Sensors and Actuators B 233 (2016) 47–54

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Sensors and Actuators B: Chemical

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

Sensitive voltammetric sensor based on polyoxometalate/reduced

graphene oxide nanomaterial: Application to the simultaneous
determination of l-tyrosine and l-tryptophan
Özlem Aktaş Yokuş a , Faruk Kardaş b , Onur Akyıldırım c , Tanju Eren d , Necip Atar d ,
Mehmet Lütfi Yola e,∗
a
Department of Science Education, Faculty of Education, Kafkas University, Kars, Turkey
b
Department of Science Education, Faculty of Education, Erzincan University, Erzincan, Turkey
c
Department of Chemical Engineering, Faculty of Engineering and Architecture, Kafkas University, Kars, Turkey
d
Department of Chemical Engineering, Faculty of Engineering, Pamukkale University, Denizli, Turkey
e
Department of Metallurgical and Materials Engineering, Faculty of Engineering, Sinop University, Sinop, Turkey

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

Article history: In this report, a novel voltammetric sensor based on polyoxometalate (H3 PW12 O40 , POM) functionalized
Received 8 December 2015 reduced graphene oxide (rGO) modified glassy carbon electrode (GCE) was presented for simultaneous
Received in revised form 3 March 2016 determination of l-tyrosine (l-Tyr) and l-tryptophan (l-Trp). The nanocomposites were characterized
Accepted 8 April 2016
by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction
Available online 11 April 2016
(XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electrochemical
determination of l-Tyr and l-Trp has been studied using square wave voltammetry (SWV) on GCE modi-
Keywords:
fied with POM-rGO composite (POM-rGO/GCE). The developed method was also applied successfully for
l-Tyrosine
l-Tryptophan
the simultaneous determination of l-Tyr and l-Trp in spiked serum sample and the linearity range of
Reduced graphene oxide l-Tyr and l-Trp was 1.0 × 10−11 − 1.0 × 10−9 M with the detection limit of 2.0 × 10−12 M.
Polyoxometalate © 2016 Elsevier B.V. All rights reserved.
Sensor

1. Introduction materials. Nevertheless, there are some important problems such

Amino acids are known as precursors for various significant
biological substances. l-Trp is one of the most important amino
acids and found in natural proteins, which is widely used in the
food industry as an antioxidant and in the pharmaceutical industry
as a biomarker In addition, it plays an important role in several
biological processes [1]. l-Tyr is also a kind of essential amino
acid and indispensable for human to establish and maintain nutri-
tional balance. The lack of l-Tyr may lead to albinism, alkaptonuria,
depression, and other psychological diseases, while an overdose of
l-Tyr could cause the increase of sister chromatid exchange [2].
Therefore, it is significant to develop a simple, accurate, rapid and
inexpensive sensor for the determination of l-Trp and l-Tyr.
The important nanomaterials in applications of nanotech-
nology can be used for the development of sensor, analysis
and catalytic effect [3–9]. In addition, the significant progress
has been performed in the production of carbon-supported
∗ Corresponding author.
E-mail address: mehmetyola@gmail.com (M.L. Yola).
as low catalytic performance. Hence, in order to increase this per-
formance, the novel nanomaterials such as graphene/graphene
oxide become very significant. Graphene/graphene oxide, consist-
ing of a monolayer of sp2 carbon atoms, is an attractive material in
many research fields including electrocatalytic applications owing
to its unique properties such as high surface area, outstanding
electrical properties, and high mechanical and thermal proper-
ties [10–16]. In addition, polyoxometalates (POMs) are nanosized
metal-oxide cluster anions with high structural, chemical and elec-
tronic versatility [17,18]. POMs possess excellent redox properties
and their structures can remain unchanged after a stepwise multi-
electron redox process in which POMs act as electron relays. The
electrochemical behavior of POMs in acidic media involves one or
two electron reversible reductions to produce reduced POMs, or
so-called heteropoly blues owing to their changed color [19]. In
reduced forms, their electron and proton transfer and/or storage
abilities make them act as efficient donors or acceptors of several
electrons without structural change. Owing to their chemical ver-
satility, they have been employed in catalysis, energy conversion,
and electronics [20,21].

http://dx.doi.org/10.1016/j.snb.2016.04.050
0925-4005/© 2016 Elsevier B.V. All rights reserved.
48 Ö.A. Yokuş et al. / Sensors and Actuators B 233 (2016) 47–54
Scheme 1. The procedure for fabrication of POM-rGO/GCE.
In addition, it was observed in the studies on POM/graphene
composites that purely electrostatic anchoring of the POMs onto
graphene/graphene oxide may form uniform and large-area com-
posite films [22–24] However, this electrostatic interaction may
cause the desorption of POMs during the electrochemical mea-
surement since the sonication and rinsing of the as-synthesized
nanocomposite materials into the electrolyte solution. To overcome
this obstacle, various covalent and noncovalent linkage modes of
POMs to graphene/graphene oxide have been developed [25,26].
In the present report, the preparation and characterization of
POM-rGO nanocomposite were performed (Scheme 1). After that,
GCE surfaces were modified with rGO and POM-rGO nanocom-
posites by using infrared heat lamp. In literature, there is no
report about simultaneous determination of l-Trp and l-Tyr which
is performed by POM-rGO/GCE. Since POM-rGO nanocomposite
provided easy handling, large specific surface area and improved
conductivity, an electrochemical sensor of l-Trp and l-Tyr was con-
structed by modifying GCE with POM-rGO nanocomposite. In this
study, the strong electrostatic interaction between POM and rGO
nanocomposites without covalent and noncovalent linkage pro-
vides reusable and stable sensor for simultaneous determination
of l-Trp and l-Tyr. In addition, the developed SWV method based
on POM-rGO nanocomposite shows high sensitivity, high selectiv-
ity in spiked serum blank and no treatment before use make it
feasible to be applied in routine determination. In addition, the per-
formance of the POM-rGO nanocomposite has also been compared
with the available materials for determination of l-Trp and l-Tyr in
the literatures. The results indicated that the POM-rGO nanocom-
posite could be a kind of good electrocatalytic nanomaterial for
determination of aminoacids.
2. Experimental
2.1. Materials
l-Tyr and l-Trp were obtained from Sigma–Aldrich. The
stock solutions of l-Tyr and l-Trp (1.0 mM) were prepared
by 0.1 M acetate buffer (pH 6.0). H3 PW12 O40 (POM), phenol,
graphite powder, acetonitrile (MeCN), isopropyl alcohol (IPA),
hydrogen peroxide (H2 O2 ), potassium permanganate (KMnO4 ), sul-
phuric acid (H2 SO4 ) and activated carbon were purchased from
Sigma–Aldrich (USA). Potassium persulfate (K2 S2 O8 ), phosphorus
pentoxide (P2 O5 ), acetic acid and sodium acetate were bought from
Merck (Germany).
2.2. Instrumentation
Square wave voltammetry (SWV) and cyclic voltammetry (CV)
were carried out IviumStat (U.S) equipped with C3 cell stand.
Electrochemical impedance spectroscopic experiments were car-
ried out with Gamry Reference 600 workstation equipped with a
PCI4/300 potentiostat in conjunction with EIS 300 software. Modi-
fied electrodes were characterized in 1.0 mM ferrocyanide/1.0 mM
ferricyanide redox couple via EIS methods. EIS data were measured
at 100 kHz to 0.1 Hz at wave amplitude of 10 mV and the formal
potential of 0.170 V for ferrocyanide/ferricyanide redox couple.
JEOL 2100HRTEM (JEOL Ltd., Tokyo, Japan) was used to investi-
gate the morphology of POM-rGO nanocomposite.
XPS analysis were performed on a PHI 5000 Versa Probe (
ULVAC-PHI, Inc., Japan/USA) model with monochromatized Al K␣
radiation (1486.6 eV) as an X-ray anode operated at 50 W. To
prepare the samples, one drop of the prepared POM-rGO nanocom-
posite were placed on clear glass and then dried in air.
A Rigaku Miniflex X-ray diffractometer was used for X-ray
diffraction measurements of POM-rGO nanocomposite. A scanning
speed of 2␪ = 2◦ /min with a step size of 0.02◦ was used to examine
the samples.
2.3. Synthesis of rGO
Graphene oxide (GO) was synthesized according to our previous
report [27]. The as-prepared GO was dispersed into 200 mL water
under mild ultrasound. Then, hydrazine hydrate (80 wt%) of 4 mL
was added and the solution was heated in an oil bath at 100 ◦ C
under a water-cooled condenser for 24 h. After that, the prepared
rGO product was collected by vacuum filtration [14].
 Ö.A. Yokuş et al. / Sensors and Actuators B 233 (2016) 47–54 49

Fig. 1. (A) TEM image of POM-rGO and (B) EDX analysis of POM-rGO nanocomposite.

Fig. 2. XPS spectrum of POM-rGO nanocomposite.

2.4. Synthesis of POM-rGO
The synthesized rGO was dissolved in ethanol at a concen-
tration of 2 mg mL−1 with the ultrasonic agitation for 1 h. The
H3 PW12 O40 (1 mL, 1 mM) was reduced by using ultraviolet (UV)
light (400–100 nm). The rGO suspension was well mixed with the
reduced POM at a 1:1 vol ratio for 2 h (POM-rGO) [28].
blank samples, the samples were spiked: 1.2 mL methanol was
added to an aliquot of 0.4 mL serum blank sample in a 2.0 mL plas-
tic centrifuge tube. After that, the centrifugation at 20,000 rpm for
15 min was performed. The upper clear layer solution was diluted
with 0.1 M acetate buffer (pH 6.0) for analysis. The informed con-
sent will be obtained for improved experimentation with human
subjects in future.

2.5. Procedure for the electrode preparation 3. Results and discussion

GCE was cleaned according to our previous report [29]. After
that, 15 ␮L of rGO and POM-rGO suspensions was dropped onto the
clean GCE. Then, the solvent was evaporated by an infrared lamp
[30,31].
2.6. Sample preparation
The serum blank samples in this study were obtained from
Hacettepe University Hospitals Blood Bank Unit in TURKEY. After
the standard l-Tyr and l-Trp solutions were added to these serum
3.1. Characterizations of POM-rGO
TEM image of POM-rGO shows (Fig. 1A) that the creased nature
of rGO is highly beneficial to provide a high surface area on GCE.
EDX analysis of POM-rGO confirmed the formation of the nanoma-
terial. The C, P, O and W peaks have been observed in EDX analysis
(Fig. 1B). The deposition of POM on rGO sheets was carried out
through electrostatic interaction between POM and rGO sheets to
make a heterogeneous catalyst [32–35]. The formation of POM-
rGO was further examined by XPS. The peaks of C1s, W4f and O1s
50 Ö.A. Yokuş et al. / Sensors and Actuators B 233 (2016) 47–54
Fig. 3. XRD spectrum of POM-rGO nanocomposite.
confirmed the formation of POM-rGO (Fig. 2). These bands con-
firmed the formation of POM-rGO. The XRD pattern of POM-rGO
nanocomposite is shown in Fig. 3. The intense and narrow peaks
at 2␪ = 30.28◦ and 41.68◦ are referred to the (002) and (004) planes
of rGO sheets, respectively. In addition, the peaks at 2␪ = 25.22◦ ,
28.35◦ , 37.32◦ and 42.28◦ are related to the (442), (642), (555) and
(953) planes of POM, respectively.
3.2. Cyclic voltammograms of l-Tyr and l-Trp at different
electrode surfaces
Fig. 4 shows the cyclic voltammetry of 1.0 × 10−6 M l-Trp and
1.0 × 10−6 M l-Tyr in 0.1 M acetate buffer (pH 6.0) at different elec-
trode surfaces. The oxidation peaks were obtained at Ea = 0.90 V of
l-Tyr and Ea = 1.15 V of l-Trp with peak-to-peak separation, Ep ,
about 250 mV at GCE. Nevertheless, the oxidations peaks at the GCE
modified rGO were much greater than those at GCE. The main oxi-
Fig. 4. Cyclic voltammograms of l-Tyr and l-Trp at GCE, rGO/GCE and POM-rGO/GCE in sodium acetate/acetic acid buffer solution of pH 6.0. Concentration of each analyte:
1.0 ␮M (Scan rate is 100 mV s−1 ).
dation peaks were more pronounced at the GCE modified rGO. In
addition, when incorporating of POM onto the surfaces of rGO, the
well-behaved anodic peaks were obtained for l-Tyr and l-Trp. The
oxidation peaks were obtained at Ea = 0.65 V of l-Tyr and Ea = 0.90 V
of l-Trp with peak-to-peak separation, Ep , about 250 mV at POM-
rGO/GCE. As a result of the presence of POM, an obvious increase in
the background current was observed. Hence, we can say that POM-
rGO/GCE can greatly accelerate the electron transfer rate between
l-Tyr and l-Trp molecules in solution and the surface. The peak
currents of the oxidation with the well separation were about four
larger than those obtained at GCE. The effective surface areas of
different modified electrodes were obtained by CV with 1.0 mM
[Fe(CN)6 ]3− solution containing 0.1 M KCl as a probe at different
scan rates according to the equation: ip = 2.69 × 105 A n3/2 D1/2 C
v1/2 , where ip refers to the peak current and A is the electrode area
(cm2 ). For 1.0 mM [Fe(CN)6 ]3− , n = 1, D = 7.6 × 10−6 cm2 s−1 (0.1 M
KCl), C is the concentration of [Fe(CN)6 ]3− , v is the scan rate. The
effective surface areas of rGO/GCE and POM-rGO/GCE were calcu-
lated from the slope of the ip versus v1/2 plot to be 294.0 cm2 /mg and
689.0 cm2 /mg, respectively. These results show that the electro-
chemical surface area of the POM-rGO/GCE is 2.34 times higher than
those of rGO/GCE. In addition, these enhanced performances were
corresponded to good electrical conductivity of rGO [36]. Owing to
chemical versatility of POM, it is also employed in catalysis, energy
conversion, and electronics [20].
3.3. Characterization of modified electrodes by EIS
EIS is an effective method for probing the features of surface
modified electrodes. It is capable of giving useful information about
defects/holes exist on the modified surfaces, the kinetics and mech-
anism of the film formation processes and surface coverage [37].
Fig. 5 shows the impedance plot (Nyquist diagram) of the bare
GCE, rGO/GCE and the POM-rGO/GCE. In addition, the inset of Fig. 5
shows the experimental data that are fitted to standard Randles
equivalent circuits for POM-rGO/GCE surface analysis, which com-
prises the solution resistance (Rs ), the charge transfer resistance
(Rct ) and the constant phase element (CPE) for the cases of POM-
 Ö.A. Yokuş et al. / Sensors and Actuators B 233 (2016) 47–54
Fig. 5. Fitting of impedance spectrum for 1.0 mM [Fe(CN)6 ]3−/4− (1:1) in 0.1 M KCl at
(a) GCE, (b) rGO/GCE and (c) POM-rGO/GCE. Inset is the Randles equivalent circuit.
Frequency range is 100,000–0.1 Hz with 10 mV wave amplitude at a formal potential
of 0.170 V. RE stands for reference electrode and WE stands for working electrode.
rGO/GCE. The EIS graph (curve a of Fig. 5) demonstrated that the
value of charge transfer resistance (Rct ) of bare GCE was calcu-
lated as 175 ohm. When the bare GCE was modified with rGO, the
value of Rct was lower (110 ohm) (curve b of Fig. 5). Because of the
lower value, we can say that the rGO increases the rate of electron
transfer. When POM was modified with rGO, the value of Rct of
POM-rGO/GCE was lower than that of rGO/GCE (curve c of Fig. 5).
Thus, the addition of POM shows the increase of catalytic activity.
The following reasons might explain the electrocatalytic response
of l-Trp and l-Tyr at the POM-rGO/GCE. According to the literature,
there are important problems for ultra-sensitive analysis. In order
to increase the performance of analysis, novel nanomaterial such
as rGO was used in this study. These enhanced performances were
corresponded to the large surface area and good electrical conduc-
tivity of rGO and the synergistic effect of rGO and POM. Hence,
POM-rGO nanocomposite is conductive and has chemically active
defect sites making it a promising candidate for the active material
in molecular sensor.
3.4. Influence of pH
The effect of the solution pH on the electrochemical oxidations
of l-Tyr and l-Trp at the POM-rGO/GCE was shown in Fig. 6. It was
clear that the anodic peak currents of l-Tyr and l-Trp increased
slightly with the increase in pH of solution. After the value of pH
was 6.0, the peak current decreased with the increase in solution
pH. It should be expected that the increase in pH value caused the
carboxylic groups in l-Tyr (pKa1 = 2.20) and l-Trp (pKa1 = 2.46) to
load negatively. These negative groups interacted efficiently with
the positive charge of the modified electrode (from 0.0 to 1.2 V).
Hence, the affinity of sensor-analyte increased. In addition, for all
two compounds, their oxidation peak potentials shifted to nega-
tive values with increase of pH. Because of this negative shift, the
protons take part in their electrode reactions (Scheme 2) [38].
3.5. Analytical application
The square wave voltammograms of l-Tyr and l-Trp in 0.10 M
acetate buffer (pH 6.0) on POM-rGO/GCE are presented in Fig. 7A.
The peak currents of l-Tyr are linear with its concentrations (0.01,
0.02, 0.04, 0.05, 0.10, 0.50, 0.60, 0.70, 0.80 and 1.0 nM l-Tyr). The
same situation is available for l-Trp. The aim of this study is simul-
taneous determination of l-Tyr and l-Trp. Because of this, the
independent calibration graphs for both of l-Tyr and l-Trp are
formed in this study. The total concentration of them is not related
51
Scheme 2. The proposed electrooxidation reactions of l-Tyr and l-Trp at POM-
rGO/GCE.
to the topic of this study. The regression equations of l-Tyr (Fig. 7B)
and l-Trp (Fig. 7C) are y = 9.459x + 0.036 and y = 10.56x + 0.543 (y
is peak current, ␮A; x is l-Tyr and l-Trp concentrations, nM; the
number of data points is 10). Each point of the calibration graph
corresponded to the mean value obtained from 6 independent mea-
surements.
Limit of quantification (LOQ) was estimated by the equation:
LOQ = 10 S/m,
Limit of detection (LOD) was estimated by the equation:
LOD = 3.3 S/m,
Where S is the standard deviation of the intercept and m is the slope
of the regression line [39]. The limit of quantitation for both of l-Tyr
and l-Trp was found to be 1.0 × 10−11 M and the calculated detec-
tion limit for both of l-Tyr and l-Trp was found to be 2.0 × 10−12 M.
Table 1 shows that the performance of the modified electrode in
this study is better than the reported results.
The POM-rGO/GCE was applied to spiked serum samples to
investigate applicability of modified electrode. After 1.00 × 10−10 M
l-Tyr and 1.00 × 10−10 M l-Trp was added to the serum samples,
the concentration values of both of l-Tyr and l-Trp in spiked
serum was calculated to be 1.07 ± (0.04) × 10−10 M for l-Tyr and
1.19 ± (0.02) × 10−10 M for l-Trp by POM-rGO/GCE. Liquid chro-
matography coupled with mass spectrometry was selected as
reference method [45]. The concentration value of both of l-Tyr and
l-Trp in spiked serum was calculated to be 1.12 ± (0.05) × 10−10 M
for l-Tyr and 1.11 ± (0.06) × 10−10 M for l-Trp by liquid chromatog-
raphy coupled with mass spectrometry. The results obtained by
POM-rGO/GCE are in well agreement with those obtained by liq-
uid chromatography coupled with mass spectrometry. The results
demonstrate the applicability of the POM-rGO/GCE for simultane-
ous determination of l-Tyr and l-Trp in real matrices. In addition,
the standard addition technique was applied to the serum blank
sample which was analyzed by calibration curves. The regres-
sion equations of standard addition curve were found to be
y = 9.53x + 7.01 for l-Tyr and y = 11.32x + 9.78 for l-Trp in spiked
serum. It is clear that there is no significant difference between
slopes of calibration curves and standard addition curves. These
results showed that there was no interference from matrix compo-
nents.
To show the selectivity of the developed voltammetric sen-
sor, three solutions such as (i) serum blank sample containing
1.0 × 10−9 M l-Tyr, 1.0 × 10−9 M l-Trp without the other real
matrices (ascorbic acid and uric acid), (ii) the standard solution
containing 1.0 × 10−9 M l-Tyr and 1.0 × 10−9 M l-Trp and (iii) blank
solution without l-Tyr and l-Trp were prepared. The voltammo-
gram (Fig. 8a) obtained from solution (i) was identical with the
52 Ö.A. Yokuş et al. / Sensors and Actuators B 233 (2016) 47–54

Fig. 6. The effect of pH on electrochemical signals of l-Tyr and l-Trp: Concentration of each analyte: 1.0 nM.

Fig. 7. (A) Square wave voltammograms with different concentrations of l-Tyr and l-Trp in sodium acetate/acetic acid buffer of pH 6.0 on POM-rGO/GCE; The calibration
graphs of (B) l-Tyr; (C) l-Trp.

Table 1
Comparison of different materials for l-Tyr and l-Trp determination.

Material Linear rangefor l-Tyr (mol/L) LOD for l-Tyr (mol/L) Linear rangefor l-Trp (mol/L) LOD for l-Trp (mol/L) Ref.

CNF-CPE 2.0 × 10−7 –1.1 × 10−4 1.0 × 10−7 1.0 × 10−7 − 1.2 × 10−4 1.0 × 10−7 [40]
SWCNHs/GCE 2.0 × 10−6 –3.0 × 10−5 4.0 × 10−7 5.0 × 10−7 –5.0 × 10−5 5.0 × 10−8 [41]
ERGO/GCE 5.0 × 10−7 –8.0 × 10−5 2.0 × 10−7 2.0 × 10−7 –4.0 × 10−5 1.0 × 10−7 [42]
Boron-doped diamond 1.0 × 10−4 –7.0 × 10−4 1.0 × 10−6 2.0 × 10−5 –1.0 × 10−3 1.0 × 10−5 [43]
Nafion/TiO2 -graphene/GCE 1.0 × 10−5 –1.6 × 10−4 2.3 × 10−6 5.0 × 10−6 –1.4 × 10−4 7.0 × 10−7 [44]
POM-rGO/GCE 1.0 × 10−11 –1.0 × 10−9 2.0 × 10−12 1.0 × 10−11 –1.0 × 10−9 2.0 × 10−12 Thisstudy

Carbon nanofiber modified carbon paste electrode (CNF-CPE), Single-walled carbon nanohorns (SWCNHs), Electrochemically reduced graphene oxide modified glassy carbon
electrode (ERGO/GCE).

voltammogram (Fig. 8b) obtained from solution (ii). In addition, we can say that there was no interference from real matrices and
the any peak currents were obtained in solution (iii) (Fig. 8c). Thus, selective sensor to l-Tyr and l-Trp was produced in this study.
 Ö.A. Yokuş et al. / Sensors and Actuators B 233 (2016) 47–54
Fig. 8. Square wave voltammograms of developed electrochemical sensor towards (a) serum blank sample containing 1.0 × 10−9 M l-Tyr, 1.0 × 10−9 M l-Trp without the
other real matrices (ascorbic acid and uric acid), (b) the standard solution containing 1.0 × 10−9 M l-Tyr and 1.0 × 10−9 M l-Trp in sodium acetate/acetic acid buffer of pH 6.0
and (c) blank solution without l-Tyr and l-Trp.
3.6. Repeatability, stability and reproducibility of the
POM-rGO/GCE
In order to show the repeatability of POM-rGO/GCE, ten dif-
ferent experiments with one POM-rGO/GCE were repeated in the
presence of 1.0 × 10−9 M l-Tyr and 1.0 × 10−9 M l-Trp. According to
the results, POM-rGO/GCE has the repeated current signals during
the ten cycles. The reproducibility was estimated with six devel-
oped electrodes that were fabricated independently by the same
procedure. The values of relative standard deviation are 0.71% for
1.0 × 10−9 M l-Tyr and 1.16% for 1.0 × 10−9 M l-Trp by using six
POM-rGO/GCE. This situation indicates the reliability of the fabri-
cation procedure. Additionally, the stability of one POM-rGO/GCE
was also presented. After 45 days, the peak signals are 99.03% of the
original value for 1.0 × 10−9 M l-Tyr and 97.75% of the original value
for 1.0 × 10−9 M l-Trp. Therefore, we can say that the developed
electrochemical sensor has good stability and reproducibility.
4. Conclusion
We developed the sensitive voltammetric sensor for simul-
taneous determination of l-Tyr and l-Trp on GCE modified
with POM-rGO nanocomposite. The prepared nanomaterials and
surfaces were well characterized by TEM, EIS, CV, XRD and
XPS. According to the results, the voltammetric sensor was
accomplished homogeneously on the glassy carbon surface. The
developed sensor showed high sensitivity towards l-Tyr and l-Trp
with the detection limit of 2.0 × 10−12 M. In addition, the prepared
sensor is reusable, selective and stable. In particular, the prepared
sensor offers the advantages of simplicity and sensitivity in target
detection from spiked serum samples. In conclusion, the voltam-
metric sensor is sensitive, rapid, cheap and easy to use and might
be preferred to the analytical methods.
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Biographies
Özlem Aktaş Yokuş, received her MSc degree in Biochemistry from Kafkas Uni-
versity, Kars, Turkey and PhD degree in Organic Chemistry from Kafkas University,
Kars, Turkey. She is working at Kafkas University, Department of Science Educa-
tion, Kars, Turkey. Her research interests are organic synthesis, acidity, cataylsis,
nanobiosensors and biochemistry.
Faruk Kardaş, received his MSc degree in Biochemistry from Kafkas University, Kars,
Turkey and PhD degree in Organic Chemistry from Kafkas University, Kars, Turkey.
He is working at Erzincan University, Department of Science Education, Erzincan,
Turkey. His research interests are organic synthesis, acidity, cataylsis, nanobiosen-
sors and biochemistry.
Onur Akyıldırım, received his MSc and PhD degrees in Organic Chemistry from
Kafkas University, Kars, Turkey. He is working at Kafkas University, Department of
Chemical Enginnering, Kars, Turkey. His research interests are organic synthesis,
acidity, surface science, cataylsis, and sensors.
Tanju Eren, received his BSc degree in Chemistry from Dumlupinar University,
Kutahya, Turkey. He is working as MSc in Physical Chemistry at Dumlupinar Univer-
sity, Department of Chemistry, Kutahya, Turkey. His research interests are surface
science, catalysis, nanoconstructions, nanoparticles, photocatalysis and adsorption.
Necip Atar, received his MSc and PhD degrees in Physical Chemistry from
Dumlupinar University, Kutahya, Turkey. He is working at Pamukkale University,
Department of Chemical Enginnering, Denizli, Turkey. He worked at Curtin Uni-
versity of Technology, Department of Chemical Engineering, Perth, Australia, as a
visiting scientist. His research interests are surface science, cataylsis, nanoconstruc-
tions, nanobiosensors, nanoparticles and adsorption.
Mehmet Lütfi Yola, received his MSc and PhD degrees in Faculty of Pharmacy,
Hacettepe University, Ankara, Turkey. He is working as Associate Professor at Sinop
University in Turkey. His interests include Surface modification and characteri-
zation, Nanobiosensors, Biosensor applications, Molecular imprinting technology,
Quartz crystal microbalance (QCM), Surface plasmon resonance (SPR), Surface
enhanced raman spectroscopy (SERS) and Electroanalytical techniques (CV, SWV,
DPV, CA, CC and stripping).