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%。     

基于石墨烯掺杂金纳米粒子的灭除威分子印迹电化学传感器的制备与性能研究

以灭除威(XMC)为模板分子,甲基丙烯酸(MAA)为功能单体,合成的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XMC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研究。DPV测试表明,XMC的浓度在1.0×10-7~2.0×10-5mol·L-1范围内呈良好线性关系,相关系数(r)为0.997 9,检出限(S/N=3)为1.5×10-8mol·L-1。选择性识别实验结果表明,XMC印迹敏感膜的印迹因子(β)达到2.94,相对于干扰物的选择因子(α)均大于1,对与XMC结构相似的速灭威的选择因子达到2.39,说明该印迹膜对XMC具有良好的选择性。识别过程动力学研究结果表明,石墨烯掺杂金纳米粒子分子印迹传感器的动力学结合速率常数k为73.05 s。将此传感器应用于蔬菜样品的加标回收检测,加标回收率为95.4%~108.0%。     

石墨烯修饰电极分子印迹电化学传感器的研制及其对多巴胺的测定

以石墨烯为电极增敏材料,多巴胺印迹聚合物为特异性识别材料,采用滴涂法组装石墨烯修饰电极的分子印迹电化学传感器。考察了pH值、石墨烯浓度、印迹聚合物浓度对传感器的影响,优化的实验条件为:pH 7.0,石墨烯浓度为0.5g/L,印迹聚合物浓度为20g/L。实验表明,该印迹传感器对多巴胺的响应电流远大于非印迹电极,同时该印迹传感器对多巴胺具有较好的选择性,检测范围为2.0×10-7～1.0×10-4mol/L,检出限(S/N=3)为6.8×10-8mol/L。该传感器用于盐酸多巴胺注射液的测定,其回收率为98%～105%。     

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。     

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。     

Graphene Nanocomposites Based Electrochemical Sensing Platform for Simultaneous Detection of Multi-drugs

Three reduced graphene oxide nanocomposites were employed to achieve the simultaneous electrochemical determination of multi-drugs including acetaminophen (ACTM), carbendazim (CB) and ciprofloxacin (CFX). All nanocomposite modified electrodes showed improved current responses for three drugs. Notably cauliflower-like platinum nanoparticles decorated reduced graphene oxide modified electrode (or Pt−RGO/GCE) exhibited the best performance in terms of electrochemical stability. Using Pt−RGO/GCE, the linear detect ranges of 30–120 μM, 25–115 μM and 10–25 μM, and detection limit values of 3.49, 2.96, and 1.53 μM were achieved for ACTM, CB and CFX respectively. The electrode was further used for the successful determination of above drugs in tap and river water using differential pulse voltammetry. From the obtained results, we believe that Pt-RGO/GCE is highly promising for the fabrication of robust electrochemical sensors for simultaneously determining ACTM, CB and CFX or similar types of drugs in the future.     

Electrochemical Detection of Alloxan on Reduced Graphene Oxide Modified Glassy Carbon Electrode

Alloxan is a toxic reagent that strongly induces the diabetes by destroying insulin‐producing β‐cells in the pancreas of living organisms. The reduction product of alloxan is dialuric acid, which is responsible for the intracellular generation of ROS to enhance the stress in living cells to cause kidney disease or diabetic nephropathy. Herein, we studied for the first time the electrochemical properties of alloxan on reduced graphene oxide modified glassy carbon electrode (rGO/GCE) in 0.1 M phosphate buffer solution (PBS) at pH 7. The obtained results were compared with graphene oxide modified GCE (GO/GCE) and bare GCE surfaces. The modified rGO/GCE showed well defined redox couple with 10 fold increase in both reduction as well as oxidation peak current for alloxan than that of GO/GCE and bare GCE. Differential pulse voltammetry (DPV) technique shows the linear increase in both oxidation and reduction peak current of alloxan in the range of 30 μM to 3 mM with LOD of 1.2 μM. An amperometric signal of alloxan is also increases with respect to each addition of 50 μM of alloxan on rGO/GCE at constant potential of ?0.05 V. The linear range of alloxan is observed between 50 μM to 750 μM (S/N=3). This kind of rGO/GCE surface is more suitable platform or sensor matrix for estimating unknown concentration of alloxan molecule in the real biological systems.     

Electrochemical Sensor‐Based Ruthenium Nanoparticles on Reduced Graphene Oxide for the Simultaneous Determination of Ethinylestradiol and Amoxicillin

The composite material of reduced graphene and Ru nanoparticles (rGO/RuNP) was obtained by electrochemical oxidation of ruthenium nanoparticles immobilised on the glassy carbon electrode (GCE) surface and used for simultaneous electroanalysis of drugs. There are many discussions in the scientific community about the decrease in therapeutic efficacy of contraceptives when associated with antibiotics. The antibiotic effect of the antagonist can increase the contraceptive excretion levels in urine, indicating a reduction in the body and thus a decrease in the desired effect. Using the DPV technique, it was possible to quantify ethinylestradiol (EE2) and amoxicillin (AMX) with a linear response range, 5.50x10⁻⁸ – 1.20x10⁻⁶ mol L⁻¹, and LOD, 2.04 nmol L⁻¹ and 1.63 nmol L⁻¹, respectively. The results for the electrochemical behaviour of EE2 and AMX using GCE/rGO/RuNP were compared with GCE/rGO and GCE. The GCE/rGO/RuNP showed greater stability and separation anodic peak currents, suitable for the quantification of organic molecules in samples of environmental interest, as well as clinical and food samples.     

基于银纳米粒子/氧化石墨烯复合薄膜制备TNP电化学传感器

利用改进的Hummers法制备了氧化石墨烯(GO), 以葡萄糖为还原剂直接在GO表面沉积银纳米粒子(AgNPs)得到性能稳定的AgNPs/GO纳米复合材料;基于该纳米复合材料修饰电极构建了一种新型的2, 4, 6-三硝基苯酚(TNP)电化学传感器。采用原子力显微镜(AFM)、扫描电镜(SEM)、透射电镜(TEM)、紫外可见光谱(UV-Vis)和交流阻抗(EIS)等多种方法对纳米复合薄膜进行了表征;并研究了TNP在复合薄膜修饰电极上的电化学行为和动力学性质。结果表明, AgNPs/GO对TNP有较强的电催化活性, 在复合薄膜修饰电极出现一灵敏的氧化峰和3个还原峰;利用氧化峰可对TNP进行定量分析。同时整个电极过程明显不可逆, 电极反应受到吸附步骤控制;复合膜电极表面覆盖度为5.617×10^-8 mol·cm^-2, 在所研究电位下的速率常数为9.745×10^-5 cm·s^-1。在pH 6.8的磷酸缓冲液中, 当富集电位为-0.70 V, 富集时间为60 s;TNP氧化峰电流与其浓度在5.0×10^-9~1.0×10^-7 mol·L^-1范围内成良好线性关系, 相关系数为0.995 8, 检出限可达1.0×10^-9 mol·L^-1。所制备的电化学传感器稳定性和选择性较好;用于实际水样中TNP的现场快速检测, 加标回收率在 97.6%~103.9%之间。     

Octahedral Cuprous Oxide Decorated Flexible Reduced Graphene Oxide Paper for Food Sensing Application

This work presents a simple method to fabricate an octahedral cuprous oxide (Cu₂O) decorated two-dimensional (2D) flexible rGOP electrode with filtration and electrodeposition strategies. The characteristic of the Cu₂O/rGOP electrodes was recorded by SEM, EDX, XPS, XRD, and Raman spectroscopy. The results clearly showed that Cu₂O was successfully electrodeposited on the surface of rGOP by controlling the electrodeposition potential without the introduction of any template or surfactant. The electrochemical characterizations of the Cu₂O/rGOP exhibited high electrocatalytic activity toward the reduction of H₂O₂. The linear detection range for the Cu₂O/rGOP flexible sensor was 5.0 μM to 5.5 mM, with a limit of detection of 1.27 μΜ. Subsequently, the developed flexible rGOP sensor was extended for H₂O₂ detection in milk samples for avoiding milk spoilage_. Such judicial preparation of rGOP as a sensing device will certainly pave the way for various other sensing applications including environmental and biomedical applications.     

基于银纳米粒子/氧化石墨烯复合薄膜制备TNP电化学传感器

利用改进的Hummers法制备了氧化石墨烯(GO),以葡萄糖为还原剂直接在GO表面沉积银纳米粒子(AgNPs)得到性能稳定的AgNPs/GO纳米复合材料;基于该纳米复合材料修饰电极构建了一种新型的2,4,6-三硝基苯酚(TNP)电化学传感器。采用原子力显微镜(AFM)、扫描电镜(SEM)、透射电镜(TEM)、紫外可见光谱(UV-Vis)和交流阻抗(EIS)等多种方法对纳米复合薄膜进行了表征;并研究了TNP在复合薄膜修饰电极上的电化学行为和动力学性质。结果表明,AgNPs/GO对TNP有较强的电催化活性,在复合薄膜修饰电极出现一灵敏的氧化峰和3个还原峰;利用氧化峰可对TNP进行定量分析。同时整个电极过程明显不可逆,电极反应受到吸附步骤控制;复合膜电极表面覆盖度为5.617×10-8mol.cm-2,在所研究电位下的速率常数为9.745×10-5cm.s-1。在pH 6.8的磷酸缓冲液中,当富集电位为-0.70 V,富集时间为60 s;TNP氧化峰电流与其浓度在5.0×10-9~1.0×10-7mol.L-1范围内成良好线性关系,相关系数为0.995 8,检出限可达1.0×10-9mol.L-1。所制备的电化学传感器稳定性和选择性较好;用于实际水样中TNP的现场快速检测,加标回收率在97.6%~103.9%之间。     

Electrochemical Determination of Hydrogen Peroxide Using a Glassy Carbon Electrode Modified with Three-Dimensional Copper Hydroxide Nanosupercages and Electrochemically Reduced Graphene Oxide

Three-dimensional copper hydroxide nanosupercages and electrochemically reduced graphene oxide were used to modify the glassy carbon electrode for the selective determination of hydrogen peroxide. The morphology and electrochemistry properties of copper hydroxide nanosupercage/electrochemically reduced graphene oxide/glassy carbon electrode were characterized using transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectra, Raman spectra, cyclic voltammetry, and electrochemical impedance spectroscopy. The resulting copper hydroxide nanosupercage/electrochemically reduced graphene oxide/glassy carbon electrode showed favorable performance for the electrocatalytic reduction of hydrogen peroxide. The amperometric current–time curve of the electrochemical sensor exhibited a wide linear range from 0.5 to 1030?µM with a limit of detection of 0.23?µM at a signal-to-noise ratio of three. Moreover, the sensor provided favorable selectivity, reproducibility, and stability and was used for the determination of H₂O₂ in tap water.     

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。     

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%。     

A Novel DNA Probe Based on Molecularly Imprinted Polymer Modified Electrode for the Electrochemical Monitoring of DNA

A DNA probe that was based on methylene blue (MB) imprinted polyvinyl pyridine polymer (MIP) modified carbon paste electrodes were developed for the first time for electrochemical monitoring of DNA. Probes were built up by adsorbing MB onto modified electrodes prior to DNA immobilization. It was shown that DNA strongly immobilizes on MIP modified electrodes when MB was adsorbed in advance of DNA immobilization. The performance of the MB imprinted polymer modified carbon paste electrodes (MIP‐CPE) to rebind the template molecule (MB) were compared to those of control polymer modified (non‐imprinted polymer NIP‐CPE) and bare (CPE) electrodes. Electrochemical signal resulting from the oxidation of guanine moiety of the immobilized probe DNA was high enough on the constructed platform, implicating that probes of this kind could be favorably used for DNA analysis. These probes exhibited high selectivity for its complementary DNA sequences (target). HBV‐DNA hybridization was studied to evaluate the selectivity of the probes for complementary, non‐complementary and mismatch sequences. The detection limit of the probe for the target DNA was 8.72 µg/mL (1.38 µM), which was better than those attained by some earlier DNA sensor studies.     

An Electrochemical Sensor Based on Reduced Graphene Oxide,Gold Nanoparticles and Molecular Imprinted Over‐oxidized Polypyrrole for Amoxicillin Determination

An electrochemical sensor for amoxicillin (AMX) detection based on reduced graphene oxide (RGO), molecular imprinted overoxidized polypyrrole (MIOPPy) modified with gold nanoparticles (AuNPs) is described in this work. The electrochemical behavior of the imprinted and non‐imprinted polymer (NIP) was carried out by cyclic voltammetry (CV) and impedance spectroscopy (IS). The structure and morphology of the prepared MIP sensor were characterized by scanning electron microscopy (SEM), UV‐Visible, Fourier transform infrared spectroscopy (FTIR) and its experimental parameters such as monomer and template concentration, pH buffer solution, incubation time of AMX and AuNPs, scan rate as well as electropolymerization scan cycles were optimized to improve the performance of the sensor. The peak current obtained at the MIP electrode was proportional to the AMX concentration in the range from 10^?8 to 10^?3 mol L^?1 with a detection limit and sensitivity of 1.22 10^?6 mol L^?1 (Signal to noise ratio=3) and 2.52×10^?6 μAmol^?1 L, respectively. It was also found that this sensor exhibited reproducibility and excellent selectivity against molecules with similar chemical structures. Besides, the analytical application of the AMX sensor confirms the feasibility of AMX detection in milk and human 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。     

尿酸在石墨烯修饰玻碳电极上的电化学行为及测定

以抗坏血酸为还原剂,采用微波水热法化学还原氧化石墨烯合成了石墨烯纳米片,制备了石墨烯修饰的玻碳电极(RGO/GCE),并采用循环伏安法、计时电量法、交流阻抗法等电化学技术研究了尿酸在该修饰电极上的电化学行为及其影响因素。结果表明,在PBS缓冲溶液中,尿酸(UA)在石墨烯修饰电极上的电极反应是一个受扩散控制的不可逆氧化过程。电极反应的转移电子数n=2,有效面积A=0.182 cm2,扩散系数D=1.51×10-6 cm2.s-1。UA的氧化峰电流与其浓度在5.0×10-6～1.5×10-4 mol/L范围内呈良好线性,r=0.995 7。利用该RGO/GCE修饰电极可以快速准确地测定UA,检出限为2.7×10-7 mol/L,加标回收率为98%～100%。     

Development of an Electrochemical Sensor Based on Covalent Molecular Imprinting for Selective Determination of Bisphenol‐A

In this study, an electrochemical sensor was developed and used for selective determination of bisfenol‐A (BPA) by integrating sol‐gel technique and multi‐walled carbon nanotubes (MWCNTs) modified paste electrode. BPA bounded by covalently to isocyanatopropyl‐triethoxy silane (ICPTS) was synthesized as a new precursor (BPA‐ICPTS) and then BPA‐imprinted polymer (BPA‐IP) sol‐gel was prepared by using tetramethoxysilane (TMOS) and BPA‐ICPTS. Non‐imprinted polymer (NIP) sol‐gel was obtained by using TMOS and (3‐Aminopropyl) triethoxysilane. Both BPA‐IP and NIP sol‐gels were characterized by nitrogen adsorption‐desorption analysis, FTIR, SEM, particle size analyzer and optical microscope. Carbon paste sensor electrode was fabricated by mixing the newly synthesized BPA‐IP with MWCNTs, graphite powder and paraffin oil. The electrochemical characterization of the sensor electrode was achieved with cyclic and differential pulse voltammetric techniques. The response of the developed sensor under the most proper conditions was linear in BPA concentration range from 4.0×10⁻⁹ to 1.0×10⁻⁷ mol L⁻¹ and 5.0×10⁻⁷ to 5.0×10⁻⁵ mol L⁻¹ and the detection limit was 4.4×10⁻⁹ mol L⁻¹. The results unclosed that the proposed sensor displayed high sensitivity and selectivity, superior electrochemical performance and rapid response to BPA.