3D石墨烯修饰的猛杀威分子印迹电化学传感器的制备

以猛杀威为模板分子、丙烯酰胺( AM)为功能单体、马来松香丙烯酸乙二醇酯( EGMRA)为交联剂、自制的3D石墨烯(3D-rGO)为增敏材料,在玻碳电极表面合成分子印迹聚合物,制备检测猛杀威的分子印迹电化学传感器。运用扫描电镜(SEM)对自制3D石墨烯的形貌进行了表征,通过循环伏安法(CV)、差分脉冲伏安法(DPV)和交流阻抗法(EIS)对猛杀威传感器的性能进行了研究。结果表明,猛杀威的浓度在8.0×10-8~8.0×10-6 mol/L范围内与响应电流值呈良好的线性关系,线性相关系数R=0.9954,检出限为7.3×10-8 mol/L (S/N=3),猛杀威分子印迹敏感膜的印迹因子β=3.88,且相对于3种结构类似物的选择因子α垌1,说明此传感器具有良好的选择性。将此传感器应用于生菜样品检测,加标回收率在96.7%~98.7%之间。     

利巴韦林原位聚合分子印迹电化学传感器的研制

利用原位聚合分子印迹技术,以3-氨基苯硼酸(3-ABBA)为功能单体,利巴韦林(RIB)为目标分子,以硼酸和顺式二醇在不同酸碱度条件下可逆形成环内酯键为原理,在玻碳电极表面原位聚合形成利巴韦林分子印迹膜,研制了测定利巴韦林的分子印迹电化学传感器。采用循环伏安法(CV)和差分脉冲法(DPV)对印迹膜性能进行研究。DPV测试表明:在最优实验条件下,利巴韦林的浓度在5.0×10~(-8)~1.0×10~(-5)mol/L范围内与峰电流呈良好的线性关系,相关系数(r~2)为0.995 3,检出限(S/N=3)为1.5×10~(-8)mol/L。特异性实验表明制备的传感器对利巴韦林的选择性良好。该分子印迹电化学传感器可用于食品中利巴韦林的检测。     

An Impedance Molecularly Imprinted Sensor for the Detection of Bovine Serum Albumin (BSA) Using the Dynamic Electrochemical Impedance Spectroscopy

A molecularly imprinted electrochemical sensor is successfully developed to detect bovine serum albumin (BSA) based on the dynamic electrochemical impedance spectroscopy (DEIS) instead of the traditional impedance spectroscopy. The sensor is prepared using chitosan and pyrrole as modified material and functional monomers, respectively, and the fast and real‐time characterization of molecular imprinting process can be obtained by DEIS. It is indicated that the removal and rebinding processes of BSA are closely related with the DEIS impedance under dynamic conditions, and the direct correlation between the resulting kinetic information and BSA concentrations can be established. As a result, the impedance changing rates in the initial 5 min of BSA adsorption are linear to the BSA concentrations ranging from 0.0001 to 0.01 ng mL^?1 and 0.01 to 1 ng mL^?1 with a detection limit of 5×10^?5 ng mL^?1 (S/N=3). In addition, the detection of BSA by DEIS does not require the system to be in equilibrium. The sensor also shows simplicity, high sensitivity, good stability and acceptable recovery in real samples, indicating its promising prospects in the fast and real‐time detection of proteins.     

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.     

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%.     

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。     

妥拉苏林分子印迹膜传感器的制备及识别特性研究

用电聚合的方法在金电极上制备了以妥拉苏林为模板分子的自组装邻氨基硫酚分子印迹膜传感器.通过差分脉冲伏安法研究传感器对妥拉苏林的响应特性,结果表明在优化的实验条件下,此传感器的峰电流响应值与妥拉苏林浓度在0.4～5μg·mL-1(r=0.9986)和5～120μg·mL-1(r=0.9953)范围内保持良好的线性关系,检测限为0.18μg·mL-1;相对标准偏差约为2.47%,响应时间约为3min.传感器具备较好的选择性和稳定性,初步用于人体尿液中妥拉苏林的分析,获得了较满意的结果.     

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 %.     

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。     

Highly Selective Molecularly Imprinted Polymer Sensor for Indium Detection Based on Recognition of In‐Alizarin Complexes

A highly selective molecularly imprinted polymer electrochemical sensor for In³⁺ detection was proposed. In³⁺ ion was chelated with alizarin red S to form a complex In‐ARS. The complex was used as the template molecule to prepare a molecularly imprinted polymer (MIP) based sensor. The selectivity of the sensor was improved significantly due to the three‐dimensional specific structure of the complex, and the selective complexation of ligands for metal ions. Moreover, the sensitivity of the proposed sensor was improved by recording the reductive current of ligand in complex. This technique was highly sensitive for quantitative analysis of In³⁺ in the concentrations ranged from 1×10^?8 mol/L to 2.5×10^?7 mol/L with a detection limit of 4.7×10^?9 mol/L. The proposed sensor has been successfully used in detecting In³⁺ in real samples.     

三氟氯氰菊酯分子印迹电化学传感器的制备及性能研究与应用

以三氟氯氰菊酯为模板分子,邻苯二胺和邻氨基苯酚为复合功能单体,通过电聚合法制备了能够特异识别模板分子及其结构类似物的分子印迹电化学传感器。 采用循环伏安法和方波伏安法优化了制备和检测条件,对传感器的印迹效应和分析性能进行了研究,并建立了农产品中三氟氯氰菊酯农药残留的快速分析方法。 在最佳条件下,三氟氯氰菊酯在1.0×10^-7~1.0×10^-5 mol/L浓度范围内线性关系良好,检出限(S/N=3)为3.0×10^-8 mol/L,样品加标平均回收率在84.8%~94.7%之间,相对标准偏差(RSD)为1.1%~4.8%(n=5)。 该传感器对三氟氯氰菊酯以及结构类似物有良好的选择性、稳定性和重现性,而且操作简便、检测快速、灵敏、成本低,具有良好的应用前景。     

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.     

A New Molecularly Imprinted Polymer (MIP)‐based Electrochemical Sensor for Monitoring Cardiac Troponin I (cTnI) in the Serum

A novel molecularly imprinted polymer (MIP) sensor for rapid determination of cardiac troponin (cTnI) was established. Since it can bind to the template molecule cTnI specifically, it can be used to detect concentration of cTnI in serum without much sample pretreatment. What's more, the electrochemical signals depend on the concentration of template molecules. The synthetic sensor possesses advantages including simplicity, high specificity, low cost of preparation, good chemical and mechanical properties, sensitive and label‐free determination. The synthetic sensor shows good dynamic linearity at concentration range from 0.05 to 5.00 nM. The limit of detection (LOD) was found to be 0.027 nM. The detection time of whole process was within 5 minutes.     

氯霉素分子印迹电化学传感器的制备与应用

以纳米氧化铝(Al2O3)和羟基化多壁碳纳米管(MWCNTs)为增敏材料,制备以氯霉素(CAP)为模板分子,间氨基苯酚(MAP)和β-环糊精(β-CD)为双功能单体的一种新型灵敏检测CAP的分子印迹电化学传感器.通过扫描电镜(SEM)、差分脉冲伏安法(DPV)和电化学交流阻抗法(EIS)对印迹传感器的表面形貌和电化学性...     

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     

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。     

Graphene Doped Molecularly Imprinted Electrochemical Sensor for Uric Acid

A highly sensitive uric acid molecularly imprinted electrochemical sensor was prepared by using graphene doped chitosan as the functional matrix and uric acid as the template molecule; a electrodeposition technique was used to form a controllable graphene–chitosan–uric acid composited film on glassy carbon electrode whose uric acid was removed via electrochemical induce elution. Under the optimized preparation and detection conditions, the detection sensitivity of uric acid at graphene doped molecularly imprinted sensor was improved significantly compared with the undoped molecularly imprinted sensor. The mechanisms of sensitivity enhancement were studied by a.c. electrochemical impedance, adsorption model, and chronocoulometry. The observations suggest the effect of sensitivity enhancement resulted from magnified surface area and good electronic conduction of graphene. Additionally, the developed sensor exhibited specific recognition to uric acid against the competitors which consisted of structure liked substances and coexisting interference in blood serum.     

基于石墨烯分子印迹电化学传感器测定芦丁

将石墨烯(GR)滴涂至裸Au电极表面,并以邻氨基酚为功能单体,芦丁为模板分子,制备了芦丁分子印迹膜电化学传感器,利用循环伏安法(CV)和差分脉冲伏安法(DPV)对制得的传感器进行了电化学性能研究,并且对制备条件和测定条件进行了优化。结果表明,与裸Au电极相比,该GR修饰的Au电极在[Fe(CN)_6]~(3-/4-)溶液中峰电流明显增大,显著提高了芦丁分子印迹传感器的灵敏度。在最优实验条件下,基于GR分子印迹电化学传感器在4.40×10~(-6)~2.80×10~(-4) mol/L范围内呈良好的线性关系,检测限为1.46×10~(-6) mol/L。用该传感器测定了黑茶中芦丁的含量,获得较好结果。     

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%。