亚微米级叉指型超微带电极阵列的加工和电化学表征

超微电极具有常规电极无法比拟的优良的电化学特性.超微电极包括单超微电极和超微电极阵列,单超微电极响应电流较小,一般仪器难以检测;而超微电极阵列除具有单超微电极的特点外,还能增加测量时的响应电流,有利于仪器检测.其中的叉指型超微带电极阵列(IDA)具有产生-收集效应,可提高检测的灵敏度,实现低浓度测量[1～4].将微电子技术和微细加工技术应用于化学和生物传感技术已引起关注,利用微细加工技术可以实现传感器的微型化、集成化和智能化;减少测量使用的样品量;使传感器的敏感元件具有确定的形状和尺寸,提高测量结果的一致性.本文用多…     

Electrochemical Detection of 2,4,6-Trinitrotoluene Using Interdigitated Array Electrodes

Abstract

We describe the use of interdigitated array gold electrodes (IDAs) for the electrochemical detection of 2,4,6-trinitrotoluene (TNT). Our protocol generates a reversible redox couple (hydroxylamine/nitroso) from the initial reduction of TNT, which can be amplified using redox cycling at IDA electrodes. The IDA electrodes give a limit of detection for TNT at ～6 ng/mL with a linear response (r² = 0.998) between 10 and 10,000 ng/mL for static conditions and between 5 and 200 ng/mL for flow conditions (r² = 0.999).     

白血病细胞酶联免疫酶催化银沉积于插指电极阵列电化学免疫分析新方法

建立了一种检测白血病细胞表面抗原的细胞酶联免疫电化学分析新方法. 该方法兼有细胞酶联免疫分析抗原、抗体结合的特异性和插指电极阵列酶催化银沉积电化学分析的灵敏性. 在聚苯乙烯微孔板中包被白血病细胞, 先后加入鼠抗人抗体及碱性磷酸酶(ALP)标记的马抗鼠抗体, ALP催化抗坏血酸磷酸酯(AAP)水解成抗坏血酸(AA), AA使银离子还原成银单质并沉积到插指电极阵列表面, 导致插指电极阵列上相邻两个梳齿导通. 通过对电导率的测定, 可实现对细胞表面抗原的高灵敏分析. 此分析方法灵敏度高(可检测出50个左右的HL-60细胞)、特异性好, 且可用于大量样品的分析, 为白血病等肿瘤疾病的早期诊断和免疫分型提供了新技术. 此外, 该方法也可用于细胞表面分子基因工程抗体活性的检测.     

Electrochemical Sensor Design Using Coplanar and Elevated Interdigitated Array Electrodes. A Computational Study

The time dependent diffusion equation for an interdigitated array (IDA) of coplanar and elevated electrodes is solved numerically by extrapolation of the fully implicit method using a problem adapted space grid. The simulations are performed for IDA electrodes in generator‐collector mode. The influence of the electrode height and the height of the diffusion space on the sensitivity and the response time is investigated.     

对插型阵列微带电极的制作及其电化学特性研究

用微电子光刻方法制作了对插型阵微带电极（ＩＤＡ），并通过ＳＥＭ对ＩＤＡ电极进行了表征，将微Ａｇ／ＡｇＣｌ参比电极和微铂丝对电极固定在ＩＤＡ电极附近，构成了微电解池，考察了该电极的循环伏安及计时电流特性，并用微带电极的扩散理论和Ｃｏｔｔｒｅｌｌ 公式对ＩＤＡ电极的准稳太电流进行了处理，指出了它们之间产生偏差的原因，研究了ＩＤＡ电极的“发生－收集”效应，测定了该电极的屏蔽因子、反馈因子和收集效率。     

Electrochemical Analysis of Acrylamide Using Screen‐Printed Carboxylated Single‐Walled Carbon Nanotube Electrodes

Acrylamide (AA) was electrochemically detected and quantified by means of its voltammetric response on carboxylic modified Single‐Walled Carbon Nanotube Screen Printed Electrodes (COOH‐SWCNT‐SPEs). The electroreduction signal of AA was proportional to AA concentration at low values (below 300 µM) and the observed sensitivity was explained in terms of AA adsorption on the COOH‐SWCNT‐SPEs that was demonstrated using the electrochemical response of [Fe(CN)₆]^3? and [Fe(CN)₆]^4? and Raman spectroscopy experiments. In order to test the suggested analytic approach (LOD of 0.03 µM, LOQ of 0.04 µM), detection and quantification of AA in fried potatoes was carried out using the proposed electrochemical method and HPLC. Both techniques showed similar contents of AA.     

Comparison of Planar and 3‐D Interdigitated Electrodes as Electrochemical Impedance Biosensors

It has been reported that the introduction of a dielectric barrier between adjacent digits of an interdigitated electrode array can improve the sensitivity of the array as an electrochemical impedance biosensor. Here we present an in‐depth analysis of the impedance in planar interdigitated electrodes and 3‐D interdigitated electrodes (with dielectric barriers). The analysis indicates that the planar geometry not only provides lower impedance but also a higher change impedance as a result of molecular immobilization on the electrode array surface.     

Characterization of Carbon Film Electrodes for Electroanalysis by Electrochemical Impedance

The interfacial behavior of electrodes fabricated from carbon film resistors of 2 and 20 Ω in supporting electrolyte solutions of varying pH used in electroanalytical experiments has been characterized by electrochemical impedance spectroscopy with complementary cyclic voltammetric experiments. Equivalent circuits are proposed to fit the experimental data and the influence of electrode pretreatment has also been investigated.     

碳纳米管阵列电极的构建及电化学研究

本文提出一种改进的氧化铝模板法制备碳纳米管阵列电极:首先结合气相化学沉积和磁控溅射在氧化铝模板中制得碳纳米管阵列电极,然后用HF溶液将沉积了碳纳米管的氧化铝模板阻挡层除去,控制溶出时间即可得到不同溶出长度的碳纳米管阵列电极.循环伏安测试表明,锂离子在该阵列电极中的嵌入脱出反应主要发生在碳纳米管的端口处.此外,还应用固定频率交流阻抗法,研究了不同溶出时间的碳纳米管阵列电极的电容性质.     

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.     

纳米铂修饰玻碳电极对邻苯二酚的电化学氧化及测定

应用循环伏安法研究了邻苯二酚在纳米铂修饰玻碳(PtNPs/GC)电极上的电化学氧化行为。实验表明,PtNPs/GC电极对邻苯二酚有很强的电催化作用,其伏安扫描氧化峰电流随着温度的升高而增大,但氧化峰电位略有负移。常温下,邻苯二酚能自发在电极表面发生聚合反应,生成具有导电性的聚合膜,其催化氧化电流与邻苯二酚浓度在1.0×10-6mol/L~5.0×10-5mol/L范围内呈良好的线性关系,检出限为2.9×10-7mol/L。     

Electrochemical Studies of Three Dimensional Graphene Foam as an Electrode Material

Graphene foam is one kind of network of three dimensional (3D) graphene, which inherits the properties of two dimensional graphene and overcomes the aggregation/stacking of graphene sheets. In this work, graphene foam has been characterized by scanning electron microscopy and Raman spectroscopy. A graphene foam electrode was evaluated as a new electrode material by cyclic voltammetry (CV) and used for the detection of trace level of Pb²⁺ by anodic stripping voltammetry (ASV). Under the optimized condition of deposition potential (‐1.2 V) and deposition time (2 min), the detection limit is estimated to be 40 nM for Pb²⁺ based on the 3σ method.     

Electrochemical Characterization of Horse Spleen Ferritin Covalently Immobilized on Self‐Assembled Monolayer Modified Gold Electrodes

Horse spleen ferritin was covalently attached to SAM‐modified gold electrodes using cross‐linking agents. Reduction of ferritin occurs at negative potentials and is electrochemically irreversible. The voltammetry reveals the presence of a new electrochemical couple that has been determined to be a dissolved iron species released upon the reduction of ferritin. Covalently attached ferritin retains its ability to release iron as evidenced by the absence of the dissolved couple peaks when ferritin is reduced in the presence of nitrilotriacetate. As the SAM chain length increases, the reduction potential becomes more negative, suggesting a tunneling mechanism is involved in the electron transfer.     

Electrochemical Detection of NADH,Cysteine, or Glutathione Using a Caffeic Acid Modified Glassy Carbon Electrode

A modified electrode was prepared using electrodeposition methods to immobilize caffeic acid (CAF) onto the surface of a glassy carbon electrode (GCE) to create a polymer suitable for biosensor development. The polymer film coverage of the surface bound species was further optimized using electrodeposition methods, thus increasing the surface coverage to ca. 10^?9 mol cm^?2. Using cyclic voltammetry, the modified carbon electrode was used to facilitate and observe the electrocatalytic oxidation of coenzymes such as NADH, cysteine, and glutathione at different concentrations. A calibration curve was determined in each case within the concentration range; 300 nM to 10 mM, with the limits of detection (LOD) of 246 µM, 99 µM, 2.2 µM for NADH, cysteine, and glutathione respectively.     

Selective Electrochemical Detection of Explosives with Nanomaterial Based Electrodes

Explosive detection technologies play a critical role in maintaining national security, remain an active research field with many devices and analytical/electroanalytical techniques. Analytical chemistry needs for homeland defense against terrorism make it clear that real-time and on-site detection of explosives and chemical warfare agents (CWAs) are in urgent demand. Thus, current detection techniques for explosives have to be improved in terms of sensitivity and selectivity, opening the way to electrochemical devices suitable to obtain the targeted analytical information in a simpler, cheaper and faster way. For the electrochemical determination of energetic substances, a large number of sensor electrodes have been presented in literature using different modification materials, especially displaying higher selectivity with molecularly imprinted polymers (MIPs). MIPs have already been utilized for the detection of hazardous materials due to their mechanical strength, flexibility, long-time storage and low cost. The sensitivity of MIP-based electrosensors can be enhanced by coupling with nanomaterials such as graphene oxide (GOx), carbon nanotubes (CNTs), or nanoparticles (NPs). Specific characteristics of involved nanomaterials, their modification, detection mechanism, and other analytical aspects are discussed in detail. Non-MIP electrosensors are generally functionalized with materials capable of charge transfer, H-bonding or electrostatic interactions with analytes for pre-concentration and electrocatalysis on their surface, whereas nanobio-electrosensors use analyte-selective aptamers having specific sequences of DNA, peptides or proteins to change the potential or current. This review intends to provide a combination of information related to MIPs and nanomaterial-based electrochemical sensors, limited to the most significant and illustrative work recently published.     

Electrochemical Detection of TNT at Cobalt Phthalocyanine Mediated Screen‐Printed Electrodes and Application to Detection of Airborne Vapours

We describe the use of cobalt phthalocyanine as a mediator to improve the sensitivity for the electrochemical detection of TNT. Commercial screen‐printed electrodes containing cobalt phthalocyanine were employed for determination of TNT. Improved sensitivities compared to screen‐printed carbon electrodes without phthalocyanine were observed, current response for cyclic voltammetric measurements at modified electrodes being at least double that of unmodified electrodes. A synergistic effect between oxygen and TNT reduction was also observed. Correlation between TNT concentrations and sensor output was observed between 0–200 µM TNT. Initial proof‐of‐concept experiments combining electrochemical determinations, with the use of an air‐sampling cyclone, are also reported.     

The Electrochemical Behavior of Nitrazepam at a Screen‐Printed Carbon Electrode and Its Determination in Beverages by Adsorptive Stripping Voltammetry

The cyclic voltammetric behavior of nitrazepam was investigated at screen‐printed carbon electrodes over the range ?1.5 V to +1.5 V. Two reduction peaks were observable on the negative scan, at ?0.7 V, and ?1.2 V using pH 6 buffer. On the return scan a single oxidation peak was obtained at ?0.05 V. For quantitative analysis of beverages, we developed an anodic adsorptive stripping voltammetric method which required only dilution with buffer. The identification of nitrazepam and flunitrazepam could be achieved using cyclic voltammetry.     

Preparation of Phthalocyanine Modified Electrodes. An Electrophoretic Approach

Ni(II) and Co(II) phthalocyanines were deposited from their solutions in pyridine. The resulting modified electrodes exhibited catalytic activity in alkaline media.     

Electrochemical Determination of Pentachlorophenol Using a Glassy Carbon Electrode Modified with a Film of CuS Nanocomposite-Chitosan

A new electrochemical sensor was fabricated by modifying the glass carbon electrode surface with CuS nanocomposites and chitosan for the determination of pentachlorophenol. CuS nanocomposites obtained by a solvothermal method were composed primarily of CuS with hexagonal phase and Cu₂Cl(OH)₃ with a tetragonal phase. The results indicated that CuS nanocomposites possessed good electrochemical activity. After optimizing the experimental conditions, the linear dependence of current vs. pentachlorophenol concentration was reached in a range from 1.88 × 10^?6–7.50 × 10^?5 mol/L pentachlorophenol, and the detection limit was 6.25 × 10^?7 mol/L. The electrode displayed a high degree of stability and reproducibility. A new, simple, rapid, and highly sensitive electrochemical detection method of pentachlorophenol was established.     

Study of the Electrostatic Interaction of Lysine Monolayer on Glassy Carbon Electrodes Using the Electrochemical Method

A covalent modified glassy carbon electrode (GCE) with Lysine (Lys) has been fabricated via an electrochemical oxidation procedure. The electrostatic interaction of the monolayer has been investigated by cyclic voltammetry (CV) with Fe(CN)₆^3? redox probe in different concentrations of protons and different charged cations, respectively. The electrochemical method can be a new feasible method for the study of electrostatic interaction of the monolayer.