Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 372–379

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Biogenic synthesis of SnO2 nanoparticles: Evaluation of antibacterial

and antioxidant activities
V.K. Vidhu, Daizy Philip ⇑
Department of Physics, Mar Ivanios College, Thiruvananthapuram 695 015, India

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

 Tin oxide nanoparticles are

synthesized using Saraca indica
flower.
 The influence of reaction parameters
on the crystallite size has been
studied.
 The structural and morphological
studies were carried out using XRD
and TEM studies.
 The optical properties of the samples
were investigated using absorption
and emission spectroscopy.
 The as synthesized sample is
potential antioxidant and
antibacterial agent.

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

Article history: Nanostructured semiconductors have been of special interest to scientific community due to their pecu-
Received 1 May 2014 liar properties. The quantum size effect results in spectacular variation in the optical and vibrational
Received in revised form 23 June 2014 characteristics of nanostructured materials compared to their bulk counterparts. The present work
Accepted 25 June 2014
emphasizes an unexploited, cost effective, and environmentally benign method of synthesizing bioactive
Available online 3 July 2014
tin oxide nanoparticles of size from 2.1 nm to 4.1 nm using Saraca indica flower. The XRD pattern and
HRTEM images of the samples revealed an increase in particle size with annealing temperature. Fine tun-
Keywords:
ing band gap could be attained as evidenced by the shift of absorption band edge and photoluminescence
Tin oxide
Saraca indica
emission. It is found that oxygen vacancies play an important role on PL emission. The synthesized nano-
Absorption band edge particles exhibit antibacterial activity against gram negative bacteria Escherichia coli. The antioxidant
Photoluminescence activity is evaluated by scavenging free radicals of 2,2-diphenyl-1-picrylhydrazyl hydrate (DPPH). The
Antibacterial activity efficiency of biogenic SnO2 nanoparticles as a promising antibacterial agent as well as an antioxidant
DPPH for pharmaceutical applications is suggested.
Ó 2014 Elsevier B.V. All rights reserved.

Introduction
Nanometer range semiconductors have been a subject of inter-
est for last several years due to their size dependent physical and
chemical properties below a critical size of the material. Functional
⇑ Corresponding author. Tel.: +91 471 2531053; fax: +91 471 2530023.
E-mail addresses: philipdaizy@yahoo.co.in, daizyp@rediffmail.com (D. Philip).
oxides are presently much investigated for their potential applica-
tions in various areas and tin oxide appears particularly interesting
when grown in nanometer range. Semiconductor nanocrystals rep-
resent a class of materials that have hybrid molecular and bulk
properties which originate from the quantum confinement effect.
Quantum confinement effect modifies the electronic structure
of the nanocrystals when the sizes of the nanoparticles are compa-
rable to that of Bohr exciton radius of those materials. When the

http://dx.doi.org/10.1016/j.saa.2014.06.131
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.
 V.K. Vidhu, D. Philip / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 372–379
particle radius falls below the excitonic Bohr radius, the band gap
energy is widened, leading to a blue shift in the band gap and emis-
sion spectra. On the other hand, the surface states play an impor-
tant role in the nanoparticles, due to their large surface-to-
volume ratio with a decrease in particle size. In the case of semi-
conductor nanoparticles, radiative or nonradiative recombination
of an exciton at the surface states becomes dominant in its optical
properties with a decrease of particle sizes. Therefore, the decay of
an exciton at the surface states will influence the qualities of the
material for an optoelectronic device. These size dependent optical
properties have many potential applications in the areas of solar
energy conversion, light emitting devices, chemical/biological sen-
sors and photo catalysis. Now, there is an urgent need to develop
reliable environmentally benign methods to synthesize nanoparti-
cles with a precisely controlled optical, magnetic, electric or cata-
lytic functionality, which strongly depends on particle size shape,
agglomeration and surface states [1–4].
Tin oxide is a wide band gap (3.6 eV) n-type semiconductor
with many potential applications. The large band gap and high
achievable carrier concentration (up to 6  1020 cm3) [5] make
tin oxide an excellent candidate for a wide range of application
such as lithium -ion batteries, transparent conducting electrodes
and solar cells [6–8], catalysts for oxidation of organics, gas sensors
and electrodes in solid state ionic devices as it is chemically inert,
mechanically hard and thermally heat resistant [9–12]. The success
in many of its technological applications depends on crystalline
SnO2 with a uniform nanosize pore structure [13]. Efforts toward
the development of tin oxide nanomaterials with high sensitivity,
excellent selectivity, quick response and recovery behavior to gases
has increased over years.
Tin oxide nanoparticles is used widely to control air pollution
and to detect toxic or smelling gases at low levels in the air and
in the field of domestic and industrial applications [14]. As the size
of the particle decreases, the surface to volume ratio increases,
which then increases the number of oxygen sites on the surfaces
in these reducing gas species [14,15] and the sensitivity of the
nanocrystalline tin oxide [9]. Therefore, the synthesis of high qual-
ity SnO2 nanoparticles is a subject of interest for basic and applied
research. In addition to the particle size, the other factors desirable
for various applications are low degree of agglomeration, monoge-
nous size and homogenous arrangement of particles which greatly
depend on the route of synthesis.
Many methods for the fabrication of SnO2 nanostructures with
particle sizes ranging from 2.5 to 10 nm have been reported earlier
which includes gas-phase methods [16–18], Sol gel method [19],
the solvothermal method [20], the evaporative decomposition of
solution [21], the laser ablation technique [22] and wet chemical
synthesis [23]. Wet chemical synthesis is more advantageous com-
pared to other methods in producing nanomaterials with a uniform
structure on large scale. Green synthesis of metal oxide nanoparti-
cles is an area of interest having significant focus in present sce-
nario with important objective of facilitating the manufacture of
nanotechnology based products eco-friendly and safer for all
beings with sustainable commercial viability. However some sur-
factants are toxic and lead to impurities in the final product and
hamper the application of these nanomaterials in electronic and
sensing devices. The surfactants have to be removed by burning
the samples at higher temperature to improve thermal stability
and the purity of the tin oxide for catalysts and electrochemistry.
Also the evaluation of antimicrobial and antioxidant activity of
metal oxide nanoparticles has become one of the significant stud-
ies in pharmaceutical science. Antibacterial agents are of great
interest in several industries such as hospital implants, medicine,
food disinfection [24,25]. Metal nanostructures are considered as
most promising candidates for this purpose due to their high ther-
mal stability, photo catalytic and antimicrobial properties [26,27].
373
Antioxidants play an important role in the functioning of all bio
systems. In biological systems; free radicals are generated due to
interaction of biomolecules with molecular oxygen [28,29] which
results in the degradation of biomolecules. Antioxidants play cru-
cial role in scavenging these toxic free radicals thereby terminating
the oxidative damage of human body.
Herein we unravel dried Saraca indica flower extract as poten-
tial candidate for the rapid and efficient synthesis of tin oxide
nanoparticles. Saraca indica is highly accepted as universal solu-
tion in the ayurvedic medicine. All the plant parts are considered
to be having medicinal value. It is used in bleeding piles, bacillary
dysentery [30]. Dried flowers are reported to have antibacterial
activity [31,32]. The dried flowers have been used earlier in the
synthesis of silver nanoparticles [33].
Our objective in this work is to reduce tin chloride to tin oxide
nanoparticles using a biomaterial that addresses two major factors,
the need for the biomaterial to be environmentally benign and pro-
duce no toxic industrial waste and for it to be cost-effective and
easily produced. We have studied the influence of reaction param-
eters like volume of extract and temperature on the formation and
crystallization of tin oxide nanoparticles. Also the antimicrobial
activity of as synthesized SnO2 nanoparticles has been investigated
on Gram negative bacteria Escherichia coli. The anti oxidant activity
of the synthesized sample is explored by monitoring the free rad-
ical scavenging potential using DPPH assay. To the best of our
knowledge, this is the first report on biosynthesized tin oxide
nanoparticles with an impeccable antibacterial and antioxidant
activity.
Materials and methods
SnCl4.xH2O was procured from sigma Aldrich. All glass wares
were cleaned with aqua regia and rinsed several times with
de-ionized water.
Preparation of extract
Saraca indica flower buds were collected locally and shade
dried. 5 g of powdered Saraca indica flowers was boiled with
100 mL of deionised water at 373 K for 2 min. The extract was
filtered and used for further experiments.
Synthesis of Tin oxide nanoparticles
Tin oxide nanoparticles (sample S1) have been synthesized by
adding 2 mL extract to 30 mL 0.5 M tin chloride solution at room
temperature and vigorously stirred for two minutes. The formation
of tin oxide nanoparticles is observed by the appearance of light
brown color precipitate within 5 min. Samples S2–S5 was synthe-
sized in the same procedure by adding 5 mL, 10 mL, 15 mL and
25 mL extracts, respectively. The samples were centrifuged and
washed several times using deionised water. In order to study
the effect of temperature, samples S1 and S5 are annealed at tem-
peratures 300 °C (S13, S53) and 900 °C (S19, S59) for one hour,
respectively.
Characterization
Ultraviolet spectra analysis was performed for all samples and
the absorption maxima were analyzed at a wavelength of 200–
700 nm using on a UV-2450 Shimadzu UV spectrometer. FTIR spec-
tra of samples and extract were recorded using IR Prestige -21
Schimadzu spectrometer. XRD pattern was recorded by XPERT-
PRO diffractometer using Cu Ka radiation (k = 1.5406 Å). The scan-
ning was performed in the region of 2h from 20° to 90°. The size of
374 V.K. Vidhu, D. Philip / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 372–379
the nanoparticles was calculated through the Scherrer’s equation.
The morphology of SnO2 nanoparticles was examined using Tecnai
G2 30 Transmission Electron Microscope. The Photoluminescence
spectra of samples S1, S13, S19 were recorded using Flurolog III
spectrometer.
Antibacterial activity
Antibacterial activities of the SnO2 nanoparticles were exam-
ined against clinically isolated; Gram negative E. coli (K-12) bacte-
ria by Agar well diffusion method. The SnO2 nanoparticles are
diffused out into the medium and interact in a plate freshly seeded
with the test organisms. The resulting zones of inhibition will be
uniformly circular as there will be a confluent lawn of growth.
The diameter of zone of inhibition was measured in centimeters.
The medium was prepared by dissolving 28 g of the commercially
available Nutrient Agar Medium (HiMedia) in 1000 mL of distilled
water. The dissolved medium was autoclaved at 15 lbs pressure at
121 °C for 15 min. The autoclaved medium was mixed well and
poured onto 100 mm petriplates (25–30 mL/plate) while still mol-
ten. One litre of nutrient broth was prepared by dissolving 13 g of
commercially available nutrient medium (HiMedia) in 1000 mL
distilled water and boiled to dissolve the medium completely.
The medium was dispensed as desired and sterilized by autoclav-
ing at 15 lbs pressure (121 °C) for 15 min. Gentamycin with con-
centration 20 mg/mL is used as the positive control.
DPPH Assay (2,2-diphenyl-1-picrylhydrazyl)
The radical scavenging activity was determined by using DPPH
assay. Different quantity of SnO2 (lg/mL) nanoparticles were made
up to 40 lL with DMSO and 2.96 mL DPPH (0.1 mM) solution was
added. The reaction mixture incubated in dark condition at room
temperature for 20 min. After 20 min, the absorbance of the mix-
ture was read at 517 nm. 3 mL of DPPH was taken as control. The
decrease in the absorption of the DPPH solution after the addition
of an antioxidant was visually monitored by measuring the absorp-
tion intensity at 517 nm. Ascorbic acid is used as the reference.
Results and discussion
XRD and HRTEM studies
The XRD patterns of the synthesized samples (S1–S5) are shown
in Fig. 1.
Fig. 2 shows the XRD pattern of samples annealed at 300 °C and
900 °C, respectively. The annealed SnO2 nanoparticles at 900 °C
show diffraction peaks at 2h values (in degrees) of 26.8, 33.9,
37.9, 51.8, 54.8, 61.8, 64.8, 66.0, 71.2 and 78.6 which are assigned
Fig. 1. XRD of as prepared samples S1–S5.
Fig. 2. XRD of as prepared samples S13, S19, S53 and S59.
to (1 1 0), (1 0 1), (2 0 0), (2 1 1), (2 2 0), (3 1 1), (1 1 2), (3 0 1), (2 0 2)
and (3 2 1) planes, respectively. The observed and standard (h k l)
planes confirmed that the product is of SnO2 having a tetragonal
structure, which is in good agreement with the literature, values
(JCPDS No 41-1445). The average particle size is calculated using
the Debye–Scherer equation
0:9k
D¼
bCosh
where D is the particle size, b is the Full Width Half Maximum
(FWHM) in radians, h is the Bragg angle.
The width of the as prepared samples are considerably broad-
ened which indicates a small crystallite size. The intensity of the
annealed samples (Fig. 2) enhanced with annealing temperature.
The estimated average crystallite sizes of the samples are given
in Table 1.
Crystallite size is a measure of the size of a coherently diffract-
ing domain. The crystallite size of the particles is not generally the
same as the particle size due to the presence of polycrystalline
aggregates [34]. The XRD results reveal that the annealing temper-
ature influences the crystallization of the powders. As the anneal-
ing temperature increases the diffraction peaks get sharper. The
two possible mechanisms involved in the narrowing of the peak,
one is particle size effect and the other is lattice strain. The increase
in particle size with temperature can be attributed to the atomic
diffusion leading to an increase of crystallite size which is pro-
nounced at higher temperatures. The increase in the intensity of
the diffraction peaks and decrease in the FWHM with the rise in
temperature is owing to the orderly arrangement of atoms in the
crystal surfaces and grain interfaces. Crystal lattice defect, espe-
cially a large amount of oxygen vacancy, exists in the ultrafine
powder, along with tiny strains during the treatment of the sam-
ples which may get removed at higher annealing temperatures
[35].
The morphology and the structure of the tin oxide samples have
been analyzed using HRTEM images. The images of the as prepared
Table 1
Particle size calculated from XRD pattern.
Sample name Particle size (nm)
S1 2.1
S2 2.7
S3 3.3
S4 3.9
S5 4.1
S13 3.5
S19 11.4
S53 4.6
S59 13.1
 V.K. Vidhu, D. Philip / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 372–379
samples show agglomeration of nanoparticles (Figs. 3a and 4a). The
particles exhibit comparatively more crystallinity and lesser
agglomeration when annealed at 300 °C (Figs. 5a and 6a). As the
annealing temperature increased to 900 °C, samples (S19 and S59)
become crystalline in nature (Figs. 7 and 8). The morphology of
the particles is observed to be spherical. The particle sizes esti-
mated from the HRTEM images are found to be 2.2 nm, 4.1 nm,
10.5 nm, 2.6 nm, 3.3 nm and 18.2 nm for samples S1, S13, S19, S5,
S53and S59, respectively. Also the d-spacing calculated from the
HRTEM images for samples S13, S19, S53, and S59 are
0.17 nm,0.18 nm,0.26 nm and 0.26 nm respectively. These d values
correspond to (2 1 1), (2 1 1), (1 0 1) and (1 0 1) planes in S13, S19, S53
and S59, respectively.
UV–visible spectra
UV–visible absorption spectroscopy is a powerful non destruc-
tive technique to explore the optical properties of semiconducting
nanoparticles. The absorbance is expected to depend on several
factors, such as band gap, oxygen deficiency, surface roughness
and impurity centers. Quantum confinement effects are expected
due to small particle size detectable as a blue-shift of optical
absorption edge caused by band gap widening in the UV region.
Fig. 9 shows the absorption spectra of as prepared tin oxide sam-
ples and that of samples annealed at different temperatures. The
inset shows the absorption spectra of samples S2, S3 and S4, respec-
tively. The typical optical absorption spectra show that S2 and S3
have absorption band at round 270 nm. The sample S4 displays a
weak and almost flat absorption over the entire range wavelength.
The spectrum of samples S1, S13, S19, S5, S53 and S59 shows absorp-
tion band at around 280 nm which depicted a red shift in the
wavelength as the temperature increases. This shift can be attrib-
uted to the increase in size of the samples with respect to increase
in annealing temperature. The tunable band gap of the samples
implies that the biogenic tin oxide is a potential candidate for opti-
cal applications.
The obtained values of the band gap energy of the samples S1,
S13, S19, S5, S53 and S59 are 4.5 eV, 3.9 eV, 3.7 eV, 4.3 eV, 4.1 eV
and 3.8 eV, respectively. The results show that the band gap energy
of the samples decreases with increase in annealing temperature
due to increase in the crystallite size. Since the band gap energies
are higher than the bulk value of SnO2 (3.6 eV), the particle sizes
have been calculated using Brus relation which is known as Effec-
tive Mass Approximation (EMA) [36]
2  
Eg ¼ Eg þ p2 h =8R2 1=me þ 1=mh  1:8e2 =eR
where Eg is the size dependant band gap of the nanoparticles, Eg is
the band gap of the bulk sample, R is the particle size, me and mh are
Fig. 3. TEM images of sample S1 at different magnifications.
375
the effective, masses of the electron and hole, respectively. The par-
ticle size calculated from EMA equation for samples S1, S13, S5 and
S53 are 1.9 nm, 2.8 nm, 4.8 nm and 3.7 nm, respectively. The incre-
ment in the band gap of the SnO2 nanoparticles from that of bulk
counterpart can be attributed to the quantum confinement effect
of the SnO2 nanoparticles. It is likely that other factors such as lat-
tice strain may affect the energy levels of the nanoparticles [37].
FTIR spectra
Fourier transform infrared spectroscopy is usually employed as
an additional probe to ensure the presence of OH groups as well as
other organic and inorganic species. Fig. 10 gives the FTIR spectra
of samples S1 (Fig. 10a), S13 (Fig. 10b) and S19 (Fig. 10c), respec-
tively. Similarly the FTIR spectra of samples S5, S53 and S59 are
shown in Fig. 11.
The band at around 616 cm1 (Fig. 10) is due to SnAO stretching
mode becomes sharper as the annealing temperature increases to
900 °C. The appearance of this band confirms the presence of
SnO2 in the crystalline phase [38]. The presence of water molecules
adsorbed on the surface of tin oxide during handling or bending
and stretching vibrations of OH groups can be seen in the 1600–
1650 cm1 and 3200–3600 cm1 regions [39,40]. The difference
in the FTIR spectra before and after annealing is that the intensity
of the bands at 1630–1680 cm1 and 3200–3600 cm1 has been
reduced due to removal of water during the annealing process.
The unannealed samples (Fig. 10) show bands at about 532 cm1,
539 cm1, which is attributed to the stretching vibrations of
SnAOH group when the samples are annealed at higher tempera-
ture these bands disappear which indicates the occurrence of con-
densation reaction upon heating to produce SnO2 [15]. The band at
490 cm1 can be assigned to the symmetric SnAO stretching mode
[41,42]. The broad band around 3400–3500 cm1 region is due to
the stretching vibration of OAH bond. This band is due to the
OAH groups and the adsorbed water bound at the SnO2 surface
[43]. The extract shows prominent bands at 1618 cm1,
1404 cm1, 1076 cm1 and 607 cm1 (Fig. 12). The band at
1618 cm1 in the spectra of extract correspond to C@C groups or
aromatic rings or C@O stretching in carboxyl group (amide I band)
of proteins [44]. The band at 1404 cm1 correspond to germinal
methyls [45]. Also the band at 607 cm1 in the spectra can be
attributed to CAH bend of alkynes [46]. The band at 1076 cm1in
the FTIR spectra of extract can be assigned to the ether linkages
[45]. The IR bands confirm the formation of SnO2 nanoparticles
which can be correlated with the XRD results. The observed IR
bands are more characteristic of flavanones and terpenoids that
is very abundant in dried Saraca indica flowers. This indicates the
presence of flavanones or terpenoids adsorbed on the surface of
tin oxide nanoparticles. The pronounced absorbance band
376 V.K. Vidhu, D. Philip / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 372–379

Fig. 4. TEM images of sample S5 at different magnifications.

Fig. 5. TEM images of sample S13 at different magnifications.

Fig. 6. TEM images of sample S53 at different magnifications.

Fig. 7. TEM images of sample S19 at different magnifications.

observed at around 1620 cm1 (amide I arising due to carbonyl of SnO2 nanoparticles. The shift in the band positions
stretch in proteins), suggest the presence of proteins on the surface (1618–1636 cm1 (Fig. 10) suggest that these functional groups
 V.K. Vidhu, D. Philip / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 372–379 377

Fig. 8. TEM images of sample S59 at different magnifications.

Fig. 9. UV–visible spectra of samples S1, S13, S19, S5, S51, and S59. Inset show the UV–
Fig. 12. FTIR spectra of extract.
visible absorption spectra of samples S2, S3 and S4.

are oxidized during the reaction and can be inferred as the capping
molecules in the formation of SnO2.

Photoluminescence spectra

To explore the possibilities of the luminescent properties of

SnO2 nanoparticles, photoluminescence spectra at room tempera-
ture were recorded. The luminescent spectra of the samples S1,
S13 and S19, respectively, at an excitation wavelength 250 nm are
shown in Fig. 13. In general, except the sharp excitonic emission,
semiconductors have another broad trapped emission, which often
contains multiple luminescent centers. There are various types of
surface states that give rise to different energy states inside the
semiconductor band gap.
Fig. 10. FTIR spectra of samples (a) S1, (b) S13 and (c) S19. In polycrystalline and nanocrystalline oxides, oxygen vacancies
are known to be the most common defects, and usually act as radi-
ative centers in the luminescence processes. The oxygen vacancies
are mostly present in three charge states of V0°, V+0 and V++
0 [47,48].
As the V0° is a very shallow donor, it is believed that the most
oxygen vacancies will be in their paramagnetic Voþ state under flat
band conditions. The recombination of the surface trapped hole
with an electron in the deep trap (Vo+) to form a Vo++ center, gives
rise to a visible emission when a conduction band electron recom-
bines with the Vo++ center [38]. The mechanism of emissions is
associated with defect energy levels within the band of SnO2. Thus,
the nature of the transition is tentatively ascribed to oxygen vacan-
cies or Sn interstitials which form a considerable number of
trapped states within the band gap. Since the energy of the emis-
sion is lower than the band gap of SnO2, this observed emission
cannot be attributed to the direct recombination between a con-
duction electron in Sn4+ band and a hole in O2 valence band. These
Fig. 11. FTIR spectra of samples (a) S5, (b) S53 and (c) S59.
bands can be attributed to electron transition, mediated by defect
378 V.K. Vidhu, D. Philip / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 372–379
Fig. 13. Photoluminescence spectra of samples S1, S13 and S19 at excitation
wavelength 250 nm.
Fig. 14. ZOI showing antibacterial activity of sample S5 against gram negative E. coli
bacteria.
levels in the band gap, such as oxygen vacancies and luminescence
centers formed by such tin interstitials or dangling in the presence
of SnO2 nanocrystals [49–53].
In the spectra (Fig. 13) a weak band at around 678 nm can be
observed for all samples which is in agreement with earlier reports
[54–57] which would be related to the crystalline defects during
the growth process. It is well known that, the intrinsic defects form
defect levels in the band gap in most semiconductor materials,
which trap electrons from valence band to contribute to lumines-
cence. In semiconductor metal oxides, oxygen vacancy is an intrin-
sic donor and considered to be the most common defect. When the
temperature increases, the oxygen vacancies decrease due to
Fig. 15. Schematic diagram showing possible mechanism of antibacterial activity.
recombination with diffused oxygen [48,49]. Thus the oxygen
vacancies really play an important role on PL for emission spec-
trum which is due to the recombination of the electrons with holes
in the valence band.
In vitro evaluation of antibacterial activity
The antibacterial activity of SnO2 nanoparticles (sample S5) on
the microorganism gram negative bacteria E. coli has been evalu-
ated (Fig. 14). It shows a significant growth inhibition of bacterial
culture by SnO2 nanoparticles when compared to control. E. coli
is a gram negative bacterium having complex cell wall. Its cell wall
is composed of a thick layer as well as outer membrane which
cover the surface membrane. Due to this complex cell wall, E. coli
shows resistance to mostly available drugs [58]. Metal oxide nano-
structures can possibly be used to break these protection layers of
bacteria. Metal oxide nanoparticles possess high surface area
which is responsible for their increased chemical and biological
activity. The active oxygen species produced due to the presence
of SnO2 nanoparticles interact with bacterial membrane cell and
allow penetration of nanoparticles into the cell. The schematic dia-
gram showing possible mechanism of antibacterial activity is sug-
gested in Fig. 15.
Due to these characteristics SnO2 nanoparticles react efficiently
with the cell membrane and inactivate the bacteria [59]. The bac-
tericidal potency is found to be increased with increase in concen-
tration of nanoparticles. Therefore, higher concentration of SnO2
nanoparticles is significant in bactericidal effect.
Several mechanisms of action against bacteria have been
reported for metal oxide nanoparticles such as decomposition of
nanoparticles and formation of reactive oxygen species, electro-
static interaction of nanostructures with cell wall and their photo
catalytic light activation [60]. Nanostructures react through these
mechanisms with bacterial cells and lead to zone of inhibition
(ZOI) around nanomaterials. The size of ZOI depends on the bacte-
ricidal potency of nanomaterials. The ZOI around SnO2 nanoparti-
cles is not as much as seen around the positive control. The
enhancement of ZOI may be achieved by varying the synthesis pro-
cedure and reaction parameters of nanoparticles or by modifying
the surface which need further in-depth study.
In vitro antioxidant activity
The antioxidant activity of the as synthesized samples can be
evaluated by estimating the free radical scavenging activity using
1, 1-diphenyl-2-picryl hydrazyl (DPPH). 1, 1-diphenyl-2-picryl
hydrazyl is a stable free radical with deep violet color in solution
which turns yellow when scavenged. The DPPH assay uses this
character to show free radical scavenging activity. The odd electron
in the DPPH free radical gives a strong absorption maximum at
517 nm. The color of DPPH gradually changes from deep violet to
pale yellow in the presence of SnO2 nanoparticles. This happens
 V.K. Vidhu, D. Philip / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 372–379
Fig. 16. Antioxidant activity of sample S5 using DPPH assay.
when the odd electron of DPPH radical becomes paired with a cat-
ion from a free radical scavenging antioxidant to form the reduced
DPPH-H. The resulting decolorisation is stoichiometric with
respect to number of electrons scavenged. The percentage of scav-
enging activity with respect to concentration of sample and refer-
ence is shown in Fig. 16. The decrease in the intensity of band at
517 nm gives the evidence toward the scavenging capacity of
SnO2 nanoparticles. The decreasing rate in the band intensity is
found to be directly proportional to the quantity of the SnO2 nano-
particles. The free radical scavenging activity is a surface reaction
since only the surface comes in contact with the free radicals.
The radical scavenging potential is dependent on various factors
such as particle size, morphology, defects etc. In order to get an
insight into the possible origin of antioxidant activity of SnO2
nanoparticles a detailed investigation on the mentioned factors is
suggested.
Conclusion
SnO2 nanoparticles have been synthesized successfully through
a novel biogenic synthesis method using Saraca indica flower
extract as reducing agent. The crystallite sizes of as prepared sam-
ples, estimated from XRD pattern and TEM images are found to be
in the range 2.1–4.1 nm. The luminescence properties of the syn-
thesized nanocrystalline SnO2 semiconductor material promise
the potential use in optoelectronic and sensor devices. The as pre-
pared bioactive tin oxide nanoparticles are excellent candidates for
biomedical applications owing to their antimicrobial and antioxi-
dant activity. Even though the samples show antibacterial activity
against gram negative bacterium E. coli, further investigations on
the bio-compatibility is a future perspective.
Acknowledgements
The facilities recording UV-visible and FTIR spectra rendered by
the Department of Chemistry, Govt. College for Women are grate-
fully acknowledged. The authors are grateful to the Biogenix
Research Center, Thiruvananthapuram for the help in the study
of antibacterial and antioxidant activities.
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