Materials Science in Semiconductor Processing 31 (2015) 446–454

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Materials Science in Semiconductor Processing

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

Green synthesis of multifunctional zinc oxide

(ZnO) nanoparticles using Cassia fistula plant
extract and their photodegradative, antioxidant
and antibacterial activities
D. Suresh a,n, P.C. Nethravathi a, Udayabhanu a, H. Rajanaika b,
H. Nagabhushana c, S.C. Sharma d,e
a
Department of Studies and Research in Chemistry, Tumkur University, Tumkur 572103, Karnataka, India
b
Department of Studies and Research in Environmental Science, Tumkur University, Tumkur 572103, Karnataka, India
c
Prof. C. N. R. Rao Centre for Advanced Materials, Tumkur University, Tumkur 572103, Karnataka, India
d
Vice Chancellor, Chattisgarh Swami Vivekanand Technical University, Bhilai, Chattisgarh, India
e
Academic Mentor and Honorary Professor of Eminence, Department of Mechanical Engineering, Siddaganga Institute of Technology,
B. H. Road, Tumkur 572103, Karnataka, India

a r t i c l e in f o abstract

The present study involves green synthesis of ZnO nanoparticles (Nps) using aqueous
Keywords: Cassia fistula plant extract as fuel by solution combustion synthesis. The ZnO Nps were
Green synthesis characterized by Powder X- ray diffraction (PXRD), UV–visible studies and Transmission
Zinc oxide electron microscopy (TEM). The Nps were evaluated for photodegradative, antimicrobial
Solution combustion and antioxidant activities. The extract was found to contain reducing components such as
X-ray diffraction polyphenols (11%) and flavonoids (12.5%). The Nps were found to have a hexagonal
Cassia fistula wurtzite structure. UV–visible absorption of ZnO Nps showed absorption band at 370 nm
which can be assigned to the intrinsic band-gap absorption of ZnO due to the electron
transitions from the valence band to the conduction band. TEM image confirms the
formation of nanoparticles and the average crystallite sizes were found to be
5–15 nm.
Methylene blue (MB) dye was effectively degraded under UV and Sun light illumination in
the presence of ZnO Nps. Significant antioxidant activity was exhibited by Nps through
scavenging of 1, 1-Diphenyl-2-picrylhydrazyl (DPPH) free radicals. Excellent bactericidal
activity was shown by the Nps on Klebsiella aerogenes, Escherichia coli, Plasmodium
desmolyticum and Staphylococcus aureus. Synthesis of multifunctional ZnO Nps using
naturally occurring plant products has been advocated as a possible environment friendly
alternative to chemical methods.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction create many environmental and health risks. Some methods

Dye contaminants from fabric, printing, manufacture and
many other industries show a vital role to damage the
environment. These wastes enter into water ecosystem and
n
Corresponding author. Mobile: þ91 9886465964.
E-mail address: pbdsuresh@gmail.com (D. Suresh).
like osmosis, adsorption, flocculation and others have been
used for dye elimination from river, but each method has its
own benefits and limitations. Photocatalytic treatment offers a
capable, relatively low cost and eco friendly method to resolve
this problem [1]. In past few years, ZnO has been most
frequently used for degradation of many organic pollutants
[2]. Along with this, microbial contamination is a thoughtful
matter in healthcare and nutrition industry. Development of

http://dx.doi.org/10.1016/j.mssp.2014.12.023
1369-8001/& 2014 Elsevier Ltd. All rights reserved.
 D. Suresh et al. / Materials Science in Semiconductor Processing 31 (2015) 446–454
antimicrobial agents and external coatings has been given
significant attention in recent years [3–5]. Antimicrobial prop-
erties with nano sized particles are of substantial interest in
the recent past [6,7]. It was specified that nanosized semi-
conductors act as an effective photocatalytic agent resulting
from either large surface area or quantum confinement effects
of charge carriers for the degradation of organic contaminants
in water under UV light and Sun light irradiation [8–10].
Photocatalytic function is very similar to that of chlorophyll in
the photosynthesis. Photo-induced molecular reactions take
place at the surface of the catalyst in a photocatalytic system.
The simplest mechanism of photocatalytic reaction is the
generation of electron–hole pair on the surface of the semi-
conductor and its endpoint is as follows. When a photocata-
lyst is exposed to the light which possess stronger energy
than its band gap energy, then electron–hole pairs diffuse out
to the surface of the photocatalyst and partake in the chemical
reaction with the electron acceptor and donor [11]. These free
holes and electrons convert to the neighboring oxygen and
water molecules into OH  free radicals and super oxides and
these act as strong oxidizing agents for the degradation of
dyes [11]. ZnO is a well known n-type wide-ranging band gap
oxide semiconductor (
3.37 eV) and it has high binding
energy (60 meV) [12,13]. ZnO is one of the hardest materials,
hence it does not suffer from dislocation degradation during
the course of operation [14]. Several approaches have been
engaged to synthesize ZnO nanocrystals such as sol–gel solv-
othermal, direct precipitation and hydrothermal etc., [15–18].
Most of these approaches require tedious processes, expensive
substrates, sophisticated equipments and rigorous experimen-
tal circumstances. Solution combustion synthesis is one of the
best and easy methods for the synthetic approach towards the
uniform mixing with combustible fuel. During solution com-
bustion, exothermic reaction between oxidizing and reducing
agent takes place. Generally metal nitrates are used because of
their unique solubility to form homogeneous solution. Metal
nitrates act as oxidizer agents and fuel acts as reducing agents
for the synthesis of ZnO nano crystals [19–21].
In this paper, we are the first to report the green synthesis
of ZnO nanoparticles via solution combustion synthesis using
Cassia fistula leaf extract. Green synthesis is more environ-
mental friendly with less side effects when compared to
chemical methods. The leaf mainly contains ( ) epiafzelechin,
( ) epiafzelechin-3-Oglucoside, () epicatechin, procyanidin
B2, biflavonoids, triflavonoids, rhein, Rheinglucoside, senno-
side A, sennoside B, chrysophanol, and physcion [22]. It is
widely used for its medicinal properties such as mild laxative
for children and pregnant women. It is also a purgative owing
to the wax aloin and a tonic [23]. It is also used for many other
intestinal disorders like healing ulcers [24]. It is also known to
exert antipyretic, analgesic, anti-inflammatory and hypogly-
cemic activities [25]. This study attempts to exploit C. fistula
extract as fuel for the green synthesis of ZnO nanoparticles.
This procedure involves a self-sustained reaction in homo-
geneous solution of Zinc nitrate and C. fistula leaf extract.
2. Materials and methods
C. fistula leaves were sourced from Devarayana Durga
forest area of Tumkur district, Karnataka, India. The plant
material was shade dried and powdered into 100 mesh
447
size and was stored at room temperature in an airtight
container.
2.1. Preparation of the extract
1:10 proportion of the coarsely powdered plant mate-
rial to water was taken in a round bottomed flask and the
extraction was carried out at 100 1C with a reflux arrange-
ment for 5 h with constant stirring. The extract was
filtered and centrifuged to remove any un-dissolved mate-
rial. The extract was then concentrated, dried using roto
evaporator and stored in airtight bottles at 4 1C.
2.2. Polyphenol assay
Folin ciocalteu reagent (FC reagent) (0.1 N) was pre-
pared by diluting (1:20) commercially available FC reagent
with distilled water. Sodium carbonate (7.5%) was pre-
pared by dissolving 7.5 g of sodium carbonate in 100 ml of
de-ionized water. Gallic acid (standard) Stock I (conc.
0.1 mg ml  1) was prepared by dissolving 1 mg of Gallic
acid in 10 ml with 50% methanol. For making standard
graph of Gallic acid, concentration range of 2–20 μg/mL
was used. The assay was carried out by using a Singleton
and Rossi method [26]. In a typical process, 1000 μl of FC
reagent was added to 200 μl of 50% methanol/standard/
test sample with various concentrations, mixed and incu-
bated at RT for 5 min. 800 μl of 7.5% sodium carbonate
solution was added, mixed and incubated at 37 1C for
30 min. The absorbance was recorded at 750 nm against
blank using spectrophotometer. Color correction was given
with the same concentration of the test sample in 50%
methanol without FC reagent.
2.3. Flavonoids assay
Vanillin, an aromatic aldehyde condenses with the flavon-
3-ols and oligomers to form soluble pigments in acidic
medium with an absorbance maximum at 500 nm, which
can be detected by a UV–visible spectrophotometer. Vanillin
Reagent (1%) was prepared by dissolving 1 g of crystallized
vanillin in 100 ml of 70% Conc. H2SO4. Conc. H2SO4 (70%) was
prepared by diluting 70 ml on Conc. H2SO4 in 100 ml de-
ionized water. Methanol (50%) was prepared by diluting 1:1
with de-ionized water. 10 mg of Phloroglucinol was dissolved
and made up to a volume of 10 ml with 50% methanol,
followed by centrifugation at 12,000 rpm for 10 min and
labeled as Stock I. Stock II was prepared by diluting Stock I
to a Conc. of 0.1 mg ml  1 with 50% methanol. For making
standard graph of Phloroglucinol, 1–10 μg/mL concentration
range was used. The flavonoid assay was carried out using a
Swain and Hillis method [27]. In a typical experiment, to a
400 μl of distilled water/positive control/test sample with
various concentrations, 800 μl of 1% vanillin reagent was
added, mixed and incubated at RT for 15 min. The absorbance
was recorded at 500 nm against blank using the spectro-
photometer. Color correction was given with the same con-
centration of the test sample in distilled water without
vanillin reagent. The flavonoid content in the plant extract
was measured with reference to the standard Gallic acid
values.
448 D. Suresh et al. / Materials Science in Semiconductor Processing 31 (2015) 446–454
2.4. Synthesis
ZnO nanoparticles were prepared by eco-friendly green
combustion route using C. fistula plant leaf extract as fuel
[28,29]. The zinc nitrate hexahydrate (Zn (NO3)3  6H2O) was
procured from SigmaAldrich (AR) and used without further
purification. Stoichiometric amount of Zn(NO3)3  6H2O
was dissolved with 0.2 g of C. fistula leaf extract in 10 ml
of distilled water. The mixture was kept in a pre-heated
muffle furnace at 400 710 1C and subjected for combus-
tion. The reaction was completed within 5 min. A fine milky
white colored material was obtained. The synthesis of nano
particles was repeated with different concentrations of the
plant extract such as 0.3, 0.4, 0.5 and 0.6 g. The obtained
product was stored in airtight container until further use.
2.5. Characterization
Optical properties of ZnO nanoparticles were character-
ized based on UV absorption spectra and photolumines-
cence (PL). The sample was sonicated for even dispersion
(30 min) and the aqueous component was subsequently
analyzed at room temperature for optical band gap (Eg)
using the UV–visible spectrophotometer (Evolution—220,
Thermo Scientific). The shape, size and microstructures of
the products were characterized using a Transmission
electron microscope (Tecnaif—30). Phase purity was deter-
mined by Powder X-ray diffraction (XRD) analysis recorded
by a diffractometer (Shimadzu—7000). All the experiments
were performed in triplicates and the data were analyzed
using Origin Pro 7.5 SRO software (Origin Lab Corporation,
USA) and the results were recorded for different C. fistula
leaf extract concentrations.
2.6. Photocatalytic degradation of dye
Photo catalytic degradation of methylene blue was carr-
ied out using a 150  75 mm batch reactor at room tem-
perature [30]. Slurry was prepared by adding 50 mg of
catalytic load to 100 ml of 5 ppm methylene blue dye. The
pH was maintained neutral by adding 0.05 M NaOH or
0.05 M H2SO4 and the prepared solution is placed in the
reactor and stirred magnetically. Instantaneously a mer-
cury vapor lamp was positioned at the axis of the reactor
to supply UV illumination while in case of Sun degradation
the slurry is directly exposed to Sun light. The concentra-
tion of residual methylene blue in the solution after
irradiation was determined by monitoring the absorbance
intensity of solution samples by withdrawing a known vol-
ume of the slurry at regular intervals. It was then subjected
for centrifugation to get rid of any interference due to the
presence of catalyst and the absorbance was recorded at
wavelength 665 nm by using the UV–visible spectrophot-
ometer to assess the rate of degradation. The photo
degradation efficiency of methylene blue was calculated
using the following equation:
Ci  Cf
% of degradation ¼  100
Ci
Here Ci: the original methylene blue dye concentration,
and Cf: the methylene blue dye residual concentration in
solution. The experiment was carried out varying experi-
mental parameters such as dye concentration, catalytic
load, pH and nature of light (UV and Sun light).
2.7. Antioxidant activity
Antioxidant activity was carried out by 1, 1-Diphenyl-2-
picrylhydrazyl (DPPH) assay using a modified method of
Brand-Williams [31,32]. DPPH (oxidized form) is a stable free
radical with purple color. In the presence of an antioxidant
which can donate an electron to DPPH radical decays, and
the change in absorbance at 520 nm was followed spectro-
photometrically. 39.4 mg of DPPH was dissolved in 100 ml of
methanol to get 0.14 mM concentration of DPPH in the assay.
Methanol (50%) was prepared by diluting methanol 1:1 with
de-ionized water. In brief, to a 2.5 ml of 50% methanol with
various concentrations like 2, 4, 6, and 8 mg of ZnO nano-
powder was added and mixed with 140 ml of 1 mM DPPH
solution. The mixture was incubated at 37 1C for 30 min. The
absorbance was recorded at 520 nm against 50% methanol
blank, a control sample was maintained without addition of
the test sample. The actual absorbance was taken as the
absorbance difference of the control and the test sample and
IC50 value was determined.
2.8. Antibacterial activity
Antibacterial activity was screened by a agar well diffu-
sion method [33,34] against four bacterial strains namely
Gram ve bacteria Klebsiella aerogenes NCIM-2098 (KA),
Escherichia coli NCIM-5051 (EC), Pseudomonas desmolyticum
NCIM-2028 (PD) and Gram þve bacteria Staphylococcus
aureus NCIM-5022 (SA). Nutrient Agar plates were prepared
and swabbed using a sterile L-shaped glass rod with 100 ml of
24 h mature broth culture of individual bacterial strains. The
well made by using sterile cork borer 6 mm wells was
created into the each Petri-plate. Different concentrations
of nano-compound (500 mg and 1000 mg/well) were used to
assess the activity of the compounds. The material was
prepared in sterile water and added into the wells by using
sterile micropipettes. Simultaneously the standard antibiotics
(as positive control) was tested against the pathogens.
Ciprofloxacin (Hi Media, Mumbai, India) was used as positive
control. Then the plates were incubated at 37 1C for 36 h.
After the incubation period, the zone of inhibition of each
well was measured and the values were noted. The studies
were conducted in triplicates and the average values were
calculated for the ultimate antibacterial activity.
3. Results and discussion
Plants are known to possess considerable amounts of
polyphenols. The contents of polyphenols can be enhanced
when the plant materials are subjected for extraction. The
dried and coarsely powdered leaves of C. fistula were subjected
for water extraction by reflux method and the polyphenol
content was determined by a Singleton method. It was found
ð1Þ that extract contains 11% of polyphenols. These polyphenols
are known to exhibit significant antioxidant activity. Flavonoids
form another important class of plant secondary metabolites
having a range of beneficial biological activities including
 D. Suresh et al. / Materials Science in Semiconductor Processing 31 (2015) 446–454
antioxidant activity. Our results suggest that the water extract
of plant leaves found to contain 12.5% flavonoids.
Fig. 1 shows the XRD patterns of ZnO nanoparticles
synthesized using C. fistula leaf extract with different con-
centrations (200, 260, 360 and 400 mg). All the peaks of the
(100), (002), (101), (102), (110), (103) and (112) can be well
indexed to the hexagonal wurtzite structure (JCPDS Card no.
89-1397) with lattice constants of a¼b¼3.242 Å and c ¼
5.205 Å [35]. The presence of (100), (002) and (101) planes
in XRD patterns indicates the formation of high purity of the
ZnO nanoparticles. Further, no peaks were observed due to
impurities. Strong intensity and narrow width of ZnO
diffraction peaks indicate that the resulting product was
highly crystalline in nature. Average crystallite size was
estimated using Scherrer's formula, average crystallite size
was estimated and it was found to be in the range of 5–
15 nm. Hence we can conclude that fuel is primarily
responsible for the reduction of the particle size
0:89λ
D¼
β cos θ
Further, strain present in nanoparticles prepared using
different concentrations of the fuel was estimated using
the W–H plots [36]
0:9λ
β cos θ ¼ þ 4ε sin θ
D absorption spectra using Wood–Tauc's relation [38]:
Graph was plotted by taking βcosθ along Y-axis and
4sinθ along X-axis. A straight line was obtained and a
slope of the line gives the strain (ε) and intercept (0.91/D)
of this line on Y-axis gives crystallite size (D). The crystal-
lite sizes are matched well with Scherrer's and W–H plots.
Fig. 2 shows the room temperature UV–visible spectra
of ZnO nanoparticles synthesized using C. fistula leaf
extract with different concentrations. The ZnO NPs were
dispersed in water with concentration of 0.1 wt % and then
Intensity (a.u)
101
002
100
102
110
103
112
30 40 50 60
2θ in degree
Fig. 1. Powder XRD spectra of ZnO nanoparticles prepared with various
concentrations of Cassia fistula leaf extract.
449
370 nm
a) 200 mg
b) 260 mg
d) c) 360 mg
1.5 d) 400 mg
Absorbance (a.u)
c)
b)
1.0
a)
300 400 500 600
Wavelength (nm)
Fig. 2. UV–visible spectra of ZnO nanoparticles prepared with various
concentrations of Cassia fistula leaf extract.
ð2Þ the solution was subjected for UV–visible measurements.
The spectra reveal characteristic absorption peaks of ZnO
at wavelength of 370 nm which can be assigned to the
intrinsic band-gap absorption of ZnO due to the electron
transitions from the valence band to the conduction band
(O2p–Zn3d) [28,37].
The band gap of the ZnO Nps were estimated from this
ð3Þ


αhγ ¼ D hγ  Eg n ð4Þ
where h is the energy of the photon, Eg is the band gap of
the material and D is a constant. The transition data prov-
ides the best linear fit in the band edge region for n ¼1/2.
The band gap was found to be
3.33 eV which is smaller
than that of the bulk ZnO (3.45 eV). This band gap
enhancementoccurs due to the size effect of the nanopar-
ticles in the thin film. In addition, this sharp peak shows
that the particles are in nanosize, and the particle size
distribution is narrow. A common way to obtain the band
gap from absorbance spectra is to get the first derivative of
the absorbance with respect to photon energy and find the
maximum in the derivative spectrum at the lower energy
400 mg
sides [36,39]. The derivative of the absorbance of the ZnO
Nps is shown in Fig. 2, and it indicates a band gap of
3.24 eV for the ZnO-NPs. The good absorption of the ZnO
NPs in the UV region proves the applicability of this
360 mg product in medical application such as sun-screen protec-
tors or as antiseptic in ointments [40].
Among the tested ZnO nanoparticles synthesized with
different concentrations of the extract, the Nps synthe-
sized with 360 mg of the extract were found to have very
260 mg
appreciable bulk density and appearance. Therefore, Nps
prepared with 360 mg of the extract were considered for
further studies.
Transmission electron microscope image of the ZnO
Nps is shown in Fig. 3. It clearly displays that the particles
200 mg consist of many agglomerated particles and sponge like
irregular shaped particles. Further, this kind of morphol-
70
ogy was commonly observed in oxides formed during
solution combustion.
The effect of photodegradative activity of fixed amount
of ZnO nanoparticles was checked against increased
450 D. Suresh et al. / Materials Science in Semiconductor Processing 31 (2015) 446–454
concentrations of dye. Fig. 4 shows the consequence of dye
concentration on the photocatalytic activity of ZnO nanopar-
ticles. Various concentrations of methylene blue dye such as 5,
10, 15, and 20 ppm/100 ml of reaction mixture was tested
with fixed catalytic load of 50 mg at pH 7 by exposing to UV
light and Sun light separately. The degradation was effective in
both the cases of exposure. It was observed that the photo-
degradation efficiency of methylene blue is inversely propor-
tional to its concentration, which means, the lower of the dye
concentration, the higher efficiency of the dye photodegrada-
tion at fixed concentrations of catalyst. Increasing the initial
dye concentration from 5 to 20 ppm decreases the photode-
gradation efficiency of Nps in both the cases. The photode-
gradation efficiency relies on the formation of hydroxyl
radicals, which is the critical species in the degradation
process. Due to fixed concentration of the catalyst there are
only fewer active sites for adsorption of HO  so the genera-
tion of HO  will be decreased. Furthermore, as the concentra-
tion of methylene blue increases with constant intensity of
Fig. 3. TEM image of ZnO Nps synthesized using Cassia fistula leaves extract.
100
80
% degradation
60
40
20
0 0
0 20 40 60 80
Time (min)
Fig. 4. Percentage degradation of (a) UV-light (b) Sun light in the presence of ZnO nanoparticles synthesized using Cassia fistula leaves extract.
light, the path length of photons entering the solution
becomes lesser, therefore only fewer photons reach the
catalyst surface. As a result, the production of holes or
hydroxyl radicals that can attack the methylene blue becomes
lesser. Therefore, the relative HO  number attaching the
compound decreases and hence the photodegradation effi-
ciency decreases [39,40]. Hence, the optimal initial dye con-
centration was found to be 5 ppm with 90% degradation.
The effect of catalyst load on the photodegradation
efficiency of methylene blue was observed by taking differ-
ent amounts of catalyst such as 50, 100, 150 and 200 mg
into 100 ml of 5 ppm dye solution at pH 7. The obtained
results are depicted in Fig. 5. These results indicate that with
increase of catalytic load the photodegradation efficiency of
methylene blue increases and after that the further increase
in catalyst load will not have any effect on the photode-
gradation efficiency.
This is attributed to the increased number of active sites
available on the catalyst surface for the reaction due to
enhanced catalyst load, which in turn increased the number
of holes and hydroxyl radicals. When the catalyst load increa-
sed above 200 mg, the photodegradation efficiency abruptly
decreased due to agglomeration and sedimentation of the
catalyst particles. This caused an increase in the particle size
and decrease in specific surface area that lead to decrease in
the number of surface active sites [42,43]. Also at high level of
catalyst, the opacity, turbidity of the suspension, and light
scattering tendency of catalyst particles increased. This leads to
decrease in the passage of irradiation through the sample [44].
Therefore, the most effective concentration for photodegrada-
tion of methylene blue was found to be 200 mg of the catalyst.
Effect of pH on photocatalytic degradation of methylene
blue was studied at fixed levels of dye and catalyst by varying
pH from 2–12. The results are depicted in Fig. 6. The results
showed that the photodegradation efficiency decreases with
the increase in pH. At low pH value (pH¼ 2) the photodegra-
dation efficiency was 96.26%. When the pH value of methylene
blue dye solution increased from 2 to 4, the photodegradation
efficiency of methylene blue almost increased to 98.71% and
then the photodegradation efficiency decreased with further
increase in pH. This is because the methylene blue is negatively
100
80
% degradation
60
40
20 5 ppm
5 ppm 10 ppm
10 ppm 15 ppm
15 ppm
20 ppm
20 ppm
100 120 0 20 40 60 80 100 120
Time (min)
 D. Suresh et al. / Materials Science in Semiconductor Processing 31 (2015) 446–454 451

100
100

80
80

% degradation
% degradation

60 60

40 50 mg 40
100 mg 50 mg
150 mg 100 mg
20 200 mg 20
150 mg
200 mg
0 0

0 20 40 60 80 100 120 0 10 20 30 40 50 60
Time (min) Time (min)
Fig. 5. Percentage degradation of MB under with different catalytic loads (50, 100, 150, 200 mg) upon exposure to (a) UV-light (b) Sun light in the presence
of ZnO nanoparticles synthesized using Cassia fistula leaves extract.

100 100

80 80
% degradation

% degradation

60
60

40
40 2 pH
4 pH
2 pH
4 pH 20 6 pH
6 pH 8 pH
20
8 pH 10 pH
10 pH 12 pH
12 pH 0
0
0 20 40 60 80 100 120 0 20 40 60 80 100
Time (min) Time (min)

Fig. 6. Percentage degradation of MB under (a) UV-light (b) Sun light in the presence of ZnO nanoparticles synthesized using Cassia fistula leaves extract.

charged in acidic medium, whereas ZnO is positively charged
around pH 12 which is reported as pH of zero point charge for
ZnO [43], therefore the increase in pH value tends to change
the charge on ZnO to negative charge by adsorbing HO  ions,
which favors the formation of HO  [45,46] and thus the
photocatalytic activity decreased due to the increase of the
electrostatic repulsion between ZnO and anionic methylene
blue dye gradually. Additionally, the increase of pH may
increase e  /h þ recombination rate and consequently decrease
the photocatalytic activity [41]. The optimum pH value for the
photodegradation of methylene blue is
4 at which the
positively charged ZnO and negatively charged methylene blue
molecules should attract each other and photocatalytic oxida-
tion happens very effectively.
Mechanism for photodegradation of MB and MG dye in
the presence of Nps can be clarified as follows. When
radiation of certain energy incidents on catalyst surface
with sufficient energy equal to or higher than the band gap
energy of the catalyst, creation of a hole (h þ ) in the valence
band and an electron (e  ) in the conduction band takes
place. The hole oxidizes water to produce OH  radicals,
while the electron in the conduction band lessens the
oxygen adsorbed on the catalyst.
ZnOþhν-ZnO (hvb
þ 
þecb)
 þ
OHads þ hvb-OHdads (in basic medium)
MB/MG þOHdads-degradation of the dyes
Experiments were performed to know the reusability of the
catalyst. It was found that
94% of the photocatalytic activity
of the catalyst was retained after three successive attempts of
photocatalysis experiments with 5 ppm methylene blue.
452 D. Suresh et al. / Materials Science in Semiconductor Processing 31 (2015) 446–454

DPPH, a stable free radical with a characteristic absorp-
tion at 520 nm, was used to study the radical scavenging
effects. The decrease in absorption is taken as a measure of
the extent of radical scavenging. The radical scavenging
activity (RSA) values were expressed as the ratio percen-
tage of sample absorbance decrease and the absorbance of
DPPḢ solution in the absence of test sample at 520 nm.
Fig. 7A and B indicates the assessment of antioxidant
potency of ZnO Nps. Fig. 7A reveals the determination of
IC50 value of ZnO Nps. Fig. 7B illustrates the successive
decrease in the absorption of DPPH over wavelength range
of 480–707 nm. The ZnO nanoparticles were proved to be
potent at inhibiting the DPPH free radical scavenging
activity with IC50 value of 2853 mg/mL.
The plant materials composed of various components such
as carbohydrates, proteins, fats, oils, fibers, pigments, second-
ary metabolites, etc. When they are extracted with suitable
solvents, they yield useful extracts enriched with selective
components. It was observed that the C. fistula leaf extract
comprise of 11% of polyphenols and 12.5% flavonoids. These
two classes of natural compounds are very well known for
their antioxidant activity. Therefore C. fistula leaf of water
extract shows IC50 value 54 mg/mL. When such an extract is
employed for the combustion synthesis of metal nitrates, they
effectively yield metal oxide nanoparticles due to the process
of reduction. Our results reveal that water extract of C. fistula
leaves has shown to have very significant antioxidant activity
and the same has been used for the synthesis of ZnO
nanoparticles. Hence polyphenols and flavonoids of the
extract could be responsible constituents for the efficient
formation of the ZnO nanoparticles. Therefore, various com-
ponents of wide variety of plants which are rich in these kinds
of antioxidants could act as potential reducing agents to
obtain functionally superior nanoparticles for various applica-
tions. Our study successfully demonstrates the utilization of
environment friendly and very simple solvents such as water
to obtain phytochemical enriched extracts from underutilized
natural resources such as plant derived components for the
synthesis of nanoparticles which could aid in various applica-
tions. Therefore, there is enhanced need to tap these bio
resources towards development of advanced materials. In
view of the potential beneficial activities of ZnO nanoparticles
prepared by C. fistula leaf extract assistance, they can be
further developed to use them as antimicrobials, antioxidants
and effective photodegradative agents.
The antibacterial properties of the ZnO nanoparticles
are evaluated against four pathogenic bacterial strains
namely Gram  ve bacteria KA, EC, PD and Gram þve

100
a) Control
a) b) 2 mg
c) 4 mg
Absorbance (a.u)

0.50 d) 6 mg
e) 8 mg
% Inhibition

50 b)

0.25 c)

d)
e)
IC50of ZnO = 2853 µg/mL
0.00
0

0 2000 4000 6000 8000 500 600 700

Concentration (µg) Wavelength (nm)

Fig. 7. Antioxidant activity of ZnO nanoparticles synthesized using Cassia fistula leaves extract (A) IC50 values of ZnO Nps. (B) Successive decrease in the
absorption of DPPH over the wavelength range measured.

Table 1
Antibacterial activity of ZnO nanoparticles on various pathogenic bacterial strains.

Sl. Treatment Klebsiella Aerogenes (B1) Escherichia coli (B2) Staphyloccus aureus (B4) Pseudomonas desmolyticum (B5)
no. (Mean7 SE) (Mean7 SE) (Mean 7SE) (Mean7 SE)

1 Standard (5 mg/50 mL) 12.6770.33nn 14.677 0.33nn 10.00 70.00 12.677 0.33nn
2 Cassia fistula (500 mg/ 7.3370.33nn 3.677 0.33nn 2.6770.33nn 3.007 0.00
50 mL)
3 Cassia fistula (1000 mg/ 9.6770.33nn 4.677 0.33nn 4.6770.33nn 4.007 0.00
100 mL)

Values are the mean 7 SE of inhibition zone in mm. Symbols represent statistical significance.
nn
P o0.01 as compared with the control group.
 D. Suresh et al. / Materials Science in Semiconductor Processing 31 (2015) 446–454 453

bacteria SA using the agar well diffusion method. In the (Table 1). Fig. 9 shows the zone of inhibition of ZnO Nps
agar well diffusion method the ZnO Nps showed signifi- against the pathogenic bacterial strains with 500 and
cant antibacterial activity on all the four bacterial strains 1000 mg concentration. The zone of inhibition for different
bacterial strains is shown in Figs. 8 and 9.
16
standard
500 microgram 4. Conclusion
14 1000 microgram
Zone of inhibition (mm)

12 The investigation demonstrates a simple green syn-

thetic approach for the synthesis of ZnO nanoparticles
10 using aqueous C. fistula plant extract as a fuel employing
solution combustion method. The fuel which was found to
8 comprise of significant amounts of polyphenols and flavo-
noids. These components effectively act as reducing agents
6
and lead to the synthesis of ZnO nanoparticles. The ZnO
nanoparticles were found to have the hexagonal wurtzite
4
structure with absorption maximum at 370 assigned to the
2 intrinsic band-gap absorption. TEM image confirms the
formation of Nps with an average crystallite size of
0
5–15 nm. Methylene blue dye was effectively degraded
um
es

under UV and Sun light illumination in the presence of

us

ic
en

i
ol

yt
re
C
og

ol

ZnO Nps. ZnO nanoparticles exhibited significant antiox-

au
E.
er

sm
S.
.a

de

idant activity. The study successfully demonstrates that

K

P.

Bacterialstrains facile synthesis of multifunctional ZnO nanoparticles was

Fig. 8. Inhibition of bacterial strains (a) Klebsiella aerogenes (b) Escherichia achieved using underutilized naturally occurring plant
coli (c) Staphylococcus aureus and (d) Pseudomonas desmolyticum. parts.

Fig. 9. Zone of inhibition of (a) Klebsiella aerogenes (b) Escherichia coli (c) Staphylococcus aureus and (d) Pseudomonas desmolyticum.
454 D. Suresh et al. / Materials Science in Semiconductor Processing 31 (2015) 446–454
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