残基,且翻译的氨基酸序列仅含有4个保守的半胱氨酸位点,表明得到的OBP基因的编码蛋白不属于典型气味结合蛋白家族,而是属于Minus-C家族。蛋白质理化性质预测显示:MtroOBP1蛋白的分子量为29 664.57 u,等电点为6.23,有18个潜在的磷酸化位点,没有明显的跨膜区,疏水指数为-2.011~3.078,有一个由19个氨基酸组成的信号肽,说明为分泌型蛋白。组织表达模式表明MtroOBP1在杨小舟蛾的各部位都表达,但在触角中表达量最高。【结论】首次克隆得到杨小舟蛾MtroOBP1基因,在触角中高表达,推测其蛋白具有运输气味分子的功能,在杨小舟蛾的嗅觉识别中起着至关重要的作用。