Capacitively coupled contactless conductivity detection (C 4 D) is presented in a progressively detailed approach. Through different levels of theoretical and practical complexity, several aspects related to this kind of detection are addressed, which should be helpful to understand the results as well as to design a detector or plan experiments. Simulations and experimental results suggest that sensitivity depends on: 1) the electrolyte co-ion and counter-ion; 2) cell geometry and its positioning; 3) operating frequency. Undesirable stray capacitance formed due to the close placement of the electrodes is of great importance to the optimization of the operating frequency and must be minimized.

Although simple equivalent circuits have been used to explain the basic functioning of a capacitively coupled contactless conductivity detector (C 4 D), more sophisticated models are required to take into account the effects of the spatial non-homogeneity of the solution conductivity as the electrophoretic zones pass inside the detector. The overshooting phenomenon observed in real electropherograms may be explained by modeling the coupling of the electrodes with the inner capillary with a network of resistors and capacitors and its dependence with the stray capacitance becomes evident. An even more detailed model of the cell based on electrostatics allows one to calculate the stray capacitances. For the typical geometries and materials, this capacitance is on the order of a few to hundreds of femtofarads. It was possible to demonstrate that the ground plane, sometimes used, reduces the capacitance, but does not eliminate it completely. Possible noise sources are also discussed. The electrode tightness minimizes a possible source of mechanical noise due to variation of the coupling capacitances. Thermal control should also be ensured; the calculations showed that a temperature fluctuation as low as 7 Â 10 À3 8C induces artifacts as high as the limit of quantification of K þ in a typical electrophoretic condition, for which the technique has one of its highest sensitivities.

A new microfabrication process based on a xerographic process is described. A laser printer is used to selectively deposit toner on a polyester film, which is subsequently laminated against another polyester film. The toner layer binds the two polyester films and allows the blank regions to become channels for microfluidics. These software-outlined channels are approximately 6 microm deep. Approximately twice this depth is obtained by laminating two printed films. The resulting devices were not significantly damaged after 24 h of exposure to aqueous solutions of H3PO4, NaOH, methanol, acetonitrile, or sodium dodecyl sulfate. Electric tests with an impedance analyzer and microchannels filled with KCl solution demonstrated that (1) wide channels suffer from deformation of the top and bottom walls due to the lamination of the polyester films and (2) the toner walls are somewhat porous. Although these drawbacks limit the maximum width of a channel and the minimum distance between two channels, the process is an attractive option to other expensive, laborious, and time-consuming methods for microchannels fabrication. The process has been used to implement devices for electrospray tip and capillary electrophoresis with contactless conductivity detection.

The use of two additional reservoirs to accommodate the electrodes of the power source is proposed to improve the stability of the running electrolyte in capillary electrophoresis. The basic idea is to use salt bridges to connect those reservoirs to the ones containing the capillary ends. Although simple, there are several issues that can be considered in the design and implementation of such system in order to prevent undesired transference of material between the electrolysis and the main reservoirs. The use of a sealed electrolysis reservoir without a gas phase, the use of materials that ensure volume stability, and the use of bridges as long as possible are three basic directions. A compromise is involved in the dimensions of the sectional area of the bridge, because a small area diminishes the amount of a species transferred by diffusion but leads to an undesirable increase of the electrical field during the electrophoretic running. Thus, a bridge composed of a main wide-bore tube connected to a small-bore capillary seems to give the best performance for practical use. A simple electrolysis-separated system was adapted to a preexisting capillary electrophoresis system, and its performance was evaluated with a mixture of tartaric, malic, and succinic acids that was separated in sodium benzoate solution (pH 5.5) using the original equipment and the modified one. Due to the water electrolysis and the small buffering capacity of the electrolyte, there was a significant pH change and consequently changes in the effective mobilities of the analytes and loss of resolution after a few runs using the original equipment. Using the electrolysis-separated system, no significant change in the migration time and resolution was observed even after 15 runs. Besides the freedom to prepare running electrolytes with electroactive species or unbuffered solution, high throughput and the use of small reservoirs, such as the ones used in microfluidic devices, are the main advantages of the system.

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