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。     

Functionalized carbon nanotubes and nanofibers for biosensing applications

This review summarizes recent advances in electrochemical biosensors based on carbon nanotubes (CNTs) and carbon nanofibers (CNFs) with an emphasis on applications of CNTs. CNTs and CNFs have unique electric, electrocatalytic and mechanical properties, which make them efficient materials for developing electrochemical biosensors.We discuss functionalizing CNTs for biosensors. We review electrochemical biosensors based on CNTs and their various applications (e.g., measurement of small biological molecules and environmental pollutants, detection of DNA, and immunosensing of disease biomarkers). Moreover, we outline the development of electrochemical biosensors based on CNFs and their applications. Finally, we discuss some future applications of CNTs.     

Electroanalytical Application of Carbon Based Electrodes to the Pharmaceuticals

Abstract

Carbon and its derivatives, as the high performance material, occupy a special place in electrochemistry due to its ‐in many ways‐ extreme properties. Recent trends and advances in the electrochemistry of carbon‐based electrodes are reviewed. The varieties of carbon‐based electrodes, their basic physicochemical properties and some characteristics are surveyed. Special attention is paid to the possibilities of carbon‐based electrodes in electroanalytical investigation in pharmaceutical dosage forms and biological samples using modern electrochemical techniques. This review includes a summary of the rules that must be considered for drug analysis from its dosage forms and biological samples using carbon‐based electrodes. The present review is the first comprehensive report on the heterogeneous and homogeneous carbon electrodes, and an addition to many excellent reviews on carbon electrodes in the literature. This review summarizes some of the recent developments and applications of carbon‐based electrodes for drug compounds in their dosage forms and in biological samples in the period from 1996 till 2006. Also some further selected designs (screen‐printed; carbon nanotubes, etc.) and applications have been discussed.     

Understanding the Physicoelectrochemical Properties of Carbon Nanotubes: Current State of the Art

Carbon nanotubes receive considerable attention in the area of electrochemistry not only due to their reported structural, mechanical or electronic properties but because they represent the world's smallest electrodes allowing electrochemistry to be performed where other electrode materials cannot penetrate. In this review, we overview recent developments in this area summarizing the fundamental advances in understanding the various factors and parameters that can significantly affect the electrochemical reactivity of carbon nanotubes, which is essential for their continual use and successful implementation in a plethora of areas and applications.     

Nanographite impurities in carbon nanotubes: their influence on the oxidation of insulin, nitric oxide, and extracellular thiols

There has been growing interest in the use of modified-carbon-nanotube electrodes in applications such as the electrochemical detection of biologically significant compounds, owing to their apparent "electrocatalytic" properties and ability to enhance oxidative signals. In spite of their salient properties, little work has been done to further examine the reasons for these reported characteristics. In this report, we present clear evidence that the presence of nanographite impurities within carbon nanotubes (CNTs) is responsible for providing the previously reported enhanced electrochemical response. We have demonstrated this effect on homocysteine, N-acetyl-L-cysteine, nitric oxide, and insulin, which are important biological agents in the body. Moreover, we also showed that the influence of nanographite impurities on the electrochemistry of carbon nanotubes is prevalent among a variety of CNTs, such as single-walled CNTs, double-walled CNTs, and few-walled CNTs. Our findings will have a profound influence upon the biomedical applications of CNTs.     

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.     

Graphene and graphene-based nanomaterials: the promising materials for bright future of electroanalytical chemistry

Similar to its popular older cousins of fullerene and carbon nanotubes (CNTs), the latest form of nanocarbon, graphene, is inspiring intensive research efforts in its own right. As an atomically thin layer of sp(2)-hybridized carbon, graphene possesses spectacular electronic, optical, magnetic, thermal and mechanical properties, which make it an exciting material in a variety of important applications. In this review, we present the current advances in the field of graphene electroanalytical chemistry, including the modern methods of graphene production, and graphene functionalization. Electrochemical (bio) sensing developments using graphene and graphene-based materials are summarized in more detail, and we also speculate on their future and discuss potential progress for their applications in electroanalytical chemistry.     

“电极/溶液”界面的椭圆偏振测量技术研究进展

椭圆偏振测量技术是通过解析偏振光束在界面上或薄膜中反射或透射时偏振状态的变化,获取界面或薄膜的厚度、复折射率等性质的一种光学方法,是一种高灵敏度、非破坏性的原位实时表征技术,被广泛应用于“电极/溶液”界面的研究. 本文简要介绍了椭圆偏振测量技术的基本原理及其最新发展,并着重评述了能源电化学、材料电化学、电分析与生物电化学等领域中,应用椭圆偏振测量技术研究“电极/溶液”界面的现状.     

The Significant Role of Carboxylated Carbonaceous Fragments in the Electrochemistry of Carbon Nanotubes

Carbon nanotubes (CNTs) have been widely employed as electrode materials in diverse branches of electrochemistry, which are claimed to display dramatically improved electrochemical behaviour compared to the conventional carbon materials. But a series of recent publications have demonstrated that the electrocatalysis of CNTs might be due to the presence of some impurities, such as metallic catalysts, nanographitic particles and amorphous carbon. For this reason, CNTs are usually purified or treated with nitric acid or nitric and sulphuric acid prior to their versatile applications. However, the strong acidic and oxidative conditions are so aggressive that serious erosion of the tube structures has inevitably taken place, which creates defects on the sidewalls and gives rise to numerous molecular byproducts, commonly referred as carboxylated carbonaceous fragments (CCFs). The adsorption of CCFs on CNTs greatly alters the surface conditions of CNTs which may significantly impact on their electrochemical properties. To this end, we wish to disclose whether the electrocatalysis of the nitric acid purified CNTs is affected by the adsorption of the CCFs. Ascorbic acid (AA) and β‐nicotinamide adenine dinucleotide (NADH) as selected as the targeting benchmarks that are known to be insensitive to the presence of metallic impurities, which may guarantee the preclusion of the promoting contributions from the metallic catalysts resident in CNTs. We have demonstrated that the electrocatalytic activities of the CNTs are actually dominated by the adsorbed CCFs generated during the acidic pre‐treatment. After removal of the CCFs by base rinse, the electrocatalytic properties of CNTs are greatly deteriorated and degraded to the level similar to the conventional graphite powder. We believe this finding is particularly meaningful to uncover the mysterious electrocatalysis of CNTs.     

《碳纳米材料电化学》专辑序言 ——方兴未艾的电化学能量转换和存储先进材料和技术

可以预见,在相当一段时期内,能源和环境将是全球发展的两大主题. 其实,人类对能源的获取方式将对地球的生态环境和人类未来的生存状态和生活方式产生重要影响. 正因为如此,世界各国正在大力发展可再生能源和清洁能源. 电化学能源是将化学能高效转变为电能的一种能量转换方式,它历史悠久,但不断被改进和创新,尤其是近年来得到了较快的发展. 目前,电化学能源转换和存储器件主要包括一次电池（如锌锰电池等）、二次电池（如铅酸电池、镍氢电池、锂离子电池等）、燃料电池、金属-空气电池以及超级电容器等. 电化学能源和其它可再生能源相互补充、交叉利用将是未来清洁能源的主要发展方向.     

Electrocatalytic Properties and Sensor Applications of Fullerenes and Carbon Nanotubes

The electrochemical behavior of fullerene and fullerene derivatives are reviewed with special reference to their catalytic and sensor applications. Recent work on carbon nanotubes, used as catalyst supports in heterogeneous catalysis and sensor development is also presented. An overview of recent progress in the area of fullerene electrochemistry is included. Several cases of electrocatalytic dehalogenation of alkyl halides, assisted by the electrode charge transfer to fullerenes, are discussed. Research work on the electrocatalysis of biomolecules, such as hemin, cytochrome c, DNA, coenzymes, glucose, ascorbic acid, dopamine, etc. have also been considered. Based on the studies of the interaction of fullerenes, fullerene derivatives, and carbon nanotubes with other molecules and biomolecules in particular, the possibilities for the preparation of electrochemical sensors and their application in electroanalytical chemistry are highlighted.     

碳纳米管在药物载体领域的进展

基于其独特的结构、电子及机械性能,碳纳米管自被发现以来就是极具吸引力的材料,被广泛研究。在药物化学领域,碳纳米管成为载运治疗药物实现靶向治疗、控制释放等的热点,研究日益深入。本文概述了近年来碳纳米管在药物载体领域的研究进展情况,评述了其未来发展趋势,认为深入考察修饰碳纳米管的毒性,探索其载药释药机制,并逐步应用于临床,...     

Bioelectrochemically functional nanohybrids through co-assembling of proteins and surfactants onto carbon nanotubes: facilitated electron transfer of assembled proteins with enhanced faradic response

Preparation and bioelectrochemical properties of functional nanohybrids through co-assembling of hemeproteins (i.e., horseradish peroxidase, hemoglobin, myoglobin and cytochrome c) and surfactants onto carbon nanotubes (CNTs) are described. The prepared protein-surfactant-CNT nanohybrids are found to possess facilitated interfacial electron transfer of the proteins with enhanced faradic responses. The enhancements are ascribed for the first time to the properties of the surfactants for facilitation of protein electrochemistry and the improved portion of electroactive proteins assembled, of which the latter assignment is closely associated with the electrochemical and structural properties of the nanotubes and the three-dimensional architecture of the CNT film confined onto the glassy carbon electrode. It is proposed that the single and/or small bundles of the nanotubes in the CNT film electrode can be rationally functionalized with surfactants to be functional nanoelectrodes capable of facilitating electron transfer of proteins. The three-dimensional confinement of these functional nanowires onto the GC electrode essentially increases the portion of electroactive proteins assembled in the nanohybrids. These properties of the protein-surfactant-CNT nanohybrids, combined with the bioelectrochemical catalytic activity, could make them useful for development of bioelectronic devices and investigation of protein electrochemistry at functional interfaces.     

Electronic Tongues Employing Electrochemical Sensors

This review presents recent advances concerning work with electronic tongues employing electroanalytical sensors. This new concept in the electroanalysis sensor field entails the use of chemical sensor arrays coupled with chemometric processing tools, as a mean to improve sensors performance. The revision is organized according to the electroanalytical technique used for transduction, namely: potentiometry, voltammetry/amperometry or electrochemical impedance. The significant use of biosensors, mainly enzyme‐based is also presented. Salient applications in real problem solving using electrochemical electronic tongues are commented.     

中空碳球合成方法及其电化学应用进展

中空碳球由于具有大的比表面积、良好的导电性以及高的化学稳定性等优异性能,现已被广泛地用于电化学储能、电化学催化和电化学传感领域。基于此,本文主要概述了中空碳球的各种合成方法及在电化学领域的研究进展,并对该领域面临的挑战及未来的发展方向进行了讨论。     

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.     

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 at High Pressures: A Review

High pressure electrochemical studies are potentially dangerous and less immediately implemented than conventional investigations. Technical obstacles related to properties of the working electrode material, preparation of its surface, availability of suitable reference electrodes, and the need for specially designed high pressure equipment and cells may account for the relative lack of experimental data on electrochemistry at high pressures. However, despite the stringent requirements for system and equipment stability, significant developments have been made in recent years and the combination of electrochemical methods with high hydrostatic pressure has provided useful insights into the thermodynamics, kinetics, and other physico‐chemical characteristics of a wide range of redox reactions. In addition to fundamental information, high pressure electrochemistry has also lead to a better understanding of a variety of processes under non‐classical conditions with potential applications in today's industrial environment from extraction and electrosynthesis in supercritical fluids to measurement of the pH at the bottom of the ocean. The purpose of this article is to detail the experimental pressurizing apparatus for electroanalytical measurements at high pressures and to review the relevant literature on the effect of pressure on electrode processes and on the properties of aqueous electrolyte solutions.     

The characteristics of highly ordered mesoporous carbons as electrode material for electrochemical sensing as compared with carbon nanotubes

In this paper, the unique properties of highly ordered mesoporous carbons modified glassy carbon electrode (OMCs/GE) are illustrated from comparison with carbon nanotubes modified glassy carbon electrode (CNTs/GE) for the electrochemical sensing applications. Electrochemical behaviors of eight kinds of inorganic and organic electroactive compounds were studied at OMCs/GE, which shows more favorable electron transfer kinetics than that at CNTs/GE. Especially, OMCs/GE exhibits remarkably strong and stable electrocatalytic response toward NADH compared with CNTs/GE. The ability of OMCs to promote electron transfer not only provides a new platform for the development of dehydrogenase-based bioelectrochemical devices, but also indicates a potential of OMCs in a wide range of sensing applications. OMCs prepared are the novel carbon electrode materials, exhibiting more favorable electrochemical reactivity than CNTs for the wide electrochemical sensing applications without pretreatments, while purification or end-opening processing was usually required in case of CNTs.     

Functionalized Carbon Nanoparticles,Blacks and Soots as Electron‐Transfer Building Blocks and Conduits

Functionalized carbon nanoparticles (or blacks) have promise as novel active high‐surface‐area electrode materials, as conduits for electrons to enzymes or connections through lipid films, or as nano‐building blocks in electroanalysis. With previous applications of bare nanoblacks and composites mainly in electrochemical charge storage and as substrates in fuel cell devices, the full range of benefits of bare and functionalized carbon nanoparticles in assemblies and composite (bio)electrodes is still emerging. Carbon nanoparticles are readily surface‐modified, functionalized, embedded, or assembled into nanostructures, employed in bioelectrochemical systems, and incorporated into novel electrochemical sensing devices. This focus review summarizes aspects of a rapidly growing field and some of the recent developments in carbon nanoparticle functionalization with potential applications in (bio)electrochemical, photoelectrochemical, and electroanalytical processes.