Journal of Molecular Liquids 215 (2016) 31–38

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Fabrication of a graphene oxide nano-sheet modified electrode for

determination of dopamine in the presence of tyrosine: A multivariate
optimization strategy
Sayed Mehdi Ghoreishi ⁎, Mohsen Behpour, Mitra Mortazavi, Asma Khoobi
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, P.O. Box. 87317-51167, Islamic Republic of Iran

a r t i c l e i n f o a b s t r a c t

Article history: In the present study, the oxidation peak current of dopamine (DA) in a 0.2 M Britton–Robinson (B–R) buffer so-
Received 28 August 2015 lution was optimized by experimental design for its determination in the presence of tyrosine (Tyr) at the surface
Received in revised form 1 November 2015 of graphene oxide modified carbon paste electrode (CPE/GO). A central composite rotatable design (CCRD) and
Accepted 8 December 2015
response surface methodology (RSM) were used to evaluate the effects of the variables by the differential pulse
Available online xxxx
voltammetry (DPV) method. These variables include scan rate, step potential, modulation amplitude, graphene
Keywords:
oxide amount and pH. Characterizing of the CPE/GO was investigated by electrochemical impedance spectrosco-
Multivariate optimization strategy py (EIS), scanning electron microscopy (SEM) and cyclic voltammetry (CV) techniques. Also other voltammetric
Graphene oxide nano-sheet techniques such as chronocoulometry and linear sweep voltammetry (LSV) were applied for electrochemical
Dopamine studies of DA. Using these methods, diffusion coefficient (D = 9.2 × 10−5 cm2 s−1) and kinetic parameters
Tyrosine such as electron transfer coefficient (α = 0.6) and exchanging current density (j0 = 14.6 μA cm−2) of DA
Electrochemical techniques were determined. Then, under the optimized conditions linear concentration range for DA was from 0.08 to
2.30 μM and the detection limit was found to be 8.60 nM. Finally CPE/GO could be employed for determination
of DA in real samples such as human blood plasma.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction electrical, thermal and mechanical properties as well as usually is

A significant discharge from mammalian cell that contributes in the
central nerve system is dopamine (DA) which is categorized in the
catecholaminse neurotransmitter [1]. In some cases DA is responsible
for some nerves and physiological diseases such as Parkinsonism and
schizophrenia [2]. Because of the important role of DA chemical, the
study of this analyte is useful to understand physiological and physical
function [3]. DA was studied using some methods, including titrimetry
[4], spectrophotometry [5] and potentiometry [6]. But because of DA is
an electroactive component, electrochemical studies of the analyte are
useful; moreover this method has many advantages such as selectivity,
sensitivity, low cost and rapid detection [7]. However, these methods
have some difficulties such as high over potential and sediment by oxi-
dation or reduction [8]. To resolve these problems many studies focus
on the electrode surfaces modified by several material including carbon
materials [9], polymers [10], enzymes [11] and self-assemble mono-
layers [12]. Lately, a new two dimensional (2-D) carbon material
graphene has been used in the fabrication of electrochemical biosensors
[13]. Graphene oxide (GO) is a graphite derivative and has unique
⁎ Corresponding author.
E-mail address: s.m.ghoreishi@kashanu.ac.ir (S.M. Ghoreishi).
made out of chemical oxidation and scratch of graphene [14]. GO is a
2-D plate with 1.0 nm thickness and big lateral dimensions in the
range of a few nanometer to hundred micrometers [15]. GO was used
as modifier in some studies such as DNA sensing [16], detection of single
nucleotide polymorphisms of DNA [17], detection of leukemia [18,19].
Tyrosine (Tyr) is a semi-essential amino acid in the body and is pri-
marily derived from phenylalanine by phenylalanine hydroxylase [20].
Abnormal concentrations of DA and Tyr have been linked with several
neurological disorders such as the debilitating ailment schizophrenia
and Parkinson's disease [21]. Thus determination of DA in the presence
of tyrosine (Tyr) seemed to be significant.
Most of the processes studied in the laboratory are the result of the
interaction and influence of several chemical and instrumental factors.
Traditionally the study of the interaction of these factors is done by
modifying one factor at a time. This univariate analysis causes carrying
out many experiments, but it does not allow statistical interpreting
results and does not detect the interactions between variables, which
can often lead to a mistaken interpreting results. Experimental design
methodology makes a joint study of the relation between a number of
factors and a specific response using a mathematical model. The
designed experiments allow one, through the controlled modification
of the experimental factors, to study the effect of a variation of experi-
mental variables on the response [22].

http://dx.doi.org/10.1016/j.molliq.2015.12.028
0167-7322/© 2015 Elsevier B.V. All rights reserved.
32 S.M. Ghoreishi et al. / Journal of Molecular Liquids 215 (2016) 31–38
The main aim of optimization is to find the experimental conditions
which give the best response. Response surface methodology [23] is an
area of the experimental design that deals with the optimization and
modeling of a system. This methodology was introduced by Box and
Wilson [24] at the beginning of the 1950s.
In this work, we introduce a new method for determination of DA in
the presence of Tyr based on a sensitive and simple nanostructured
sensor and multivariate optimization strategy. This method presents
electrochemical studies along with central composite rotatable design
(CCRD) and response surface methodology (RSM) for optimization of
all effective factors on electrochemical responses. Moreover, we
described preparation a GO modified carbon paste electrode (CPE/GO)
as a sensitive sensor for the determination of DA in the presence of
Tyr. Finally, to demonstrate the potential of the modified electrode for
electrooxidation of DA in real samples, we have examined this method
for the voltammetric determination of DA in human blood plasma
samples.
2. Experimental
2.1. Chemicals
All solutions were prepared using deionized water. All reagents
were from Merck with analytical grade and used without any other pu-
rification. Graphite powder with high purity and paraffin oil (DC 350,
ρ = 0.88 g cm−3) were used as a binding factor for the graphene
paste. Britton–Robinson (B–R) buffer solution (0.2 M) was used as
supporting electrolyte that containing 0.2 M of phosphoric acid, boric
acid and acetic acid. The value of pH was adjusted using a saturated
solution of sodium hydroxide. GO was obtained from Nanjing XFNano
Materials Tech Co., Ltd. All experiments were done at the room temper-
ature (25 ± 0.5 °C).
2.2. Instruments
Electrochemical determinations involving cyclic voltammetry (CV),
differential pulse voltammetry (DPV), chronocoulometry and linear
sweep voltammetry (LSV), were done using a Sama 500 potentiostate
(Isfahan, Iran). Electrochemical impedance spectroscopy (EIS) mea-
surements were done by an Autolab potentiostat-galvanostat PGSTAT
35 (Eco Chemie Utrecht, Netherlands), equipped with NOVA 1.6 soft-
ware and a personal computer (Pentium IV) was used for data storage
and processing. Scanning electron microscopy (SEM) micrographs
were performed using a KYKY-EM3200. A digital pH meter (metrohm
model 691) was used for pH adjusting, and an ultrasonic bath (Bandelin
Sonorex, Germany) at a constant frequency of 35 kHz was used for
dispersing of GO during the experiment. Our electrochemical cell
contained three electrodes including CPE/GO, a platinum electrode
(Metrohm, Switzerland) and a silver/silver chloride (Ag/AgCl/KCl
(sat.)) (Metrohm, Switzerland) as working, counter and reference
electrode, respectively. Carbon paste was pushed into a polyethylene
tube with 2 mm diameter and 5 mm deep.
2.3. Preparation of the modified electrode
The bare electrode was prepared by mixing of 0.5 g graphite powder
with 0.18 g paraffin oil. For preparation of the CPE/GO, 0.01 g graphene
oxide (optimum amount) was added to 5.0 mL deionized water and
sonicated for 30 min using ultrasonic bath to achieve a homogenous
suspension and then added into 0.5 g graphite powder and allow this
mixture to stay in the room temperature to evaporate the water. Then
0.18 g of paraffin oil was added to this mixture and mixed for 30 min
till uniformly carbon paste was formed.
3. Results and discussion
3.1. Surface analysis by EIS and SEM studies
EIS technique is very sensitive for the investigations of electrode/
electrolyte interaction. EIS spectrums in Fig. 1 show two distinct parts:
(1) a semi-circle part related to the charge transfer process, (2) a line
defining a region of semi-infinite diffusion of species in the electrode,
recognizable different of charge-transfer resistance (Rct) value was ob-
served upon the stepwise formation of the modified electrode. The Rct
value for the bare CPE was 5.87 kΩ while it was 1.53 kΩ for CPE/GO. It
might be because of the presence of GO on the CPE surface, which
played an important role in accelerating the transfer of the electrons.
In addition to EIS measurements, SEM was used to investigate the
surface morphological characters of the CPE and GO (Fig. 2A [25] and
Fig. 2B, respectively). Fig. 2B shows the GO has a typical flake-like
shape with slight wrinkles on the surfaces.
3.2. Electrochemical properties of the modified CPE/GO
The catalytic function of the CPE/GO at pH 6.0 is shown in Fig. 3 in
the absence (curve a) and presence of 2.30 μM DA (curves b and c) at
the surface of the bare CPE and the CPE/GO by DPV. As can be seen by
scanning from 0.15 V toward a positive potential at a bare CPE, a rela-
tively small anodic peak at 0.25 V was observed (Fig. 3, curve b), while
at the surface of CPE/GO large enhancement in current response at
+0.217 V is observed (Fig. 3, curve c).
3.3. Experimental design and data analysis
Optimizing of effective chemical and instrumental variables for de-
termination of DA in the presence of Tyr was carried out by CCRD.
CCRD is a good method for simultaneous optimization of factors and in-
vestigating the interaction between variables with minimum number of
experiments. These experiments were performed based on two group
of factors containing concentration of GO and the pH value as chemical
factors and the values of scan rate, step potential and modulation ampli-
tude as instrumental factors. For optimizing of the first group, 11 exper-
iments were designed and carried out for pH ranging between 2.0 to 6.0
and the GO amount between 6 to 14 mg. The second group contained 17
experiments that the range of variables was 0.02–0.18 V s−1 for scan
rate, 0.001–0.005 V for step potential and 0.01–0.09 V for modulation
amplitude. Also three replication experiments were designed in this
optimization. Figs. 4 and 5 show the optimum response values can be
obtained by the graphical analysis of the surface related to chemical
Fig. 1. (A) The Nyquist plot of the bare CPE and modified CPE/GO in 0.2 M B–R buffer
solution containing 5.0 mM [Fe(CN)6]3−/4−.
 S.M. Ghoreishi et al. / Journal of Molecular Liquids 215 (2016) 31–38 33

Fig. 2. (A) SEM micrograph of CPE. (B) SEM micrograph of GO.

and instrumental factors, respectively. Also the optimum values of each

factor are represented in Table 1.

3.4. Effect of pH on oxidation of dopamine

The effect of pH values on the DA oxidation signal was investigat-

ed by DPV method using 0.2 M B–R buffer solution with pH values
ranging from 2.0 to 6.0 (Fig. 6A) at the surface of CPE/GO. Fig. 6B
shows in pH = 4.0 anodic current of DA oxidation has a maximum
value; therefore this point was used as optimum value. According
to the Nernst equation (Eq. 1), where a, b is used to show reagent co-
efficients in the reaction equation and n and m represent the number
of electrons and protons involved in reaction, a slop of 60.5 mV pH− 1
indicate that the proportion of the involved proton and electron in
the reaction is 1:1 (Fig. 6C). Therefore according to previous studies
a two electrons and two protons process was obtained for oxidation
of DA (Scheme 1) [26,27]. Also the standard formal potential of DA
was obtained 0.5832 V.

h i
Fig. 3. Differential pulse voltammograms of (a): CPE/GO in B–R buffer solution, (b): CPE in
Ep ¼ E þ ð0:0591=nÞ log ðOxÞa =ðRedÞ –ð0:0591 m=nÞ pH
b
ð1Þ
the presence of 2.30 μM DA, and (c): (a) + 2.30 μM DA.

Epa ðVÞ ¼ −0:0605 pH þ 0:5832

Fig. 4. Three-dimensional (3-D) response obtained from the regression equation (coded Fig. 5. Three-dimensional (3-D) response obtained from the regression equation (coded
values of variables) for chemical factors. A and B variables correspond to pH and graphene values of variables) for instrumental factors. A, B and C variables correspond to scan
content respectively. rate, step potential and modulation amplitude respectively.
34 S.M. Ghoreishi et al. / Journal of Molecular Liquids 215 (2016) 31–38

Table 1 (Eq. 2) is used for determination of diffusion coefficient of analytes

The optimum values for experimental factors achieved with CCRD. [28].
Factors Optimum point
Q ¼ 2nFACO D1=2 п‐1=2 t1=2 ð2Þ
pH 4.0
GO (mg) 0.01
Scan rate (V s−1) 0.15 Where D (cm2 s−1) is the diffusion coefficient, CO (mol cm−3) is the
Modulation amplitude (V) 0.0366 bulk concentration and other symbols have their usual meanings. A plot
Step potential (V) 0.001 of Q versus t1/2 (s1/2) will be linear under the diffusion limited transport
(mass transport) (Fig. 8B). So the value of D can be extracted from the
slope of Fig. 8C, this value was obtained to be 9.2 × 10−5 cm2 s−1.

3.5. Linear sweep voltammetry study

3.7. Effect of scan rate

LSV of CPE/GO in 0.2 M B–R buffer solution (pH 4.0) containing var-
DA behavior at the surface of CPE/GO was also investigated by
ious concentration of DA with a sweep rate of 150.0 mV s−1 are shown
changing in scan rate in CV techniques. Fig. 9A shows the cyclic
in Fig. 7A. Tafel region is the rising part of voltammograms, which is
voltammogrames of DA at the CPE/GO surface in different scan rates
effected by the electron transfer kinetics between DA and CPE/GO. If
(ν). Randles–Sevcik equation (Eq. 3) is used for quasi-reversible process
deprotonation of DA is an enough fast step, and assuming the number
[28]:
of electrons involved in the rate determining step is nα = 2, by averag-
ing the slopes and intercepts of Tafel plot (Fig. 7B), the charge transfer
Ip ¼ 2:69  105 n3=2 AD1=2 C ν1=2 ð3Þ
coefficient (α) and the exchanging current density (j0) are calculated
to be 0.60 and 14.08, respectively [28].
Where n is the number of electron involved in the oxidation process,
A is the surface area, D is diffusion coefficient, C is concentration of
3.6. Chronocoulometry measurements reagent and ν is scan rate ranging of 30.0–130.0 mV s−1 for this study.
The oxidation peak current of a solution containing 2.00 μM DA in B–R
The catalytic oxidation of DA at the surface of CPE/GO was stud- buffer (pH = 4.0) increases linearly with square root of scan rate
ied using chronocoulometry. Fig. 8 shows chronocoulograms ob- (Fig. 9B) that suggesting a diffusion-controlled process of DA at the
tained from solution containing different concentration of DA from modified electrode, so the linear regression equation was found to be:
0.67 to 1.12 μM in B–R buffer by setting the working electrode po-
tential at 400.0 mV. In chronocoulometric studies, Cottrell equation Ipa ¼ 0:4979 ν1=2 −0:0596 R2 ¼ 0:9921

Fig. 6. (A): DPV of 2.00 μM DA with pH of 2.0, 3.0, 4.0, 5.0 and 6.0 (from a to e, respectively) collected at a 365.6 mV s−1 scan rate at the surface of CPE/GO. (B): Plot of intensity: I/μA vs. pH
and (C) Plot of electrochemical potential:Epa/V vs. pH.

Scheme 1. Mechanism of DA oxidation at the CPE/GO.

 S.M. Ghoreishi et al. / Journal of Molecular Liquids 215 (2016) 31–38 35

Fig. 7. (A): Linear sweep voltammograms of CPE/GO in B–R buffer (pH = 4.0) containing 1.85, 2.01 and 2.30 μM DA (a–c) at a sweep rate of 150.0 mV s−1, (B): Tafel plot derived from linear
sweep voltammograms.

3.8. Differential pulse voltammetry measurements of dopamine and concentration of DA in the range of 0.079–2.30 μM. The respective
calibration equation is obtained:
DPV technique has a much higher current sensitivity and better res-
olution than CV; therefore it was used to estimate the limit of detection Ipa ðμAÞ ¼ 0:4899 C ðμMÞ þ 0:0381; R2 ¼ 0:9961
of DA. Fig. 10A shows the differential pulse voltammogrames of DA at
the CPE/GO in 0.2 M B–R buffer solution (pH = 4.0) under other opti- Therefore from the analysis of the data, the limit of detection (3 s) of
mized conditions. Also Fig. 10B shows the relationship between Ipa DA was found to be 8.6 nM.

Fig. 8. Chronocoulograms obtained at CPE/GO in 0.2 M B–R buffer solution (pH = 4.0) for various concentrations of DA, with potential step at 400.0 mV and a to d correspond to 0.67, 0.82,
0.98 and 1.12 μM of DA, (B): Plots of I vs. t1/2 (s1/2) obtained from chronoamperograms a-e, and (C): A plot of the slope of the straight lines versus the concentration of DA.
36 S.M. Ghoreishi et al. / Journal of Molecular Liquids 215 (2016) 31–38

Fig. 9. Cyclic voltammograms of CPE/GO in a B–R buffer solution (pH = 4.0) for 2.00 μM DA, in various scan rates: 30.0, 40.0, 50.0, 70.0, 80.0, 90.0, 100.0 and 130.0 mV s−1 (from inner to
outer). (A): Peak current vs. E (mV) and (B): intensity, I (μA) vs. ν1/2.

3.9. Determination of DA in the presence of Tyr slope) at the surface of CPE/GO in the absence and presence of Tyr is
same (Fig. 11B). Therefore the modified CPE/GO is a capable sensor for
One of the main purposes of this study was sensitive detection of DA determination of DA in the presence of Tyr.
in the presence of Tyr. For achieving the purpose, DPV technique was
performed in the constant concentration of Tyr (6.0 μM) and varied con- 3.10. Interference studies
centration of DA (0.27–1.80 μM). Fig. 11A shows differential pulse
voltammogrames of a solution containing differential concentration of The proposed method with mentioned modified electrode showed
DA in the presence of Tyr at the CPE/GO in 0.2 M B–R buffer solution. good selectivity for determination of DA in the presence of common in-
− − −
As can be seen high concentration of Tyr dose not interfere in detection terfering species such as Na+, NH+ 2− +
4 , NO3 , Cl , CO3 , K and I . Also,
of DA. According to this study, the sensitivity of DA (calibration curve some amino acids such as phenylalanine, cysteine and tryptophan had

Fig. 10. (A): DPV of CPE/GO in 0.2 M B–R buffer solution (pH = 4.0), containing different concentrations of DA. The letters a–g corresponds to: 0.19, 0.23, 0.43, 0.97, 1.80, 2.01 and 2.30 μM
of DA and (B): Plot of the electrocatalytic peak current as a function of DA concentration.
 S.M. Ghoreishi et al. / Journal of Molecular Liquids 215 (2016) 31–38 37

Fig. 11. (A): DPV of CPE/GO in 0.2 M B–R buffer solution (pH = 4.0) containing 6.00 μM Tyr and various concentrations of DA containing a-f corresponding to: 0.27, 0.43, 0.82, 1.43, 1.57 and
1.80 μM and (B): Plot of Ip (μA) as a function of DA concentration (μM).

Table 2 pH = 4.0, by sequential determination of DA for two week period and

Influence of some foreign substances for DA. by five separately prepared CPE/GO for stability and repeatability
properties, respectively. From the first group of data decreasing in
Foreign substances Tolerance level
− −
peak current was only 95.75% (Fig. 12) that suggests good stability of
Na+, NH+ 2−
4 , NO3 , CI , CO3 500
the modified electrode. In the repeatability study, the relative standard
K+, I− 50
L-phenyl alanine, cysteine 500 deviation obtained for peak current was between 3.98 to 4.16% and for
Tryptophan 5 peak potential was between 0.27 to 0.31%. These results indicate a good
repeatability of CPE/GO in determination of DA.

no effect on the oxidation peak of DA. The results are shown in Table 2.
The tolerance limit was taken as the maximum concentration of the
foreign substances which caused an approximately ±5% relative error
in determination of DA [29].
3.11. Stability and repeatability of CPE/GO
Two important factors for preparation of a modified electrode are
stability and repeatability. These properties were checked using DPV
data obtained in optimized experimental conditions. These studies
were carried out in B–R buffer solution containing 1.80 μM DA in
3.12. Real sample analysis
In order to demonstrate the capability of the proposed method in
real samples, direct determination of DA was performed in human
blood serum. Prior to investigation of the samples were diluted 100
times in pH 4.0, B–R buffer solution. Standard addition method is used
to determine of DA with DPV technique. Recovery results are shown
in Table 3. These results were obtained by three repeatable determina-
tions on each sample and were acceptable, showing that this method is
useful for the determination of DA in real samples.
4. Conclusion

In this work CCRD was used to optimize voltammetric parameters

for measurement of DA in the presence of Tyr. This method allows us
to optimize parameters with the minimum number of experiments.
DPV method was used to detect trace amount of DA in the presence of
Tyr at the surface of CPE/GO under the optimized conditions. Results
show the oxidation of DA is dependent on the pH and rise at the surface
of the modified electrode. Also some voltammetric methods were also
used for electrochemical and kinetic studies of DA. The detection limit
for DA in the presence of Tyr at the surface of CPE/GO was founded to

Table 3
Determination of DA in human blood serum samples.

Sample no. Added (g L−1) Found Recovery (%)

1 0.00 0.00 –
2 0.20 0.20 101.26
3 0.40 0.39 99.15
4 0.60 0.59 98.63
5 0.80 0.81 101.37
6 1.00 0.99 99.58
Fig. 12. Stability of CPE/GO in the presence of DA.
38 S.M. Ghoreishi et al. / Journal of Molecular Liquids 215 (2016) 31–38

Table 4
Comparison of the efficiency of some modified electrodes used in the detection of DA.

Analyte Electrode Limit of detection for dopamine Reference

(μM)

Dopamine Flower-like graphene-nanosheet clusters modified glassy 3.00 [30]

carbon electrode
Ascorbic acid, dopamine, and uric acid Pristine graphene 2.00 [31]
Dopamine and uric acid in the presence of ascorbic acid Multi-nanopore graphene, modified glassy carbon electrode 1.50 [32]
Dopamine, ascorbic acid, and uric acid Graphene/SnO2 nanocomposite modified glass carbon electrode 1.00 [33]
Dopamine in the presence of ascorbic acid Graphene oxide modified glassy carbon electrode 0.27 [34]
Ascorbic acid, dopamine and uric acid Graphene-nickel hydroxide flower-like graphene-nanosheet clusters 0.12 [35]
Dopamine Gold nanoparticles/tryptophan functionalized graphene 0.056 [36]
Dopamine in the presence of ascorbic acid and uric acid Sulfonated-graphene glassy carbon modified electrode 0.020 [37]
Dopamine in the presence of tyrosine Graphene oxide modified carbon paste electrode 0.0086 This work

be 9.01 nM. This value was close to the value obtained in the absence of
Tyr (8.6 nM). A comparison of the proposed method with the other re-
search groups for detection of DA at the surface of chemically modified
electrodes indicates that the CPE/GO is superior to the existing elec-
trodes with regard to detection limit and multivariate optimization
(Table 4). The results indicate that the modified CPE/GO is very sensitive
with high selectivity for electrochemical sensor applications.
Acknowledgments
We are grateful to University of Kashan for supporting this work
with Grant 211037-19.
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