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A Selective Voltammetric Method for Detecting Dopamine at

Quercetin Modified Electrode Incorporating Graphene
Zonghua Wang,* Jianfei Xia, Lingyan Zhu, Xiaoyin Chen, Feifei Zhang, Shuyan Yao, Yanhui Li, Yanzhi Xia
Laboratory of Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, Qingdao University, Qindao,
Shandong 266071, P. R. China
*e-mail: wangzonghua@qdu.edu.cn

Received: May 10, 2011;&

Accepted: July 28, 2011

Abstract
The development of a quercetin-graphene composite-modified glassy carbon electrode (Qu/GH/GCE) for the selec-
tive and sensitive detection of dopamine (DA) is described in this paper. To fabricate the Qu/GH/GCE, graphene
(GH) was first coated onto the surface of a glassy carbon electrode (GCE) and then quercetin (Qu) was electrode-
posited on the GH matrix. Transmission electron microscopy (TEM) was used to characterize the morphology of
the obtained GH and Qu/GH, and the electrochemical properties of the modified electrode were studied using elec-
trochemical techniques. The as-prepared Qu/GH/GCE occupied a synthetic property between GH and Qu. The
common overlapped electrochemical oxidation peaks of DA and AA were completely separated and a remarkable
increasing electron-oxidation current of DA occurred on the Qu/GH/GCE, which enabled the sensitive and selec-
tive electrochemical detection of DA in the presence of ascorbic acid (AA) with peak difference of ca. 452 mV be-
tween DA and AA. The peak current obtained at 0.174 V (vs. saturated calomel electrode, SCE) from differential
pulse voltammetry (DPV) is linearly dependent on the DA concentration in the range from 3.0  108 to 4.0 
104 mol/L with a detection limit of 1.0  108 mol/L. Furthermore, the Qu/GH/GCE exhibits good reproducibility
and stability, and has been used for the determination of DA in samples of rats striatum tissue with satisfactory re-
sults.

Keywords: Graphene, Quercetin, Dopamine, Ascorbic acid, Selectivity

DOI: 10.1002/elan.201100256

1 Introduction have been constructed for this purpose [5–9], such as

The interests in fabricating modified electrodes for elec-
trochemical determination of neurotransmitters such as
dopamine (DA) have been growing strongly in the past
decade. DA is an important neurotransmitter and plays a
very significant role in the central nervous, renal, hormo-
nal and cardiovascular systems [1–2]. A DA level be-
tween 0.01 and 1 mM in serum samples provide additional
diagnostic information for other disorders such as Schizo-
phrenia and Alzheimers disease [3]. Low level of DA
may cause Parkinsons disease. Therefore, it is of clinical
significance to develop sensitive and selective analytical
methods for determining DA. Among the different meth-
ods for detecting DA, electrochemical determination of
DA has been considered to be a preferred method owing
to its simplicity, fast response, and high sensitivity. A
major problem in electrochemical detection of DA is that
the coexisting electroactive interferent of ascorbic acid
(AA) has an overlapping oxidation potential with DA on
the bare electrode, and this makes it very difficult to de-
termine DA selectively [4]. In a word, it remains a chal-
lenge to detect DA directly and accurately in the pres-
ence of AA. With the efforts of bioelectrochemical and
electroanalytical chemists, various modified electrodes
polymers [10], metal nanoparticles [11] and multiwalled
carbon-nanotube composite [12]. These modified electro-
des showed good selectivity, stability and antifouling
properties for determination of DA.
Flavonoids have attracted an increasing interest in elec-
trochemical sensing which are benzo-g-pyrone derivatives
with several hydroxyl groups attached to the ring struc-
tures C6C3C6 ; of which some contain o-dihydroxy cate-
chol (the B-ring) such as quercetin (Qu), rutin, catechin
and luteolin, etc. It has been reported that flavonoids im-
mobilized on electrode surface could serve as the good
electron transfer mediators for the electrocatalytic oxida-
tion of organic electroactive species such as ascorbic acid
and uric acid. For example, hematoxylin was reported to
show an excellent electrocatalytic activity for adrenaline
oxidation, with a diminution of the electrode overpoten-
tial of about 395 mV at hematoxylin multi-walled carbon
nanotube modified glassy carbon electrode [13]. Qu, a
natural antioxidant in the plants and common human
diets [14], is one of the most bioactive flavonoids. A Qu-
modified wax-impregnated graphite electrode was pre-
pared and it was reported to be an effective electron me-
diator for the electrochemical oxidation uric acid (UA)
[15]. A glassy carbon electrode modified with MWCNTs,

Electroanalysis 2011, 23, No. 10, 2463 – 2471  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2463

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quercetin, and Nafion was made for electrochemical de-
tecting DA by Chen et al, and this type of modified elec-
trode was selective for sensitively detecting DA in the
presence of AA [16].
Recently, a new kind of carbon nanomaterial, graphene
(GH) [17], a single layer of carbon atoms with two-di-
mensional sheet in a hexagonal lattice, has generated in-
creasing interest both in fundamental science [18] and for
the potential applications in batteries [19], super capaci-
tors [20], field-effect transistors and electrochemical sen-
sors [21] due to its good conductivity, high electron mobi-
lity, superior chemical stability and large surface-to-
volume ratio. Many researchers have investigated the fea-
sibility of GH in electroanalytical chemistry as a novel
electrode modified material. For instance, Wang et al.
[22] fabricated a graphene modified electrode for selec-
tive determination of DA in a large excess of AA and the
resulted electrode showed a better performance than
multi-walled carbon nanotubes-modified electrode. It was
considered that the phenomena resulted from the elusive
two-dimensional structure and unique electronic proper-
ties of graphene. In addition, the large surface area of
graphene and related derivates also allows it to be an ex-
cellent carrier to load more active probes and active do-
mains for molecules binding, offering a significant am-
plification on the electrochemical sensing signals. There-
fore, graphene-based sensors should be an appropriate
platform for electrochemical sensing.
In this study, we developed a Qu/GH composite modi-
fied glassy carbon electrode (Qu/GH/GCE) for sensitive
and selective electrochemical detecting of DA. The Qu/
GH/GCE was prepared by electrochemical deposition of
Qu at a GH modified gassy carbon electrode (GH/GCE).
The composite is based on the controllable adsorption of
the Qu onto the GH/GCE electrode through the p–p
conjugation interaction between the GH and Qu mole-
cule. Basically, the GH sheets of carbon with p-conjuga-
tive and highly hydrophobic layers interact with, for ex-
ample, surfactants and some kinds of aromatic com-
pounds through hydrophobic or p–p electronic interac-
tion. The as-made electrode exhibits a strongly catalytic
activity for the oxidation of DA. More importantly, it is
also capable of resolving the voltammetric responses of
DA and AA compounds into individual signals. Our pre-
vious work has demonstrated that carbon nanotubes-
modified electrodes have advantages such as low back-
ground current, low noise, fast base line stabilization [23–
25] and especially the strong adsorption effect on Qu.
Therefore, as a new carbon nanomaterial, the GH was se-
lected as the substrate for the immobilization of Qu to
fabricate biosensors. The results demonstrate that Qu/
GH/GCE is superior in terms of extraordinary stability,
good reproducibility, wide linear concentration range,
technical simplicity, high surface charge transfer rate con-
stant, repulsive interaction for AA and low detection
limit for DA.
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Z. Wang et al.
2 Experimental
2.1 Chemicals and Instrument
Dopamine (DA) was purchased from Aldrich Corpora-
tion. Ascorbic acid (AA) and quercetin (Qu) were ob-
tained from Shanghai Reagent Factory (Shanghai,
China). All reagents were of analytical-reagent grade. All
solutions were prepared with doubly distilled water. Gra-
phene (GH) was prepared with graphite from Qingdao
Fujin graphite Co., Ltd. (Qingdao, China).
Cyclic voltammetry (CV) and differential pulse voltam-
metry (DPV) experiments were performed using a CHI-
660A electrochemical workstation (Shanghai Chen Hua
Instrument Co., Ltd.) with a conventional three-electrode
cell. A glass carbon electrode (GCE) and the modified
electrodes were used as the bare and working electrodes
respectively. The auxiliary electrode was a platinum wire.
All the potentials quoted in this work were referred to a
saturated calomel electrode (SCE) as the reference. A S-
4800 transmission electron microscopy (TEM, Hitachi,
Japan) was used for the morphology characterization of
graphene.
2.2 Synthesis of Graphene
To prepare GH from graphite, graphite oxide was first
synthesized with graphite using a modified Hummers
method [26]. The as-prepared graphite oxide suspensions
were then dispersed in water (0.1 wt%) and centrifuged
at 3000 rpm for 30 min to obtain a brown homogeneous
graphite oxide dispersion. About 20 mL dispersion was
further stirred in a vial at 50 8C for 12 h and cooled to
room temperature. To the resulting dispersion were
added 3.5 mL of hydrazine solution and 40.0 mL of ammo-
nia solution. After being vigorously shaken or stirred for
a few minutes, the vial was incubated in an oil bath at
95 8C for 1 h. The stable black dispersion in the vial was
filtered with doubly distilled water and methyl alcohol,
and then dried to obtain pure graphene that can be redis-
persed readily in water by ultrasonication.
2.3 Preparation of Modified Electrodes
Prior to surface modification, the GCE was polished with
emery paper and chamois leather containing Al2O3 slurry
(0.05 mm after 0.3 mm), and then ultrasonically cleaned in
doubly distilled water. As-synthesized GH was dispersed
by sonication in water to form a homogenous suspension
(1 mg/mL). The GH/GCE was prepared by dropping 6 mL
of GH dispersion on the GC surface and evaporating the
remaining water using an IR lamp. To prepare the Qu/
GH/GCE, the obtained GH/GCE was dipped in the Qu
solution (5  104 mol/L) and electrodeposited with CV
from 0.2 to 1.0 V for 10 circles. Scheme 1 is the sche-
matic diagram for fabricating Qu/GH/GCE. The Qu/
GCE was prepared following the same procedure for pre-
Electroanalysis 2011, 23, No. 10, 2463 – 2471
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Detecting Dopamine at Quercetin Modified Electrode

Scheme 1. Schematic diagram for fabricating a Qu/GH/GCE electrode.

paring Qu/GH/GCE except for the step of dropping GH

on the bare GCE.

3 Results and Discussion

3.1 Electrochemical Deposition of Qu at the GH/GCE
Surface
During the progress of electrochemical deposition of Qu,
the Qu molecule was oxidized to form oxidized Qu
(QuO). Scheme 2 is the electrochemical oxidation equa-
tion of Qu molecule. The electrodeposition CV curves of
5  104 mol/L Qu in 0.1 mol/L PBS (pH 7.0) at the GH/
GCE electrode is shown in Figure 2. Anodic peak and
cathodic peak of Qu during the process of electrochemi-
cal deposition can be observed with the peak potential at
0.149 V (peak 1) and 0.114 V (peak 2), respectively. As Fig. 1. CV curves of Qu electrodeposition on the GH/GCE
the scan continues (from inner to outer in the Figure 1), electrode with a scan circle of 10 times and scan rate of 20 mV/s.
the peaks become larger, reflecting the continuous
growth of the Qu film. With the electrooxidation ending,
a homogeneous brown polymer film was seen on the elec- removed carefully from the GCE for the further test. The
trode surface. These facts indicated that the Qu film was general patterns of the FT-IR spectra for Qu/GH compo-
formed on the surface of GH/GCE uniformly with this site (curve a), Qu (curve b), and GH (curve c) on the sur-
electrodeposition method. face of GCE obtained in our study were typical for flavo-
To verify the case of Qu electrodeposition, a prelimina- noids and carbon materials (Figure 2). The FT-IR spec-
ry experiment was performed. The Qu/GH sample was trum of GH (Figure 2c) showed no sharp absorbance

Scheme 2. Electrooxidation equation of Qu during electrodeposition at GH/GCE.

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Fig. 2. FT-IR spectra of Qu/GH composite (a), Qu (b) and GH
(c).
peaks, and the Figure 2b showed two typical peaks of Qu
at 1640 cm1 from the stretching vibrations of structural
C=O groups of Qu and 3450 cm1 from the stretching vi-
brations of structural OH groups of Qu. Compared with
the spectrum of Qu, the absorbance at wavenumber
1630 cm1 was larger, which indicated that the more C=O
was appeared in Qu/GH. And the absorption band at
3450 cm1 was narrow indicating the less OH association.
During the process of electrodeposition of Qu on GH,
part of OH were oxidized to form C=O. These results
showed that the Qu was electrodeposited on GH success-
fully. The peak at 2360 cm1 is from the CO2 in atmos-
phere.
The TEM images of the GH and Qu/GH nanocompo-
sites are presented. As shown in Figure 3, it is observed
Fig. 3. TEM images of GH (A) and Qu/GH composite (B) on the surface of modified electrodes.
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Z. Wang et al.
that the graphene sheet looks like the thin transparent
papers (Figure 3A). And in Figure 3B, on the surface of
GH, there is an organic membrane layer. TEM confirms
that the GH nanosheets are decorated successfully with
many well-dispersed Qu film.
3.2 Electrochemical Impedance Spectroscopy (EIS) of
the Modified Electrodes
Electrochemical impedance spectroscopy (EIS) is an ef-
fective method for probing the electrochemical features
of the modified electrodes. Therefore, electrochemical im-
pedance measurements were performed to study the
GCEs modified by different interfacial processes.
Figure 4 shows the EIS in the form of a Nyquist plot
obtained from different modified electrodes. It can be
seen that the bare GCE and the GH/GCE electrode be-
haved as ideal conductors and the electrochemical impe-
dance spectroscopies gave nearly linear plots (curve a
and c). After electrodeposition of Qu film, the two above
electrodes all exhibited much larger impedance (curve b
and d). Interestingly, the impedance on the Qu/GH/GCE
electrode was smaller than that on the Qu/GCE elec-
trode, even though the GH/GCE electrode shown a little
larger impendence than the bare GCE electrode. It was
confirmed that GH incorporated in the Qu film could
promote the electron transfer between the electrode sur-
face and the electrolyte solution, indicating a synergetic
effect between GH and Qu.
3.3 Electroanalysis of DA and AA at Qu/GH/GCE
It has been reported that the film porosity and the
amount of negative charge of some polymer electrodes
might eventually help to enhance the sensitivity and se-
Electroanalysis 2011, 23, No. 10, 2463 – 2471

Detecting Dopamine at Quercetin Modified Electrode
Fig. 4. Nyquist plots of 0.02 mol/L [Fe(CN)6]3/4 in 0.01 mol/L
KCl at bare GCE (a), Qu/GCE (b), GH/GCE (c), and Qu/GH/
GCE (d). Frequency range: 0.05–100 kHz, Ac amplitude: 5 mV.
lectivity of DA detection. This prompted us to investigate
the performance of Qu/GH/GCE for the DA detection.
The results show that DA exhibited a characteristic
anodic peak at 0.172 V and a cathodic peak at 0.139 V at
Qu/GH/GCE. The peak potential difference of ~Ep (DA)
on Qu/GH/GCE is 33 mV, close to 2.3RT/nF or 59/n mV
at 25 8C, suggesting that the number of electrons involved
in the electrochemical oxidation process is 2 (n  1.8).
At pH 7.0, DA exists as a cation with a positively
charged amino group. QuO hydrolyzes and takes some
negative charges. The mechanism of DA interaction with
QuO can be explained by assuming that QuO with nega-
tive charge at the electrode surface attracts DA molecule
onto the surface of modified electrode by electrostatic at-
traction and then subsequently reacts with the QuO,
Scheme 3. Proposed electrochemical reaction scheme of DA at Qu/GH/GCE.
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which resulting the DA is oxidized (DAO) and QuO is
deoxidized (Scheme 3).
Figure 5 illustrates the DPVs of the mixture of 1.0 
104 mol/L DA + 1.0  103 mol/L AA in PBS (pH 7.0) on
bare GCE, Qu/GCE, GH/GCE and Qu/GH/GCE, re-
spectively. DA and AA showed a small overlapped DPV
peak at 0.16 V on the bare GCE (curve a). The over-
lapped DPV peak was completely separated with a peak
potential difference of 390 mV after the bare GCE was
covered with a Qu film (curve b). Coating the bare GCE
with GH resulted in increased DPV responses and part
separation of the overlapped DPV peak (curve c). These
results indicated that the Qu film acted mainly to sepa-
rate the oxidation potentials and the GH to promote the
oxidation current of DA and AA. It was very interested
that DA exhibited a much larger DPV response on the
Qu/GH/GCE than that on the GH/GCE, indicating that
the synthetical effect between Qu and GH could remark-
ably increase the electrochemical activity toward to the
electron-oxidation of DA.
The GH bears highly p-conjunctive and hydrophobic
layers consisting of sp2 carbons and open ends, which ac-
tually enables them to act as a support for organic and in-
organic electrocatalysts. Furthermore, the unique structur-
al and electronic properties, such as two dimension struc-
ture, high specific surface area, porous interfacial layer
and a good conductivity of the GH, make it possible to
form a conducting matrix which helps biomolecules to
penetrate through the conductive porous channels onto
the electrode more easily with enhanced faradiac respons-
es.
The Qu film is negatively charged in a neutral buffer
solution. It can attract the positively charged DA and ex-
cluse the negatively charged AA through electrostatic
effect, which results in increased concentration of DA
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Full Paper Z. Wang et al.

Fig. 5. DPVs of the mixture of DA + AA in PBS (pH 7) on the

bare GCE (a, dashed), Qu/GCE (b, dotted), GH/GCE (c, dash
dotted) and Qu/GH/GCE (d, solid). CAA = 1.0  103 mol/L,
CDA = 1.0  104 mol/L.

and decreased concentration of AA on the modified elec-

trode surface. The other reason was that GH was a strict-
ly two-dimensional material and had its whole volume ex-
posed to surface adsorbates, maximizing their effect. GH
is also highly conductive material. Additionally, the elec-
tron transfer between DA and graphene is more feasible
through p–p interaction since DA has phenyl moiety
unlike AA. Compared with Qu/GC, addition of GH in-
creased the porosity and the deposited amount of QuO
on the Qu/GH/GCE. Due to the reasons mentioned
above, more and more DA was absorbed onto the surface Fig. 6. A) CVs of DA at Qu/GH/GCE with different scan rates.
of Qu/GH/GCE. Therefore, the Qu/GH/GCE can detect B) Relationship between scan rate and the peak potential of
1.0  104 mol/L DA at Qu/GH/GCE.
DA in the presence of AA sensitively and selectively.

3.4 Effect Factors the Electrochemical Response of DA

on Qu/GH/GCE 0 2:303RT 2:303RT nFð1  aÞ
Epa ¼ EO þ log v þ log ð1Þ
ð1  aÞnF ð1  aÞnF RTks
The CVs of DA at Qu/GH/GCE were recorded at differ-
ent scan rates (from 10 to 500 mV/s). The anodic (ipa) and 0 2:303RT 2:303RT anF
cathodic peak currents (ipc) are found to be linearly de- Epc ¼ EO  log v  log ð2Þ
anF anF RTks
pendent on v at scan rates of 10 to 500 mV/s. A linear
correlation is obtained between the peak current and the RT
log ks ¼ a logð1  aÞ þ ð1  aÞ log a  log
scan rate, indicating that the redox process is controlled nFv
ð3Þ
by adsorption. The regression equation is ipa (mA) = að1  aÞnFDEP
2.017 + 1.062 v (mV/s) (r2 = 0.998); ipc (mA) = 4.254– 
2:3RT
0.102 v (mV/s) (r2 = 0.998) (Figure 6A).
Take the anodic peak potentials (Epa) and the cathodic According to the slope of two curves (Epa vs. v and Epc
peak potentials (Epc) as a function of the logarithm of the vs. v) and Equation 1 and 2, a/(1a) was equal to 1.127,
scan rate (Figure 6B). The values of Epa and Epc are pro- and a was calculated to be 0.527. The value of n was fur-
portional to the logarithm of the scan rate ranging from ther calculated to be 2.01. With the Equation 3, a mean
10 to 500 mV/s. When the scan rate was higher, two value of ks = 0.84 s1 is obtained from all the extracted ex-
straight lines were got with two linear regression equa- perimental data.
tions as Epa (V) = 0.063 log v + 0.148 (r2 = 0.996) and Epc The effects of solution pH on the peak currents and
(V) = 0.056 log v + 0.170 (r2 = 0.995). Under these condi- peak potentials of DA were evaluated using DPV method
tions, the ks can be obtained according to the following (Figure 7). It has been found that the anodic peak current
equations [27]. increases as the pH of the solution increases until 7.0, and

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Detecting Dopamine at Quercetin Modified Electrode
Fig. 7. A) CVs of DA at the Qu/GH/GCE in 0.1 mol/L PBS (a)
pH 5.0, (b) pH 6.0, (c) pH 7.0, (d) pH 8.0, (e) pH 9.0. B) Rela-
tionship between pH of solution and peak potential of 1.0 
104 mol/L DA at Qu/GH/GCE.
then, decreases rapidly as the pH further increases (Fig-
ure 7A). Hence, pH 7.0 is chosen for the electrochemical
detection of DA. The DA oxidation potentials shift to-
wards negative when the pH increased. The anodic peak
potential (Epa) is proportional to the pH of the solution
in the range of 5.0 to 9.0. The linear regression equation
of DA is thus obtained as Epa (V) = 0.395–0.028 pH with a
correlation coefficient of 0.997 (Figure 7B).
3.5 Analytical Performance of the Qu/GH/GCE for
Measurement of DA in the Presence of AA
The DPV responses of different concentration DA at the
Qu/GH/GCE was investigated (Figure 8). The results
show that the oxidation peak current of DA is propor-
tional to the concentration of DA in the range of 3.0 
108 to 4.0  104 mol/L, which can be described with a
linear equation of ip (mA) = 4.13–0.49 C (mmol/L) and a
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Fig. 8. Relationship between the concentration of DA and the
peak current of DA.
correlation coefficient of 0.9992 (n = 11). The detection
limit (S/N = 3) is 1.0  108 mol/L.
The primary potential interfering agent in electrochem-
ical detection of DA is AA. To figure out the impact of
AA, the electrochemical response of DA in the presence
of AA at Qu/GH/GCE was studied. DPVs of a 1.0 
103 mol/L AA (a), 1.0  104 mol/L DA (b) and its mixed
solution (c) were performed by using Qu/GH/GCE as a
work electrode. The results obtained are shown in
Figure 9. The peak current and peak potential of DA
have little change in the presence and absence of AA.
Two well-defined DPV peaks, at a molar ratio AA/DA of
10/1, are observed at 0.174 and 0.278 V for the oxida-
tion of DA and AA with the potential difference of
452 mV, which is large enough for selective determination
of DA in the presence of a mass of AA.
We also studied the influences of potential interfering
compounds such as uric acid, epinephrine, cysteine, aspir-
in, urea, and citric acid plus sugars as fructose and su-
Fig. 9. DPVs of AA (a, dotted), DA (b, dashed) and the mix-
ture of DA + AA (c, solid) in PBS (pH 7.0) on the Qu/GH/GCE.
CAA = 1.0  103 mol/L, CDA = 1.0  104 mol/L.
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Full Paper Z. Wang et al.

crose. Keeping the relative standard deviation below 5 %, Table 1. Analytical parameters and recovery (n = 5) for DA in
with 1 mmol/L of uric acid, epinephrine, cysteine, aspirin, the rats striatum sample using standard addition method.
urea, citric acid, 0.6 mmol/L fructose and sucrose in i (mA) Added amount Analyzed result Recovery
50 mmol/L DA, no shift in the oxidation peak potential of (mmol/L) (mmol/L) (%)
DA was observed. The current response of DA was also 4.47 0 0.69
not affected in the presence of these interferents. There- 4.91 1.00 1.65 97.6
fore, the Qu/GH/GCE could be used to determine DA in 6.94 5.00 5.73 100.7
complex environment containing common physiologically 9.34 10.00 10.63 99.4
interferents.

tained by Qu/GH/GCE are acceptable. The electrode

3.6 Stability, Reproducibility and Repeatability
The stability and reproducibility of the Qu/GH/GCE
were examined. A series of DPV measurements were
conducted in 1  104 mol/L DA (n = 50), and the relative
standard deviation (RSD) was found to be less than
2.0 %, indicating that the modified electrode had good re-
producibility. The response was measured after 10 and 20
days of storage at room temperature, and its long-term
stability was checked. It has been found that the response
of the Qu/GH/GCE retains at 99 % and 97 % of its initial
value, which is acceptable for most of the practical appli-
cations.
To demonstrate the repeatability of the modified elec-
trode, six electrodes were made by the same procedure
independently and the RSD value for the determination
of 1  104 mol/L DA was calculated as 4.3 %, which indi-
cated the electrode had good repeatability.
3.7 Method Application
In order to pave the way for the use of modified elec-
trode for in vivo and in vitro determination of DA in
brain studies, taking the homogenized brain tissue solu-
tion as the electrolyte, the experiment was carried out
under the same conditions. The pretreated sample (1 g)
was diluted with a ratio of 100 times using pH 7.0 PBS.
The DPV was used for detection of DA species. Each
sample solution undergoes five parallel detections, and
the RSD is below 5 %, suggesting that the results ob-
system recovers excellently as evidenced by the data in
Table 1. This implied that the rats brain homogenate pre-
sented no interference to DA detection in an excess of
AA.
A comparison of the proposed method with the recent-
ly reported methods listed in Table 2 indicates that Qu/
GH/GC is superior to the existing electrodes in the work-
ing concentration range in terms of detection limit, stabil-
ity, and ability for the effective determination of DA.
4 Conclusions
A novel modified electrode based on Qu/GH composite
has been developed for sensitive and selective electro-
chemical detecting of DA. The prepared Qu/GH/GCE
occupied a synthetic property, which combined the poten-
tial-separation effect and electron mediator of Qu and
the current-enhancement effect of GH. The proposed
Qu/GH/GCE increases the rate of electron transfer of
DA. In comparison with other reported electrochemical
detection systems for DA, the electron-oxidation re-
sponse to DA was remarkably improved, in which the de-
tection limit of DA can reach 1.0  108 mol/L with a peak
potential difference of 452 mV between DA and AA. The
verification of this enhanced response of the GH in the
presence of Qu may point the way toward the use of
other flavones for the chemical manipulation and process-
ing of GH for sensor applications. Further more, this

Table 2. Comparison of linear range, detection limit and peak separation of Qu/GH/GCE for detection of DA with reported methods.
CA: chronamperometry.
Serial Reference Electrochemical Linear range Detection limit Peak separa- Analysis of real sample
detection method (mmol/L) (mmol/L) tion (mV)
1 [11] DPV 0.2–45.8 0.07 220 Drugs, urine, synthesis samples
2 [28] DPV 200–950 0.151 230 NO
3 [6] DPV 0.1–1.0 0.02 204 Injection
1.0–10
10–100
4 [29] DPV 2.0–70 1.4 180 Dopamine hydrochloride injection,
human urine samples
5 [30] DPV 0.2–1.0 0.017 210 NO
6 [31] CV, CA, SWV 1.0–300 0.25 140 Drugs, urine
7 [32] CV, DPV 0.103–1.65 0.05 120 Injection solution
8 [33] CV, DPV 1.0–20 0.11 222 Human urine, serum, blood
9 [34] DPV 0.5–160 0.2 244 Injectable medicine
10 This work CV, DPV 0.03–400 0.01 452 Rats striatum tissue

2470 www.electroanalysis.wiley-vch.de  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2011, 23, No. 10, 2463 – 2471

Detecting Dopamine at Quercetin Modified Electrode
study has also demonstrated the practical analytical utility
of the modified electrode for the detection of DA in rats
striatum tissue samples with satisfactory results.
Acknowledgements
This work was financially supported by the National Nat-
ural Science Fundation of China (authorized number:
50802045 and 20975056), the Natural Science Fundation
of Qingdao (09-1-3-30-jch), Program of NSFC-JSPS
(21111140014) and The Taishan Scholar Program of Shan-
dong Province (TS20070711), China.
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