粗糙化银电极上氰基钴胺素的电化学行为

比较研究氰基钴胺素在光滑和粗糙化银电极上的电化学行为，发现在光滑银电极上氰基钴胺素的还原为一个二电子过程，而在粗糙化银电极上则为两个一电子过程，其原因是由于粗糙化银电极对氰根的强吸附作用。     

生物小分子次黄嘌呤在银电极上的电化学性质

本文研究了银电极上次黄嘌呤的电化学特性。在含次黄嘌呤的醋酸～醋酸钠缓冲溶液中(pH3.7)，在0.35～0V电位区间内，银电极上出现一个还原峰，扫速50 mV/s时，其峰电位约在0.15V。该电极过程为单电子单质子过程。电化学和光谱电化学结果表明：这是由于次黄嘌呤与银形成难溶性化合物吸附于银电极表面而造成的。实验测得此难溶化合物的组成为1∶1，其溶度积为3.10×10^-7。用DPSV作阴极溶出分析，峰电流与次黄嘌呤浓度在8.0×10^-7～1.0×10^-     

血红蛋白电化学分析检测的研究进展

根据基体电极的不同,对血红蛋白电化学分析检测进行了综述,包括:血红蛋白的银电极检测和玻碳修饰电极检测等方法的应用和各方法对血红蛋白检测的研究现状。     

辅酶Ⅰ电化学配位反应机理的紫外光谱电化学研究

用薄层池原位紫外光谱电化学法研究了辅酶Ⅰ(NAD)在银电极上的电化学配位反应机理。实验结果表明：NAD能与溶出的银离子生成配合物，该配合物的配位反应是一种可逆过程，用光谱电化学的Nernst图解分析获得银离子与NAD配合物的主要存在形式是［Ag(NAD)₂］⁺，银离子是与NAD分子的腺嘌呤基团形成配合物的。配合物的银离子与银电极表面发生异相电子交换反应，该电化学反应是受吸附控制的准可逆电极过程。     

硒代蛋氨酸的电化学行为及其定量分析

本文采用循环伏安法(CV)研究了硒代蛋氨酸(SeMet)在银电极表面的电化学行为。实验发现,在0.03mol/L的硼砂 NaOH(pH9.5)介质中,于+0.30V(vs.SCE)电位下进行吸附,在-0.62V和-0.68V处获得一对氧化还原峰。探讨了SeMet在银电极表面的电极反应机理,并建立其定量分析方法。方法线性范围为2.0×10-11～8.0×10-9mol/L,检出限为4.0×10-12mol/L。该方法用于谷物样品中SeMet含量的测定,结果满意。     

银纳米修饰电极的制备及其对灿烂甲酚蓝的催化研究

用共价修饰法制备了银纳米修饰电极,通过透射电子显微镜(TEM)、紫外可见光谱和电化学交流阻抗谱进行了表征和研究。实验表明,该修饰电极对灿烂甲酚蓝(BCB)的电化学氧化还原有较强的催化作用,氧化峰电流与其浓度在4.0×10-7～2.1×10-4mol L范围内成线性关系,相关系数为0.9989,检出限为1.5×10-8mol L。     

L-半胱氨酸修饰银电极及其对铜离子的电化学测定

引　　言半胱氨酸 (ｃｙｓｔｅｉｎｅ)是自然界 2 0种基本蛋白质的重要成分之一 ,具有良好的电化学活性。同时 ,半胱氨酸 (ＣｙＳ)含有极活泼的巯基 (-ＳＨ) ,易于通过形成Ａｕ Ｓ和Ａｇ Ｓ键吸附于金、银电极表面 ,借此可将ＣｙＳ引入电极表面制成修饰电极。本文采用自组装方法制备ＣｙＳ修饰银电极 (ＣｙＳ Ａｇ/ＣＭＥ) ,并用此电极对可乐样品中Ｃｕ2 + 进行吸附伏安测定 ,取得了令人满意的结果。本方法具有简便、便捷的优点 ,检测限为 10 -9ｍｏｌ/Ｌ ,可满足某种程度上对Ｃｕ2 + 含量测定的要求 ,具有一定的实际意义。2　实验部分2 …     

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.     

纳米电极上单个银纳米颗粒氧化电流分辨能力的研究

在单体电化学的研究中,提高信号分辨能力是一项挑战.缩小电极尺寸有利于对体系噪音电流的控制,有望提高电流的分辨能力.本研究制备了直径为480 nm的铂纳米圆盘电极,选用银纳米颗粒碰撞电极产生银电化学氧化行为作为模型,考察了纳米电极相对于微米电极在单体电化学信号分辨能力上的优化作用.研究表明,不同尺寸电极上观察到的银纳米颗粒的碰撞频率符合扩散控制的碰撞规律.说明单个电流信号对应于单个纳米颗粒的电化学氧化过程.同时,当电极尺寸缩小至纳米尺度后,噪音电流下降50%左右,提高了对银纳米颗粒碰撞电极过程中氧化电流的分辨能力.研究结果表明使用纳米电极能进一步提高对单体电化学中微小电流的检测能力.     

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。     

银离子交换的沸石修饰电极的循环伏安新特性

银离子交换沸石Y修饰电极(Ag⁺-沸石Y)的循环伏安(CV)行为, 不同于溶液中的银离子在固体银电极表面上的CV行为. Ag⁺-沸石电极中银离子还原电位明显受沸石体内银簇影响. 依据Ag⁺-沸石修饰电极在含有能够与银离子形成难溶盐的电解质中的CV行为, 本文发现了沸石对溶液中阴离子具有尺寸选择效应, 并解释了银离子交换沸石修饰电极的循环伏安反应特性.     

A New Neutral Carrier for Silver Ions Based on a Bis(Thiothiazole) Derivative and its Evaluation in Membrane Electrodes

Membrane electrodes based on 2,2-dithiobis(benzothiazole), DTBBT, as a neutral carrier for silver ions are described. Silver-selective membrane electrodes formulated with 2wt% DTBBT ionophore and 50mol% TFPB in an FPNPE plasticized poly (vinyl chloride) exhibited near-Nernstian responses towards silver ions (60.3±0.5mVdecade^–1) over a wide silver ion activity range of 0.83µM to 94mM. Increasing the amount of anionic sites, TFPB, to 100 or 150mol% (relative to the DTBBT weight) resulted in super-Nernstian responses toward silver ions. Membrane electrodes prepared using a low dielectric constant plasticizer, however, exhibited sub-Nernstian responses. Polymer membrane electrodes with optimal composition (i.e., 2wt% DTBBT, 50mol% TFPB in FPNPE plasticized poly(vinyl chloride)) exhibited high potentiometric selectivity towards silver ions over alkali, alkaline earth, transition metal ions, as well as heavy metal ions such as Hg²⁺ and Pb²⁺. A good correlation was found between the potentiometric selectivity coefficients and the change in the UV-visible spectra of the ionophore upon exposure to different metal ions. The overall performance of the silver-selective membrane electrodes based on DTBBT ionophore, which is available at low cost, was found to be comparable to the performance of silver electrodes prepared with Fluka silver ionophore-IV. A DTBBT-based silver electrode was used as an indicator electrode for titrations of silver ions using standard sodium chloride solutions. Sharp inflections occur at the end point, and the data obtained showed 99.4% recovery with a standard deviation of 0.7% (n=3). In addition, the applicability of the DTBBT-based silver-selective electrode is illustrated by measuring the silver concentrations in natural water spiked with silver nitrate and by analyzing the silver in electroplating wastewater samples. The results obtained utilizing a DTBBT-based silver electrode showed very good agreement with the standard methods of analysis.     

Behaviour of Ion Selective Electrodes Based on Silver or Mercuric Sulfide Selenide and Telluride Matrices

Abstract

The analytical behaviour of solid state, ion-selective electrodes based on silver or mercury sulfide, selenide, or telluride matrices was studied. As the active component, the chalcogenides of Cu, Pb, Cd, Zn, Ni, Co, and Bi for the cation electrodes and silver or mercurous halides for the anion electrodes were included. It was found that all possible combinations of matrix compounds are suitable for the preparation of the electrodes, silver being superior to mercury in respect to redox sensitivity. Prepared Ag⁺, Hg²⁺, Pb²⁺, Cu²⁺ and Cd²⁺ electrodes performed well, whereas Zn²⁺, Ni²⁺, Co³⁺ and Bi³⁺ electrodes showed unsatisfactory performances. Anion-selective electrodes constructed from mercuric chalcogenide-mercurous halide were more sensitive than those made from silver chalcogenide-silver halide system. The performance characteristics of all electrodes are described in terms of sensitivities, selectivities, response times, stabilities, reproducibilities, effect of pH and redox potential.     

Surface Changes at Platinized Platinum Based Hydrogen Gas Electrodes Following Use in Highly Saline Aqueous Solutions

Platinized platinum based hydrogen gas electrodes, Pt(Pt)|H₂(g)|H⁺(aq), and silver‐silver chloride electrodes, Ag|AgCl|Cl^? (aq), make up the Harned cell, without transfer, working in the potentiometric mode at Cl^? concentrations and ionic strengths, I, below 0.1 mol kg^?1, for assigning primary pH values to reference pH buffer solutions. This work reports on experiments performed at higher I and Cl^? solutions up to 0.7 mol kg^?1, aiming at addressing seawater conditions with results of equally high quality. In the course of measurements, the occasional occurrence of highly unstable potentials denoted electrode malfunction; Pt metal surfaces observed by SEM/EDS and XRD exhibit strong Ag and Cl peaks corresponding to the presence of AgCl crystals deposited at both surfaces.     

银负载量对网状TiO2柔性薄膜电极储锂性能的影响

本工作采用水热法结合银镜反应制备出一系列不同Ag负载量（2.2%、4.0%、6.4%,w/w）改性的3D纳米网状结构Ag@TiO₂薄膜电极。利用电感耦合等离子体技术（ICP）、X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）和X射线能谱（EDX）等表征手段测试所合成材料的形貌及成分,实验结果表明Ag纳米颗粒可以成功沉积在TiO₂纳米线表面。电化学测试数据则表明,4.0%（w/w）负载量的Ag@TiO₂相比于未改性和其他负载量的TiO₂纳米线具有更好的倍率性能和更稳定的可逆容量。在50,100,200,400,800和1 200 mA·g^-1的电流密度条件下,该改性电极的放电容量可分别达到261.4,253.7,239.5,216.5,193.1和185.1 mAh·g^-1,在200 mA·g^-1下循环80次后容量保持率仍能达到99.8%。     

银负载量对网状TiO_2柔性薄膜电极储锂性能的影响

采用水热法结合银镜反应制备出一系列不同Ag负载量(2.2%、4.0%、6.4%,w/w)改性的3D纳米网状结构Ag@Ti O2薄膜电极。利用电感耦合等离子体技术(ICP)、X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和X射线能谱(EDX)等表征手段测试所合成材料的形貌及成分,实验结果表明Ag纳米颗粒可以成功沉积在Ti O2纳米线表面。电化学测试数据则表明,4.0%(w/w)负载量的Ag@Ti O2相比于未改性和其他负载量的Ti O2纳米线具有更好的倍率性能和更稳定的可逆容量。在50,100,200,400,800和1 200 m A·g~(-1)的电流密度条件下,该改性电极的放电容量可分别达到261.4,253.7,239.5,216.5,193.1和185.1 m Ah·g~(-1),在200 m A·g~(-1)下循环80次后容量保持率仍能达到99.8%。     

Electrochemical Properties and Application of Mixed Silver‐Bismuth Electrodes

Electrochemical properties of silver electrodes with 2, 4, 6, 10 and 15% bismuth have systematically been investigated with cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). Increased overpotential towards hydrogen evolution reaction (HER) was found as a result of increasing amount of added bismuth. This was also demonstrated in acid solution where zinc was successfully detected on mixed electrodes, but failed on pure silver electrodes. Formation and decomposition of oxide products formed on the different electrode surfaces were studied by cyclic voltammetry, and in addition to known species found on sliver, also peaks attributed to bismuth were achieved and examined. Zinc, cadmium, and lead were measured in the low μg/L range on the mixed electrodes, and good linearity (r²=0.998) was found for 2 to 10 μg/L. Lead was measured down to 0.1 μg/L. Further it was found in DPASV that the zinc peak significantly shifted towards a more negative value with increasing amount of bismuth in the silver electrodes. The same was also observed for cadmium and lead, but in a less extent. Finally a silver electrode containing 15% bismuth was used for continuous analyses in a polluted river for 6 weeks.     

A new high‐performance blue to transmissive electrochromic material and use of silver nanowire network electrodes as substrates

Synthesis of a novel, high‐performance blue to transmissive switching electrochromic material is described. The polymer (P1) was prepared by both electrochemical ( P1E ) and chemical ( P1C ) means from the corresponding monomer. The electrochemically synthesized polymer ( P1E ) revealed 64% optical contrast change (on ITO) in the visible region and very fast switching times of 0.32 s (coloration) and 0.90 s (bleaching). On the other hand, the chemically synthesized, solution processable polymer ( P1C ) also showed a high optical contrast value (49%, on ITO) with very fast switching times of 0.86 s for coloration and 0.57 s for bleaching. These high optical contrast values coupled with fast switching times place these materials along with high‐performance blue to transmissive electrochromic polymers. Significantly, these improved characteristics were achieved by side chain engineering of a known, inferior blue to transmissive polymer, PBEBT. Towards fabrication of flexible electrochromic devices, the performance of P1C was also tested on silver nanowire network electrodes. Even though the full potential of the material could not be demonstrated, a good optical contrast of 24% was achieved using these electrodes. Under the same potential range allowed by silver nanowire network electrodes, P1C on ITO showed an optical contrast of 30%. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1680–1686     

The microporous structure of silver/silver chloride electrodes and the implications for Harned cell operation

The stability of silver/silver chloride reference electrodes when moved between different electrolyte solutions is limited by the small amount of solution transferred. The time required for the Ag/AgCl electrode potential to stabilize has been shown to increase with electrode size in an empirical fashion. The results presented suggest the presence of a microporous structure in the electrodes that limits the rate at which traces of any previous solutions are diluted by any new solution environment. Operational implications for the stability and accuracy of the Harned Cell used as the primary standard for pH measurements and the certification of primary reference buffers are discussed. Presented to the CCQM Electrochemical Analysis Working Group, Paris, April 2004.