Combining a Commercial Mixer with a Wall-Tube Electrode Allows the Arbitrary Control of Concentrations in Protein Film Electrochemistry.

Protein film electrochemistry is a technique in which an enzyme is immobilized on an electrode in a configuration that allows following the changes in turnover frequency as a response to changes in the experimental conditions. Insights into the reactivity of the enzyme can be obtained by quantitatively modeling such responses. As a consequence, the more the technique allows flexibility in changing conditions, the more useful it becomes. The most commonly used setup, based on the rotating disc electrode, allows easy stepwise increases in the concentration of nongaseous substrates, or exposure to constant concentration of dissolved gas, but does not permit to easily decrease the concentration of nongaseous substrates, or to change the concentration of dissolved gas in a stepwise fashion. To overcome the limitation by mass transport of the substrate toward the electrode when working with fast enzymes, we have designed another kind of electrochemical cell based on the wall-tube electrode (WTE). We demonstrate here that by using a system combining two syringe pumps, a commercial mixer, and the WTE, it is possible to change the concentration of species in a stepwise fashion in all directions, opening new possibilities to study redox enzymes. As a proof of concept, this device was applied to the study of the electrochemical response of the cytochrome c nitrite reductase of Desulfovibrio desulfuricans.

A new electrochemical cell with a uniformly accessible electrode to study fast catalytic reactions.

The electrochemical study of fast catalytic reactions is limited by mass transport when using the conventional electrochemical cell with a rotating disk electrode (RDE). To overcome this issue, it is important to find a new device with improved transport properties that respects electrochemical constraints. We used numerical simulations of computational fluid dynamics to design a new electrochemical cell based on the so-called "jet flow" design for the kinetic studies of catalytic chemical reactions at the surface of an electrode. The new cell is characterized by a high, reliable and uniform mass transport over the electroactive part of its surface. We investigated the effects of the nozzle and the electrode diameters, the nozzle-electrode distance and the Reynolds number on the performance of the jet-electrode in the flow system. Through the optimization of the geometry of this jet electrode cell, we achieved a factor of 3 enhancement in transport compared to the rotating disk electrode. We succeeded in constructing the designed electrode, characterized it with electrochemical techniques, and found an excellent agreement between the transport properties deduced from the numerical simulations and those from the measurements.