Journal of Colloid and Interface Science 504 (2017) 626–632

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Journal of Colloid and Interface Science

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

Regular Article

Electrochemical determination of morin in Kiwi and Strawberry fruit

samples using vanadium pentoxide nano-flakes
Ragu Sasikumar a, Mani Govindasamy a, Shen-Ming Chen a,⇑, Yu Chieh-Liu a, Palraj Ranganathan b,
Syang-Peng Rwei b,⇑
a
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan, ROC
b
Institute of Organic and Polymeric Materials, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan, ROC

g r a p h i c a l a b s t r a c t

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

Article history: Herein, we report the synthesis of Vanadium Pentoxide Nanoflakes (V2O5 NF) using ionic liquid and
Received 8 February 2017 employed the V2O5 NF in electrochemical determination of Morin (MR) in fruit samples. The V2O5 NF
Revised 4 March 2017 were characterized by Powder X-ray diffraction (PXRD), scanning electron microscope (SEM), energy-
Accepted 7 March 2017
dispersive X-ray analyzer (EDX), differential pulse voltammetry (DPV), and cyclic voltammetry (CV).
Available online 9 March 2017
Remarkably, the as-synthesized V2O5 NF exhibited excellent electrochemical behavior and electrochem-
ical ability towards MR. The CV and DPV studies were recognized that the electrochemical performance of
Keywords:
V2O5 NF film modified glassy carbon electrode (V2O5 NF/GCE) towards detection of MR is outstanding in
Vanadium pentoxide
Nano-flakes
comparison with unmodified GCE. The proposed MR sensor shows a wide linear range, high sensitivity,
Morin and low limit of detection are 0.05–10.93 lm, 1.130 lA lM 1 cm 2, and 9 nM respectively. The fabulous
Electro-oxidation analytical parameters of the developed sensor surpassed the previously reported modified electrodes,
Drug analysis rendering the potential application of V2O5 NF in environmental, biomedical, and pharmaceutical
samples.
Ó 2017 Published by Elsevier Inc.

1. Introduction

Flavonoids, polyphenols, steroids, tannins, and terpenoids are

broadly spread in plants, fruits, flowers, and plant-derived foods
which are the responsible for their color, and flavor. All the flavo-
⇑ Corresponding authors. noids have a huge amount of hydroxyl groups containing ring
E-mail addresses: smchen78@ms15.hinet.net (S.-M. Chen), f10714@ntut.edu.tw structures and they have anti-oxidant, anti-bacterial, anti-
(S.-P. Rwei).

http://dx.doi.org/10.1016/j.jcis.2017.03.039
0021-9797/Ó 2017 Published by Elsevier Inc.
 R. Sasikumar et al. / Journal of Colloid and Interface Science 504 (2017) 626–632
inflammatory, anti-allergic, and anti-tumor properties due to the
aromatic hydroxyl groups [1–4]. Moreover, they have medicinal
applications in curing headache, duodenal ulcer, and tummy bug
[5–8]. 2-(2,4-dihydroxyphenyl)-3,5,7-trihydroxy-4H-chromen-4-o
ne (MR) is the most commonly found flavonol in nature and it
can be extracted from Moraceae family, such as mulberry and
some of the historic Chinese healing herbs. MR possesses various
biochemical, and biological effects including anti-viral, anti-
inflammatory, anti-tumor, and cardio protective activities [9].
Remarkably, epidemiological studies revealed that adequate intake
of flavonoid-rich foods may decrease certain cancers, and coronary
heart diseases [10,11].
Morin (MR) has excellent antioxidant property and chelating
capacity for metal ions and it is widely speared in vegetables,
fruits, and some Chinese herbs. It has been reported that MR has
excellent pharmacologic effects such as inhibiting proliferation of
tumors, preventing coronary artery disease, ventricular myocytes,
protecting human erythrocytes, preventing coronary artery dis-
ease, and inhibiting of some cancer tumors [12] The chemical
structure of MR as shown in Scheme 1. Metal oxides are critically
acclaimed for their interesting physicochemical properties, and
excellent electro-catalytic activities [13,14]. Metal oxides have
widespread applications in environmental monitoring, biomedical
diagnosis, photo catalysis, and drug delivery applications [15,16].
Vanadium Pentoxide (V2O5) NF is one of the familiar metal oxides
known for its applications in the battery, biosensor, and solar cells
due to its excellent optical, catalytic, and electrical properties. The
excellent catalytic activity is due to the result of simple oxidation
and reduction between the many oxidation states of vanadium in
V2O5 [17]. V2O5 is the mediator in electrochemical oxidation of
the goal molecule, while the reduced V2O4 can be simultaneously,
and continuously improved by electrochemical oxidation due to
their higher surface to volume ratio, but, V2O5 is in synthetic,
and battery applications [18–21], reports on the electrochemical
behavior of V2O5 NF. The various synthetic methods are available
for the preparation of V2O5 such as direct synthesis, template base
electro deposition, solvothermal method, ionic liquid method, and
hydrothermal method [22–25]. Among this, the synthesis of V2O5
by an ionic liquid method is low cost, easy to synthesis, easy to
use, and high activity. Therefore, we believe that the excellent cat-
alytic attributes of V2O5 NF can be beneficial to the fabrication of
real-time enzyme-free sensor for MR.
Till now several traditional analytical methods are reported in
the literature for detection of flavonols detection which includes
gas chromatography [26,27], spectrofluorometric and HPLC [28],
UV–Vis absorption spectrophotometry [29,30], and electrochemi-
cal analysis [31–36]. Among this, the electrochemical detection
of MR is considerable importance because electroanalytical tech-
niques are low-cost, fast, portable, easy to use, low power con-
sumption, highly sensitive, and selective. Nevertheless, not many
efforts are made to develop an electrochemical sensor for MR.
3'
HO
2' 4'
8 1 B perature was increased from 100 °C for 24 h. Then the reaction
HO 7 9 O 2
5'
1'
A C 6'
3
6 2.4. Fabrication of V2O5 NF/GCE
10 OH
5 4
OH O (0.05 mg mL 1) through ultra-sonication treatment for 1 h. Next,
Scheme 1. Chemical structure of MR.
627
Due to the excellent high conductivity, and large surface area of
V2O5 NF has superior electro-catalytic ability to the oxidation of
MR. The main objective of this present work is to fabricate a highly
sensitive, and selective electrochemical sensor based on V2O5 NF/
GCE for the determination of MR. First, V2O5 NF was synthesized
through simple wet chemical approach, and the as-synthesized
NF were characterized using various analytical techniques, and
have been successfully applied as a new electrochemical sensor
for the detection of MR. The V2O5 NF/GCE has excellent sensing
ability to MR and the overall performance surpassed the perfor-
mances of previous literature reports.
2. Experimental section
2.1. Materials
Materials used for the current study, vanadium(III) isopropox-
ide, butyl-1-methyl pyrrolidinium bis(trifluoromethyl sulfonyl)
amide, acetone, isopropyl alcohol, morin (>95%), ethanol, uric acid,
ascorbic acid and common metal ions were purchased from Sigma-
Aldrich. All the reagents, chemicals, and solvents used were of ana-
lytical grade. Double distilled water was used throughout the full
experiments.
2.2. Methods
The structure and surface properties of as-synthesized V2O5 NF
was studied by X-ray diffraction (XRD; XPERT-PRO PANalytical B.
V., The Netherlands), scanning electron microscopy (SEM; Hitachi
S-3000 H), field emission scanning electron microscopy (FE-SEM;
model, JEOL) attached with energy-dispersive X-ray analyzer. The
electrochemical response of V2O5 NF was studied by DPV (CHI
900), and CV (CHI 1205a) electrochemical analyzer (CH instru-
ments). A conventional three- electrode system composed of
V2O5 NF film modified GCE as working electrode, saturated Ag/AgCl
as a reference electrode, and Pt wire as a counter electrode was
used to carry the electrochemical experiments. The supporting
electrolyte is 0.05 M phosphate buffer which was prepared from
Na2HPO4 and NaH2PO4 0.05 M phosphate buffer solution (PBS).
The electrochemical experiments were carried out in N2 saturated
conditions.
2.3. Synthesis of V2O5 NF
V2O5 NF was synthesized by using an ionic liquid method which
has been previously reported [37]. Briefly, a 5 mL of vanadium (III)
isopropoxide was added to the ionic liquid followed by the addi-
tion of 10 mL of butyl-1-methyl pyrrolidium bis (trifluoromethyl
sulfonyl) amide. The tightly closed vessel was transferred outside
the glove box, about 10 mL of isopropyl alcohol was added drop-
wise to the solution, and stirred at 40 °C for 1 h, a clear solution
was formed. Then 2.5 mL of double distilled water was added
slowly with constant stirring. After 1 h, the reaction flask was
OH
moved to an ultrasonic bath for another 1 h to release trapped
water. The reaction flask was connected to refluxed and the tem-
mixture was cooled, filtered, and dried at 60 °C for 24 h to yield a
yellow colored powder of V2O5 NF.
The as-synthesized V2O5 NF was dispersed in water
the GCE surface was carefully cleaned by using alumina slurry
and dried at ambient conditions. The optimized concentration of
628 R. Sasikumar et al. / Journal of Colloid and Interface Science 504 (2017) 626–632

V2O5 NF (8 lL) was drop cast on GCE surface and allowed to dry at
30 °C for 1 h.
3. Results and discussion
3.1. Characterization studies for V2O5 NF
The XRD spectrum of V2O5 recorded in the 2h range between
10° and 70° is shown in Fig. 1. The diffraction peaks observed at
2h of 15.2°, 20.1°, 21.5°, 26.1°, 31.2°, 34.3°, 41.1°, 45.4°, 47.3°,
51.2°, and 55.7° are related to the corresponding planes of (2 0 0),
(0 0 1), (1 0 1), (1 1 0), (4 0 0), (0 1 1), (3 1 0), (0 0 2), (4 4 1), (6 6 0),
and (0 2 0) which are in good agreement with the crystal structure
of Orthorhombic V2O5 (JCPDS 41-1426).
Next, the morphology of the V2O5 NF was studied using SEM,
and FE-SEM with different magnifications as shown in Fig. 2a–c.
The SEM image reveals the presence of numerous NF of V2O5 along
with the occasional observation of some nanoparticles
(Fig. 2a and b). FE-SEM image (Fig. 2c) reveals that the nature of
the NF has asymmetrical morphology. The elemental spectrum
and quantitative results of the elements in V2O5 NF were con-
firmed through EDX analysis, as shown in Fig. 2d.
In addition, we have performed electrochemical impedance
spectroscopy (EIS) experiments to analyze the electrochemical
kinetics at the electrode/electrolyte interface. The Nyquist plots
obtained from bare GCE, and V2O5 NFs/GCE samples (Fig. 3)
show a well-defined semicircle in the high-medium frequency
region accompanied by a vertical line in the low frequency
region. Moreover, the diameter of the semicircle signifies the
charge transfer resistance at electrode/electrolyte interfaces.
Compared to the bare GCE, and V2O5 NFs/GCE samples dis-
played a lower charge transfer resistance, because of the syner-
gistic effect between the V2O5 NFs and GCE. Hence the obtained
analytical parameter suggest that the V2O5 NFs/GCE high surface
area and high conductivity.

Fig. 1. XRD data for V2O5 NF.

Fig. 2. (a and b) SEM images (c) FE-SEM image of the V2O5 NF with different magnifications, (d) EDX spectrum, and (e) quantitative analysis of elements.
 R. Sasikumar et al. / Journal of Colloid and Interface Science 504 (2017) 626–632
Fig. 3. EIS for (A) Bare GCE, and (B) V2O5 NFs/GCE.
3.2. Electro-catalysis behavior of MR at different modified electrodes
Fig. 4 displays the cyclic voltammograms (CVs) obtained for the
electro-catalytic activities of bare GCE and V2O5 NF/GCE towards
200 lM MR. The voltammograms were performed in PBS (pH 7),
and the scan rate was applied at 50 mV s 1. In the absence of
MR, the bare GCE doesn’t produce any peak, while in the presence
of MR, an observable peak is detected at 0.202 V, however the peak
current is very low (curve a). However, well-defined, and highly
enhanced oxidation peak was observed at 0.183 V for the V2O5
NF/GC (curve b). Comparatively, V2O5 NF/GCE showed maximum
electro-catalytic performance than bare GCE in terms of high peak
currents and less overpotential. Thus, the V2O5 NF/GCE has the
superior electro-catalytic ability to the oxidation of MR due to
the excellent high conductivity, and large surface area of V2O5
NF. The oxidation peaks observed at peak potentials of 0.183 V at
V2O5 NF/GCE can be related to the 2e /2H+ oxidation of MR to
OMR (oxidized morin). From the previous reports, we understood
that the respective electrochemical reaction of MR is an irre-
versible oxidation reaction involving with two electrons, and two
protons as given in the mechanism in Scheme 2 [38].
3.3. Effects of scan rate and concentration
In order to examine reaction kinetics, the guidance of scan rate
on oxidation peaks currents of MR at the V2O5 NF/GCE was exam-
Fig. 4. CVs of (a) bare GCE in the presence of 200 lM MR, and (b) V2O5 NF/GCE in
presence of 200 lM MR.
629
Scheme 2. Oxidation of MR on V2O5 NF/GCE.
ined by CVs. Fig. 5A shows the effect of scan rate on the electrocat-
alytic behavior of V2O5 NF/GCE towards MR. The anodic peak
currents are linearly increased as the scan rate increases from 20
to 200 mVs 1. The linear plot among square root of the scan rates
versus oxidation peak current has exhibited a linear relationship
which signifying that the oxidation process of MR taking place at
the V2O5 NF/GCE is a diffusion controlled electron transfer process
(Fig. 5B). The corresponding linear regression equation can be
expressed as, Epa (V) = 0.021x + 0.085, R2 = 0.987. From the results,
we authorize that the viewed cyclic voltammetry responses are
due to the detection of MR diffused on the surface of the V2O5
NF/GCE [39–41]. Fig. 5C reveals that the CV curves of V2O5 NF/
GCE in pH 7 PBS containing MR with various concentrations. The
oxidation peak current increases gradually with increase in every
addition of MR. The inset figure represents the plot between cur-
rent (lA) versus different concentrations of MR (lM) which shows
good linearity. The linear plot among oxidation peak current versus
concentration of MR has exhibited a linear relationship which sig-
nifying that the oxidation process of MR taking place at the V2O5
NF/GCE (Fig. 5D).
3.4. Effect of pH
The plot between pH and current is given in Fig. 6A, while the
plot between pH and peak potential is given in Fig. 6B. As shown
in the figure, the MR oxidation peak current increases as the pH
increases from 3 to 7. This result proposes that the electrochemical
oxidation performance of MR is pH dependent, while the concen-
tration of hydrogen ion disturbs the rate of the oxidation reaction.
Furthermore, the oxidation of MR to OMR is more encouraging and
active in neutral medium. Therefore, the pH 7 was nominated as
the working pH condition for additional electrochemical studies.
3.5. Calibration curve of MR
Differential pulse voltammetry (DPV) was adopted in order to
enhance the sensitivity of the fabricated MR sensor. Fig. 7A shows
the DPV response of V2O5 NF/GCE towards different concentrations
of MR (0.05–10.93 lM) in 0.05 M PBS with pH 7. The electrocat-
alytic response current of MR increases with increasing concentra-
tion. The linear regression equation was Ipa (V) = 0.0815x + 0.4688
with correlation co-efficient R2 = 0.9838. The sensitivity calculated
from the slope of the calibration plot is shown in the of Fig. 7B. The
observed sensitivity is 1.130 (±0.002) lA lM 1 cm 2. Next, the
limit of detection (LOD) is calculated using the slope of the calibra-
tion plot and standard deviation of the mean value for ten blank
measurements (Sb) and by adopting the formula, LOD = 3Sb/b
630 R. Sasikumar et al. / Journal of Colloid and Interface Science 504 (2017) 626–632

Fig. 5. (A) CVs obtained at V2O5 NF/GCE in PBS (pH 7) containing 200 lM MR at different scan rates (20–200 mV s 1). (B) The plot between oxidation peak current, and the
square root of scan rate, (C) CVs of V2O5 NF/GCE in PBS (pH 7) in the absence, and presence of MR with different concentrations (a = absence of MR, b to k = presence of MR) at
a scan rate of 50 mV s 1, and (D) The plot between oxidation peak current and the concentration of MR.

Fig. 6. Plot between (A) peak current (lA) vs. pH, and (B) peak potential (V) vs. pH.
CVs are carried out in PBS (pH 7) containing 200 lM MR.
[42–43]. The calculated detection limit was 9 nM. The observed
linear range was 0.05–10.93 lM, sensitivity was 1.130 lA lM 1 -
cm 2 and LOD was 9 nM. The analytical parameters such as sensi-
tivity, limit of detection and concentration range of the described
MR sensor were compared with previously reported sensors and
given as Table S1. As revealed by the table, the described V2O5
NF/GCE sensor has shown outstanding sensor performance and
surpassed the performance of previously reported sensors. Thus,
V2O5 NF/GCE is an excellent electrocatalyst and outstanding signal
(current) amplifier towards sensing of MR.
rutin (RT) at the V2O5 NF/GCE, due to its higher sensitivity and
selectivity than that of CVs. The selective determination of MR in
their mixed components will slightly affect the detection of QR,
and RT because its oxidation potential is closer to that of MR. As
shown in Fig. 8 the Ipa increases linearly with an increasing the
concentration of MR. The peak to peak separation of these three
components is good at from lower concentration levels with differ-
ent potentials. The peaks increase linearly with increasing the con-
centration of MR meanwhile there are no peaks appeared of QR
and RT. These results indicate the as-synthesized V2O5 NF/GCE is
an excellent sensor for MR.
3.7. Interference study and accumulation time
The selectivity of the sensor is more significant in the presence
of the compounds which are oxidized at near oxidation potential of

3.6. Simultaneous and selective determination of MR, QR, and RT

DPV was used to evaluate the simultaneous and selective elec-

trochemical detection of MR in the presence of quercetin (QR), and

Fig. 7. (A) DPVs of V2O5 NF/GCE towards increasing concentration of MR in PBS (pH Fig. 8. DPV curves of under varied MR, QR, and RT concentrations in 0.05 M PBS (pH
7) (a to p = 0.05–10.93 lM), and (B) The inset shows the calibration plot. 7). Inset: anodic oxidation peak currents vs biomolecules concentrations.
 R. Sasikumar et al. / Journal of Colloid and Interface Science 504 (2017) 626–632 631

Fig. 9. DPV curves of the V2O5 NF/GCE in (A) Kiwi (Actinidia deliciosa), and (B) Strawberry (Fragaria ananassa) fruit samples. The fruit samples containing MR was added
consecutively to PBS (pH 7). All DPV curves were obtained at a scan rate of 50 mV s 1.

MR. Hence, we have examined the choosiness of the sensor in pres- Table 1
ence of possible interfering compounds such as Ca2+, Hg2+, K+, Na+, Performance of V2O5 NF/GCE for the determination of MR in fruit samples.

Pb2+, Zn2+, uric acid, and ascorbic acid. Fig. S1 shows the DPV S. Fruit samples Added Found Recovery RSD
response of V2O5 NF/GCE in presence of 1 lM MR and 100 lM of No (lM) (lM) (%) (%)
Hg2+, K+, Na+, Pb2+, Zn2+ and 50 lM of uric acid and ascorbic acid. 1 Kiwi (Actinidia deliciosa) 10 9.45 105.82 3.49
Fig. S1 clear shows that the aforementioned interferents had not 20 20.49 97.6 3.86
produced any measurable signals. However, MR (1 lM) had pro- 30 29.15 102.91 4.55

duced a good response which representing the good anti- 2 Strawberry (Fragaria 10 18.52 95.23 2.56
interference capability of the V2O5 NF/GCE. Fig. S2A shows the ananassa) 20 31.32 100.65 3.12
30 42.35 96.12 4.69
accumulation time study. As shown in the figure, the oxidation
peak current of MR increases gradually with the increase of accu- RSD = Relative standard deviation for three measurements.
mulation time from 0 to 150 s. The highest current response of
MR was observed when the accumulation time reached at 30 s.
The results suggest that the maximum accumulation of OMR via The DPV results in Fig. 9 clearly establish that the V2O5 NF/GCE is
MR to OMR occurs at 30 s [44–46]. Thus, an optimized accumula- definitely extremely suitable for real food sample analysis and data
tion time of 30 s was adopted for all the experiments. are obtained in Table 1.

3.8. Reproducibility and operational stability

In order to investigate the reproducibility of the sensor, five dif-
ferent V2O5 NF/GCEs were fabricated and tested towards 100 lM
MR. The obtained reproducibility results are shown in Fig. S2B
which indicates that the V2O5 NF/GCEs have a good reproducible
capacity and the electrode can be used for accurate detection of
MR. The cyclic voltammetry response of 50 continuous cycles of
the V2O5 NF/GCE in the absence of MR is given in Fig. S3. The
results indicated long-term stability of the electrode [47].
3.9. Real sample analysis
The suggested MR sensor was additionally tested using real
food samples, such as an Actinidia deliciosa (Kiwi), and Fragaria
ananassa (Strawberry) sample, obtained from a local market in Tai-
pei, Taiwan. The Kiwi and Strawberry samples are extracted using
water in a mortar, and pestle pretreated first by systematic
grounding in an agate mortar, which yields to extracts. For the real
sample studies, the pretreated fruit extract was added successively
(spiked method) to 10 mL PBS solution, as shown in Fig. 9
(A) and (B) for the Kiwi and Strawberry samples, correspondingly.
4. Conclusions
V2O5 NF was successfully prepared and nanoflakes structures
were revealed by morphological studies. V2O5 NF/GCE has shown
strong electrocatalytic activity towards oxidation of MR owing to
the good electrostatic interaction between hydroxyl groups of
MR and oxygen of V2O5 through hydrogen bonding. From the pH
results, the optimum pH medium is 7 due to maximum response.
The DPV studies revealed that the developed electrode has excel-
lent sensing attributes with the low detection limit (9 nM), and
good sensitivity (1.130 (±0.002) lA lM 1 cm 2) which are either
comparable or superior over previous reports. The fabricated sen-
sor displayed suitable choosiness for the detection of MR in the
presence of possibly active metal ions and biological compounds.
In addition, the MR sensor has good reproducibility, and opera-
tional stability interpreting practical industrial applications.
Acknowledgments
This project was supported by the National Science Council and
Ministry of Education, Taiwan (Republic of China).
632 R. Sasikumar et al. / Journal of Colloid and Interface Science 504 (2017) 626–632
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcis.2017.03.039.
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