Anal. Chem.
1998, 70, 563-567
Contactless Conductivity Detection for Capillary
Electrophoresis
1 nther K. Bonn
Andreas J. Zemann,* Erhard Schnell, Dietmar Volgger, and Gu
Institute of Analytical Chemistry and Radiochemistry, Leopold-Franzens-University Innsbruck, Innrain 52a,
A-6020 Innsbruck, Austria
A contactless capacitively coupled conductivity detector
for capillary electrophoresis is introduced. The detector
consists of two electrodes which are placed cylindrically
around the outer polyimide coating of the fused-silica
capillary with a detection gap of 2 mm. The electrodes
form a cylindrical capacitor, and the electric conductivity
of the solution in the gap between the electrodes is
measured. A high audio or low ultrasonic frequency for
coupling of the ac voltage is used in order to minimize
the influence of reactance of the liquid. For an improved
version of the detector, two syringe cannulas are used as
the electrodes and the capillary is simply assembled into
the tubing. This allows an easy placement of the detector
on various positions along the capillary. The limit of
detection of inorganic cations and anions is 200 ppb, as
determined for sodium and chloride, respectively.
Efficient on-column detection for capillary electrophoresis is
aggravated by the small volumes when capillaries with inner
diameters between 25 and 75 µm are used. However, ionic species
in the injection plug are being concentrated by electrostacking
while forming distinctively separated and narrow zones when an
electric field is applied. This effect also contributes to the high
separation efficiencies of the method. As a consequence, the
concentration of the solutes in the respective band zones can be
many times higher as compared to the original injection plug,
which significantly facilitates on-column detection.1
The most widely used mode of detection is UV absorptivity
detection, which requires the presence of chromophoric moieties.
However, inorganic cations and anions do not exhibit a sufficiently
high absorptivity to be detected by UV absorption at low
concentration levels. As a consequence, indirect photometric and
fluorometric UV detection modes have been introduced.2-18
* Corresponding author: (Tel) +43-512-507-5180; (Fax) +43-512-507-
2965; (e-mail) andreas.zemann@uibk.ac.at.
(1) Jandik, P.; Bonn, G. Capillary Electrophoresis of Small Molecules and Ions;
VCH Publishers: New York, 1993; p 118ff.
(2) Yeung, E. S. Acc. Chem. Res. 1989, 22, 125.
(3) Kuhr, W. G.; Yeung, E. S. Anal. Chem. 1988, 60, 2642.
(4) Gross, L.; Yeung, E. S. J. Chromatogr. 1989, 480, 169.
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(6) Yeung, E. S.; Kuhr, W. G. Anal. Chem. 1991, 63, 275A.
(7) Vorndran, A. E.; Oefner, P. J.; Scherz, H.; Bonn, G. K. Chromatographia
1992, 33, 163.
(8) Beck, W.; Engelhardt, H. Chromatographia 1992, 33, 313.
(9) Bächmann, K.; Haumann, I.; Groh, T. Fresenius J. Anal. Chem. 1992, 343,
901.
S0003-2700(97)00759-2 CCC: $15.00 © 1998 American Chemical Society
Published on Web 02/01/1998
Another possibility to specifically detect ionic species with a
high equivalent conductivity is to measure the differences in
conductivity of the solute zones and the separation electrolyte.
By using separation electrolytes with a low conductivity, a sensitive
detection is thus possible. Several devices have been described
that use direct conductivity detection for cations and anions. The
detection can be accomplished either by a direct contact of the
solution with the electrodes19-26 or by contactless methods which
require inductively or capacitively coupled devices using high
frequencies.27-35 Most of these instruments were originally
intended to work for chromatographic and isotachophoretic
purposes; however, on principle they could be used for capillary
electrophoresis as well.
A certain drawback of instruments working with conductivity
detection measured by direct contact of electrodes and sample
are the high instrument costs, as the capillary has to be modified
to a specific extent and a rather complicated geometry and
(10) Bächmann, K.; Boden, J.; Haumann, I. J. Chromatogr. 1992, 626, 259.
(11) Xue, Y.; Yeung, E. S. Anal. Chem. 1993, 65, 2923.
(12) Shamsi, S. A.; Danielson, N. D. Anal. Chem. 1994, 66, 3757.
(13) Buchberger, W.; Cousins, S. M.; Haddad, P. R. Trends Anal. Chem. 1994,
13, 313.
(14) Shamsi, S. A.; Danielson, N. D. Anal. Chem. 1995, 67, 4210.
(15) Salimi-Moosavi, H.; Cassidy, R. M. Anal. Chem. 1995, 67, 1067.
(16) Desbene, P. L.; Morin, C. J.; Monvernay, A. M. D.; Groult, R. S. J.
Chromatogr., A 1995, 689, 135.
(17) Collet, J.; Gareil, P. J. Chromatogr., A 1995, 716, 115.
(18) Weston, A.; Brown, P. R.; Jandik, P.; Heckenberg, A. L.; Jones, W. R. J.
Chromatogr. 1992, 608, 395.
(19) Huang, X.; Pang, T. K. J.; Gordon, M. J.; Zare, R. N. Anal. Chem. 1987, 59,
2747.
(20) Harrold, M.; Stillian, J.; Bao, L.; Rocklin, R.; Avdalovic, N. J. Chromatogr., A
1995, 717, 371.
(21) Avdalovic, N.; Pohl, C. A.; Rocklin, R.; Stillian, J. Anal. Chem. 1993, 65,
1470.
(22) Huang, X.; Luckey, J. A.; Gordon, M. J.; Zare, R. N. Anal. Chem. 1989, 61,
766.
(23) Huang, X.; Zare, R. N.; Sloss, S.; Ewing, A. G. Anal. Chem. 1991, 63, 189.
(24) Huang, X.; Zare, R. N. Anal. Chem. 1991, 63, 2193.
(25) Avdalovic, N.; Pohl, C. A.; Rocklin, R. D.; Stillian, J. R. Anal. Chem. 1993,
65, 1470.
(26) Haber, C.; Jones, W. R.; Soglia, J.; Surve, M. A.; McGlynn, M.; Caplan, A.;
Reineck, J. R.; Krstanovic, C. J. Capillary Electrophor. 1996, 3, 1.
(27) Alder, J. F.; Drew, P. K. P. Anal. Chim. Acta 1979, 110, 325.
(28) Müller, D.; Jelinek, I.; Opekar, F.; Stulik, K. Electroanalysis 1996, 8, 722.
(29) Pal, F.; Pungor, E.; Kovats, E. Anal. Chem. 1988, 60, 2254.
(30) Alder, J. F.; Drew, P. K. P. Anal. Chim. Acta 1979, 110, 325.
(31) Gas, B.; Demjanenko, M.; Vacik, J. J. Chromatogr. 1980, 192, 253.
(32) Everaerts, F. M.; Rommers, P. J. J. Chromatogr. 1974, 91, 809.
(33) Vacik, J.; Zuska, J.; Muselasova, I. J. Chromatogr. 1985, 320, 233.
(34) Decristoforo, G. Thesis, University of Innsbruck, 1979.
(35) Schnell, E.; Zemann, A. J.; Volgger, D.; Bonn, G. K. Patent pending (No.
A1016/97), 1997.
Analytical Chemistry, Vol. 70, No. 3, February 1, 1998 563
construction is required. Furthermore, changes in the cell
geometry can be considered disadvantageously.28 As a conse-
quence, for capillary electrophoresis purposes, a detector without
galvanic connection of solutes and electrodes with, at the same
time, equal sensitivity as compared to a directly connected
conductivity detector is a certain demand.
An oscillometric detector for ion chromatography has already
been described with electrodes being separated from the elec-
trolyte by a silicon lacquer or Teflon coating.29 This device enables
a better reproducibility and stability than detectors with a galvanic
contact. Generally, with detectors using a high-frequency volt-
age29,31,34 a signal resulting from both ohmic resistance and
reactance of the liquid is recorded. Inductively coupled contact-
less conductivity detectors have been described as well.27,30
Figure 1. Schematic drawing of the capacitively coupled conductiv-
Several attempts have been made to use contactless conductiv-
ity detector (CCCD). The electrodes are made of either a conducting
ity detection for capillary isotachophoretic purposes. Instruments silver varnish or of metallic syringe cannulas with the capillary
consisting of an arrangement of four electrodes placed outside assembled through.
the PTFE capillary have been described which use a high-
frequency voltage.32,33 Polarization of the measuring electrodes
or undesirable redox reactions are thus prevented. The applica- to the power supply, an RFI line filter was used in order to avoid
tion of conductivity detection in isotachophoresis is described in noise from impulses and spikes.
detail in various books on isotachophoresis.36-38
The present paper describes the application of a capacitively RESULTS AND DISCUSSION
coupled conductivity detection system (CCCD) which works on The conductivity detector described in this paper works on a
a contactless basis for the detection of cationic and anionic contactless basis. It is used in connection with a commercial
compounds after capillary electrophoretic separation. capillary electrophoresis instrument (Waters Quanta 4000) which
enables free handling and accessibility of the capillary along almost
its complete length. Among other advantages, this system enables
EXPERIMENTAL SECTION
an arbitrary placement of the detector as no capillary cartridge is
Instrumentation. A Quanta 4000 capillary electrophoresis
used. Virtually any effective separation length can be adjusted
system (Waters Chromatography, Milford, MA) connected with
without the need of removing the polyimide coating which is
an AD changer (System Interface Module, Waters) and a personal
necessary for on-column UV detection. Thus, fragile detection
computer was used. Data acquisition and processing was carried
windows are avoided and the risk of breaking the capillary during
out with a commercial chromatography software (Maxima 820,
handling is reduced.
Waters). Fused-silica capillaries (Composite Metal Services,
Figure 1 depicts a schematic drawing of the CCCD. Two
Worchester, U.K.) with an inner diameter of 50 µm and an outer
cylindrical conducting surfaces (electrodes) are placed around the
diameter of 375 µm were used. Sample injection was carried out
polyimide coating on the outside of an uncoated fused-silica
hydrostatically at an elevation of 10 cm.
capillary. The electrodes can be made either of a conducting silver
Reagents. All reagents were of analytical grade (Sigma-
varnish which is painted around the polyimide coating of the
Aldrich Handels-Ges.m.b.H, Vienna, Austria, and Merck GmbH,
capillary or of two syringe cannulas with the appropriate length
Vienna, Austria). Standard and buffer solutions were prepared
where the capillary is passed through.
by dissolving the respective compounds in ultrapure water
For experimental testing of the detector, 30 mm was chosen
(Barnstead/Thermolyne, Dubuque, IA).
as the length of each of the electrodes. This length can be varied
Electronic Parts. The contactless detection device was built
from 15 to 50 mm, which then, as a consequence, requires
from electronic components which were purchased from local
different amplification to obtain equal signal intensities. In fact,
electronic dealers. Two directly coupled transistors (BC 414),
changing the length of the electrodes has only little effect. An
which are connected to a potentiometer (100 kΩ) and an
increase of length to 50 mm renders only slightly differing
integrated circuit (U420B), were used for amplification. The
electropherograms in terms of sensitivity. For shorter electrodes,
rectification was performed using two diodes (BA4148). The
however, the respective amplification has to be increased which,
frequency generator that is suitable for a frequency of 40 kHz
at this time with the components used in this system, causes the
sinus was built from an LC oscillator circuit with a transistor (BC
signal-to-noise (S/N) ratio to become worse. The electrodes are
337). The 20-kHz rectangular form frequency generator was made
connected to an oscillator through a resistor with a resistance of
from an integrated circuit (Telefunken NE 555). The dc voltage
50 kΩ. Together with the reactance of the shielded cable
for the amplifier was stabilized to 9 V. For the mains connection
connection to the detector and the input resistance of the amplifier,
(36) Everaerts, F. M.; Beckers, J. L.; Verheggen, Th. P. E. M. Isotachophoresis: a resistance R of approximately 10 kΩ is formed. A voltage drop
Theory, Instrumentation and Application; J. Chromatogr. Library Vol. 6; of 0.2-2 mV is observed along resistance R, which is then
Elsevier: Amsterdam, 1976. amplified and rectified to direct current. The employed amplifier
(37) Everaerts, F. M. Analytical Isotachophoresis; Elsevier: Amsterdam, 1981.
(38) Bocek, P.; Deml, M.; Gebauer, P.; Dolnik, V. In Analytical Isotachophoresis; has a variable amplification of 500-1500-fold. After rectification,
Radola, B. J., Ed.; VCH Publishers: Weinheim-Basel, 1988. a direct voltage of 0.1-0.5 V is fed in the input of the AD changer
564 Analytical Chemistry, Vol. 70, No. 3, February 1, 1998
which itself is part of the data acquisition and processing system.
However, any conventional integrator or other AD changer can
be used for this purpose.
A detection gap between the two electrodes of 2 mm is chosen,
which can be increased to 5 mm, depending on the length of the
capillary and the required separation efficiency. A distance of
approximately 2 mm is sufficiently long with respect to important
separation parameters such as resolution and separation efficiency.
If the detection gap is too narrow, a capacitive transfer between
the electrodes may occur. As a consequence, if resolution
between specific solute zones is too low, it is advisable to increase
the capillary length instead of narrowing the detection gap.
The detection device described in this paper differs significantly
from other contactless conductivity detectors for isotachophoresis
or capillary electrophoresis purposes. Most of the other contact-
less conductivity detectors measure the signal radially across the
capillary, a principle that suffers from the very short path lengths.
Furthermore, the use of a low frequency bears several advantages
when compared to high-frequency conductivity detectors. In
addition to the ohmic resistance, a considerable dielectric con-
tribution of the reactance can also be assumed when high
frequencies are used. As a consequence, whenever the liquid
inside of one of the electrodes changes its dielectric properties,
which is likely when sample component zones are passing
through, a shift of the baseline would be detected before and after
the actual signal. Thus, comparable results with galvanically Figure 2. Separation of a standard mixture of inorganic cations
coupled detectors should be obtained in terms of relative signal comparing UV and conductivity detection. Conditions: fused-silica
intensities when low frequencies are used as primarily the ohmic capillary, L ) 60 cm, l1 ) 40 cm to conductivity detector, l2 ) 52.5
cm to UV detector (214 nm), U ) +20 kV, I ) 3.0 µA, and T ) 23
resistance along the detection gap is responsible for the signal. A
°C; electrolyte, 10 mM lactic acid, 8 mM 4-methylbenzylamine, and
frequency of 40 kHz sinus form or 20-30 kHz rectangular form 15% methanol, pH 4.9; injection, 30 s; sample concentration, 0.1 mM.
is used to keep the influence of reactance considerably low. With
the long cylindrical electrodes used in this investigation, this
frequency range works well with voltage amplitudes of 7-10 Vpp, the resistors are connected in series, this causes the voltage of
preferably with 8 Vpp. A higher oscillator voltage may improve all the other resistors to change significantly. As a consequence,
the S/N ratio to a certain extent, however, due to the limitations a voltage increase can be measured on resistance R. After
of the components and parts that build up the present detection amplification and rectification, the signal is fed into the AD
device, a significant improvement of the sensitivity is not achieved. changer.
The voltage drop on resistance R is below 1 mV. Thus, the The applicability of the developed device for capillary electro-
detector and all the connections have to be shielded to ground. phoretic purposes can be demonstrated for the detection of
In order to measure the differences of the conductivity between inorganic cations and anions. A comparison of the contactless
conductivity detection method with indirect UV detection provides
the electrolyte and the separated ions, an electric zero point
satisfactory results in terms of sensitivity as depicted in Figure 2.
depression is recommended as is found in any other instruments
The buffer consists of lactic acid, 4-methylbenzylamine, and
using direct conductivity with galvanically connected electrodes
methanol at a pH of 4.9. This system was originally introduced
or UV detection.
for indirect UV detection of cations.39 A 5-fold amplification of
The detector presents a series connection of two capacitors
the UV signal is necessary to achieve comparable peak heights
and two resistors. The electrodes serve as two independent
at given system settings.
cylindrical capacitors with the liquid inside the capillary being the
However, for practical purposes, a detector considered easy
corresponding internal wire. The detection gap between the
to use has to meet several basic requirements. Handling and
electrodes acts as one of the resistors and resistance R as the
mounting of the detection electrodes should be as easy as possible
other. A reactance between 2 and 4 MΩ at a frequency of 40
with only little pretreatment and modifications of the capillary.
kHz is calculated by assuming cylindrical capacitors. Using a
Although painting of silver conducting varnish on the outside of
buffer electrolyte with a low conductivity, the resistance of the
the capillary is both an inexpensive and easy pretreatment
liquid inside the capillary from the inlet to the outlet end is in the
procedure, the electrodes were subject to further improvement
range of several gigaohms. Thus, the electrolyte in the detection
of the detector. Two metallic syringe cannulas with an inner
gap between the electrodes, which measures approximately 0.3%
diameter slightly larger than the outside diameter of the silica
of the total capillary length, exhibits a resistance in the megaohm
capillary were cut to the appropriate length and used as electrodes.
range. If an ionic solute zone passes through the detection gap,
the resistance decreases due to the increasing conductivity. As (39) Shi, Y.; Fritz, J. S. J. Chromatogr. 1993, 640, 473.

Analytical Chemistry, Vol. 70, No. 3, February 1, 1998 565

Figure 3. Separation of a standard mixture of inorganic cations
using conductivity detection. Conditions: fused-silica capillary, L )
58 cm, l ) 45 cm to conductivity detector, U ) +20 kV, I ) 3.9 µA,
and T ) 24 °C; electrolyte, 20 mM MES and 20 mM histidine, pH 6;
injection, 10 s; sample concentration, 10 ppm.
Thus, the fused-silica capillary can be simply passed through the
tubes. The sensitivity of the signals obtained from the flexible
detector is only slightly inferior as compared to the fixed varnish
detector. This is due to the fact that a small gap of air between
the polyimide coating of the capillary and the metal tubing
increases the dielectric volume between the electrodes.
This arrangement generally exhibits some significant advan-
tages over detection systems based on photometric absorptivity
or end-capillary conductivity detection. For example, more than
one conductivity detector can be easily and reversibly placed at
any position along the capillary without the need of removing the
polyimide coating with the danger of breaking. This is useful,
for example, if kinetic phenomena are investigated or if the
effective separation length has to be optimized. With the
described detection device a simultaneous UV detection is also
possible.
In Figure 3, the electropherogram of seven inorganic cations
using a low-conductivity electrolyte consisting of 20 mM 2-(N-
morpholino)ethanesulfonic acid (MES) and 20 mM histidine at
pH 6 recorded with a flexible on-column conductivity detector is
shown. A sample concentration of 10 ppm was chosen with an
injection time of 10 s. A different amplification was used for the
experiments with the flexible detector as compared to Figure 2
which results in increased signal heights.
The conductivity detector is not only suitable for the detection
of cations but also for inorganic anions. Figure 4 shows the
separation of a mixture of inorganic anions at a concentration of
10 ppm with a buffer system consisting of 20 mM MES and 20
566 Analytical Chemistry, Vol. 70, No. 3, February 1, 1998
Figure 4. Separation of a standard mixture of inorganic anions using
conductivity detection. Conditions: fused-silica capillary, L ) 70 cm,
l ) 57 cm to conductivity detector, U ) -25 kV, I ) 3.9 µA, and T )
24 °C; electrolyte, 20 mM MES, 20 mM histidine, and 0.0001%
hexadimethrine bromide, pH 6; injection, 10 s.; sample concentration,
10 ppm.
mM histidine at pH 6. In order to reverse the electroosmotic flow
(EOF) direction, a polycationic surfactant was added to the
separation electrolyte (hexadimethrine bromide; HDB).40-43 As
the EOF modifier is required only in nanomolar to micromolar
concentrations, a significant contribution of this additional ionic
buffer component to the background conductivity of the separation
electrolyte is not observed. This is advantageous compared to
other dynamic EOF modifiers such as the commonly used
alkyltrimethylammonium-based modifiers that have to be used at
concentrations in the millimolar range, which significantly in-
creases the background conductivity.
The limit of detection for the flexible conductivity detector is
200 ppb (S/N ) 3) for cations and anions as determined for
sodium and chloride, respectively, with the MES-histidine
system. For both species, a linear range of more than 3 orders
of magnitude from 0.5 to more than 1000 ppm with a coefficient
of correlation superior than 0.9995 (nine concentrations measured
three times each) was obtained. An exact determination of the
high end of the linear range was not carried out due to the high
peak asymmetry at concentrations above 500 ppm where a
separation of components is difficult, anyhow. Limits of detection
and the linear range for quantitative analysis also depend on the
(40) Masselter, S. M.; Zemann, A. J. Anal. Chem. 1995, 67, 1047.
(41) Zemann, A. J. J. Capillary Electrophor. 1995, 2, 131.
(42) Volgger, D.; Zemann, A. J.; Bonn, G. K.; Antal, M. J., Jr. J. Chromatogr., A
1997, 758, 263.
(43) Zemann, A. J.; Volgger, D. Anal. Chem. 1997, 69, 3243.
buffer system as well as on the linearity of the diode rectifier. It
has to be emphasized that not only inorganic ions but also organic
ions can be detected by conductivity detection. However, limits
of detection for organic ions are inferior compared to inorganic
species because of the considerably lower ionic equivalent
conductivities.
The S/N ratio could be further reduced by using better
components for the amplifier. Baseline noise is presumably due
to the homemade amplifier, which consists of simple electronic
components as described in the Experimental Section. Despite
the fact that all connections to the detector were well screened
and both detector and amplifier are shielded to ground, a
considerable part of the noise is caused by components of the
device, such as the high-voltage generator of the CE system and
the AD changer.
For future work, better electronic components and shielding
are required to further lower the limits of detection. Furthermore,
for specific purposes, an optimization of the buffer composition
will also be necessary to increase resolution and separation
efficiency.
CONCLUSION
Contactless capacitively coupled conductivity detection is a
suitable detection method for inorganic anions and cations in
capillary electrophoresis. Placement of the capillary into two metal
tubings, which act as two cylindrical capacitors, allows a fast and
easy-to-use adjustment of the detector on virtually any position
along the capillary. The changes of the electric conductivity in
the capillary inside the gap between the electrodes are measured,
and by this means, inorganic cations as well as anions can be
detected. Detection limits are in the range of 200 ppb for both
cations and anions. By improving the electronic components, a
further reduction of detection limits is likely. As the device works
contactlessly, any cleaning or flushing of the detection cell is not
necessary and it can be easily used without modification of the
geometry of the capillary or of the polyimide coating.
ACKNOWLEDGMENT
The authors dedicate this paper to Prof. Karl-Eberhard
Schwarzhans on the occasion of his sixtieth birthday. Thanks to
Karl Mayrhofer for experimental help, Dr. Günter Grienberger
for fruitful discussions, and DI Friedrich Neumann for advices
on the construction of the homemade amplifier and rectifier.
Further information on the electronic details of the amplifier and
the mechanical construction of the detector is available on request
from Prof. Erhard Schnell via the corresponding author.
Received for review July 15, 1997. Accepted October 30,
1997.X
AC9707592
X
Abstract published in Advance ACS Abstracts, December 15, 1997.
Analytical Chemistry, Vol. 70, No. 3, February 1, 1998 567