On Practical Aspects of Single-Entity Electrochemical Measurements with Hot Microelectrodes.

When a 10s-100s MHz frequency alternating current (ac) waveform is applied to a disk ultramicroelectrode (UME) in an electrochemical cell, one achieves what is known as a hot microelectrode, or a hot UME. The electrical energy generates heat in an electrolyte solution surrounding the electrode, and the heat transfer leads to formation of a hot zone with the size comparable to the electrode diameter. In addition to heating, ac electrokinetic phenomena generated by the waveform include dielectrophoresis (DEP) and electrothermal fluid flow (ETF). These phenomena can be harvested to manipulate the motion of analyte species and achieve significant improvements in their single-entity electrochemical (SEE) detection. This work evaluates various microscale forces observable with hot UMEs in relation to their utility to improve the sensitivity and specificity of the SEE analysis. Considering only mild heating (with a UME temperature increase not exceeding 10 K), the sensitivity of the SEE detection of metal nanoparticles and bacterial (