Electrochemistry and electroanalytical applications of carbon nanotubes: a review.

This review addresses recent developments in electrochemistry and electroanalytical chemistry of carbon nanotubes (CNTs). CNTs have been proved to possess unique electronic, chemical and structural features that make them very attractive for electrochemical studies and electrochemical applications. For example, the structural and electronic properties of the CNTs endow them with distinct electrocatalytic activities and capabilities for facilitating direct electrochemistry of proteins and enzymes from other kinds of carbon materials. These striking electrochemical properties of the CNTs pave the way to CNT-based bioelectrochemistry and to bioelectronic nanodevices, such as electrochemical sensors and biosensors. The electrochemistry and bioelectrochemistry of the CNTs are summarized and discussed, along with some common methods for CNT electrode preparation and some recent advances in the rational functionalization of the CNTs for electroanalytical applications.     

电化学原子力显微镜的应用

评述了电化学原子力显微镜的原理和技术及其在现场电化学和电分析化学领域的应用,如观察电镀、腐蚀和防腐的过程,电化学沉积膜的形成和特点,测定两表面间的静电力等,指出其存在的一些缺陷,并对经过改造后的电化学原子力显微镜进行了综述。     

The principles of bipolar electrochemistry and its electroanalysis applications

The present study reports the wireless technique that generates asymmetric reactivity on the surface of the conducting substrate without any direct electrical connection in the electrolyte solution by inducing external power. In recent years, bipolar electrochemical systems have received special attention that they are used for new kinds of electrochemical applications ranging from electrodeposition to electroanalytical chemistry. Bipolar electrochemistry is a unique technique because of the lack of direct electrical connection to the bipolar electrode. In this perspective article, we first illustrate the concept and history of the bipolar electrochemistry as well as their application based on the open and closed bipolar configuration in different fields.     

Recent progress on nanopore electrochemistry and advanced data processing

Nanopore-based technology offers nanoscale chemical environments with intriguing confinement effects, which isolates individual analytes from the bulk solution. This confined space combines mass transportation and electrochemical measurement, providing new insight into single entity sensing. In this mini-review, we highlight the exciting progress on nanopore electrochemistry. Starting with a concise summary of nanopore-based electrodes, we introduce the fabrication methods and characterizations of the various nanopore electrodes. Then, the special attention focuses on the application of nanopore electrochemistry in single nanoparticle analyzing and intracellular electrochemical sensing. The advanced data analysis tools and Machine Learning algorithms for rapid encoding single-molecule characteristic sets are also covered, which promotes the sensitivity of nanopore electrochemistry and opens a new possibility for revealing single-entity heterogeneity.     

Application of electrochemistry to single-molecule junctions: from construction to modulation

State-of-the-art molecular electronics focus on the measurement of electrical properties of materials at the single-molecule level.Experimentally, molecular electronics face two primary challenges. One challenge is the reliable construction of single-molecule junctions, and the second challenge is the arbitrary modulation of electron transport through these junctions. Over the past decades, electrochemistry has been widely adopted to meet these challenges, leading to a wealth of novel findings. This review starts from the application of electrochemical methods to the fabrication of nanogaps, which is an essential platform for the construction of single-molecule junctions. The utilization of electrochemistry for the modification of molecular junctions,including terminal groups and structural backbones, is introduced, and finally, recent progress in the electrochemical modulation of single-molecule electron transport is reviewed.     

Abrasive stripping voltammetry — an electrochemical solid state spectroscopy of wide applicability

Abrasive stripping voltammetry is a new electroanalytical technique designed for the qualitative and quantitative analysis of solid materials. It is based upon a preliminary mechanical transfer of trace amounts of a solid sample onto the surface of an electrode. All conventional electrochemical measuring methods can be used. The technique is applicable in many fields of solid state analysis and for fundamental studies of the electrochemistry of solid compounds.     

自组装膜技术在电分析化学中的研究与应用

本文对自组膜（ＳＡＭｓ）在电分析化学中的研究和应用进行了比较全面的综述。ＳＡＭｓ是单分子膜化学修饰电极发展的最高形式，本文着重阐述了硫醇／金单分子层自组膜在微电极、生物电化学和生物传感器、液相色谱电化学、电催化、光谱电化学等电分析化学研究领域中的应用，并进行了展望。     

Diamond microelectrodes for in vitro electroanalytical measurements: current status and remaining challenges

An emerging research field in electrochemistry today is the preparation, characterization and application of diamond microelectrodes for electroanalytical measurements in biological media. Interest in this new electrode material stems from its outstanding properties: (i) hardness, (ii) low, stable and pH-independent background current, (iii) morphological and microstructural stability over a wide range of potentials, (iv) good electrochemical responsiveness for multiple redox analytes without any conventional pre-treatment and (v) weak molecular adsorption of polar molecules that leads to a high level of resistance to response deactivation and electrode fouling. Diamond electrodes have advanced in recent years from being simply a scientific curiosity into a viable material for electroanalysis. In this article, we highlight the current state of progress by our laboratory and others on the preparation, study of the basic electrochemical properties, and application of this new type of microelectrode for in vitro electroanalytical measurements, and discuss some of the remaining challenges.     

Electrochemistry of complex molecular and biomolecular scale entities

Structural mapping of intermediate size and large molecules and biomolecules at ultra-high resolution using single-crystal electrodes and in situ scanning tunnelling microscopy continues to disclose surprising findings. In situ scanning tunnelling spectroscopy has also recently disclosed new electrochemical conductivity features at the level of the single molecule. We overview briefly elements of this development over the last few years, with focus on three recent discoveries: (1) a new packing mode of a core monolayer target thiol, the amino acid cysteine (Cys) on Au(100)-electrodes, quite different from Cys packing on Au(111)- and Au(110)-electrodes; (2) transition of a core ferrocene in situ scanning tunnelling spectroscopy probe from stochastic single-molecule to macroscopic behaviour, a concept at the heart of nanoscience; and (3) unexpected behaviour of the large molybdenum enzyme sulfite oxidase, when going from macroscopic to single-molecule electrochemistry. We compare these studies with other recent discoveries of single-molecule protein conductivity and molecular scale inorganic nanostructures.     

Sonoelectrochemical processes: A review

The considerable progress made in the development of fundamental and applied aspects of sonoelectrochemistry, the coupling of power ultrasound into an electrochemical experiment, is reviewed with respect mainly to the measurement and analysis of effects observed in conventional sonoelectrochemical experiments in homogeneous environments. Based on the tools and methods now available it is hoped that the application of ultrasound in areas as diverse as electroanalytical and synthetic electrochemistry will be beneficial and new innovative approaches employing the various mechanical and chemical effects of ultrasound will result.     

磺胺二甲嘧啶的基本电化学性质及其与DNA的相互作用

研究了磺胺二甲嘧啶在多壁碳纳米管修饰电极上的电化学行为,优化了实验参数,在此基础上建立了一种直接测定磺胺二甲嘧啶的电分析方法.并用循环伏安法和紫外光谱法对磺胺二甲嘧啶与DNA的相互作用进行了研究,结果表明,磺胺二甲嘧啶与DNA的作用模式是静电作用.     

原子力显微镜及其在电化学和电分析化学中的应用

本文评述了原子力显微镜原理和技术及其在现场电化学和电分析化学领域中的应用，并展望了扫描隧道显微镜和原子力显微镜在电化学和电分析化学中的发展方向。     

High‐Temperature Electrochemistry: A Review

High‐temperature electrochemistry remains a relatively unexplored field of research, although in recent years significant developments have been made. This report details the main experimental methods and approaches to heating an electrochemical system under both isothermal and non‐isothermal conditions and gives an insight into the experimental and electroanalytical results obtainable under such conditions. It has been shown that the promotion of mass transport at high‐temperatures, through diffusion or convection, often results in increased current signals. This increase benefits electroanalytical measurements by lowering detection limits. High temperatures also usefully enhance the sensitivity of systems with sluggish kinetics.     

Carbon Paste Electrodes in Facts,Numbers, and Notes: A Review on the Occasion of the 50‐Years Jubilee of Carbon Paste in Electrochemistry and Electroanalysis

This article reviews the electrochemistry and electroanalytical applications of carbon paste‐based electrodes, sensors, and detectors on the occasion of the half‐of‐century anniversary since the discovery of carbon paste. The review (with 333 references) has been prepared in the form of a retrospective compilation presenting the field by means of various facts, notes, data, surveys, and summaries, including numerous rarities or curiosities that illustrate the individual achievements and milestones. Carbon paste‐based electrodes are discussed in their entirety by covering all important areas of the field, starting from basic characterization of carbon paste as the electrode material, via its typical physicochemical and electrochemical properties or specific features, up to a representative documentation of their applicability in electrochemical and electroanalytical measurements.     

Smart functionalized thin gel layers for electrochemical sensors,biosensors and devices

Combining hydrogels sensitive to external stimuli with conducting surfaces opens new possibilities in electrochemistry. Thin hydrogel layers as unique electrode-modifying materials provide highly permeable matrix for easy diffusion of analytes. In addition, larger individuals, for example, nanoparticles and enzymes, can be straightforwardly immobilized in the polymeric networks at electrode surfaces. Such properties are strongly desired for construction of sensors and biosensors. In addition, sensitivity to external stimuli allows to significantly enhance or weaken the electroanalytical signal. Recently, a significant number of articles concerning switchable sensors/biosensors, switchable electrochemical systems and signal–responsive interfaces have been published. This report is also focused on the construction of various devices based on electrode surfaces modified with smart hydrogel layers, for example, logic gates and electroresponsive hydrogel layers as potentially advanced drug delivery systems, artificial muscles and electrochemical valves.     

A Glassy Carbon Electrode Modified with LangmuirBlodgett Film Composed of DNA and Polyaniline for the Sensitive Determination of Salbutamol

A composite Langmuir? Blodgett film prepared from DNA and polyaniline was deposited on the surface of a glassy carbon electrode (GCE) to give a new voltammetric sensor for the β2‐agonist salbutamol (SAL). Cyclic voltammetry and electrochemical impedance spectroscopy were employed to study the characteristic of the modified electrode. The electrochemistry of SAL at the modified electrode was investigated at pH 6.8 by cyclic voltammetry and differential pulse anodic voltammetry. The oxidation of SAL at this electrode is an adsorption‐controlled irreversible process. A sensitive electroanalytical method for determination of SAL was worked out that displays high precision and good reproducibility. The method was applied to quantify SAL in tablets with satisfactory results.     

电化学门控调节具有平行路径的单分子电路中电子传输

电化学门控已成为一种可行且高效调节单分子电导的方法。在本研究中,我们证实了具有两个平行苯环的单分子电路中电子传输可以通过电化学门控控制。首先,我们利用STM-BJ技术以金为电极构筑了具有两条平行路径的单分子结。与单条路径的单分子结相比,两条路径的分子结由于具有增强性量子干涉效应,具有2.82倍的电导值。进一步地,我们利用电化学门控对具有两个平行苯环的单分结的电导进行调控,获得了333%·V^-1调节比。结合DFT计算,发现在E=E_F附近的V形透射系数谱图导致了实验观测的电导门控行为。本研究揭示了具有平行路径的单分子电路的电化学门控行为,并为设计高性能分子器件的分子材料提供了新的途径。     

Single-molecule fluorescence spectroelectrochemistry of cresyl violet

Here we report a new path to study single molecule electron transfer dynamics by coupling scanning fluorescence microscopy with a potentiostat via a conventional electrochemical cell to enable single-molecule fluorescence spectroelectrochemistry of cresyl violet in aqueous solution, demonstrating that the single-molecule fluorescence intensity of cresyl violet is modulated synchronously with the cyclic voltammetric potential scanning.     

Glazunov’s electrography—the first electrochemical imaging and the first solid-state electroanalysis

Aleksandr Il’ich Glazunov developed the first electrochemical technique to image the surface of conducting solids giving the technique the name electrography. The electrographic images can mirror the distribution of elements on the surface of solid materials and also the electrochemical activity, caused by variations of “dissolution tension”. Thus, he has established for the first time a kind of spatially resolved electrochemistry. Electrography is also the first direct electroanalytical technique for solid materials. The present paper gives an account of his turbulent life in Russia, Czechoslovakia and Chile, and a discussion of his main scientific achievement, the development of electrography.

     

Multi-walled carbon nanotube modified basal plane pyrolytic graphite electrodes: Exploring heterogeneity, electro-catalysis and highlighting batch to batch variation

We highlight the heterogeneity and electro-catalysis of multi-walled carbon nanotubes which is shown to be dependant on batch to batch variation via the use of cyclic voltammetry, X-ray photoelectron spectroscopy and transmission electron microscopy. Batch to batch variation is often an overlooked parameter which may limit their use in electrochemistry, and in particular, in the development and realisation of commercial electroanalytical sensors and therefore needs to be considered.