水杨酸分子印迹膜电化学传感器的制备

以水杨酸为模板分子,采用循环伏安法电聚合形成聚吡咯膜,以固定电位过氧化法去除印迹分子,制备了水杨酸分子印迹膜电极.本印迹电极能促进水杨酸电氧化过程,有效地避免结构类似物(如苯甲酸)对其测定的干扰.循环伏安法用于电化学检测,当富集时间为10 min,磷酸盐缓冲溶液的pH=6.86 时,在1.0×10-6～2.0×10-3 mol/L浓度范围内,水杨酸氧化峰电流与其浓度呈良好的线性关系,检出限为0.8 μmol/L, 用分子印迹膜电极对加标样品进行分析,回收率为94.6%～103.4%.     

葛根素分子印迹电化学传感器的制备及研究

以丙烯酰胺为功能单体,葛根素为模板分子,马来松香丙烯酸乙二醇酯为交联剂,采用循环伏安法合成了葛根素分子印迹膜,并以此为识别元件制备了葛根素电化学传感器。该传感器对葛根素具有高度的选择性和良好的敏感度,葛根素氧化峰电流与其浓度在6.0×10-8～1.6×10-3mol/L范围内呈良好的线性关系,检出限为2.0×10-8mol/L。将此传感器用于葛根素注射液和木瓜葛根片中葛根素的含量测定,回收率为97.7%～106.4%。     

呋喃妥因分子印迹电化学传感器的制备及应用

以甲基丙烯酸为功能单体,呋喃妥因为模板分子,马来松香丙烯酸乙二醇酯(EGMRA)为交联剂,在玻碳电极表面制备了呋喃妥因分子印迹膜。采用循环伏安(CV)法、差分脉冲伏安(DPV)法及交流阻抗(EIS)法对印迹膜进行表征。实验表明,DPV法测定的氧化峰电流与呋喃妥因浓度在8.0×10-8~5.0×10-6 mol/L范围内呈良好的线性关系(R=0.9939),检出限为6.5×10-8 mol/L。该传感器用于呋喃妥因肠溶片的测定,其回收率为96.6%~101.6%。     

利用分子印迹传感器选择性测定绿麦隆

以绿麦隆为模板分子,邻氨基酚为功能单体,在金电极表面电聚合制得具有特异性识别孔穴的绿麦隆分子印迹膜。采用循环伏安、差分脉冲伏安法研究了印迹膜的性能、结构、分子印迹效应和模板分析物,并比较了传感器对其它结构相似化合物的选择性响应,发现该传感器对绿麦隆检测具有良好的选择性。绿麦隆浓度在3.0×10-7~1.5×10-6mol/L范围内与峰电流呈线性关系,检出限为1.0×10-7mol/L,在干扰物质共存情况下的回收率为105%~116%。     

分子印迹电化学传感器检测水杨酸

以水杨酸(SA)为模板分子,邻苯二胺(o-PPD)及吡咯(Py)为复合功能单体,在石墨烯修饰的玻碳电极表面制备分子印迹电化学传感器(MIP/GO/GCE),用扫描电镜(SEM)观察印迹膜的表面形貌,方波伏安法(SWV)和循环伏安法(CV)对分子印迹传感器的性能进行表征。通过优化实验条件,显示SA浓度在1.0×10-8~1.0×10-2 mol/L范围内,分子印迹传感器峰电流与SA浓度负对数具有良好的线性关系,检出限为8.6×10-9 mol/L。该传感器对SA具有良好的选择性,样品回收率为101%~106%,相对标准偏差(RSD)为3.8%。SA分子印迹传感器的制备简单、抗干扰性好、灵敏度高、成本低廉,具有较好实用价值。     

基于金纳米粒子及石墨烯量子点的四环素分子印迹电化学传感器研究

该文以四环素为模板分子,4-氨基苯硫酚(4-ATP)为功能单体,采用循环伏安法在金纳米粒子和石墨烯量子点复合材料修饰的玻碳电极表面电聚合分子印迹膜,制备四环素(TC)分子印迹传感器(MIPs/GQDs-AuNPs/GCE),并通过循环伏安法(CV)、电化学交流阻抗法(EIS)和线性扫描伏安法(LSV)等研究了其电化学响应性能。结果表明,该传感器对四环素具有良好的电流响应。在最佳实验条件下,TC氧化峰电流值与其浓度在2.0×10~(-8)～3.0×10~(-5) mol/L范围内呈良好的线性关系,相关系数为0.999 4,检出限为1.5×10~(-9) mol/L,加标回收率为97.9%～106%。该传感器稳定性好、响应灵敏、选择性高,具有良好的应用前景。     

基于分子印迹膜修饰丝网印刷电极的地西泮电化学传感器

以地西泮为模板分子,采用循环伏安法在一次性丝网印刷电极表面原位电聚合形成聚邻苯二胺膜,洗脱除去模板分子后得到地西泮分子印迹膜修饰丝网印刷电极。利用差示脉冲法对印迹膜和非印迹膜进行评价,表征了电极表面膜的电化学性质。以KI为印迹电极和底液间的探针,建立了一种间接检测地西泮的传感方法。该传感器的敏感元件为修饰有分子印迹膜的丝网印刷电极,其制备和更换非常方便。用于电化学检测时,样品的富集时间为3min,地西泮的浓度在2.0×10-7～1.0×10-5mol/L范围内与峰电流呈良好的线性关系,检出限为2.5×10-8mol/L,基于猪肉样品的加标回收率为92%～95%。将该传感器初步用于实际样品分析,结果满意。     

尼泊金乙酯分子印迹膜电化学传感器的制备

以邻苯二胺为功能单体,尼泊金乙酯为模板分子,通过电化学聚合在玻碳电极表面制备了尼泊金乙酯分子印迹膜,采用循环伏安法及方波伏安法,以K3[Fe(CN)6]为电活性探针,建立了间接测定尼泊金乙酯的分析方法。实验结果表明,制备的分子印迹膜电化学传感器对尼泊金乙酯具有较高的选择性和灵敏度,测定尼泊金乙脂的线性范围为2.5×10-6~1.0×10-5 mol/L,检出限为8.61×10-8 mol/L。     

复合纳米粒子修饰的柔性分子印迹传感器对四环素的检测研究

本文以酸化碳布(CC)作为柔性工作电极,采用恒电位沉积法在碳布上修饰纳米Au-Cu复合粒子(Au-Cu NPs),以四环素(TC)为模板分子,邻苯二胺为功能单体,采用循环伏安法在修饰了纳米粒子的活化碳布上电聚合分子印迹膜,制备了四环素分子印迹柔性传感器(Cu-Au NPs/PANI/TC/CC),通过循环伏安法(CV)、差分脉冲伏安法(DPV)研究了其电化学性能。结果显示,在优化实验条件下,TC的DPV峰值电流与其浓度在1.0×10~(-7)～3.0×10~(-5) mol/L范围内成良好的线性关系,相关系数为0.9996,检出限为2.57×10~(-11) mol/L,实际样品的加标回收率为97.3%～105%。该传感器柔软稳定,灵敏度高,抗干扰性和重复性好,可应用于柔性可穿戴传感器的设计。     

电聚合分子印迹传感器选择性测黑茶中槲皮素的含量

以槲皮素作为模板分子,邻氨基苯酚作为功能单体,在金电极表面通过电聚合法,制备了具有选择性识别槲皮素的分子印迹传感器。采用循环伏安法、差分脉冲伏安法研究了印迹膜的性能、结构和分子印迹效应。对功能单体与模板分子的配比、洗脱时间和印迹时间等实验参数进行了优化,并与其结构相似的化合物芦丁的选择性响应进行了比较,发现该传感器对槲皮素分子具有良好的选择性。槲皮素浓度在6.0×10-6~1.0×10-4mol/L范围内与峰电流呈线性关系,线性方程为:I(μA)=27.79+9.48lgc(mol/L)(R=0.9939),检出限为2.0×10-6mol/L。用此传感器测定黑茶中槲皮素含量的结果较为满意。     

Enhanced adsorption of atrazine from aqueous solution by molecularly imprinted TiO2 film

TiO₂ film imprinted by atrazine molecule at the surface of quartz crystal was prepared using molecular imprinting and surface sol-gel process. The molecularly imprinted TiO₂ film was characterized by scanning electron microscopy and cyclic voltammetry, and the atrazine adsorption was investigated by quartz crystal microbalance (QCM) technique. In comparison with non-imprinted TiO₂ film, the molecularly imprinted TiO₂ film exhibits high selectivity for atrazine, better reversibility and a much higher adsorption capacity for the target molecule, the adsorption equilibrium constant estimated from the in situ frequency measurement is about 6.7 × 10⁴ M⁻¹, which is thirteen times higher than that obtained on non-imprinted TiO₂ film.     

Synthesis of a molecularly imprinted polymer on mSiO2@Fe3O4 for the selective adsorption of atrazine

Atrazine contamination of water is of considerable concern because of the potential hazard to human health. In this study, a magnetic molecularly imprinted polymer for atrazine was prepared by the surface‐imprinting technique using Fe₃O₄ as the core, mesoporous silica as the carrier, atrazine as the template, and itaconic acid as the functional monomer. The magnetic molecularly imprinted polymer was characterized by Fourier‐transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, and vibration‐sample magnetometry. The binding properties of the magnetic molecularly imprinted polymer toward atrazine were investigated by adsorption isotherms, kinetics, and competitive adsorption. It was found that the adsorption equilibrium was achieved within 2 h, the maximum adsorption capacity of atrazine was 8.8 μmol/g, and the adsorption process could be well described by the Langmuir isotherm model and pseudo‐second‐order kinetic model. The magnetic molecularly imprinted polymer exhibited good adsorption selectivity for atrazine with respect to structural analogues, such as cyanazine, simetryne, and prometryn. The reusability of the magnetic molecularly imprinted polymer was demonstrated for at least five repeated cycles without a significant decrease in adsorption capacity. These results suggested that the magnetic molecularly imprinted polymer could be used as an efficient material for the selective adsorption and removal of atrazine from water samples.     

Development of molecularly imprinted polymeric nanofibers by electrospinning and applications to pesticide adsorption

Novel polystyrene‐based molecularly imprinted polymer nanofibers were synthesized through the electrospinning technique. The molecularly imprinted polymers were prepared using a non‐covalent approach and atrazine as template. For comparison, nonimprinted polymer nanofibers were also synthesized. The morphology of the synthesized nanofibers was characterized using scanning electron microscopy. The adsorption of pesticides, atrazine, atrazine desisopropyl, atraton, carboxin, linuron, and chlorpyrifos was studied under equilibrium (batch) conditions. To describe the adsorption capability of the synthesized polymers, Langmuir and Freundlich models were used. The Freundlich model provided a better mathematical approximation of the sorption characteristic for polymers nanofibers. To evaluate the adsorption capacity in the presence of interferents experiments on river water samples spiked with a mixture of six pesticides were also performed. The results obtained for the highest concentration levels investigated, show a greater amount of pesticide adsorbed on molecularly imprinted polymers and non‐imprinted polymers compared to those obtained using commercial stationary phases used as reference.     

碳纳米管修饰电极分子印迹传感器快速测定沙丁胺醇

以单壁碳纳米管(SWNTs)为电极材料,应用分子印迹技术,以邻苯二胺为功能单体、沙丁胺醇为模板,采用电化学聚合法制备了一种新型的快速检测沙丁胺醇分子印迹传感器,并运用电化学方法去除模板.在磷酸盐缓冲溶液(PBS)中,利用线性溶出伏安法对印迹和非印迹膜的性能进行了比较,对分子印迹膜的影响因素进行了优化.实验表明,本传感器...     

Monodispersed Molecularly Imprinted Polymer Beads with Enhanced Atrazine Retention Ability Synthesized with Polymeric Diluents

Molecular imprinting technique was applied for the preparation of polymer beads selected for a triazine herbicide, atrazine. Polystyrene, poly(methyl methacrylate) and poly(ethylene glycol) were examined as polymeric diluents, and the morphology of the resultant molecularly imprinted polymers was investigated by scanning electron microscopy. Among the examined polymeric diluents, styrene was shown to be favorable for obtaining monodispersed spherical polymer with high retention ability for atrazine.     

Preparation and Characterization of Prometryn Molecularly Imprinted Solid‐Phase Microextraction Fibers

Abstract

A novel reproducible solid‐phase microextraction (SPME) coating was prepared on the surface of silanized silica fibers by molecularly imprinted polymerization using prometryn as template molecule. The structure and extraction performance of molecularly imprinted polymer (MIP) coating was studied with the scanning electron microscope and high performance liquid chromatography (HPLC). Specific selectivity was found with the prometryn MIP‐coated fiber to prometry and its structural analogues such as atrazine, simetryn, terbutylazin, ametryn, propazine and terbutryn. In contrast, these triazines could not be selectively extracted by the non‐imprinted polymer fiber or commercial polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), polyacrylate (PA) fibers.     

Molecularly imprinted polymers bearing spiropyran‐based photoresponsive binding sites capable of photo‐triggered switching for molecular recognition activity

Photoresponsive molecularly imprinted nanocavities were prepared using a newly designed functional monomer bearing a photoresponsive spiropyran moiety with a carboxy group that can interact with atrazine (the template molecule), in which the spiropyran moiety was incorporated into the binding cavities. Spectrophotometric analysis confirmed that the spiropyran moiety was photoresponsive even after polymerization. The selectivity of the EDMA‐based molecularly imprinted polymer (MIP_EDMA) was tested to examine the binding behavior of atrazine and other agrochemicals, revealing that the atrazine‐imprinted polymer can bind selectively to triazine herbicides. Photo‐triggered switching of the binding activity in MIP_EDMA was investigated, and the binding activity was found to decrease dramatically after UV light irradiation, suggesting that the spiropyran moiety in the binding cavities was transformed to the merocyanine form, resulting in unfavorable translocation of the carboxy group for atrazine binding. Consequently, the spiropyran‐based MIP_EDMA demonstrated in this study could open a way to realizing reliable photoresponsive smart materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1637–1644     

新型多壁碳纳米管/白藜芦醇印迹溶胶-凝胶层层组装电化学传感器研究

采用电化学沉积方法将印迹溶胶-凝胶膜沉积到功能化碳纳米管(MWNT-COOH)修饰的碳电极表面,成功研制一种新型多壁碳纳米管/白藜芦醇印迹溶胶-凝胶电化学传感器.采用扫描电镜(SEM),循环伏安法(CV),方波伏安法(SWV)和计时电流法(i-t)详细考察该印迹溶胶-凝胶膜的形态和电化学性能.结果表明该传感器对白藜芦醇具有较高的选择性和亲和性.与无多壁碳纳米管修饰的印迹传感器比较,MWNT层修饰的印迹传感器电流响应信号明显提高.白藜芦醇与印迹溶胶-凝胶膜的特异性结合使该传感器的电流发生变化,电流变化与白藜芦醇浓度在5.0×10-7～8.0×10-5mol?L-1范围内呈良好线性关系,检测限为5.1×10-8mol?L-1,该传感器成功应用于葡萄酒中白藜芦醇含量的检测.     

L-色氨酸分子印迹传感器敏感膜的制备与性能

以L-色氨酸(L-Trp)为模板分子, 邻苯二胺(o-PD)为功能单体, 在金电极表面原位合成了分子印迹聚合物敏感膜; 通过循环伏安法(CV)、 差示脉冲伏安法(DPV)和电化学阻抗谱法(EIS)考察了该电极的性能. DPV测试结果表明, 在1×10^-8~2×10^-7 mol/L范围内, 峰电流与L-Trp的浓度呈线性关系, 检出限为0.3×10^-8 mol/L; 选择识别性实验结果表明, L-Trp印迹敏感膜的印迹因子达到3.72, 相对于干扰物的选择因子均大于1, 对与L-Trp结构相似的L-酪氨酸(L-Tyr)的选择因子也达到2.30, 说明该印迹膜对L-Trp具有良好的选择性; 识别过程动力学研究结果表明, 印迹膜对L-Trp的识别是一个两步连续发生的过程, 即快结合过程和慢吸附过程.     

Acetylsalicylic acid electrochemical sensor based on PATP-AuNPs modified molecularly imprinted polymer film

A novel electrochemical sensor based on molecularly imprinted polymer film has been developed for aspirin detection. The sensitive film was prepared by co-polymerization of p-aminothiophenol (p-ATP) and HAuCl(4) on the Au electrode surface. First, p-ATP was self-assembled on the Au electrode surface by the formation of Au-S bonds. Then, the acetylsalicylic acid (ASA) template was assembled onto the monolayer of p-ATP through the hydrogen-bonding interaction between amino group (p-ATP) and oxygen (ASA). Finally, a conductive hybrid membrane was fabricated at the surface of Au electrode by the co-polymerization in the mixing solution containing additional p-ATP, HAuCl(4) and ASA template. Meanwhile, the ASA was spontaneously imprinted into the poly-aminothiophenol gold nanoparticles (PATP-AuNPs) complex film. The amount of imprinted sites at the PATP-AuNPs film significantly increases due to the additional replenishment of ASA templates. With the significant increasing of imprinted sites and doped gold nanoparticles, the sensitivity of the molecular imprinted polymer (MIP) electrode gradually increased. The molecularly imprinted sensor was characterized by electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV), and cyclic voltammetry (CV). The linear relationships between current and logarithmic concentration were obtained in the range from 1 nmol L(-1) to 0.1 μmol L(-1) and 0.7 μmol L(-1) to 0.1 mmol L(-1). The detection limit of 0.3 nmol L(-1) was achieved. This molecularly imprinted sensor for the determination of ASA has high sensitivity, good selectivity and reproducibility, with the testing in some biological fluids also has good selectivity and recovery.