Electrochemically modified semiconductor gallium arsenide electrodes for the argentometric titration of chlorides with silver nitrate in natural samples

An electrochemical method is proposed for the modification of the surface of semiconductor gallium arsenide sensors. The electrochemical modification of the surface of GaAs-electrodes leads to the improvement of their electrochemical characteristics: an increase in the slope of the electrode function, a decrease in response time, and the extension of the concentration range. Potentiometric titration using unmodified and modified GaAs-electrodes for the determination of chlorides with silver nitrate in soil has been performed. The application of the modified sensors ensures the detection of the titration end-point with a higher accuracy.     

Recent developments in electrochemical flow detections—A review: Part I. Flow analysis and capillary electrophoresis

Recent years have provided numerous new examples of applying flow-through electrochemical detectors in chemical analysis. This review, based on about 250 original research papers cited from the current analytical literature, presents their application in flow analysis and capillary electrophoretic methods. Example applications are also given for arrays of electrochemical sensors in flow analysis and electrochemical detection in microfluidic systems. Potentiometric detection with ion-selective electrodes predominates in flow analysis carried out mostly in a flow-injection system, while amperometric and conductivity detections are most commonly employed in capillary electrophoresis.     

The double life of conductive nanopipette: a nanopore and an electrochemical nanosensor

The continuing interest in nanoscale research has spurred the development of nanosensors for liquid phase measurements. These include nanopore-based sensors typically employed for detecting nanoscale objects, such as nanoparticles, vesicles and biomolecules, and electrochemical nanosensors suitable for identification and quantitative analysis of redox active molecules. In this Perspective, we discuss conductive nanopipettes (CNP) that can combine the advantages of single entity sensitivity of nanopore detection with high selectivity and capacity for quantitative analysis offered by electrochemical sensors. Additionally, the small physical size and needle-like shape of a CNP enables its use as a tip in the scanning electrochemical microscope (SECM), thus, facilitating precise positioning and localized measurements in biological systems.

Conductive nanopipettes: a useful tool for localized detection and analysis of single nanoscale objects.     

Integrated electrochemical transistor as a fast recoverable gas sensor

A new design of conductometric chemical sensors based on conducting polymers as chemosensitive elements was suggested. The sensor includes six electrodes. Four inner electrodes coated by chemosensitive polymer are used for simultaneous two- and four-point resistance measurements thus providing information on the bulk polymer resistance and on the resistance of the polymer/electrode contacts. Two outer electrodes wired to inner electrodes by polymeric electrolyte are used for electrical control of redox state of the chemosensitive polymer. The outer electrodes are connected to potentiostat as reference and counter electrodes. It allows us to control redox state of the inner (working) electrodes. This new measurement configuration, resembling chemosensitive electrochemical transistors, provides an internal test of the sensor integrity and an electrically driven sensor regeneration. It was tested as a sensor for the detection of nitrogen dioxide. Polythiophene or polyaniline was used as receptors. Cyclic voltammograms of these polymers on the sensor surface measured in air atmosphere were very similar to that measured in aqueous electrolyte. A control of conductivity of these chemosensitive polymers by electrical potential applied vs. incorporated reference electrode was demonstrated. This effect was used for the regeneration of the chemosensitive material after exposure to nitrogen dioxide: in comparison to usual chemiresistors displaying an irreversible behavior in such test even in the time scale of hours, a completely reversible sensor regeneration within few minutes was observed.     

Modified sensors based on semiconductor and metallic materials for the determination of cyan- and iodine-containing pesticides by potentiometric titration

Potentiometric sensors based on semiconductor and metallic materials modified by electrochemical techniques are proposed. It is demonstrated that the electrochemical modification of the surface improves the electroanalytical properties of the electrodes. Nonmodified and modified electrodes are recommended for the potentiometric titration of iodides. Procedures are developed for the potentiometric determination of cyanide- and iodine-containing pesticides using GaAs- and Ti-electrodes.     

Review: Carbon nanotube based electrochemical sensors for biomolecules

Carbon nanotubes (CNTs) have been incorporated in electrochemical sensors to decrease overpotential and improve sensitivity. In this review, we focus on recent literature that describes how CNT-based electrochemical sensors are being developed to detect neurotransmitters, proteins, small molecules such as glucose, and DNA. Different types of electrochemical methods are used in these sensors including direct electrochemical detection with amperometry or voltammetry, indirect detection of an oxidation product using enzyme sensors, and detection of conductivity changes using CNT-field effect transistors (FETs). Future challenges for the field include miniaturizing sensors, developing methods to use only a specific nanotube allotrope, and simplifying manufacturing.     

Design and construction of nickel hexacyanoferrate – Starburst PAMAM dendrimer modified gold electrodes for the potentiometric detection of potassium in aqueous media

Potentiometric sensors for potassium detection were prepared by chemical modification of polycrystalline gold electrodes with sub-monolayers of 3-mercaptopropionic acid or 2-aminoethanethiol (SC and SA, respectively) followed by the covalent attachment of PAMAM dendrimers (generation 4.0, DA, and 3.5, DC, respectively) in order to obtain films suitable for further electrostatic adsorption of nickel hexacyanoferrate (NiHCF) complexes. The characterization of the resulting electroactive layers by cyclic voltammetry (CV) experiments showed that the use of dendrimers in the synthesis of the films not only enhances the surface coverage of NiHCF when compared to thiol modified electrodes, but also the electroanalytic performance of the modified surfaces for the detection and quantification of potassium in aqueous medium under controlled ionic strength (I) conditions.     

Polymeric nanofiber-based ion-selective sensors

Ion-selective sensors are established tools of chemical analysis used in both electrochemical and optical sensing modes. They allow insight into ion concentrations in various samples, offering reliable performance. One of the ways of improving this class of devices is to explore the benefits of nanoscale receptor layers. In this respect, nanofibers seem to be a highly attractive option because of unique properties related to the geometry of this class of nanomaterials. This paves the way to explore alternative approaches to design ion-selective receptors architecture, to benefit from receptor molecules that are not compatible with classical ion-selective membranes.     

Aptamers as molecular recognition elements for electrical nanobiosensors

Recent advances in nanotechnology have enabled the development of nanoscale sensors that outperform conventional biosensors. This review summarizes the nanoscale biosensors that use aptamers as molecular recognition elements. The advantages of aptamers over antibodies as sensors are highlighted. These advantages are especially apparent with electrical sensors such as electrochemical sensors or those using field-effect transistors. Figure Feeling proteins with aptamer-functionalized carbon nanotubes     

The effect of the layer structure on the activity of immobilized enzymes in ultrathin films

The molecular engineering capability of the layer-by-layer (LbL) method for fabricating thin films has been exploited in order to immobilize glucose oxidase (GOD) in films with alternating layers of chitosan. Chitosan was proven a good scaffolding material, as GOD molecules preserved their catalytic activity towards glucose oxidation. Using electrochemical measurements, we showed that chitosan/GOD LbL films can be used to detect glucose with a limit of detection of 0.2 mmol l-1 and an activity of 40.5 microA mmol-1 L microg-1, which is highly sensitive when compared to other sensors in previous reports in the literature. The highest sensitivity of the LbL film was achieved when only the top layer contained GOD, thus indicating that GOD in inner layers did not contribute to glucose oxidation, probably because it hampers analyte diffusion and electron transport through the deposited layers. This may be explained by the dense packing of GOD molecules in the LbL films with chitosan, as inferred from estimates of the amount of GOD adsorbed per layer using a quartz crystal microbalance.     

Conductimetric and potentiometric detection in conventional and microchip capillary electrophoresis

Potentiometric detection is rarely used in separation methods but is promising for certain classes of analytes which can only with difficulty be quantified by more standard methods. Conductimetric detection of ions is very versatile and has recently received renewed interest spurned by the introduction of the capacitively coupled contactless configuration. Both are useful and complementary alternatives to the established optical detection methods, and to the more widely known electrochemical method of amperometry. The simplicity of the electrochemical methods makes them particularly attractive for microfabricated devices, but relatively little work has to date been carried out with regard to potentiometric and conductimetric detection.     

Functional layers for chemical sensors based on conducting polypyrrole

Functional thin layers based on polypyrrole were used in electrochemical sensors as mixed conducting interfaces between ion‐selective membranes and the wiring. In particular, new types of ion‐selective electrodes for potentiometric measurement of pH value and concentration of sulfate ions in solutions were developed. The resulting electrodes do not need any inner liquid junction. First determinations of the sensor parameters sensitivity, selectivity and long term stability indicate a good performance of the prepared sensors. The results imply that interfaces, containing polypyrrole, could be an interesting basis for the construction of a new type of all‐solid‐state ion‐selective electrodes.     

Electrochemical immunoassays

Immunoassays (IA) use the specific antigen antibody complexation for analytical purposes. Radioimmunoassays (RIA), fluorescence immunoassays (FIA) and enzyme immunoassays (EIA) are well established in clinical diagnostics. For the development of hand-held devices which can be used for point of care measurements, electrochemical immunoassays are promising alternatives to existing immunochemical tests. Moreover, for opaque or optically dense matrices electrochemical methods are superior. Potentiometric, capacitive and amperometric transducers have been applied for direct and indirect electrochemical immunoassays. However, due to their fast detection, broad linear range and low detection limit, amperometric transducers are preferred. Competitive and non-competitive amperometric immunoassays have been developed with redox compounds or enzymes as labels. This review will give an overview of the most frequently applied principles in electrochemical immunoassays. The potential of an indirect competitive amperometric immunoassay for the determination of creatinine within nanomolar range and the circumvention of the most serious problem in electrochemical immunoassays, namely regeneration, will be discussed.     

Carbon nanomaterials and metallic nanoparticles-incorporated electrochemical sensors for small metabolites: Detection methodologies and applications

Detection of small metabolite biomarkers at different concentrations could be powerfully used for disease diagnosis and progression. To enhance detection capabilities, nanomaterials possessing excellent optical and electrochemical properties have been integrated into a wide range of sensing or detection platforms. This review will highlight recent developments in creating electrochemical sensors alongside biosensors using carbon nanomaterials and metallic nanoparticles that target small metabolites. Moreover, electrochemical sensors having different detection strategies toward metabolites (such as amino acids, amino acid–derived neurotransmitters, vitamins, adenosine triphosphate, and purine derivatives) will be discussed. Finally, certain challenging issues and future aspects of nanomaterials-integrated electrochemical sensors for small metabolites will be discussed.     

Electrochemical immunoassays

Immunoassays (IA) use the specific antigen antibody complexation for analytical purposes. Radioimmunoassays (RIA), fluorescence immunoassays (FIA) and enzyme immunoassays (EIA) are well established in clinical diagnostics. For the development of hand-held devices which can be used for point of care measurements, electrochemical immunoassays are promising alternatives to existing immunochemical tests. Moreover, for opaque or optically dense matrices electrochemical methods are superior. Potentiometric, capacitive and amperometric transducers have been applied for direct and indirect electrochemical immunoassays. However, due to their fast detection, broad linear range and low detection limit, amperometric transducers are preferred. Competitive and noncompetitive amperometric immunoassays have been developed with redox compounds or enzymes as labels. This review will give an overview of the most frequently applied principles in electrochemical immunoassays. The potential of an indirect competitive amperometric immunoassay for the determination of creatinine within nanomolar range and the circumvention of the most serious problem in electrochemical immunoassays, namely regeneration, will be discussed.     

锈层下碳钢的腐蚀电化学行为特征

采用极化曲线、线性极化电阻(LPR)和电化学阻抗(EIS)研究了海水中带锈碳钢的电化学行为,结果发现:长期浸泡的内锈层对电极过程有较大影响;短期浸泡,LPR和EIS测定的极化电阻(Rp)逐渐增大;而长期浸泡,Rp却逐渐减小;随着浸泡时间的延长,Rp出现了先增大后减小的变化趋势.将锈层逐层剥离后研究了碳钢的电化学行为,并结合傅里叶变换红外(FTIR)光谱和横截面结构分析表明,这主要是因为长期浸泡后,内锈层中出现了具有较高电化学活性的β-FeOOH,并且其含量随着浸泡时间的延长而逐渐增加.当进行电化学测试时,在对体系进行一定程度极化的过程中,β-FeOOH参与了阴极还原反应,使电极过程不再是简单的阳极金属溶解和阴极氧还原,加快了阴极反应速度,从而导致Rp逐渐减小.     

Characterization of the Outer Layer Nanostructure in the Electrochemical Response of Stainless Steel in Aqueous Sodium Hydroxide

The outer layer nanostructure of stainless steel’s passive film in 0.1?M NaOH has been studied by electrochemical atomic force microscopy and the role of the outer layer in the electrochemical response of stainless steel has been characterized. The outer layer is mainly composed of nanoscale particles whose average diameter is up to 13.14?±?3.52?nm at the end of the formation period. The formation process is characterized by the nucleation, growth, and contact of oxide particles. Based on the study on the outer layer nanostructure, the gaps/boundaries between particles in the outer layer should be diffusion paths for ions across the layer. The electrochemical impedance spectroscopy analysis revealed that the ion diffusion resistance first increased and then remained stable due to the three-dimensional growth of nanoscale particles.     

Recent progress in the design of nanofiber-based biosensing devices

This review addresses recent progress made in the use of nanofibers for analyte detection and sample preparation within analytical devices. The unique characteristics of nanofibers make them ideal for incorporation within sensors designed to allow for sensitive detection of clinical, environmental, and food safety analytes. In particular, the extremely large surface area provided by nanofiber mats and arrays drastically increases the availability of immobilization sites within biosensors. Additionally, nanofibers can be made from a variety of biocompatible materials and can be functionalized through the incorporation of nanoscale materials within spinning dopes or polymerization solutions. Finally, methods of nanofiber formation are largely well understood, allowing for controlled synthesis of nanofiber mats with specific sizes, shapes, pore sizes, and tensile strengths. In this paper, we present a survey of the different materials that are currently being used to produce nanofibers for use within sensing devices. In addition, we compare the limits of detection and linear ranges of nanofiber-based sensors and conventional sensors to determine if detection is improved by the inclusion of nanoscale materials.     

Stretchable Electrochemical Sensor for Real‐Time Monitoring of Cells and Tissues

Stretchable electrochemical sensors are conceivably a powerful technique that provides important chemical information to unravel elastic and curvilinear living body. However, no breakthrough was made in stretchable electrochemical device for biological detection. Herein, we synthesized Au nanotubes (NTs) with large aspect ratio to construct an effective stretchable electrochemical sensor. Interlacing network of Au NTs endows the sensor with desirable stability against mechanical deformation, and Au nanostructure provides excellent electrochemical performance and biocompatibility. This allows for the first time, real‐time electrochemical monitoring of mechanically sensitive cells on the sensor both in their stretching‐free and stretching states as well as sensing of the inner lining of blood vessels. The results demonstrate the great potential of this sensor in electrochemical detection of living body, opening a new window for stretchable electrochemical sensor in biological exploration.     

基于多肽的电化学传感器在蛋白质检测中应用的研究进展

生物体内的细胞通常会分泌各种各样的蛋白质,这些蛋白质在生物体中发挥着重要作用,尤其是可被用于诊断各种疾病的发生和发展。多肽具有良好选择性、空间适应能力和识别灵活的特点,可与不同类型的蛋白分子形成非共价键,用于蛋白质的生物检测。将多肽与电化学生物传感器结合用于蛋白质的广谱检测具有良好的发展前景。本文介绍了多肽修饰的电化学传感器在不同蛋白质检测方面的研究进展,分析了待测蛋白质的不同对多肽修饰的电化学传感器分类的影响及其优缺点,提出了基于多肽的电化学传感器在不同蛋白质检测中存在的问题,并展望了其未来发展。