再生碳纤维电极的新方法

本文根据火焰熔融法自制碳纤维电极的特点，提出了一种简便、易行的火焰灼烧再生电极的新方法。由此法再生电极的各种性能与原电极相当，结果令人满意。     

铅笔芯电极作为工作电极-导数伏安法测定核黄素

用1B铅笔芯制成聚甲基丙烯酸甲酯包裹的铅笔芯电极。将此电极置于pH 2.20磷酸盐缓冲溶液中,在-1.5~+2.0V(vs.SCE)电位区间,以0.1V·s-1扫描速率连续扫描30圈使其活化。试验表明:在pH 4.8的乙酸盐底液中,核黄素在此电极上产生还原峰,其峰电位在-0.300V(vs.SCE)。其峰电流的导数与核黄素的质量浓度在1.88×10-4~0.376mg·L-1范围内呈线性关系,其检出限(3S/N)为4.42×10-5 mg·L-1,应用此方法测定了维生素B2片剂中核黄素的含量,所得测定值与其标示值相符。在此样品的基础上做加标回收试验,测得回收率在96.5%~111%之间,测定值的相对标准偏差(n=5)为2.5%。     

循环伏安法用于钇在钼和镍电极上的电极过程研究

使用了较为简单的数学方法,对不溶性反应产物的电极过程的循环伏安理论公式进行了推导。并将推导结果应用于LiCl—KCl—YCl_3熔盐体系,钇在钼电极上的电极过程研究,获得了很好的结果。同时还对钇在镍电极上阴极还原进行了研究,循环伏安结果表明钇和镍能够拖成金属间化合物。能谱及X射线衍射结果表明,金属间化合物的组成为Ni_2Y。     

活化玻碳电极伏安法测定锰的研究

采用活化玻碳电极(GC)以伏安法对测定锰进行了研究。结果表明:沉积于电极表面的二氧化锰对锰(Ⅱ)的电化学氧化具有自催化作用,活化GC电极可极大地提高测定锰的灵敏度。在0.04mol LNH3 NH4Cl(pH9.0)底液中,锰浓度在6.0×10-8～1.0×10-5mol L范围内成线性关系,检出限为4.0×10-8mol L。用3×10-7mol L锰溶液重复测定9次,RSD为1.6%。     

印制电极—金（Ⅲ）—盐酸体系电分析化学的研究

印制电极在盐酸介质中，正电位条件下对ＡｕＣｌ４＾－有强烈的化学吸附作用，文中提出了质子化的二醋酸纤维素与ＡｕＣｌ４＾－缔合的修饰机理，结合对Ａｕ＾３＋预富集后伏安测定的实验程序，分析讨论了其吸附热力学平均与阴极扫描伏安动力学行为，初步证明该体系是强吸附和接近完全不可逆的。     

Amperometric enzyme electrode for theophylline.

An amperometric biosensor for theophylline, based on the recently isolated enzyme theophylline oxidase, is described. The enzyme is entrapped, together with a ferricytochrome C cofactor, within a polymeric (Nafion) coating. The anodic detection (at +0.4 V versus Ag-AgCl) is facilitated by the addition of a redox-mediating hexacyanoferrate(III) ion. The influence of various experimental variables is described. The limit of detection is 2 x 10(-6) mol dm-3 theophylline, with linearity prevailing up to 3 x 10(-4) mol dm-3. The fast response and wash times permit rapid flow-injection measurements, with a frequency of 180 samples h-1 and a relative standard deviation of 3.0-4.0%. Prospects of using this electrode for clinical diagnostics are discussed.     

The tube electrode and e.s.r.

The convective diffusion equation for the downstream distribution of products and intermediates produced on a tube electrode under conditions of laminar flow is solved. For distances which are large compared to the thickness of the electrode, an analytical solution in real space can be found. The solution of the equation has been applied to an apparatus in which the intermediates and products are detected by e.s.r. The species are transported by laminar flow from the electrode through an e.s.r. cavity. Results are presented for two systems and are found to be in good agreement with the theory.     

Rotating electrode d.c. solution conductivity device

In an electrochemical cell with one electrode rotating asymmetrically with respect to a second fixed electrode, a constant current produces an a.c. component of the voltage between the pair at the rotational frequency. This a.c. signal arises from the varying iR drop between the extremes of rotational position and thus is a measure of the conductivity of the cell electrolyte. When such a rotating electrode is added to an operating two-electrode cell (e.g. a plating bath), the a.c. signal derived from the rotating element may be used additionally to map the spatial current distribution in the cell. The filtered and amplified signal in either system has also been used to trigger a counter for digital measurement of electrode rotational speed.     

Tunnel electrode: Part II. Electron-transfer theory at an n-type semiconductor tunnel electrode

The formula for the cathodic tunnel current at an n-type semiconductor tunnel electrode was derived from the double adiabatic perturbation theory considering the vibration in the first coordination sphere. In the low-temperature limiting case, the apparent difference between the normal and the abnormal regions was observed in both the transfer coefficient α and the activation energy E* as a function of potential. It was concluded that the semiconductor tunnel electrode has advantageous characteristics for investigation of the electron-transfer mechanism at high overvoltage.     

Part I. A specific electrode for urea.

A specific simple enzyme stirrer electrode is described for the assay of urea in blood serum. The enzyme is placed directly on a magnetic stirrer and held in place with a nylon net. The enzyme stirrer both stirs the solution and effects an enzymatic transformation, permitting the direct assay of a substrate such as urea. Potassium, Na⁺ , NH₄⁺ and other organic and inorganic species present in blood do not interfere. Linear curves are obtained from 5· 10^-2M to 1· 10^-4M urea with slopes close to Nernstian, 0.95 pH/decade. Urea in blood was assayed with an accuracy of 1.8% and a precision of 2.0% with immobilized urease in the stirrer. The stirrers were used for 15 weeks and over 500 assays with excellent results.     

Potentiometric enzyme electrode for uric acid.

An enzyme electrode for uric acid, with immobilized uricase on a pCO₂ membrane electrode, is described. Evaluation studies show that the enzyme electrode attains performance characteristics similar to homogeneous enzymatic conversion of uric acid under optimum solution conditions. Comparison of analyses carried out with the enzyme electrode and classical procedures on urine control samples demonstrates acceptable accuracy and precision for the electrode method.     

Molecular-level functionalization of electrode surfaces. An overview

Electrochemical reactions occur at electrode/electrolyte interfaces. Hence, manipulation and design of electrochemical interfaces accompanied by surface modifications have assumed vital importance. Molecular level modification, either at the monolayer or multilayer level of electrode surfaces and leading to functionalization of electrodes, is being actively pursued by researchers. Modification based on the self-assembled monolayer approach has enabled electrodes to acquire molecular recognition and molecular electronic characteristics. Functionalization of electrode surfaces using polymeric materials and enzymes has facilitated electrodes in exhibiting properties like catalysis, molecular recognition, electrochromism and birefringence. The results of such molecular level functionalization studies of electrode surfaces carried out recently in our laboratories are presented in this overview. Besides, some representative results reported from elsewhere are also included.     

Solvent effect on standard electrode potential: Part IV. Silver-silver chloride electrode in glycerol-water mixtures

Standard potentials of the silver-silver chloride electrode in eighteen glycerol-water mixtures containing up to 90% by weight glycerol, have been determined from e.m.f. measurements of cells of the type Pt, H₂ (gas, 1 atm); HCl (m), X% glycerol, Y% water; AgCl, Ag, at nine different temperatures in the range 15 to 55°C. The standard molal potential in the various solvent mixtures has been expressed as a function of temperature. Standard thermodynamic quantities for cell reaction and the primary medium effects of various solvents upon HCl were also calculated. The temperature variation of the standard potential was utilized to calculate the thermodynamic quantities for the transfer of one mole of HCl from water to glycerol-water media. The results have been interpreted in regard to the acid-base properties and the structure of the solvent.     

Solvent effect on standard electrode potential: Part III. Silver-silver chloride electrode in methanol-water mixtures

From measurements of the electromotive force of the Pt, H₂ (gas, 1 atm); HCl (m), X% methanol, Y% water; AgCl, Ag cells at nine temperatures from 15 to 55°C at 5° intervals, the standard potential of the silver-silver chloride electrode has been determined over a broad range of methanol concentrations (0–90 wt. % methanol). The standard molal potential in the various solvent mixtures has been expressed as a function of temperature. The primary medium effects of various media on hydrochloric acid, and the standard thermodynamic quantities accompanying the transfer of HCl from water to the respective solvent media have been computed. The results have been discussed both in terms of the acid-base behaviour of the solvent mixtures and also their structural effects on the transfer process.