Intrinsic electrochemical activity of single walled carbon nanotube-Nafion assemblies.

The intrinsic electrochemical properties and activity of single walled carbon nanotube (SWNT) network electrodes modified by a drop-cast Nafion film have been determined using the one electron oxidation of ferrocene trimethyl ammonium (FcTMA(+)) as a model redox probe in the Nafion film. Facilitated by the very low transport coefficient of FcTMA(+) in Nafion (apparent diffusion coefficient of 1.8 × 10(-10) cm(2) s(-1)), SWNTs in the 2-D network behave as individual elements, at short (practical) times, each with their own characteristic diffusion, independent of neighbouring sites, and the response is diagnostic of the proportion of SWNTs active in the composite. Data are analysed using candidate models for cases where: (i) electron transfer events only occur at discrete sites along the sidewall (with a defect density typical of chemical vapour deposition SWNTs); (ii) all of the SWNTs in a network are active. The first case predicts currents that are much smaller than seen experimentally, indicating that significant portions of SWNTs are active in the SWNT-Nafion composite. However, the predictions for a fully active SWNT result in higher currents than seen experimentally, indicating that a fraction of SWNTs are not connected and/or that not all SWNTs are wetted completely by the Nafion film to provide full access of the redox mediator to the SWNT surface.

Quantitative visualization of passive transport across bilayer lipid membranes.

The ability to predict and interpret membrane permeation coefficients is of critical importance, particularly because passive transport is crucial for the effective delivery of many pharmaceutical agents to intracellular targets. We present a method for the quantitative measurement of the permeation coefficients of protonophores by using laser confocal scanning microscopy coupled to microelectrochemistry, which is amenable to precise modeling with the finite element method. The technique delivers well defined and high mass transport rates and allows rapid visualization of the entire pH distribution on both the cis and trans side of model bilayer lipid membranes (BLMs). A homologous series of carboxylic acids was investigated as probe molecules for BLMs composed of soybean phosphatidylcholine. Significantly, the permeation coefficient decreased with acyl tail length contrary to previous work and to Overton's rule. The reasons for this difference are considered, and we suggest that the applicability of Overton's rule requires re-evaluation.

Assessment of the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes.

Scanning electrochemical microscopy (SECM) has been employed in the feedback mode to assess the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes (SWNTs). It is shown that, even though the network comprises both metallic and semiconducting SWNTs, at high density (well above the percolation threshold for metallic SWNTs) and with approximately millimolar concentrations of redox species the network behaves as a thin metallic film, irrespective of the formal potential of the redox couple. This result is particularly striking since the fractional surface coverage of SWNTs is only approximately 1% and SECM delivers high mass transport rates to the network. Finite element simulations demonstrate that under these conditions diffusional overlap between neighboring SWNTs is significant so that planar diffusion prevails in the gap between the SECM tip and the underlying SWNT substrate. The SECM feedback response diminishes at higher concentrations of the redox species. However, wet gate measurements show that at the solution potentials of interest the conductivity is sufficiently high that lateral conductivity is not expected to be limiting. This suggests that reaction kinetics may be a limiting factor, especially since the low surface coverage of the SWNT network results in large fluxes to the SWNTs, which are characterized by a low density of electronic states. For electroanalytical purposes, significantly, two-dimensional SWNT networks can be considered as metallic films for typical millimolar concentrations employed in amperometry and voltammetry. Moreover, SWNT networks can be inexpensively and easily formed over large scales, opening up the possibility of further electroanalytical applications.

Visualization and modeling of the hydrodynamics of an impinging microjet.

The use of fluorescence confocal laser scanning microscopy (CLSM) for flow visualization is described, with a focus on elucidating the pattern of flow in the microjet electrode (MJE). The MJE employs a nozzle, formed from a fine glass capillary, with an inner diameter of approximately 100 microm, to direct solution at an electrode surface, using high velocity but at moderate volume flow rates. For CLSM visualization, the jetted solution contains a fluorescent probe, fluorescein at high pH, which flows into a solution buffered at low pH, where the fluorescence is extinguished, thereby highlighting the flow field of the impinging microjet. The morphology of the microjet and the hydrodynamic boundary layer are shown to be highly sensitive to the volume flow rate, with a collimated jet and thin boundary layer formed at the faster flow rates (approximately 1 cm(3) min(-1)). In contrast, at lower flow rates and for relatively large substrates, an unusual recirculation zone is observed experimentally for the first time. This effect can be eliminated by employing small substrates. The experimental observations have been quantified through numerical solution of the Navier-Stokes equations of continuity and momentum balance. The new insights provided by CLSM imaging demonstrate that flow in the MJE, and impinging jets in general, are more complex than predicted by classical models but are well-defined and quantifiable.

Fluorescence confocal laser scanning microscopy as a probe of pH gradients in electrode reactions and surface activity.

The application of fluorescence confocal laser scanning microscopy (CLSM) to quantify three-dimensional pH gradients near electrode surfaces is described. The methodology utilizes a trace quantity of a fluorescent dye, fluorescein, in solution, which fluoresces strongly above pH 6.5, to map the pH adjacent to various ultramicroelectrodes undergoing electrochemical processes that lead to pH changes. The experimental fluorescence profiles, determined by CLSM, have been compared to models by solving the underlying mass transport equations, including the effect of natural convection, using the finite element method. The methodology has been validated through studies of the galvanostatic reduction of water at both disk and ring ultramicroelectrodes. The fluorescence profiles were found to be highly sensitive to both the initial bulk solution pH and applied current in a predictable fashion. The potentiostatic reduction of oxygen has been investigated at 25- and 10-microm-diameter platinum electrodes to confirm the effective number of electrons transferred in the reaction. Finally, the application of this methodology to observe defects in microelectrode arrays, particularly those that cannot be seen by optical microscopy, is described.