Food Chemistry 173 (2015) 11721178

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Synthesis, characterisation and antioxidant activity

of luteolinvanadium(II) complex
Souvik Roy , Sougata Mallick, Tania Chakraborty, Nilanjan Ghosh, Amit Kumar Singh, Subhadip Manna,
Sumana Majumdar
Department of Pharmaceutical Technology, NSHM Knowledge Campus, 124 B.L. Saha Road, Kolkata 700053, West Bengal, India

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

Article history: The complex formation between luteolin (L) and vanadium(IV) oxide sulphate monohydrate (VOSO4H2-
Received 22 May 2013 O) was examined under UVvisible, infra-red spectroscopy, mass spectroscopy and NMR techniques. The
Received in revised form 11 September spectroscopic data indicated that luteolin reacts with vanadium oxide cation (VO+2) through 4-carbonyl-
2014
5-hydroxy chelation site in the two luteolin molecule. The free radical antioxidant activity of the complex
Accepted 26 October 2014
Available online 3 November 2014
with respect to the parent molecule was evaluated using 1,1-diphenyl-2-picrylhydrazyl (DPPH), ferric
reducing antioxidant power (FRAP) and 2,20 -azinobis 3-ethylbenzothiazoline-6-sulphonic acid diammo-
nium salt (ABTS) methods. It was observed that the free radical scavenging activity and ferric ion reduc-
Keywords:
Luteolinvanadium(II) complex
ing potential of luteolin was increased after the formation of complex with vanadium oxide (VO+2) cation.
Spectral characterisation 2014 Elsevier Ltd. All rights reserved.
Antioxidant activity
Radical scavenging activity

1. Introduction lion (ppm), whereas in canned foods, especially those with an

Canned food and beverages constitute a major part of the global
food supply. Consumers expect canned food and beverages to
maintain their avour, texture and colour and must be free of dis-
ease causing pathogens. This is mainly obtained by coating in
canned inner wall by various materials (Lugscheider, Kraimer,
Barimani, & Zimmermann, 1995). Cans for human foods and bever-
ages are made of aluminium or steel or more materials like Cu, Mn,
Mg, Zn, Si, Cr, Fe and Ti and others (Robertson, 2006). Although
cans are prepared from various materials but mainly tin coated
aluminium and steel cans are used now a days for global food
supply.
Steel made cans are usually coated with tin and used for light
coloured fruits and fruit juices which have an additional organic
coating. In addition tin prevents the oxidative degradation along
with the darkening and avour changes of the food material during
storage via self-oxidation (Blunden & Wallace, 2003). In cans with-
out organic coating the iron of steel has been protected electro-
chemically by tin dissolution (Coles & Kirwan, 2011). Most of the
cases, foods and beverages are in contact with tin results in pitting
corrosion and also in hydrogen production, which further causes
swelling and potential can damage (Ellis, 1979). Concentrations
of tin in the majority of foods are usually less than 1 part per mil-
Corresponding author. Tel.: +91 9831345318; fax: +91 33 24033424.
E-mail address: souvikroy35@gmail.com (S. Roy).
acidic pH, noticeably higher levels, e.g., 100500 ppm (0.01
0.05%) or more (Blunden & Wallace, 2003). The signs of inorganic
tin poisoning in mammals include local and systemic effects such
as vomiting, diarrhoea, ataxia, paralysis, growth retardations, eye
and nose irritation (Boogaard et al., 2003). Recent investigation
also found that tin existed in canned products are most likely che-
lated by avonoids of canned fruits and vegetables which may
decrease the redox potential of tinavonoids complex (Dehghan
& Khoshkam, 2012). Hence new strategies need to be developed
to reduce the risk of tin induced toxicity. Aluminium cans with
vanadium enriched steel coating in inner surface can be a fruitful
alternatives and to minimising the health risk.
Trace amount of vanadium present in steel can play a signi-
cant role in performance improvement. The addition of vanadium
into steel can enhance the strength, toughness, plasticity, improve
fabrication and service performance of the steel. Therefore, vana-
dium is inevitable to produce high performance, high strength,
high ductility, low yield ratio, corrosion resistant steel and incorpo-
ration of vanadium in steel is considered as an alloying element
within the range of 0.53.0% (Todie, Cikara, Todie, & Camagic,
2011).
Though vanadium is very toxic in nature but in trace amounts it
shows a variety of therapeutic activity (Crans, Mahroof-Tahir, &
Keramidas, 1995; Tsiani & Fantus, 1997). In the last decades, vana-
dium compounds have gained attention due to its variety of
valences and coordination chemistry of vanadium and a wide

http://dx.doi.org/10.1016/j.foodchem.2014.10.141
0308-8146/ 2014 Elsevier Ltd. All rights reserved.
 S. Roy et al. / Food Chemistry 173 (2015) 11721178
range of potential applications of its complex (Maurya & Kumar,
2006). Incorporation of the oxo-vanadium ion into chelating sys-
tem improves the gastro-intestinal absorption and reduce the tox-
icity of metal ion. Such ligands are obtained mainly from poly-
phenols and avonoids, having numerous therapeutic activities
(Badea et al., 2010).
Flavonoids (2-phenyl-benzo-c-pyrones) are a large group of
polyphenolic natural compounds, extensively distributed in
plant-based foods (Andersen & Markham, 2006; Shahidi,
McDonald, Chandrasekara, & Zhong, 2008). Flavonoids exhibit a
variety of biological and pharmacological properties, including
antiulcer, antiallergic, cardiovascular protection, anticancer, antivi-
ral, anti-inammatory potentials (Dehghan, Shaee, Ghahremani,
Ardestani, & Abdollahi, 2007). Most of the bioavonoids are potent
metal chelators and possessed strong antioxidant and free radical
scavenging activity (Dehghan & Khoshkam, 2012).
Flavonoids like rutin and quercetin are good chelating ligand
and contain three domains that can interact with metal ions: the
30 ,40 -dihydroxy group located on the B ring, the 3-hydroxy or 5-
hydroxy and the 4-carbonyl groups in the C ring. A number of
recent studies have suggested that the chelating properties of
avonoids can be assigned to the presence of the 3- or 5-hydrox-
ypyran-4-one, rather than the orthohydroxyl groups in the B ring
(Uivarosi et al., 2010). Complexation of avonoids like quercetin
with a large number of metal cations [Mo(VI), Fe(II), Fe(III), Cu(II),
Zn(II), Al(III), Tb(III), Pb(II), Co(II)] in different stoichiometries
ratios has already been reported (Ahmadi, Dehghan,
Hosseinpourfeizi, Ezzati, & Kashanian, 2011; Chen, Sun, Cao,
Liang, & Song, 2009; Cornard & Merlin, 2002; Leopoldini, Russo,
Chiodo, & Toscano, 2006; Shaghaghi, Manzoori, & Jouyban, 2008;
Torreggiani, Tamba, Trinchero, & Bonora, 2005; Zhou, Wang,
Wang, & Tang, 2001).
Luteolin (30 ,40 ,5,7-tetrahydroxyavone, Fig. 1a) is one of the most
common avonoids present in various fruits and vegetables and has
contributed to the antioxidant activity (Leung, Kuo, Yang, Lin, & Lee,
2006). Luteolin is reported to have anti-inammatory properties and
mediates its action by inhibiting of nitric oxide production (Kim,
Cheon, Kim, & Kim, 1999). A recent report established that luteolin
is a potent inhibitor of human mast cell activation through inhibition
of protein kinase-C activation and Ca++ inux (Chowdhury et al.,
2002). Previous reports were also suggested that luteolin arrest cell
cycle in the G phase of human melanoma cells (Casagrande &
Darbon, 2001) and also able to reduce postprandial blood glucose
level (Matsui, Kobayshi, & Hayashida, 2002).
The purpose of our investigation was to examine the chelation
property of luteolin which is common avonoids exists in many
Fig. 1. (a) Chemical structure of luteolin, different types of bands such as I and II related to UVVis absorption of: ring A (band II) benzoyl ring system; ring B (band I)
cinnamoyl ring system in luteolin molecular structure. (b) Proposed coordination complex of luteolinvanadium(II).
1173
fruits and vegetables even in canned foods and beverages, with
vanadium and also to investigate the variation of antioxidant prop-
erties of luteolin after chelation with vanadium.
2. Experimental
2.1. Chemicals and reagents
All reagents used for experimental purpose were of analytical
reagent grade. Extra pure methanol, luteolin, DPPH (2,2-diphe-
nyl-1-picryhydrazyl), ABTS (2,20 -azinobis 3-ethylbenzothiazoline-
6-sulphonic acid diammonium salt), TPTZ (tripyridyl-S-triazine)
and vanadium(IV) oxide sulphate monohydrate were purchased
from Sigma Aldrich Chemical Co. (St. Louis, MO, USA).
2.2. Synthesis of the complex
2.2.1. Synthesis of luteolin vanadium(II) complex
The proposed co-ordination complex was depicted in Fig. 1b.
Complex was prepared by taking 2.00 g of luteolin and dissolved
in 50 ml of distilled water containing few NaOH pellets. To the
resulting solution a saturated solution of VOSO4H2O (in the molar
ratio VO:ligand 1:2) was added drop wise, under continuous stir-
ring. The pH of the solution was adjusted to 6 with 1 (M) H2SO4.
After a few days a green solid precipitated. The sparingly soluble
product was ltered off through a Buckner funnel. Wash several
times with water and dried in desiccators over CaCl2. The green
colour product of luteolinvanadium complex was soluble in
methanol and dimethyl sulphoxide (DMSO).
2.3. Physical measurements
UVVis spectra of 4  104 M solutions of luteolin and its vana-
dium(II) complex were obtained in MeOH by UV-1800 Shimadzu
double beam Spectrophotometer using standard 1.00 cm quartz
cells. IR spectra were recorded in KBr pellets with a FT-IR
(ALPHA-T, Bruker, Rheinstetten, Germany) spectrophotometer in
the range 5004000 cm1. 1H-NMR spectra were recorded on a
Bruker- Avance-500 MHz spectrometer in DMSO using TMS (tetra-
methyl silane) as internal reference. Mass spectra were recorded
by electrospray ionisation tandem mass spectrometry (ESI-MS)
technique with the following procedure: a sample (1 mg) was dis-
solved in 1:1 chloroformmethanol and after 30 s of exposure to an
ultrasound bath the solution was injected directly into the electro-
spray interface of a 1200 L/MS/MS (Varian) mass spectrometer. The
1174 S. Roy et al. / Food Chemistry 173 (2015) 11721178
injection was performed using a Prostar 240 SDM (Varian) pump
with 0.02 ml/min. ow. Air at 200 C and 19 psi was used for des-
iccation and nitrogen at 42 psi was used for dispersion. Molecular
ions scanning range (m/z) was 1501000.
2.4. Measurement of antioxidant activity of complex by DPPH, ABTS
and FRAP methods
The antioxidant activity of free luteolin and luteolinvana-
dium(II) complex was evaluated using, DPPH and ABTS radical
scavenging activity and ferric reducing antioxidant power (FRAP).
In the DPPH radical scavenging method, different concentrations
(20 lg, 40 lg, 50 lg, 70 lg, 90 lg/ml) of luteolin and luteolin
vanadium(II) complex were taken. Then 1 ml of the sample and
3 ml of DPPH solution and the reaction mixture was shaken vigor-
ously and kept in completely dark for a better reaction. The reduc-
tion of DPPH absorbance was followed by monitoring at 517 nm
every 5 min for about 3035 min (As) (Dehghan & Khoshkam,
2012). As a control the absorbance of blank solution of DPPH was
also determined at 517 nm (Ac).
The percentage of radical scavenging activity (RSA%) was calcu-
lated according to the following equation:
100Ac  As
RSA%
Ac
Reduction of metal ions like Fe+3, is related to the antioxidant
potential of most synthetic and natural antioxidant like avonoids.
FRAP assay was conducted according to the Benzie and Strain
(1999) with some modied form. 2.5 ml solution of TPTZ
(10 mM, dissolved in the 40 mM of HCl), and FeCl3 (20 mM) in
25 ml acetate buffer (300 mM, pH 3.6) were mixing freshly to form
FRAP reagent having bluish tint which changes to dark or intense
blue after interaction with antioxidant, which thereby conrms
the presence of Fe+3-TPTZ in the FRAP reagent. The different obser-
vation was carried out by using 593 nm for different concentration
(10, 15, 20, 30, 40 lM) of both luteolin and luteolinvanadium(II)
complex.
ABTS radical scavenging activity was based on the method of
Pennycooke, Cox, and Stushnoff (2005). ABTS radical scavenging
activity was done by dissolving ABTS powder (54.2 mg) in 10 ml
of phosphate buffer solution (having 5 mM and pH 7.0) and mixed
with 1 g of MnO2 and incubated in room temp for about 30 min. A
greenish colour solution was observed. Centrifugation was carried
out for 56 min and after ltration the ltrate was diluted with
phosphate buffer until the absorbance of the resultant solution
equals to 0.70 0.01 at 723 nm. Different concentration (5
25 lM) of luteolin and luteolinvanadium(II) complex were mixed
with 2 ml of ABTS solution and incubated for 10 min at room tem-
perature. The decrease of absorbance was monitored at 734 nm
after 1012 min. The percentage of radical scavenging activity
(RSA%) was calculated by the following equation:
1  Af
Radical scavenging activity at 750 nm %  100
A0
where A0 referred to absorbance of the uninhibited radical cation
and Af referred to the absorbance measured 1012 min after the
addition of the samples.
2.5. Data analysis
The data collected were subjected to descriptive statistics of
mean, standard error mean and inferential statistics of students t
test.
3. Results and discussion
3.1. UV visible spectroscopic study of the complex
In the absorption spectrum of luteolin, two prominent charac-
teristic absorption peaks were visualised with corresponding max-
ima at 365 and 260 nm for band I and band II, respectively. Band I
is annotated for the absorption of cinnamoyl system (ring B), while
band II is interpreted for benzoyl system (A ring). From the molec-
ular structure of luteolin, it can also be inferred that luteolin can
chelate the metal ions via one site i.e., 5-hydroxy-4-oxo system.
When vanadium solution was added to a methanolic solution of
luteolin, it caused the signicant change in the luteolin spectrum
due to the displacement of band I, appeared the peak at 420 nm
kmax (band III). It shows that the bathochromic shift of about
55 nm takes place. The spectral change can be easily observed in
Fig. 2. It conrms that complex formation takes place between
luteolin and vanadium. That change takes place in band I. The dis-
placement of band II was also observed from 260 to 265 nm (band
IV). Therefore, it supports the clue that newly appeared peak at
420 nm in vanadium complex of luteolin may arise due to com-
plexation of vanadium at 5OH and 4CO of luteolin. High delocaliza-
tion of oxygen electrons of 5-hydroxyl group facilitate the p
electrons delocalization. Thus, complex formation at band I caused
by the interaction of 5-hydroxyl group of luteolin with vanadium
subsequently follows the electronic redistribution between the
vanadium and luteolin to form a big extended p bond system. It
changes the electronic distribution in luteolin from np to pp
transition of lower energy. Thus, new ring formation in complex
is caused by the increased conjugative effect with inclusion of
the C ring, which provides the additional molecular stabilization
resulting from the formation of extended 4 bond system. Hence,
this information is supportive in the sense that the chelation ability
of luteolin is attributable to the presence of 5OH and 4CO groups in
ring C. Thus the red shift in the luteolin spectrum is highly infor-
mative for the coordination site in ligand having chelating site
and due to the acidic nature of 5OH proton and more suitable loca-
tion of 4CO, they may be a proper site to be involved in complex
formation.
3.2. Infrared spectral study of the complex
Fig. 3A depicted FTIR of luteolin (a) and luteolinvanadium(II)
complex (b) and the data were analysed in Table 1. The presence
of peak at 943.47 cm1 in IR spectrum of the complex represented
Fig. 2. UVVis spectra of (a) luteolin and (b) luteolinvanadium(II) complex.
 S. Roy et al. / Food Chemistry 173 (2015) 11721178
Fig. 3. (A) Infra-Red (IR) spectra of (a) luteolin and (b) luteolinvanadium complex. (B) Mass spectroscopy of the luteolinvanadium(II) complex.
Table 1
Assignment of the IR spectra of the luteolin and the complex (band position in cm1).
Compound m (OAH) m (C@O)
Luteolin 3394.64 1666.09
Complex 3394.31 1655.17
the formation of (V@O) bond via the complex formation. The
stretching mode of C@O in free ligand was found at
1666.09 cm1. Due to the interaction of luteolin with vanadium
oxide the band of C@O stretching mode has been shifted from
1666.09 cm1 to a absorption band at 1655.17 cm1 in the com-
plex which can be explained by co-ordination of carbonyl oxygen
with metal ion that conrms the vanadium(II) had bonded to
5-hydroxyl of ring A and 4 carbonyl of ring C. The bands located
at 1612.52 and 1262.36 cm1, respectively, are related to m (C@C)
and m (CAOAC) vibration frequencies in luteolin spectrum which
are slightly shifted after complexation with vanadium. Apart from
that an increase in vibrational frequency of m (CAOH) in complex,
which was shifted from 1342.59 to 1343.30 cm1, indicated the
involving of m (CAOH) deformation mode conrms that the vana-
dium(II) had bonded to 5-hydroxyl of ring A and 4 carbonyl of ring
C. The big band of m (OAH) vibrational frequency in the complex
indicates the existence of water in the complex.
3.3. Mass spectroscopy study of the complex
Fig. 3B depicted the MASS spectrometry where the base signal
at m/z 305.25 designated as luteolin + water, whereas m/z 287.42
represents one single luteolin. The peak m/z at 337.48 designates
luteolin + vanadium. The peak at m/z 623.11 and m/z 639.89 repre-
sents two luteolin + one molecule of vanadium and two luteo-
lin + vanadium oxide respectively. Two luteolin + vanadium oxide
with one molecule of water represent at m/z 658.21.
3.4. 1H NMR study
1
H NMR spectra of free luteolin and luteolinvanadium(II) com-
plex were obtained by using DMSO as a solvent.
1175
m (C@C) m (CAOH) m (CAOAC) m (O@V)
1612.52 1342.59 1262.36
1613.64 1343.30 1261.10 943.47
Luteolin: d 12.61 (1H, 5-OH); d 10.76 (1H, 7-OH); d 9.39 (1H, 40 -
OH); d 9.31 (1H, 30 -OH); d 7.37(1H, 60 -H); d 7.35 (1H, 20 -H); d
6.84(1H, 50 -H); d 6.63 (1H, 3-H); d 6.40 (1H, 8-H), 6.14 (1H, 6-H).
Luteolinvanadium(II) complex: d 10.74 (1H, 7-OH); d 9.24 (1H,
40 -OH); d 9.22 (1H, 30 -OH); 7.31 (1H, 60 -H); d 7.28 (1H, 20 -H); d
6.80 (1H, 50 -H); d 6.59 (1H, 3-H); d 6.38 (1H, 8-H), d 6.14 (1H, 6-H).
Luteolin shows a sharp singlet at 12.61 ppm produced from the
intramolecular hydrogen bond. This is the hydroxyl group of ring A
located at C5 position which can interact with the acceptor car-
bonyl group of ring C at C4 position.
In addition with this, the 1H NMR data shows the values d of
luteolin-vanadium complex which were shifted to lower eld as
compared to the pure luteolin. This is due to the increase of the
conjugation caused by the effect of coordination when the complex
is formed, which increases the planarity of the avonoid mole-
cules. The above data of the complex also indicates that 5-OH
group proton in not present in the complex; however three other
hydroxyl groups (7-OH, 30 -OH and 40 -OH) protons were remained
after chelation. Therefore it can be presumed that metal ions must
probably replace 5OH protons by undergoing coordination through
oxygen atom.
3.5. DPPH radical scavenging activity of luteolin and luteolin
vanadium(II) complex
Luteolin is a bioavonoid and well known for its good antioxi-
dant and radical scavenging activity and to form chelate with tran-
sition metals. Formation of metal and avonoid complex cations
changes its natural free radical scavenging ability signifying that
the complex has increased ability to scavenge oxidants and free
radicals. DPPH test shows that the antioxidants have inheritant
potential to reduce the DPPH radical from violet to yellow col-
1176 S. Roy et al. / Food Chemistry 173 (2015) 11721178

Fig. 4. (a) Kinetic behaviour of DPPH free radical scavenging activity (RSA%) of different concentration of luteolin. The radical scavenging activity was carried on for 35 min.
(b) DPPH Radical scavenging activity of luteolin and luteolinvanadium complex with increasing concentration (lg/ml) for 5 min.

oured diphenyl-picrylhydrazine. In the chemical reaction antioxi-
dants donate the hydrogen to DPPH and convert it into DPPH-H.
Therefore, by using DPPH method the antioxidant activity of both
the compounds was evaluated. Actually antioxidant activity of
luteolin and vanadium(II) complex depends upon their structure,
especially their hydrogen donating ability. The reaction between
luteolin and DPPH occurs in two several steps, they are as follows:
in the fast step the DPPH absorbance diminishes very quickly and
in the next slow step in which the absorbance of DPPH diminishes
slowly in near about 1 h to reach a xed or constant value. Fast
step corresponds to abstraction of most liable H-atom, whereas
slow step shows the oxidative degradation in the remaining
product.
However, the antioxidant activity of the compounds depends
upon their molecular structures, but complexation made with
the metal ions may affect the chemical properties of ligand mole-
cules hence variation in the activity (Ensa, Hajiana, &
Ebrahimib, 2009). Our recent study has also in an agreement with

Fig. 5. (a) Ferric reducing antioxidant power (FRAP) of luteolin and luteolinvanadium(II) complex of different concentrations (lM). (b) ABTS radical scavenging activity (%)
of different concentration of luteolin and luteolinvanadium(II) complex.
 S. Roy et al. / Food Chemistry 173 (2015) 11721178
the previous ndings that our coordination complex may affect the
ability of parent antioxidants. The antioxidant activities of the
compounds have been studied in a concentration dependent man-
ner. Thus the plot illustrated in Fig. 4 showed that luteolin scav-
enged free radical to about 53% while the complex scavenged to
about 65%, thus complex represented better inhibitory effect com-
pared to the parent compound, luteolin. The marked antioxidant
activity of luteolinvanadium complex, in comparison to luteolin
could be due to the coordination of metal in the 4 and 5 positions
of the condensed ring system, increasing its capacity to stabilize
unpaired electrons and, thereby, to scavenge free radicals.
3.6. Ferric reducing antioxidant power of luteolin and luteolin
vanadium(II) complex
By using the FRAP method the reduced ability of antioxidant
can be measured. The FRAP antioxidant assay is based on the abil-
ity of antioxidants to reduce Fe3+ to Fe2+ in the presence of TPTZ.
The TPTZFe2+ complex show an intense blue colour which shows
absorption at 593 nm. The absorbance decrease is proportional to
the antioxidant content (Dehghan et al., 2007). Here the FRAP
result for luteolin and luteolin vanadium complex were measured
at 593 nm via an absorbance variation during 10 min of interaction
of subjected compound with FRAP reagent and relevant data are
shown in Fig. 5a. The values of ferric reducing ability of the luteolin
on 10, 15, 20, 30, and 40 lM concentration were 0.4 0.05,
0.54 0.24, 0.6 0.05, 0.60 0.01, and 0.81 0.05 respectively
whereas the complex showed a signicant increases of ferric
reducing ability while comparing with luteolin i.e., 0.77 0.01,
0.81 0.05, 0.82 0.08, 0.89 0.03, and 1.22 0.04 (P < 0.05,
t = 9.09). All these above ndings suggest that the luteolin and
luteolin vanadium complex, the metal chelation increase electron
transfer from luteolin after complex formation. It is suggested that
the chelation of metal ions by luteolin increase the redox potential
of luteolinvanadium(II) complex.
3.7. ABTS radical scavenging activity of luteolin and luteolinvanadium
(II) complex
Finally for to conrming the radical scavenging activity of avo-
noid itself and metal complex was observed by performing the
ABTS assay. Fig. 5b, depicted the absorption of active ABTS solution
at 723 nm in presence of different concentration (025 lM) of
luteolin and luteolinvanadium(II) complex. The complex showed
a signicant increase in percentage of ABTS radical scavenging
activity i.e., 52.25 0.28, 64.06 1.67, 72.45 0.22, 71.78 0.68,
and 70.75 0.61 (P < 0.05, t = 10.36). The antioxidant behaviour
of avonoids is more signicantly correlated to their molecular
structure. Pure luteolin showed some decreasing antioxidant activ-
ity than the complex. The high antioxidant activity of the complex
is due to the hydroxyl groups and their hydrogens are replaced
from two luteolin molecule during chelation by square pyramidal
VO+2 ion. This suggests that the metal ion signicantly changes
the chemical properties of luteolin and affects its antioxidant
activity.
4. Conclusion
The complex of vanadium with luteolin was prepared and char-
acterised by spectroscopic techniques. Using UVVis and IR spec-
troscopy, the coordination to the carbonyl group of the ligand
and one of the adjacent hydroxyl groups is assumed. Spectroscopic
data suggest that luteolin molecule can chelate vanadium cation
from 4 carbonyl 5 hydroxyl chelation site. The results from DPPH,
ABTS and FRAP methods denoted that luteolin and luteolinvana-
1177
dium(II) complex were capable of donating electron or hydrogen
atom, and can therefore react with free radicals or terminate the
chain reaction in a time and dose dependent manner. The results
of the study indicated that the chelations of metal ions by luteolin
increased the redox-potential of metal luteolin complex.
Conict of interest
The authors declare that there is no conict of interest.
Acknowledgements
The authors are indebted to the Hari Charan Garg Charitable
Trust for the nancial support to carry this work. The authors
would like to thank Dr. Santanu Sannigrahi for editing and proof
reading of the manuscript and acknowledged to Mr. Subhash
Kumar Manna for technical help and Mr. Lal Mohan Masanta for
providing laboratory support.
References
Ahmadi, S. M., Dehghan, G., Hosseinpourfeizi, M. A., Ezzati, N. D. J., & Kashanian, S.
(2011). Preparation, characterization and DNA binding studies of water soluble
quercetinmolybdenum(VI) complex. DNA and Cell Biology, 30, 517523.
Andersen, O. M., & Markham, K. R. (2006). Flavonoids Chemistry, biochemistry and
applications. Boca Raton: CRC Taylor & Francis.
Badea, M., Olar, R., Marinescu, D., Uivarosi, V., Aldea, V., & Nicolescu, T. O. (2010).
Thermal stability of new vanadyl complexes with avonoid derivatives as
potential insulin-mimetic agents. Journal of Thermal Analysis and Calorimetry, 99,
823827.
Benzie, I. F. F., & Strain, J. J. (1999). Ferric reducing/antioxidant power assay: Direct
measure of total antioxidant activity of biological uids and modied version
for simultaneous measurement of total antioxidant power and ascorbic acid
concentration. In Methods in Enzymology, 299, 1527.
Blunden, S., & Wallace, T. (2003). Tin in canned food: A review and understanding of
occurrence and effect. Food Chemistry and Toxicology, 41, 16511662.
Boogaard, P. J., Boisset, M., Blunden, S., Davies, S., Ong, T. J., & Taverne, J. P. (2003).
Comparative assessment of gastrointestinal irritant potency in man of tin(II)
chloride and tin migrated from packaging. Food Chemistry and Toxicology, 41,
16631670.
Casagrande, F., & Darbon, J. (2001). Effects of structurally related avonoids on cell
cycle progression of human melanoma cells: Regulation of cyclin-dependent
kinases CDK2 and CDK1. Biochemical Pharmacology, 61, 12051215.
Chen, W., Sun, S., Cao, W., Liang, Y., & Song, J. (2009). Antioxidant property of
quercetinCr(III) complex: The role of Cr(III) ion. Journal of Molecular Structure,
918, 194197.
Chowdhury, A. R., Sharma, S., Mandal, S., Goswami, A., Mukhopadhay, S., &
Majumder, H. K. (2002). Luteolin, an emerging anti-cancer avonoid, poisons
eukaryotic DNA topoisomerase I. Biochemistry Journal, 366, 653661.
Coles, R., & Kirwan, M. J. (Eds.). (2011). Food and beverage packaging technology (2nd
ed.. UK: John Wiley and Sons Ltd.
Cornard, J. P., & Merlin, J. C. (2002). Spectroscopic and structural study of complexes
of quercetin with Al(III). Journal of Inorganic Biochemistry, 92, 1927.
Crans, D. C., Mahroof-Tahir, M., & Keramidas, A. D. (1995). Vanadium chemistry and
biochemistry of relevance for use of vanadium compounds as antidiabetic
agents. Molecular and Cellular Biochemistry, 153, 1724.
Dehghan, G., & Khoshkam, Z. (2012). Tin(II)quercetin complex: Synthesis, spectral
characterization and antioxidant activity. Food Chemistry, 131, 422426.
Dehghan, G., Shaee, A., Ghahremani, M. H., Ardestani, S. K., & Abdollahi, M. (2007).
Antioxidant potential of various extracts from ferula szovitsiana in relation to
their phenolic contents. Pharmaceutical Biology, 45, 19.
Ellis, R. F. (1979). Rigid metal containers. In Jackson, J. M., Shinn, B. M. (Eds.),
Fundamentals of food canning technology (pp. 95122). Westport, CT: AVI
Publishing Company.
Ensa, A. A., Hajiana, R., & Ebrahimib, S. (2009). Study on the interaction between
MorinBi(III) complex and DNA with the use of methylene blue dye as a
uorophore probe. Journal of the Brazilian Chemical Society, 20, 266276.
Kim, H. K., Cheon, B. S., Kim, S. Y., & Kim, H. P. (1999). Effects of naturally occurring
avonoids on nitric oxide production in the macrophage cell line RAW.
Biochemical Pharmacology, 58, 759765.
Leopoldini, M., Russo, N., Chiodo, S., & Toscano, M. (2006). Iron chelation by the
powerful antioxidant avonoid quercetin. Journal of Agriculture and Food
Chemistry, 54, 63436351.
Leung, H. W. C., Kuo, C. L., Yang, W. H., Lin, C. H., & Lee, H. Z. (2006). Antioxidant
enzymes activity involvement in luteolin induced human lung squamous
carcinoma CH27 cell apoptosis. European Journal of Pharmacology, 508, 7783.
Lugscheider, E., Kraimer, G., Barimani, C., & Zimmermann, H. (1995). PVD coatings
on aluminium substrates. Surface and Coatings Technology, 7475, 497502.
1178 S. Roy et al. / Food Chemistry 173 (2015) 11721178
Matsui, T., Kobayshi, M., & Hayashida, S. (2002). Luteolin, a avone, does not
suppress post prandial blood glucose absorption through the inhalation of
alpha-glucosidase action. Bioscience, Biotechnol and Biochemistry, 66,
689692.
Maurya, M. R., & Kumar, A. (2006). Oxovanadium(IV) based coordination polymers
and their catalytic potentials for the oxidation of styrene, cyclohexene and
trans-stilbene. Journal of Molecular Catalysis A: Chemical, 250, 190198.
Pennycooke, J. C., Cox, S., & Stushnoff, J. C. (2005). Relationship of cold acclimation,
total phenolic content and antioxidant capacity with chilling tolerance in
petunia (Petunia  hybrida). Environmental and Experimental Botany, 53,
225232.
Robertson, G. M. (2006). Food packaging Principles and practice. Boca Raton: CRC
Taylor & Francis.
Shaghaghi, S., Manzoori, J., & Jouyban, A. (2008). Determination of total phenols in
tea infusions, tomato and apple juice by terbium sensitized uorescence
method as an alternative approach to the FolinCiocalteu spectrophotometric
method. Food Chemistry, 108, 695701.
Shahidi, F., McDonald, J., Chandrasekara, A., & Zhong, Y. (2008). Phytochemicals of
foods, beverages and fruit vinegars: Chemistry and health effects. Asia Pacic
Journal of Clinical Nutrition, 17, 380382.
Todie, A., Cikara, D., Todie, T., & Camagic, I. (2011). Inuence of vanadium on
mechanical characteristics of air handling steels. FME Transaction, 39, 4954.
Torreggiani, A., Tamba, M., Trinchero, A., & Bonora, S. (2005). Copper(II)quercetin
complexes in aqueous solutions: Spectroscopic and kinetic properties. Journal of
Molecular Structure, 744747, 759766.
Tsiani, E., & Fantus, I. G. (1997). Vanadium compounds biological actions and
potential as pharmacological agents. Trends in Endocrinology and Metabolism, 8,
5158.
Uivarosi, V., Barbuceanu, S. F., Aldea, V., Arama, C. C., Badea, M., Olar, R., &
Marinescu, D. (2010). Synthesis, spectral and thermal studies of new rutin
vanadyl complex. Molecules, 15, 15781589.
Zhou, J., Wang, L., Wang, J., & Tang, N. (2001). Synthesis, characterization,
antioxidative and antitumor activities of solid quercetin rare earth(III)
complexes. Journal of Inorganic Biochemistry, 83, 4148.