Voltammetric determination of L-cysteine at conductive diamond electrodes

Boron-doped diamond (BDD) electrodes were used to examine L-cysteine (CySH) oxidation in alkaline media. The results of the voltammetric and polarization measurements showed that at BDD electrodes the overall CySH oxidation reaction is controlled by the initial electrochemical step, i.e., the oxidation of the CyS- electroactive species. The same conclusion was supported by the results of a study of pH effects. Conversely, at glassy carbon (GC) electrodes, the same reaction is controlled by the desorption of the reaction products. These results account for the poor response for CySH determination at GC compared to BDD. It was found that BDD exhibits excellent behavior for CySH determination, clearly outperforming GC. The results demonstrate that measurement of the peak current for CySH oxidation can be used as a basis for simple method for determining CySH in the micromolar concentration range by the use of BDD electrodes.     

Electrochemical sensing platform based on the highly ordered mesoporous carbon-fullerene system

In this paper, we report a novel all-carbon two-dimensionally ordered nanocomposite electrode system on the basis of the consideration of host-guest chemistry, which utilizes synergistic interactions between a nanostructured matrix of ordered mesoporous carbon (OMC) and an excellent electron acceptor of nanosized fullerene (C 60) to facilitate heterogeneous electron-transfer processes. The integration of OMC-C 60 by covalent interaction, especially its electrochemical applications for electrocatalysis, has not been explored thus far. Such integration may even appear to be counterintuitive because OMC and C 60 provide opposite electrochemical benefits in terms of facilitating heterogeneous electron-transfer processes. Nevertheless, the present work demonstrates the integration of OMC and C 60 can provide a remarkable synergistic augmentation of the current. To illuminate the concept, eight kinds of inorganic and organic electroactive compounds were employed to study the electrochemical response at an OMC-C 60 modified glassy carbon (OMC-C 60/GC) electrode for the first time, which shows more favorable electron-transfer kinetics than OMC/GC, carbon nanotube modified GC, C 60/GC, and GC electrodes. Such electrocatalytic behavior at OMC-C 60/GC electrode could be attributed to the unique physicochemical properties of OMC and C 60, especially the unusual host-guest synergy of OMC-C 60, which induced a substantial decrease in the overvoltage for NADH oxidation compared with GC electrode. The ability of OMC-C 60 to promote electron transfer not only suggests a new platform for the development of dehydrogenase-based bioelectrochemical devices but also indicates a potential of OMC-C 60 to be of a wide range of sensing applications because the electrocatalysis of different electroactive compounds at the OMC-C 60/GC electrode in this work should be a good model for constructing a novel and promising electrochemical sensing platform for further electrochemical detection of other biomolecules.     

纳米Fe3O4-还原氧化石墨烯复合修饰玻碳电极的制备及电化学检测多巴胺

通过电化学还原法制备纳米Fe₃O₄-还原氧化石墨烯复合修饰玻碳（Fe₃O₄-rGO/GCE）电极,用于多巴胺（DA）的检测。采用SEM、TEM和循环伏安对纳米Fe₃O₄-rGO复合材料进行表征。在pH为7.0的磷酸盐缓冲液（PBS）中,采用循环伏安法研究了DA在纳米Fe₃O₄-rGO/GC上的电化学行为。实验结果表明,较裸GC电极和rGO修饰（rGO/GC）电极,由于纳米Fe₃O₄与rGO的协同作用,纳米Fe₃O₄-rGO/GC显著增大了Fe₃O₄-rGO/GC复合材料电极电化学活性面积和氧化峰电流强度i_pa。DA的浓度在6.0×10^-8~2.0×10^-6 mol/L和2.0×10^-6~8.0×10^-5 mol/L范围内,与氧化峰电流强度i_pa呈良好的线性关系,检出限达4.0×10^-9 mol/L（信噪比S/N=3）。抗坏血酸和尿酸共存物几乎不干扰DA的测定,选择性高。Fe₃O₄-rGO/GC修饰电极用于盐酸DA注射液中的DA含量测定,获得结果较好,回收率为97.1%~103.9%。     

三氯生在石墨烯修饰电极上的电化学行为及其测定

采用循环伏安法研究三氯生在石墨烯修饰电极上的电化学行为及建立对其含量测定的电化学分析方法。在pH 7.0 PBS缓冲液中,氧化峰电流与三氯生的浓度在(2.0×10-8～1.2×10-7)mol/L范围内呈良好的线性关系,检测限为3.0×10-9mol/L。已用于实际样品中三氯生含量的直接测定。该方法灵敏度高、检测范围宽,结果令人满意。     

Carbon nanotube-chitosan system for electrochemical sensing based on dehydrogenase enzymes

Multiwalled carbon nanotubes (CNT) were solubilized in aqueous solutions of a biopolymer chitosan (CHIT). The CHIT-induced solubilization of CNT facilitated their manipulations, including the modification of electrode surfaces for sensor and biosensor development. The colloidal solutions of CNT-CHIT were placed on the surface of glassy carbon (GC) electrodes to form robust CNT-CHIT films, which facilitated the electrooxidation of NADH. The GC/CNT-CHIT sensor for NADH required approximately 0.3 V less overpotential than the GC electrode. The susceptibility of CHIT to chemical modifications was explored in order to covalently immobilize glucose dehydrogenase (GDH) in the CNT-CHIT films using glutaric dialdehyde (GDI). The stability and sensitivity of the GC/CNT-CHIT-GDI-GDH biosensor allowed for the interference-free determination of glucose in the physiological matrix (urine). In pH 7.40 phosphate buffer solutions, linear least-squares calibration plots over the range 5-300 microM glucose (10 points) had slopes 80 mA M(-1) cm(-2) and a correlation coefficient 0.996. The detection limit was 3 microM glucose (S/N = 3). The CNT-CHIT system represents a simple and functional approach to the integration of dehydrogenases and electrodes, which can provide analytical access to a large group of enzymes for wide range of bioelectrochemical applications including biosensors and biofuel cells.     

Determination of pentachlorophenol at carbon nanotubes modified electrode incorporated with beta-cyclodextrin

A facile and reliable electrochemical technique at beta-cyclodextrin incorporated carbon nanotubes modified glassy carbon electrode (beta-CD/CNTs/GCE) was proposed for determination of pentachlorophenol (PCP). The electrochemical behavior of PCP at the beta-CD/CNTs/GCE was investigated by cyclic voltammetry and linear sweep voltammetry. The beta-CD/CNTs/GCE showed good analytical performance characteristics in electrocatalytic oxidation of PCP, compared with the simple carbon nanotube modified electrode (CNTs/GCE) and bare glassy carbon electrode (GCE). After accumulation for 5 min on beta-CD/CNTs/GCE, the peak current increased linearly with the concentration of PCP in the range from 8.0 x 10(-7) to 1.04 x 10(-5) mol/L. The detection limit was 4.0 x 10(-8) mol/L at 3 sigma level. The proposed electrode presented good repeatability for the determination of PCP in artificial wastewater, and the recovery was 97%-103%. This modified electrode combined the advantages of carbon nanotubes and supramolecular cyclodextrin, leading to new capabilities for electrochemical detection of PCP.     

基于有序介孔碳/PDDA固定化漆酶的邻苯二酚传感器性能研究

采用有机交联水性环氧树脂为碳源,以SBA-15为模板,制备了有序介孔碳(OMC),并对其电化学性能进行研究。透射电镜结果表明其具有典型的二维有序六角介孔结构,孔径大约为3nm。电化学测试结果表明OMC/Lac/Au电极对邻苯二酚具有很好的电催化氧化活性。将OMC应用于构建漆酶生物传感器,结果表明,传感器对邻苯二酚的线性检测范围为0.67~8.59μmol/L,灵敏度为0.349A/(mol/L),检测限为0.117μmol/L。     

Voltammetric detection of bisphenol a by a chitosan-graphene composite modified carbon ionic liquid electrode

In this paper 1-ethyl-3-methylimidazolium tetrafluoroborate based carbon ionic liquid electrode (CILE) was fabricated and further modified with chitosan (CTS) and graphene (GR) composite film. The fabricated CTS-GR/CILE was further used for the investigation on the electrochemical behavior of bisphenol A (BPA) by cyclic voltammetry and differential pulse voltammetry. A well-defined anodic peak appeared at 0.436 V in 0.1 mol/L pH 8.0 Britton-Robinson buffer solution, which was attributed to the electrooxidation of BPA on the modified electrode. The electrochemical parameters of BPA on the modified electrode were calculated with the results of the charge transfer coefficient (α) as 0.662 and the apparent heterogeneous electron transfer rate constant (k_s) as 1.36 s^− 1. Under the optimal conditions, a linear relationship between the oxidation peak current of BPA and its concentration can be obtained in the range from 0.1 μmol/L to 800.0 μmol/L with the limit of detection as 2.64 × 10^− 8 mol/L (3σ). The CTS-GR/CILE was applied to the detection of BPA content in plastic products with satisfactory results.     

MnO2纳米棒-还原石墨烯复合修饰玻碳电极用于苋菜红的检测

利用电化学还原法制备MnO₂纳米棒-还原石墨烯复合修饰电极（MnO₂ NRs-ErGO/GCE）用于苋菜红的检测。采用SEM和XRD分别对修饰电极材料进行微观形貌和成分结构表征。通过循环伏安法考察了苋菜红在裸电极、ErGO/GCE和MnO₂ NRs-ErGO/GCE上的电化学行为,并对测定条件如pH值、富集电位、富集时间进行了优化。结果表明,MnO₂ NRs-ErGO增大了GCE电化学活性面积,提高了苋菜红的电化学氧化响应。在最优的检测条件下,MnO₂ NRs-ErGO/GCE线性扫描伏安法检测苋菜红线性范围为2.0×10^-8~1.0×10^-5 mol/L和1.0×10^-5~4.0×10^-4 mol/L,检测限为1.0×10^-8 mol/L。MnO₂ NRs-ErGO/GCE用于真实饮料样品检测,获得满意结果。     

纳米TiO2/还原石墨烯复合修饰电极用于食品中 柠檬黄的检测

为了检测食品中柠檬黄的含量,利用滴涂法和电化学还原法制备纳米TiO_2/还原石墨烯复合修饰玻碳电极(TiO_2-Er GO/GCE)。采用透射电子显微镜和X射线粉末衍射仪对TiO_2和TiO_2-GO两种修饰电极材料进行表征;通过循环伏安法观察了柠檬黄在不同电极上的电化学行为,并对检测条件如p H值、富集电位、富集时间进行了优化。实验结果表明:TiO_2-Er GO/GCE增大了电极的电化学活性面积,提高了柠檬黄的电化学氧化响应;最优的检测条件为p H值为3.7、富集电位为-0.20 V、富集时间为180 s;在最优的检测条件下,采用线性扫描伏安法检测柠檬黄的线性范围为2.0×10-8~2.0×10-5 mol/L,检测限为8.0×10-9 mol/L(信噪比为3)。     

Electrocatalytic reduction of chloramphenicol at multiwall carbon nanotube-modified electrodes

A multiwall carbon nanotube-modified glassy carbon (GC) electrode was employed for the investigation of chloramphenicol (CAP) reduction. Carbon nanotube coating can greatly lower the overpotential of the electrochemical reduction of CAP and promote the electrode reaction. CAP undergoes an irreversible reduction process in phosphate buffer by the modified electrode. The reduction peak current (Ip) was significantly increased. Effects of some important factors, including pH, scan rate, and amount of modifier, on the determination of CAP were investigated. In the range of 3 x 10(-7) to 1.2 x 10(-5) M, the reduction peak current (Ip) has a good linear relationship with the concentration of CAP. When the signal-to-noise ratio is 3, the detection limit is 4.5 x 10(-8) M. The relative standard deviation of 10 measurements for 3 x 10(-6) M CAP is 5.3%, suggesting an excellent reproducibility of the modified electrode. Interfering experiments show that the modified electrode has excellent selectivity for the detection of CAP. The modified electrode was used to determine CAP in eyedrops, and the recoveries were approximately 100%.     

氨基-β-环糊精-石墨烯-二茂铁修饰电极对多巴胺的电化学行为研究

利用制备的氨基-β-环糊精-石墨烯-二茂铁(β-CD-NH2/GNs/Fc)复合膜修饰电极,研究了多巴胺(DA)的电化学行为。结果表明,该复合膜修饰电极在pH值=7.00的磷酸盐缓冲溶液(PBS)中对DA有良好的电催化性能,DA的氧化峰电流在0.1～100μmol/L浓度范围内呈良好的线性关系,检出限为8.5×10-8mol/L。结果表明该修饰电极具有较高的检测灵敏度,可用于实际样品的检测。     

纳米Fe2O3-还原氧化石墨烯复合材料的制备及对双酚A的检测

双酚A（BPA）被广泛应用于食品包装材料中,它会引起人体内分泌失调,并导致免疫和生殖系统异常,因此对生活用水中BPA的检测十分重要。本文采用一步水热法合成纳米Fe₂O₃-还原氧化石墨烯（Fe₂O₃-rGO）复合材料并进行表征,基于Fe₂O₃-rGO复合材料构建电化学传感器Fe₂O₃-rGO/玻碳电极,用于检测水样中的BPA。通过FTIR、XRD和SEM分析,表明纳米Fe₂O₃粒子成功附着到rGO上;采用微分脉冲伏安法（DPV）进行BPA的电化学检测,结果显示BPA在0.1~100 μmol/L范围内呈现良好的线性关系,检出限为0.033 μmol/L（信噪比为3）。同时,Fe₂O₃-rGO/玻碳电极电化学传感器对电活性物质和常见金属离子具有良好的抗干扰能力,且实样检测结果理想。      

Simultaneous determination of ultratrace lead and cadmium by square wave stripping voltammetry with in situ depositing bismuth at Nafion-medical stone doped disposable electrode

An ultrasensitive electrochemical method for simultaneous determination of lead and cadmium was first developed using the novel bismuth-Nafion-medical stone doped disposable electrode (an improved wax-impregnated graphite electrode). Through the synergistic sensitization effect of the resulting composite material, the disposable electrode showed remarkable electrochemical responses to lead and cadmium. The oxidation of the two metals produced two well-defined and separated square wave peaks at about -0.62 V for Pb(2+) and -0.85 V for Cd(2+), respectively. The effects of the amount of medical stone, concentration of Nafion, thickness of bismuth, pH of buffer solution, deposition potential, accumulation time, voltammetric measurement and possible interferences were investigated in detail. Under the optimal conditions, the fabricated electrode exhibited linear ranges from 2.0 to 12.0 μg L(-1) with detection limit of 0.07 μg L(-1) for lead and 2.0-12.0 μg L(-1) with detection limit of 0.47 μg L(-1) for cadmium. The assay results of heavy metals in wastewater with the proposed method were in acceptable agreement with the atomic absorption spectroscopy method.     

Determination of paraquat by square-wave voltammetry at a perfluorosulfonated ionomer/clay-modified electrode

A novel Nafion/clay-modified electrode (NCME) was developed for the determination of paraquat by square-wave cathodic stripping voltammetry. The clay that showed the best performance for the fabrication of the NCME is nontronite (SWa-1, ferruginous smectite). The electrochemical behavior of paraquat showed that the cathodic peak at -0.70 V vs Ag/AgCl permits adequate quantification of the analyte. Linear calibration curves are obtained over the 0-80 ppb range, with a detection limit of 0.5 ppb in pH 8 phosphate buffer solution for 4 min preconcentration time. Various factors influencing the determination of paraquat were thoroughly investigated in this study. The practical analytical utility is illustrated by selective measurements of paraquat in real water samples.     

异鼠李素的电化学行为及其测定

采用循环伏安法研究异鼠李素在电极上的电化学行为,建立差示脉冲伏安法测定其含量的电化学分析新方法。在pH 4.0醋酸盐缓冲液中,氧化峰电流与异鼠李素浓度在2.0×10~(-7)～1.2×10~(-6)mol·L~(-1)范围内呈良好的线性关系,检测限为3.0×10~(-8)mol·L~(-1)。玻碳电极可有效消除样品中其它组分对异鼠李素测定的干扰,已成功用于实际样品中异鼠李素含量的直接测定。该方法灵敏度高、检测范围宽,结果令人满意。     

Electrochemically reduced graphene modified carbon ionic liquid electrode for the sensitive sensing of rutin

In this paper a graphene (GR) modified carbon ionic liquid electrode that was obtained by one-step potentiostatic electroreduction of a graphene oxide solution was described. The resulting electrode displayed excellent electrochemical performance due to the formation of highly conductive GR film on the electrode surface. Electrochemistry of rutin was carefully studied with a pair of well-defined redox peaks appeared in pH 2.5 buffer solution. Rutin exhibited a diffusion-controlled two-electron and two-proton transfer reaction on the modified electrode with the electrochemical parameters calculated. The reduction peak currents are linearly related to rutin concentration in the concentration range from 0.070 to 100.0 μmol/L with a detection limit as low as 24.0 nmol/L (3σ). The modified electrode displayed excellent selectivity with good stability, and was applied to the determination of rutin content in tablet, human serum and urine samples with satisfactory results.     

Wiring of enzymes to electrodes by ultrathin conductive polyion underlayers: enhanced catalytic response to hydrogen peroxide

Stable electroactive films were grown layer by layer on rough pyrolytic graphite electrodes featuring 4-nm underlayers of sulfonated polyaniline (SPAN) covered with a film containing myoglobin or horseradish peroxidase grown in alternating layers with poly(styrenesulfonate). The self-doped polyanionic SPAN layer, grown on a 2-nm polycation layer, was conductive between about 0.1 and -0.4 V vs SCE at pH 4.5. The enzyme films had the architecture PDDA/SPAN/(enzyme/PSS)3, where PDDA is poly(diallyldimethylammonium) ion. Comparisons of voltammetric measurements of electroactive protein with quartz crystal microbalance measurements of total protein showed that 90% or more of the protein was coupled to the electrode when the SPAN underlayer was present, as opposed to approximately 40% protein electroactivity when SPAN was absent. As a consequence of the highly efficient coupling between enzymes and electrode, the PDDA/SPAN/(enzyme/PSS)3 films exhibited a higher sensitivity for the electrochemical catalytic reduction of hydrogen peroxide. Amperometry at a rotating disk electrode at 0 V gave sensitivity for hydrogen peroxide up to 14 microA microM(-1) cm(-2) in the submicromolar concentration range and a detection limit of approximately 3 nM. Results suggest the future utility of ultrathin layers of conductive self-doping polyions in improving sensitivity of enzyme biosensors.     

A reduced graphene oxide based electrochemical biosensor for tyrosine detection

In this paper, a 'green' and safe hydrothermal method has been used to reduce graphene oxide and produce hemin modified graphene nanosheet (HGN) based electrochemical biosensors for the determination of l-tyrosine levels. The as-fabricated HGN biosensors were characterized by UV-visible absorption spectra, fluorescence spectra, Fourier transform infrared spectroscopy (FTIR) spectra and thermogravimetric analysis (TGA). The experimental results indicated that hemin was successfully immobilized on the reduced graphene oxide nanosheet (rGO) through π-π interaction. TEM images and EDX results further confirmed the attachment of hemin on the rGO nanosheet. Cyclic voltammetry tests were carried out for the bare glass carbon electrode (GCE), the rGO electrode (rGO/GCE), and the hemin-rGO electrode (HGN/GCE). The HGN/GCE based biosensor exhibits a tyrosine detection linear range from 5?×?10(-7)?M to 2?×?10(-5)?M with a detection limitation of 7.5?×?10(-8)?M at a signal-to-noise ratio of 3. The sensitivity of this biosensor is 133 times higher than that of the bare GCE. In comparison with other works, electroactive biosensors are easily fabricated, easily controlled and cost-effective. Moreover, the hemin-rGO based biosensors demonstrate higher stability, a broader detection linear range and better detection sensitivity. Study of the oxidation scheme reveals that the rGO enhances the electron transfer between the electrode and the hemin, and the existence of hemin groups effectively electrocatalyzes the oxidation of tyrosine. This study contributes to a widespread clinical application of nanomaterial based biosensor devices with a broader detection linear range, improved stability, enhanced sensitivity and reduced costs.     

制备印迹分子电化学传感器检测食品接触材料中DDM

目的 将分子印迹技术与电化学相结合，实现食品接触材料中4,4''–二氨基二苯甲烷(DDM)的快速检测。方法 采用分子印迹技术，以羧基化碳纳米管(OH–MWCNT)为增敏材料，分别以DDM和吡咯(PPY)作为模板分子和功能单体，在玻璃碳电极(GCE)表面电沉积制备DDM印迹分子薄膜(MIP)，对印迹电极的检测能力使用扫描电镜(SEM)和电化学分析法进行表征。结果 电沉积的DDM电化学传感器具有优良的检测性能和可重复性，其线性范围为10~50 μmol/L，检出限为116 ng/L。结论 该方法具备操作简单、精度高、速度快等优点，能够实现对食品接触材料中DDM的痕量检测。