基于电聚合的苯巴比妥分子印迹电化学传感器的制备及其应用研究

以马来松香丙烯酸乙二醇酯(EGMRA)为交联剂,甲基丙烯酸为功能单体,在玻碳电极表面电聚合了一种对苯巴比妥分子具有专一性识别的聚合膜。在最佳实验条件下,采用循环伏安法(CV)、差分脉冲伏安法(DPV)及电化学交流阻抗法(EIS)对印迹传感器的性能进行研究。实验结果表明:该印迹传感器对苯巴比妥具有快速响应、专一性识别和高灵敏度的特点,且苯巴比妥的浓度在8.0×10-7~1.0×10-4mol/L范围内与DPV电流信号呈良好的线性关系,相关系数(r)为0.998 3。检出限(S/N=3)为5.4×10-8mol/L。将此印迹传感器应用于实际样品中苯巴比妥的检测,加标回收率为95.7%~105.0%。     

磁性石墨烯修饰辛基酚印迹传感器制备及应用研究

以辛基酚(4-OP)为模板分子,多巴胺为功能单体,采用电聚合技术在磁性石墨烯修饰碳电极表面制备对辛基酚具有高选择性与灵敏性的印迹电化学传感器。采用循环伏安法(CV)和差分脉冲伏安法(DPV)对此印迹传感器的电化学性能进行详细表征;采用扫描电子显微技术对修饰电极的形貌进行表征。结果表明,此印迹电化学传感器对辛基酚具有良好的特异识别性能。采用 DPV 法考察了孵化时间和洗脱溶剂对印迹传感器性能影响,结果表明,最佳孵化时间为14 min。此印迹电化学传感器的响应电流(△IR )与辛基酚在5.0×10-6~5.0×10-9 mol/ L 范围内浓度的负对数(-lgC)呈良好的线性关系,线性方程为△IR ( mA)=-0.25lgC(mol/ L)+2.35,检出限为3.64×10-10 mol/ L (S/ N=3)。此印迹电化学传感器对辛基酚具有良好的选择性和灵敏性,成功用于实际水样中辛基酚的检测,回收率为96.0%~104.0%。     

基于分子印迹聚合物掺杂氧化石墨烯膜的利巴韦林电位传感器

以利巴韦林为模板分子,甲基丙烯酸为功能单体,采用沉淀聚合法制备利巴韦林分子印迹聚合物(MIP).以利巴韦林分子印迹聚合物掺杂氧化石墨烯(GO)为离子载体,聚氯乙烯为基质,癸二酸二辛酯为增塑剂制备电极敏感膜.结果表明,敏感膜组成为100.8 mg MIP、14.7 mg GO、450.8 mg聚氯乙烯和901.6 mg癸二酸二辛酯,内充液组成为0.1 mol/L NaCl+0.05 mol/L NaAc-0.05 mol/L HAc缓冲溶液+ 1.0×10.-5 mol/L利巴韦林,电极的响应性能最好.此电极的能斯特响应斜率为45.565 mV/decade,线性范围为1.0×10.-6~1.0×10.-4 mol/L, 检出限为1.0×10.-7 mol/L(S/N=3),工作pH范围为3~5,响应时间小于3 min.此电极对利巴韦林具有高选择性,可用于检测饲料和注射液中利巴韦林含量,加标回收率为90%~110%,RSD为3.0%~7.9%.     

基于石墨烯掺杂金纳米粒子的速灭威分子印迹电化学传感器

以速灭威(MTMC)为模板分子,甲基丙烯酸(MAA)为功能单体,马来松香丙烯酸乙二醇酯(EGMRA)为交联剂,在石墨烯掺杂金纳米粒子修饰玻碳电极表面合成分子印迹膜,研制了测定MTMC的分子印迹电化学传感器。采用扫描电镜(SEM)对传感膜的形貌进行了表征,通过循环伏安法(CV)、电化学阻抗谱法(EIS)和差示脉冲伏安法(DPV)对传感器的性能进行了研究。DPV测试表明,MTMC的浓度在1.0×10-7~1.0×10-4mol/L范围内呈现良好的线性关系(线性相关系数为R=0.9936),检出限2.9×10-8mol/L(S/N=3)。传感器应用于蔬菜样品的加标回收检测,回收率在93.4%~106.4%之间。     

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。     

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。     

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。     

基于纳米氧化铜修饰的异戊巴比妥的新型电化学传感器的制备与应用

在纳米氧化铜修饰的玻碳电极表面电聚合一种能够快速检测尿液中异戊巴比妥(AMB)的分子印迹敏感膜,研究了该敏感膜的最佳成膜条件及最佳工作条件.通过扫描电子显微镜(SEM)、循环伏安(CV)和电化学交流阻抗法(EIS)研究了印迹膜的表面形貌及性能.电化学实验结果表明,纳米氧化铜能提高传感器对AMB的灵敏度.在最佳实验条件下,铁氰化钾分子探针的差分脉冲伏安(DPV)峰电流响应值与AMB的浓度在1.0×10-7~1.4×10-4mol/L范围内呈现良好的线性关系(线性相关系数R=0.9966);检出限为2.1×10-9mol/L(S/N=3).此印迹传感器可用于尿液中AMB的检测,加标回收率为94.00%~104.67%.     

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%。     

肉桂酸苄酯分子印迹膜电化学传感器的制备

以肉桂酸苄酯为模板,巯基苯胺为单体,采用电聚合的方法合成了肉桂酸苄酯分子印迹聚合物膜,并以此印迹膜构建电化学传感器,采用差分脉冲伏安(DPV)法对化妆品中肉桂酸苄酯进行检测,结果表明在1.0×10~(-11)~1.0×10~(-8) mol/L浓度范围内与峰电流线性良好,相关系数R~2=0.9915,检测限为2.9pmol/L,并且具有较高的选择性识别能力、良好的再生性和稳定性。该方法实现了洗发水样品中痕量肉桂酸苄酯的检测,为测定和监控化妆品中痕量过敏原提供了一条有效途径。     

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.     

钯纳米粒子修饰的三甲氧苄啶分子印迹膜传感器的制备及其识别性能研究

采用N,N′-亚甲基双丙烯酰胺(MBA)为功能单体、钯纳米粒子为掺杂剂、马来松香丙烯酸乙二醇酯为交联剂,在玻碳电极上热聚合具有三甲氧苄啶(TMP)识别性能的钯纳米材料修饰的分子印迹传感膜.采用扫描电镜及红外光谱对合成的钯纳米材料、印迹传感膜的形貌及其结构进行了表征;采用循环伏安法(CV)、交流阻抗法(EIS)对钯纳米粒子掺杂的印迹电极与无掺杂电极的电化学性能进行了研究.结果表明,纳米粒子掺杂的印迹电极与无掺杂电极的表面形貌及电化学性能明显不同.差分脉冲伏安法(DPV)表征结果表明,TMP的浓度在5.0×10-7~4.0 ×10-3 mol/L范围内与脉冲峰电流呈良好的线性关系(R=0.9995),检出限为3.2×10-8 mol/L (S/N=3).此钯纳米粒子掺杂的印迹传感器具有较高的灵敏度.即时电流测定结果表明,新诺明(SMZ)、磺胺嘧啶(SDZ)、葡萄糖 (Glu)、尿素 (Urea)对三甲氧苄啶(TMP)的测定不产生干扰.将此印迹传感器用于实际样品中TMP的检测,加标回收率为96.8%~102.0%.     

Determination of Oxytetracycline with a Gold Electrode Modified by Chitosan-Multiwalled Carbon Nanotube Multilayer Films and Gold Nanoparticles

A molecularly imprinted electrochemical sensor was fabricated based on a gold electrode modified by chitosan-multiwalled carbon nanotube composite (CS-MWCNTs) multilayer films and gold nanoparticles (AuNPs) for convenient and sensitive determination of oxytetracycline (OTC). The multilayer of CS-MWCNTs composites and AuNPs were used to augment electronic transmission and sensitivity. The molecularly imprinted polymers (MIPs) were synthesized using OTC as the template molecule and o-phenylenediamine (OPD) as the functional monomer. They were modified on a gold electrode by electropolymerization. The electrochemical behavior of OTC at the imprinted sensor was characterized by cyclic voltammetry (CV), scanning electron microscopy (SEM), and amperometry. The molecularly imprinted sensor showed high selectivity and excellent stability toward OTC. The linear range was from 3.0 × 10^?8 to 8.0 × 10^?5 mol/L, with a limit of detection (LOD) of 2.7 × 10^?8 mol/L (S/N = 3). The developed sensor showed good recovery in spiked samples analysis.     

Construction of a novel electrochemical sensor based on molecularly imprinted polymers for the selective determination of chlorpyrifos in real samples

We present a novel electrochemical sensor based on an electrode modified with molecularly imprinted polymers for the detection of chlorpyrifos. The modified electrode was constructed by the synthesis of molecularly imprinted polymers by a precipitation method then coated on a glassy carbon electrode. The surface morphology of the modified electrode was characterized by using field‐emission scanning electron microscopy and transmission electron microscopy. The performance of the imprinted sensor was thoroughly investigated by using cyclic voltammetry and differential pulse voltammetry. The imprinted electrochemical sensor displayed high repeatability, stability, and selectivity towards the template molecules. Under the optimal experimental conditions, the peak current response of the imprinted electrochemical sensor was linearly related to the concentration of chlorpyrifos over the range 1 × 10⁻¹⁰–1 × 10⁻⁵ mol/L with a limit of detection of 4.08 × 10⁻⁹ mol/L (signal‐to‐noise ratio = 3). Furthermore, the proposed molecularly imprinted electrochemical sensor was applied to the determination of chlorpyrifos in the complicated matrixes of real samples with satisfactory results. Therefore, the molecularly imprinted polymers based electrochemical sensor might provide a highly selective, rapid, and cost‐effective method for chlorpyrifos determination and related analysis.     

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。     

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     

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.     

基于分子印迹电聚合膜的褪黑素传感器的研究

在弱酸条件下,以邻苯二胺为功能单体,褪黑素为模板,以电化学聚合物法在铂电极表面合成了性能稳定的褪黑素分子印迹聚合物膜.采用循环伏安法(CV)和差分脉冲法(DPV)对分子印迹传感器的识别性能进行了研究.结果表明:此传感器对褪黑素具有快的响应、良好的选择性和高的灵敏度.以K3Fe(CN)6为电子传递媒介,建立了一种差分脉冲伏安法(DPV)间接检测褪黑素的分析方法.在1×10-10～1×10-8 moL/L范围内,褪黑素的浓度与K3Fe(CN)6的相对峰电流变化呈良好的线性关系;检出限为1×10-11 mol/L(S/N=3).将此传感器应用于复合褪黑素及尿样中褪黑素含量的测定,加标平均回收率大于94％.