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Full Paper

Preparation and Characterization of GCE Coatings Combining

DDDMAB and PDADMAC with FAD and HCM for
Electrocatalytic Detection of Oxygen and Sulfur Oxoanions
Shen-Ming Chen,* Wen-Yan Chzo, R. Thangamuthu
Department of Chemical Engineering and Biotechnology National Taipei University of Technology No. 1, Section 3, Chung-Hsiao
East Road Taipei, Taiwan 106, Taiwan
*e-mail: smchen78@ms15.hinet.net
Received: April 17, 2009
Accepted: June 27, 2009
Abstract
Electrochemically active hybrid coatings based on cationic films, didodecyldimethylammonium bromide (DDDMAB)
, and poly(diallyldimethylammonium chloride) (PDADMAC) are prepared on glassy carbon electrode surface by
cycling the film-covered electrode repetitively in a pH 7 solution containing flavin adenine dinucleotide (FAD), and
anionic hexacyanometalate (HCM) complexes, Fe(CN)63 and Ru(CN)64. Cyclic voltammetric features of hybrid
coatings resemble that of electron transfer process of surface-confined redox species. Electrochemical quartz crystal
microbalance (EQCM) was used to monitor the deposition of FAD on DDDMAB film. Cyclic voltammetric peak
potentials of modified electrode were found to be shifted to more negative region with increasing pH of contacting
solution with a slope value of 63.3mV per pH unit. The electrocatalytic behavior of FAD-modified DDDMAB-coated
GCE and hybrid film electrodes was tested towards reduction of oxygen, S2O82, SO52 and oxidation of SO32. The
application of FAD-modified DDDMAB-coated GCE for S2O82 estimation was demonstrated in amperometric
mode. The sensitivity and detection limit (S/N 3) were 267.6 mA mM1 and 2  106 M, respectively.
Keywords: DDDMAB, PDADMAC, Modified GCE, FAD, HCM; Oxygen, Sulfur Oxoanions
DOI: 10.1002/elan.200904691

1. Introduction
Modification of electrode surfaces with electroactive materials is an important and interesting area of research in
electrochemistry for more than three decades [1 5].
Application of chemically modified electrodes in electroanalysis offers several advantages such as it can lower the
overpotential, increase the reaction rate and sensitivity,
improve the selectivity, and prevent surface fouling [1 8]. A
variety of compounds have been used for the modification of
electrode surfaces with different procedures [2 5].
Recently, flavins such as flavin adenine dinucleotide
(FAD) and flavin mononucleotide (FMN) have been
proposed as electrocatalyst for NADH oxidation [9, 10].
The common electroactive moiety in FAD, FMN and
riboflavin (RF) is the isoalloxazine group that can exist in
three forms: the fully oxidized quinone form, the radical
semiquinone (after the first electron transfer) and the fully
reduced hydroquinone form (after the second electron
transfer). Depending on the solution pH, each of these
species can exist in either neutral or ionic forms [11 13].
FAD has been studied quite extensively on different
electrode materials using various electrochemical techniques [13 20]. Gorton and Johansson [16] have reported
that FAD adsorbed on graphite and strong adsorption did
not occur on noble metals and glassy carbon electrode.
 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Therefore, it is essential to find out simple and effective

procedure to immobilize the flavins on electrode surfaces
for the fabrication of new electrocatalytic assemblies.
Two different approaches have been described in the
literature to immobilize flavins [9, 10, 21]. In the first
approach, carbon fiber electrodes were modified with
titanium oxide and used to adsorb FAD and FMN on the
electrode surface [9]. In the second approach, modified
electrodes were prepared by electropolymerzation of flavins [10, 21] from acidic medium. However, later it was
demonstrated that the catalytic activity of second approach
arose from the surface quinone groups of electrodes and not
from poly(FAD) [22]. In our earlier work, modified electrodes have been prepared by immobilizing FAD on various
matrices such as zinc oxide [23, 24], poly(luminol) [25] and
nordihydroguaiaretic acid (NDGA) [26] and their electrocatalytic behavior was studied. Recently, we have prepared
poly(MnTAPP)/flavins hybrid films and their electrocatalytic activity was studied [27].
In the present work, FAD modified electrodes are
prepared by immobilizing FAD on positively charged
DDDMAB and PDADMAC coatings on glassy carbon
electrode. Also, hybrid films are prepared by simultaneously
immobilizing FAD, hexacyanoferrate and hexacyanoruthenate on DDDMAB and PDADMAC coatings. The
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S.-M. Chen et al.

des were investigated using cyclic voltammetry. The catalytic activity of FAD modified DDDMAB coating and
PDADMAC-based hybrid coatings were tested towards
reduction of oxygen, S2O82, SO52 and oxidation of SO32.
The analytical application of FAD modified DDDMAB
film electrode in S2O82 determination was also demonstrated.

2. Experimental
Didodecyldimethylammonium bromide, poly(diallyldimethylammonium chloride), K4[Fe(CN)6] 3H2O and K4
[Ru(CN)6] xH2O, FAD were obtained from Aldrich and
were used as received. All other chemicals used were of
analytical grade and used without further purification.
Generally, all the electrochemical experiments were carried
out using pH 7 phosphate buffer solutions. For pH variation
study, solutions of different pH values varying from 1 to 11
were prepared from 0.1 M NaCl and then adjusted to
desired value with H2SO4 (pH 1 3), 0.01 M acetic acid
(pH 4 6), NaH2PO4 and Na2HPO4 (pH 6 8), sodium
borate (pH 8 10) and sodium carbonate (pH 10 12).
Aqueous solutions were prepared using doubly distilled
deionized water and high purity nitrogen gas was used to
deaerate as well as flow over the solutions during experiments. All the measurements were carried out at room
temperature.
The electrochemical experiments were carried out with
Bioanalytical system (Model CV-50W) and CH Instruments
(Model CHI-400). Cyclic voltammograms were recorded in
a three-electrode cell configuration, in which a glassy carbon
electrode (area 0.07 cm2) purchased from Bioanalytical
systems (BAS) was used as working electrode. The auxiliary
compartment contained a platinum wire that was separated
by a medium-sized glass frit. All cell potentials were
recorded using Ag j AgCl j KCl(sat) reference electrode.
Rotating disk electrode (RDE) experiments were performed using PINE Instrument (USA) in conjunction with
CHI-750 potentiostat connected to a Model AFMSRX
analytical rotator. The rotating ring-disk electrode (RRDE)
consisted of a glassy carbon disk electrode and a platinum
ring electrode. The working electrode for the electrochemical quartz crystal microbalance (EQCM) measurements
was an 8 MHz AT-cut quartz crystal coated with gold on
both sides (projected area 0.19 cm2), and experiments
were carried out using CH Instruments. The mass sensitivity
was 1.4 ng Hz1.
DDDMAB (or PDADMAC) film-modified electrode
was prepared as follows. First, measured aliquots of
DDDMAB (or PDADMAC) solution was used to cover
the pretreated electrode surface, and then dried in warm
flow of air (at about 50 8C) from 10 cm away from the
electrode surface and formed a film on it. Cyclic voltammetry was used for immobilization of FAD onto DDDMAB
(or PDADMAC). After coating the GCE with DDDMAB
(or PDADMAC), the electrode was immersed in pH 7 PBS
containing 5  104 M FAD and the potential was repetiElectroanalysis 2009, 21, No. 21, 2331 2338

tively cycled between  0.6 to 1.2 V for immobilization of

FAD. GCE/DDDMAB (or PDADMAC)/FAD/hexacyanoferrate and hexacyanoruthenate film-modified electrodes
were prepared by cycling the potential of DDDMAB (or
PDADMAC) coated GCE at a scan rate of 100 mV s1 in
pH 7 PBS solution containing FAD, Fe(CN)63 and
Ru(CN)63 between a desired potential range. Prior to
modification, glassy carbon electrode was polished with
0.05 mm alumina on Buehler felt pads and then ultrasonically cleaned for about a minute in water. After film
formation, the electrode was rinsed with distilled water and
used for further characterization.

3. Results and Discussion

3.1. Preparation of FAD Modified DDDMAB-Coated
Glassy Carbon Electrodes
Figure 1A shows the repetitive cyclic voltammetric response of DDDMAB-coated glassy carbon electrode in
phosphate buffer solution (pH 7) containing 5  104 M
FAD. The potential was cycled between  0.6 and 1.2 V.
The first cycle was started at  0.6 V toward the positive
direction. As shown in Figure 1A, oxidation and reduction
peak currents of redox couple corresponding to FAD with a
formal potential around  0.35 V were increased with
increasing number of cycles. This observation indicates the
growth of FAD film on DDDMAB-coated GCE. Under the

Fig. 1. Consecutive cyclic voltammograms of DDDMAB-modified GCE in pH 7 PBS: in the presence (A) and absence (C) of 5
 104 M FAD. (B) Response of bare GCE in pH 7 PBS
containing 5  104 M FAD. Scan rate 100 mV s1. (D) Consecutive cyclic voltammograms of DDDMAB-modified gold electrode in pH 7.0 PBS containing 5  105 M FAD. (E) Change in
EQCM frequency. Scan rate 20 mV s1.

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Detection of Oxygen and Sulfur Oxoanions

similar experimental conditions, electrochemical response

of FAD was not observed on bare GCE as shown in
Figure 1B during continuous cycling. Similarly, there was no
cyclic voltammetric response if the DDDMAB-coated GCE
cycled in pH 7 PBS in the absence of FAD in the bath
(Fig. 1C). Comparison of Figures 1A, B and C reveals that
the presence of DDDMAB film is essential for the
immobilization of FAD. The electrostatic interaction between the positively charged DDDMAB film and negatively charged phosphate group present in the FAD
molecules may be responsible for FAD deposition on
DDDMAB.
Immobilization of FAD on DDDMAB film-coated
electrode was monitored and confirmed by performing
concurrent voltammetric and microgravimetric experiments. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance EQCM measurements
permit continuous monitoring of surface mass changes
without disturbing experimental conditions. Figure 1D
shows cyclic voltammograms recorded during immobilization of FAD on the DDDMAB film on gold electrode from
pH 7.0 PBS containing 5  105 M FAD. Figure 1E illustrates the change in EQCM frequency during the first ten
cycles of consecutive cyclic voltammetry between 0.1 and
 0.5 V. A steady decrease of frequency of quartz corresponding to an increase in the number of FAD molecules
immobilized on DDDMAB film is observed during repeated cycling. The increase in cyclic voltammetric peak current
in Figure 1D and decrease (or mass increase) in Figure 1E
are consistent with immobilization of FAD on DDDMAB
film. The calculation according to Sauerbrey equation [28]
shows that the total mass increase due to immobilization of
FAD after first ten cycles was about 1143 ng cm2.

3.2. Electrochemical Characterization of FAD Modified

DDDMAB-Coated Glassy Carbon Electrodes
In order to investigate the electrochemical behavior of FAD
immobilized on DDDMAB film, cyclic voltammetric response of the modified electrode in pure PBS (pH 7) was
recorded. Figure 2A shows the cyclic voltammograms of
FAD-modified DDDMAB-coated electrode in deaerated
PBS at different scan rates. A redox couple with well defined
peaks having formal potential (E8) of  0.37 V was
observed. As shown in the inset, both anodic and cathodic
peak currents increase linearly with scan rates up to 200 mV
s1 as expected for a surface-confined redox species [29].
Also, the peak-to-peak separation (DEp) was small (35 mV
at the scan rate of 200 mV s1), suggesting facile charge
transport in the film [29].
The electrochemical behavior of FAD-modified electrodes was further examined in supporting electrolyte of
different pH values. Figure 2B shows cyclic voltammetric
response of FAD-modified DDDMAB-coated electrode in
contacting solution of pH values 1 to 11. As can be seen in
the figure, the formal potential of surface redox couple was
pH dependence, i.e., the anodic and cathodic peak poten 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Fig. 2. (A) Cyclic voltammograms of GCE/DDDMAB/FAD

electrode in pH 7 PBS at different scan rates (inner to outer
voltammograms correspond to 10, 20, 30, 45, 60, 80, 100, 120, 140,
160, 180 and 200 mV s1). (B) Cyclic voltammograms of GCE/
DDDMAB/FAD electrode in 0.1 M NaCl solutions of different
pH: (a) 1, (b) 2, (c) 3, (d) 5, (e) 6.5, (f) 8, (g) 9, (h) 10, and (i) 11.
The inset shows a plot of the formal potential versus pH. Scan
rate 100 mV s1.

tials of the modified electrode were shifted to a less positive

value with increasing pH of the contacting solution. The
formal potential (E8) of FAD film was evaluated as the
average of the anodic and cathodic peak potentials of the
cyclic voltammograms recorded at various pH values and
the E8 pH plot was constructed. The plot yields straight
line with a slope of 63.3 mV per unit change in solution pH as
shown in the inset of Figure 2B. The pH dependence
voltammetric response was due to the involvement of
proton transfer (protonation) during electrochemical oxidization (quinone form) to reduced form (the fully reduced
hydroquinone form) of FAD. The overall redox reaction
involved in this process can be represented by Scheme 1.

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Scheme 1. Electrochemical oxidization (quinone form) to reduced form (the fully reduced hydroquinone form) of FAD (overall redox
reaction).

3.3. Electrocatalytic Behavior of FAD Modified

DDDMAB-Coated Glassy Carbon Electrodes

cathodic reaction was either due to formation of H2O2 or H2

O as represented by the following equations

3.3.1. Mediated Reduction of Oxygen

O2 2e 2H ! H2O2

Figure 3A shows the cyclic voltammetric responses of

DDDMAB/FAD film in pH 7 PBS in the presence and
absence of oxygen. In Figure 3A, the reduction peak
corresponding to FAD in DDDMAB/FAD film was found
to be increased with increasing O2 concentration and anodic
peak diminished. Compared to unmodified electrode (curve
a), oxygen reduction occurs on modified electrode with
substantial reduction of overpotential. The catalytic current
of DDDMAB/FAD film arose from the electrocatalytic
reduction of O2 through the FADH2 molecule immobilized
in the DDDMAB film. Thus, the modified electrode reduces
the overpotential of oxygen reduction. The electrocatalytic
reduction of oxygen by DDDMAB/FAD film was further
investigated using RRDE technique. Rotating GC electrode modified with DDDMAB/FAD film as disk and
platinum ring electrode were used to carry out RRDE
experiments. Figure 3B shows the voltammetric curves for
dioxygen reduction recorded at the RRDE with
DDDMAB/FAD film modified GC disk electrode. The
disk potential was scanned from  0.1 to  0.5 V, while the
ring potential was kept at 0.6 V to oxidize the H2O2
generated by O2 reduction on the disk. The results showed
that oxygen reduction started at about  0.2 V on
DDDMAB/FAD film and anodic current was simultaneously observed at platinum ring for different concentrations
of O2. It can also be noticed that a large disk current was
observed while the ring current was smaller. This is an
indication that oxygen reduction proceeds on modified
electrode along a pathway where H2O was the major
product, and small amount of H2O2 was formed. Thus, the

or

Electroanalysis 2009, 21, No. 21, 2331 2338

O2 4e 4H ! 2H2O

(1)

(2)

And the anodic current (ring current, IR) was the result of
following reaction:
H2O2 ! O2 2e 2H

(3)

The ratio of ring to disk current, IR/ID, was found to be 0.08

for the electrocatalytic reduction by DDDMAB/FAD film.
The reaction pathway for oxygen reduction at DDDMAB/
FAD film is proposed as follows with the reduction products
are being H2O2 and H2O:
GCE/DDDMAB/FAD 2H 2e !
GCE/DDDMAB/FADH2

(4)

GCE/DDDMAB/FADH2 O2 !
GCE/DDDMAB/FAD H2O2

(5)

GCE/DDDMAB/FADH2 1/2O2 !
GCE/DDDMAB/FAD H2O

(6)

3.3.2. Mediated Reduction of S2O82

Figure 4A shows cyclic voltammograms of DDDMAB/
FAD film modified electrode in pH 7 PBS (curve a) and in
the presence of different concentration of S2O82 in the
range of 1  105 to 4  105 M (curve b e). Curve a

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Detection of Oxygen and Sulfur Oxoanions

Fig. 3. (A) Cyclic voltammograms of GCE/DDDMAB/FAD

electrode in pH 7 PBS containing different concentrations of
oxygen: a) 0, b) 1  105, c) 2  105, d) 5  105 e) 1  104, f)
1.5  104, g) 2  104, and h) 2.5  104 M. Curve a represents
2.5  104 M oxygen reduction at bare GCE. Scan rate 100 mV
s1. (B) RRDE voltammograms of DDDMAB/FAD film modified GC disk electrode in pH 7 PBS containing different concentrations of oxygen: a) 0, b) 1  105, c) 2  105, d) 5  105 e) 1 
104, f) 1.5  104, g) 2  104, and h) 2.5  104 M, at a constant
electrode rotation speed of 400 rpm. The ring potential (ER)
0.6 V (vs. Ag j AgCl). Scan rate 0.015 V/s. The inset shows a
plot of ID vs. cO2 and IR vs. cO2.

Fig. 4. Cyclic voltammograms of GCE/DDDMAB/FAD electrode in pH 7 PBS containing different concentrations of (A)
S2O82: (a) 0, (b) 1  105, (c) 2  105, (d) 3  105, and (e) 4 
105 M. Curve a represents 4  105 M S2O82 reduction at bare
GCE. Scan rate 100 mV s1. (B) Chronoamperometric responses for 7 sequential additions of S2O82 (each addition corresponds
to 5  105 M) at (a) GCE/DDDMAB/FAD film electrode and (b)
bare GCE. Electrode was rotated at 400 rpm. Electrode
potential  0.6 V (vs. Ag j AgCl). Inset: calibration curves.

represents reduction of 4  105 M S2O82 on bare electrode.

It can be seen that there is no appreciable direct reduction of
S2O82 occurred on bare electrode. On the other hand, the
cathodic peak currents of DDDMAB/FAD film electrode
increases noticeably with increasing concentration of S2
O82, while the anodic peak currents decreased. These
results indicate that the DDDMAB/FAD film mediated the
reduction of S2O82. The DDDMAB/FAD film has also
been found to be electrocatalytically active towards reduction of SO52, nitrite and L-cysteine, and oxidation of S2O42
(results not shown).

The DDDMAB/FAD film electrode was finally tested for

its analytical applications. For comparison, similar experiments were carried out with bare GCE. Figure 4B shows the
chronoamperogram
response
of
FAD-Modified
DDDMAB-coated electrode (curve a) for successive addition of 5  105 M S2O82 solution to continuously stirred
solution of pH 7 PBS. The electrode was rotated at 400 rpm
and its potential held at  0.6 V. FAD-modified electrode
responded rapidly and the catalytic current increases in
proportion to concentration of S2O82. While the current of
bare GCE (curve b) was not appreciable compared to

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S.-M. Chen et al.

modified electrode as illustrated in the figure. The response

of FAD-Modified DDDMAB-coated electrode was linear
in the concentration range from 5  105 and 3.5  104 M
(curve a of inset) with a correlation coefficient of 0.9895. The
detection limit was 2  106 M based on a signal-to-noise
ratio 3 (S/N 3). The sensitivity within the dynamic range
was calculated to be 267.6 mA mM1.

3.4. Preparation and Characterization of DDDMAB and

PDADMAC/FAD/Hexacyanometalates Hybrid
Coating Modified Electrodes

pH 7 phosphate buffer solution containing 5  104 M FAD

and 2  104 M of Fe(CN)63 and Ru(CN)64. The voltammograms exhibited three reversible redox couples corresponding to FAD/FADH2, Fe(CN)63/4 and Ru(CN)64/3
redox reactions. The result confirms doping of anionic
complexes as well as deposition FAD on DDDMAB
coatings during continuous potential cycling. Similarly,
PDADMAC/FAD/hexacyanoferrate and hexacyanoruthenate hybrid coating was fabricated on GCE by repetitive cycling of PDADMAC-coated electrode in doping
solution between  0.6 and 1.2 V. As shown in Figure 5B,
cyclic voltammetric peak currents of three redox couples
corresponding to FAD, Fe(CN)63/4 and Ru(CN)64/3

In the further study, hybrid coatings were prepared by

simultaneous doping of multiply charged anionic complexes
into cationic films besides depositing FAD for both fundamental as well as catalytic applications. Here, DDDMAB
and PDADMAC coated electrodes were simultaneous
doped with Fe(CN)63 and Ru(CN)64 complexes. Since
the redox potentials of anionic complexes and FAD are well
separated, they were chosen so that the electrochemical
responses of these redox couples could be observed and
used as bifunctional electrocatalytic coating to mediate
electrochemical oxidation and reduction.
Figure 5A shows a series of cyclic voltammograms
obtained with DDDMAB film-coated GC electrode in

Fig. 5. Consecutive cyclic voltammograms of (A) DDDMABmodified GCE, (B) PDADMAC-modified GCE in pH 7 PBS
containing 5  104 M FAD 2  104 M hexacyanoferrate 2 
104 M hexacyanoruthenate. Scan rate 100 mV s1.
Electroanalysis 2009, 21, No. 21, 2331 2338

Fig. 6. Cyclic voltammograms of (A) GCE/DDDMAB/FAD/

hexacyanoferrate and hexacyanoruthenate film electrode, and (B)
GCE/PDADMAC/FAD/hexacyanoferrate and hexacyanoruthenate film electrode in pH 7 PBS at different scan rates (inner to
outer voltammograms correspond to 10, 20, 30, 45, 60, 80, 100,
120, 140, 160, 180 and 200 mV s1). Insets: plot of anodic and
cathodic peak currents vs. scan rates.

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Detection of Oxygen and Sulfur Oxoanions

redox couples increases with number of cycles, which

indicates formation of hybrid film.
Figure 6A shows cyclic voltammograms of DDDMABbased hybrid film at different scan rates after transferring to
pH 6.5 phosphate buffer solution. The presence of three
chemically reversible redox couples indicates that the
DDDMAB film could retain anionic complexes as well as
FAD firmly by electrostatic interaction. The anodic and
cathodic currents of complexes increase linearly with scan
rates as shown in the insets. Similar observation was made
with PDADMAC-based hybrid film also as demonstrated in
Figure 6B. The voltammetric features showed that the
hybrid films are stable and consistent with a diffusionless,
reversible electron transfer process as we observed in our
previous study, in which hybrid films were formed in the
absence of FAD [30].

3.5. Electrocatalytic Behavior of PDADMAC/FAD/

Hexacyanoferrate and Hexacyanoruthenate Hybrid
Coating
The electrocatalytic behavior of hybrid coatings derived
from PDADMAC was investigated towards reduction of
oxygen and oxidation of SO32 using cyclic voltammetry.
3.5.1. Mediated Reduction of Oxygen
Figures 7A shows cyclic voltammograms of hybrid film
coated electrodes in pure pH PBS (curve a) and in the
presence of different concentrations of O2 (curves b f).
Curve a represents reduction of O2 on unmodified electrode. As shown in the figure, there is no detectable current
for direct reduction of O2 on bare GCE. On the other hand,
the cathodic peak current of hybrid film corresponding to
FAD/FADH2 redox couple increases with increasing oxygen concentration, while the anodic peak current decreased.
However, the peak currents of hexcayano metal complexes
were remained unchanged. The results suggested that FAD/
FADH2 redox couple showed electrocatalytic activity
towards reduction of O2 as observed with GCE modified
with DDDMAB/FAD.
3.5.2. Mediated Oxidation of SO32
Figure 7B shows the cyclic voltammetric responses of SO32
on PDADMAC hybrid film coated electrode and bare GCE
in pH 7 PBS. In Figure 7B, curve a represents response of
modified electrode in the absence of SO32 ions. Compared
to modified electrode, there is no appreciable oxidation
current on unmodified electrode (curve a). Then, the anodic
peak current of Ru(CN)63/4 redox couple in the modified
electrode increased with increasing concentration of SO32
ions. Finally, the peak currents of Fe(CN)63/4 and FAD/
FADH2 redox couples were remained unaffected. These
observations collectively suggested that electrochemically
generated Ru(CN)63 ions mediate the oxidation of SO32
ions. The above mediated electrochemical reactions dem 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Fig. 7. Cyclic voltammograms of GCE/PDADMAC/FAD/hexacyanoferrate and hexacyanoruthenate film electrode in pH 7 PBS

containing different concentrations of (A) O2: (a) 0, (b) 1  105,
(c) 2  105, (d) 3  105, (e) 5  105, and (f) 1  104 M; (B)
SO32: (a) 0, (b) 1  105, (c) 3  105 , and (d) 5  105 M. Curve a
represents the highest concentration of respective substance on
bare GCE. Scan rate 100 mV s1.

onstrate that PDADMAC based hybrid coatings showed

bifunctional electrocatalytic activity towards reduction of
oxygen and oxidation of SO32. Thus, the hydrid film
modified electrode can be used to determine the different
analytes.

3.6. Stability of Modified Electrodes

The stability of both FAD-modified DDDMAB-coating
and hybrid coatings derived from DDDMAB and PDADMAC was evaluated by cycling the modified electrodes in
dopant free buffer solution at different scan rates as
discussed during characterization studies of respective
coating. The peak currents of redox couples present in the
coatings increased with increasing scan rates. In addition,
the stability of these modified electrodes was also tested by
scanning the electrode potential continuously 50 cycles in
pure supporting electrolyte. After continuous cycling, the
decrease in peak current of modified electrodes was less
than 10%, indicating high stability of modified films and
promising for sensor applications.

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4. Conclusions
In the present study, stable electrochemically active hybrid
coatings were obtained by cycling the cationic coatingcovered electrode repetitively in pH 7 PBS containing FAD,
Fe(CN)63 and Ru(CN)63 anionic complexes. Modified
electrodes exhibited three redox couples corresponding to
FAD/ FADH2, Fe(CN)64/3 and Ru(CN)64/3 redox transitions. All the three redox couples present in the hybrid
films showed voltammetric characteristics of thin-layer
electrochemistry. The modified electrodes showed good
stability and the FAD-modified DDDMAB-coated electrode exhibited pH dependence redox response with slope
of 63.3 mV per pH unit from the plot of E8 vs. pH. The FADmodified DDDMAB-coated GCE and hybrid film electrodes showed electrocatalytic activity towards reduction of
oxygen, S2O82, SO52 and oxidation of SO32. In amperometric mode, the FAD-modified DDDMAB-coated electrode has a sensitivity of 267.6 mA mM1, and detection limit
2  106 M (S/N 3) for the determination of S2O82.

5. Acknowledgement
This work was financially supported by The National
Science Council of Taiwan (ROC).

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