Characterization of solute distribution following iontophoresis from a micropipet.

Iontophoresis uses a current to eject solution from the tip of a barrel formed from a pulled glass capillary and has been employed as a method of drug delivery for neurochemical investigations. Much attention has been devoted to resolving perhaps the greatest limitation of iontophoresis, the inability to determine the concentration of substances delivered by ejections. To further address this issue, we evaluate the properties of typical ejections such as barrel solution velocity and its relation to the ejection current using an amperometric and liquid chromatographic approach. These properties were used to predict the concentration distribution of ejected solute that was then confirmed by fluorescence microscopy. Additionally, incorporation of oppositely charged fluorophores into the barrel investigated the role of migration on the mass transport of an ejected species. Results indicate that location relative to the barrel tip is the primary influence on the distribution of ejected species. At short distances (<100 µm), advection from electroosmotic transport of the barrel solution may significantly contribute to the distribution, but this effect can be minimized through the use of low to moderate ejection currents. However, as the distance from the source increases (>100 µm), even solute ejected using high currents exhibits diffusion-limited behavior. Lastly a time-dependent theoretical model was constructed and is used with experimental fluorescent profiles to demonstrate how iontophoresis can generate near-uniform concentration distributions near the ejection source.

Submicroliter electrochemistry and spectroelectrochemistry using standard electrodes and a polymer electrolyte salt bridge.

The development of spectroscopic and electrochemical devices that can accommodate very small samples is of considerable importance to many areas of science and technology. We report here on the design and characteristics of a simple apparatus for the electrochemical and spectroelectrochemical analysis of submicroliter aqueous samples. The device is easily assembled from common laboratory materials and equipment, utilizing a bifurcated fiber-optic probe, standard disk electrodes of millimeter dimensions, and a polymer electrolyte film salt bridge to enable the analysis of nanoliter-scale sample volumes in a thin-layer configuration. Excellent performance has been demonstrated via measurements on aqueous ferricyanide solutions using sample volumes as low as 20 nL.

Easily Constructed Microscale Spectroelectrochemical Cell.

The design and performance of an easily constructed cell for microscale spectroelectrochemical analysis is described. A cation exchange polymer film, Nafion, was used as a salt bridge to provide ionic contact between a small sample well containing a coiled wire working electrode and separate, larger wells housing reference and auxiliary electrodes. The cell was evaluated using aqueous ferri/ferrocyanide as a test system and shown to be capable of relatively sensitive visible absorption measurements (path lengths on the order of millimeters) and reasonably rapid bulk electrolysis (~ 5 min) of samples in the 1 to 5 µL volume range. Minor alterations to the cell design are cited that could allow for analysis of sub-microliter volumes, rapid multi-sample analysis, and measurements in the ultraviolet spectral region.

Easily constructed spectroelectrochemical cell for batch and flow injection analyses.

The design and performance of an easily constructed spectroelectrochemical cell suitable for batch and flow injection measurements are described. The cell is fabricated from a commercially available 5-mm quartz cuvette and employs 60 ppi reticulated vitreous carbon as the working electrode, resulting in a reasonable compromise between optical sensitivity and thin-layer electrochemical behavior. The spectroelectrochemical traits of the cell in both batch and flow modes were evaluated using aqueous ferricyanide and compare favorably to those reported previously for similar cells.