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2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0173-0835/02/2010–3520 $17.501.50/0
Electrophoresis 2002, 23, 3520–3527 High-frequency contactless conductivity detector 3521
Miniaturization
described the axial CCD implemented in microchips.
Such a circuit diagram allows a complete analysis of all The resistances Ri of an individual resistor representing
complex currents in all loops, when Cv, all Ri, Di, Ci, the the solution in the i-th segment are:
generator voltage U, and frequency f are known. The
1 ls
absolute value of the current I10 is in fact the output cur- Ri for i = 1, . . ., 59 (3)
ki pr 2in
rent of the cell sensed by the receiving electrode and pro-
cessed by the I/U converter. To perform the analysis of the Here, ki is the conductivity of the electrolyte solution in the
diagram we wrote the computer program HF_Cell. The i-th segment. The voltage of the generator is U = 50 V, the
program enables to set individually a value of any of the frequency of the generator voltage is f = 625 kHz.
Ri, Ci, Di elements. Though in Fig. 4 only nine Ri elements
and ten Ci, Di elements are depicted for simplicity, the The HF_Cell program simulates electrical behavior of the
number of segments can be arbitrary in the program, the conductivity cell where it can perform, e.g., the following
only limit is computation time and the capacity of the tasks: (i) Calculation of the calibration curve showing the
computer memory available. For all calculations pre- dependence of the cell current I60 on conductivity of a
sented in this paper we divided the cell into 60 segments, homogeneous solution in the cell. (ii) Calculation of the
which means that the number of resistors Ri is 59 and the cell current I60 if a certain conductivity profile (say a peak
number of Ci and Di capacitors is 60. The cell current pro- or a boundary) passes through the CCD. The response on
cessed by the I/U converter is then I60. Any value of the Ci, the conductivity profile will represent the spatial behavior
Di capacitors can even be set to zero at any position, of the cell.
which means that there is no capacitive coupling at such
a position. In other words, this means that there is no
electrode at such position (when Ci = 0) or no shielding 3.2 Computer simulation of the CCD
(when Di = 0). This way any spatial configuration of the
The simulation reveals the role of many parameters and
cell can be analyzed.
dimensions of the cell, such as the dimensions of the cap-
Here, we will show the application of the model for the illary, dimension of the electrodes, length of the gap be-
cylindrical format corresponding with construction of the tween electrodes, influence of the shielding in the gap,
cell 1. It has both electrodes of the same length Lc = 5 mm frequency of the generator voltage, etc. It enables to learn
and the length of the gap between electrodes is Lg = what parameters significantly influence the cell features
2.5 mm. The length of the segment is then ls = (2Lc 1 Lg)/ and, consequently, it helps to design optimally the config-
60. Diameters of the capillary are 75/360 mm ID/OD, so uration of the cell to reach the desired function. This is a
the inner radius is rin = 37.5 mm, the outer radius is rout = complex task so to demonstrate the ability of the model
180 mm. The i-th electrode segment is considered as a we will inspect a particular configuration of the cell 1 and
cylindrical concentric condenser with capacity Ci with will show and discuss influence of only several param-
the solution inside the capillary: eters.
2pe0 er ls
Ci for i = 1, . . ., 24 or i = 37, . . ., 60 (1)
ln r out ln r in
3.2.1 Influence of crosstalk between electrodes
Ci = 0 for i = 25, . . ., 36 (2)
The HF electric current sensed from the solution by the
where e0 is the permitivity of vacuum, er is the relative per- receiving electrode and processed by the I/U converter
mitivity of the silica capillary wall, e0 = 8.854610212 Fm21, is dependent on the resistivity of the electrolyte solution
er = 4.4. and has a certain phase shift to the voltage of the genera-
3524 B. Gaš et al. Electrophoresis 2002, 23, 3520–3527
Figure 9. Real electrophoretic run of the overloaded Figure 10. Real electrophoretic separation of cations with
Cs1 ion with the CCD with the cell 1. Sample: 0.5 mM the CCD with the cell 1. Sample: 10 mM Cs1 accompanied
Cs1 accompanied with K1. Sampling: hydrodynamic, with K1, Ca1, Na1. Sampling: hydrodynamic, 125 mbar.
125 mbar. Background electrolyte: 5 mM acetic acid, Background electrolyte: 10 mM acetic acid, 5 mM LiOH,
2.5 mM LiOH, pH 4.7. Capillary: 75 mm ID, 360 mm OD, pH 4.7, experimental conductivity 0 039 S/m. Other con-
total length of 80 cm, length to the detector 66 cm. Driving ditions as in Fig. 9.
voltage, 20 kV. Temperature, 307C.
We have never observed local maxima or minima (such as phoretic zones, the boundaries of which are generally
were demonstrated by, e.g., Chvojka et al. [21]) in fre- very sharp and are much thinner than the gap between
quency dependence of the detector signal in the range electrodes. All these observations support strongly a
of 100 kHz – 2 MHz. On the contrary, the results of simula- validity of the proposed model.
tion shown in Fig. 6 encouraged us to use even a higher
frequency. In our nowadays detectors equipped with the The utilization of the cell 2 in practical applications is
cell 2 we use frequency of 1.25 MHz and a gap of 1.5 mm demonstrated in another papers by us [24; Coufal et al.,
between electrodes, which gives us substantially better submitted)]. Here we will demonstrate only a sensitivity
signal/noise ratio and better axial resolution in compari- attained with the cell 1. Figure 10 shows a separation of
son with the cell 1. metal cations as detected by the CCD. One of the peaks
is a peak of cesium ions, which is introduced from a
As pointed out in Section 1, many constructions of the sample containing 10 mM Cs1 ions. Sampled amount of
axial conductivity cell described so far (e.g., in [16, 20, Cs1 ions is 130 fmol. Peak height to baseline noise ratio
22]) exhibit overshooting phenomena when a steep con- is 6:1.
ductivity profile, the width of which is less than the gap In conclusion, the proposed model of the contactless cell
between electrodes, passes the cell. It was shown by enabled us to understand influence of decisive param-
simulation (see Fig. 7) that this is an inherent feature of eters of the detector cell and make construction changes
the axial arrangement of the conductivity cell. Both con- in the design to improve its properties. This is a promising
structions of the axial conductivity cell presented here feature of the model, which becomes especially useful for
(Figs. 1 and 2) have the same behavior. Figure 9 is a con- the inspection of various configurations of the detector
ductivity record (with the cell 1) of separation of metal cell in the microchip format. There, naturally, a great vari-
cations with a peak of Cs1 ions that is intentionally over- ety of shapes and configurations of the channels and
loaded to reach a triangular peak shape with one steep electrodes comes into play, so the theoretical prediction
edge. The experimental signal has the same pattern and of the properties of the CCD can spare a substantial
exhibits exactly the same overshoots as previously calcu- amount of experimental work.
lated. Quite analogous overshooting phenomena are
encountered in records (not shown here) of isotacho- Received June 10, 2002
Electrophoresis 2002, 23, 3520–3527 High-frequency contactless conductivity detector 3527
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