AMPEROMETRY

Amperometry in chemistry is detection of ions in a solution based on electric current or changes in

electric current.

Amperometry is used in electrophysiology to study vesicle release events using a carbon fiber electrode.
Unlike patch clamp techniques, the electrode used for amperometry is not inserted into or attached to
the cell, but brought in close proximity of the cell. The measurements from the electrode originate from
an oxidizing reaction of a vesicle cargo released into the medium. Another technique used to measure
vesicle release is capacitive measurements.

Analysis and Detection by Capillary Electrophoresis

Amperometry is the measurement of the resulting current after a constant potential is applied to the
working electrode. A reference and auxiliary electrodes are also present. In some cases, only a working
and an auxiliary electrode may be employed in a two-electrode configuration [64]. Amperometry has
the advantage of generally good detection limits but is restricted to electroactive species. Selectivity is
achieved through a judicious choice of the detection potential, with the optimal detection potential
normally being determined by hydrodynamic voltammetry. It is the most widely reported
electrochemical method for conventional CE, and a number of research groups have recently reported
its implementation for microchannel-based separations. The designs described in Section 5.2.3 use
amperometry as detection mode, and several will be mentioned later in section 14.3 of this chapter.
Therefore, only the most important amperometric detection advances incorporated into CE–ED
microchips will be described below.

SV employs a large amplitude sine wave as the excitation waveform. The resulting faradic current
response is non-linear and contains both the signal components at the excitation frequency and the
harmonics. The charging current associated with scanning the electrochemical double layer, which is the
major background component, is primarily linear, and therefore resides predominantly at the excitation
frequency. There is an increase in the discrimination between signal and background at the higher
harmonics, resulting in greater sensitivity and selectivity of the amperometric response. Hebert and co-
workers [72] have reported an interesting contribution employing SV on microchip detection. Recently,
the same authors have reported on a comprehensive direct comparison between constant potential
amperometry and SV using microchip platforms [73]. SV was found to be more sensitive (nM) than
constant potential amperometry (μM) for the neurotransmitters studied (dopamine, isoproterenol and l-
dopa). Applied SV using a pyrolyzed photoresist carbon film has also been described [71].