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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
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
In addition, it was observed in the studies on POM/graphene hydrogen peroxide (H2 O2 ), potassium permanganate (KMnO4 ), sul-
composites that purely electrostatic anchoring of the POMs onto phuric acid (H2 SO4 ) and activated carbon were purchased from
graphene/graphene oxide may form uniform and large-area com- Sigma–Aldrich (USA). Potassium persulfate (K2 S2 O8 ), phosphorus
posite films [22–24] However, this electrostatic interaction may pentoxide (P2 O5 ), acetic acid and sodium acetate were bought from
cause the desorption of POMs during the electrochemical mea- Merck (Germany).
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 2.2. Instrumentation
POMs to graphene/graphene oxide have been developed [25,26].
In the present report, the preparation and characterization of Square wave voltammetry (SWV) and cyclic voltammetry (CV)
POM-rGO nanocomposite were performed (Scheme 1). After that, were carried out IviumStat (U.S) equipped with C3 cell stand.
GCE surfaces were modified with rGO and POM-rGO nanocom- Electrochemical impedance spectroscopic experiments were car-
posites by using infrared heat lamp. In literature, there is no ried out with Gamry Reference 600 workstation equipped with a
report about simultaneous determination of l-Trp and l-Tyr which PCI4/300 potentiostat in conjunction with EIS 300 software. Modi-
is performed by POM-rGO/GCE. Since POM-rGO nanocomposite fied electrodes were characterized in 1.0 mM ferrocyanide/1.0 mM
provided easy handling, large specific surface area and improved ferricyanide redox couple via EIS methods. EIS data were measured
conductivity, an electrochemical sensor of l-Trp and l-Tyr was con- at 100 kHz to 0.1 Hz at wave amplitude of 10 mV and the formal
structed by modifying GCE with POM-rGO nanocomposite. In this potential of 0.170 V for ferrocyanide/ferricyanide redox couple.
study, the strong electrostatic interaction between POM and rGO JEOL 2100HRTEM (JEOL Ltd., Tokyo, Japan) was used to investi-
nanocomposites without covalent and noncovalent linkage pro- gate the morphology of POM-rGO nanocomposite.
vides reusable and stable sensor for simultaneous determination XPS analysis were performed on a PHI 5000 Versa Probe (
of l-Trp and l-Tyr. In addition, the developed SWV method based ULVAC-PHI, Inc., Japan/USA) model with monochromatized Al K␣
on POM-rGO nanocomposite shows high sensitivity, high selectiv- radiation (1486.6 eV) as an X-ray anode operated at 50 W. To
ity in spiked serum blank and no treatment before use make it prepare the samples, one drop of the prepared POM-rGO nanocom-
feasible to be applied in routine determination. In addition, the per- posite were placed on clear glass and then dried in air.
formance of the POM-rGO nanocomposite has also been compared A Rigaku Miniflex X-ray diffractometer was used for X-ray
with the available materials for determination of l-Trp and l-Tyr in diffraction measurements of POM-rGO nanocomposite. A scanning
the literatures. The results indicated that the POM-rGO nanocom- speed of 2 = 2◦ /min with a step size of 0.02◦ was used to examine
posite could be a kind of good electrocatalytic nanomaterial for the samples.
determination of aminoacids.
2.1. Materials Graphene oxide (GO) was synthesized according to our previous
report [27]. The as-prepared GO was dispersed into 200 mL water
l-Tyr and l-Trp were obtained from Sigma–Aldrich. The under mild ultrasound. Then, hydrazine hydrate (80 wt%) of 4 mL
stock solutions of l-Tyr and l-Trp (1.0 mM) were prepared was added and the solution was heated in an oil bath at 100 ◦ C
by 0.1 M acetate buffer (pH 6.0). H3 PW12 O40 (POM), phenol, under a water-cooled condenser for 24 h. After that, the prepared
graphite powder, acetonitrile (MeCN), isopropyl alcohol (IPA), 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.
2.4. Synthesis of POM-rGO 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-
The synthesized rGO was dissolved in ethanol at a concen- tic centrifuge tube. After that, the centrifugation at 20,000 rpm for
tration of 2 mg mL−1 with the ultrasonic agitation for 1 h. The 15 min was performed. The upper clear layer solution was diluted
H3 PW12 O40 (1 mL, 1 mM) was reduced by using ultraviolet (UV) with 0.1 M acetate buffer (pH 6.0) for analysis. The informed con-
light (400–100 nm). The rGO suspension was well mixed with the sent will be obtained for improved experimentation with human
reduced POM at a 1:1 vol ratio for 2 h (POM-rGO) [28]. subjects in future.
GCE was cleaned according to our previous report [29]. After 3.1. Characterizations of POM-rGO
that, 15 L of rGO and POM-rGO suspensions was dropped onto the
clean GCE. Then, the solvent was evaporated by an infrared lamp TEM image of POM-rGO shows (Fig. 1A) that the creased nature
[30,31]. of rGO is highly beneficial to provide a high surface area on GCE.
EDX analysis of POM-rGO confirmed the formation of the nanoma-
2.6. Sample preparation 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
The serum blank samples in this study were obtained from through electrostatic interaction between POM and rGO sheets to
Hacettepe University Hospitals Blood Bank Unit in TURKEY. After make a heterogeneous catalyst [32–35]. The formation of POM-
the standard l-Tyr and l-Trp solutions were added to these serum 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. 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 ).
Ö.A. Yokuş et al. / Sensors and Actuators B 233 (2016) 47–54 51
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 53
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.
[23] D. Zhou, B.-H. Han, Graphene-Based nanoporous materials assembled by [41] S. Zhu, J. Zhang, X.E. Zhao, H. Wang, G. Xu, J. You, Electrochemical behavior
mediation of polyoxometalate nanoparticles, Adv. Funct. Mater. 20 (2010) and voltammetric determination of l-tryptophan and l-tyrosine using a
2717–2722. glassy carbon electrode modified with single-walled carbon nanohorns,
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Electrochemical-Reduction-Assisted assembly of a [42] K.-Q. Deng, J.-h. Zhou, X.-F. Li, Direct electrochemical reduction of graphene
Polyoxometalate/Graphene nanocomposite and its enhanced lithium-Storage oxide and its application to determination of l-tryptophan and l-tyrosine,
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Polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids and tyrosine at boron-Doped diamond electrode, Electroanalysis 18 (2006)
for flexible, all-solid-state supercapacitors, Chem. Commun. 51 (2015) 830–834.
12377–12380. [44] Y. Fan, J.H. Liu, H.T. Lu, Q. Zhang, Electrochemistry and voltammetric
[26] W. Guo, X. Tong, S. Liu, Polyoxometalate/chitosan—electrochemically reduced determination of l-tryptophan and l-tyrosine using a glassy carbon electrode
graphene oxide as effective mediating systems for electrocatalytic reduction modified with a Nafion/TiO2-graphene composite film, Microchim. Acta 173
of persulfate, Electrochim. Acta 173 (2015) 540–550. (2011) 241–247.
[27] M.L. Yola, T. Eren, N. Atar, A sensitive molecular imprinted electrochemical [45] P. Ramalingam, Y.T. Ko, A validated LC-MS/MS method for quantitative
sensor based on gold nanoparticles decorated graphene oxide: application to analysis of curcumin in mouse plasma and brain tissue and its application in
selective determination of tyrosine in milk, Sens. Actuators B 210 (2015) pharmacokinetic and brain distribution studies, J. Chromatogr. B 969 (2014)
149–157. 101–108.
[28] M.L. Yola, N. Atar, T. Eren, H. Karimi-Maleh, S. Wang, Sensitive and selective
determination of aqueous triclosan based on gold nanoparticles on
polyoxometalate/reduced graphene oxide nanohybrid, RSC Adv. 5 (2015) Biographies
65953–65962.
[29] M.L. Yola, N. Atar, M.S. Qureshi, Z. Üstündağ, A.O. Solak, Electrochemically
grafted etodolac film on glassy carbon for Pb(II) determination, Sens. Özlem Aktaş Yokuş, received her MSc degree in Biochemistry from Kafkas Uni-
Actuators B 171-172 (2012) 1207–1215. versity, Kars, Turkey and PhD degree in Organic Chemistry from Kafkas University,
[30] M.L. Yola, V.K. Gupta, N. Atar, New molecular imprinted voltammetric sensor Kars, Turkey. She is working at Kafkas University, Department of Science Educa-
for determination of ochratoxin A, Mater. Sci. Eng. C 61 (2016) 368–375. tion, Kars, Turkey. Her research interests are organic synthesis, acidity, cataylsis,
[31] B. Ertan, T. Eren, İ. Ermiş, H. Saral N. Atar, M.L., Yola, Sensitive analysis of nanobiosensors and biochemistry.
simazine based on platinum nanoparticles on polyoxometalate/multi-walled
Faruk Kardaş, received his MSc degree in Biochemistry from Kafkas University, Kars,
carbon nanotubes, J. Colloid Interface Sci. 470 (2016) 14–21.
Turkey and PhD degree in Organic Chemistry from Kafkas University, Kars, Turkey.
[32] Z. Ma, Y. Qiu, H. Yang, Y. Huang, J. Liu, Y. Lu, C. Zhang, P. Hu, Effective
He is working at Erzincan University, Department of Science Education, Erzincan,
synergistic effect of dipeptide-Polyoxometalate-Graphene oxide ternary
Turkey. His research interests are organic synthesis, acidity, cataylsis, nanobiosen-
hybrid materials on peroxidase-like mimics with enhanced performance, ACS
sors and biochemistry.
Appl. Mater. Interfaces 7 (2015) 22036–22045.
[33] Z. Xian, R. Liu, H. Li, S. Zhang, Z. Yang, W. Zheng, C. Chen, H. Cao, G. Zhang, Onur Akyıldırım, received his MSc and PhD degrees in Organic Chemistry from
Photocatalytic reduction synthesis of ternary Ag Kafkas University, Kars, Turkey. He is working at Kafkas University, Department of
Nanoparticles/Polyoxometalate/Graphene nanohybrids and its activity in the Chemical Enginnering, Kars, Turkey. His research interests are organic synthesis,
electrocatalysis of oxygen reduction, J. Cluster Sci. (2015). acidity, surface science, cataylsis, and sensors.
[34] W. Guo, X. Tong, S. Liu, Polyoxometalate/chitosan-electrochemically reduced
graphene oxide as effective mediating systems for electrocatalytic reduction Tanju Eren, received his BSc degree in Chemistry from Dumlupinar University,
of persulfate, Electrochim. Acta 173 (2015) 540–550. Kutahya, Turkey. He is working as MSc in Physical Chemistry at Dumlupinar Univer-
[35] Y. Kim, K. Ketpang, S. Jaritphun, J.S. Park, S. Shanmugam, A polyoxometalate sity, Department of Chemistry, Kutahya, Turkey. His research interests are surface
coupled graphene oxide-Nafion composite membrane for fuel cells operating science, catalysis, nanoconstructions, nanoparticles, photocatalysis and adsorption.
at low relative humidity, J. Mater. Chem. A 3 (2015) 8148–8155.
[36] V.K. Gupta, M.L. Yola, T. Eren, F. Kartal, M.O. Çağlayan, N. Atar, Catalytic Necip Atar, received his MSc and PhD degrees in Physical Chemistry from
activity of Fe@Ag nanoparticle involved calcium alginate beads for the Dumlupinar University, Kutahya, Turkey. He is working at Pamukkale University,
reduction of nitrophenols, J. Mol. Liq. 190 (2014) 133–138. Department of Chemical Enginnering, Denizli, Turkey. He worked at Curtin Uni-
[37] V.K. Gupta, M.L. Yola, M.S. Qureshi, A.O. Solak, N. Atar, Z. Üstündağ, A versity of Technology, Department of Chemical Engineering, Perth, Australia, as a
novel impedimetric biosensor based on graphene oxide/gold nanoplatform visiting scientist. His research interests are surface science, cataylsis, nanoconstruc-
for detection of DNA arrays, Sens. Actuators B 188 (2013) 1201–1211. tions, nanobiosensors, nanoparticles and adsorption.
[38] S. Zhu, J. Zhang, X.-e. Zhao, H. Wang, G. Xu, J. You, Electrochemical behavior
Mehmet Lütfi Yola, received his MSc and PhD degrees in Faculty of Pharmacy,
and voltammetric determination of l-tryptophan and l-tyrosine using a
Hacettepe University, Ankara, Turkey. He is working as Associate Professor at Sinop
glassy carbon electrode modified with single-walled carbon nanohorns,
University in Turkey. His interests include Surface modification and characteri-
Microchim. Acta. 181 (2014) 445–451.
zation, Nanobiosensors, Biosensor applications, Molecular imprinting technology,
[39] M.L. Yola, N. Özaltin, Square-wave voltammetric determination of ezetimibe,
Quartz crystal microbalance (QCM), Surface plasmon resonance (SPR), Surface
Rev. Chim. 62 (2011) 420–426.
enhanced raman spectroscopy (SERS) and Electroanalytical techniques (CV, SWV,
[40] X. Tang, Y. Liu, H. Hou, T. You, Electrochemical determination of
DPV, CA, CC and stripping).
l-Tryptophan, l-Tyrosine and l-Cysteine using electrospun carbon nanofibers
modified electrode, Talanta 80 (2010) 2182–2186.