Fe(Ⅱ)-EDTA剪切DNA在悬汞电极上的电化学行为研究

在足迹图谱技术中,Fe(Ⅱ）-EDTA常被作为DNA断裂工具用于双链DNA的非特异性断裂^[1],因而Fe(Ⅱ）-EDTA作为核酸构象变化的探针及DNA－配体复合物分析的羟基自由基足迹试剂在生物化学、分子生物学和基因工程学等中获得广泛应用^[2]。虽然DNA在汞电极上的电化学行为研究报道较多^[3-7],但有关Fe(Ⅱ）-EDTA非特异性剪切DNA的电化学研究报道较少^[8-10]。本文对Fe(Ⅱ）-EDTA剪切DNA在悬汞电极上的电化学行为进行了初步研究。结果表明,由于Fe(Ⅱ）-EDTA对DNA的裂解作用,导致DNA的结构发生变化,使DNA在悬汞电极上的电化学行为发生变化,还原峰电流显著增大,因而用电化学方法研究DNA的裂解有望成为研究DNA结构变化的辅助手段。     

超微电极测定单细胞中神经传质的进展

本文评述了近年来用超微电极测定单细胞中神经传质的沿革，方法及进展，着重介绍了超微碳纤维电极的制备以及用超微碳纤维电极测定单细胞中神经传质的技术步骤，对存在的问题，应用前景和该方法进一步发展的方向进行了探讨。     

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…     

芯片毛细管电泳集成电化学检测装置和4种碳纤维电极的比较研究

自行设计组装了微流控芯片安培检测系统,以自制的碳纤维微米电极、碳纤维纳米电极、单壁碳纳米管修饰的碳纤维微米电极以及碳纤维微盘电极等4种电极为检测器,采用柱末检测的模式,考察了其对儿茶酚胺类物质多巴胺与异丙肾上腺素的分离检测效果以及电极的灵敏度。结果表明,在检测电位为0.6V、0.02mol/LTris-HCl(pH8.0)为缓冲溶液的优化条件下,检测多巴胺与异丙肾上腺素的分离度分别为0.64、1.06、0.61和1.22;灵敏度(S/N=3)分别为1.7×10-7、5.9×10-8、2.3×10-8和5.3×10-7,碳纤维纳米电极同时具备了较高的分离度与灵敏度。将碳纤维纳米电极应用于测定鼠嗜铬神经细胞瘤细胞(PC12)中神经递质多巴胺,以异丙肾上腺素为内标,测得单个PC12细胞中多巴胺含量为(0.57±0.07)fmol(n=5),与文献报道值相符。     

稀土硝酸盐与１，１，１—三（４—二苯胺甲酰基—２—氧杂丁基）丙烷配合物

三角架型配体由于其独特的配位方式而具有许多优良的物理和化学性质,如能稳定高氧化态的过渡金属离子^[1~3],用作优良的电极活性物质^[4],具有生物活性^[５]等,因此近十余年来对该类配合物的研究一直是配位化学研究领域的一个重要部分,但到目前为止,对具有三角架结构的三酰胺型开冠醚的研究却很少,且主要集中于研究它与过渡金属和碱金属离子的相互作用及其性质^[4,5],有关该类配体与稀土离子的配位形式及性质的研究则更少^[6]。     

超微电极的新进展

超微电极是当前电化学前沿领域和研究热点之一。本文主要介绍了超微电极的基本原理、种类和特点 ,并结合国际上超微电极的最新研究现状 ,介绍了超微修饰电极的特点及其在电分析化学中的应用 ;超微电极在扫描探针显微学、固态电化学、生物细胞体内检测和分析化学等方面中的应用。     

聚苯胺修饰碳纤维超微pH传感器研究及其在植物柱头活体测试中的应用

作为探测生命奥秘的重要手段,微电极技术已广泛应用于活体分析[1－3]．传统的pH玻璃电极难以实现活体微区或微环境分析,因此,研制微型和超微型pH传感器意义重大．本文采用电化学聚合法将聚苯胺修饰在碳纤维微柱电极上,制成对pH具有能斯特响应的超微型pH传感器,与pH玻璃电极比较,发现它具有响应快、稳定性高、重现性好及选择性高等特点．用该超微pH传感器首次实现了对答苔属植物活体柱头乳突细胞和花粉粒表面微环境的pH值测定．为生物学家深入研究花粉萌发的生理过程和机理提供了十分有用的信息．1实验部分1．1仪器和试剂M366双恒…     

微流控芯片中超微电极的制作及其在芯片-电化学检测中的应用

设计并制作了集成有超微电极的玻璃微流控芯片.在电化学检测芯片1(EC-1)中,以光刻方法制作13μm宽的Pt超微电极,距分离管道末端30μm,优化电极体系和分离电压,检测了电泳分离的神经递质.在电化学检测芯片2(EC-2)中,制作7μm宽的超微电极,在其上游集成城墙式的膜结构,进一步腐蚀后的膜厚度为10μm,具有良好的导电性和散热性能,成功地将高压电场截至在超微电极之前,具有进一步应用于电化学检测的能力.     

中性载体水杨酸根离子电极的研究

近年来,反Hofmeister行为的阴离子选择性电极的研究是离子电极研究领域中重要的研究方向之一[1],其中许多平面结构的Schiff碱金属配合物对特种阴离子表现较高选择性,以此研制了许多高选择性I-电极[2,3]、S al-电极[4-6]、SCN-电极[7,8].     

醌类化合物在苯酚羟化反应中的电子传递作用

Fenton试剂是某些烃类化合物的有效氧化剂^[1],该体系对芳香化合物具有羟化作用。我们^[2]曾报道了含Cu类钙钛石型复合氧化物在苯酚烃化反应中的催化活性,并提出了相应的反应机理。高价态的过渡金属离子如C^3 [2]和Fe^3 [3]通常被认为是中间自由基的氧化剂。实际上,醌类化合物及其还原形式半醌、氢醌与生物体内许多电子转移过程密切相关^[4],如泛醌或辅酶Q在生物体呼吸链电子传递过程中起重要作用^[5]。在实验中我们观察到苯酚羟化反应中不仅有苯醌生成,而且生成的苯醌还能促进羟化反应。本文报道了醌类化合物在苯酚羟化循环中的传递电子作用。     

Quantitative characterization of shear force regulation for scanning electrochemical microscopy

The quest for higher spatial resolution in scanning electrochemical microscopy (SECM) calls for the application of smaller probe electrodes. When electrodes are to be used in the feedback mode, smaller electrodes require higher intrinsic kinetics at the sample. The fabrication of nanoelectrodes, as well as their use as SECM probes at constant distance, are reported. The properties of shear force regulation system are characterized quantitatively. Simultaneous topography and reactivity imaging were demonstrated using gold microstructures on a glass substrate.     

Amorphous carbon nitride a-CNx microelectrode: Fabrication and characterization

Fabrication and characterization of amorphous carbon nitride a-CN_x microelectrodes are reported. These electrodes were prepared by DC-sputtering of a thin carbon layer on sharpened glass tip. The kinetic parameters (k⁰ and α) and the diffusion coefficient of the ferri-ferrocyanide redox probe were determined by steady-state voltammetry (CV) and by electrochemical impedance spectroscopy (EIS), and were used for characterizing both the electrochemical sensitivity of microelectrodes and their dimensions. The cathodic activation procedure of the electrode resulted in an increase of the electron rate constant. This procedure provides a new way for the fabrication of carbon microelectrodes for local electrochemical measurements.     

Fabrication of nanometre-sized platinum electrodes by controllable electrochemical deposition

A new and simple method for fabricating controllable insulated nanometer-sized platinum electrodes is presented. Electrochemical etching of platinum wire is employed, and then a repeated process of cycle voltammetric deposition of electrophoretic paint and heat curing for shrink film follows which effectively controls the size of the nanoelectrodes, which is different from previous DC electrolysis deposition. This technique allows complete insulation of the whole body of the etched platinum wire, except for the very tip with the shrink film during heat curing of the film, leaving an electrochemical active area with effective diameters of nanometers. The process overcomes the pinhole formation resulting from the electrophoretic paint deposition process. The size of the platinum electrodes and the thickness of the deposed paint for insulation can be properly controlled and reproduced. The fabricated electrodes show ideal steady-state voltammetric behaviors from which the effective areas of the nanoelectrodes are measured. The effective radius of the prepared nanoelectrodes ranges from 3.1 nm to hundreds of nanometers.     

Fabrication and Characterisation of Leak-Tight Glassy Carbon Electrodes,Sealed in Glass Employing Silicon Coating,for Use in Electrochemical Detection

Abstract

Glassy carbon discs have been coated with silicon in a chemical vapour deposition process to obtain leak-tight electrodes, sealed in glass. Electrodes with coatings thicker than 5μm prove to be leak-tight in contrast with uncoated ones. Silicon-coated electrodes show faster decay of charging current, less noise and decreased background current. Leak-tightness and electron microscope information correlate well with the electrochemical data. All results can be ascribed to the absence of a void between glassy carbon and glass at Si-coated electrodes. By silicon coating, signal-to-noise ratios are improved with a factor of about 5, as is demonstrated for catecholamines and metabolites in liquid chromatography with electrochemical detection.     

An efficiently halogen-free flame-retardant long-glass-fiber-reinforced polypropylene system

In order to solve the “candlewick effect” caused by glass fibers, which results in the decrease of flame retardancy of flame-retardant long-glass-fiber-reinforced polypropylene (LGFPP) systems, and the deterioration of mechanical properties caused by adding an additional amount of flame retardants compared with flame-retardant non-glass-fiber-reinforced polypropylene systems so as to keep a same flame retardancy, a novel intumescent flame retardant (IFR) system, which is composed of a charring agent (CA), ammonium polyphosphate (APP) and organically-modified montmorillonite (OMMT), was used to flame retard LGFPP. The thermal stability, combustion behavior, char formation, flame retardant mechanism and mechanical properties of the IFR-LGFPP samples were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL-94 test, cone calorimeter test, scanning electronic microscopy, and mechanical property tests. When the content of IFR is 20 wt%, the LOI value of IFR-LGFPP reaches 31.3, and the vertical burning test reaches UL-94 V-0 rating, solving the “candlewick effect” caused by long glass fiber without additional amount of the IFR. All the relevant cone calorimeter parameters also show that IFR-LGFPP has much better flame-retardant behaviors than LGFPP. Furthermore, the mechanical properties of IFR-LGFPP almost remain unchanged in comparison with those of LGFPP containing no IFR. The flame retardant mechanism was also discussed.     

Platinized carbon nanoelectrodes as potentiometric and amperometric SECM probes

Micrometer-sized platinized carbon electrodes have previously been used for the detection of reactive oxygen and nitrogen species (ROS and RNS) in biological systems. Here, we report the preparation and characterization of quartz-sealed platinized carbon nanoelectrodes. Such electrodes can be employed as tips in the scanning electrochemical microscope (SECM). The prepared electrodes were characterized by steady-state voltammetry, scanning electron microscopy, and SECM. In addition to ROS/RNS detection, the high surface area of a platinized nanoelectrode makes it a useful potentiometric probe. Unlike previously fabricated platinized electrodes, carbon electrodes possess a very thin insulating sheath, which is essential for experiments inside biological cells and high-resolution SECM imaging.     

Electrocapillary studies of fluoride solutions on mercury using polyethylene capillary

The electrocapillary curves in concentration range 0.001 M to 1 M in sodium and potassium fluoride solutions and in 12.25 M potassium fluoride were measured using a glass capillary with a polyethylene tip. In very dilute solutions the lowering of the interfacial tension at potentials more positive than p.z.c. described several times in experiments with glass capillary electrometer was not observed, and the electrocapillary curves coincided very well with those obtained from double integration of capacitance data. At large concentration of fluoride an increase of maximum interfacial tension was noticed. The fabrication of polyethylene capillary electrode is described and its advantages discussed.     

Fabricating Nanogaps between Nanoelectrodes using Dielectrophoresis Technique for Molecular Fluorescence Enhancement

Here we demonstrate the fabrication of nanometer-sized gaps by assembling single coreshell nanoparticles between metallic nanoelectrodes. Protein coated SiO₂@Au coreshell nanoparticles are synthesized and positioned between uorescent molecules-covered electrodes in a controllable way using dielectrophoretic trapping, forming nanogaps sandwiched between nanoparticle and nanoelectrodes. Preliminary photoluminescence measurements show that enhanced molecular uorescence could be detected from the uorescent molecules inside the nanogaps. These results pave the way for realizing electrically driven molecular uorescence based on nanogap electrodes.     

Conical tungsten tips as substrates for the preparation of ultramicroelectrodes

Here we describe a simple method to prepare voltammetric microelectrodes using tungsten wires as a substrate. Tungsten wires have a high tensile modulus and enable the fabrication of electrodes that have small dimensions overall while retaining rigidity. In this work, 125 microm tungsten wires with a conical tip were employed. For the preparation of gold or platinum ultramicroelectrodes, commercial tungsten microelectrodes, completely insulated except at the tip, were used as substrates. Following removal of oxides from the exposed tungsten, platinum or gold was electroplated, yielding surfaces with an electroactive area of between 1 x 10-6 and 2 x 10-6 cm2. Carbon surfaces on the etched tip of tungsten microwires were prepared by coating with photoresist followed by pyrolysis. The entire electrode was then insulated with Epoxylite except the tip, yielding an exposed carbon surface with an area of around 4 x 10-6 to 6 x 10-6 cm2. All three types of ultramicroelectrodes fabricated on the tungsten wire had similar electrochemical behavior to electrodes fabricated from wires or fibers insulated with glass tubes.     

Carbon fiber nanoelectrodes applied to microchip electrophoresis amperometric detection of neurotransmitter dopamine in rat pheochromocytoma (PC12) cells

Microelectrodes have been adopted in electrochemical detection for CE or microchip CE in recent years. In this paper, the use of nanoelectrodes (with tip diameter of 100-300 nm) as the electrochemical detector in microchip CE is firstly reported. The experimental results indicated that both the sensitivity and resolution of microchip CE with the carbon fiber nanoelectrode (CFNE) amperometric detection have been improved markedly comparing with the traditional microelectrodes. The detection limit of dopamine (S/N = 3) is 5.9x10(-8) M, which is one or two orders of magnitude lower than that reported so far, and the resolution of dopamine (DA) and isoprenaline (IP) has also improved from 0.6 (using 7 mum carbon fiber microelectrodes, CFME) to 1.0. We assembled a novel and easily operated microchip CE system with end-column amperometric detection, which allows the convenient and fast replacement of the passivated electrodes. Under the optimized condition, the RSDs of peak height and migration time are 1.47 and 0.31%, respectively (n = 40), indicating that the system displays excellent reproducibility. The nanoelectrode-based microchip CE system has been successfully applied to the determination of DA in cultured rat pheochromocytoma (PC12) cells, and the average content of DA in an individual PC12 cell is 0.54 +/- 0.07 fmol, which is in good agreement with that reported in the literature.