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。     

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。     

磁性分子印迹电化学传感法检测痕量奥卡西平

该文以4-乙烯基吡啶和甲基丙烯酸酯为原料制备了一种可用于检测奥卡西平（OXC）的磁性分子印迹 电化学传感器（MNPs－MIP/MCPE）。首先,依据密度泛函数理论（DFT/B3LYP/6－31 + G）计算,实验成功地 筛选和构建出 OXC与功能单体的最佳组合及比例。随后,基于沉淀聚合法合成了能够识别 OXC的磁性分子 印迹膜（MNPs－MIP）,将MNPs－MIP覆于碳糊电极（MCPE）表面制成MNPs－MIP/MCPE。采用差分脉冲伏安 法（DPV）将 MNPs－MIP/MCPE 传感器用于不同浓度 OXC 的测定。结果显示,传感器的峰电流信号随 OXC 浓 度的增大而增大,且OXC分别在5 × 10－8 ～3 × 10－6 mol/L和3 × 10－6 ～1. 5 × 10－4 mol/L浓度范围内与其峰电流 信号呈线性关系,其线性方程分别为：Ip （μA）= 1. 755 + 1. 097c（μmol/L）,相关系数（r）= 0. 999 7 和 Ip （μA）= 0. 131 + 5. 177c（μmol/L）,r = 0. 999 6。OXC的检出限（LOD = 3S/m）为2. 06 × 10－8 mol/L。该传感器成 功用于实际样品中OXC含量的检测,其回收率为99. 4%~101%,相对标准偏差（RSD）为1. 5%～2. 5%。     

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%.     

以马来松香丙烯酸乙二醇酯为交联剂的茶碱分子印迹膜电化学传感器的研究

利用分子印迹技术, 以马来松香丙烯酸乙二醇酯为交联剂, 丙烯酸为功能单体研制了测定茶碱的新型电化学传感器. 以自由基热聚合的方式于玻碳电极表面制备茶碱分子印迹聚合物膜. 通过循环伏安法、电化学交流阻抗法及计时电流法研究了传感器对茶碱的响应特性. 结果表明, 在最佳的实验条件下, 传感器的峰电流与茶碱浓度在2.00×10^-7～3.45×10^-4 mol/L 范围内呈现出良好的线性关系(线性相关系数为0.9961), 检出限(S/N＝3)为1.00×10^-7 mol/L;该传感器的选择性高, 稳定性和重现性好, 将此传感器用于茶碱缓释片中茶碱的含量测定, 回收率为95.6%～103.8%.关键词 马来松香丙烯酸乙二醇酯; 茶碱; 分子印迹聚合物; 电化学传感器     

Electrosynthesis of Molecularly Imprinted Poly‐o‐phenylenediamine on MWCNT Modified Electrode for Selective Determination of Meldonium

In this study, a molecularly imprinted polymer (MIP) was synthesized by electrochemical polymerization and used to construct an electrochemical sensor for determination of meldonium (MEL) selectively for the first time. The polymer film was generated by using o‐phenylenediamine (o‐PD) as a monomer on the surface of carboxylic acid functionalized multiwalled carbon nanotube (MWCNT) modified pencil rod electrode in the presence of MEL as a template. MEL imprinted (MEL‐imp) and non‐imprinted (N‐imp) polymer films and coated electrodes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), profilometry, electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Voltammetric measurements were carried out in a ferrocyanide/ferricyanide redox probe solution for MEL‐imp and N‐imp electrodes in the presence and absence of template molecule. The decrease in peak current of redox probe was linear with the concentration of MEL in the range of 0.1–5 μg/mL and the limit of detection (3 s/b) was found to be 0.066 μg/mL under optimized experimental conditions. The proposed sensor was successfully applied for selective determination of MEL in human urine sample with long term stability and good reproducibility.     

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.     

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。     

固相微萃取-气相色谱法分析水中痕量1-萘酚

利用固相微萃取（ＳＰＭＥ）－气相色谱法（ＧＣ）分析了水中前量的１－萘酚。对于ＳＰＭＥ萃取头,溶液介质条件、吸附和解吸时间进行了研究。结果表明,ＰＡ＿８５萃取头对于水中１－萘酚的富集效果最佳。而无机盐氯化钠的加入和降低ＰＨ值可以明显地改善萃取效果。在优化后的条件下,ＳＰＭＥ－ＧＣ方法对于水中１－萘酚的检测限可达０．５μｇ／Ｌ,分析过程中标准偏差均小于４％。     

分子印迹电化学传感器测定L-色氨酸的研究

报道了一种由溶胶-凝胶法制备的分子印迹电化学传感器,并用于L-色氨酸的测定.印迹聚合物是由四乙氧基硅烷、甲基三甲氧基硅烷、苯基三甲氧基硅烷等聚合而成,L-色氨酸为模板分子.通过循环伏安法验证了印迹膜与模板分子的结合和去除.该传感器对L-色氨酸具有良好的选择性以及高的灵敏度,线性范围为1.0×10-9～1.0×10-5m...     

盐酸金霉素分子印迹电化学传感器的研制

构建了一种选择性检测盐酸金霉素(CTC)的分子印迹电化学传感器。在NaClO4溶液中,以邻氨基酚(OAP)为功能单体,盐酸金霉素(CTC)为模板,通过循环伏安法在玻碳电极表面上聚合制备了CTC印迹敏感膜(MIPs)。在含0.005 mol/L K3[Fe(CN)6]及0.1 mol/L KCl的磷酸盐缓冲液(PBS)中,应用差分脉冲伏安法(DPV)研究了传感器的响应性能。DPV峰电流差与CTC浓度在2.0×10!8~6.1×10!7mol/L范围内呈线性关系,检出限为1.5×10!8mol/L(3σ)。实验表明,用甲醇/H2SO4混合洗脱溶液可以使传感器再生,对CTC的测定具有良好的重现性,并具有良好的储存稳定性。传感器对于干扰物氯霉素及青霉素没有响应,结构相似的四环素、土霉素有微弱的响应,显示了良好的选择性。在牛奶和鸡肉实际样品中所测得的CTC加标回收率为86.4%~96.9%。与文献报道的CTC检测方法相比,本传感器具有低的检测限,操作简便,整个过程无需衍生化处理,响应快,成本低。     

Surface Polymers on Multiwalled Carbon Nanotubes for Selective Extraction and Electrochemical Determination of Rhodamine B in Food Samples

In this study, we combine magnetic solid phase extraction (MSPE), with the screen-printed carbon electrode (SPCE) modified by a molecular imprinted polymer (MIP) for sensitive and selective extraction and electrochemical determination of Rhodamine B in food samples. A magnetic solid phase extraction (MSPE) was carried out using magnetic poly(styrene-co-divinylbenzene) (PS-DVB) and magnetic nanoparticles (MNPs) synthetized on the surface of multiwalled carbon nanotubes (MWCNTs). An MIP was prepared on the surface of MWCNTs in the presence of titanium oxide nanoparticles (TiO₂NPs) modifying the SPCE for the rapid electrochemical detection of Rhodamine B. The MIPs synthesis was optimized by varying the activated titanium oxide (TiO₂) and multiwalled carbon nanotubes (MWCNTs) amounts. The MSPE and electrochemical detection conditions were optimized as well. The present method exhibited good selectivity, high sensitivity, and good reproducibility towards the determination of Rhodamine B, making it a suitable method for the determination of Rhodamine B in food samples.     

导数-可变角同步荧光法用于1-萘酚和2-萘酚的同时测定

同步扫描和导数光谱法是两类很有用的荧光分析新技术。固定波长或恒能量同步荧光法和导数技术的结合可进一步提高光谱分辨率和排除基体干扰。本文将导数技术和可变角同步荧光法结合起来,用于1-萘酚和2-萘酚的同时分析,效果良好。研究表明,导数-可变角同步荧光法可望发展为荧光分析复杂样品的新技术。     

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%。     

Selective Electrochemical Determination of Salicylic Acid in Wheat Using Molecular Imprinted Polymers

Salicylic acid is a phytohormone, playing crucial roles in signal transduction, crop growth, and development, and defense to environmental challenges. In this study, a highly selective electrochemical sensor was designed and used to determine salicylic acid using molecularly imprinted polymers for recognition. The electrochemical sensor was fabricated via stepwise modification of gold nanoparticle–graphene–chitosan and molecularly imprinted polymers on a glassy carbon electrode. With electrochemical deposition, a gold nanoparticle–graphene–chitosan film was deposited on the glassy carbon electrode and enhanced the sensitivity. Molecularly imprinted polymers with adsorbed template salicylic acid were added to the surface of the modified electrode. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the modified electrodes. Salicylic acid in wheat was quantified by the sensor using the molecularly imprinted polymer/gold nanoparticle–graphene–chitosan/glassy carbon electrode. Concentrations of salicylic acid from 5?×?10^?10 to 5?×?10^?5?mol?L^?1 were determined showing that the developed sensor was suitable for the analysis of food.     

Computational Modelling and Sustainable Synthesis of a Highly Selective Electrochemical MIP-Based Sensor for Citalopram Detection

A novel molecularly imprinted polymer (MIP) has been developed based on a simple and sustainable strategy for the selective determination of citalopram (CTL) using screen-printed carbon electrodes (SPCEs). The MIP layer was prepared by electrochemical in situ polymerization of the 3-amino-4 hydroxybenzoic acid (AHBA) functional monomer and CTL as a template molecule. To simulate the polymerization mixture and predict the most suitable ratio between the template and functional monomer, computational studies, namely molecular dynamics (MD) simulations, were carried out. During the experimental preparation process, essential parameters controlling the performance of the MIP sensor, including CTL:AHBA concentration, number of polymerization cycles, and square wave voltammetry (SWV) frequency were investigated and optimized. The electrochemical characteristics of the prepared MIP sensor were evaluated by both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Based on the optimal conditions, a linear electrochemical response of the sensor was obtained by SWV measurements from 0.1 to 1.25 µmol L⁻¹ with a limit of detection (LOD) of 0.162 µmol L⁻¹ (S/N = 3). Moreover, the MIP sensor revealed excellent CTL selectivity against very close analogues, as well as high imprinting factor of 22. Its applicability in spiked river water samples demonstrated its potential for adequate monitoring of CTL. This sensor offers a facile strategy to achieve portability while expressing a willingness to care for the environment.     

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.     

Sensitive and Selective Electrochemical Sensor Based on Molecularly Imprinted Polypyrrole Hybrid Nanocomposites for Tetrabromobisphenol A Detection

Abstract

A sensitive and selective electrochemical sensor based on electropolymerized molecularly imprinted polypyrrole and gold nanoparticles–multiwalled carbon nanotubes (AuNPs–MWCNTs) hybrid nanocomposites was developed for the determination of tetrabromobisphenol A (TBBPA). A glassy carbon electrode (GCE) was modified with MWCNTs, and the AuNPs–MWCNTs/GCE was prepared by an electrodeposition method in HAuCl₄ solution. The AuNPs–MWCNTs nanocomposite showed high electrocatalytic activity, good conductivity, and sufficient reactive sites for the direct electro-oxidation of TBBPA. The molecularly imprinted polymers (MIPs) as recognition elements were synthesized through in situ electro-polymerization of pyrrole as functional monomers in the presence of the TBBPA template molecules. Under the optimal conditions, the developed sensor exhibited good selectivity towards TBBPA compared with structural analogs, high sensitivity, and excellent producibility. The electrochemical responses of the sensor toward TBBPA were obtained in the linear range from 0.5?nM to 1?μM with a limit of detection equal to 0.24?nM at a signal-to-noise ratio of 3.     

Determination of Tetracyclines in Milk with a Molecularly Imprinted Polymer-Based Microtiter Chemiluminescence Sensor

A molecularly imprinted polymer (MIP) capable of recognizing five tetracyclines using minocycline as the template was synthesized for the first time. The MIP was employed as the recognition reagent to prepare a chemiluminescence sensor on a conventional microtiter plate. The light signal was initiated using the highly efficient bis(2,4,6-trichlorophenyl) oxalate-hydrogen peroxide-imidazole chemiluminescence system. After optimization of several appropriate factors, the sensor was employed to determine five tetracyclines in milk. The developed assay contained only one sample-loading step, so each measurement was completed within 12?min. The limits of detection for these analytes were in the range from 0.5 to 2.0?pg/mL, while the recoveries from the fortified milk samples were between 78.1 and 105%. In addition, the sensor was shown to be reusable for up to four measurements. Hence, this sensor has been demonstrated to be a simple, rapid, sensitive, and durable tool for the determination of tetracyclines in animal-derived food.