Carbon-Filled Polymer Paste Reference Electrodes

Abstract

Inexpensive, disposable, carbon-filled polymer paste reference electrodes are reported. These electrodes are designed for use in conjuction with carbon-filled polymer paste ion-selective probes reported earlier. Attachment of integrated electronics is easily achieved.     

Electrochemical Sensing Platform Integrated with Solid-state Reference Electrode Based on Indium Tin Oxide Interdigitated Array Electrodes

We present a new strategy for the fabrication of a fully integrated electrochemical platform. The three-electrode system consists of an indium tin oxide interdigitated array as working electrode, a solid-state reference electrode, and an electrodeposited Pt counter electrode that are placed in microfluidic channel. By controlling the electrodeposition conditions, such as the applied potential and time, the stability and uniformity of the films can be optimized. A solid-state reference electrode was fabricated on the nanoporous Pt via electropolymerization of poly-1,3-phenylenediamine. This system provides a simple method for the fabrication of three-electrode system and opens the possibility for an electroanalytical platform.     

N-N二甲基甲酰胺/纳米银修饰电极的制备与应用研究

用N-N二甲基甲酰胺和纳米银对导电玻璃(ITO)进行修饰得到了N-N二甲基甲酰胺/纳米银修饰电极。研究了电极的电化学行为,在pH=6.64的PBS缓冲溶液中,盐酸二甲双胍在0.075~0.2mg/mL浓度范围内与氧化峰电流呈现很好的线性关系,线性方程为y=317.19x+30.076,最低检出限为0.000 7mg/mL,线性相关线性系数R2为0.959 5。平行测量5组数据,其RSD值为0.75%,在盐酸二甲双胍缓释片溶液中5次加标回收率平均值为101%。精密度和准确度的分析结果表明方法可应用于药物中盐酸二甲双胍含量的测定。     

Electrochemical Behaviour of Carbamazepine in Acetonitrile and Dimethylformamide Using Glassy Carbon Electrodes and Microelectrodes

The electrochemical reduction of carbamazepine in acetonitrile (ACN) and dimethylformamide (DMF) using a glassy carbon electrode and microelectrodes has been studied. The reduction process is consistent with an electrochemical‐chemical mechanism (EC) involving a two electron transfer followed by a first order reaction, as shown by the cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Half‐wave potential, number of electron transferred, diffusion coefficient and rate constant of the associated chemical reaction are reported. Limits of detection (LOD) for DPV are 0.92 and 0.76 µg mL^?1 (3.89×10^?6 mol L^?1 and 3.21×10^?6 mol L^?1) in ACN and DMF, respectively. Precision (%RSD) and recovery (%) values when pharmaceutical compounds (200mg carbamazepine tablets) and spiked plasma samples were tested ranged from 1.09 to 9.04 % and % recoveries ranged from 96 to 104.1 %.     

Intercalation Compounds as Inner Reference Electrodes for Reproducible and Robust Solid‐Contact Ion‐Selective Electrodes

With billions of assays performed every year, ion‐selective electrodes (ISEs) provide a simple and fast technique for clinical analysis of blood electrolytes. The development of cheap, miniaturized solid‐contact (SC‐)ISEs for integrated systems, however, remains a difficult balancing act between size, robustness, and reproducibility, because the defined interface potentials between the ion‐selective membrane and the inner reference electrode (iRE) are often compromised. We demonstrate that target cation‐sensitive intercalation compounds, such as partially charged lithium iron phosphate (LFP), can be applied as iREs of the quasi‐first kind for ISEs. The symmetrical response of the interface potentials towards target cations ultimately results in ISEs with high robustness towards the inner filling (ca. 5 mV dec^?1 conc.) as well as robust and miniaturized SC‐ISEs. They have a predictable and stable potential derived from the LiFePO₄/FePO₄ redox couple (97.0±1.5 mV after 42 days).     

Reference Electrodes Based on Solid Amalgams

A reference saturated calomel electrode based on the non‐toxic silver solid amalgam (SCE‐AgSA) as a substitute for liquid mercury is described. Long‐term as well as short‐term tests made during a period of one year confirmed the SCE‐AgSA potential to be equal to that of SCE within the limits of ±1 mV (the difference ΔE_SCE‐AgSA=+1.08±0.24 mV (vs. SCE); SD=0.87; N=51). The voltammograms of four selected metal ions registered vs. SCE‐AgSA and vs. SCE could practically overlap each other. None of the mentioned electrodes were polarized to a significant degree even if the electric current applied reached 2 mA. On the basis of the obtained results the SCE‐AgSA could be considered as equivalent substitute for SCE. Owing to practically identical electrode potential of both types of the mentioned electrodes the results obtained using SCE‐AgSA are completely comparable to those measured vs. SCE, without any correction of peak potentials.     

Miniaturized Reference Electrodes. II. Use in Corrosive,Biological, and Organic Media

In a recent paper [9] we reported the manufacturing and performance of miniaturized reference electrodes (MREs) with low sensitivity to chloride ions and pH. Here, we demonstrate the wide range applicability of a MRE based on an Ag/Ag₂S internal reference element (IRE), imbedded in a photopolymerized hydrogel of improved composition, which contains the supporting electrolyte. Exchange current density, temperature coefficient, impedance value, and the voltammetric and potentiometric use of the Ag/Ag₂S‐based MRE are discussed relative to the previously reported Ag/AgSCN, Ag/Ag₃PO₄, and Ag/AgCl‐based MREs. No special or extensive conditioning is required when moving these MREs from aqueous supporting electrolyte to an organic solution or from one organic medium to another, and the equilibration time in a new medium is very rapid (<6 min). The new Ag/Ag₂S MRE has a highly stable potential in various media, including aqueous solutions (salt buffers and 20 wt.% H₂SO₄), biological samples (bovine serum albumin), mixed aqueous‐organic, and organic supporting electrolytes (methanol, ethanol, acetonitrile, propylene carbonate, methylene chloride, and DMSO). This is particularly advantageous when in the course of the electrochemical analysis an organic solution is being added to an aqueous supporting electrolyte. Such MREs are suitable for analyses of μL sample volumes and for use in protein‐containing media.     

Formylation of Secondary Amines with Dimethylformamide Dimethylacetal

Abstract

Secondary amines are formylated by dimethylformamide dimethylacetal, contradicting recent reports on the ethylation of secondary amines by this reagent. This explains why a single derivative is obtained regardless of the alkyl acetal that is used. These formyl derivatives, also formed by reaction with formic acid, are eluted later than the starting material or the corresponding ethyl derivative. Deuterated imipramine and related antidepressants can be prepared by reducing the formyl derivative of the appropriate desalkyl compound with lithium aluminum deuteride.     

Application of Dimethylformamide in the Determination of Aluminium and Beryllium

Abstract

During sweep polarography in dimethylformamide (DMF) both Al (III) and Be (II) perchlorates produce well defined peaks which can be used for analytical purposes. The extent of solvolysis with time of the perchlorates in this medium was measured. In the presence of a complexing agent such as fluoride ions the rate of solvolysis is much lower and can be neglected. Therefore it is suitable to perform amperometric titration of Al(III) and Be (II) ions with fluoride.     

二甲基甲酰胺中钐盐的电导研究

通过电导测量研究了4种钐盐:Sm(CF3SO3)3,Sm(ClO4)3,Sm(NO3)3,和SmCl3在极性非质子溶剂DMF中的电导性质。利用线性拟合方法求得在25℃下Sm(CF3SO3)3和Sm(ClO4)3的极限摩尔电导率分别为274 5和283 2S·cm2·mol-1。用间接方法求得Sm(NO3)3与SmCl3的极限摩尔电导率分别为299 7,289 8S·cm2·mol-1。在25～65℃温度范围内,Sm(CF3SO3)3和Sm(ClO4)3的电导率随温度呈线性变化。Sm(NO3)3,SmCl3的电导行为表现出明显的离子缔合。     

Nature of Initiators for Indirect Electrochemical Reductive Degradation of Polycarbonates in Dimethylformamide

We have established the nature of the species initiating indirect electrochemical reductive degradation of polycarbonates in dimethylformamide solutions. Such compounds include two types of nucleophiles: hydroxide ions, and also their complexes with dimethylformamide. We have shown that it is possible to use indirect electrochemical reductive degradation for surface and bulk modification of polycarbonates.     

Room Temperature Ionic Liquid Carbon Nanotube Paste Electrodes: Overcoming Large Capacitive Currents Using Rotating Disk Electrodes

The voltammetric response of graphite or carbon nanotube paste electrodes, which incorporate the room temperature ionic liquid, N‐butyl‐N‐methyl pyrrolidinium bis(trifluoromethylsulfonyl) imide or [C₄mpyrr][NTf₂], (RTIL‐CNTPE and RTIL‐CPE respectively) as the binder, towards anionic, cationic and neutral redox probes is examined and compared to conventional paste electrodes which use mineral oil as the binder. The RTIL paste electrodes are found to suffer from very large background currents due to capacitive charging. This is exacerbated further when CNTs are combined with RTILs in the paste. The large charging currents obscure any Faradaic processes of interest, especially at low analyte concentrations. By employing steady state voltammetry at a rotating disk electrode made of the RTIL pastes this problem can be overcome. This allows the electroanalytical properties of these interesting electrode substrates, which combine the attractive properties of CNTs with RTILs to be further explored and developed.     

适用于钢筋混凝土腐蚀监测的长效MnO2参比电极的研制

以电解法制备的MnO₂粉体为原料,研制了可用于混凝土环境中的固体MnO₂长效参比电极. 在饱和Ca(OH)₂溶液中近一年的监测数据显示,该参比电极具有较好的电位稳定性和抗干扰能力,其电极电位的漂移< 10 mV. EIS和极化曲线测试结果表明,相对于化学法合成的MnO₂电极,电解法制备的MnO₂参比电极具有较小的内阻、较大的交换电流密度、较强的抗极化能力和较低的温度系数（~ 0.68 mV·°C^-1）. 在硬化砂浆中的长期测试表明,该电极在混凝土中的电极电位基本不受Cl^-、有机胺阻锈剂的影响,能作为埋入式参比电极,满足混凝土中Cl^-浓度、pH值和钢筋半电池电位的长期监测的要求,这对于海洋混凝土工程的耐久性监测具有较高的应用价值.     

冠醚载体离子电极的选择特性研究

阴离子选择电极选择性系数随干扰离子r_j/z_j的变化规律已有报道,但冠醚为中性载体的金属离子电极的选择性系数规律未见报道。本文采用不同桥间结构的11种苯并双冠醚作为中性载体,从钾电极出发探讨了不同冠醚电极选择性系数与干扰离子r_j/z_j间的关系;并以4种烃型双冠醚为中性载体,分别考察了它们对Li~+、Rb~+、Cs~+、Ag~+、Ba~(2+)离子的响应规律。 1 实验部分     

用氧化还原聚合物修饰多孔电极

对３种类型Ｎａｆｉｏｎ／Ｏｓ（ｂｐｙ）３Ｃｌ２修饰电极的研究结果表明，单位表观电极面积上中继体载量比为：乙炔黑粉末微电极（Ａ）：Ｔｅｆｌｏｎ粘结的乙炔黑膜电极（Ｂ）：平面玻碳电极（Ｃ）＝１０＾３：１０＾２：１．Ａ比Ｂ及Ｃ更容易在真实表面上形成花天酒地而均匀的修饰层而有利于层内的电荷传递。在Ａ类电极基础上制行的葡萄糖酶电极在１０ｍｍｏｌ／Ｌ葡萄糖溶液中的响应电流密度高达４．６×１０＾－＾４Ａ／ｃｍ＾     

Application of Ion-Selective Electrodes as Reference Electrodes

Abstract

Reference electrodes limiting interfering effects of conventional reference electrodes on the measurement involving ion-selective electrodes have been developed. They are constructed of a plastic body with porous plug or sleeve junction. Solid state, low impedance, ion-selective electrodes (cupric, cadmium, fluoride) in the equilibrium of corresponding ion solution are used as the half-cells. The absence of interfering ions in the electrolyte allows the determination of the ion of interest at extremely low levels without interference. The electrodes have good reproducibility and stable intercomparison potentials of ± 0.2 mV. The performance of the electrodes has been tested for the measurement of sub-ppm halide levels. Data on stability, reproducibility, effects of temperature, ionic strengthand pH is presented and compared to that of conventional reference electrodes.     

全钒液流电池铂氢微型参比电极体系的构筑与性能

铂丝电极表面上电沉积一层金属钯,用阴离子交换隔膜材料封装,制得铂氢微型参比电极,工艺简单、稳定性高. 将该微型参比电极应用于全钒储能电池性能研究,可内置于电池多孔电极内部,监测电池正负极充放电性能. 结果显示,电池容量衰减主要归因于电解液中的活性物质V(IV)的逐渐减少及V(V)的积累导致正负极活性物质不平衡.