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Alfred J. Baca: Quantification of Metals Released
by Metallothionein Adsorbates at Mercury Film Electrodes by Differential
Pulse Voltammetry and Electrochemical ICP-Atomic Emission Spectrometry |
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Electrodes and Cells. A schematic representation
of the homemade thin-layer electrochemical cell is shown in Figure 1a.
This design is similar to that in References [[30]] and [[32]], except
for two minor modifications. First, a 0.5-mm-diameter Ag wire was embedded
in the PEEK square block adjacent to a 6-mm-diameter glassy carbon electrode
(Bioanalytical Systems, Inc., West Lafayatte, IN). The distance between
the working and the Ag electrodes is 1.2 mm (face view of Figure 1a).
Upon polishing the glassy carbon electrode and the Ag disk, a layer of
AgCl was formed on top of the Ag disk by carefully leaving a drop of the
coating solution (Bioanalytical Systems, CF-2200) onto the Ag disk for
60 s, followed by rinsing the electrode with a copious amount of water.
The resultant quasi reference electrode was found to possess a stable
potential and was calibrated against a standard Ag/AgCl reference electrode.
The second change is that the Pt foil is not affixed onto the stainless
steel block. The contact of the Pt foil counter electrode with the stainless
steel block was made by aligning and tightening the working electrode,
the separation Teflon gasket (MF-1047, Bioanalytical System), and the Pt
foil assembly with four stainless steel screws (Figure 1a). Since the Pt
foil is not permanently attached onto the stainless steel cell block, cleaning
and replacement of it becomes easier. The choice of a specific cell design
and the valve configuration is dependent on the consideration of sample
consumption, the influence of the cell volume on the elution profile, and
the necessity of maintaining a stable cell potential. Since the present
work is concerned with protein samples, we opted to use a low-volume cell
(ca. 2 ?L) that does not contain a reference electrode compartment. The
absence of a separate electrode compartment also helps eliminate any possible
sample entrapment in dead space.
- Instruments. The combination of the homemade thin-layer
cell with an ICP-atomic emission spectrometer (ICP-AES) is described elsewhere.[30,
32] Briefly, the cell was positioned upstream of the sample introduction
system of an axially viewed ICP-AES (Spectro Analytical Instruments, Fitchburg,
MA) through a six-port rotary valve and a MicroMist nebulizer (Spectron,
Santa Barbara, CA) mounted onto a Scott-type spray chamber. A Microneb
2000 controller (CETAC Technologies), consisting of a gas displacement
pump and a module for changing the valve configuration (Figure 1b), was
used to control the carrier flow rate and the valve configuration. Throughout
this work, a flow rate of 75 ?L/min was chosen. This value is optimal in
terms of preserving the mercury film on the glassy carbon electrode and
delivering a sufficient amount of sample to the ICP-AES for reasonable
signal intensity.
Figure 1

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