Flame etching enhances the sensitivity of carbon-fiber microelectrodes

Small sensors are useful for in vivo measurements and probing small spaces. In this paper, we compare two methods of fabrication of small, cylindrical carbon-fiber microelectrodes: flame-etching and electrochemical etching. With both methods, microelectrodes can be fabricated with tip diameters of 1 to 3 microm. Electrodes were tested with fast-scan cyclic voltammetry. Flame etching resulted in electrodes that have larger S/N ratios and higher currents per unit area for 1 microM dopamine than normal carbon-fiber microelectrodes or electrochemically etched electrodes. Therefore, the increased sensitivity is not just a property of size. The flame-etched surfaces had nanometer-scale surface features that were not observed on the other electrodes and exhibited increased sensitivity for other electroactive compounds found in the brain, including ascorbic acid, DOPAC, and serotonin. Faster kinetics and a faster response to a step change in dopamine were also observed, when the applied waveform was -0.4 to 1.0 V and back at 400 V/s. The sensitivity of the flame-etched electrodes was enhanced by overoxidizing the surface. The flame-etched electrodes were used to detect dopamine release in anesthetized rats after a single stimulation pulse. The small flame-etched electrodes will facilitate measurements of low concentrations in discrete brain regions or small organisms.     

Higher sensitivity dopamine measurements with faster-scan cyclic voltammetry

Fast-scan cyclic voltammetry (FSCV) with carbon-fiber microelectrodes has been successfully used to detect catecholamine release in vivo. Generally, waveforms with anodic voltage limits of 1.0 or 1.3 V (vs Ag/AgCl) are used for detection. The 1.0 V excursion provides good temporal resolution but suffers from a lack of sensitivity. The 1.3 V excursion increases sensitivity but also increases response time, which can blur the detection of neurochemical events. Here, the scan rate was increased to improve the sensitivity of the 1.0 V excursion while maintaining the rapid temporal response. However, increasing scan rate increases both the desired faradaic current response and the already large charging current associated with the voltage sweep. Analog background subtraction was used to prevent the analog-to-digital converter from saturating from the high currents generated with increasing scan rate by neutralizing some of the charging current. In vitro results with the 1.0 V waveform showed approximately a 4-fold increase in signal-to-noise ratio with maintenance of the desired faster response time by increasing scan rate up to 2400 V/s. In vivo, stable stimulated release was detected with an approximate 4-fold increase in peak current. The scan rate of the 1.3 V waveform was also increased, but the signal was unstable with time in vitro and in vivo. Adapting the 1.3 V triangular wave into a sawhorse design prevented signal decay and increased the faradaic response. The use of the 1.3 V sawhorse waveform decreased the detection limit of dopamine with FSCV to 0.96 ± 0.08 nM in vitro and showed improved performance in vivo without affecting the neuronal environment. Electron microscopy showed dopamine sensitivity is in a quasi-steady state with carbon-fiber microelectrodes scanned to potentials above 1.0 V.     

Dopamine transport into a single cell in a picoliter vial

The analysis of chemical events in small volumes requires careful manipulation of samples and sensitive detection methods. Here, we describe the measurement of the neurotransmitter dopamine in a picoliter vial with electrochemical techniques. The vials were fabricated from fused-silica capillaries that provided a transparent container suitable for the observation and manipulation of a biological cell, sample solutions, and electrodes. Evaporation of the sample was prevented with a mineral oil layer, allowing for experiments lasting for several minutes. The small volume of these vials (100-200 pL) allows rapid mixing of all of the solution reagents. Similarly, the small volume allows exhaustive electrolysis of the vial contents with a 3-microm radius, disk-shaped carbon fiber microelectrode within 60 s. Fast-scan cyclic voltammetry at carbon fiber microelectrodes was used to monitor the concentration of analyte in the vial without depleting its contents. The concentration of dopamine introduced by pneumatic injection remained stable when sampled by cyclic voltammetry, and no evidence for adsorption to the walls was observed. However, when the vial contained a single HEK-293 cell transfected to express the dopamine transporter, the dopamine concentration decreased with time at a rate consistent with the uptake kinetics mediated by the transporter located on the cell membrane.     

Simultaneous measurement of dopamine and ascorbate at their physiological levels using voltammetric microprobe based on overoxidized poly(1,2-phenylenediamine)-coated carbon fiber

Overoxidized poly-(1,2-phenylenediamine) (OPPD)-coated carbon fiber microelectrodes (CFMEs) exhibit, in combination with square-wave voltammetry (SWV) detection mode, the attractive ability to simultaneously measure low nM dopamine (DA) and mM ascorbate (AA) in a pH 7.4 medium. The PPD polymer film is electrodeposited onto a carbon fiber at a constant potential of 0.8 V versus Ag/AgCl using a solution containing sodium dodecylsulfate as the dopant. After overoxidation using cyclic voltammetry (CV) in the potential range from 0 to 2.2 V at a scan rate of 10 V/s, the resulting OPPD-CFME displays a high SWV current response to cationic DA at approximately 0.2 V and has a favorably low response to anionic AA at approximately 0.0 V vs Ag/AgCl. The preparation of the new OPPD-sensing film has been carefully studied and optimized. The OPPD properties and behavior were characterized using CV and SWV under various conditions and are discussed with respect to DA and AA detection. The linear calibration range for DA in the presence of 0.3 mM AA is 50 nM to 10 microM, with a correlation coefficient of 0.998 and a detection limit of 10 nM using 45-s accumulation. The detection limit for DA in the absence of AA was estimated to be 2 nM (S/N = 3). The linear range for AA in the presence of 100 nM DA is 0.2-2 mM, with a correlation coefficient of 0.999 and a detection limit of 80 microM. The reproducibilities of SWV measurements at OPPD-CFCMEs are 1.6% and 2.5% for 100 nM DA and 0.3 mM AA, respectively. Potential interfering agents, such as 3,4-dihydroxyphenylacetic acid, uric acid, oxalate, human serum proteins, and glucose, at their physiologically relevant or higher concentrations did not have any effect. These favorable features offer great promise for in vitro and in vivo application of the proposed OPPD-coated microprobe.     

Boron-doped diamond microelectrodes for use in capillary electrophoresis with electrochemical detection

The fabrication and characterization of boron-doped diamond microelectrodes for use in electrochemical detection coupled with capillary electrophoresis (CE-EC) is discussed. The microelectrodes were prepared by coating thin films of polycrystalline diamond on electrochemically sharpened platinum wires (76-, 25-, and 10-microm diameter), using microwave-assisted chemical vapor deposition (CVD). The diamond-coated wires were attached to copper wires (current collectors), and several methods were explored to insulate the cylindrical portion of the electrode: nail polish, epoxy, polyimide, and polypropylene coatings. The microelectrodes were characterized by scanning electron microscopy, Raman spectroscopy, and cyclic voltammetry. They exhibited low and stable background currents and sigmoidally shaped voltammetric curves for Ru(NH3)6(3+/2+) and Fe(CN)6(3-/4-) at low scan rates. The microelectrodes formed with the large diameter Pt and sealed in polypropylene pipet tips were employed for end-column detection in CE. Evaluation of the CE-EC system and the electrode performance were accomplished using a 10 mM phosphate buffer, pH 6.0, run buffer, and a 30-cm-long fused-silica capillary (75-microm i.d.) with dopamine, catechol, and ascorbic acid serving as test analytes. The background current (approximately 100 pA) and noise (approximately 3 pA) were measured at different detection potentials and found to be very stable with time. Reproducible separation (elution time) and detection (peak current or area) of dopamine, catechol, and ascorbic acid were observed with response precisions of 4.1% or less. Calibration curves constructed from the peak area were linear over 4 orders of magnitude, up to a concentration between 0.1 and 1 mM. Mass limits of detection for dopamine and catechol were 1.7 and 2.6 fmol, respectively (S/N = 3). The separation efficiency was approximately 33,000, 56,000, and 98,000 plates/m for dopamine, catechol, and ascorbic acid, respectively. In addition, the separation and detection of 1- and 2-naphthol in 160 mM borate buffer, pH 9.2, was investigated. Separation of these two analytes was achieved with efficiencies of 118,000 and 126,000 plates/m, respectively.     

Rapid, Sensitive Detection of Neurotransmitters at Microelectrodes Modified with Self-assembled SWCNT Forests

Carbon nanotube (CNT) modification of microelectrodes can result in increased sensitivity without compromising time response. However, dip coating CNTs is not very reproducible and the CNTs tend to lay flat on the electrode surface which limits access to the electroactive sites on the ends. In this study, aligned CNT forests were formed using a chemical self-assembly method, which resulted in more exposed CNT ends to the analyte. Shortened, carboxylic acid functionalized single-walled CNTs were assembled from a dimethylformamide (DMF) suspension onto a carbon-fiber disk microelectrode modified with a thin iron hydroxide-decorated Nafion film. The modified electrodes were highly sensitive, with 36-fold higher oxidation currents for dopamine using fast-scan cyclic voltammetry than bare electrodes and 34-fold more current than electrodes dipped in CNTs. The limit of detection (LOD) for dopamine was 17 ± 3 nM at a 10 Hz repetition rate and 65 ± 7 nM at 90 Hz. The LOD at 90 Hz was the same as a bare electrode at 10 Hz, allowing a 9-fold increase in temporal resolution without a decrease in sensitivity. Similar increases were observed for other cationic catecholamine neurotransmitters, and the increases in current were greater than for anionic interferents such as ascorbic acid and 3,4-dihydroxyphenylacetic acid (DOPAC). The CNT forest electrodes had high sensitivity at 90 Hz repetition rate when stimulated dopamine release was measured in Drosophila . The sensitivity, temporal resolution, and spatial resolution of these CNT forest modified disk electrodes facilitate enhanced electrochemical measurements of neurotransmitter release in vivo.     

Simultaneous electrochemical measurements of oxygen and dopamine in vivo.

Fast-scan cyclic voltammetry, a demonstrated analytical method for the in vivo detection of catecholamine neurotransmitters, is extended to the simultaneous determination of molecular oxygen (O2). Cyclic voltammograms were recorded at a scan rate of 400 V/s at carbon-fiber disk electrodes coated with a perfluorinated ion-exchange material. The peak current for O2 occurs near -1.2 V under these conditions. In flow-injection experiments, these electrodes respond to step changes in dopamine and O2 with a half-rise time of less than 200 ms. The voltammetric peak current is independent of flow rate, indicating a diffusion-limited response unaffected by convection. Several compounds present in the in vivo matrix (adenosine, glutathione, and NAD and glutamic, lactic, and uric acids) were tested and shown not to interfere with the voltammetric signal for O2. These electrodes maintain a stable response in vivo for at least 6 h. They have been used to measure transient increases in both dopamine and O2 in the extracellular fluid of the caudate nucleus of an anesthetized rat in response to an electrical stimulus.     

Determination of picomolar levels of iron in seawater using catalytic cathodic stripping voltammetry

A new procedure for the direct determination of picomolar levels of iron in seawater is presented. Cathodic stripping voltammetry (CSV) is preceded by adsorptive accumulation of the iron(III)-2,3-dihydroxynaphthalene (DHN) complex from seawater, containing 20 microM DHN at pH 8.0, onto a static mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is catalytically enhanced by the presence of 20 mM bromate. Optimized conditions include a 60-s adsorption period at -0.1 V and a voltammetric scan using sampled dc modulation at 10 Hz. In these conditions, a detection limit of 13 pM iron in seawater was achieved which can be lowered further by extending the adsorption time to 300 s. The new catalytic CSV method is approximately 5 times more sensitive than existing CSV methods and was tested on samples from the Atlantic Ocean.     

Response times of carbon fiber microelectrodes to dynamic changes in catecholamine concentration

The electrode response time and the measured concentrations during dynamic catecholamine changes were compared using constant potential amperometry and fast-scan cyclic voltammetry. The amperometric response to a rectangular pulse of catecholamine is more rectangular than the cyclic voltammetric response; however, the response times are very similar when, during cyclic voltammetry, the temporal lag due to adsorption and desorption of catecholamine to the electrode is removed by deconvolution. Deconvolution of cyclic voltammetry data was applied to stimulated dopamine release in vivo, allowing for modeling of release and uptake kinetics and to measure catecholamine release from single cells, resulting in better resolution of peaks from single vesicles. In vitro postcalibrations were performed to calculate concentrations of catecholamine measured with cyclic voltammetry and amperometry. The addition of 600 microM ascorbic acid to the postcalibration buffer, allowing a catalytic reaction to regenerate dopamine, resulted in similar calculated concentrations for stimulated release of dopamine using amperometry and cyclic voltammetry. Using deconvoluted cyclic voltammetry to remove the response time lag and adding ascorbic acid to the calibration buffer, the shape and concentration of dynamic catecholamine changes are very similar when measured with constant potential amperometry and cyclic voltammetry.     

Oxidation-state speciation of

The analytical utility of chemically modified microelectrodes for oxidation-state speciation of redox couples by cyclic voltammetry has been explored. [Re(I)(DMPE)3]+/[Re(II)(DMPE)3]2+, where DMPE = 1,2-bis(dimethylphosphino)ethane, was studied at carbon-fiber microelectrodes of approximately 5 microm in radius coated with Nafion-entrapped solgel-derived silica (Nafion-silica) composite. The results are compared with cyclic voltammetry of [Fe(CN)6]3-/[Fe(CN)6]4- at bare carbon-fiber microelectrodes. At both microelectrodes, the cathodic and anodic limiting currents are linearly proportional to the concentrations of the reducible and oxidizable species of a redox couple, respectively. The shape of the cyclic voltammogram and the magnitude of the steady-state limiting current are not affected by the potential at which the scan starts. Speciation of both forms of a redox couple could be achieved voltammetrically at the microelectrodes. However, a considerably slower scan rate was required to achieve steady state at the modified electrode because of the smaller diffusion coefficients of [Re(I)(DMPE)3]+ and [Re(II)(DMPE)3]2+ in the Nafion-silica composite. The detection limit at the modified electrode was considerably lower (5 x 10(-9) M for [Re(I)(DMPE)3]+) than at the bare electrode (6 x 10(-5) M for [Fe(CN)6]3- and [Fe(CN)6]4-) because of the substantial preconcentration of [Re(I)(DMPE)3]+ by the Nafion-silica composite.     

Charge transfer property of self-assembled viologen derivative by electrochemical quartz crystal microbalance response

Viologen modified electrodes have been extensively investigated with quartz crystal microbalance (QCM), which has been known as a nano-gram order mass detector, because of their highly reversible electrochemical properties, especially the first reduction-oxidation cycle of V2+ <--> V*+. The purpose of this work was to study the charge transfer characteristics of self-assembled monolayer (SAM) by changing electrolyte solutions where the cations and anions are different. The redox peak currents were nearly equal charges during redox processes and showed an excellent linear interrelation between the scan rates and second redox peak currents. The charge transfer of self-assembled viologen monolayer was determined by the mass change during the cyclic voltammetry (CV). The total frequency change was about 17.8 Hz, 19.6 Hz, 9.5 Hz, and 8.4 Hz. From this data, we could know the transferred mass was about 19.0 ng, 20.9 ng, 10.2 ng, and 9.0 ng. Finally, the electrochemical quartz crystal microbalance (EQCM) has been employed to monitor the electrochemically induced adsorption of self-assembled monolayer.     

A Study of the Electrochemical Behavior of Poly [N-Vinyl Carbazole] Formed on Carbon-Fiber Microelectrodes and Its Response to Dopamine

N-vinyl carbazole (NVCz) random polymers were electrochemically coated onto micron-size carbon fibers in lithium perchlorate/acetonitrile $({hbox {LiClO}}_{4} /{hbox {ACN}})$, sodium perchlorate/acetonitrile $({hbox {NaClO}}_{4} /{hbox {ACN}})$, and tetraethylammonium tetrafluoroborate/acetonitrile $({hbox {TEABF}}_{4} /{hbox {ACN}})$ solutions in order to form dopamine-sensing layers on the carbon fiber microelectrodes (CFMEs). The resulting micron-thick polymer films were characterized by using scanning electron microscopy and Fourier transform infrared reflectance spectroscopy. Electrocoating of polymeric film was performed by three different electrochemical methods such as cyclic voltammetry and chronoamperometric and chronopotentiometric polarizations. These modified CFMEs were tested against dopamine by applying only cyclovoltammetric techniques. Under optimum experimental conditions, the electrode shows a reversible and stable behavior during 24 days in a 0.1-M ${hbox {TEABF}}_{4} /{hbox {ACN}}$ solution and, hence, can be considered as a promising sensor for dopamine detection. The dopamine detection limit as low as 0.01 nM (3S/N) was obtained for the polymer film formed among applied cyclic voltammetry, chronoamperometry, and chronopotentiometry. The polymer film was demonstrated to offer high selectivity toward dopamine detection in the presence of ascorbic acid.      

Quantitative X-ray diffraction analysis of development of Z phase in 12%Cr–Nb–V–N steel

Abstract

To study the evolution of nitrides (Nb,V)N, (V,Nb)N and Cr₂N, and in particular the formation of the Z phase Cr(V, Nb)N, a model alloy with composition similar to that of 12%Cr steels for high temperature applications, microalloyed with Nb and V but with a very low carbon content, has been designed. A quantitative determination of the volume fractions of the extracted nitrides that had formed after aging treatments at 650°C for up to 10 000 h was carried out by an X-ray diffraction procedure, based on the Rietveld approach. The investigation of the Z phase evolution by the Johnson–Mehl–Avrami–Kolmogorov kinetics at 650 and 700°C revealed that, as the kinetic exponent is very close to unity, the formation mechanism of this phase is not associated with a conventional process of nucleation but hints at a gradual diffusion controlled transformation of the pre-existing V and Nb nitrides.     

Cyclic voltammetric detection in capillary electrophoresis with application to metal ions

Fast cyclic voltammetry (CV) was evaluated over sweep rates of 20-1000 V/s at Au disk electrodes (25 and 10 μm) for end-capillary detection in capillary electrophoresis with metal ions as test analytes; some studies were also done with 25-μm Pt disk electrodes. The waveform applied to the electrode consisted of a preconcentration period (55-330 ms) followed by cyclic voltammetry (2-100 ms). Maximum signal-to-noise was obtained with the integrated CV current as the analytical signal, and this was linearly proportional to sweep rate; maximum response was obtained at sweep rates of >100 V/s for 10-μm electrodes and >200 V/s for 25-μm electrodes; sweep rates of >400 V/s caused peak tailing due to trapping of the analyte at the electrode. With this CV detection approach, comigrating analytes could be identified and determined. Reproducibilities for six analytes over the range 1.0 × 10(-)(7)-1.0 × 10(-)(5) mol/L were 2%-5%, and calibration curves were linear, with response factors in the range of 2%-6%. Detection limits (2 × peak-to-peak baseline noise) were in the range of 5 × 10(-)(9)-4 × 10(-)(8) mol/L, which are 1-2 orders of magnitude better than results obtained previously with square-wave pulsed amperometric detection of metal ions.     

Subsecond detection of physiological adenosine concentrations using fast-scan cyclic voltammetry

Adenosine modulates blood flow and neurotransmission and may be protective during pathological conditions such as ischemia and stroke. A real-time sensor of adenosine concentrations is needed to understand its physiological actions and the extent of receptor activation. Microelectrodes are advantageous for in vivo measurements because they are small and can make fast measurements. The goal of this study was to characterize detection of physiological adenosine concentration changes at carbon-fiber microelectrodes with subsecond temporal resolution. The oxidation potential of adenosine is +1.3 V, so fast-scan cyclic voltammetry (FSCV) was performed with an applied potential from -0.4 to 1.5 V and back at 400 V/s every 100 ms. Two oxidation peaks were detected for adenosine with T-650 carbon fibers. The second oxidation peak at 1.0 V occurs after the initial oxidation at 1.5 V and is due to a sequential oxidation step. Adsorption was maximized to obtain detection limits of 15 nM, lower than basal adenosine concentrations in the brain. The electrode was insensitive to the metabolite inosine and seven times more sensitive to adenosine than ATP. The enzymatic degradation of adenosine was monitored with FSCV. This microelectrode sensor will be valuable for biological monitoring of adenosine.     

Coupled electrochemical reactions at bipolar microelectrodes and nanoelectrodes

Here we report the voltammetric study of coupled electrochemical reactions on microelectrodes and nanoelectrodes in a closed bipolar cell. We use steady-state cyclic voltammetry to discuss the overall voltammetric response of closed bipolar electrodes (BPEs) and understand its dependence on the concentration of redox species and electrode size. Much of the previous work in bipolar electroanalytical chemistry has focused on the use of an "open" cell with the BPE located in an open microchannel. A closed BPE, on the other hand, has two poles placed in separate compartments and has remained relatively unexplored in this field. In this work, we demonstrated that carbon-fiber microelectrodes when backfilled with an electrolyte to establish conductivity are closed BPEs. The coupling between the oxidation reaction, e.g., dopamine oxidation, on the carbon disk/cylinder and the reduction of oxygen on the interior fiber is likely to be responsible for the conductivity. We also demonstrated the ability to quantitatively measure voltammetric properties of both the cathodic and anodic poles in a closed bipolar cell from a single cyclic voltammetry (CV) scan. It was found that "secondary" reactions such as oxygen reduction play an important role in this process. We also described the fabrication and use of Pt bipolar nanoelectrodes which may serve as a useful platform for future advances in nanoscale bipolar electrochemistry.     

Dynamics and performance of fast linear scan anodic stripping voltammetry of cd, pb, and cu using in situ-generated ultrathin mercury films

The dynamics of fast linear scan (LS) ASV for the simultaneous detection of Cd, Pb, and Cu was investigated at various scan rates (0.5-10 V/s) and at different metal ion concentrations (50-800 nM) utilizing ultrathin mercury films (9 nm) at a conventional size (d(0) = 1 mm) electrode. Results of the investigation show that when the thin films were utilized, diffusion of metals through the mercury film was not the rate-limiting step of the stripping process at moderate to fast scan rates (0.5-10 V/s). A fairly linear relationship between the peak height and scan rate was observed at scan rates (0.5-10 V/s) beyond the upper limit of the theoretical model for the behavior of LS-ASV. In addition, peak width at half-height (b(1/2)) as low as 33 mV was achieved at 0.5 V/s. The behavior of LS-ASV in terms of peak width at these scan rates is thus different from what the theoretical model of LS-ASV would have predicted. For the ultrathin mercury films, at least two additional factors, kinetics and concentration, have significant effects on practical LS-ASV. Experimental results show that the stripping process of Cu was primarily kinetic-controlled for fast scans, while those for Cd and Pb were dependent on both scan rates and concentrations. The ultrathin mercury film resulted in a significant enhancement of the ratio of signal-to-baseline slope (i(p)/Δi(b), a ratio used to measure the effectiveness of discrimination of the peak signal against the steep sloping baseline in LS-ASV) for Cd and Pb stripping peaks, but only a slight enhancement for Cu stripping peaks. The optimal performance of LS-ASV in terms of sensitivity, peak width, and enhancement of the i(p)/Δi(b) ratio for the three metals was achieved at 2 V/s. Because of the high reproducibility of the background currents of the stable in situ MTFs, background subtraction was carried out at 2 V/s with little hysteresis. This feature, combined with the enhancement of the i(p)/Δi(b) ratio at the fast scan rate of 2 V/s, allowed for the detection of sub-ppb levels of Cd, Pb, and Cu at a deposition time of 2 min.     

Fabrication of Boron-Doped CVD Diamond Microelectrodes

Diamond microelectrodes are fabricated using microwave plasma CVD for the growth of electrically conducting single microcrystallite diamonds as well as diamond films on etched tungsten wires which are subsequently sealed in glass. The electroactive diamond is exposed by either mechanical polishing or by chemical etching of the glass. The resulting microelectrodes yield steady-state cyclic voltammograms at low scan rates.     

Probing electric fields inside microfluidic channels during electroosmotic flow with fast-scan cyclic voltammetry

Fast-scan cyclic voltammetry (FSCV) at carbon-fiber microelectrodes was used in microfluidic channels. This method offers the advantage that it can resolve electroactive species not separated in the channel. In addition, this method provides a route to investigate the distribution of applied electrophoretic fields in microfluidic channels. To probe this, microelectrodes were inserted at various distances into channels and cyclic voltammograms recorded at 300 V/s were repeated at 0.1-s intervals. The use of a battery-powered laptop computer and potentiostat provided galvanic isolation between the applied electrophoretic field and the electrochemical measurements. In the absence of an external field, the peak potential for oxidation of the test solute, Ru(bpy)3(2+), was virtually unaltered by insertion of the microelectrode tip into the channel. When an electrophoretic field was applied, the peak potential for Ru(bpy)3(2+) oxidation shifted to more positive potentials in a manner that was directly proportional to the field in the channel. The shifts in peak potential observed with FSCV enabled direct compensation of the applied electrochemical potential. This approach was used to explore the electrophoretic field at the channel terminus. It was found to persist for more than 50 microm from the channel terminus. In addition, the degree of analyte dispersion was found to depend critically on the electrode position outside the channel.     

Feedback effects in combined fast-scan cyclic voltammetry-scanning electrochemical microscopy

Fast-scan cyclic voltammetry at scan rates between 5 and 1000 V s(-1) was performed at the tip of a scanning electrochemical microscope immersed in a solution of redox mediator. The effect of conducting and insulating substrates on the voltammetric signal was investigated as a function of scan rate and tip-substrate distance. It was found that diffusional interactions between the tip and the substrate are greatest at lower scan rates and on the reverse sweep of the voltammogram. At the fastest scan rates used, the tip could be brought to with 1 microm of the substrate without appreciable perturbation of the voltammogram. By selecting scan rates and tip-substrate distances such that feedback effects were negligible, it was possible to image the diffusion layer of a 10 microm Pt substrate electrode. With the tip placed 1 microm above a biological cell, tip-substrate diffusional interactions were greatly diminished at a scan rate of 100 V s(-1) and absent at a scan rate of 1000 V s(-1). These results suggest conditions can be selected that allow chemical imaging of substrates without the feedback interactions typically encountered in scanning electrochemical microscopy.