Journal of Electroanalytical Chemistry 776 (2016) 18

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Journal of Electroanalytical Chemistry

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

Selective and sensitive determination of tannic acid using a

1-benzoyl-3-(pyrrolidine) thiourea lm modied glassy carbon electrode
mmihan Takoparan Ylmaz a,, Elif alk a, Demet Uzun b, Fatma Karipcin c, Haim Ylmaz a
a
Gazi University, Polatl Science and Art Faculty, Department of Chemistry, 06900 Polatl, Ankara, Turkey
b
Gazi University, Science Faculty, Department of Chemistry, 06500 Ankara, Turkey
c
Nevsehir University, Science and Art Faculty, Department of Chemistry, 50300, Nevsehir, Turkey

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

Article history: In this study the selective determination of tannic acid (TA) was performed using a glassy carbon (GC) electrode
Received 25 March 2016 modied with 1-benzoyl-3-(pyrrolidine) thiourea (PrTu). PrTu was deposited on the GC electrode in nonaque-
Received in revised form 27 June 2016 ous media by cyclic voltammetry. PrTu-GC electrode demonstrated an electrocatalytic effect on the oxidation
Accepted 27 June 2016
of TA using differential pulse voltammetry (DPV) method in 0.1 M Britton Robinson (BR) buffer solution of
Available online 28 June 2016
pH 2. Under optimum conditions, linear calibration graphs were obtained over the TA concentration range
Keywords:
2.0 106 to 4.2 105 M. The limit of detection (LOD) was found as 0.6 M. The proposed electrode was ap-
Surface modication plied to the determination of spiked TA in tea. The proposed method was also applied for the determination of TA
Voltammetry in orange juice samples and the results of the experiments were in agreement with that obtained by the spectro-
Tannic acid photometric comparison method.
2016 Elsevier B.V. All rights reserved.

1. Introduction drawbacks. For example, chromatographic methods allow the determi-

Tannic acid (TA), a water soluble polyphenol compound has been in-
vestigated for many years, especially to cure many diseases [14]. Due
to its wide range of applications, analysis of TA is important not only
in food but also in the medical and environmental elds. TA is present
commonly in the human diet including fruits and different kinds of veg-
etables and can be found in several beverages, including wine, beer, cof-
fee, black tea and white tea. It is used as a food additive as clarifying
agent, avor adjunct and avoring agent [5] as well as additive in med-
ical and veterinary elds due to its antimicrobial activity, anticarcino-
genic and antimutagenic potentials and also antioxidant nature
protect cellular oxidative damage [6,7]. Although TA has useful proper-
ties, it may cause serious problems because TA can form carcinogenic
disinfection byproducts such as trihalomethanes during chlorination
of water. Moreover, TA has toxicity for species which are aquatic such
as algae, phytoplankton and sh [810]. The content of TA in fruits,
tea and beer inuences their taste and also it is an important standard
used to evaluate the quality of the products [11].
Several methods including spectrophotometry [12], colorimetry
[13], liquid chromatography [14] and chemiluminescence [1517]
have been applied for the determination of TA content in the waters,
pharmaceuticals and foods. Each method has its advantages and
nation of TA, but they are time consuming and expensive. Compared to
these methods, the electrochemical method has several advantages
such as its low cost, the options of analysis without extraction or pre-
concentration, highly selective and sensitive and the short time re-
quired for analysis. But, only very few reports were accessible in the lit-
erature for the electrochemical determination of TA [18,19].
Electroanalytical methods with different types of electrodes were used
for TA determination, but the presence of ascorbic acid limits the use
of some of these methods, or sample pretreatments are needed to re-
move ascorbic acid before analysis [5,20,21]. These examples show
that rapid, sensitive and selective TA determination is still a problem.
In this study, a modied surface was prepared by covering the GC
electrode with PrTu. The modied surface was characterized by cyclic
voltammetry (CV), electrochemical impedance spectroscopy (EIS) and
X-ray photoelectron spectroscopy (XPS). The prepared modied elec-
trode was used as a sensor for TA determination by applying the stan-
dard addition method in tea and orange juice samples. The interfering
effect of some ions and biological species were also studied at pH 2
Britton-Robinson (B-R) buffer.
2. Experimental
2.1. Reagents and chemicals

Corresponding author.
E-mail addresses: ummihan@gazi.edu.tr (.T. Ylmaz), elif__calik@hotmail.com
(E. alk), demetuzun@gazi.edu.tr (D. Uzun), fkaripcin@nevsehir.edu.tr (F. Karipcin),
hasim@gazi.edu.tr (H. Ylmaz).
The reagents and solutions in the study are all of reagent grade. TA
was purchased from Merck and a primary stock solution of
1 10 3 M TA was prepared in distilled water. Working solutions

http://dx.doi.org/10.1016/j.jelechem.2016.06.037
1572-6657/ 2016 Elsevier B.V. All rights reserved.
2 .T. Ylmaz et al. / Journal of Electroanalytical Chemistry 776 (2016) 18

were then prepared by diluting the stock solution with distilled water.
Tetraethylammonium tetrauoroborate (TEATFB) used for the
supporting electrolyte, were of the highest purity available from
Merck and Acetonitrile (ACN) as a solvent were of available from
Sigma-Aldrich. A stock solution of ferrocene (1 103 M) was prepared
by dissolving it in ACN containing 0.1 M TEATFB.
Britton-Robinson (B-R) buffer solution was prepared in such a way
that 2.3 mL of glacial acetic acid, 2.7 mL of phosphoric acid (85%), and
2.47 g of boric acid were dissolved by dilution with water to 1.0 L;
50 mL portions of this solution were taken, and the pH was adjusted
by the addition of an appropriate amount of 2.0 M NaOH to the desired
value.

2.2. Apparatus

A BAS model electrochemical analyzer (Bioanalytical Systems, Epsi-

lon Basic Plus Potentiostat/Galvanostat, USA) was used for differential
pulse voltammetry (DPV) and cyclic voltammetry (CV) measurements.
A conventional three-electrode system was used. Glassy carbon (GC)
electrode (BAS Model) was used as working electrode. The reference
electrode was an Ag/AgCl/KCl (sat.) used in aqueous media and an Ag/
AgNO3 (0.01 M) used in ACN nonaqueous media. The counter electrode
was Pt wire. pH values were measured using a Thermo Scientic Orion
4-Star Plus pH/Conductivity Meter with combined glass electrode was
used to measure pH of all the solutions. Absorption spectra and absor-
bances were recorded using SHIMADZU UVmini-1240 UVvisible
spectrophotometer.
Fig. 1. The CVs of 1 mM PrTu solution on GC electrode vs. Ag/Ag+, supporting electrolyte is
0.1 M TEATFB in acetonitrile, scan rate is 100 mV s1.
3. Results and discussion
3.1. Electrochemical preparation of PrTu modied electrode
Fig. 1 shows cyclic voltammograms (CVs) of GC electrode in 1 mM
PrTu solution in ACN containing 0.1 M TEATFB. The parameters for CV
were as follows: initial E = 2 V, nal E = 2 V, Scan rate =
100 mV s1, sensitivity = 1 105 A/V. As seen in Fig. 1, the peak

2.2.1. CV measurements
EIS measurements were performed in the presence of a 1.0 mM fer-
rocyanide/1.0 mM ferricyanide (1/1) mixture with 0.1 M KCl as
supporting electrolyte. EIS data were performed in the frequency
range from 100 kHz to 0.05 Hz by applying an Ac voltage with 5 mV
wave amplitude and at an electrode potential of 0.215 V, the formal po-
tential of ferrocyanide/ferricyanide redox couple.
XPS determination was carried out at Thermo K-Alpha spectrome-
ter. The X-ray source is Al K X-rays (monochromatic) which is carried
out at 90 electron take-off angle. The experiments were conducted at
pressures below 107 mbar. All samples were scanned without ion
beam surface cleaning procedure.
A Jeol (Jeol JSM-6060LV) Scanning Electron Microscope (SEM) was
used to observe the surface morphology on GC surface. Olympus SZX7
stereomicroscope was used for optical measurement.

2.3. Cleaning and modication of GC electrode surfaces

GC electrode was mechanically polished rst with ne wet emery

papers with grain size of 4000 (Buehler) and then with 0.3 m and
0.05 m alumina slurries (Baikowski Int. Corp.) on a microcloth pad
(Buehler). Polished GC electrode was sonicated in ultra-pure water
and then with ACN for 10 min. for removal of trace alumina from the
surface. After these procedures, GC electrode was rinsed with ACN.
Anodically surface modication of cleaned GC electrode was per-
formed in a solution of 1 mM PrTu (synthesized by the reported proce-
dure [22]), in ACN containing 0.1 M TEATFB as a supporting electrolyte
vs. Ag/AgNO3 (0.01 M) reference electrode using CV with a scan rate of
100 mV s1 for 25 cycles between 2 V and 2 V. The electrode was then
rinsed with ACN to remove any physisorbed or unreacted materials
from the electrode surface.

2.4. Preparation of tea sample

The solution sample of tea was prepared by adding deionized water

Fig. 2. Cyclic voltammograms of 1 mM (a) ferricyanide (in 0.1 M KCl) vs. Ag/AgCl/KCl (sat.)
to 3 g dry tea in an Erlenmeyer ask, stirring on a hot plate at 90 C for reference electrode and (b) ferrocene (in acetonitrile containing 0.1 M TEATFB) vs. Ag/Ag+
1 h, cooling to room temperature, ltering and then TA is diluted with reference electrode on PrTu-GC electrodes with different (15, 20, 25, 30) scan cycles, scan
ltrate as its concentration will be 1 103 M. rate is 100 mV s1.
 .T. Ylmaz et al. / Journal of Electroanalytical Chemistry 776 (2016) 18
currents are increased and reached a steady state value after 25 cycles
by the increasing number of potential cycle [23].
CV was used for electrochemical oxidation and covalent attachment
of PrTu (amino compound) onto GC electrode. The polymerization by
oxidation of amino compounds was reported for RNH2 compounds
to perform the grafting of organic layers. Thiourea has an amino
group, which can be immobilized on the surface GC electrode through
CV [24,25].
3.2. Characterization of PrTu-GC surface
3.2.1. Cyclic voltammetry (CV)
CV is most commonly used in characterization techniques [26]. Elec-
trochemical characterization of PrTu-GC surface was carried out using
ferricyanide and ferrocene redox probes. Shown in Fig. 2 was CVs of
the PrTu-GC and bare GC with redox active molecule in 1.0 103 M
ferricyanide solution at as-prepared electrodes with different (15, 20,
25, 30) scan cycles. The electron transfer kinetic of a redox couple de-
pends on the compactness and the thickness of the PrTu on the GC sur-
face. As it can be seen from Fig. 2, the currents of the redox peaks were
obviously increased until 25 CV indicating that the role of PrTu lm
played is not only the electrostatic interaction, but also catalysis [27]
and after this cycle the currents were decreased. Therefore,
electrooxidation of 25 CV cycles were used as an optimum condition
for the preparation of the modied electrode. This results suggest that
Fig. 3. Nyquist plots for (a) bare GC and (b) PrTu-GC in 1 mM ferrocyanide/ferricyanide.
Supporting electrolyte, 0.1 M KCl. The Randle's equivalent circuit model for modied GC
electrode is at the bottom on the right hand side of the Fig. 3(b). Frequency range is
100 kHz0.05 Hz with 5 mV wave amplitude at a formal potential of 0.215 V.
3
the rate of electron transfer is increased due to attachment of PrTu to
GC surface [28,29].
3.2.2. Electrochemical impedance spectroscopy (EIS)
EIS can be employed to evaluate the surface changes of the electrode
in the modied process [30,31]. The measured EIS data were tted with
an equivalent circuit to understand clearly the electrical properties of
the electrodes/solution interfaces. Fig. 3(a) and Fig. 3(b) show the im-
pedance spectrum as Nyquist plots of the GC electrode before and
after being coated with a PrTu in the redox couple solution and the
inset shows the equivalent electrical circuit model of the electrochemi-
cal process on the PrTu modied surface, obtained using CHI 660B soft-
ware. After testing a number of different electrical circuit models, which
are used in the simulation of the impedance behavior of the lm from
the experimental data, it was found that the whole set of data could
be satisfactorily tted with the equivalent circuit given in Fig. 3b.
It seems that the impedance responses of GC and PrTu-GC electrodes
are quite different from each other. As can be seen from Fig. 3a, a semi-
circular part of the high frequency region and an almost straight line at
the low frequency region, which is a characteristic of diffusion limited
step of the electrochemical process were observed at the bare GC elec-
trode with 3.55 k Rct value. This was calculated from tting the spec-
trum to the Randle equivalent circuit in Fig. 3a. On the other hand, the
electrochemical impedance spectrum at PrTu-GC (Fig. 3b) has a de-
creased Rct value (0.165 k) indicating that that the PrTucovered GC
electrode accelerated the electron communication between the redox
couple ferrocyanide/ferricyanide and the electrode surface. Also, low
electron transfer resistance is due to its large surface area and high elec-
trical conductivity. The fast electron-transfer kinetics demonstrated the
potential of the modied electrode for sensing applications [32].
3.2.3. X-ray photoelectron spectroscopy (XPS)
X-ray photoelectron spectroscopy is a useful technique to identify
the characteristic elements, as well as their chemical state and the per-
cent on the surface [33]. To show that PrTu has been coated on the GC
surface, XPS analysis was performed and the results are shown in
Fig.4. XPS survey spectrum showed that C1s, N1s, O1s and S2p elements
were appeared on the PrTu-GC surface (Fig. 4 (b)). The bare GC surface
showed only C1s and O1s peaks (Fig. 4 (a)). The presence of a O1s peak
on the bare GC surface is likely due to surface oxidation and surface
preparation procedure [23,34]. The XPS spectra of PrTu-GC electrode ex-
hibited N1s and S2p signals at about 401.63 eV and 164.65 eV, respec-
tively. The appearance of the N1s and S2p signals as well as
decreasing the percentage of C1s peak provides strong phenomena of
Fig. 4. XPS survey spectra of (a) bare GC and (b) PrTu-GC surface.
4 .T. Ylmaz et al. / Journal of Electroanalytical Chemistry 776 (2016) 18
Fig. 5. XPS spectra for PrTu lm deposited on GC electrode: (a) C1s, (b) N1s and S 2p
narrow regions.
the presence of PrTu molecules on the GC surface. The C1s spectrum
(Fig. 5a) displays three peaks at 284.67 eV, 286.22 eV and 287.01 eV.
The rst peak is due to aromatic or aliphatic C\\C and C\\H bonds
[35]; the second peak is attributed to the nitrogen-bound carbons of
the pyrrolidine ring and C_S bonds [35] and the last peak is ascribed
to the C_O bond in PrTu [36].
The N1s spectrum (Fig. 5b) presents four peaks with the binding en-
ergies centered at 398.76 eV, 399.806 eV, 400.386 eV and 402.09 eV. The
peak at the lowest binding energy at 398.76 eV can be attributed to the
N-H group [37], the second peak is attributed to pyrrolidine nitrogen
[38] and the third peak is ascribed to the N\\C_S bond [39]. The highest
energy contribution at 402.09 eV can be attributed to the amide group
(NH\\C_O) [40,41].
S 2p region is characterized by a doublet (2p1/2 and 2p3/2), due to the
spin-orbit coupling. The more intense 2p3/2 peak (163165 eV) general-
ly denes the region (Fig. 5c). S2p spectra were tted and evaluated in
terms of 2p1/2 and 2p3/2 peaks that appeared at 164.1 eV and 162.8 eV,
as well as a trace peak at 168.48 eV for PrTu. The S2p3/2 and S2p1/2
peaks separation of 1.3 eV agrees with the expected value of 1.2 eV for
this spin-orbit doublet and the peak positions are denotative of the
C_S band [42]. The trace peak at higher binding energy (168.48 eV) is
located at the expected position for oxidation of sulfur. It is also possible
that this peak is due to beam-induced damage from X-ray source [36].
The increased intense peak at 531.88 eV clearly demonstrates the
presence of oxygen atoms from quinone groups in PrTu [35].
3.2.4. Scanning electron microscopy (SEM)
Microstructure of coating surface was studied by using optical and
scanning electron microscopy (SEM). Fig. 6a and b show the SEM micro-
graphs of uncoated GC electrode and PrTu-GC. Fig. 6a shows that SEM
image of the GC electrode without coating. Fig. 6b shows the electrode
covered by PrTu. Regular and smooth the surface of the coating is
clear from the SEM image [43,44].
Fig.6c and d show before and after coating images for electrodes. In a
larger surface area relative to the SEM micrographs and optical micros-
copy of the coated surface, the entire surface of the coating was deter-
mined off feature. The grain structure of the coating and interface
studies have been made that can grow at higher rates SEM. As shown,
the distribution of PrTu particles on the amorphous GC electrode surface
is low. In addition to small submicron particles distributed on the sur-
face, large agglomerated particles are also observed on the micrograms.
However, the distribution of PrTu on the amorphous GC electrode sur-
face is high.
3.3. Effect of supporting electrolyte solution
In most cases, the supporting electrolyte solution and pH are signif-
icant factors in electrochemical reactions. Their effects are important on
the peak currents and peak potentials of TA [45]. The effects of
supporting electrolyte and pH of solutions were investigated on the ox-
idation of the TA by DPV technique. In order to understand the inuence
of supporting electrolyte on the DPV behavior of TA, three types of
supporting electrolyte solutions at pH 3 (phosphate buffer, BR and ace-
tate buffer) were used. The highest anodic peak current of TA was ob-
served in BR buffer solution which was chosen as working media.
3.4. Effect of solution pH
TA is a weak acid and the pH of aqueous solution is an important fac-
tor for its ionization and adsorption. Below pH 4.5, TA presents in molec-
ular form and shows approximate zero surface charge. As the solution
pH increases, TA start to dissociate and at higher pH, it is highly dissoci-
ated in ions and every TA unit having approximately four negative
charges [10,46]. The peak currents and oxidation potentials of TA were
changed with the increase of BR buffer pH from 1.0 to 12.0. It can be
seen from Fig. 7a that the oxidation peak current of TA decreases slightly
with an increase in the BR buffer pH between 26 and above this pH
value the peaks were disappeared. When pH N 2 the peak-shape be-
comes ill-dened. The highest peak intensity was found with pH 2 BR
buffer. Therefore, the optimum BR buffer pH was selected as 2.0. In ad-
dition, the peak potentials for the oxidation of TA shifted towards the
negative direction with an increase in pH (Fig. 7b), showing that
 .T. Ylmaz et al. / Journal of Electroanalytical Chemistry 776 (2016) 18 5

Fig. 6. Scanning electron microscope (SEM) and optical micrographs of uncoated GCE (a and c) and PrTu (b and d) organic material.

protons have taken a part in their electrode reaction processes. The plot
of the peak potential versus pH shows linearity in the pH range of 16
with a slope of 68.5 mV pH 1 (as shown in Eqs. (1)) According to
the Nernstian value (59 mV pH1) this implies that the electron trans-
fer through the PrTu lm was accompanied by an equal number of pro-
tons [47].
orange juice sample were examined. A certain amount of diluted tea
sample was spiked into cell with different concentrations of standard
TA and voltammogram was taken (Table 2). For the determination of
TA in natural orange juice, 3.0 mL orange juice sample was added into
a voltammetric cell containing 7.0 mL pH 7.0 BR buffer and

Ep TA 0:06846pH 0:7308 R2 0:9846 1

3.5. Linear range and detection limit

Under the recommended conditions described, TA determination

was performed to validate the PrTu-GC electrode by DPV (Fig. 8A).
The parameters for DPV were as follows: initial E = 0 V, nal E =
1.5 V, pulse amplitude E = 0.05 V, pulse time = 5 ms, E step = 2 mV,
Scan rate = 50 mV s1, sensitivity = 1 105 A/V. The peak currents
of different concentrations of TA at PrTu-GC are linear (Fig. 8B) ranging
from 2 to 42 M with the linear regression equation given by: Ip /
1 106 A: 1.6205 C / 1 106 A + 1.5904 (R2 = 0.9998). The ratio
of signal and noise (S/N) was accepted as 3 to nd the limit of detection
(LOD). LOD was calculated to be 0.6 M (n = 10) and limit of quanti-
cation (LOQ) value was obtained as 2 M.

3.6. Synthetic samples analysis

As an example of the analytical performance of the developed meth-

od for the determination of TA, three synthetic samples in different con-
centrations were analyzed using standard addition method by DPV. The
results are listed in Table 1. The acceptable recoveries indicate the suc-
cessful application of the PrTu-GC electrode for TA determination.

3.7. Analytical procedures for real samples

The utilization of the modied electrode for the determination of TA

in real samples was also investigated. A black dry tea sample and natural Fig. 7. Effect of pH on the peak current (a) and the peak potential (b) of TA.
6 .T. Ylmaz et al. / Journal of Electroanalytical Chemistry 776 (2016) 18

Table 2
Determination of TA in tea and orange juice.

Sample Detected (M) Added (M) Found (M) XTA ts/Na RSD %

Tea N.D.b 10 10.2 1.7 9c

Orange juice 22.5 1.2 10 33.1 2.3 5c
Orange juice 23.6 2.6 10 31.6 4.2 7d
a
90% condence interval (N = 3).
b
N.D.: not detected.
c
Data found by DPV method.
d
Data found by UV method.

Table 3
Comparison of proposed method with the reported data for TA determination.

Reference Detection limit Working concentration range of

Methods
no. (mol L1) TA (mol L1)

[48] 0.01 0.021 AASV

[49] 0.02 216 DPV
[50] 1 10170 DPV
[51] 3 10500 CV
[52] 8 251025 Potentiometric
[53] 10 40147 Flow injection
This work 0.6 242 DPV

following regression equation: A = 66,739 (C) + 0.0993, where A is

the absorbance of TA at 205 nm and C is molar concentration.
The analytical results are presented in Table 2 compared with the UV
method. The results show no signicant difference between the perfor-
mance of the two methods regarding the accuracy and precision, re-
spectively. The developed electrochemical method was both more
sensitive and without a need for separation or enrichment procedures.
To reveal the performance of the present method on the basis of its
detection limit and working concentration ranges, it was compared
with some other methods reported in the literature for TA determina-
tion, and the results are presented in Table 3.

3.8. Interference studies

In order to evaluate the selectivity of the modied electrode, some

common interferences were tested under optimized conditions. The ef-
fects of Al3+, Cu2+, Pb2+, K+, Ba2+, Zn2+, Fe2+, Cd2+, Na+, Cl, NO 3 ,
Ni2+, Mn2+, selenate, uric acid, histamine, ascorbic acid and gallic acid
were studied (Table 4) by recording the current responses of 10 M

Table 4
Effects of interfering species (200 M) in the determination of TA (10 M) by DPV.

Interfering species (200 M) Recovery of TA (%)

K+ 101
Fig. 8. (A) DPVs of different TA concentrations (from b to i) at PrTu-GC in pH 2.0 BR (a). (B)
Zn2+ 103
Calibration graph of TA concentration.
Na+ 105
NO3 105
voltammogram was taken. TA was determined by standard additions Mn2+ 100
2
SO4 104
method. The results obtained were compared with the spectrophoto-
Co2+ 87
metric method. For UV spectrophotometric determination, absorbances Ni2+ 104
of TA solutions were measured at 205 nm and had a linear dependence Cl 106
with TA concentration. The linear domain range was 5 M to 50 M for Ba2+ 107
TA with a correlation coefcient of 0.999 and can be expressed by the Pb2+ 99
Al3+ 100
Cu2+ 106
Hg2+ 82
Selenate 105
Table 1 Mg2+ 126
Recovery of TA in synthetic sample determined by DPV. Fe2+ 109
Cd2+ 106
Number [TA] added (M) [TA] found (M)a N RSD % Recovery %
Gallic acid 101
1 2 2.13 0.3 3 11.7 106.5 Ascorbic acid 92
2 10 10.0 1.21 3 7.2 100.0 Histamine 102
3 20 21.2 3.03 3 8.5 106 Uric acid 94
a Dopamine 84
90% condence interval.
 .T. Ylmaz et al. / Journal of Electroanalytical Chemistry 776 (2016) 18
TA in the presence of 20 fold excess of interferences. No shift was ob-
served in the oxidation peak potential of TA in the presence of all the
interferents. These results indicate that most of the compounds do not
interfere with the determination of TA, and thus the method is highly
selective for TA. Although the tolerable amount of Mg2+, Co2+, Hg2+
and dopamine is quite low, they usually occur at trace levels in tea,
which make it suitable for the determination of TA in tea samples
[11]. The tea and orange samples were analyzed using DPV.
4. Conclusions
In this paper, a novel high-sensitive electrochemical sensor is fabricat-
ed for determination of TA by DPV. The practical application of the present
modied electrode was demonstrated by determining the concentration
of TA in tea and orange samples. This modied electrode was proved to
be of high sensitivity, excellent selectivity, reproducibility and stability
in comparison with PrTu-GC and GC. Also, it was shown to be accurate, re-
liable, simple and quick to prepare, and of low cost, offering an alternative
analytical procedure for the determination of TA.
Acknowledgment
Authors want to express their great acknowledgments to Dr. Hani
Cinici from Gazi University, Faculty of Technology, for his contribution
in taking the SEM images and to the Scientic Research Unit of Gazi Uni-
versity for nancial support with Grant number: 63/2015-01.
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