辛硫磷分子印迹聚合物修饰电极的制备及应用研究

以辛硫磷为模板分子,甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,在乙腈中沉淀聚合,研究制备了辛硫磷分子印迹聚合物(MIPs),并采用红外光谱、扫描电镜对合成的聚合物进行表征。Scatchard分析表明MIPs对辛硫磷有两种结合方式,最大表观吸附量(Qmax)和平衡解离常数(KD)分别为:Qmax1=70.58μmol/g,KD1=0.72 mmol/L;Qmax2=531.8μmol/g,KD2=7.80 mmol/L。将聚氯乙烯(PVC)5 mg和15 mg印迹聚合物超声分散于20 mL四氢呋喃(THF)中,取32μL分散液涂敷在玻碳电极上制备成辛硫磷分子印迹聚合物修饰电极,线性伏安法(LSV)检测。选择开路富集时间为5min,于0.03 mol/L HCl-0.02 mol/L KCl溶液(pH 2.2)中,辛硫磷在1.2×10-7~6.0×10-3mol/L浓度范围内,其在修饰电极上的还原峰电流与浓度的负对数呈良好的线性关系,检出限为6.0×10-8mol/L。用分子印迹聚合物修饰电极对实际样品进行分析,回收率为93.8%~96.2%。将印迹聚合物修饰电极对辛硫磷及其类似物(如三唑磷、毒死蜱、乐果等)进行检测,该电极对辛硫磷显示了良好的选择性和灵敏度。     

一种分子印迹聚合物荧光敏感膜的制备及对胺碘酮含量的测定

利用分子烙印技术,合成了含甲基丙烯酸功能单体的分子印迹聚合物,其对胺碘酮存在特异性作用;通过Scatchard分析了印迹聚合物的选择性结合特性,结果表明存在两类结合位点,其平衡离解常数近似值分别为Kd1=8.73×10-2mol/L和Kd2=3.48×10-2mol/L。以芘丁酸为荧光试剂,λex=349nm。通过测试λem=376.3nm处2~20mg/L胺碘酮对印迹聚合物荧光敏感膜荧光猝灭,线性良好(r=0.9970),该方法测定片剂中胺碘酮含量,回收率分别为99.8%、99.7%、101.7%,RSD分别为1.5%、6.2%、1.4%(n=5)。     

分子印迹荧光传感器的研制及其对呋喃妥因的特异性识别

采用柠檬酸作为碳源合成了荧光碳量子点(CDs),经硅烷化试剂改性后,以呋喃妥因为模板分子,在其表面合成了分子印迹聚合物(MIP-CDs)。以傅立叶变换红外光谱仪(FTIR)和扫描电镜(SEM)对合成产物进行结构和形貌表征;通过一系列吸附实验研究了MIP-CDs对呋喃妥因的识别性能。实验结果表明:在最佳吸附条件下,MIP-CDs的荧光猝灭程度与呋喃妥因的浓度符合Stern-Volmer方程,呋喃妥因在0~10mg/L质量浓度范围内具有良好的线性关系(r2=0.991 4),方法检出限(S/N=3)为2μg/L。在水样和饲料样品中添加不同浓度的呋喃妥因,加标回收率为78.0%~95.2%,相对标准偏差(RSD)不大于6.4%,符合分析方法学要求。该方法简单、快速、选择性好,可直接用于水体和饲料中痕量呋喃妥因的监测。     

Extending Time Profile of Morphine‐Induced Analgesia Using a Chitosan‐Based Molecular Imprinted Polymer Nanogel

Chitosan‐based molecular imprinted polymer (CS‐MIP) nanogel is prepared in the presence of morphine template, fully characterized and used as a new vehicle to extend duration of morphine analgesic effect in Naval Medical Research Institute mice. The CS‐MIP nanogel with ≈25 nm size range exhibits 98% loading efficiency, and in vitro release studies show an initial burst followed by an extended slow release of morphine. In order to study the feasibility of CS‐MIP nanogel as morphine carrier, 20 mice are divided into two groups randomly and received subcutaneous injection of morphine‐loaded CS‐MIP and morphine (10 mg kg^?1) dissolved in physiologic saline. Those received injection of morphine‐loaded CS‐MIP show slower and long lasting release of morphine with 193 min effective time of 50% (ET50) analgesia compared to 120 min ET50 in mice received morphine dissolved in physiologic saline. These results suggest that CS‐MIP nanogel can be a possible strategy as morphine carrier for controlled release and extension of its analgesic efficacy.

     

Electrochemical Detection of Vascular Endothelial Growth Factor by Molecularly Imprinted Polymer

In this study, we report the development of a sensitive label‐free impedimetric sensor based on molecularly imprinted polymer (MIP) as biomimetic receptor coupled with screen‐printed electrodes (SPEs) for the detection of vascular endothelial growth factor (VEGF). Firstly, electropolymerization of o‐phenylenediamine (o‐PD) in the presence of VEGF molecule by cyclic voltammetry was performed onto graphite screen‐printed electrodes. The solvent extraction of the target was then carried out. The MIP based sensor was characterized by electrochemical techniques and scanning electron microscopy (SEM). Using optimized experimental conditions, the single‐use MIP‐based sensor showed a good analytical performance for VEGF detection from 20 to 200 pg mL^?1 with limit of detection of 0.08 pg mL^?1. Finally, the developed MIP‐based sensor in human serum samples was also tested.     

分子印迹技术和荧光分析技术在爆炸物检测中的应用*

爆炸品危害社会安定、国家安全,引起国际社会的关注。开发爆炸品的在线监测技术成为当今热点研究领域之一。爆炸物的种类多种多样,它们的检测方法也各不相同。本文简要地回顾了爆炸物的常规检测方法,介绍了爆炸物的新颖检测技术,重点介绍了分子印迹技术和荧光分析技术在爆炸物检测中的应用,总结了分子印迹聚合物和荧光共轭聚合物检测爆炸物的特点,并对它们的发展趋势进行了展望。     

儿茶素活性成分分子印迹聚合物的分子识别特性及固相萃取研究

以表没食子儿茶素没食子酸酯(EGCG)为模板分子，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，合成EGCG分子印迹聚合物。利用该聚合物对EGCG及其异构体和结构类似物进行分子识别特性研究。结果表明：分子印迹聚合物对模板分子具有较高的选择性和识别能力，而空白聚合物却不具备这样的特性。在此基础上，把聚合物用于固相萃取茶叶提取物茶多酚，分离富集其中的儿茶素活性成分单体EGCG，获得了满意的效果。     

依诺沙星分子印迹聚合物的分子识别

分子印迹聚合物;依诺沙星;分子识别;固相萃取     

Molecular Imprinting-Chemiluminescence Determination of Norfloxacin Using a Norfloxacin-Imprinted Polymer as the Recognition Material

A selective molecular imprinting-chemiluminescence method was developed for the determination of norfloxacin by using a norfloxacin-imprinted polymer as recognition material and the Ce(IV)-sodium sulfite-norfloxacin chemiluminescence reaction as the detection system. The chemiluminescence intensity responded linearly to the concentration of norfloxacin within 1.0×10^–71.0×10^–5molL^–1 with a detection limit of 3×10^–8molL^–1. The relative standard deviation for 5.0×10^–7molL^–1 norfloxacin solution was 2.4% (n = 7). This method was applied to the determination of norfloxacin in urine samples, and the results obtained were satisfactory.     

药物头孢氨苄分子模板聚合物水中结合性质的研究

采用分子模板技术合成了以头孢氨苄为模板分子以三氟甲基丙烯酸和４－乙烯基吡啶同时为功能单体的分子模板聚合物。将得到的棒状聚合物研磨过筛后,运用平衡结合实验研究了头孢氨苄分子模板聚合物的结合性质,Ｓｃａｔｃｈａｒｄ分析表明,在所研究的浓度范围内,在聚合物中形成了两类不同的结合位点。头孢氨苄分子模板聚合物与其化学组成相同的非模板聚合物相比,有很高的结合容量。底物选择性实验表明,与其它结构相似的药物相比,     

蛋白质分子待定模板印迹聚合物的合成及应用

提出了一种合成蛋白质分子印迹聚合物的新方法——待定模板印迹。即不使用任何标准蛋白质,在一个实际样品(鸡蛋清)的存在下合成了印迹聚合物。利用原位聚合法得到印迹整体柱及一根对比柱。比较鸡蛋清在两根柱子中的电泳分离,发现印迹聚合物整体柱能够保留高丰度组分。并观察到部分高丰度蛋白质的谱图信号降低或消失,同时出现新的谱峰,表明相同样品中的低丰度组分得到富集。这预示着研究分子印迹的新途径,即基于其内在复杂性(通过一系列样品本身的印迹聚合物)来分析复杂样品。     

Determination of Melamine Using Magnetic Molecular Imprinted Polymers and High Performance Liquid Chromatography

A novel method using magnetic molecular imprinting polymers (MMIP) specific for recognizing, separating, and extracting melamine in bovine milk was developed with an external additive magnetic shelf in this paper. The MMIP was synthesized with Fe₃O₄ nanoparticles and molecular imprinted polymer synthesis technology. With the help of an elution step using methanol/acetic acid mixture elution, the melamine could be collected and concentrated. By using high performance liquid chromatography combined with this pretreatment technique, the analytes eluted from the magnetic polymers can be determined. This extraction method was validated by analysis of incurred bovine milk matrix. The proposed method simplified the procedures of classical solid-phase extraction method and improved the reliability of method. The obtained recoveries of this method were in the range of 85.04–105.2% in spiked milk samples. The limit of detection (LOD) was below 29.2 ng g^?1.     

莠去津分子印迹聚合物的合成及其吸附性能

以莠去津(1)为模板分子,甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,在偶氮二异丁腈(AIBN)的引发下,于65℃聚合17 h合成了对1有特异识别性能的分子印迹聚合物(2)。用紫外分光光度法探索了1与MAA的最佳比例,研究了2的吸附性能力,并利用高效液相色谱法对2的选择性进行了考察。用Scatchard法分析表明,2通过氢键作用力结合,存在两种结合位点,对1的吸附存在两种形态,最大表观吸附量(Qmax,1)为130.9 nmol.g-1,平衡离解常数(Kd,1)为30.8 nmol.L-1,Qmax,2为540.5 nmol.g-1,Kd,2为450.5 nmol.L-1。与西玛津相比,2对1显示出一定的选择性。以2作为填料制备出具有莠去津分子印迹的固相萃取柱,可对水质中2×10-8mol.L-1以下的待测物进行富集和分离,回收率近90%。     

Selective Adsorption and Molecular Recognition by a Molecularly Imprinted Polymer: Kinetic Study and Analysis

This article presents an original work aiming at kinetically surveying the substrate‐selective mechanism from a molecularly imprinted polymer. With Bisphenol A (BPA) as the template, the imprinted polymer was prepared. The result indicates that the imprinted polymer presents a much more complicated sorption toward the template than toward its analogue. The rate constant in the case of the template appears to be a function of coverage degree. There are also significant deviations from the idealized Langmuir model. Related information indicates that these logically can be a result from the induced molecular memory within the binding framework, which makes the polymer capable of selectively adsorbing the imprint species.     

磺胺二甲嘧啶分子印迹聚合物的合成及其识别性能

磺胺二甲嘧啶分子印迹聚合物的合成及其识别性能;磺胺二甲嘧啶;分子印迹聚合物;硅胶;分子识别     

Synthesis,Application, and Molecular Recognition Mechanism Study of Phenylalanine Molecularly Imprinted Polymer

Abstract

Phenylalanine molecularly imprinted polymer was synthesized in the presence of triflouroacetic acid. HPLC‐MS evaluation showed it had good affinity toward its template among 16 amino acid mixtures. It was used for quantification of phenylalanine in protein hydrolysis solution and in serum without sample pre‐treatment. Further study revealed the molecular recognition mechanism involved size exclusion, hydrophobic interaction, and hydrogen bonding interaction. The molecularly imprinted polymer presented here can be used for actual sample analysis and the well characterized recognition mechanism can benefit the design, synthesis, and application of MIP.     

双酚A分子印迹聚合物的制备和识别性能研究

生物分子间的特异性亲和识别作用在分析化学领域中已得到广泛应用, 但由于这些生物分子获得的途径复杂, 不易保存和使用条件苛刻等局限性而引发人工合成这样一类具有特异性识别和保留性能的吸附材料, 即所谓的分子印迹聚合物(简称为MIP)[1～4]. 双酚A是一种重要的环境内分泌干扰物, 它能与人体的内源雌激素雌二醇竞争结合雌激素受体, 并可能引起一系列病变[5,6]. 本文选择4-乙烯基吡啶作为功能单体, 加入交联剂乙二醇二甲基丙烯酸酯和引发剂偶氮二异丁腈引发聚合, 分别制备了以双酚A为模板分子的分子印迹聚合物和相应的空白聚合物. 研究了几种酚类结构类似物在所得分子印迹柱上的保留特性, 对双酚A分子印迹聚合物用作固相萃取剂的性能进行了初步研究.     

Determination of Parathion‐methyl in Vegetables by Fluorescent‐Labeled Molecular Imprinted Polymer

A novel sensor for the determination of parathion‐methyl based on couple grafting of functional molecular imprinted polymers (MIPs) was fabricated which is developed by anchoring the MIP layer on surfaces of silica particles embedded CdSe quantum dots by surface imprinting technology. The synthesized molecular imprinted silica nanospheres (CdSe@SiO₂@MIP) allow a high selectivity and sensitivity of parathion‐methyl via fluorescence intensity decreasing when the MIP material rebinding the parathion‐methyl molecule. Compared with the MIP fabricated in traditional method, the template of parathion‐methyl was easier to remove from the CdSe@SiO₂@MIP imprinted material. Under optimal conditions, the fluorescence intensity of parathion‐methyl at the imprinted sensor was detected by spectrofluorophotometer. The relative fluorescence intensity of CdSe@SiO₂@MIP decreased linearly with the increasing concentration of parathion‐methyl ranging from 0.013 mg·kg⁻¹ to 2.63 mg·kg⁻¹ with a detection limit (3δ) of 0.004 mg·kg⁻¹ (S/N=3), which is lower than the MIP in tradition. The imprinted film sensor was applied to detect parathion‐methyl in vegetable samples without the interference of other organophosphate pesticides and showed a prosperous application in the field of food safety.     

基于电化学聚合技术的分子印迹化学传感器研究进展

作为传感器中最重要的研究方向之一,分子印迹传感器在近十年的发展中取得了巨大进展。分子印迹聚合物膜在转换器表面的固定化方法有涂膜法、原位引发聚合法和电化学聚合法等,其中电聚合法因具有制备简单快速、膜厚可控、膜与电极附着紧密、重现性好等优点而成为极具潜力的制备方法。该文评述了基于电化学聚合技术的分子印迹传感器的主要研究进展,对聚合膜制备过程中单体的选择和模板的去除进行了讨论,对电聚合制备的印迹传感器在传感领域的分析应用进行了总结,并在此基础上对其未来发展进行了展望。     

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.