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Electrochemical artifacts originating from nanoparticle

Cite this: Lab Chip, 2014, 14, 602
Received 6th September 2013,
Accepted 7th November 2013
DOI: 10.1039/c3lc51029h
www.rsc.org/loc
contamination by Ag/AgCl quasi-reference electrodes†
Alexey Yakushenko,a Dirk Mayer,a Johan Buitenhuis,b Andreas Offenhäusserac
and Bernhard Wolfrum*ac
Electrochemical techniques rely on the stability of a defined reference potential. Due to the need for
miniaturization, electrochemical lab-on-a-chip platforms often employ Ag/AgCl quasi-reference electrodes
for this purpose. Here, we report on electrochemical artifacts resulting from nanoparticle–electrode
collisions originating from standard chlorinated silver wires.

Introduction electrodes are made in different forms, for example, as

Electrochemical techniques have been widely used in the
lab-on-a-chip community for biosensing applications.1–10 The
range of electrochemical methods applied for chip-based
devices is very broad and a significant number of investiga-
tions focus on electrochemical impedance spectroscopy,
cyclic voltammetry, and amperometry. All these techniques
usually employ either three-electrode (working, reference,
and counter electrode) or two-electrode (working and
combined reference and counter electrode) configurations.
The most commonly used reference electrodes in the biosensor
community are Ag/AgCl electrodes. In a conventional Ag/AgCl
microelectrode, the Ag/AgCl wire is usually isolated from the
solution by a nanoporous ceramic or glass frit and kept in a
KCl solution of defined concentration. Owing to the frit, large
molecules or ions cannot pass through this barrier, which
establishes an ohmic contact between the reference electrode
and the sample solution, restricting chemical exchange.
However, quite often, the so called quasi- or pseudo-reference
electrodes are used for on-chip biosensors due to convenience
and the need for miniaturization.11–14 Unlike conventional
Ag/AgCl reference electrodes, these electrodes are not isolated
from the sample solution and, therefore, present certain
disadvantages regarding potential stability. Quasi-reference
a
Institute of Bioelectronics (PGI-8/ICS-8) and JARA—Fundamentals of Future
Information Technology, Forschungszentrum Jülich, 52425 Jülich, Germany.
E-mail: b.wolfrum@fz-juelich.de; Fax: +49 2461 61 8733; Tel: +49 2461 61 3285
b
Institute of Complex Systems (ICS-3), Forschungszentrum Jülich,
52425 Jülich, Germany
c
IV. Institute of Physics, RWTH Aachen University, 52074 Aachen, Germany
† Electronic supplementary information (ESI) available: Amperograms of
uncontaminated MEAs; ICP-MS analysis of a liquid sample from a MEA
exposed to an Ag/AgCl wire, EDX analyses of a MEA exposed to an Ag/AgCl wire
and of an uncontaminated MEA; DLS measurements of a liquid sample
exposed to an Ag/AgCl wire. See DOI: 10.1039/c3lc51029h
pressed Ag/AgCl pellets, chlorinated silver wires (widely used
in electrophysiology), and on-chip Ag/AgCl reference electrodes
fabricated via chlorination of silver15–18 or printable Ag/AgCl
pastes.19–21 Their small size and the possibility of on-chip
integration in microfluidic devices render them perfect
candidates for reference electrodes in lab-on-a-chip biosensor
or μTAS platforms.
For example, extracellular potential changes, caused by
action-potential generation in cells, have been measured on the
working electrodes vs. the quasi-stable potential of the refer-
ence electrodes.22–24 Small potential drifts over longer times,
associated with quasi-reference electrodes, thus, do not
significantly affect the results of such experiments, as the
signals are rapid compared to drift with much longer time-
scales. Nevertheless, the electrochemical properties of the
electrode material and its chemical reactivity may play a
significant role in the shape of acquired voltage signals.25 As
opposed to electrophysiological voltage measurements,
electrochemical experiments require the measurement of
faradaic currents. These can result from electron transfer
caused by redox-active enzymatic reactions or direct oxidation
or reduction of chemical or biochemical molecules at the
electrode. To actually oxidize or reduce the molecule of
interest, the working electrode has to be biased to a certain
potential higher or lower than the redox potential of that
molecule, respectively. This, in turn, leads to oxidation or
reduction of all species having redox potentials in this
range, which eventually contribute to the overall current.
Electrochemical signals may manifest over a broad range of
timescales. Sometimes, very rapid signals are detected in
real time, which last for only several milliseconds or less.
Release of redox active neurotransmitters from synaptic or
dense core vesicles is one such example. On-chip detection
of dopamine release via oxidative faradaic currents showed
electrochemical spikes with a duration of less than 1 ms.26

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Lab on a Chip
Hence, real cellular signals may be compromised by interfering
electrochemical events having similar temporal features.
In this work, we report on a phenomenon associated with
the use of Ag/AgCl quasi-reference electrodes, which, as we
have observed, can interfere with the electrochemical measure-
ments and cause non-negligible artifacts. The artifacts are
attributed to the redox reactions and adsorption/desorption
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processes of Ag/AgCl residues of quasi-reference electrodes that
dissolve in solution on top of a microelectrode array chip.
Having performed a range of investigative experiments, we
come to a conclusion that these signals come from direct
oxidation/reduction of Ag/Ag+ nanoparticles at the microelectrodes.
Experimental
Microelectrode arrays (MEAs)
In the present study, we used previously described micro-
electrode arrays (MEAs).26 The working microelectrodes
were made of either Pt or Au (150 nm). The whole chip was
passivated with a stack of five alternating SiO2 and Si3N4 layers
(200 nm/100 nm, respectively). There were 64 individually
addressable electrodes on every chip (see Fig. 1). Electrode
radii were identical on the same chip (apart from two large
electrodes with a radius of 75 μm) but varied between different
chips (from 1.5 to 10 μm). Typically, we use these microelec-
trode arrays (MEAs) to detect the release of neurotransmitters
from dopaminergic cells growing on the chip using either
amperometry or fast scan cyclic voltammetry (FSCV).
Electrochemical experiments
Cyclic voltammetry (CV) experiments were conducted in a
3-electrode configuration using a platinum counter electrode
CHI 1030B potentiostat (CH Instruments Inc., Austin, TX).
The experiments were performed in phosphate buffer saline
(PBS) and a platinum counter electrode was used in all
CV experiments. Quasi-reference electrodes were prepared
using standard electrochemical chlorination.27–29 Briefly, a
silver wire (Ø 0.008′′, A-M Systems, Sequim, WA) was
immersed in a 1 M HCl solution applying a potential of
Fig. 1 64-channel microelectrode array. A.) MEA with a reservoir
formed by a glass ring (20/5/1 mm: diameter/height/thickness) glued
on top of the chip. B.) Zoom into the active electrode area with
62 microelectrodes of 12 μm diameter and 2 larger electrodes of
150 μm diameter.
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+1.5 V vs. a Pt counter electrode for 60 s and then washed
thoroughly with deionized water.
Amperometric experiments were performed to detect
oxidation/reduction events of Ag/Ag+ nanoparticles upon
impact with the MEA microelectrode surface over time. For
parallel measurements across all 64 microelectrodes at high
temporal resolution, we used a low-noise current amplifier
system, PicoAmp64.26 Measurements were conducted on
chips that had not been previously exposed to an Ag/AgCl
electrode. The potential of the working electrode was
switched every 10 s between reducing (−0.3 V) and oxidizing
(+0.6 V) potentials. A piece of chlorinated silver wire was
placed into the reservoir on top of the MEA, and the testing
protocol was repeated several times.
Inductively coupled plasma mass spectroscopy (ICP-MS)
In ICP-MS experiment, 1 mL of PBS solution was placed on
a MEA chip previously exposed to an Ag/AgCl wire. After 24 h
incubation, the liquid was withdrawn from the chip and
subjected to ICP-MS analysis (ELAN 6100, PerkinElmer Inc.,
Waltham, MA) for the detection of metal residues in the
solution.
Scanning electron microcopy (SEM) with energy-dispersive
X-ray spectroscopy (EDX)
SEM images were taken with a Magellan XHR scanning elec-
tron microscope (FEI, Hillsboro, OR) equipped with an EDX
detector. Voltage and current were set to 20 kV and 0.4 nA,
respectively.
Dynamic light scattering (DLS) measurements
Dynamic light scattering measurements were performed on
an ALV/CGS-8F goniometer system with a 632.8 nm HeNe
laser and an ALV-5000 multiple tau digital correlator (ALV,
Langen, Germany) at 25 °C. Samples were prepared by soni-
cating a chlorinated silver wire in PBS solution, after which
they were filtered through a syringe filter with a 5 μm average
pore size. Measurements were performed for scattering
angles from 30 to 150 degrees in steps of 15 degrees with a
measurement time of 150 s per angle. Contin fits were
performed using the standard ALV software. Note that con-
sidering the irregular shape of the particles (as observed in
SEM), the average radius given here is only a rough estimate,
because the analysis assumes spherical particles and, further-
more, the average value of the radius is the scattering inten-
sity weighted averaged radius.
Results and discussion
In CV experiments, the potential was swept at a rate of 50 mV s−1
from −0.3 V to +0.6 V, first in positive direction and back.
Fig. 2 shows two cyclic voltammograms on one of the MEA
microelectrodes with a commercial Ag/AgCl reference elect-
rode (RE-6, BASi, Kenilworth, United Kingdom) (Fig. 2A) and
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then with an Ag/AgCl wire as a quasi-reference electrode
(Fig. 2B).
Before exposure to the chlorinated silver wire, using a com-
mercial conventional Ag/AgCl reference electrode, a clean
voltammogram was obtained (Fig. 2A). There were no faradaic
peaks or other peaks suggesting adsorption/desorption effects,
and only the capacitive current due to the electrode–electrolyte
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interface and the onset of oxygen reduction are present. After
the chips were exposed to the chlorinated silver wire by using it
as a quasi-reference electrode or by just placing it into the solu-
tion on the chip, clear peaks manifested on the voltammograms.
Different types of reference electrodes were tested in the study,
yet the strongest artifacts were observed when using chlori-
nated silver wire quasi-reference electrodes. As can be seen in
Fig. 2B, there is a distinct sharp peak at +112 mV on the
forward scan and a wider peak on the backward scan covering
potentials from +87 mV down to −26 mV. The forward scan
peak reached amplitudes of up to 0.8 nA, whereas the back-
ward peak had amplitudes of around 0.1 nA. We performed
the experiments with approximately 20 chips and reference
electrodes and observed peak locations during the forward
scan distributed from +67 mV to +130 mV. While the peaks on
the forward scan had a prominent sharp form, peaks on the
backward scan were broader and presented their highest ampli-
tude in the potential range from +42 mV to −94 mV. We varied
the sweep rates in the CV experiments from 50 mV s−1 to 200 V s−1
and observed a linear increase in the peak's charge as a func-
tion of sweep rate (1.32 ± 0.13 pC V−1 s−1). This suggests that
the measured charge consists not only of the faradaic currents
due to oxidation of steadily adsorbed silver atoms/ions.
To further investigate this phenomenon, we recorded
amperometric traces monitoring the contamination process
over time. Approximately 1 min after placing the wire inside
the MEA chip and initiating the amperometric protocol, a
few characteristic peaks during the cathodic phase were
clearly observed in the trace. After several minutes, the peaks
Fig. 2 Cyclic voltammograms on a single MEA microelectrode and a
proposed chemical equation taking place at the peaks. A.) Cyclic
voltammogram measured with a commercial conventional Ag/AgCl
reference electrode. B.) Cyclic voltammogram measured with a
chlorinated silver wire as a quasi-reference electrode. Scan rate 50 mV s−1.
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appeared on almost all 64 channels of the MEA. Fig. 3 shows
a trace of a single microelectrode recorded 5 minutes after
the exposure to the chlorinated silver wire. As one can clearly
distinguish in the representative amperometric trace, there
are only a limited number of peaks before the switch to the
negative cathodic potential. This was indeed the picture on all
other electrodes across different chips: very few rather small
peaks (amplitudes of approximately 0.1 nA) appeared at the
anodic potential of +0.6 V. Immediately after switching to
the cathodic potential, multiple peaks with a wide range of
amplitudes from under 1 nA to over 10 nA appeared.
The cathodic peaks almost vanished 5 to 10 seconds after the
switch to the potential of −0.3 V. The peaks across different
channels were temporally uncorrelated, which indicated that
these were indeed independent electrochemical events. After
performing amperometric experiments, single microelectrodes
were investigated using CV and peaks similar to those seen
in Fig. 2 were recorded. The transient peaks described above
were not observed on chips that had not been exposed to the
chlorinated silver wire. Comparative amperometric measure-
ments from an uncontaminated MEA with a reliable conven-
tional Ag/AgCl reference electrode or a calomel reference
electrode are shown in the ESI,† Fig. S1 and S2.
We used ICP-MS as a method to verify the chemical com-
position of the nanoparticles observed using electrochemical
techniques. Liquid from a MEA chip previously exposed to
the chlorinated silver wire was analyzed. High concentrations
of Pt and Ti were found (see the ESI,† Table S3), which were
the base materials of the electrode and the adhesion layers.
The element with the second highest concentration on the
list was silver, which strengthens our hypothesis that the
measured signals were caused by nanoparticles originating
from the Ag/AgCl quasi-reference electrode. Other elements
could be attributed to the contaminants coming from either
the target or target holder, or the walls of the physical vapor
deposition chamber used for metal deposition.
Uncontaminated MEAs and MEAs that had been exposed
to an Ag/AgCl wire were subjected to additional surface analy-
sis using SEM while elementary analysis was simultaneously
performed with an EDX detector. We analyzed three chips
with different exposure times to the Ag/AgCl wire: long (more
than 5 h and additional washing steps), short (10 minutes),
and no exposure. All chips had been subjected to multiple
CVs but only the first two exhibited the characteristic peaks.
Elementary analysis of the contaminated microelectrode
surface using EDX revealed the presence of silver among
other expected elements constituting the microelectrode and
passivation surfaces (see the ESI,† Fig. S4, S5). SEM images
of the contaminated electrodes with Ag deposits can be seen
in Fig. 4; a clean uncontaminated electrode is shown in the
ESI,† Fig. S6.
We attribute the peaks observed in our experiments to
redox reactions as well as adsorption/desorption processes
of a Ag/Ag+ pair emerging from the Ag/AgCl nanoparticles
originating from the chlorinated silver wire, after it was
inserted into the solution. Most probably, the dissolution of
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Fig. 3 Amperometric measurement of a MEA exposed to an Ag/AgCl wire. Switching between the anodic and cathodic potentials. A.) Trace with
3 anodic/cathodic cycles. B.) Zoom into the anodic part at +0.6 V. C.) Zoom into the cathodic part at −0.3 V. Inset: example of a single
amperometric peak.
Fig. 4 SEM images of individual MEA microelectrodes (Ti/Au/Ti)
exposed to Ag/AgCl wire. A.) Microelectrode after prolonged exposure.
Inlay: zoom onto the aggregates of particles. B.) Microelectrode after a
short 10-minute exposure. Inlay: zoom onto individual particles.
the Ag/AgCl wire is caused by the chemical gradient of ions
and mechanical instability of the wire surface, as this process
was also observed when the wire was not a direct part of the
electrochemical set-up (passively inserted in the solution).
The peaks demonstrated in our research are similar to those
recently reported from silver nanoparticle–electrode colli-
sion events. This phenomenon is gaining increasing interest
in the electrochemistry community and is extensively investi-
gated by the Compton group and others.30–33 For example,
in the work of Zhou et al.,34 silver nanoparticles were oxi-
dized using glassy carbon microelectrodes at a potential
of approximately +100 mV. Current amplitudes of the single
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nanoparticles were on the order of 0.1 to 1 nA, similar to
what was observed in our work. A wider range of anodic
potentials seen in our experiments (+67 mV to +130 mV) was
most probably due to the oxidation of different sizes of the
silver nanoparticles originating from the Ag/AgCl wire.35,36
If we assume a spherical form and a complete oxidation of
the nanoparticle upon contact with the electrode, the radii of
the particles can be calculated from the measured charge
using the following equation:
3 Ar Qmax
rnp  3 (1)
4 F 
where Qmax is the measured charge, F is the Faraday
constant, ρ is the bulk density, and Ar is the relative atomic
mass. Based on eqn (1) and the data acquired from 10 different
chips, the average equivalent radius of the detected
nanoparticles was 104 ± 7 nm (n = 76, error is standard
error of the mean). The smallest detected particles had a
radius of just 3.0 nm (probably truly single nanoparticle),
whereas the biggest particles or, probably, aggregates37 had a
calculated radius of 250 nm (most probably multiple particles
or aggregates). The particle size was also analyzed using
dynamic light scattering (DLS) measurements, showing a
broad size distribution with the peak radius ranging from
148 to 190 nm depending on the scattering angle (ESI† S7).
The assumption of the spherical shape of the particles is
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not entirely accurate as aggregates of the nanoparticles can be
observed on the SEM images of the extensively used chip
(see Fig. 4). Additionally, SEM images support the assumption
that the measured charges represent not only single but also
multiple particles or particle aggregates. Hence, when com-
paring the detected signals in our experiment, we also use the
measured number of electrons, which is proportional to the
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number of the oxidized/reduced silver atoms/ions, and can be
directly derived from the measured charge:
N
Qmax
(2)
qe
The average number of electrons or, presumably, silver
atoms/cations per detected event according to eqn (2) was
5.73 × 108 ± 0.97 × 108 (n = 76, error is standard error of
the mean). The smallest detected particles contained mere
6.3 × 103 atoms, whereas the bigger particles or aggregates of
particles had 3.79 × 109 atoms.
Summarizing all the findings from different experiments
performed within the scope of this study, we conclude that
the most probable explanation of the documented peaks on
the microelectrodes during electrochemical measurements
is collisions of Ag/AgCl nanoparticles with the electrode
surface. The particles originate from the Ag/AgCl wire from a
quasi-reference electrode exposed to the solution. It seems
that, when the electrode is held at cathodic potentials, the
particles diffuse towards the electrode, come in contact with
the surface of the microelectrode and are first reduced from
Ag+ to Ag0. Frequent reduction peaks, regularly observed
at the cathodic potential on an amperogram in the first
5–10 seconds, support this argument. After this initial period,
the solution layer closest to the electrode surface is depleted
of the cations and the frequency of the reduction events dras-
tically decreases. We also believe that after the reduction,
most particles are adsorbed at the electrode surface.35 This
is supported by a rather broad cathodic peak on the CV, which
represents a combination of a reduction reaction and an
adsorption process manifesting in the increase of the elec-
trode capacitance over time. Another aspect confirming the
adsorption hypothesis is that only a few oxidation peaks are
detected when the potential is switched to +0.6 V. In case the
silver particles become part of the electrode, after the potential
switch, they are almost instantaneously oxidized to silver
cations, which either are stabilized by hydroxyl groups or might
form silver oxides (Ag2O) or chlorides (AgCl). In this case,
the oxidation occurs in the first moments after the potential
switch, during the so called blind time, induced by capacitive
charging, when no signals can be detected. Afterwards,
only sporadic peaks appear, probably from some silver parti-
cles that were not adsorbed during the reduction or coming
directly from the silver wire. Also, the sharp anodic peaks
during cyclic voltammetry (Fig. 2) point to the instantaneous
oxidation of silver deposits on the electrode surface.38
During the oxidation, some particles might desorb from the
electrode. However, based on the permanent nature of the
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microelectrode contamination, either not all the particles are
desorbed or the desorbed particles do not diffuse far away from
the electrode and are drawn to the surface again, probably
due to electrostatic interaction on the backward scan. The
ICP-MS analysis revealed an evident presence of high amounts
of silver in the solution that has been exposed to a chip
contaminated with Ag/AgCl nanoparticles. Moreover, SEM
images showed aggregation of silver deposits after continuous
exposure to an Ag/AgCl wire.
Conclusions
In this work, we have shown electrochemical artifacts
resulting from collisions of silver atoms/ions from the chlori-
nated silver, employed as a quasi-reference electrode wire,
with the surface of MEA microelectrodes. Future investiga-
tions of this phenomenon are required to completely under-
stand the redox reactions and adsorption/desorption
processes taking place in the studied system. Nevertheless,
the message we would like to convey in this work is
that special care has to be taken when employing Ag/AgCl
quasi-reference electrodes for electrochemical detection.
Especially for on-chip applications, where the quasi-reference
electrode is integrated on the chip or in a microfluidic
system, a direct contact between an Ag/AgCl electrode and
the test solution should be prevented. Alternatively, stable
non-brittle compositions of Ag/AgCl materials have to be
used to avoid the release of such particles into the solution.
Besides, due to the possible release of silver nanoparticles,
probable toxicological effects on the biological system in
question have to be considered.39,40
Acknowledgements
We thank Marko Banzet for the fabrication of MEAs, Elke
Brauweiler-Reuters and Gregor Panaitov for assistance with
the SEM images, and Elmar Neumann and Andreas Everwand
for help with EDX measurements. Additionally, we would like
to acknowledge Enno Kätelhön and Jan Schnitker for helpful
discussions. This work was funded by the Helmholtz Young
Investigators program.
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