High Selective Parathion Voltammetric Sensor Development by Using an Acrylic Based Molecularly Imprinted Polymer‐Carbon Paste Electrode

The design and construction of an extra high selective voltammetric sensor for parathion by using a molecularly imprinted polymer (MIP) as recognition element was introduced. A parathion selective MIP and a nonimprinted polymer (NIP) were synthesized and then incorporated in the carbon paste electrode. The MIP‐CP electrode showed very high recognition ability in comparison to NIP‐CP. It was shown that electrode washing after parathion extraction, led to enhanced selectivity. Some parameters affecting the sensor response were optimized and then the calibration curve was plotted. A dynamic linear range of 1.7–900 nM was obtained. The detection limit of the sensor was calculated as 0.5 nM. This sensor was used successfully for parathion determination in real samples such as ground water and vegetables.     

Determination of Trace Copper by Adsorptive Voltammetry Using a Multiwalled Carbon Nanotube Modified Carbon Paste Electrode

A new method for the determination of trace copper was described. A multiwalled carbon nanotube modified carbon paste electrode was prepared and the adsorptive voltammetric behavior of copper‐alizarin red S (ARS) complex at the modified electrode was investigated. By use of the second‐order derivative linear sweep voltammetry, it was found that in 0.04 mol/L acetate buffer solution (pH 4.2) containing 4×10^?6 mol/L ARS, when accumulation potential is 0 mV, accumulation time is 60 s and scan rate is 100 mV/s, the complex can be adsorbed on the surface of the electrode, yielding one sensitive reduction peak at ?172 mV (vs. SCE). The peak current of the complex is proportional to the concentration of Cu(II) in the range of 2.0×10^?11–4.0×10^?7 mol L^?1 with a detection limit (S/N=3) of 8.0×10^?12 mol/L (4 min accumulation). The proposed method was successfully applied to the determination of copper in biological samples with satisfactory results, the recoveries were found to be 96%–102%.     

碳纳米纤维修饰碳糊电极用于双酚A的电化学检测

制备了碳纳米纤维修饰碳糊电极,并用于双酚A的高灵敏和高选择性电化学检测。碳纳米纤维材料经静电纺丝和碳化过程相结合制备而成,采用滴涂的方法修饰于碳糊电极表面制成电化学传感器。利用循环伏安法、交流阻抗法以及微分脉冲伏安法考察了传感器的性质及双酚A的电化学行为。结果表明,双酚A的峰电流响应与其浓度在0.8~50μmol/L之间呈良好的线性关系,检测限为0.1μmol/L。构建的电化学传感器用于环境水样中双酚A的检测具有较高的回收率。     

Molecularly Imprinted Poly-o-phenylenediamine Electrochemical Sensor for Entacapone

We have developed a molecularly imprinted polymer (MIP) electrochemical sensor for entacapone (ETC) based on an electropolymerised polyphenylenediamine (Po-PD) on a glassy carbon electrode (GCE) surface. The direct electropolymerisation of the o-phenylenediamine monomer (o-PD) was carried out with ETC as a template. The steps of electropolymerization process, template removal and binding of the analyte were tested by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using [Fe(CN)₆]³⁻/[Fe(CN)₆]^{4 −} as a redox probe. The operation of the sensor has been investigated by differential pulse voltammetry (DPV). Under optimal experimental conditions, the response of the DPV was linearly proportional to the ETC concentration between 1.0×10⁻⁷ and 5.0×10⁻⁶ M ETC with a limit of detection (LOD) of 5.0×10⁻⁸ M. The developed sensor had excellent selectivity without detectable cross-reactivity for levodopa and carbidopa. The MIP sensor was successfully used to detect ETC in spiked human serum samples.     

基于石墨烯的毒死蜱分子印迹电化学传感器的制备及对毒死蜱的测定

利用分子印迹技术,以马来松香丙烯酸乙二醇酯为交联剂,使用自由基热聚合法在石墨烯修饰的玻碳电极表面合成毒死蜱( CPF)分子印迹聚合膜,制得了CPF分子印迹电化学传感器。采用循环伏安法、线性扫描伏安法和电化学交流阻抗法等,考察了此CPF分子印迹膜的电化学性能。在最佳检测条件下,传感器的峰电流与CPF浓度在2.0×10-7~1.0×10-5mol/L范围内呈线性关系,线性方程为Ip(μA)=-7.1834-0.2424C (μmol/L),相关系数r2=0.9959,检出限为6.7×10-8 mol/L(S/N=3)。构建了CPF分子印迹电化学传感器的动力学吸附模型,测得印迹传感器的印迹因子β=2.59,结合速率常数k=12.2324 s。传感器表现出良好的重现性和稳定性,并成功用于实际水样和蔬菜样品中CPF的测定,加标回收率为94.1%~101.4%。     

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%。     

Electrochemical Determination of Tetracycline Using Molecularly Imprinted Polymer Modified Carbon Nanotube‐Gold Nanoparticles Electrode

This paper reports the use of a tetracycline (TC) sensor constructed from a combination of molecularly imprinted polymer (MIP) and gold nanoparticles modified multiwall carbon nanotubes (MWNTs‐GNPs). The results demonstrated that the amount of recognition sites in the polymer was significantly increased and the electron transfer ability of the sensor was improved. The relationship between the peak current and the TC concentration was linear in the range from 0.1 to 40 mg L^?1, and the detection limit was 0.04 mg L^?1 (S/N=3). The peak current to TC was 4.3, 6.2 and 6.8 times larger than that of oxytetracycline, chloramphenicol and nafcillin, respectively. Thus, the combination of MIP and MWNTs‐GNPs provides a sensitive and selective electrochemical detection method for tetracycline.     

Molecularly Imprinted Impedimetric Sensor for Determination of Mycotoxin Zearalenone

The mycotoxin zearalenone (ZEA) prompts reproductive toxicity due to its strong estrogenic effects. In this work, an electrochemical sensor for determination of ZEA was developed by electropolymerization of a molecularly imprinted poly (o‐phenylenediamine) (PPD) film on screen‐printed gold electrode (SPGE) surface. The sensor was examined by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using K₃[Fe(CN)₆]/K₄[Fe(CN)₆] as redox probe. The molecularly imprinted polymer (MIP) sensor showed a wide determination range from 2.50 to 200.00 ngmL^?1 for ZEA. The Limit of detection (LOD) was calculated to be 0.20 ngmL^?1, based on the signal to noise (S/N) ratio equal to 3.0. The sensor displayed good repeatability, with RSD values≤4.6 %, and maintained 93.2 % of its initial response after storage for 10 days in air at room temperature. The developed method was successfully applied for the determination of ZEA in corn flakes with mean recoveries ranged from 96.2 % to 103.8 % and RSDs within the interval of 2.1 % to 3.8 %.     

Electrochemical Sensor for trans‐Resveratrol Determination Based on Indium Tin Oxide Electrode Modified with Molecularly Imprinted Self‐Assembled Films

A voltammetric sensor for sensitive and specific determination of trans‐resveratrol (RES) were prepared based on immobilization of an RES‐imprinted film on the surface of functionalized Indium Tin Oxide (ITO) electrode, which was modified with γ‐methacyloxypropyl trimethoxysilane (γ‐MPS). Cyclic Voltammetry (CV) was presented to extract RES from the molecularly imprinted polymer film and RES were extracted rapidly and completely. The binding performance of the imprinted electrode with the template RES were investigated using differential pulse voltammetry (DPV). The results showed that the imprinted ITO film can give selective recognition to the template RES over that of structurally analogous molecules. A linear response to RES in the concentration range of 2.0×10^?6 M to 2.0×10^?5 M was observed with a correlation coefficient of 0.992, and the detection limit of the electrochemical sensor was 8.0×10^?7 M. Whereas, binding to the reference nonimprinted electrode, made in the same way but without the addition of template RES, there was almost no response to RES.     

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。     

A Novel Electrochemical Sensor Based on Molecularly Imprinted Solid-Phase Extraction for Rapid Determination of Ractopamine in Pig Urine

A new absorbent (polymer) for solid-phase extraction of ractopamine (RAC) was synthesized on the multi-walled carbon nanotubes (MWCTs) using grafting technique and surface imprinting methods. The superficial characteristics of the polymer were studied by scanning electron microscopy (SEM) and UN spectrometry was applied to investigate the static and kinetic adsorption capacity of the new absorbent. After the experimental conditions for the solid-phase extraction of RAC were optimized, a sensing system for the determination of RAC was established by connecting the solid-phase extraction column with a portable amperometric sensing system. The SEM study showed that numbers of imprinted micro-pores were exhibited on the surface of the imprinted polymers, and the absorption experiments indicated that the molecularly imprinted absorbent possessed satisfactory kinetics for the adsorption of ractopamine. The current response of the amperometric sensor demonstrated a linear correlation to the concentration of RAC over the range of 50 to 450 nM (r = 0.998) and the detection limit was 15 nM. Satisfactory sensitivity and stability was also presented under the optimized experimental conditions. The recoveries of RAC samples reached 87.3–94.8% in urine sample.     

碳纳米管修饰电极分子印迹传感器的制备及其对氧乐果的测定

以氧乐果为模板分子,邻苯二胺为功能单体,在碳纳米管修饰的玻碳电极表面通过电聚合方法制成氧乐果分子印迹聚合物膜,用无水乙醇洗脱后制备出对氧乐果有特异响应的电化学传感器。通过循环伏安法和电化学阻抗法对分子印迹传感器的电化学性能进行表征。以K_3Fe(CN)_6为探针,采用差分脉冲伏安法研究了该分子印迹传感器的分析性能,建立了氧乐果的间接测定方法。结果表明,K_3Fe(CN)_6的相对峰电流与氧乐果浓度在1.0×10~(-7)~2.0×10~(-6)mol/L范围内呈良好的线性关系,检出限为3.6×10~(-8)mol/L。     

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。     

自组装碳纳米管-氯洁霉素分子印迹溶胶-凝胶电化学传感器研究

结合自组装技术, 采用电聚合方法在碳纳米管修饰金电极表面制备对氯洁霉素具有特异性识别位点的分子印迹溶胶-凝胶薄膜, 成功构建了一种新型印迹溶胶-凝胶电化学传感器. 通过循环伏安法(CV)、示差脉冲法(DPV)、安培计时法(I-t)和扫描电镜(SEM)表征了该印迹溶胶-凝胶膜的电化学性能和表面形貌. 结果表明, 该传感器具有良好的选择性和灵敏度, 氯洁霉素在多壁碳纳米管修饰的印迹溶胶-凝胶传感器上的响应明显提高. 该印迹溶胶-凝胶传感器对氯洁霉素的浓度响应线性范围为5.0×10^-7~8.0×10^-5 mol/L, 检出限为2.44×10^-8 mol/L. 该传感器被成功地用于人体尿液中氯洁霉素的分析测定.     

Selective Solid‐phase Extraction of Bisphenol A Using a Novel Stir Bar Based on Molecularly Imprinted Monolithic Material

In this paper, a novel monolithic stir bar based on molecularly imprinted polymer (MIP) was firstly developed by filling modified neodymium magnet (Nd₂Fe₁₄B) powders into a glass tube (60 × 4 mm), followed by the imprinted grafting with bisphenol A (BPA) as the template molecule by thermal polymerization. It has been successfully used for the stir bar sorptive extraction (SBSE) and its extraction performance illustrated that the MIP‐encapsulated stir bar had stronger affinity to the template molecule, compared with the stir bar based on the non‐imprinted molecularly polymer (NIP). Under the optimal extraction conditions, a simple method based on the coupling of MIP‐SBSE with high performance liquid chromatography (HPLC) was used for the selective determination of the model mixtures of BPA, 4‐phenylphenol (PP) and phenol (P) in bottled water. The recoveries of BPA, PP and P were in the range of 88.5‐96.1%, 78.2‐89.7%, 81.3‐89.5% at three spiked levels, respectively, demonstrating that higher extraction and the specific absorption occurred between the template molecule and the prepared MIP stir bar.     

A Polypyrrole‐Imprinted Electrochemical Sensor Based on Nano‐SnO2/Multiwalled Carbon Nanotubes Film Modified Carbon Electrode for the Determination of Oleanolic Acid

A sensitive molecularly imprinted electrochemical sensor with specific recognition ability for oleanolic acid was synthesized by modification of multiwalled carbon nanotubes (MWNTs) decorated with tin oxide nanoparticles (nano‐SnO₂/MWNTs) and polypyrrole‐imprinted polymer on a carbon electrode. The morphology and electrochemical performance of the imprinted sensor were investigated by using scanning electron microscope (SEM), X‐ray diffraction (XRD), cyclic voltammetry (CV), linear sweep voltammetry (LSV) and amperometric i–t curve. The results showed that the imprinted sensor displayed excellent selectivity toward oleanolic acid. A linear relationship between the response currents and oleanolic acid concentrations ranging from 5.0×10^?8 g/L to 2.0×10^?5 g/L was obtained for the imprinted sensor. The limit of detection (LOD) of the imprinted sensor toward oleanolic acid was calculated as 8.6×10^?9 g/L at a signal to noise ratio (S/N) of 3. This imprinted sensor was successfully applied to the determination of oleanolic acid in Acitinidia deliciosa root samples.     

Simultaneous Electrochemical Determination of Hydroquinone and Bisphenol A using a Carbon Paste Electrode Modified with Silver Nanoparticles

In this paper, a rapid and sensitive modified electrode for the simultaneous determination of hydroquinone (HQ) and bisphenol A (BPA) is proposed. The simultaneous determination of these two compounds is extremely important since they can coexist in the same sample and are very harmful to plants, animals and the environment in general. A carbon paste electrode (CPE) was modified with silver nanoparticles (nAg) and polyvinylpyrrolidone (PVP). The PVP was used as a reducing and stabilizing agent of nAg from silver nitrate in aqueous media. The nAg‐PVP composite obtained was characterized by transmission electron microscopy and UV‐vis spectroscopy. The electrochemical behavior of HQ and BPA at the nAg‐PVP/CPE was investigated in 0.1 mol L⁻¹ B−R buffer (pH 6.0) using cyclic voltammetry (CV) and square wave voltammetry (SWV). The results indicate that the electrochemical responses are improved significantly with the use of the modified electrode. The calibration curves obtained by SWV, under the optimized conditions, showed linear ranges of 0.09–2.00 μmol L⁻¹ for HQ (limit of detection 0.088 μmol L⁻¹) and 0.04–1.00 μmol L⁻¹ for BPA (limit of detection 0.025 μmol L⁻¹). The modified electrode was successfully applied in the analysis of water samples and the results were comparable to those obtained using UV‐vis spectroscopy.     

吲哚-3-乙酸分子印迹聚合物膜电化学传感器的研制

利用分子印迹技术,以吲哚-3-乙酸(IAA)为模板分子,甲基丙烯酸为单体,在玻碳电极表面采用原位聚合制备分子印迹敏感膜.采用方波伏安法对吲哚乙酸在该印迹电极上的电化学行为进行了研究.结果表明,0.62 V(vs.SCE)处的峰电流与吲哚乙酸的浓度在5.0×10-6～2.0×10-4mol/L范围内呈线性关系,检出限(S...     

An Electrochemical Sensor Based on Nitrogen‐doped Carbon Nanofiber for Bisphenol A Determination

In this paper, bisphenol A was determined by electrochemical method at a nitrogen‐doped carbon nanofiber modified carbon paste electrode (NCNF/CPE) with high sensitivity and good selectivity. NCNF was obtained by a simple electrospinning followed by carbonization procedure, in which polyacrylonitrile (PAN) as precursor and nitrogen doping was realized by re‐utilizing the tail gas that produced in the thermal pretreatment process. Good reproducibility and high stability were obtained for BPA detection at NCNF modified CPE. Current response plotted with BPA concentration was linear in the range of 0.1–60 μM with LOD of 0.05 μM. The proposed electrochemical sensor was employed for BPA determination with satisfactory recoveries for real water samples, indicating the practical applicability of NCNF/CPE.     

盐酸阿霉素分子印迹传感器的制备及识别特性

采用自组装以及电聚合的方法,在磷酸盐缓冲液(PBS)中以3,4-乙烯二氧噻吩(EDOT)为功能单体,盐酸阿霉素(DOX)为模板,在金电极表面电聚合制备DOX印迹敏感膜(MIPs),构建了一种选择性检测DOX的分子印迹电化学传感器.采用循环伏安法(CV)及交流阻抗法(EIS)对其性能进行了表征.优化实验条件后,在含0.005 mol/L K3[Fe(CN)_6]及0.1 mol/L KCl的PBS中,应用差分脉冲伏安法(DPV)测试了该传感器的响应性能.实验结果表明,该传感器检测DOX的线性范围为4.0×10~(-7)~1.0×10~(-6)mol/L,相关系数为0.9967,检出限(S/N=3)达6.5×10~(-8)mol/L;采用电化学洗脱法可使传感器再生,对DOX的测定具有良好重现性及稳定性;该传感器对于干扰物长春碱、放线菌素D及5-氟尿嘧啶有微弱的电流响应,显示出良好的选择性.将该传感器用于人体血样中盐酸阿霉素的分析,回收率为96.0%~106.7%,表明其具有潜在的实用价值.