Sensors and Actuators B 173 (2012) 274–280

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Sensors and Actuators B: Chemical

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Highly sensitive amperometric sensor for carbamazepine determination based

on electrochemically reduced graphene oxide–single-walled carbon nanotube
composite film
Binesh Unnikrishnan, Veerappan Mani, Shen-Ming Chen ∗
Electroanalysis and Bioelectrochemistry Lab, Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3,
Chung-Hsiao East Road, Taipei 106, Taiwan, ROC

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

Article history: We report a highly sensitive amperometric sensor for the determination of carbamazepine (CBZ) at an
Received 2 May 2012 electrochemically reduced graphene oxide (ERGO) and single walled carbon nanotube (SWCNT) compos-
Received in revised form 26 June 2012 ite film modified glassy carbon electrode (GCE). The – stacking interactions between ERGO and SWCNT
Accepted 30 June 2012
add good stability to the composite film which was confirmed by UV–visible and FTIR spectroscopy. Com-
Available online 11 July 2012
pared with SWCNT modified electrode, ERGO–SWCNT composite film modified electrode exhibits a 3.2
fold enhancement in peak current for CBZ oxidation. The proposed sensor detects CBZ as low as 29 nM
Keywords:
and has a sensitivity of 5.1076 ␮A ␮M−1 cm−2 in the linear range of 50 nM to 3 ␮M. The practicality of this
Carbamazepine
Graphene–SWCNT composite
sensor has been evaluated by the determination of CBZ from Tegratol tablets showing good sensitivity
Graphene oxide and linearity.
Electrochemical reduction © 2012 Elsevier B.V. All rights reserved.
Amperometry

1. Introduction fouling due to the adsorption of the oxidized products on the

electrode surface. Veiga et al. demonstrated that this imperative
Carbamazepine (CBZ) is an antiepileptic drug widely used in shortcoming could be overcome by treating the electrode in open
the treatment of nueralgia, seizure disorders, mental depression, circuit potential and rotating at a speed of 1000 rpm for 3 min
etc. [1]. It has been accepted that CBZ is superior in efficacy to between each run in voltammetric analysis [7]. Differential pulse
antiepileptic drugs such as gabapentin, phenobarbital, primidone, adsorptive–stripping voltammetry using horseradish peroxidase
valproate and vigabatrin, though the mode of action is different. modified screen printed carbon electrode displays good selectivity
In some cases it has also been used in non epileptic treatment and and silver nanoparticles modified electrode shows good sensitiv-
it can act as a mood stabilizing agent [2]. However, CBZ can pro- ity toward CBZ [8]. Atkins et al. achieved a limit of detection (LOD)
duce some adverse effects such as neurotoxicity which leads to of 3.89 × 10−6 M in acetonitrile electrolyte using differential pulse
blurred vision, dizziness, impaired task performance, hypersensi- voltammetry (DPV) [9]. Though the afore-mentioned electrode
tivity and leukopenia [3]. Cases of vertigo and nausea caused by a materials displayed good performance toward CBZ sensing, the
pharmacodynamic interaction of CBZ with lamotrigine have also quest for novel materials is still in progress for achieving highly sen-
been reported [4]. The neurotoxicity of CBZ is highly dependent sitive and selective determination. Recently, multiwalled carbon
on the dosage and notably, about 28% of the orally adminis- nanotube (MWCNT) modified electrode has been demonstrated as
tered CBZ is discharged to the environment through feces [5,6]. an excellent electrocatalyst for the oxidation of CBZ [10].
Therefore its determination in biological samples, pharmaceutical Graphene is a 2D material [11,12] with excellent electronic
preparations and environmental samples are of great importance. [13,14] and mechanical properties. It can be synthesized from
Though electrochemical methods have several advantages over graphite, an easily available material through an inexpensive
other conventional analytical methods, only a few reports are route involving an oxidative treatment and formation of graphite
available for electrochemical determination of CBZ. The great chal- oxide [15]. Graphite oxide can be exfoliated to produce graphene
lenge in the electrochemical determination of CBZ is the electrode oxide (GO), which possess plenty of oxygen functionalities on its
basal plane and edges [16]. These oxygen functionalities make
it hydrophilic, thus it can form stable aqueous dispersions [17].
∗ Corresponding author. Tel.: +886 2270 17147; fax: +886 2270 25238. Besides it posses unoxidized aromatic regions which provide
E-mail address: [email protected] (S.-M. Chen). hydrophobicity and hence it can also be dispersed in non-aqueous

0925-4005/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
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 B. Unnikrishnan et al. / Sensors and Actuators B 173 (2012) 274–280 275

solvents [18]. Owing to the various versatile characteristic fea- mixture (30:70) and stored in a refrigerator at 4 ◦ C when not in
tures including the amphiphilic nature, GO has drawn considerable use.
attention. The large surface area and the folded architecture of GO
has promoted it as an attractive material for electrochemical sensor
2.3. Preparation of GO and fabrication of ERGO–SWCNT
and biosensor applications [19]. Nevertheless, its insulating prop-
composite modified electrode
erty limits its electrochemical applications. Therefore to improve
the electronic properties of GO, it is reduced to graphene by chemi-
Graphite oxide was synthesized by modified Hummer’s method
cal [20] or electrochemical methods [21]. However, the basal plane
as reported elsewhere [15,28]. The graphite oxide was then dis-
of graphene does not exhibit good electrochemical properties [22].
persed in deionized water (0.5 mg/mL) and exfoliated to GO by
On the other hand, the rolled version of graphene, carbon
ultrasonication for 2 h [21]. It was then centrifuged at 4000 rpm
nanotube (CNT) has excellent mechanical, electrical, catalytic and
for 30 min to remove the excess, unoxidized graphite and unexfo-
electrocatalytic properties [23]. Enormous amount of work has
liated graphite oxide. The as-obtained GO solution is used as stock
been done on the application of MWCNT and single walled carbon
solution. To 10 mL of the GO solution, 5 mg pristine SWCNT was
nanotubes (SWCNT) for electrochemical applications [24]. Pristine
added and dispersed by ultrasonicsation for 2 h. A homogeneous
CNTs are highly hydrophobic and as a result it is impossible to
solution of GO–SWCNT composite was thus obtained. The loosely
prepare its stable aqueous dispersion [25]. Recent studies reveal
bounded SWCNT and excess GO were removed by subjecting it to
that GO and CNTs can interact through – stacking to form a
two centrifugation cycles (30 min each) at 8000 and 14,000 rpm,
stable dispersion of GO–CNT composite [26,27]. The hydrophilic
respectively [27]. Finally, the as-obtained composite material was
properties of GO in combination with the excellent electronic and
washed with copious amounts of water and dried. 0.5 mg/mL of
antifouling properties of CNTs endorse this composite material for
GO–SWCNT solution was prepared in water by ultrasonication and
fascinating electrocatalytic applications. To further increase the
it was used for the fabrication of ERGO–SWCNT modified GCEs.
conductivity of this composite, it was reduced via electrochem-
Before each experiment, GCE was polished well with Buel-
ical route to prepare electrochemically reduced graphene oxide
her polishing cloth and 0.5 ␮m alumina slurry. The polished GCE
(ERGO)–SWCNT. Keeping the afore-mentioned advantages in mind,
surface was washed and ultrasonicated in water for 5 min to
we attempt to employ the ERGO–SWCNT composite as a novel
remove the adsorbed alumina particles and dried. 5 ␮L of the
electrocatalyst for the electrocatalytic oxidation of CBZ. The devel-
GO–SWCNT dispersion was drop casted onto clean GCE surface
oped GO–SWCNT composite based amperometric sensor displayed
and dried at room temperature to get GO–SWCNT modified GCE
enhanced electrocatalytic activity, high sensitivity and low limit of
(GCE/GO–SWCNT). The GCE/GO–SWCNT was then transferred to
detection toward CBZ.
0.1 M PBS solution (pH 5). The GO in the GO–SWCNT composite
film was electrochemically reduced to ERGO by applying a constant
potential of −1.3 V for 400 s (figure not shown) [21,26]. The elec-
2. Experimental
trochemical reduction pattern was in accordance with the reports
of Qiu et al. [26] indicating the reduction of oxygen functionali-
2.1. Apparatus
ties of GO. The obtained electrode is noted as GCE/ERGO–SWCNT.
GO modified GCE (GCE/GO), ERGO modified GCE (GCE/ERGO) and
The electrochemical measurements were carried out using CHI
SWCNT modified GCE (GCE/SWCNT) also have been prepared for
611a work station with a conventional three electrode cell using
comparison.
BAS GCE as working electrode (area 0.0706 cm2 ), Ag|AgCl (sat. KCl)
as reference electrode and Pt wire as counter electrode. Prior to each
experiment, all the solutions were deoxygenated by passing pre- 3. Results and discussions
purified N2 gas for 15 min. Amperometric (i–t curve) measurements
were performed with analytical rotator AFMSRX (PINE instruments, 3.1. Characterization of ERGO–SWCNT composite film
USA). EIM6ex ZAHNER (Kroanch, Germany) was used for electro-
chemical impedance spectroscopy (EIS) studies. Surface morpho- Fig. 1(A) represents the FESEM image of the ERGO–SWCNT com-
logical studies were carried out using Field emission scanning elec- posite film. The surface morphology of the film reveals the well
tron microscopic (FESEM) JSM-6500F. Fourier Transform Infra-red dispersed SWCNTs are adhered well to the ERGO sheets. The wide
(FTIR) spectroscopy measurements were carried out using Perkin size distribution of ERGO sheets is assessed by the presence of
Elmer spectrum RXI. UV–visible absorption spectroscopy measure- numerous small ERGO platelets along with fewer larger sheets
ments were carried out using Hitachi U-3300 spectrophotometer. ranging over few nano meter to sub micro meter range. Several
fine nanotube networks have also been distributed widely. The
hydrophobic basal plane of ERGO [29] interacts with the sidewalls
2.2. Reagents and materials of SWCNT through – electronic interactions to form a stable
composite film [30], which is further confirmed from the UV–visible
Graphite powder (<20 ␮m), SWCNTs (90%, OD: <2 nm, L: spectral data provided in Fig. 1(B).
<20 ␮m), and carbamazepine (CBZ) were purchased from The UV visible absorption spectra of GO and GO–SWCNT com-
Sigma–Aldrich. All the chemicals used were of analytical grade and posite is given in Fig. 1B. GO exhibits two characteristic absorption
used without further purification. Tegretol tablets with 200 mg peaks; a broad absorption peak at 230 nm and a shoulder peak at
CBZ, from Novartis was acquired from a local pharmacy for real 280 nm. The peak at 230 nm is due to the –* transition of the C C
sample analysis. 0.1 M phosphate buffer solutions (PBS) were bonds in the aromatic region of GO sheets and the latter one is due
prepared using Na2 HPO4 and NaH2 PO4 . The pH was adjusted using to the n–* transition in the C O bonds of the functional groups.
dilute HCl or NaOH. Double distilled water (conductivity ≥ 18 M) In the absorption spectra of GO–SWCNT, the peak at the 230 nm is
was used for all the experiments. All the experimental solutions shifted to higher wavelength (247 nm), indicating a – stacking
were deoxygenated with pre-purified N2 gas for 15 min prior to interaction between the aromatic basal plains of GO and the SWCNT
each experiment. The supporting electrolyte used for electro- [27,31]. Whereas the peak at 280 nm (due to n–* transition) does
chemical studies was 0.1 M pH 5 phosphate buffer solution (PBS). not shift, revealing the composite formation has not occurred via
A stock solution of CBZ (1 mM) was prepared in acetonitrile/water the functional groups.
276 B. Unnikrishnan et al. / Sensors and Actuators B 173 (2012) 274–280

Fig. 2. (A) FTIR spectra of (a) exfoliated GO, (b) SWCNT, (c) GO–SWCNT and (d)
ERGO–SWCNT; (B) EIS recorded for modified GCEs in 5 mM Fe(CN)6 3− /Fe(CN)6 4− in
Fig. 1. (A) FESEM image of ERGO–SWCNT composite film, (B) UV–visible spectra of
pH 5. Applied AC voltage: 5 mV, frequency: 0.1 Hz to 100 kHz. Inset shows the EIS of
GO and GO–SWCNT composite.
GCE/GO and GCE/ERGO.

The FTIR spectroscopy can provide information about the func-

from Fig. 2(B) that the diameter of the semicircles obtained for
tional groups present in GO, ERGO and the composite (Fig. 2A).
various electrodes are different. The inset of Fig. 2(B) is the Nyquist
Curve (a) is the FTIR spectrum of GO. A broad peak at around
plots of GO and ERGO modified electrodes. GO film exhibits a
3413 cm−1 and a small dip at the 3200 cm−1 are due to O H
higher Ret value than ERGO film, indicating the significant decrease
stretching of the intercalated water molecules and O H coupling
in Ret value upon the electrochemical reduction of GO to ERGO. In
vibrations of the carboxylic acid group in the GO, respectively [21].
comparison with bare GCE, the Ret value of GCE/SWCNT decreased
The C O vibrations of the carboxylic acid and carbonyl groups
considerably, ascribed to the excellent conducting properties of
appear at 1730 cm−1 , while the C C (epoxy group) and C C vibra-
the SWCNT. Compared with GO and GO–SWCNT, ERGO–SWCNT
tion peaks of the unoxidized graphitic domains appear at 1073 and
composite film shows the lowest Ret value, suggesting a very good
1623 cm−1 respectively. However, the pristine SWCNT does not
interaction between GO and SWCNT as well the excellent conduc-
show any absorption peak (curve b) over the investigated wave-
tance. EIS results also support the evidence for the formation of
length range. When the GO forms composite with SWCNT, the
ERGO–SWCNT composite through – stacking interactions.
characteristic peaks of GO still appears in the FTIR spectrum (curve
c) [27]. Notably, when the GO–SWCNT composite is electrochem-
ically reduced to ERGO–SWCNT, the intensity of the absorption 3.2. Electrochemical behavior of CBZ at various electrodes
peaks of oxygen functionalities are significantly reduced (curve d),
indicating an efficient electrochemical reduction of GO. Cyclic voltammetric behavior of CBZ at GCE [34] reveals that
GCE surface modification with GO, ERGO, SWCNT or CBZ exhibits two irreversible anodic peaks at 1.183 and 1.401 V,
ERGO/SWCNT changes the double layer capacitance and interfacial respectively, in pH 7.4 in the potential range between 0.8 and 1.7 V.
electron transfer resistance of the electrode. Electrochemical The peak at 1.183 V is well defined and stable; hence, it could be
impedance spectroscopy (EIS) can reveal the interfacial changes well used for electroanalytical purposes. In this work, the cyclic
due to the surface modification of electrodes [32]. Fig. 2(B) voltammograms were recorded at various electrodes in pH 5 con-
demonstrates the EIS measurements of the modified electrodes taining 10 ␮M CBZ over the potential range of 0.6–1.3 V (Fig. 3A). At
represented as Nyquist plots. The semicircle appeared in the bare GCE and GCE/ERGO feeble anodic peaks are observed for CBZ.
Nyquist plot indicates the parallel combination of electron transfer Whereas compared with these electrodes, GCE/SWCNT exhibits an
resistance (Ret ) and double layer capacitance (Cdl ) at the electrode irreversible anodic peak at 1.14 V with a peak current (Ipa ) of 54 ␮A.
surface resulting from electrode impedance [33], while the linear Remarkably, GCE/ERGO–SWCNT exhibits a tremendous increase in
portion represents the diffusion limited process. It can be seen sensitivity with Ipa of 173 ␮A (3.2 times than that of GCE). This result
 B. Unnikrishnan et al. / Sensors and Actuators B 173 (2012) 274–280 277

Fig. 4. (A) Cyclic voltammograms of 10 ␮M CBZ in N2 saturated pH 5 at different

scan rates; (a) 25, (b) 50, (c) 75, (d) 125, (e) 150, (f) 175, (g) 225, (h) 250 and (i)
275 mV s−1 . Inset is the plot of log Ipa vs. log ␯, (B) plot of 1/2 vs. Ipa , (C) plot of log 
vs. Epa .

Fig. 3. (A) Cyclic voltammograms of 10 ␮M CBZ in N2 saturated PBS (pH 5) at (a)

bare GCE, (b) GCE/ERGO, (c) GCE/SWCNT and (d) GCE/ERGO–SWCNT. Scan rate:
50 mV s−1 . (B) Cyclic voltammograms of 10 ␮M CBZ at GCE/ERGO–SWCNT in various
pH aqueous solutions (N2 saturated). Scan rate: 50 mV s−1 . increase in scan rate. The inset of Fig. 4 shows the plot of log 
vs. log Ipa . The dependence of Ipa on the scan rate can be repre-
sented as log Ipa = 0.564 log  + 2.642, R2 = 0.982. Where Ipa and  are
measured in ␮A and Vs−1 respectively. The slope of 0.564 shows
reveals the high sensitivity of the composite film modified elec- that the anodic process of CBZ taking place at the composite elec-
trode toward CBZ oxidation. Although high sensitivity is achieved trode is diffusion controlled [34,35]. The effect of scan rate on
for CBZ by CV, the oxidized products are adsorbed at the electrode the Ip of CBZ oxidation at room temperature can be described by
surface and decrease the sensitivity of the electrode after each run. Randles–Sevcik equation as given in Eq. (1) [36]:
Therefore, the removal of the products after each run is necessary
Ip = 2.99 × 105 n[(1 − ˛)n˛ ]1/2 ACb D1/2 v1/2 (1)
in electroanalytical applications [7]. So, amperometric technique
is a more efficient method compared to CV, in which the oxidized where Ip is the forward peak current, n is the number of electrons
products are thrown away by the rotating electrode, and helps the exchanged per molecule, ˛ is the electron transfer coefficient, n˛
analyte to diffuse easily to the electrode surface. Fig. 3(B) shows is the number of electrons involved in the rate-determining step,
the cyclic voltammetric response of 10 ␮M CBZ at ERGO–SWCNT A is the area of the electrode, Cb is the bulk concentration of CBZ,
composite film in the pH range 1–11. With increase in pH the peak D is the diffusion coefficient of CBZ and  is the scan rate. From the
potential shifts toward lower potential and the peak disappears in Eq. (1) and Fig. 4(B), it is clear that Ip increases linearly with 1/2 in
pH 9 and above. Since the electrode shows maximum performance the range of 25–275 mV s−1 . It can be described by the following
in pH 5, we conducted all the electrochemical and electroanalytical linear regression equation: Ip (␮A) = 569.3 1/2 + 56.01, R2 = 0.978,
experiments in pH 5 PBS. suggesting that the process is controlled by diffusion. Also, the
The effect of scan rate () on the oxidation of CBZ has been stud- oxidation peak potential (Epa ) shifts to higher positive potentials
ied by CV in the potential range, 0.7–1.3 V. Ipa increases with the with the increase in scan rate. A plot of Epa vs. log  presume a linear
278 B. Unnikrishnan et al. / Sensors and Actuators B 173 (2012) 274–280

Table 1
Comparison of analytical parameters of various electrodes.

Electrode Method pH Linear range Limit of detection Ref.

ERGO–SWCNT Amperometry 5 50 nM–3 ␮M 29 nM This work

GCE DPV 1 5 × 10−6 –6 × 10−4 M 1.8 ␮M [34]
Graphite DPV a
ACN 8.46 × 10−5 –8.46 × 10−4 M 3.89 × 10−6 mol L−1 [9]
GCE/MWCNT b
LSV 6.89 0.13–1.60 ␮M 40 nM [7]
GCE DPV ACN – 4 ␮M [38]
GCE/fullerene-C60 DPV 7.2 90 nM–10 ␮M 16.2 nM [39]
c
Au/graphene–AuNp LSV ACN 5 × 10−6 –1 × 10−2 M 3.03 × 10−6 M [40]
d
BnMIM]PF6 /CPE DPV 6.8 7.0 ␮M–0.7 mM 0.98 ␮M [41]
a
Acetonitrile.
b
Linear sweep voltammetry.
c
AuNP is Au nanoparticles.
d
1-Benzyl-3-methylimidazole hexafluorophosphate modified carbon paste electrode.

relationship, and the regression equation is: calculated to be 0.501. Assuming n˛ = 1 for one electron transfer
Epa (V) = 1.302 + 0.118 log  (Fig. 4C). This result process, the value of ˛ is obtained as 0.499 for CBZ.
implies that CBZ electrocatalytic oxidation
process is chemically irreversible. For the irreversible process, Epa 3.3. Amperometric determination of CBZ at
can be described as given in Eq. (2) [36] ERGO–SWCNTcomposite
 2.303 RT

Epa = log v + K (2) Fig. 5(A) represents the amperometric response of CBZ at
[n(1 − ˛)n˛ F]
ERGO–SWCNT modified rotating disc electrode (RDE) with surface
where R is the universal gas constant, T is the temperature in Kelvin area of 0.236 cm2 . The experiment was conducted in pH 5 PBS at
and F is the Faraday constant. From the slope, (1 − ˛)n˛ has been an applied potential of 1.155 V with a rotation rate of 2500 rpm.
CBZ solution was added at regular intervals of time (100 s). For
every addition a quick response was observed and electrocatalytic
oxidation of CBZ occurs at RDE in a totally mass transfer controlled
condition. The inset of Fig. 5 shows the calibration plot (without
background current correction). The linear regression equation
for dependence of current with concentration of CBZ can be rep-
resented as Ip (␮A) = 1.2054 ␮M + 8.5032, R2 = 0.9968. The sensor
shows a linear range of 50 nM to 3 ␮M. The sensitivity of the
electrode is 5.1076 ␮A ␮M−1 cm−2 . The limit of detection (LOD)
and the limit of quantification (LOQ) were calculated as 29 nM
and 96 nM respectively. LOD has been calculated from the formula
LOD = 3Sb /S and LOQ from LOQ = 10Sb /S, where, Sb is the standard
deviation of blank signal and S is the sensitivity of the electrode
[37]. A comparison of linear range and LOD of various electrodes
reported earlier are given in Table 1.

3.4. Reproducibility and CBZ determination in pharmaceutical

preparations

To demonstrate the reproducibility of the sensor, relative

standard deviation (RSD) of seven individual modified electrodes
was determined by measuring the current response obtained in pH
5 containing 10 ␮M CBZ using CV. The RSD % value is obtained as
3.5%, indicating the good reproducibility of the developed sensor.
The practical feasibility of the proposed method has been evalu-
ated by determination of CBZ from commercially available Tegratol
tablets. 20 tablets (200 mg CBZ/tablet) were powdered well in
a mortar using pestle. Then, aliquots of the sample solutions
(1 × 10−4 M CBZ) were prepared in pH 5 using calculated amounts
of the powdered sample. Amperometry experiments were con-
ducted under the same experimental conditions as mentioned in
Section 3.3. The amperomtric response of CBZ in the real sample
is presented in Fig. 5(B). The linear relationship between current

Table 2
Determination of CBZ in pharmaceutical sample.

No. Added (␮M) Found (␮M) Recovery (%)

Fig. 5. (A) i–t amperometric response of CBZ at ERGO–SWCNT modified rotating disc
1 0.3 0.28 94.80
glassy carbon electrode in N2 saturated pH 5, applied potential: 1.155 V. Rotation
2 0.6 0.57 95.1
speed: 2500 rpm. Inset is the plot of Ipa vs. [CBZ]. B) Amperometric response of real
3 0.9 0.866 96.3
sample with the same conditions as that of A and the inset is the plot of Ipa vs. [CBZ].
 B. Unnikrishnan et al. / Sensors and Actuators B 173 (2012) 274–280 279

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Chemical Physics Letters 287 (1998) 53–56. Binesh Unnikrishnan received his B.S Degree in chem-
[17] S. Stankovich, R.D. Piner, X. Chen, N. Wu, S.T. Nguyen, R.S. Ruoff, Stable aqueous istry in 1999 from University of Calicut, Kerala, India. He
dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite received M.S Degree in chemistry in 2002 and M.Phil.
oxide in the presence of poly(sodium 4-styrenesulfonate), Journal of Materials Degree in chemistry in 2005 from Bharathiar University,
Chemistry 16 (2006) 155–158. Tamilnadu, India. Currently he is a fulltime Ph.D. stu-
[18] D.R. Dreyer, S. Park, C.W. Bielawski, R.S. Ruoff, The chemistry of graphene oxide, dent in the research group of Dr. Shen-Ming Chen at
Chemical Society Reviews 39 (2010) 228. the Department of Chemical Engineering and Biotechnol-
[19] L. Liu, D. Yu, C. Zeng, Z. Miao, L. Dai, Biocompatible graphene oxide-based ogy, National Taipei University of Technology, Taiwan. His
glucose biosensors, Langmuir 26 (2010) 6158–6160. research interests include electrocatalysis using compos-
[20] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, ites of MWCNT, graphene, nanometals, nanometal oxides,
S.T. Nguyen, R.S. Ruoff, Synthesis of graphene-based nanosheets via chemical study of the direct electrochemistry of redox enzymes and
reduction of exfoliated graphite oxide, Carbon 45 (2007) 1558–1565. proteins for biosensor and biofuel cell applications.
280 B. Unnikrishnan et al. / Sensors and Actuators B 173 (2012) 274–280

Veerappan Mani received his B.S Degree in chemistry Dr. Shen-Ming Chen received his B.S. Degree in Chem-
from Periyar University, Tamilnadu, India, in 2007 and istry in 1980 from National Kaohsiung Normal University,
M.S Degree in chemistry from Bharathidasan University, Taiwan. He received his M.S. Degree (1983) and Ph.D.
Tamilnadu, India, in 2009. Currently he is a Ph.D. stu- Degree (1991) in Chemistry from National Taiwan Univer-
dent in the Department of Chemical Engineering and sity, Taiwan. He is currently a professor at the Department
Biotechnology, National Taipei University of Technology, of Chemical Engineering and Biotechnology, National
Taipei, Taiwan. His research interest mainly focusing on Taipei University of Technology, Taiwan. His current
the graphene based composite materials for electrochem- research interests include electroanalytical chemistry,
ical sensor and biofuel cell applications. bioelectrochemistry, fabrication of energy conservation
and storage devices and nanomaterial synthesis for elec-
trochemical applications. He has published more than 240
research articles in SCI journals.