Powder Technology 286 (2015) 744749

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Powder Technology
journal homepage: www.elsevier.com/locate/powtec

Biogenic synthesis of iron nanoparticles using Amaranthus dubius leaf

extract as a reducing agent
Muthukumar Harshiny, Chandrasekaran Nivedhini Iswarya, Manickam Matheswaran
Department of Chemical Engineering, National Institute of Technology, Tiruchirappalli 620015, India

a r t i c l e

i n f o

Article history:
Received 28 December 2014
Received in revised form 15 September 2015
Accepted 18 September 2015
Available online 21 September 2015
Keywords:
Iron
Amaranthus dubius
UVvisible spectrum
Photocatalyst
Antioxidants

a b s t r a c t
The biogenic synthesis of nanosize powder is of great interest due to its multifunctional applications and easy and
eco-friendly process. The biosynthesis of nanosize iron particles using Amaranthus dubius leaf aqueous extracts
that are reduced from ferric chloride was investigated. A. dubius aqueous leaf extraction process parameters
were optimized based on the antioxidant capacity for attaining efcient extract. The leaf extract contains a rich
source of amaranthine and phenolic compounds that are used as reducing agents. The effects of different process
parameters like pH, temperature, concentration of leaf extract and time on the nanoparticle synthesis were
examined. The synthesised nanoparticle size, morphology, crystallinity, composition, and stability were investigated. Results showed that A. dubius extract mediated nanoparticles are in spherical shape with a cubic phase
structure and a diameter range from 43 to 220 nm with less aggregation. A. dubius and sodium borohydride
mediated iron nanoparticles for decolouration efciency against methylene orange and antioxidant against 1,
1-diphenyl-2-picrylhydrazyl were studied.
2015 Elsevier B.V. All rights reserved.

1. Introduction
The effective and efcient synthesis of nanoparticles (Nps) with
properties like high monodispersity and biocompatibility is needed for
a wide range of application from environment to biomedics [1]. Various
techniques applied to the synthesis of metallic Nps like chemical [2,3],
physical [4,5], and laser ablation [6], electric arc discharge [7] and microbial methods [8] were already reported by many investigators. These
methods require expensive instruments, high-energy [9], release of
inimical chemicals [10,11], and culture of cell [12] and wasteful purications [13]. The biogenic synthesis of Nps has been considered as a rapid,
clean, nontoxic, cost-effective and environmental friendly compared to
other conventional techniques [10,14,15]. Several investigations reported
that constituents of various herbs, spices and plants have high levels of
powerful antioxidant compounds such as polyphenols, reducing sugars,
nitrogenous bases, and amino acids [16]. These compounds are used as
reducing [17] and capping agents for the synthesis of Nps [16,18].
The plant extracts used for Np synthesis could be advantageous by
eliminating the elaborate process like maintaining cell cultures [17,
19], recovery steps, lesser reaction time [12] and it does not produce
any hazardous waste [20]. Praveen et al. reported that plant leaf extract
implicated Nps can be suitably scaled up for large scale production;
besides, the process can be economically viable [21]. The plant
extract-mediated metal and metal oxide Nps are quite stable and no
visible changes were observed even after a month [19]. The biogenic
Corresponding author.
E-mail address: math.chem95@gmail.com (M. Matheswaran).

http://dx.doi.org/10.1016/j.powtec.2015.09.021
0032-5910/ 2015 Elsevier B.V. All rights reserved.

synthesis of Nps using various plant extracts like Dodonaea viscosa

[22], Camellia sinensis [23], Sargassum muticum [24], Ipomea carnea
[25], Mukia maderaspatana [26] Mangifera indica, Syzygium aromaticum,
Rosa indica, Murraya koenigii and Azadirachta indica [27] were investigated. Bashir et al. synthesised Fe2O3 Nps using C. sinensis plant extract
and tested its catalytic performance by decolourization of aqueous dye
solution [23,28]. Albergaria et al. utilized 26 different tree leaf extractions
for the production of zero-valent iron Nps and tested an antioxidant
capacity for dried leaf extract [29].
Iron nanoparticles (FeNps) have unique characteristics like catalytic
activity [28] and optical [29], electronic [30] and antibacterial properties [31]. Thus, it has a wide range of applications, including cosmetics
[32], biomedicine [33], bioremediation [34], clinical [35] materials and
engineering [36]. Due to its enhanced properties and multifunctional
application it highly encourages us to choose FeNp synthesis. The conventional synthesis of FeNps used a variety of organic solvents and reducing
agents like sodium borohydride (NaBH4) [27], hydrazine, sodium dodecyl
sulphate, etc [22,37]. These reducing agents pose great risks to the
environment; it also creates harmful by-products to human health [37,
38]. In spite of this difculty, high amounts of organic compounds in the
plant extracts are used for the reduction process; it stabilizes Nps by
preventing agglomeration [39,40] and Nps produced from biogenic synthesis compared to the traditional methods that demonstrate less toxicity
[17,28]. The problems associated with conventional methods initiate us to
synthesise biocompatible FeNps using leaf extracts.
The aqueous extract of Amaranthus species leaves was used for
synthesising Nps, because the species has many remedial properties
that are cheap and easily available [41]. Amaranthus dubius leaf extract

M. Harshiny et al. / Powder Technology 286 (2015) 744749

contains various photochemicals like amaranthine, isoamaranthine,

phenols, avonoids, and lysine that are used as reducing agents [42,
43]. The economical and eco-friendly leaf extract from A. dubius is an
alternative reducing agent for synthesising FeNps.
In this study, biosynthesis of nanosized iron particles reduced from
FeCl3 using A. dubius leaves aqueous extract was investigated. The
extraction process parameters like temperature, time and mass of
leaves were optimized in order to achieve a higher antioxidant capacity.
For synthesising FeNps, various operating parameters like pH, time,
concentration ratio of leaf extract and FeCl3 were optimized. The Nps
were characterized using a UVvis spectrophotometer, X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (FTIR), Particle size
analyzer (PSA) and scanning electron microscopy (SEM). The catalytic
activity of both NaBH4 (BFeNps) and A. dubius (DFeNps) mediated Nps
were tested through the decolourization efciency of methyl orange
(MO) by UV irradiation and antioxidant capacity by 2,2-diphenyl-1picryl-hydrazyl (DPPH) radical scavenging assay. The effect of initial
MO concentration and FeNps loading on decolourization was also
investigated.

745

XRD using step scan technique and with Cu-K radiation (1.500 ,
40 kV, 30 mA). The PSD and zeta potential were measured by SZ-100
Nanopartica (Hiroba USA).
2.4. Photocatalytic activity
The photocatalytic activity of DFeNps and BFeNps was performed by
decolourization of MO solution under UV irradiation. The experiments
were carried out in a cylindrical double jacket vessel that is equipped
with a magnetic stirrer under UV light of 20 W. Twenty milligrammes
of Nps were added to 500 mL of 20 ppm aqueous MO solution. The
solution was continuously exposed to a UV light maintained at 37
1 C with continuous stirring (100 rpm) for 6 h. The samples were
collected at a regular interval of time and analyzed using a UVvisible
spectrophotometer with a wavelength range of 200900 nm. The
photocatalytic decolouration efciency of the Nps for MO solution was
calculated using the following formula:
Colour removal %

C 0 C t
 100
C0

2. Materials and methods

2.1. Preparation of leaf extract
Fresh A. dubius leaves were collected and thoroughly washed with
deionized water, then chopped into small pieces. Twenty grammes of
leaves were heated with 100 mL distilled water at 50 C for 45 min.
The supernatant was ltered through a Whatmann lter paper to
yield the leaf extract and stored at 4 C for further use. The reducing
capacity of A. dubius leaf extract was evaluated using DPPH radical scavenging activity. The experiments were performed at different temperatures from 40 to 70 C, contact time of 20 to 120 min, and volume ratio
of leaf mass (5 to 25 g):water (100 mL) for attaining an optimized
condition with a higher antioxidant capacity of leaf extract.
2.2. Synthesis of NaBH4 and A. dubius mediated Fe nanoparticles
The BFeNps were carried out as a control experiment. 100 mL of
0.5 M FeCl3 was placed in an Erlenmeyer ask and maintained at
60 1 C with continuous stirring using a magnetic stirrer. 50 mL of
0.2 M NaBH4 solution was added drop by drop using a burette. The
colour changes from brown to colourless solution with a black precipitate of Nps conrm the formation of BFeNps. The Np synthesis was
also carried out using 40 mL of leaf extract and 50 mL of 0.5 M FeCl3
solution. The leaf extract (pH 6) was added drop wise to the FeCl3
solution with continuous stirring for 90 min. The solution pH was
adjusted using 0.1 N HCl and 0.1 N NaOH. The yellowish solution was
turned into a blackish green colour with the formation of DFeNps as
black precipitate [28]. Both precipitates of BFeNps and DFeNps were
collected and washed with absolute ethanol; nally FeNps were dried
in an oven at 60 C for 180 min. The Np samples were stored in sealed
bottles under dry condition. The effect of pH, temperature, time,
concentration of leaf extracts and FeCl3 ratio were studied for synthesis
of DFeNps with conditions of pH varied from 4 to 9, concentration ratio
of 1:5 to 5:5, temperature from 25 to 60 C and time from 15 to 120 min
for attaining a higher yield of Nps.

where Co and Ct are the absorbance of the initial concentration and after
time t of MO solution, respectively.
3. Results and discussion
3.1. Leaf extract optimization
In the aqueous leaf extraction process, temperature, time and leaf
mass played a major role in getting an efcient extract. The effect of
leaf mass on the antioxidant activity of extract is shown in Fig. 1. For
the increasing mass of leaves from 5 to 20 g per 100 mL of water
which increases the percentage of antioxidant activity from 34.2 to
94.9%, respectively. Pablo et al. also reported that the chemical score of
the essential amino acids of A. dubius leaf extract was 92.83% [44].
Hence the increasing mass of the leaves increase the concentrations of
several organic substances in the leaf extract; therefore, the antioxidant
activity was increased. The effect of leaf extraction process temperatures,
which varies from 40 to 70 C was investigated. Fig. 2 shows that the
antioxidant activity increases along with temperature from 40 to 50 C.
In the case of temperature above 50 C, it shows that the inhibitory rate
decreases from 94.9 to 52% with an increasing temperature from 50 to
70 C. A. dubius leaf extraction heating at 50 C conferred scavenging
activities on DPPH radical higher with an inhibitory rate of 94.9%. By
increasing the temperature above 50 C, it can degrade the active

2.3. Analytical techniques

The absorbance spectra of the samples were measured within a
wavelength range of 200800 nm using a Shimadzu UV-1800 spectrophotometer (Kyoto, Japan). The functional group of leaf extract and
Nps were recorded by a PerkinElmer FTIR spectrophotometer
(Massachusetts, USA) over the spectral range of 4004000 cm 1 .
The morphologies of the Nps were analyzed using SEM (Tecson,
Czech Republic). The XRD data were obtained by Rigaku Ultima III

Fig. 1. The effect of different leaf masses: water volume ratios on percentage of antioxidant
activity for leaf extract. (conditions: temperature: 50 C, Time: 45 min).

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M. Harshiny et al. / Powder Technology 286 (2015) 744749

Fig. 2. The effect of temperature on the percentage of antioxidant activity (conditions: leaf
mass: 20 g; time: 45 min).

constituent amino acids. The effect of extraction time varies from 15

to 60 min from 20 g of leaves per 100 mL of water at 45 C on the
antioxidant activity was shown in Fig. 3. The contact time of 45 min
was sufcient for the leaf extraction process. The heating time
exceeded more than 45 min that can degrade the antioxidant compound
and less than 45 min was not enough for extraction [45]. The leaf extract
was obtained under an optimized condition of 20 g of leaves boiled at
50 C for 45 min with an antioxidant of 94.9%. The decolouration of
20 ppm MO using the leaf extract was performed at 37 1 C as a control
experiment. The photocatalytic result showed 10% of colour removal
within 4 h; after that there was no signicant change in the percentage
of removal. It may be due to hydrolysation of bioactive compound.
3.2. UVvisible spectrometric analysis of synthesised nanoparticles
The formation of FeNps was monitored by UVvis spectrophotometer
wavelength, which ranges from 200800 nm. An absorption peak at
214 nm and 260 nm corresponds to the Nps and the presence of peptide
bonds, respectively. The solution pH was one of the key factors for Np
synthesis and its absorbance peaks were shown in Fig. 4(a). The leaf
extracts at acidic pH 4 conferred formations of less particles. The spectrum
showed a peak at 260 nm: it was due to unreacted organic compounds
present in the nal products. At pH 6, high intensity absorbance band

appeared at 214 nm. The extract pH 6 conferred high yields of Nps due
to the activation of the phytochemicals involve in the synthesis. But in
the case of extract at pH 9, the colour change was rapid after adding the
FeCl3 and the absorbance peak shifted to 300 nm which was due to agglomeration of Nps. The temperature is also one of the parameters that inuenced the DFeNps formation and its absorbance spectrum were shown
in Fig. 4(b). The yield of Nps observed was higher at 37 1 C. The formation of precipitation was slow at 25 C; also it conferred a low yield of Nps
due to a low reaction rate. The temperature increases above 37 1 C;
formation of precipitation decreased with increasing temperature,
owing to denaturing of extract. The different concentration ratios of
A. dubius leaf extract and FeCl3 (1:5, 2:5, 3:5, 4:5 and 5:5) were used in
the formation of Nps and its corresponding UVVis spectrum was
shown in Fig. 4(c). The immediate colour change was observed for all concentration ratios, but low yield of particles was obtained for the ratios 1:5,
2:5 and 3:5. The concentration ratios 4:5 and 5:5 conferred higher yield of
particles. The response time was changed from 15 to 120 min for attaining
higher yield of Nps. Fig. 4(d) absorbance spectrum showed that the
reaction time of 90 min was sufcient to get a higher yield of Nps and
also for a complete reaction. The optimized conditions obtained a
high yield of DFeNps at pH 6 with a concentration ratio 4:5 for
90 min at 37 1 C. The UVVis spectrum of extract and NaBH4 mediated Nps conrmed the formation of Fe by the absorbance peak at
214 nm for both methods as shown in Fig. 5. The broad absorption
spectrum of BFeNps may be due to its size and aggregation of
nanoparticles.

3.3. XRD analysis of synthesised Nps

The phase structure of synthesised FeNps was conrmed using XRD.
The XRD spectra of DFeNps and BFeNps are shown in Fig. 6. The 2
peaks at 45.7 and 53.35 were assigned to planes (111) and (200) of
iron. These peaks were matched to the standard XRD data of Fe
(JCPDS le No. 88-2324) and the formed Nps were cubic phase in structure. However, an additional peak at 26.8 and also a signicant noise in
DFeNps are possibly due to biomolecules merging with FeNps. The
identied diffraction peaks belonged to zero valent Iron (ZVI) Nps and
iron-oxohydroxide (FeOOH) [24]. The Braggs reections were observed
in the XRD pattern of BFeNps 2 peaks at 24.1 (012), 33.15 (104), 35.6
(110), 40.8 (113), 49.45 (024) and 54.05 (116); these diffraction
peaks match the standard XRD data for Fe2O3 (JCPDS le No. 33-0664)
[46]. It indicated that synthesised BFeNps were rhombohedral crystalline in structure.

3.4. FTIR analysis of synthesised nanoparticles

Fig. 3. The effect of extraction time on the percentage of antioxidant activity of 20 g leaves
per 100 mL at 50 C.

The interaction of aqueous leaf extract on the surface of Nps was

conrmed by FTIR characterizations. FTIR spectrum of aqueous leaf
extracts of A. dubius and DFeNps are shown in Fig. 7. The peak located
at 3250 cm1 may be due to the presence of amaranthine and phenolic
compound functional groups like NH or OH. The peak at 1634 cm1
revealed the presence of strong C_O stretching in the extract. IR peaks for
CC variable, not present in the symmetrical alkynes bond were observed
at around 2109 cm1. The peaks from 10501150 cm1, 776 cm1,
and 556 cm 1 were assigned to C\\O stretch, C\\Cl stretch and
\\CH\\stretch bond, respectively. The DFeNps synthesis by biomolecules, particularly those free from C\\O stretch, C\\Cl stretch and
\\CH\\ stretch. A. dubius leaf extract IR band of Nps showed peaks
for hydroxyl (3100 cm 1, 3250 cm 1 and 1500 cm 1). The disappearance of other groups indicates the formation of Nps. Ratul et al.
also reported the presence of many compounds with functional
groups (hydroxyl or imino) that can donate hydrogen atoms and
many free amino or carboxylic moieties capable of binding to free
Fe surface [45].

M. Harshiny et al. / Powder Technology 286 (2015) 744749

747

Fig. 4. UVvis absorbance spectra of DFeNps synthesis process conditions (a) effect of pH, (b) temperature, (c) concentration of ratio leaf extracts and FeCl3 and (d) time.

3.5. Morphology and particle size analysis of FeNps

The -potential value of DFeNps increased from 44 to 66 mV
and it assessed the good stability of the particles. The higher negative
value of -potential may be due to the capping of polyphenolic constituents present in the extract and also demonstrates the repulsion between
the particles which avoid the agglomeration of Nps. The -potential value
of BFeNps increased from 22 to 41 mV; this lower negative value was
due the agglomeration of Nps. The PSA was measured for DFeNps and
BFeNps size ranges from 43 to 220 nm and 70 to 700 nm, respectively
shown in Fig. 8. In addition, SEM image of DFeNps and BFeNps was
shown in Fig. 9 possessing a sphere-like morphology, less aggregation
and sizes that approximately range from 60 to 300 nm for DFeNps. The

Fig. 5. UVvis absorbance spectra of synthesised BFeNps and DFeNps.

analytical techniques PSA, SEM and -sizer of BFeNps conrmed the

nanoscale with good stability. The size distribution and agglomeration
of Nps was measured periodically using UVvis absorbance and PSA to
assess the stability of the Nps. The DFeNps UVvis spectrum does not
show any signicant changes in the absorbance band peak at 214 nm
even after months of incubation period. The PSA result showed DFeNps
and BFeNps size ranges varying from 58 to 530 nm and 105 to
2300 nm, respectively and also apparently depicts that biogenic synthesised DFeNps have less agglomeration than BFeNps even after 1 month.
It is known that biomolecules bind to the surface of iron nanoparticles
and signicantly increase their surface charge, and thus enhance their stability by inhibiting aggregation [17].

Fig. 6. XRD patterns of synthesised (a) DFeNps and (b) BFeNps.

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M. Harshiny et al. / Powder Technology 286 (2015) 744749

Fig. 7. FTIR spectra of A. dubius leaf extract and DFeNps.

concentrations 25, 50, 75 and 100 ppm of MO solution was studied on

the decolourization efciency with 20 mg of DFeNPs and BFeNps. Fig. 10
showed that the removal efciency was decreased with increasing initial
concentration of MO solution. This may be due to the non-availability of
adequate amount of hydroxyl radicals and also owing to the poor
penetration of UV light into the strong coloured MO solution. At high concentrations of a dye, the strong coloured solution would be less transparent to UV light and the dye molecules may possibly absorb a signicant
amount of UV light, causing less light to get to the catalyst and thus reducing the OH radical formation [47]. The Np loadings which varied from 10
to 25 mg were investigated at initial concentration MO of 20 ppm. Fig. 11
showed that increasing the Np concentration resulted in an increase of
colour removal efciency of MO. Decolourization occurred due to excited
surface electrons from the nanoparticles that are captured through
dissolved oxygen molecules on its surface and generate hydroxyl radical.
The created hydroxyl radicals further oxidize MO molecules [48]. The
colour removal efciency was observed at 90 and 81% using BFeNps and
DFeNPs, respectively under the experimental condition of 20 ppm MO
and 20 mg of Nps. The result shows that the removal efciency of BFeNps
was slightly higher than DFeNps which may due to the surface constituent of Nps [49].
The antioxidant potency estimation of DFeNPs and BFeNps has also
been carried out using DPHH assay. 100 g of the each nanoparticle
sample was transferred to a separate reaction vial, 150 L 1 mM DPPH
solutions were added to 3 mL ethanol to start the reaction. The mixture
was performed vigorously for the ne surface reaction between the Nps
and the DPPH reagent. The mixed solution was incubated at 37 1 C
for 30 min under dark condition. The result clearly depicted that DFeNps
and BFeNps conferred scavenging activities on DPPH radical with an inhibitory rate of 72 and 68%, respectively. The antioxidant activity of
BFeNps and DFeNps may be due to the shifting of the electron to be
found in oxygen to the odd electron located at surface orbits of oxygen
in OH and O 2 radicals [50]. The antioxidant activity of DFeNps
exhibited higher than BFeNps. This was due to the site of attachment
of the metals and its consequent impact on the activity of the antioxidant
agent [51].

Fig. 8. Size distributions of synthesised DFeNps and BFeNps measured by PSA.

4. Conclusions
3.6. Photocatalytic and antioxidant activity
The DFeNps and BFeNps catalytic activity was investigated by
monitoring the decolourization of MO dye using UV irradiation. 500 mL
of 20 ppm MO solution with 20 mg of Fe Nps was used for testing the
decolourization efciency and photocatalytic activity. The effect of initial

A. dubius leaf extract was used for synthesis of FeNps. The leaf
extraction process was optimized with the conditions of 20 g of
leaves boiled at 50 C for 45 min. The UVvis spectrum of the aqueous
extract showed the strong peak at 260 nm and FTIR spectrum also
conrmed the presence of peptide bonds, amine and a carboxylic group

Fig. 9. SEM micrographs of synthesised (a) DFeNps and (b) BFeNps.

M. Harshiny et al. / Powder Technology 286 (2015) 744749

749

References

Fig. 10. The effect of MO initial concentration on colour removal with 20 mg of NPs.

belongs to amaranthine, isoamaranthine and phenolic compounds. The

syntheses of Nps conditions were optimized. DFeNps seem to possess
different morphologies and structural characteristics to BFeNps. XRD
and SEM studies conrmed that DFeNps were cubic structure, and
roughly spherical in shape. The PSA, SEM and -sizer conrmed DFeNps
in nanoscale with less aggregation. The decolourization efciency and
antioxidant capacity were studied for DFeNps and BFeNps. The DFeNps
showed decolourization efciency of 81% against MO. DFeNps were
found to have a high antioxidant activity against DPPH than BFeNps.
This result indicates that A. dubius leaf extract synthesis is a better
alternative to toxic reducing agents used like NaBH4. The synthesis of
nanoparticles by A. dubius leaf extracts does not produce any other
toxic by-products. It can be suggested that green FeNps could be used
effectively in environmental applications and also to address future
biomedical concerns.

Acknowledgements
The authors sincerely acknowledge the nancial assistance from the
Department of Science and Technology (DST) (Pro.No.SB/FT/CS-047/
2012) and the Department of Biotechnology (DBT) Government of
India (RTGS No: BT/PR6080/GBD/27/503/2013).

Fig. 11. The effect of nanoparticle mass on colour removal with the concentration of
20 ppm of MO.

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