新型电流传感器-双拄碳纤维微电极

本文报道了双拄碳纤维微电极的研究及应用,分别用循环伏安法,计市电流法考察了该电极的性能,并用实验验证了双微电极的稳态电流理论公式,探讨了理论曲线与结果偏离的原因,采用发生一收集模式,提出间接测定维生素B~1的方法,并取得了满意的结果,维生素B~1的检测限为1.0×10^-^6mol.dm^-^3,线性范围为7.5 ×10^-^6-7.5×10^-^4mol.dm^-^3     

Mercury-coated carbon fiber microelectrodes : Preparation and some properties

Carbon fibre microelectrodes were made by sealing the fibres into glass and by using heat-shrinkable tubing. The electrodes can be coated with mercury by deposition at ?0.9 V vs. SCE from 0.1 M thiocyanate containing 0.05 mM mercury(II) at pH 2.5. Coulometric measurements and square-wave voltammetry were used to establish the properties of the deposit. Conditions for the deposition and stripping of cadmium are outlined.     

Optimized carbon nanotube fiber microelectrodes as potential analytical tools

The preparation and interesting electrochemical properties of carbon nanotube (CNT) fiber microelectrodes are reported. By combining the advantages of CNT with those of fiber electrodes, this type of microelectrode differs from CNT-modified or CNT-containing composite electrodes, because they are made solely of CNT without other components, for example additives or binders. The performance of these electrodes has been characterized with regard to, among others, the electrocatalytic oxidation of analytes via dehydrogenase-mediated reactions. In this context the reversible regeneration of the coenzyme NAD(+) using a mediator is a key step in the development of new amperometric sensor devices and we have successfully immobilized mediator molecules that are very efficient for this purpose on the surface of the CNT fiber electrode. The microelectrodes thus obtained have been compared with classic carbon microelectrodes and have promising behavior in biosensing applications, especially after specific pretreatments such as CNT alignment inside the fiber or expansion of the specific surface by chemically induced swelling.     

氧化铱纳米颗粒修饰碳纤维电极用于水果中pH在线检测

pH检测在农业生产、食品加工、环境保护、疾病诊断等领域有着重要意义.电化学法具有响应速度快、灵敏度高和操作简单等优点,是目前最常用的pH检测方法之一.然而,商品化的pH计存在体积大、质子敏感膜易损等问题,仅能在相对稳定的样本溶液环境中工作,并不适用于植入式pH分析.本文将氧化铱纳米颗粒修饰在碳纤维微电极表面,构建了一种...     

Carbon nanotube fiber microelectrodes

Carbon nanotube (CNT) fibers have been used to fabricate microelectrodes with an attractive electrochemical behavior. By combining the advantages of CNT materials and fiber microelectrodes, the new material expands the scope of CNT-based electrochemical devices. The CNT fiber offers a marked decrease in the overvoltage for the NADH, dopamine, and hydrogen peroxide and circumvents NADH surface fouling effects. Heat treatment is shown to be extremely useful for activating the CNT fiber surfaces for electron transfer. SEM imaging and cyclic-voltammetric data indicate that the heat treatment leads to the removal of nonconducting residues and exposure of a "fresh" CNT surface. The new electrode material thus presents new opportunities for a wide range of electrochemical and analytical applications.     

Multimembrane carbon fiber microelectrodes for amperometric determination of serotonin in human urine

An electrochemical sensor for the determination of serotonin in urine was prepared using Ni(II)-phthalocyanine and Nafion to modify the surface of a 4 mm length carbon fiber microelectrode. The resultant sensor was found to improve the response towards this neuronal amine versus the microelectrode without the polymer films. Different polymerization conditions, as well as different conditioning solutions and buffer systems, were investigated in order to optimize the response of the electrodes. Square wave voltammetry (SWV) is proposed as a direct method for determination of serotonin in human urine, after a solid-liquid extraction process. The proposed method enables a detection limit for serotonin of 0.80 +/- 0.04 microgram L-1 to be achieved at a reduction potential of 0.35 V, with an overall prediction error of 2.2% and recoveries of 93%.     

Paracetamol voltammetric microsensors based on electrocopolymerized-molecularly imprinted film modified carbon fiber microelectrodes

A molecularly imprinted polymer is presented as a carbon fiber microelectrode coating for determining the presence of paracetamol. The polymeric film was obtained by electrocopolymerization of o-phenylenediamine and aniline in the presence of the template molecule, through the use of cyclic voltammetry. After removing the template, the signals of the microsensor were converted into physical ones by a voltammetric transductor using square wave voltammetry. Various parameters influencing the electropolymerization and voltammetric determination processes were examined and optimized. The response of the imprinted microsensor to paracetamol was linearly proportional to its concentration over the range 6.5 x 10(-6) to 2.0 x 10(-3) mol l(-1), with good stability and reproducibility (RSD < 5.6%). The detection limit was 1.5 microM. Under the experimental conditions used the voltammetric microsensor was able to differentiate between paracetamol and other closely structurally-related compounds present in biological fluids, such as certain catecholamines.     

Analytical applications of poly(3-methylthiophene)-coated cylindrical carbon fiber microelectrodes

Some analytical applications of carbon fiber microelectrodes (CFMEs) modified with cyclic voltammetric electrogenerated poly(3-methylthiophene) (P3MT) coatings are described. Cyclic voltammograms in aqueous solutions of the phenolic antioxidants tert-butylhydroxyanisole (BHA), tert-butylhydroquinone (TBHQ), propylgallate (PG), and tert-butylhydroxytoluene (BHT) showed that electrocatalytic effects and an improved electrode kinetics occurred at the modified microelectrodes when compared with GC electrodes of conventional size. Moreover, reproducible voltammograms were obtained, obviating the need of cleaning or pretreatment of the coated microelectrode. Another important analytical advantage was the greatly improved resolution for mixtures of analytes. The behavior of P3MT-CFMEs in organized media was tested by considering their voltammetric response towards the electrochemical oxidation of PG. The nonionic surfactant Pluronic F 68 was selected as the most suitable to form micellar solutions of PG, as well as the emulsifying agent for the preparation of oil-in-water emulsions. A 20:80 ethyl acetate:n-hexane mixture was used as the organic phase and a 0.05 mol L⁻¹ H₃PO₄/H₂PO₄⁻ buffer solution of pH 2.0 as the aqueous continuous phase. Cyclic voltammetry demonstrated that the PG oxidation current was purely diffusion-controlled in the organized medium. The analytical characteristics obtained by using differential pulse voltammetry were slightly better than those obtained in aqueous solution. Furthermore, the improved resolution for mixtures of analytes is retained in the oil-in-water emulsified medium. The proposed method was applied with good results to the determination of PG in spiked commercial dehydrated soup samples by direct emulsification of aliquots of the sample extract in the ethyl acetate:n-hexane mixture.     

电化学活化碳纤维微电极和脑神经递质及抗坏血酸在体测定

本文采用一种简单电化学方法,即恒电流法处理自制碳纤维电极,在脑神经递质测定中显示了很高的灵敏度和分辨能力.活化后的电极对多巴胺的检测限达5×10^-8mol.dm^-3,对多巴胺和抗坏血酸的伏安峰分离达170mV.作者使用该电极,采用半微分伏安法测定了活体大鼠脑内抗坏血酸,3,4-二羟苯乙酸和5-羟吲哚乙酸的浓度分别为1.7×10^-4,2.1×10^-5和 3.3×10^-6mol·dm^-3.本文对电极的制作,活化条件,伏安峰判别,在体药物实验和电极活化机理等进行了研究和探讨.     

A Miniature glucose/O2 biofuel cell with single-walled carbon nanotubes-modified carbon fiber microelectrodes as the substrate

This study demonstrates a new kind of miniature glucose/O₂ biofuel cells (BFCs) based on carbon fiber microelectrodes (CFMEs) modified with single-walled carbon nanotubes (SWNTs). SWNTs are used as a support both for stably confining the electrocatalyst (i.e., methylene green, MG) for the oxidation of NADH and the anodic biocatalyst (i.e., NAD⁺-dependent glucose dehydrogenase, GDH) for the oxidation of glucose and for efficiently facilitating direct electrochemistry of the cathodic biocatalyst (i.e., laccase) for the O₂ reduction. The prepared micro-sized GDH-based bioanode and laccase-based biocathode exhibit good bioelectrocatalytic activity toward the oxidation of glucose and the reduction of oxygen, respectively. In 0.10 M phosphate buffer containing 10 mM NAD⁺ and 45 mM glucose under ambient air, the power density of the assembled miniature compartment-less glucose/O₂ BFC reaches 58 μW cm⁻² at 0.40 V. The stability of the miniature glucose/O₂ BFC is also evaluated.     

Carbon fiber microelectrodes modified with carbon nanotubes as a new support for immobilization of glucose oxidase

Carboxylated carbon nanotubes were coated onto carbon microfiber electrodes to create a micron-scale bioelectrode. This material has a high surface area and can serve as a support for immobilization of enzymes such as glucose oxidase. A typical carbon nanotube loading of 13???g?cm^?1 yields a coating thickness of 17???m and a 2000-fold increase in surface capacitance. The modified electrode was further coated with a biocatalytic hydrogel composed of a conductive redox polymer, glucose oxidase, and a crosslinker to create a glucose bioelectrode. The current density on oxidation of glucose is 16.6?mA?cm^?2 at 0.5?V (vs. Ag/AgCl) in oxygen-free glucose solution. We consider this approach to be useful for designing and characterizing surface treatments for carbon mats and papers by mimicking their local microenvironment.

Microvolume electrochemical cell employing cylindrical graphite fiber microelectrodes

A microvolume electrochemical cell was designed that allows voltammetric measurements to be conducted in less than 10-μl volumes of solutions. The cell body consists of a stainless-steel needle functioning as both the reference and auxiliary electrodes. A cylindrical graphite fiber microelectrode, inserted into the needle, serves as the working electrode. Microliter samples of solution can be aspirated into the cell by means of an Eppendorf micropipet attached to the needle. The performance of the microvolume cell was investigated by conducting square-wave anodic stripping voltammetry of lead and cadmium and square-wave voltammetry of epinephrine, both in solutions containing dissolved oxygen. The cell functioned very well in both methods; however, a needle preplated with mercury was found to improve the performance of the cell in anodic stripping voltammetry.     

微电极研究 III: Hg^2^+的电沉积过程的研究

研究了不同浓度的Hg^2^+在碳纤维微电极电沉积Hg的形态, 沉积机制和实验参数对汞膜性质及溶出电流的影响; 剖析了Hg的成核过程, 验证了成核理论; 借扫描电镜观察了汞晶体图象。约在6×10^-^5mol·L^-^1Hg^2^+时镀汞, 可形成密布型微汞滴构成的类汞膜, 微滴直径在0.03-0.2μm, 汞微滴密度约为5.7×10^6个/cm^2, 提出了优化汞膜的实验条件和依据。     

The oxidation and reduction behavior of nitrite at carbon nanotube powder microelectrodes

Carbon nanotube electrodes were fabricated using powder microelectrode method, and the carbon nanotube powder microelectrodes (CNTPMEs) were characterized by the electro-oxidation and electro-reduction of nitrite. It was found that the kinetics of oxidation and reduction were greatly improved at CNTs compared with that at conventional graphite, indicating that CNTs could catalyze the electrochemical process of nitrite. The kinetic parameters of these process at CNTs were calculated, i.e. k was 0.593 cm s⁻¹, and (1-α)n_α was 0.501±0.018 for the nitrite oxidation. This CNTPME was also used as a nitrite carbon nanotube sensor, and the results showed that the detection limit was 8 μM.     

二茂铁修饰碳黑微电极同时测定多巴胺和抗坏血酸

研究了神经递质多巴胺(DA)和抗坏血酸(AA)在二茂铁修饰碳黑微电极上的电化学行为。实验结果表明,在pH4.5的磷酸盐中,DA在该电极上的线性范围为2.0×10-6～4.0×10-3mol/L,检出限(3σ)为1.0×10-6mol/L;AA在该电极上的线性范围为6.0×10-6～1.0×10-3mol/L,检出限(3σ)为2.0×10-6mol/L;用这种电极可以同时测定多巴胺,抗坏血酸。     

Fabrication of carbon microelectrodes with an effective radius of 1 nm

A method for producing insulated nanometer-sized carbon electrodes is presented. These electrodes are produced using electrochemical etching of carbon fibers followed by deposition of electrophoretic paint. A new deposition approach for insulating the tips, the so-called “inverted deposition” technique, is introduced. This technique allows complete insulation of the whole body of the etched carbon fiber except for the very tip, leaving an electrochemical active area with effective diameters as small as a few nanometers. The process overcomes pinhole formation that can be a problem with the normal electrophoretic paint deposition process. The fabricated electrodes show ideal steady-state voltammetric behavior. The voltammetric response corresponding to the reduction of hexacyanoferrate(III) and hexaammineruthenium(III) is investigated on these small electrodes in the absence and presence of supporting electrolyte. For these two multiple-charged ions the steady-state voltammetric behavior in the absence of supporting electrolyte is found to deviate from expected behavior, especially at very small electrodes.     

Voltammetric determination of chloramphenicol in milk at electrochemically activated carbon fibre microelectrodes

Electrochemical activation of cylindrical carbon fibre microelectrodes (CFMEs) by repetitive square-wave (SW) voltammetric scans between 0.0 and +2.6 V has shown to increase dramatically the cathodic current of chloramphenicol (CAP). This is attributed to the increase of the carbon fibre surface area due to its fracture and the appearance of deep fissures along the main fibre axis. Cyclic voltammograms of CAP suggested a contribution to the total current from most likely thin-layer electrolysis. The current density:concentration ratio calculated for the reduction of CAP at an activated fibre was 6.5×10⁷ μA cm⁻² mol⁻¹ l. A method for the determination of CAP at low concentrations levels, using SW voltammetry at electrochemically activated cylindrical microelectrodes, was developed. Different chemical and electrochemical variables involved in the activation step were optimised. Calibration graphs were linear (r=0.9990) in the 1.0×10⁻⁷ to 1.0×10⁻⁵ mol l⁻¹ concentration range, with a slope of (2.69+0.03) × 10⁵ μA mol⁻¹ l. A limit of detection of 4.7×10⁻⁸ mol l⁻¹ (15 ng ml⁻¹) was found. The SWV method was applied for the determination of CAP in milk samples spiked with the antibiotic at two concentration levels: 64 and 320 ng ml⁻¹. Recoveries >97% were obtained in all cases by following a very simple experimental procedure.     

Novel estradiol sensors based on carbon nanotube multilayer modified gold hair microelectrodes

Multi-walled carbon nanotube multilayers were modified onto a newly proposed gold hair microelectrode via a simple layer-by-layer assembling method.The resulting electrode showed a sensitive oxidation response to estradiol with detection limit as low as 1.0×10~(-8) mol/L,foreseeing a promising approach to the fabrication of high-sensitive microsensors.     

Integration of multi-microelectrode and interface circuits by silicon planar and three-dimensional fabrication technology

A multi-microelectrode for simultaneous recording of single-unit action potentials is a useful device for studying the organization and function of neural systems.We have fabricated a silicon probe which integrates a multi-microelectrode and interface circuits (preamplifier and analog switches) on a silicon chip by silicon planar and three-dimensional fabrication technology. This electrode has the following advantages: (1) it is easy to arrange the location of recording sites simply by changing photomasks; (2) crosstalk between the multi-electrodes can be reduced by the shielding effect of the silicon substrate; (3) integration of microelectrodes and preamplifiers on the same silicon chip eliminates the undesirable effects of stray lead capacitance; (4) analog swithces serve as selectors or multiplexers for a parallel to series conversion of multichannel signals of neural activities.In this paper, the design and fabrication processes of multi-microelectrode and interface circuits are described. In particular, the characteristics of polysilicon electrodes, design of a low-noise MOSFET for the preamplifier and silicon three-dimensional processes for the electrode probe are considered.     

Surface modification of carbon fiber for improving the interfacial adhesion between carbon fiber and polymer matrix

In this study, the reinforcing mechanism of amine functionalized on carbon fibers (CFs) has been precisely discussed, and the differences between aliphatic and aromatic compounds have been illustrated. Polyacrylonitrile‐based CFs were functionalized with ethylenediamine, 4,4‐diaminodiphenyl sulphone, and p‐aminobenzoic acid (PAB), and CF‐reinforced epoxy composites were prepared. The structural and surface characteristics of the functionalized CFs were investigated using X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT‐IR), and scanning electron microscopy (SEM). Mechanical properties in terms of tensile and flexural strengths and moduli were studied. The FT‐IR results confirm the success in bonding amines on the CF surface. After treatment of CFs, the oxygen and nitrogen contents as well as the N/C ratio showed an increase. XPS results provided evidence of the chemical reaction during functionalization, rather than being physically coated on the CF surface. Chemical modification of CF with diamines led to considerable enhancement in compatibility of CF filaments and epoxy resin, and remarkable improvements were seen in both tensile and flexural properties of the reinforced composites. SEM micrographs also confirmed the improvement of interface adhesion between the modified CFs and epoxy matrix. Finally, it can be concluded that PAB is a promising candidate to functionalize CF in order to improve interfacial properties of CF/epoxy composites. Copyright © 2015 John Wiley & Sons, Ltd.