分子印迹技术用于模拟酶及分子反应器的研究进展

分子印迹技术是制备特异性分子识别材料的新技术. 分子印迹聚合物(Molecularly-imprinted polymer, MIP)具有可同酶相媲美的选择性识别能力, 能够催化手性及区域选择性的反应, 是一种新型的分子反应器; 同时MIP具有良好的化学和物理稳定性, 因而在替代酶用于某些苛刻条件下的催化反应方面有良好的应用前景. 就近年来利用MIP模拟酶催化有机合成反应, 以及利用MIP作为分子反应器反面的研究进展进行了综述.     

表面分子印迹研究进展

为了拓展分子印迹聚合物(Molecularly Imprinted Polymers,MIP)的应用领域,表面分子印迹作为一种新的方法,受到了极大的关注。本文首先分析了MIP传统制备方法存在的问题;然后依据印迹位点所处位置的不同,分类综述了表面分子印迹的各种方法。     

L-肉碱分子表面印迹聚合物的制备及其识别性能研究

以L-肉碱(L-carnitine)作为印迹模板分子,甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,采用硅胶表面分子印迹技术合成了L-肉碱分子印迹聚合物(MIP)和非印迹聚合物(NMIP).通过紫外光谱研究了MAA与L-肉碱之间的结合作用.利用IR和SEM测试分别对产物进行了结构表征和表面形貌观察,说明分子印迹聚合物成功接枝到了硅胶表面.吸附动力学实验结果表明,MIP对L-肉碱有较好的识别性和吸附性;Scatchard分析表明该印迹聚合物中存在着一类等价的结合位点,最大表观结合量为71.00μmol/g,离解常数Kd=2.76×10-4mol/L;选择性吸附实验结果表明,MIP对L-肉碱的吸附结合量高于其D型异构体和其他类似物;拆分实验结果表明,MIP对DL-肉碱的拆分有一定作用.     

关于分子印迹技术的研究

分子印迹聚合物 (MIP)可在分子水平上对物质进行选择性识别 ,类似于酶和底物、抗体和抗原的关系 ,且具有生物活性物质无法比拟的稳定性 ,所以分子印迹技术引起了众多学者的关注 ,使其成为一个新兴的热门研究课题     

蛋白质分子印迹

分子印迹技术是一种新型的高效分离技术，具有空间选择性识别特性。本文介绍了分子印迹技术在蛋白质大分子上的应用和发展，包括蛋白质分子印迹选用的单体和交联剂、印迹方法、印迹机理、蛋白质分子印迹技术的应用以及存在的一些问题。     

分子印迹聚合物的制备研究进展北大核心CSCD

分子印迹聚合物(MIP)是一种能特异性识别模板分子的聚合物,它具有选择性高、稳定性良好、使用寿命长、应用广泛等优点,MIP已经成为化学、材料等学科研究的热点。本文分类对MIP的制备方法进行了全面的综述,分析比较了各类合成制备方法的优缺点,并对不同方法的研究现状进行详细论述。同时,阐述了智能MIP的前沿进展,通过分析pH敏感性、光智能性和温敏性MIP等典型智能MIP的研究现状以及功能领域应用,较为全面地归纳总结智能MIP的制备合成特征,并基于文献基础展望智能MIP的未来的研究方向。     

以锌原卟啉为功能单体的分子印迹聚合物对胞嘧啶的识别作用

以锌原卟啉(ZnPP)为功能单体,甲基丙烯酸为共功能单体合成了生物碱基———胞嘧啶的分子印迹聚合物.通过静态吸附紫外检测的方法,对印迹和非印迹聚合物与胞嘧啶及腺嘌呤、尿嘧啶、胸腺嘧啶的结合特性分别进行了对比,分子印迹聚合物(MIP)与非分子印迹聚合物(NMIP)对胞嘧啶的吸附率差值为20.8%,远远高于其他三种碱基,说明MIP对胞嘧啶具有分子识别能力,实现了对胞嘧啶的分子识别.     

模板结构与分子印迹效果间关系的研究

以一些分子量和体积都较小的简单化合物作为模板分子,合成分子印迹聚合物 。通过总结43种化合物的分子印迹聚合物的色谱数据,来研究模板分子的分子量、 作用位点数目、分子刚性等因素与印迹效果的关系。根据免疫学中免疫原性的定义 ,我们提出“印迹原性”的概念,即,化合物能够产生印迹效应的性质称为印迹原 性;具有印迹原必的化合物称为印迹原;并讨论了具有较强选择性的印迹原的化学 基础。所得到的结论将有助于对分子印迹聚合物的识别机理的进一步理解,并且对 于根据模板分子性质预测MIP分子识别能力将具有一定的指导意义。     

分子印迹技术研究进展

分子印迹是制备具有分子特异识别功能聚合物的一种技术。本文从分子印迹聚合物的识别机理、分子印迹聚合制备条件和制备技术三个方面综述了分子印迹的研究进展,最后展望了分子印迹发展前景。引用文献66篇。     

配位印迹聚合物在分析化学中的应用进展

分子印迹聚合物(MIP)是一种对目标分子(模板分子)具有选择性结合能力的聚合物.配位印迹聚合物(CIP)是基于金属离子与功能单体、模板分子间配位作用的分子印迹聚合物,既沿袭了MIP的优点,又具有适用于极性环境等优点,在食品、环境、生物、医药等领域目标物的识别中有良好的应用潜力.本文介绍了CIP的原理和特点,综述了CIP在分析化学中的应用进展,展望了CIP的发展前景.     

Molecular recognition properties of salicylic acid-imprinted polymers

Summary Two molecularly imprinted polymers (MIP) have been prepared using the acidic drug salicylic acid, which can form intramolecular hydrogen bond, as the template and acrylamide or 4-vinylpyridine as the functional monomer. HPLC was used to evaluate the binding performance of the MIP for the template and for several analogues. The results showed that the MIP (P₂) prepared using acrylamide as the functional monomer had no molecular imprinting effect whereas that (P₁) prepared using 4-vinylpyridine as the functional monomer had a significant molecular imprinting effect. The reason the molecular imprinting effect was different for the two MIP was elucidated and the molecular recognition properties of P₁ were studied in detail. It was confirmed that electrostatic interaction played an important role in the molecular recognition of P₁. Scatchard analysis showed that two types of binding site with distinctly different affinity were formed in P₁. Their dissociation constants were estimated to be 7.6×10⁻⁵ mol L⁻¹ and 3.2×10⁻³ mol L⁻¹, respectively. Because P₁ has high affinity and selectivity for salicylic acid not only in organic systems but also in water-containing systems, it gives P₁ the potential for use in the enrichment, separation, and detection of salicylic acid in biological fluids.     

三元交联剂分子烙印手性固定相

采用２－乙烯基吡啶＋丙烯酰胺复合功能单体,以三甲氧基丙烷三甲基丙烯酸酯为三元交联剂制备了苯甲氧羰基－Ｌ－色氨酸烙印手性固定相,并与二元交联剂烙印相同氨基酸衍生物的情况进行了对比,发现三元交联剂在较小的用量下就可使分子烙印聚合物达到足够的交联度,实现烙印分子对映体的基线分离。     

分子烙印传感器的研究进展

分子烙印技术是制备具有选择性分子识别能力的聚合物的新兴技术,其应用之一是将分子烙印聚合物用作分析化学中化学传感器的识别元件。本文综述了分子烙印技术的原理方法及其在传感器方面的应用,评述了分子烙印传感器的发展方向,展望了其在有机磷化合物检测中的应用前景。     

Development of a model for the rational design of molecular imprinted polymer: Computational approach for combined molecular dynamics/quantum mechanics calculations

A new rational approach for the preparation of molecularly imprinted polymer (MIP) based on the combination of molecular dynamics (MD) simulations and quantum mechanics (QM) calculations is described in this work. Before performing molecular modeling, a virtual library of functional monomers was created containing forty frequently used monomers. The MD simulations were first conducted to screen the top three monomers from virtual library in each porogen-acetonitrile, chloroform and carbon tetrachloride. QM simulations were then performed with an aim to select the optimum monomer and progen solvent in which the QM simulations were carried out; the monomers giving the highest binding energies were chosen as the candidate to prepare MIP in its corresponding solvent. The acetochlor, a widely used herbicide, was chosen as the target analyte. According to the theoretical calculation results, the MIP with acetochlor as template was prepared by emulsion polymerization method using N,N-methylene bisacrylamide (MBAAM) as functional monomer and divinylbenzene (DVB) as cross-linker in chloroform. The synthesized MIP was then tested by equilibrium-adsorption method, and the MIP demonstrated high removal efficiency to the acetochlor. Mulliken charge distribution and ¹H NMR spectroscopy of the synthesized MIP provided insight on the nature of recognition during the imprinting process probing the governing interactions for selective binding site formation at a molecular level. We think the computer simulation method first proposed in this paper is a novel and reliable method for the design and synthesis of MIP.     

Selectivity features of molecularly imprinted polymers recognising the carbamate group

The molecular recognition properties of molecular imprinted polymers which bind the carbamate function were studied. Functional monomers potentially able to form non-covalent interactions with the model molecule N,O-dibenzylcarbamate were selected on the basis of a computational approach describing possible interactions between the template and a small library of vinylic monomers. These results were in accordance with N,O-dibenzylcarbamate batch-rebinding measurements performed on several miniMIPs prepared with the same library. From these preliminary results, four polymers were prepared by thermoinduced radical polymerization, using ethylene dimethacrylate as a cross-linker, chloroform (MIP1, MIP3) or acetonitrile (MIP2, MIP4) as porogens and methacrylic acid (MIP1, MIP2) or acrylamide (MIP3, MIP4) as functional monomers. Molecular recognition features of these materials were studied by high-performance liquid chromatography. In this manner selectivity was evaluated by considering the column retention of a library of sixteen structural analogues of dibenzylcarbamate, characterized by the transformation of the carbamate into a related function, or by the alteration of the molecular structure.The experimental results show that methacrylic acid is more efficient than acrylamide as a functional monomer (imprinting factors: MIP1 = 24.1, MIP2 = 25.6, MIP3 = 13.3, MIP4 = 2.44), and that chloroform enhances polymer selectivity. As regards structural motifs which conditionate the selectivity, the carbamate function strictly controls the presence/absence of molecular recognition, while shape and dimension of the substituents modulate the recognition itself. In particular, a marked recognition for analogs which were slightly bigger than the template was observed (N-benzyl-O-phenethylcarbamate: MIP1 α = 1.13, MIP2 α = 1.41, MIP3 α = 0.97; N-phenethyl-N-benzylcarbamate: MIP1 α = 1.61, MIP2 α = 1.17, MIP3 α = 0.81; N,O-diphenethylcarbamate: MIP1 α = 0.89, MIP2 α = 1.20, MIP3 α = 0.55).     

腈菌唑分子印迹聚合物的制备及识别性能研究

以腈菌唑为模板分子，采用原位分子印迹技术，制备具有特定识别性能的连续棒状分子印迹聚合物。考察了流动相中酸量对分离的影响，研究了几种结构类似物在所得分子印迹柱上的保留特性。结果表明，这种棒状分子印迹聚合物比相应的空白聚合物有高的识别性能和选择性。     

尼卡地平分子聚合物的制备及识别性能研究

采用分子印迹技术合成了以尼卡地平为模板分子,甲基丙烯酸为功能单体的分子印迹聚合物(MIP).运用平衡结合实验研究了聚合物的吸附特性和选择识别能力.通过Scatchard方程分析,结合位点的离解常数Kd=1.03 mmol·L-1,最大表观结合常数Qmax=18.76 μmol·g-1.结果表明,分子印迹聚合物对尼卡地平呈现出较高的吸附性和选择识别性,对尼卡地平药物的分离富集和检测具有实际临床意义.     

Molecular imprinting of β-cyclodextrin/cholesterol template into a silica polymer for cholesterol separation

The molecular assembly formed by the inclusion complex of cholesterol in β-cyclodextrin (β-CD:chol) was used as a template for the molecular imprinting of a sol–gel polymer (MIP/β-CD:chol), produced with tetraethoxysilane (TEOS) as precursor. The MIP/β-CD:chol and pure silica matrix (PSM) were tested for the efficiency of cholesterol removal from solutions at different cholesterol concentrations (1–10 mg/mL). The adsorption tests were run at 25°C using 1% (w/v) solid/liquid suspensions during 24 h. The MIP/β-CD:chol data on cholesterol adsorption was fitted by the Langmüir isotherm model, giving a maximum adsorption capacity of 76.5 mg cholesterol/g-adsorbent. The PSM data did conform to the Langmüir model. The maximum cholesterol adsorption achieved with the PSM was higher, 251 mg/g, probably due to multilayer adsorption. The hydrophobic silica matrix, imprinted with the inclusion complex of β-CD and a target molecule, has the potential of being used as an adsorbent for other organic molecules.     

分子烙印聚合物固定相分离咖啡因和茶碱的研究

分子烙印是一种新兴的分子识别技术,利用该技术可制备对烙印分子具有“预定”识别能力的高分子聚合物,即分子烙印聚合物（MIP）,从而可以对性质和组成相近的组如对映体等进行分离^[1,2],咖啡因与茶碱的分子烙印聚合物的制备以及二者分析已有报道^[3-9],但存在两种完全相反的结论。一种观点认为,即使以咖啡因为烙印分子,所制备的聚合物对咖啡因分子的选择性吸附能力也小于茶碱^[3-6]。而另一种观点则认为,在一定条件下,如以咖啡因分子为烙印分子的烙印聚合物对咖啡因分子具有更强的吸附能力^[7-9]。本文分别采用茶碱和咖啡因作为烙印分子,以甲基丙烯酸等为功能单体,在不同条件下制备了多种非共价型分子烙印聚合物,并系统地考察了其作 为HPLC固定相对咖啡因和茶碱的分离能力,同时也对烙印分子应具备的条件加以探讨。     

Evaluation of the Polymerization and Recognition Mechanism for Phenol Imprinting SPE

In order to develop more efficient preparation technologies for imprinted polymers (MIPs), the nature of pre-polymerization and molecular recognition in MIP was investigated by molecular dynamics modeling (MD), ¹H NMR, FTIR and some indirect techniques. Phenol was used as the template for the study of mechanism through the analysis of hydrogen bonding, hydrophobic and π–π bonding interaction. The 4-vinylpyridine-based MIP had the highest selectivity to its phenol template. Hydrogen bonding was proved to be present by characterizing the pre-polymerization complex and evaluating the recognition process and the effects of rebinding solvents were also studied. It was found that a good rebinding solvent should have less affinity with both template and polymer, but good solubility. MD modeling and some indirect techniques demonstrated that 4-vinylpyridine-based MIP recognized phenol mainly through hydrophobic interactions when the rebinding medium was water, while hydrogen bonding was present in the recognition process when the rebinding solvent was n-hexane.