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Electrochemical Microscopy (electrochemical + microscopy)

Distribution by Scientific Domains

Chemistry	100%

Kinds of Electrochemical Microscopy

scanning electrochemical microscopy

Selected Abstracts

Fabrication of Active Horseradish Peroxidase Micropatterns with a High Resolution by Scanning Electrochemical Microscopy

ELECTROANALYSIS, Issue 16 2007
Xuemei Li
Abstract We used a new reactive species OH, to fabricate active horseradish peroxidase (HRP) micropatterns with a high resolution by scanning electrochemical microscopy (SECM) coupled with a carbon fiber disk electrode as the SECM tip. In this method, except for active HRP micropatterns predesigned other regions on a HRP-immobilized substrate were deactivated by OH, generated at the tip held at ,1.7,V in 1.0,mol/L KCl containing 2.0×10,3 mol/L benzoquinone (BQ) (pH,8.0). The feedback mode of SECM with a tip potential of ,0.2,V was used to characterize the active HRP micropatterns in 1.0,mol/L KCl containing 2.0×10,3 mol/L BQ and 2.0×10,3 mol/L H2O2. [source]

Spatial Imaging of Cu2+ -Ion Release by Combining Alternating Current and Underpotential Stripping Mode Scanning Electrochemical Microscopy

ELECTROANALYSIS, Issue 2-3 2007
Dirk Ruhlig
Abstract Anodic underpotential stripping voltammetry was integrated into SECM in order to characterize local corrosion of metallic copper deposits on metal surfaces as a model for copper containing alloys. Primarily, the alternating current mode of SECM was applied in an electrolyte of low ionic strength for localizing possible corrosion sites without any perturbation of the corroding surface, e.g., by the presence of any redox mediator. Sequentially, the release of Cu2+ -ions was confirmed and locally visualized at the previously detected electrochemically active sites by means of spatially resolved anodic underpotential stripping voltammetry performed during SECM scanning. Underpotential stripping voltammetry of Cu2+ -ions was performed at a specifically developed 15,,m gold-coated Pt microelectrode used as SECM tip with a detection limit of 0.15,nM Cu2+ (N=4, RSD=6%) for an accumulation of 45,s at ,0.4,V. SECM images of model samples such as copper coated microelectrodes and lacquered metallic copper workpieces demonstrated the feasibility and applicability of combining AC- and underpotential stripping mode of SECM for local visualization of Cu2+ -ion release from corroding surfaces. [source]

Scanning Electrochemical Microscopy as an In Vitro Technique for Measuring Convective Flow Rates Across Dentine and the Efficacy of Surface Blocking Treatments

ELECTROANALYSIS, Issue 3 2005
Julie
Abstract Scanning electrochemical microscopy (SECM) is shown to be a powerful technique for both the measurement of local solution velocities through human dentine slices, in vitro, and for assessing quantitatively the effect of surface treatments on the flow process. SECM employs a small ultramicroelectrode (micron dimensions) as an imaging probe to provide information on the topography and transport characteristics of dentine, with high spatial resolution. In these studies the dentine sample is a membrane in a two compartment cell, which contains solutions of identical composition, including a redox active mediator (Fe(CN). In the absence of an applied pressure, the transport-limited current response at the probe electrode is due to diffusion of Fe(CN) to the UME, which depends on the probe to sample separation. Under an applied hydrostatic pressure, hydrodynamic flow across the sample enhances mass transport to the UME. With this methodology it was possible to accurately measure effective fluid velocities, by recording tip currents with and without pressure, and assess the efficacy of potential flow retarding agents for the treatment of dentinal hypersensitivity. For native dentine, the solution velocity was found to vary dramatically with location on the sample. The application of a glycerol monooleate - base paste treatment to the surface of dentine was found to lower local flow velocities significantly. This electroanalytical methodology is simple to implement and is generally applicable to assessing the efficacy and mode of action of a wide variety of potential fluid flow retarding agents. [source]

Patterning of Surfaces by Oxidation of Amine-Containing Compounds Using Scanning Electrochemical Microscopy,

ANGEWANDTE CHEMIE, Issue 40 2009
Charles Cougnon Dr.
Ein Verfahren zur Herstellung von Mikromustern, das auf der Oxidation eines Amins beruht, beginnt mit der Reduktion einer nitrohaltigen Verbindung an der Spitze eines elektrochemischen Mikroskops (siehe Bild). Nach der Diffusion in der Lücke zwischen den Elektroden wird das Amin an einer Goldprobe oxidiert, was einer lokalen Derivatisierung entspricht. Dieses Verfahren sollte sich für die Erzeugung großer Mikrostrukturen auf Oberflächen eignen. [source]

Frequency-Dependent Alternating-Current Scanning Electrochemical Microscopy (4D AC-SECM) for Local Visualisation of Corrosion Sites

CHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2008
Kathrin Eckhard Dr.
Abstract For a better understanding of the initiation of localised corrosion, there is a need for analytical tools that are capable of imaging corrosion pits and precursor sites with high spatial resolution and sensitivity. The lateral electrochemical contrast in alternating-current scanning electrochemical microscopy (AC-SECM) has been found to be highly dependent on the frequency of the applied alternating voltage. In order to be able to obtain data with optimum contrast and high resolution, the AC frequency is swept in a full spectrum at each point in space instead of performing spatially resolved measurements at one fixed perturbation frequency. In doing so, four-dimensional data sets are acquired (4D AC-SECM). Here, we describe the instrument set-up and modus operandi, along with the first results from the imaging of corroding surfaces. Corrosion precursor sites and local defects in protective organic coatings, as well as an actively corroding pit on 304 stainless steel, have been successfully visualised. Since the lateral electrochemical contrast in these images varies with the perturbation frequency, the proposed approach constitutes an indispensable tool for obtaining optimum electrochemical contrast. Um die Entstehung lokaler Korrosionsphänomene untersuchen zu können, bedarf es ortsauflösender Methoden, die beispielsweise Lochfraß oder Korrosionsvorstufen mit hoher lateraler Auflösung visualisieren können. Bei der Abbildung lokaler elektrochemischer Aktivität mittels wechselstrombasierter elektrochemischer Rastermikroskopie (AC-SECM) ist der Kontrast in hohem Maße abhängig von der gewählten Anregungsfrequenz. Um den Informationsgehalt der erhaltenen Bilder zu erhöhen und optimalen elektrochemischen Kontrast zu erzielen, wird vorgeschlagen, an jedem Punkt des Rastergitters, ein komplettes Frequenzspektrum aufzunehmen, anstatt die Oberfläche mit einer einzigen, willkürlich gewählten Anregungsfrequenz abzurastern. Dadurch werden vierdimensionale Datensätze erhalten (4D AC-SECM). Wir berichten hier über den Aufbau des neu entwickelte Instrumentes, seine Funktionsweise und über erste Ergebnisse zur Abbildung korrodierender Oberflächen. Korrosionsvorstufen und Defekte in organischen Schutzschichten konnten ebenso erfolgreich visualisiert werden wie ein Korrosionsherd auf einer 304 Edelstahl-Oberfläche. Die hier vorgestellte Herangehensweise garantiert die Erfassung des optimalen elektrochemischen Kontrastes und damit eine hohe Auflösung bei der Visualisierung korrodierender Oberflächen. [source]

Evaluation of the Chemical Reactions from Two Electrogenerated Species in Picoliter Volumes by Scanning Electrochemical Microscopy

CHEMPHYSCHEM, Issue 13 2010
Qian Wang
Abstract The volume created by the positioning of two scanning electrochemical microscope (SECM) probes (tip and substrate) at a micrometric distance defines a "picoliter beaker" where homogeneous electron-transfer reactions are studied. The SECM is used to concurrently electrogenerate in situ two reactive species and to evaluate the possibility of detecting their reactivity. Two reaction cases are studied: the first, called the "reversible case", occurs when the electrochemically generated species at the substrate electrode can also react at the tip to yield the same product as the reaction in the gap. The second case, named the "irreversible case", occurs when the electrochemically generated species at the substrate are not able to react at the tip. Digital simulations are performed and compared to experimental studies. These show that an unusual compensation between collection and feedback effects render the analysis inapplicable in the "reversible case". The "irreversible case" is shown experimentally. [source]

Analytical Expressions for Quantitative Scanning Electrochemical Microscopy (SECM)

CHEMPHYSCHEM, Issue 3 2010
Christine Lefrou Dr.
Abstract Scanning electrochemical microscopy (SECM), is a recent analytical technique in electrochemistry, which was developed in the 1990s and uses microelectrodes to probe various surfaces. Even with the well-known disc microelectrodes, the system geometry is not as simple as in regular electrochemistry. As a consequence even the simplest experiments, the so-called positive and negative feedback approach curves, cannot be described with exact analytical expressions. This review gathers all the analytical expressions available in the SECM literature in steady-state feedback experiments. Some of them are claimed as general expressions, other are presented as approximate. Their validity is discussed in the light of the current understanding and computer facilities. [source]

Imaging Local Proton Fluxes through a Polycarbonate Membrane by Using Scanning Electrochemical Microscopy and Functionalized Alkanethiols

CHEMPHYSCHEM, Issue 1 2009
Norman Baltes Dr.
Abstract A new application of scanning electrochemical microscopy (SECM) to probe the transport of protons through membranes is described. Herein, a probe ultramicroelectrode (UME) is modified with a self-assembled monolayer (SAM) of 11-mercaptoundecanoic acid to qualitatively image areas within different pH regions above a track-etched membrane. The current response of the modified electrode in the presence of potassium hexacyanoferrate as electroactive component is different in acidic and alkaline solutions. Depending on the pH value of the solution, the SAM-covered electrode exposes either a neutral or a negatively charged insulating monolayer at pH 3 or 7, respectively, which leads to an increase/decrease in the faradaic current due to electrostatic interactions between the neutral/charged surface and the charged redox mediator. Therefore, local pH changes in the close vicinity of a membrane-like substrate lead to different current responses recorded at the tip electrode when scanning above the surface. [source]

Using Scanning Electrochemical Microscopy to Determine the Doping Level and the Flatband Potential of Boron-Doped Diamond Electrodes

CHEMPHYSCHEM, Issue 1 2006
Jérôme Chane-Tune Dr.
A new approach for determining the doping level (NA) and the flatband potential () of electrochemically activated boron-doped diamond electrodes is presented. Scanning electrochemical microscopy is used to monitor an electrode's approach to a diamond surface (see figure): The obtained approach curves are then used to determine NA (8.3×1019 B,cm,3) and (0.654 V vs. Ag/AgCl). [source]

Solid Contact Micropipette Ion Selective Electrode II: Potassium Electrode for SECM and In Vivo Applications

ELECTROANALYSIS, Issue 17-18 2009
Gergely Gyetvai
Abstract Micropipette ion selective electrodes are very small, but fragile, short-life time sensors with very high resistance. Their high resistance is a draw back considering application in scanning electrochemical microscopy (SECM) and in life sciences. New, low resistance potassium micropipette electrodes were prepared, and applied. The electrode contains solid internal contact made of a carbon fiber lowered down all the way close to the orifice of the micropipette. The internal contact potential was kept constant by applying a doped, electrochemically prepared PEDOT coating on the fiber surface. The electrode performed well in in vivo experiments both in plant and animal tissue without capacitance neutralization and in SECM. [source]

Fabrication of Active Horseradish Peroxidase Micropatterns with a High Resolution by Scanning Electrochemical Microscopy

Solid Contact Micropipette Ion Selective Electrode for Potentiometric SECM

ELECTROANALYSIS, Issue 10 2007
Gergely Gyetvai
Abstract New solid contact ammonium micropipette electrodes (ISE), well applicable in scanning electrochemical microscopy are reported. The solid contact was made of a PEDOT nanowire coated carbon fiber, lowered down close to the orifice, and dipped inside the cocktail being in the pipette tip. This configuration provided low electrical resistance and good potential stability. Submicron tip size, usual in case of micropipette ISE-s easily can be fabricated in this way. The applicability of the electrode in SECM has been proved in SG/TC mode imaging urease enzyme active spots in urea solutions. [source]

Electrooxidation of DNA at Glassy Carbon Electrodes Modified with Multiwall Carbon Nanotubes Dispersed in Chitosan

ELECTROANALYSIS, Issue 7-8 2007
Soledad Bollo
Abstract We report on the analytical performance of glassy carbon (GCE) electrodes modified with a dispersion of multiwall carbon nanotubes (CNT) in chitosan (CHIT) for the quantification of DNA. The electroanalytical response of the resulting electrodes was evaluated using differential pulse voltammetry, while the electrochemical reactivity of the film surface was characterized using scanning electrochemical microscopy. Different treatments of the modified GCE were evaluated to improve the stability of the film and the accumulation of DNA. The guanine oxidation signal of double stranded calf-thymus DNA after 3-min accumulation was 20 times higher at GCE/CHIT-CNT cross-linked with glutaraldehyde (GTA) than at bare GCE, while the peak potential was around 45,mV less positive. The guanine oxidation signal demonstrated to be highly reproducible, with 3.4% RSD for 5 different electrodes. The treatment with sodium hydroxide demonstrated to be not effective since the resulting films were less stable and the guanine oxidation signal was ten times smaller compared to electrodes prepared with the GTA treated films. The effect of chitosan molecular weight used to prepare the dispersion and the amount of carbon nanotubes dispersed were evaluated. The response of single stranded DNA and oligo(dG)15 is also discussed. [source]

Preparation of Tip-Protected Poly(oxyphenylene) Coated Carbon-Fiber Ultramicroelectrodes

ELECTROANALYSIS, Issue 23 2006
El-Deen
Abstract A high-yield, reliable, and reproducible method has been successfully developed to fabricate poly(oxyphenylene)-coated carbon fiber ultramicroelectrodes (POCF UMEs) with tip radii r<2,,m. During the insulation process, the tip of the electrochemically etched electrode is protected by inserting it into an inert polymer while the remainder of the electrode is insulated by electrochemical deposition of a 1,3,,m thick poly(oxyphenylene) film. Optimum conditions for poly(oxyphenylene) deposition are developed and the resulting carbon fiber UMEs showed good cyclic voltammetric behavior even after storage for more than one year. These UMEs were tested for use as amperometric scanning electrochemical microscopy (SECM) tips and successfully imaged Au/Kel-F and Al/SiCp metal matrix composites. [source]

SECM Visualization of Spatial Variability of Enzyme-Polymer Spots.

ELECTROANALYSIS, Issue 19-20 2006
2: Complex Interference Elimination by Means of Selection of Highest Sensitivity Sensor Substructures, Artificial Neural Networks
Abstract Polymer spots with entrapped glucose oxidase were fabricated on glass surfaces and the localized enzymatic response was subsequently visualized using scanning electrochemical microscopy (SECM) in the generator,collector mode. SECM images were obtained under simultaneous variation of the concentration of glucose (0,6,mM) and ascorbic acid (0,200,,M), or, in a second set of experiments, of glucose (0,2,mM) and 2-deoxy- D(+)-glucose (0,4,mM). Aiming at the quantification of the mixture components discretization of the response surfaces of the overall enzyme/polymer spot into numerous spatially defined microsensor substructures was performed. Sensitivity of sensor substructures to measured analytes was calculated and patterns of variability in the data were analyzed before and after elimination of interferences using principal component analysis. Using artificial neural networks which were fed with the data provided by the sensor substructures showing highest sensitivity for glucose, glucose concentration could be calculated in solutions containing unknown amounts of ascorbic acid with a good accuracy (RMSE 0.17,mM). Using, as an input data set, measurements provided by sensing substructures showing highest sensitivity for ascorbic acid in combination with the response of the sensors showing highest dependence on the glucose concentration, the error of the ascorbic acid concentration calculation in solution containing the unknown amount of glucose was 10,,M. Similarly, prediction of the glucose concentration in the presence of 2-deoxy- D(+)-glucose was possible with a RMSE of 0.1,mM while the error of the calculation of 2-deoxy- D(+)-glucose concentrations in the presence of unknown concentrations of glucose was 0.36,mM. [source]

Characterization of Nanopore Electrode Structures as Basis for Amplified Electrochemical Assays

ELECTROANALYSIS, Issue 19-20 2006
Sebastian Neugebauer
Abstract A nanopore electrode structure was fabricated consisting of ensembles of nanopores with separately addressable electrodes at the pore bottoms and the rims. A metal/insulator/metal layer structure allowed for adjusting the spacing between the bottom and rim electrodes to be in the range of about 200,nm. Pore diameters varied between 200 and 800,nm. The electrochemical properties of this electrode structure and its perspectives for applications in bioelectronics were studied using cyclic voltammetry and chronoamperometry along with high-resolution scanning electrochemical microscopy (SECM) in constant-distance mode. It was possible to visualize the electrochemical activity of a single nanometric electrode using high-resolution SECM in a combination of sample-generation-tip-collection mode and positive feedback mode. The SECM images suggested an influence of the unbiased rim electrode on redox amplification which was used as a basis for evaluating the feasibility of current amplification by means of redox cycling between the bottom and rim electrodes. Amplification factors superior to those obtained with interdigitated array electrodes could be demonstrated. [source]

Comparison of Different Strategies on DNA Chip Fabrication and DNA-Sensing: Optical and Electrochemical Approaches

ELECTROANALYSIS, Issue 22 2005
Sabine Szunerits
Abstract New strategies for the construction of DNA chips and the detection of DNA hybridization will be discussed in this review. The focus will be on the use of polypyrrole as a linker between a substrate and oligonucleotide probes. The modification step is based on the electrochemical copolymerization of pyrrole and oligonucleotides bearing a pyrrole group on its 5, end. This strategy was employed for the immobilization of oligonucleotides on millimeter-sized electrodes, microelectrode arrays, as well as for the local structuring of homogeneous gold surfaces. Our approaches for the localized patterning of gold surfaces will be also discussed. Localized immobilization was achieved by using an electrospotting technique, where a micropipette served as an electrochemical cell where spot sizes with 800,,m diameters were fabricated. The use of a microcell using a Teflon covered metal needle with a cavity of 100,,m resulted in immobilized probe spots of 300,,m. Scanning electrochemical microscopy (SECM) was also used, and surface modifications of 100,,m were obtained depending on the experimental conditions. Different detection methods were employed for the reading of the hybridization event: fluorescence imaging, surface plasmon resonance imaging (SPRI), photocurrent measurements, and voltamperometric measurements using intercalators. Their advantages concerning the various immobilization strategies will also be discussed. [source]

Scanning Electrochemical Microscopy as an In Vitro Technique for Measuring Convective Flow Rates Across Dentine and the Efficacy of Surface Blocking Treatments

Frequency-Dependent Alternating-Current Scanning Electrochemical Microscopy (4D AC-SECM) for Local Visualisation of Corrosion Sites

A Dual-Electrode Approach for Highly Selective Detection of Glucose Based on Diffusion Layer Theory: Experiments and Simulation

CHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2005
Kang Wang Dr.
Abstract A dual-electrode configuration for the highly selective detection of glucose in the diffusion layer of the substrate electrode is presented. In this approach, a glassy carbon electrode (GCE, substrate) modified with a conductive layer of glucose oxidase/Nafion/graphite (GNG) was used to create an interference-free region in its diffusion layer by electrochemical depletion of interfering electroactive species. A Pt microelectrode (tip, 5 ,m in radius) was located in the diffusion layer of the GNG-modified GCE (GNG-G) with the help of scanning electrochemical microscopy. Consequently, the tip of the electrode could sense glucose selectively by detecting the amount of hydrogen peroxide (H2O2) formed from the oxidization of glucose on the glucose oxidase layer. The influences of parameters, including tip,substrate distance, substrate potential, and electrolyzing time, on the interference-removing efficiency of this dual-electrode approach have been investigated systematically. When the electrolyzing time was 30 s, the tip,substrate distance was 1.8,a (9.0 ,m) (where a is the radius of the tip electrode), the potentials of the tip and substrate electrodes were 0.7 V and 0.4 V, respectively, and a mixture of ascorbic acid (0.3,mM), uric acid (0.3,mM), and 4-acetaminophen (0.3,mM) had no influence on the glucose detection. In addition, the current,time responses of the tip electrode at different tip,substrate distances in a solution containing interfering species were numerically simulated. The results from the simulation are in good agreement with the experimental data. This research provides a concept of detection in the diffusion layer of a substrate electrode, as an interference-free region, for developing novel microelectrochemical devices. [source]

Fabrication of Nanoelectrodes and Metal Clusters by Electrodeposition

CHEMPHYSCHEM, Issue 13 2010
Jeyavel Velmurugan
Abstract Most nanometer-sized electrodes reported to date are made from either Pt or Au. For technical reasons, it is difficult to make nanoelectrodes from many other metals (e.g. Hg) by heat-sealing microwires into glass capillaries or by other established techniques. Such nanoelectrodes can be useful for a wide range of analytical and physicochemical applications from high sensitivity stripping analysis (Hg) to pH nano-sensors to studies of electrocatalysis. In this paper, nanometer-sized metal electrodes are prepared by electrodeposition of Hg or Pt on disk-type, polished or recessed nanoelectrodes. The deposition of Hg is monitored chronoamperometrically to produce near-hemispherical electrodes, which are characterized by voltammetry and scanning electrochemical microscopy (SECM). The well-shaped deposits of a solid metal (Pt) at Au nanoelectrodes are prepared and imaged by scanning electron microscopy (SEM). Catalytic metal clusters can also be prepared using this methodology. Electrodes with the metal surface flush with glass insulator, most suitable for quantitative voltammetric and SECM experiments are fabricated by electrodeposition of a metal inside an etched nanocavity. [source]