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Umesh Chandra*
School of Materials Science and Engineering,
Jimma Institute of Technology,
Jimma University,
Jimma, P.O. Box 378, Ethiopia
Email: umeshkiran17@gmail.com
*Corresponding author
Mohan Kumar
Department of P.G. Studies and Research in Industrial Chemistry,
Kuvempu University,
Shankaraghatta 577 451,
Shimoga, Karnataka, India
and
School of Materials Science and Engineering,
Jimma Institute of Technology,
Jimma University,
Jimma, P.O. Box 378, Ethiopia
Email: mohankumar.mogi@gmail.com
M. Praveen
Department of Chemistry,
M.S. Ramaiah Institute of Technology (MSRIT),
Bengaluru 560097, India
Email: saintypraveen@gmail.com
Abstract: The simple graphite pencil electrode (GPE) tip was etched
by burning it using match stick. A dark black coloured deposition was
observed in the etched portion. This etched portion of GPE was subjected
to characterisation by X-ray diffraction (XRD), and Scanning Electron
Microscopy. Further this etched electrode was used for simultaneous
investigation of dopamine and ascorbic acid in 0.2 M phosphate buffer of
pH 7.4. The modified GPE was stable and reproducible towards detection of
dopamine. The stability of this flame etched electrode towards dopamine was
characterised by applying multiple cycles. The effect of scan rate was found to
be adsorption-controlled electrode process. The detection limit was found to be
3.4708 107 M and quantification limit was found to be 11.5693 107 M.
The flame etched electrode applied for the detection of dopamine in presence of
ascorbic acid and uric acid. The electrode showed excellent selectivity for the
resolution of dopamine, ascorbic acid and uric acid with respective oxidation
and reduction peak potentials. The effect of interference was done by varying
the concentration of one species while other two are kept constant by using
differential pulse voltammetric technique.
Biographical notes: Umesh Chandra received his MSc and PhD in Industrial
Chemistry in 2007 and 2012, respectively from Kuvempu University,
Karnataka, India. He worked under Department of Science and Technology
major research project as JRF for two year (20082010). After completion
of this, he got Rajiv Gandhi National Fellowship from University Grant
Commission, New Delhi. He worked as Lecturer in Sahydri Science College,
Shimoga, Karnataka, for one academic year. He is currently working as an
Assistant Professor in the School of Materials Science and Engineering and
Chair for PhD in Materials Science and Engineering Program, Jimma Institute
of Technology, Jimma University, Ethiopia from 2014. His research area
is electrochemical biosensor. His research interest involves modification
of carbon based electrode for electrochemical investigation of several
neurotransmitters. He presented his research in various national and
international conferences by both oral and poster presentation. He has
published more than 30 research papers in reputed international journals.
Aboma Wagari Gebisa is currently a School Dean and Lecturer at the School of
Materials Science and Engineering, Jimma Institute of technology, Jimma
University. He has done his MSc in Materials Engineering at the University of
Trento, Italy. During his Masters study, he had an opportunity to work
his thesis with corporate research group of Robert Bosch GmbH, Stuttgart,
Germany. He also worked as Graduate Assistant II and Assistant Lecturer at
Mechanical Engineering Department, Jimma University after graduating in
BSc from Bahirdar University in Mechanical Engineering.
This paper is a revised and expanded version of a paper entitled Simple flame
etching of pencil electrode for dopamine oxidation in presence of ascorbic acid
and uric acid presented at Second Indo-Canadian Symposium on Nano-Science
and Technology-2016, The National Institute of Engineering, Mysore, India,
1819 February, 2016.
1 Introduction
Electroanalytical methods have been used through the past three decades to explore the
function of neurotransmitters in the brain owing to their electroactive nature. Such
methods offer great promise for the biomolecule detection with features that consist of
4 U. Chandra et al.
2 Experimental part
2.1 Reagents
Graphite pencil (Camlin, Hi Par Pencil Lead, 0.5 mm in diameter, HB) and match box
were purchased from local shops. Dopamine, ascorbic acid and uric acids were purchase
from Himedia. 25 104 M stock solution AA was prepared by dissolving in double
distilled water and 25 104 M stock solution of UA in 0.1 M NaOH. The stock solution
DA (25 105 M) was prepared by dissolving in 0.1 M perchloric acid solution.
The phosphate buffer solutions of different pH were used as supporting electrolyte.
Above mentioned all chemicals were of analytical grade and used without further
purification. The double distilled water was used in the preparation of all aqueous
solutions.
Simple flame etching of pencil electrode for dopamine oxidation 5
2.2 Apparatus
The electrochemical experiments were carried out using a model-660 electrochemical
workstation (CHI660C). All experiments were carried out in a conventional
three-electrode system. The electrode system contained a working GPE, a platinum wire
as a counter electrode, and a saturated calomel electrode as a reference electrode.
The surface morphology of bare graphite pencil and burnt graphite pencil were
analysed by using a JEOL JSM-848 SEM and the XRD patterns of the burnt and unburnt
pencil were measured using CuK radiation ( = 0.1543 nm) in a PAN analytical
X PERT PRO X-ray diffractometer.
probably because of the use of the match stick for the etching process. During the process
of etching the possibly the surface coating organic binder on the BGPE get evaporated
and the dark black particles produced from the match stick were deposited on the surface.
Figure 1 XRD of BGPE and FEGPE (see online version for colours)
Figure 2 SEM images of BGPE and FEGPE with different magnifications (see online version
for colours)
obtained with anodic peak potential located at 0.25 V and cathodic peak potential was at
0.1 V (vs. SCE). The separation of redox peaks (Ep) was found to be 0.15 V. However,
at the FEGPE, during the first cycle we observed a pair of redox peaks obtained with
strong increased redox peak current signals (hallow circle) because of the formation of
smooth surface after flame etching . The anodic peak potential and cathodic peak
potential were located at 0.21 V and 0.1 mV, respectively. The Ep (Epa1 and Epc1) was
found to be 0.11 V. This reducing the overpotential and strong increase in the redox peak
current shows the electrocatalytical property of the FEGPE. The interesting thing was
that FEGPE showed another reduction peak (Epc2) around 0.38 V, it could be because
of oxidised dopamine molecule contains electron deficient ring and an electron-donation
amine. When amine is deprotonated, the molecule undergoes cyclisation resulting to the
formation of lucodopachrome. During the second cycle an additional oxidation peak
(Epa2) was found around 0.19 V because of the lucodopachrome oxidised to
dopachrome [25,26]. The probable mechanism was shown in Scheme 2.
Figure 3 Cyclic voltammograms of 50 M DA at BGPE (solid line) and FEGPE, first cycle
(hallow circle) and second cycle (solid circle) in 0.2 M phosphate buffer of pH 7.0 at
0.1 Vs1 scan rate
The effect of scan rate on the anodic peak current of 50 M DA was studied by cyclic
voltammetric technique with increasing the scan rate (0.05 Vs1 0.6 Vs1). The graph of
anodic peak current verses scan rate () was plotted (data was not shown) and showed
superior linearity between the scan rate and anodic peak current. The correlation
coefficient was found to be 0.9984 which indicates the electrode transfer reaction was
adsorption controlled.
To understand whether the Epc2 and Epa2 were exist or not, the experiment was
carried out at FEGPE by applying successive multiple cycle in the same above mentioned
solution and condition. The voltammogram was recorded for 15 multiple cycles
(Figure 4). The voltammogram shows negligible decrease for second and third cycles and
almost constant for further cycles and the results shows Epc2 and Epa2 were existing
strongly. This confirms that DA was undergoing ring cyclisation, that is, lucodopachrome
and that was oxidising to dopachrome [25,26].
8 U. Chandra et al.
FEGPE has ability to separate the oxidation peak potentials of DA, AA and UA. Figure 5
shows the cyclic voltammograms for solution containing mixture of 50 M DA, 100 M
UA and 200 M AA in pH 7.0 phosphate buffer solution at sweep rate of 0.1 Vs1.
The BGPE (solid line) showed only one broad and less sensible anodic peak for mixture
of sample. The FEGPE (solid circle) has able to separate the oxidation peaks of DA, UA
and AA by showing three well separated anodic peaks. The electrochemical response of
DA was showed at 0.25 V, AA was found to be at 0.03 V and the UA at 0.41 V by cyclic
voltammetric techniques. The resolutions of this mixture of three samples were also
performed by using differential pulse voltammetric technique (Figure 6). The oxidation
potentials of DA, AA and UA were found at 0.18 V, 0.06 V and 0.34 V, respectively.
The peak-to-peak separation between DA-AA was found to be 0.24 V and between
DA-UA was 0.16 V.
limit of quantification (LOQ) were calculated by using the formula (1) and (2)
respectively, and by using the values of standard deviation and slope obtained for first
three dots. The detection limit was found to be 3.4708 107 M and quantification limit
was found to be 11.5693 107 M. The comparison of the experimentally obtained LOD
and LOQ with previous literatures was shown in Table 1 [2733].
LOD = 3S/M (1)
LOQ = 10S/M (2)
Figure 7 Graph of anodic peak current vs. dopamine concentration (for first three points shown
in inset figure) (see online version for colours)
Simple flame etching of pencil electrode for dopamine oxidation 11
4 Conclusion
The prepared FEGPE shows smooth surface and exhibits excellent electrocatalytic
activity towards the detection of DA. The obtained results revealed that determination of
DA can be easily performed using FEGPE and this modified electrode has dramatically
enhanced electrocatalytic activity towards DA with good stability. The detection limit
and quantification limit of DA at FEGPE were found to be 3.4708 107 M and
11.5693 107 M, respectively. The applicability of FEGPE is able to identify the DA,
AA and UA in mixture of sample. AA and UA were not interferences in the
electrochemical investigation of DA. FEGPE also has good stability and this fabricated
electrode can be applied for study of other bioactive molecules and real samples.
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