分子印迹电化学传感器

分子印迹电化学传感器能够选择性识别并检测特定目标化合物,因其设计简单、灵敏度高、价格低廉、携带方便、易于微型化和自动化等优点,在临床诊断、环境监测、食品分析等方面越来越受到人们的关注.本文作者主要论述分子印迹技术与电化学技术相结合构建分子印迹电化学传感器,包括分子印迹电化学传感器的种类,以及电化学方法制备分子印迹聚合物膜的常用单体等.对分子印迹电化学传感器领域新出现的分子印迹聚合物-纳米材料复合物以及纳米结构分子印迹聚合物也一并做了评述.     

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。     

基于磁性分子印迹聚合物的电化学传感器的研究进展

分子印迹聚合物与磁性纳米材料结合,制备成磁性分子印迹纳米敏感膜,这样做不仅可以发挥分子印迹聚合材料的优势,而且磁性纳米粒子可有效提高电化学传感器的灵敏度、稳定性以及生物相容性等.近年来将磁性分子印迹纳米敏感膜应用于电化学传感器制备成的磁性分子印迹电化学传感器得到了较快的发展.本文就近5年来磁性分子印迹电化学传感器敏感膜...     

聚苯胺分子印迹膜电化学传感器检测氯霉素

以苯胺为功能单体和交联剂,氯霉素(chloramphenicol,CAP)为模板分子,采用电化学聚合法(循环伏安法)在金电极上合成了对CAP具有快速响应能力的聚苯胺分子印迹膜;结合差示脉冲伏安法建立了针对氯霉素的检测方法,并将所制备的聚苯胺分子印迹膜用作电化学传感器以测定氯霉素眼药水中的氯霉素.结果表明,所制备的聚苯胺分子印迹膜具有制备简单、响应快速、灵敏度高、再生性能良好等特点;其对氯霉素眼药水中的氯霉素的检测结果令人满意,有望用于实际样品中氯霉素的检测.     

表面分子印迹磁性纳米粒子的制备及其血红蛋白传感应用

以Fe₃O₄磁性纳米粒子为载体、多巴胺（DA）为功能单体、血红蛋白（Hb）为模板分子,用氯铂酸氧化DA生成聚多巴胺（PDA）,同时氯铂酸还原为铂纳米粒子（PtNPs）,与Hb一起负载于Fe₃O₄纳米粒子表面,洗脱Hb后合成了表面分子印迹磁性纳米粒子（印迹Fe₃O₄/PDA-PtNPs）. 将印迹Fe₃O₄/PDA-PtNPs修饰于磁性玻碳基底表面,制得印迹Fe₃O₄/PDA-PtNPs修饰电极. 实验结果表明,印迹Fe₃O₄/PDA-PtNPs具有良好的水溶性,粒径分布均匀,生成的PtNPs具有良好的导电性和刚性. 用印迹Fe₃O₄/PDA-PtNPs构建的传感器对Hb具有良好的识别性,在0.14 ~ 2.7 μg·mL^-1 Hb浓度范围与交流阻抗变化值呈良好的线性关系,检出限（S/N=3）为0.05 μg·mL^-1.     

分子印迹电化学传感器的研究进展

本文综述了分子印迹电化学传感器的制备及其在电分析化学领域中的应用研究。引用文献83篇。     

分子印迹电化学传感器检测水产品中孔雀石绿

以孔雀石绿(MG)为模板,以邻氨基酚为功能单体通过循环伏安法(CV)在玻碳电极表面上聚合制备了MG分子印迹电化学传感器,用CV法和差分脉冲法(DPV)研究了传感器的响应性能,并用于水产品中MG检测。结果表明,DPV峰电流减少量与MG浓度在0.02～0.5μg·mL^-1范围内呈线性关系,线性方程为ΔI(μA)=26.77C_MG+2.663;在0.5～2.5μg·mL^-1范围内呈线性关系,线性方程为ΔI(μA)=2.662C_MG+14.25,检出限为1.2×10^-2μg·mL^-1。MG分子印迹电化学传感器操作简单快捷,具有较好的特异性、重复性和稳定性,可满足水产品中MG的快速检测需要。     

盐酸环丙沙星分子印迹电化学传感器

本文将电化学合成与分子印迹技术相结合,采用循环伏安法在石墨电极表面,形成盐酸环丙沙星(CPX)分子印迹聚吡咯薄膜,制备了CPX分子印迹传感器。实验对传感器的制备条件进行了优化,用铁氰化钾作为活性电子探针,采用方波伏安法研究了传感器性能。结果表明,在1×10~(-8)~1×10~(-4)mol/L范围内,峰电流与CPX浓度负对数呈良好的线性关系,检出限(S/N=3)为3.5×10~(-9)mol/L。传感器对模板分子CPX选择性强,重现性和稳定性好,置于室温下15d峰电流强度无明显变化。     

分子印迹电化学发光分析

分子印迹电化学发光兼具分子印迹技术及电化学发光方法两者的优点,即高灵敏度、高选择性、可控性好、易于微型化和操作简单等特点。近几年来在生物仿生传感器、有害农药残留物质及食品安全监测等方面具有广泛的应用。本综述简要介绍分子印迹电化学发光传感器及分子印迹固相萃取电化学发光的概况,并对其今后的研究趋势进行展望。     

对羟基苯甲酸酯分子印迹电化学传感器的研制

利用分子印迹技术,以对羟基苯甲酸乙酯为模板分子,甲基丙烯酸为单体,在玻碳电极表面原位聚合分子印迹聚合物敏感膜.采用方波伏安法对对羟基苯甲酸乙酯在该印迹电极上的电化学行为进行了研究,当响应时间为15 min时,0.95 V(vs SCE)处的峰电流与对羟基苯甲酸乙酯的浓度在2.0×10-6 ～2.0×10-4 mol/L范围内呈线性关系,检出限(S/N=3)为1.0 μmol/L,而相同条件下,对羟基苯甲酸乙酯在控制电极上的响应非常小并对浓度变化不灵敏;同时在印迹电极上氧化峰电位较在裸电极上发生了微弱正移.同一支印迹电极对对羟基苯甲酸乙酯响应值的RSD为4.3%(n=10).该印迹电极对尼泊金酯类具有良好的选择性,对对羟基苯甲酸甲酯、丙酯以及丁酯的选择性系数分别为1.89、1.70和2.01;对结构相似的苯酚、对羟基苯甲酸、对氨基苯甲酸等响应不灵敏,对结构差异较大的如维生素C等几乎无响应.用该分子印迹电极对实际样品进行分析,加标回收率大于90%.     

没食子酸丙酯印迹电化学传感器的构建及应用研究

以羧基化的多壁碳纳米管(MWCNT)为基底,通过酰胺化表面接枝聚乙烯亚胺(PEI)得到MWCNT-PEI复合物功能单体,进而以没食子酸丙酯(PG)为模板分子、乙二醇二缩水甘油醚为交联剂,制备了PG表面分子印迹聚合物,最后采用滴涂法在玻碳电极(GCE)表面构建PG分子印迹电化学传感器。通过循环伏安、电化学阻抗和差分脉冲伏安等手段对所构建传感器的导电性以及PG分子的线性响应、特异识别性、检测稳定性和重复性等进行了测试与表征。结果表明,传感器在PG浓度为1×10~(-8)～1×10~(-5)mol/L的范围内具有良好的线性关系,相关系数为0. 9964,检出限达2. 5×10~(-9)mol/L。此外,该传感器在实际样品中的PG回收率为95%～98%。     

Molecularly Imprinted Electrochemical Sensor for the Detection of Organophosphorus Pesticide Profenofos

The presence of profenofos (PFF) in food has been strictly limited by legislation due to its genotoxic and toxic effects on health. It is therefore very important to establish simple and rapid analytical methods to detect traces of this insecticide. A reusable molecularly imprinted polypyrrole MIP(O-PPy) on a glassy carbon electrode (GCE) has been developed to measure PFF. The PPy was polymerized by cyclic voltammetry (CV) in the presence of template molecules (PFF) in an acidic solution on a GCE. The various experimental parameters such as film thickness, analyte/monomer ratio, and removal/rebinding requirements were examined and optimized. The signal of the redox probe (ferrocyanide/ferrocyanide) was used for the electrochemical detections. All steps of the sensor manufacturing, removal/rebinding of template molecules, and response to different PFF concentrations were tested by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). The MIP sensor was able to detect PFF in the linear ranges of 1.0×10⁻⁹ to 1.0×10⁻⁶ M and 1.0×10⁻⁹ to 5.0×10⁻⁶ M, with detection limits, a signal-to-noise ratio (S/N) of three was used to estimate LOD, of about 1 nM using DPV and EIS, respectively. The MIP (PPy) GCE provided excellent PFF recognition performance and was successfully used to quantify PFF in sweet pepper samples, yielding recoveries not greater than 108 %.     

Determination of Bisphenol A Using an Electrochemical Sensor Based on a Molecularly Imprinted Polymer-Modified Multiwalled Carbon Nanotube Paste Electrode

A novel electrochemical sensor for bisphenol A was developed through the combination of a molecular imprinting technique with a multiwalled carbon nanotube paste electrode. A molecularly imprinted polymer and nonimprinted polymer were synthesized in the presence and absence of bisphenol A, and then used to prepare the electrode. The bisphenol A imprinted polymer was applied as a selective recognition element in the electrochemical sensor. Differential pulse voltammetry was used to characterize the electrochemical behavior of bisphenol A at the modified electrodes. The results showed that the imprinted sensor had highest response for bisphenol A. Parameters including the carbon paste composition, pH, and adsorption time for the imprinted sensor were optimized. Under the optimized conditions, the differential pulse voltammetry peak current was linear with the concentration of bisphenol A from 0.08 to 100.0 µM, with a detection limit of 0.022 µM. The imprinted sensor for bisphenol A exhibited good selectivity, stability, and reproducibility. This sensor was successfully used for the determination of bisphenol A in real water samples.     

基于纳米孔金与离子印迹聚合物结合的新型电化学传感器用于测定砷离子(III)

砷是一种有毒的化学元素,尤其对环境和人体健康有害. 因此,简单、快速和准确的砷离子（As³⁺）检测方法的开发引起了广泛的关注. 本项工作研究了基于离子印迹聚合物（MIP）和纳米多孔金（NPG）改性氧化铟锡（ITO）电极（MIP/NPG/ITO）用于检测不同水质中砷离子（As³⁺）测定的电化学传感器. 通过步骤简单、易操控、绿色环保的电沉积方法在ITO表面原位制备具有高导电,大比表面积,高生物相容性的NPG. 然后通过电聚合在NPG表面上原位合成一层MIP,其中As³⁺用作模板分子,邻苯二胺用作功能单体. 通过扫描电镜（SEM）和能谱仪（EDS）对MIP/NPG/ITO的制备过程进行了跟踪. 采用铁氰化钾与亚铁氰化钾螯合物作为电化学探针产生信号,采用循环伏安法（CV）和电化学阻抗谱（EIS）研究了MIP/NPG/ITO的电化学行为. 通过优化实验条件,采用循环伏安法对As³⁺进行了定量检测,其测量As³⁺的线性范围为2.0×10^-11至9.0×10^-9 mol·L^-1,检测下限为7.1×10^-12 mol·L^-1（S/N = 3）. 所构建传感器的检出限远低于10 ppb,符合世界卫生组织（WHO）和环境保护局（EPA）设定的饮用水标准. 另外,该传感器具有制备和确定步骤简单,重复性好,重现性和稳定性优异的优点. 值得一提的是,所制备的传感器已成功应用于测量景观河水、地下水、自来水和生活污水等四种水质中As³⁺. 可以预见,这种简单而廉价的传感器在环境监测,食品分析和临床诊断领域具有潜在的实际应用价值.     

分子印迹电化学传感器的制备及其快速检测饮水中草甘膦残留的应用研究

以吡咯(Py)为功能单体,草甘膦(Gly)为模板,采用电化学聚合法构建了草甘膦分子印迹电化学传感器。通过循环伏安法(CV)、差分脉冲伏安法(DPV)、电化学交流阻抗法(EIS)对印迹电极性能进行了表征,筛选了印迹电极的聚合体系和模板分子的洗脱方法,优化了检测体系的p H值和吸附时间等。结果表明,以铁氰化钾为电活性探针,在最优检测体系中该印迹传感器对草甘膦具有特异性快速响应、灵敏度高和稳定性好的优点,传感器的峰电流与草甘膦浓度在5~800 ng/m L范围内呈良好的线性关系,相关系数(r2)为0.981 7,检出限(S/N=3)为0.27 ng/m L。该传感器具有良好的重现性和稳定性,放置3周后对目标物的响应峰电流无明显变化。用于实际样品中草甘膦的测定,加标回收率为78.6%~99.0%,能满足现场快速检测的要求。     

Preparation of Molecularly Imprinted Electrochemical Sensor for Detection of Vincristine Based on Reduced Graphene Oxide/Gold Nanoparticle Composite Film

An innovative molecularly imprinted electrochemical sensor was fabricated based on reduced graphene oxide (RGO) and gold nanocomposite (Au) for rapid detection of vincristine (VCR). The RGO‐Au composite membrane was obtained via direct one‐step electrodeposition technique of graphene oxide (GO) and chloroauric acid (HAuCl₄) on the surface of a glassy carbon electrode (GCE) by means of cyclic voltammetry (CV) in the potential range between ?1.5 and 0.6 V in phosphate buffer solution (PBS) of pH 9.18, which is capable of effectively utilizing its superior electrical conductivity, larger specific surface area due to its synergistic effect between RGO and Au. The molecularly imprinted polymers (MIPs) were synthesized on the RGO‐Au modified glassy carbon electrode surface with VCR as the template molecular, methyl acrylic acid (MAA) as the functional monomer, and ethylene glycol maleic rosinate acrylate (EGMRA) as a cross‐linker. The performance of the sensor was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) in detail. Under the optimum conditions, the fabricated sensor exhibited a linear relationship between oxidation peak current and VCR concentration over the range of 5.0×10^?8–5.0×10^?6 mol·L ^minus;1 with a correlation coefficient of 0.9952 and a detection limit (S/N=3) of 2.6×10^minus;8 mol·L^minus;1. The results indicated that the imprinted polymer films exhibited an excellent selectivity for VCR. The imprinted sensor was successfully used to determine VCR in real samples with recoveries of 90% –120% by using the standard addition method.     

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。     

多巴胺有序介孔硅表面分子印迹传感器的研制

以多巴胺(DA)为模板,氨基修饰的介孔硅为载体,制得对多巴胺具有特异选择性的表面分子印迹聚合物(MIP)。将所得的MIP制成碳糊电极,用循环伏安法对多巴胺进行检测。在优化实验条件下,传感器的氧化峰电流与多巴胺浓度在1.0×10-7～2.0×10-6mol/L和2.0×10-6～1.0×10-4mol/L范围内呈良好的线性关系,相关系数分别为0.992 5和0.996 9,检出限为1.3×10-9mol/L。该传感器对DA具有较高的灵敏度和选择性,将其用于实际样品检测,结果满意。