The preparation of molecularly imprinted poly(o‐phenylenediamine) membranes for the specific O,O‐dimethyl‐α‐hydroxylphenyl phosphonate sensor and its characterization by AC impedance and cyclic voltammetry

A molecularly imprinted polymer (MIP) membrane for sensing O,O‐dimethyl‐α‐hydroxylphenyl phosphonate (DHP) has been prepared by electropolymerizing o‐phenylenediamine on the glassy carbon electrodes in the presence of DHP. Optimization studies with the aim to enhance insulating properties and response kinetics of the polymer membrane were carried out with respect to template molecular concentration, the monomers concentration, the polymer membrane thick and scan rate. Cyclic voltammetry and electrochemical impedance have been used to characterize the behavior of MIP polymer membrane. The capacitive measurements were also certified the imprinting effect of the polymer layers. The experimental results showed that DHP imprinted polymer has better recognition property for the template than that of a blank polymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2222–2227, 2006     

On the Influence of Crosslinker on Template Complexation in Molecularly Imprinted Polymers: A Computational Study of Prepolymerization Mixture Events with Correlations to Template-Polymer Recognition Behavior and NMR Spectroscopic Studies

Aspects of the molecular-level basis for the function of ethylene glycol dimethacrylate and trimethylolproprane trimethacrylate crosslinked methacrylic acid copolymers molecularly imprinted with (S)-propranolol have been studied using a series of all-component and all-atom molecular dynamics studies of the corresponding prepolymerization systems. The crosslinking agents were observed to contribute to template complexation, and the results were contrasted with previously reported template-recognition behavior of the corresponding polymers. Differences in the extent to which the two crosslinkers interacted with the functional monomer were identified, and correlations were made to polymer-ligand recognition behavior and the results of nuclear magnetic resonance spectroscopic studies studies. This study demonstrates the importance of considering the functional monomer–crosslinker interaction when designing molecularly imprinted polymers, and highlights the often neglected general contribution of crosslinker to determining the nature of molecularly imprinted polymer-template selectivity.     

Molecular Imprinted Polymer of Methacrylic Acid Functionalised β-Cyclodextrin for Selective Removal of 2,4-Dichlorophenol

This work describes methacrylic acid functionalized β-cyclodextrin (MAA-βCD) as a novel functional monomer in the preparation of molecular imprinted polymer (MIP MAA-βCD) for the selective removal of 2,4-dichlorophenol (2,4-DCP). The polymer was characterized using Fourier Transform Infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) and Field Emission Scanning Electron Microscopy (FESEM) techniques. The influence of parameters such as solution pH, contact time, temperature and initial concentrations towards removal of 2,4-DCP using MIP MAA-βCD have been evaluated. The imprinted material shows fast kinetics and the optimum pH for removal of 2,4-DCP is pH 7. Compared with the corresponding non-imprinted polymer (NIP MAA-βCD), the MIP MAA-βCD exhibited higher adsorption capacity and outstanding selectivity towards 2,4-DCP. Freundlich isotherm best fitted the adsorption equilibrium data of MIP MAA-βCD and the kinetics followed a pseudo-second-order model. The calculated thermodynamic parameters showed that adsorption of 2,4-DCP was spontaneous and exothermic under the examined conditions.     

格列美脲分子印迹聚合物应用于固相萃取的研究

以降血糖药物格列美脲为模板分子,ɑ-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,偶氮二异丁腈(AIBN)为引发剂,采用本体聚合法制备了格列美脲分子印迹聚合物(MIP),用于血浆样品前处理,建立了对加标兔血浆中格列美脲含量的固相萃取检测方法,通过高效液相色谱法测定,分子印迹固相萃取柱的回收率可达80%以上,有效地减少了基体中蛋白质等杂质对目标物检测的干扰,适用于生物样品中模板分子的富集和纯化。     

分子印迹膜SPR传感器检测氯磺隆的方法

研究使用了中国科学院电子学研究所自行研制的高灵敏度单通道SPR分析仪和进样装置,仪器为棱镜耦合型SPR传感器结构,其检测角度范围是40°～70°,折射率检测范围为1.04～1.47,谐振角的精度在0.001°。适用于SPR分析仪的分子印迹芯片采用PVC-MIP共聚膜法制备,SPR角度扫描结果表明,200nm以下厚度芯片具有较好的SPR吸收特性。以氯磺隆为模板的分子印迹膜与不加氯磺隆的分子印迹膜对比实验发现前者具有特异性结合的能力。实验对浓度0.1,0.2,0.5和1μg/mL的氯磺隆进行了SPR定点检测,这四种浓度氯磺隆的折射率响应信号满足线性关系,相关系数R=0.996 4。实验中对低浓度的氯磺隆进行反复检测,检测到50ng/mL的氯磺隆,满足农残检测的要求。     

分子印迹固相萃取/毛细管电泳法同时测定水中酚

采用悬浮聚合方法合成了分子印迹高分子微球,建立了分子印迹固相萃取/毛细管电泳同时测定水样中苯酚、间苯二酚和对硝基苯酚的新方法。在优化的固相萃取条件下,模板分子获得了95%的吸附率和较高的富集倍数(33倍)。在一定浓度范围内3,种酚均呈现良好的线性关系(r≥0.999 2),方法检出限为0.048 8～0.809μg/kg,回收率为87.2%～100.4%,日内(n=5)、日间(n=3)精密度(RSD)分别为(1.89%～5.63%)(、6.91%～8.14%)。该方法简便、快速、准确,适用于环境水中酚类物质的测定。     

Encapsulation of quantum dots and carbon nanotubes with polypyrrole in a syringe needle for automated molecularly imprinted solid phase pre-concentration of ochratoxin A in red wine analysis

Nanometer-sized semiconductor quantum dots (QDs with CdSe core and ZnS shell) and carbon nanotubes (CNTs with multi-walls) were encapsulated inside a stainless steel syringe needle by electrodeposition of polypyrrole (PPy). By cross-linking the PPy with ethylene glycol dimethacrylate (EGDMA) in the presence of ochratoxin A (OTA) as a template, molecularly imprinted polypyrrole (MIPPy) was formed on the nano-hybrid structure at an increased specific surface area. The MIPPy/CNTs/QDs-modified needle was readily adapted in an autosampler for micro-solid phase preconcentration (μSPP) of OTA from a red wine sample. After pulsed elution (PE) with 2% triethylamine (TEA), the OTA was determined by high performance liquid chromatography (HPLC) with fluorescence detection (FD). In comparison with MIPPy/CNTs, this new nano-hybrid structure of MIPPy/CNTs/QDs significantly improved the % recovery of OTA. The method, MIPPy/CNTs/QDs-μSPP-HPLC-FD, demonstrated that the MIPPy was truly a molecularly imprinted polymer (MIP) with specific recognition for OTA. All red wine matrix components could be differentially washed out, prior to accurate determination of the strongly bound OTA.     

Study on preparation of protein‐imprinted soft‐wet gel composite microspheres with magnetic susceptibility and their characteristics. I. Preparation and particle morphology

Protein‐imprinted soft‐gel composite microspheres with magnetic susceptibility (MS‐PIGMs) were prepared by inverse suspension polymerization, using Fe₃O₄ particles as magnetically susceptible component, acrylamide (AM) and N,N′‐methylenebisacrylamide (BisAM) as polymeric matrix components, toluene as solvent, and bovine serum albumin (BSA) and lysozyme (Lyz) as templates, respectively. The surface morphology of MS‐PIGMs was observed by environmental scanning electron microscope (ESEM) and scanning electron microscope (SEM). The effects of the kinds and amount of dispersants, stirring rate, the amount and adding methods of initiator, the amount of Fe₃O₄ and monomer concentration on particle morphology of MS‐PIGMs, as well as the effects of crosslinking degree on swelling ratio and particle morphology in wet condition were investigated in detail. ESEM and SEM photographs showed that the resulting MS‐PIGMs were all spheroid form and had large quantity of regularly distributed pores in wet condition, which close in dry condition, and the experimental results indicated that all the affecting factors had obvious effects on particle morphology of MS‐PIGMs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 684–694, 2006     

Electrochemical sensors based on conducting polymer—polypyrrole

Conducting polymers can be exploited as an excellent tool for the preparation of nanocomposites with nano-scaled biomolecules. Polypyrrole (Ppy) is one of the most extensively used conducting polymers in design of bioanalytical sensors. In this review article significant attention is paid to immobilization of biologically active molecules within Ppy during electrochemical deposition of this polymer. Such unique properties of this polymer as prevention of some undesirable electrochemical interactions and facilitation of electron transfer from some redox enzymes are discussed. Recent advances in application of polypyrrole in immunosensors and DNA sensors are presented. Some new electrochemical target DNA and target protein detection methods based on changes of semiconducting properties of electrochemically generated Ppy doped by affinity agents are introduced. Recent progress and problems in development of molecularly imprinted polypyrrole are considered.