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Journal of
Copyright © 2014 American Scientific Publishers
Nanoscience and Nanotechnology
All rights reserved Vol. 14, 4437–4442, 2014
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Biosynthesis of CdS Nanoparticles in

Banana Peel Extract
Guang Ju Zhou1 , Shuo Hao Li1 , Yu Cang Zhang1 , and Yun Zhi Fu1
2
∗
1
Hainan University College of Materials and Chemical Engineering Hainan, Haikou 570228, China
2
Key Laboratory of Colloids and Surfaces, Chinese Academy of Sciences, Institute of Chemistry,
Beijing 100081, P. R. China

Cadmium sulfide (CdS) nanoparticles (NPs) were synthesized by using banana peel extract as a con-
venient, non-toxic, eco-friendly ‘green’ capping agent. Cadmium nitrate and sodium sulfide are main
reagents. A variety of CdS NPs are prepared through changing reaction conditions (banana extracts,
the amount of banana peel extract, solution pH, concentration and reactive temperature). The pre-
pared CdS colloid displays strong fluorescence spectrum. X-ray diffraction analysis demonstrates
the successful formation of CdS NPs. Fourier transform infra-red (FTIR) spectrogram indicates the
involvement of carboxyl, amine and hydroxyl groups in the formation of CdS NPs. Transmission elec-
tron microscope (TEM) result reveals that the average size of the NPs is around 1.48 nm.
Keywords: Banana Peel Extract, Cds Nps, Fluorescence Performance.
Delivered by Publishing Technology to: Chinese University of Hong Kong
IP: 74.119.71.124 On: Thu, 15 Oct 2015 18:58:32
Copyright: American Scientific Publishers
1. INTRODUCTION always involves poisonous and harmful chemicals which
During the past decades, CdS NPs are important semi- limit application of product in biosystem. The biosynthesis
conductor materials that have been studied extensively. of NPs can effectively decrease the damage of toxic sub-
The II–VI semiconductor CdS is well suited for nonlin- stances and make the product package in the plant pro-
ear optics,1 photovoltaics (PV),2
3 and photoelectrochem- tection solution. More importantly, they can be used in
4 biosystem due to their excellent biocompatibility. For this
ical (PEC) applications owing to its visible band gap
(∼ 490 nm) that aligns well for water-splitting and can reason, scientists pay more attention to developing biosyn-
be made using a variety of techniques including chemi- thetic route of NPs recently. For example, Murali et al.
5
6 7
8 reported the synthesis of gold and silver NPs by using
cal bath deposition, vapor–liquid–solid growth, and
electrochemical deposition (ECD). 9
10
CdS NPs have spe- emblica offcinalis fruit extract as reducing agent.15 Njagi
cial properties different from bulk phase material to single et al. used aqueous sorghum bran extracts to prepare iron
molecule. NPs surface effect can cause CdS NPs surface and silver NPs.16
atomic transport and configuration change. Besides, it also Banana peel is an abundant natural material and peo-
leads to surface electron spin conformation and electronic ple often discard it. The banana peel mainly is com-
energy spectrum change.11 The size quantization of CdS posed of pectin, cellulose and hemicellulose which can
NPs has important influences on optical, electrical, mag- act as protective agents for stabilizing NPs in water.17 For
netic, push chemical and nonlinear optical properties. So it example, gold, silver and palladium NPs were prepared
has extensive application prospects.12 in solution containing banana peel extract. To the best
CdS NPs with certain size and morphology can be of our knowledge, none report using banana peel extract
synthesized with several methods. Amutha et al. used to biosynthesize CdS NPs. Herein, we demonstrate that
microwave-combustion to achieve the synthesis of wurtzite banana extracts can serve as stabilizing agent to prepare
CdS NPs.13 Rajasekhar et al. prepared anisotropic CdS CdS NPs. Experimentally, S2− and Cd2+ ions were solu-
14
nanostructures via a single-source route. The most widely bilized in the micelles composed by organic substances in
used technology is colloidally chemical route which allows banana peel extract. The ionic reaction between above two
preparing various NPs. However, colloidally chemical route ions creates CdS NPs (Fig. 1). The organic substances of
banana peel extract absorb on NP surface and protect them
∗
Author to whom correspondence should be addressed. against aggregation. The NPs have been characterized by

J. Nanosci. Nanotechnol. 2014, Vol. 14, No. 6 1533-4880/2014/14/4437/006 doi:10.1166/jnn.2014.8259 4437

Biosynthesis of CdS Nanoparticles in Banana Peel Extract
S2–
Cd2+ CdS
S2–
Cd2+ Biological protectants
CdS particles
Figure 1. The schematic sketch of forming CdS NP.
using PL, UV-Vis, XRD, FTIR and TEM analysis. The
biosynthesized CdS NPs might have applications in bio-
chemical probes (cellular labels, DNA probes)18
19 due to
biocompatibility of product. Besides, because banana peel
extract is obtained easily, our method facilitates large-scale
production of biocompatible CdS NPs.
2. EXPERIMENTAL METHODS
2.1. Chemicals
Cadmium nitrate (Cd(NO3 2 · 4H2 O, AR), sodium sulfide
(Na2 S, AR), acetone were purchased from sigma aldrich.
All chemicals were used as received without further purifi-
cation. The banana was purchased from the fruit mar-
ket in Hainan. Deionized
Deliveredwater · cm) from to:white
(18.2 M Technology
by Publishing
Milli-Q academic water purification IP: 74.119.71.124 On: Thu,subjected
system (Millipore
Corp., Billerica, MA, USA) was usedCopyright:
in all cases.American Scientific the 60  C oven for 12 h and then a white powder
2.2. Banana Extracts Preparation
Banana stem, leaf and peel were collected and washed,
spread on filter paper, and finally sterilized with the ultra-
violet light for ten minutes. The obtained materials (100 g)
were crushed by a blender and then poured into the
beaker. After 200 mL water was added, the solution was

heated with microwave at 80 C for 90 s (the power is
about 57%20 ). The heat treated solution was cooled down
to room temperature and then filtered with a buchner fun-
nel. A light yellow filtrate was obtained and 4 g active
carbon was introduced to remove color. The solution was
subjected to another filtering to give a white solution.
In order to ensure the experiment comparability, the same
method was used to treat banana stem and leaf. The extract
was saved under 4  C environment for further use.
2.3. Synthesis of CdS NPs
In a typical synthesis, 2 mL Na2 S (0.01 M) aqueous solu-
tion and 1 mL banana peel extracted solution were mixed
in a clean and dry beaker, forming a solution A. 2 mL
Cd(NO3 2 (0.01 M) was added to 1 mL banana peel
extracted solution to give a homogenous solution B. The
solution B was poured into the solution under vigorous
magnetic stirring. After reaction for 5 min, the mixtures
turned to transparent yellowish. The prepared CdS colloid
4438
Zhou et al.
is very stable and no aggregates are observed within
30 days. 3 mL acetone was added to induce NP aggrega-
tion which was collected through centrifuge (15000 rpm,
15 min). The precipitation was dispersed in 1.5 mL solvent
(volume ratio of water and acetone is 1:1) and NPs was
re-precipitated again. The purification was repeated three
times and the resulted NPs were dried in oven (60  C) for
24 hours to obtain orange–yellow CdS NPs.
2.4. Characterization of CdS NPs
The CdS NPs were characterized with a UV-Vis spec-
trophotometer (TU-1901), fluorescence spectrophotometer
(970CRT). The TEM images of the NPs were acquired
with JEOL TEM-2010 instrument at an accelerating volt-
age of 200 KV. XRD powder diffractometer (D/MAX-IIIC
Physics Co.) was used for analysis (nickel filter copper
K-alpha radiations,  = 015418 nm). The 2 mode pri-
marily was in the 10∼80 (2) range and step-scan of
2 = 002 . The tube voltage was 40 kV, and the tube cur-
rent was 35 mA.
2.5. FTIR Analysis
In order to determine the main substances of the banana
peel extract which are possibly involved in the formation
of CdS NPs, FTIR analysis was carried out. For the sam-
ple preparation of FTIR, 5 mL acetone was added to 5 mL
Chinesebanana peel extract
University solution
of Hong Kongand the mixture was
15 Oct 2015to centrifuge.
18:58:32 The resulting precipitation was
dried in Publishers
formed. The banana peel extract powder was blended with
KBr to obtain a pellet. The FTIR spectra was recorded
at resolution of 4 cm−1 in the transmission mode through
using a shimadzu FTIR spectrophotometer (FTIR 8400).
A same procedure was used to prepare the FTIR sample
of the CdS NP powder except that NPs powder acted as
detected substances.
3. RESULTS AND DISCUSSION
3.1. Discussion of Influencing Factors
3.1.1. The Effect of Different Extracts
Experimentally, we carried out a set of studies in which
the effect of different extracts (banana peel, banana leaf,
banana stem) on NP colloid stability was investigated. The
results are showed in Figure 2. The sample 1, 2 and 3
are protected by banana peel, banana leaf and banana
stem respectively. In cases of samples 2 and 3, sediment
were observed. The sample 3 protected by banana stem
extract precipitated immediately and increasing the amount
of protective agents still could not improve NPs stabil-
ity, demonstrating that the banana stem has no protec-
tion effect. The colloid protected by banana leaf extract
only can keep stabilized for only a few minutes, indicat-
ing that its protection effect was not very well. The CdS
NPs protected by banana peel extract is bright yellow and
transparent. Besides, no precipitation or aggregation was
J. Nanosci. Nanotechnol. 14, 4437–4442, 2014
Zhou et al.
Figure 2. The effect of banana peel, leaf and stem on NPs stability:
(1) banana peel; (2) banana leaf; (3) banana stem.
observed. The observation demonstrates that the protective
effect of banana peel extract was remarkable. The possible
reasons are that the banana peel contains a large number
of big biomolecules and strong viscosity which can protect
the produced CdS NPs against aggregation. Highly stable
NPs are very important to further application and therefore
the main investigations were focused on the NPs protected
by banana peel extract.
3.1.2. The Effect of Banana Peel Extract Amount
Different CdS NPs were prepared through changing the
amount of banana peel extract (the volume ratio of extract
solution and NPs precursor solution:
Delivered 1:2; 1:1.5;Technology
by Publishing 1:1; 1.5:1; to:(5∼6),
2:1). In five cases, there were noIP:any
74.119.71.124
precipitationsOn:
andThu,observations
Copyright:
solutions are bright yellow. They remained American Scientific
unchanged
within two days, confirming their excellent stability. Their
fluorescence properties were also investigated. With the
increasing of banana peel extract solution, the fluores-
cence intensity of CdS NPs gradually descend due to
size effect and defects of CdS (Fig. 3). Size and defect
change with the amount of the banana peel extract could be
explained dynamically because it can largely influence the
Figure 3. The CdS florescence intensity as function of the amount of
protective agents.
J. Nanosci. Nanotechnol. 14, 4437–4442, 2014
Biosynthesis of CdS Nanoparticles in Banana Peel Extract
Table I. The effect of pH on CdS fluorescence intensity.
pH 3∼4 5∼6 7∼8 9∼10
Color Pale yellow Yellow–green Bright–yellow Orange–yellow
sediment
Wavelength 4896 4896 4896 –
Fluorescence 225483 257873 948933 –
intensity
nucleation and growth rate of CdS NPs. When the amount
of banana peel extracts increase, they can form complex
with Cd2+ and S2− ions. This reduces the collision rate
between Cd2+ and S2+ . Therefore, nucleation rate of CdS
NPs becomes slow and the crystal nucleus number of CdS
decreases, producing low concentration of CdS NPs col-
loid. As a result, the florescence intensity reduces. Other-
wise, reducing the amount of banana peel extract promotes
the nucleation of CdS NPs and favors the formation of
high concentration of CdS NPs colloid.
3.1.3. The Effect of pH
We also carried out the preparations of CdS NPs in which
the solution pH were adjusted (see Table I). Precipita-
tion was observed when the solution pH was adjusted to
9∼10. If the growing solution had 7∼8 pH, the fluores-
cence intensity of prepared CdS NPs colloid was very
strong. However, in case of acidic (3∼4) or weakly acidic
Chinese
the University
fluorescence of intensity
Hong Kong was very weak. Above
15 Oct 2015 18:58:32 that weak alkaline (pH is 7∼8)
demonstrates
favors thePublishers
formation of high concentration of CdS NPs.
The fluorescence intensity difference of products pre-
pared in different pH solutions was attributed to the effect
of H+ and OH− on the growth kinetics of CdS NPs.
As presented by Eqs. (1) and (2), there are two reaction
equilibriums in our system. During the reaction, the ion
reaction between Cd2+ and S2− is very fast and the for-
mation rate of CdS mainly depends on mass transfer rate
and the direction of hydrolyze equilibrium. When the pH
decreases, the equilibrium (1) shifts to left. Meanwhile, the
concentration of Cd2+ increases, the equilibrium (2) shifts
to right, and the density of S2− decreases. If the solution
pH increases, the equilibrium (1) shifts to right and the
concentration of Cd2+ decreases. Besides, increasing pH
also can shift the equilibrium (2) to left and increase the
concentration of S2− . According to above discussion, too
high and low solution pH decreases the concentration of
Cd2+ and S2+ respectively, which do not facilitate the for-
mation of high concentration of CdS NPs at high yield.
Therefore, in later preparations, the solution pH was kept
at 7∼8. In our experiment, because Na2 S solution is alka-
line (pH 7∼8), there was no need to adjust the pH. It can
prevent the banana peel against the damage from strong
acid or alkali chemicals.
Cd2+ + H2 O = CdOH+ + H+ (1)
S2− + H2 O = HS− + OH− (2)
4439
Biosynthesis of CdS Nanoparticles in Banana Peel Extract
Figure 4. The effect of reaction temperature on NPs fluorescence inten-
sity: (1) adding CdNO3 to Na2 S; (2) adding Na2 S to CdNO3 .
3.1.4. The Effect of Reactive Temperature
We also investigated the effect of reactive temperature
(4  C, 25  C and 50  C) on CdS NPs and results are
shown in Figure 4. In low temperature (curve 1 in 4  C),
the CdS colloid has lowest fluorescence intensity (curve
1 in Fig. 4). When reaction temperature was increased to
25  C or 50  C, the prepared CdS colloids had the same
fluorescence intensityDelivered byFig.
(curve 1 in Publishing Technology to:emission
4). The fluorescence
intensity difference is attributed IP: 74.119.71.124
to the On: Thu,position
effect of tempera-
ture on the reaction kinetics. In case Copyright: American Scientific Publishers
of high temperature,
2+ 2−
the motion of Cd and S is accelerated and therefore
their collision frequency increases, promoting the forma-
tion of high concentration of CdS NPs and causing high
fluorescence intensity. The products prepared at 25  C or
50  C have the same fluorescence intensity which also
demonstrates that temperature-based fluorescence intensity
modification only can be achieved at lower than 25  C.
In order to achieve synthesizing high fluorescence inten-
sity CdS NPs at low temperature, our preparations mostly
proceeded at 25  C. We also changes the programs of the
preparation in which the adding order of agents is different
and found that the adding order has no effect on the prod-
uct (Curves 1 and 2 in Fig. 4). In both cases, the generated
CdS colloids were transparent bright yellow and have the
same fluorescence intensity.
3.1.5. The Effect of Reactant Concentration
The concentration of Cd(NO3 2 and Na2 S can affect the
growth kinetics of CdS NPs. A set of experiments were
carried out to investigate the effect of the concentration
of precursor (Cd(NO3 2 and Na2 S). The volume of solu-
tion was kept unchanged and various concentrations of
precursors (0.1 M, 0.05 M, 0.01 M, 0.001 M) were tested.
The prepared samples were diluted 100 times and then
their fluorescence intensities were measured (Table II). The
Table II shows that the high concentration of precursors
4440
Zhou et al.
Table II. The effect of reactant’s concentration.
Density 0.1 M 0.05 M 0.01 M 0.001 M
Color Orange–yellow Orange–yellow Bright–yellow Yellow–green
sediment sediment
Wavelength – – 4898 4898
Fluorescence – – 93448 12899
intensity
(0.1 M and 0.05 M) causes the formation of orange–
yellow precipitation and no dispersed CdS NPs colloid
were observed. In cases of 0.01 M and 0.001 M, well dis-
persed colloids formed. Dynamically, high concentration
of precursor causes fast growth rate of CdS NPs and favors
the formation of large amount of CdS NPs. For this rea-
son, the distance among NPs becomes small and the Van
der Waals force among NPs is enhanced, facilitating the
precipitation. Otherwise, the low concentration of precur-
sor (0.01 M and 0.001 M) favors the slow growth rate of
CdS NPs and therefore dispersed colloid formed. The flu-
orescence intensity of prepared samples also confirms this
result. For example, when the concentrations of precur-
sor were 0.01 M and 0.001 M, the fluorescence intensities
were 934.48 and 128.99 respectively.
3.2. CdS NPs Characterization
NPs fluorescence emission mainly includes excitation
Chineseand University of Hong Kong
defect emission. Excitation emission peak
15 Oct 2015
usually18:58:32
is close to the used exciting laser wave-
length and defect emission has broad and big stokes
displacement. Nanosized crystal CdS has two characteris-
tic absorption peaks at 520∼570 nm (defect emission) and
410∼490 nm (excitation emission). Figure 5 is the fluores-
cence emission spectrum of CdS NPs colloid. An intense
emission peak at 489.8 nm was present when exciting light
wavelength was 485 nm. This emission is belong to exci-
tation emission. However, the defect emission at 550 nm
was not observed possibly due to the interaction between
Figure 5. Fluorescence emission spectroscopy of CdS NPs.
J. Nanosci. Nanotechnol. 14, 4437–4442, 2014
Zhou et al.
Figure 6. The UV-Vis spectra of CdS NPs (the area marked by the
dotted line is the absorption band).
the formed CdS NPs and water molecule. This is the char-
acteristic fluorescence emission spectroscopy of CdS NPs,
confirming that the CdS colloid was nanosized.
UV-Vis spectrum is often used to study the effect of
particle size on optical property of CdS materials. It is
well known that the UV-Vis absorption peak of CdS bulk
materials is about 520 nm.21 In case of CdS NPs with size
less than 10 nm, the quantum size effect can be observed
clearly because the band gap of material becomes broader.
Delivered by Publishing Technology to: Chinese University of Hong Kong
The quantum size effect always IP: causes the blue shift of
74.119.71.124 On: Thu,to15beOctexcellent stabilizing effect.27
28 The conclusion is
UV-Vis absorption. We used UV-Vis absorption
Copyright:toAmerican
investi- Scientific
gate the prepared NPs and result is shown in Figure 6. The
UV-Vis absorption of prepared CdS NPs is at a broad band
ranging from 425 to 475 nm. Compared with the bulk CdS
materials, the sample UV-Vis absorption has clear blue
shift due to its quantum size effect, demonstrating that the
CdS NPs have small diameter.
In order to determine the key functional group of banana
peel extract in the synthesis of CdS NPs, FTIR analysis
was performed. The spectrum of banana peel extract has a
Figure 7. FTIR spectra of CdS NPs (A) and banana peel extract (B).
J. Nanosci. Nanotechnol. 14, 4437–4442, 2014
Biosynthesis of CdS Nanoparticles in Banana Peel Extract
number of peaks which reflect its complex nature (Fig. 7).
The spectra show that there was a shift in the follow-
ing peaks: 3396–3448 cm−1 , 2934–2925 cm−1 , 1743–1741
cm−1 , 1615–1627 cm−1 and 1405–1401 cm−1 . The peak t
around 3396 cm−1 is attributed to –OH or N H stretching
vibrations. The peak shift from 3396 to 3448 cm−1 impli-
cates that these groups were involved in the formation of
CdS NPs possibly. The peak at 2934 cm−1 can be assigned
to –CH3 symmetric stretching vibration or –CH2 stretch-
ing vibration. The peak shift from 2934 to 2925 cm−1
suggests the saturated C H bonding was involved. The
1743 cm−1 peak is related with C O stretching of car-
boxyl. At 1615 cm−1 , a peak was observed and it was due
to C N bending or C C and C O stretching vibra-
tion. It was implied by the peak shift (from 1743 to
1741 cm−1 ; from 1615 to 1627 cm−1  that carboxyl, ben-
zene or amino groups of the banana peel extract might
play important roles in growth and stabilization of CdS
NPs. The vibration shift around 1405–1401 cm−1 suggests
aliphatic and aromatic (C–H) plane deformation vibrations
of methyl, methylene and methoxy groups in the CdS NPs
growth. In comparison with previous reports,22–25 the stabi-
lizing effect might be due to carboxyl, hydroxyl and amide
groups of banana peel extract in our system. As stated by
other group,26 banana peel is mainly composed of pectin,
cellulose and hemicellulose. Those substances contain lots
of NH and COOH groups which have been demonstrated
2015 18:58:32
consistentPublishers
with Bankar’s report in which siver, gold, pal-
ladium NPs were protected with banana peel.29–31
For X-ray diffraction analysis, the diffraction result
was showed as Figure 8. In the diffraction spectrum, the
main peaks corresponding 2 theta values are 27.17, 44.18,
52.26. According to bragg diffraction formula (2d sin =
k
k = 089 and  = 0154056 nm in our experiment),
the corresponding interplanar spacings of diffraction peak
Figure 8. CdS NPs X-ray diffraction mapping.
4441
Biosynthesis of CdS Nanoparticles in Banana Peel Extract
Figure 9. TEM image of CdS NPs. The inset is the high resolution
TEM image.
are 0.323 nm, 0.202 nm and 0.171 nm which could be
assigned to the crystal faces (111), (220) and (311) respec-
tively. The diffraction pattern of our products is consistent
with standard PDF card of CdS (JCPDS No. 10-0454).
Figure 8 also shows that the half-peak width of prepared
NPs is very broad, demonstrating that the synthesized CdS
NPs size is small. According to Debye-Scherrer formula
d = k/ cos  estimation,  = 00950 nm, the particles
average diameter is about 1.477 nm. The TEM image
(Fig. 9) shows that the well dispersed CdS NPs gathered
into wire-like nanostructures. Most of the NPs are spheri-
cal and average size is about 1.48 nm. This result agrees
Delivered by Publishing Technology to:17.
well with XRD analysis. Above IP: result demonstratesOn:
74.119.71.124 thatThu, 15T.Oct
the extract solution of banana peel Copyright:
has excellent effect Scientific
American
on stabilizing CdS and allows preparing well dispersed
CdS NPs.
4. CONCLUSIONS
We report a facile and versatile bioapproach to synthe-
size CdS NPs in which the banana peel extract was
used as stabilizer and no other organic agents were used.
The modification of conditions (pH, reaction temperature,
the amount of banana peel extract) allows controlling the
NPs size, stability and fluorescence properties. Banana has
rich resource in the south of china and the banana peel
was always discarded as waste. Therefore, our method is
friendly to environment and low cost. There are many
reports about using fruit to synthesize NPs, indicating that
the ‘green’ synthesis route is very interesting due to its low
cost preparation and friendly environment feature. More-
over, the prepared NPs can be directly used in biosystem
because of their excellent biocompatibility.
Acknowledgment: This work was supported by Hainan
province natural science foundation of china (211009),
4442
Zhou et al.
the National Natural Science Foundation of China
(51263006/E031301).
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Received: 12 April 2013. Accepted: 7 June 2013.
J. Nanosci. Nanotechnol. 14, 4437–4442, 2014