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Ceramics International ] (]]]]) ]]]]]]
www.elsevier.com/locate/ceramint
Abstract
The use of natural polymers in the synthesis of nanomaterials can have a low cost and eco-friendly approach. In this work we would like to
report the green chemistry synthesis of ZnO nanopowders (ZnO-NPs) using gelatin. Spherical ZnO-NPs were synthesized at different
calcination temperatures and eld emission scanning electron microscopy (FESEM) imaging showed the formation of most of nanopowders in
nanoscale. The powder X-ray diffraction (PXRD) analysis revealed wurtzite hexagonal ZnO with preferential orientation at (101) reection plane.
In vitro cytotoxicity studies on neuro2A cells, a dose dependent toxicity with non-toxic effect of concentration below 2 mg/mL was shown. The
synthesis of ZnO-NPs in gelatinous media were found to be comparable to those obtained from the conventional reduction methods using
hazardous polymers or surfactants which can be an excellent alternative for the synthesis of ZnO-NPs using biomaterials.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.09.032
Please cite this article as: M. Darroudi, et al., Green chemistry approach for the synthesis of ZnO nanopowders and their cytotoxic effects, Ceramics
International (2013), http://dx.doi.org/10.1016/j.ceramint.2013.09.032
2 M. Darroudi et al. / Ceramics International ] (]]]]) ]]]]]]
interesting materials in synthesis of nanomaterials because they seeded at a density of 1 104 cells per well in 96-well plates
are biodegradable and bioabsorbable with degradation pro- and incubated for 24 h. Thereafter, the cells were treated with
ducts that are non-toxic [2729]. Gelatin (GL) is a natural various concentrations of nanoparticles in the presence of 10%
biopolymer extracted from the partial hydrolysis of collagen FBS. The calcined ZnO-NPs at 600 1C was suspended in a
which has good biocompatibility and biodegradability, as it stock solution at 5 g/mL in a solution of dimethyl sulfoxide
has been widely used in wound dressings, drug carriers, and (DMSO)/double distilled water. After 24 h of incubation, 20 l
tissue scaffolds in recent years [30]. In this study, we of 5 mg/mL MTT in the PBS buffer was added to each well,
demonstrate a solgel method using GL to synthesize ZnO- and the cells were further incubated for 4 h at 37 1C. The
NPs. Zinc nitrate was used as the zinc source at different medium containing unreacted dye was discarded, and 100 l of
calcination temperatures. The synthesized samples were then DMSO was added to dissolve the formazan crystal formed by
characterized using FESEM, XRD, TGA/DTA, FT-IR, and live cells. Optical absorbance was measured at 590 nm
UVvis spectroscopy. The majority of this research has (reference wavelength 630 nm) using a microplate reader
investigated synthesis of nanoparticles in natural protein (Statfax-2100, Awareness Technology, USA), and cell viabi-
media, proving that this method is eco-friendly, low cost, lity was expressed as a percent relative to untreated control
and can consequently be used as an economic and valuable cells. Values of metabolic activity are presented as mean 7 SD
alternative for the large-scale production of metal and metal of triplicates.
oxide nanoparticles.
3. Results and discussion
2. Materials and methods
This section reports the results of synthesized ZnO-NPs in
2.1. Materials and reagents gelatinous media. In this study, we attempted the fabrication of
ZnO-NPs using the solgel method and GL as a green
All the materials used were of analytical grade and were stabilizer. The extensive number of hydroxyl and amine groups
used without any purication. Zinc nitrate was purchased from present in GL molecular structure can facilitate the complexa-
Merck (Germany). Gelatin (GL, type B) was purchased from tion of zinc cations (Zn2 ) to an initial molecular matrix. This
Sigma-Aldrich (USA). All glassware used in the laboratory structure enables GL to coat and stabilize zinc species and
experiments were cleaned with a fresh solution of HNO3/HCl nally ZnO-NPs while inhibiting their excessive aggregation
(3:1, v/v), washed thoroughly with doubly distilled water, and or crystal growth. As shown in Fig. 1, the color of solgel
dried before use. Double distilled water was used in all derived ZnO-NPs due to the increased calcination temperature
experiments. changed from black to white.
The thermogravimetric and derivative analysis (TGA/DTA)
2.2. Synthesis of ZnO-NPs curves of the as-prepared gel by the solgel method in a GL
environment are presented in Fig. 2. The heating process was
To prepare 1.5 g of ZnO-NPs, 4.5 g of Zn(NO3)2d6H2O started at 20 1C, and then increased up to 490 1C with a
was dissolved in 10 mL of distilled water and then stirred for temperature rate change of 10 1C/min. The TGA curve
30 min. Meanwhile, 0.2 g of GL was dissolved in 40 mL of descends until it becomes horizontal around 490 1C, and about
distilled water and stirred for 10 min at 40 1C to achieve a clear 77% weight loss was observed during the heating process. The
GL solution. After that, the zinc nitrate solution was added to TGA/DTA traces show three main regions. The rst weight
the GL solution, and the container was moved to an oil bath. loss between 20 and 175 1C (17%) is an initial loss of water,
The temperature of the oil bath was xed at 60 1C. Stirring was bend Ed1. The second weight loss from 175 1C to 185 1C
continued for 12 h to obtain a light brown color resin. The nal (45%) is attributed to the decomposition of chemically bound
product was then divided to four parts and calcined at different groups, which corresponds to bend Ed2. The third step from
temperatures (400, 500, 600 and 700 1C) in air for 1 h to 185 to 490 1C (15%) is related to the formation of the
obtain ZnO-NPs. pyrochlore phases and decomposition of the pyrochlore phases
and the formation of ZnO pure phases indicated by bend Ed3.
2.3. Characterization of ZnO-NPs
Please cite this article as: M. Darroudi, et al., Green chemistry approach for the synthesis of ZnO nanopowders and their cytotoxic effects, Ceramics
International (2013), http://dx.doi.org/10.1016/j.ceramint.2013.09.032
M. Darroudi et al. / Ceramics International ] (]]]]) ]]]]]] 3
Fig. 2. The TGA/DTA curves of initial gel from 20 1C to 950 1C. It shows Fig. 4. UVvis spectrum and band gap estimation (inset) of prepared ZnO-NPs
about 77% loss weight in three steps to achieve ZnO-NPs. at 600 1C.
No weight loss between 490 and 950 1C was detected on the the samples in this study, a broad absorption band was
TGA curve, which indicates the formation of nanocrystalline observed at around 398 cm 1. The band at 398 cm 1 corre-
ZnO as the decomposition product. Compare to our previous sponds to the E2 mode of hexagonal ZnO (Raman active) [33].
works, the pure phase is obtained at lower temperature [17,19]. There was also an absorption band at around 1114 cm 1 is
Fig. 3 shows the FTIR spectra of the ZnO-NPs calcined at related to CO and therefore can be neglected.
400 and 600 1C. For the FTIR spectra of the calcined samples The room temperature UVvis absorption spectrum of the
a series of absorption peaks from 1000 to 4000 cm 1 can be ZnO-NPs is shown in Fig. 4. The ZnO-NPs were dispersed in
found, which correspond to the carboxylate and hydroxyl water with concentration of 0.1 wt% and then the solution was
impurities in the sample. More specically, the broad band at used to perform the UVvis measurement. The spectrum
3394 cm 1 was assigned to the OH stretching mode of the reveals a characteristic absorption peak of ZnO at wavelength
hydroxyl group. The peaks observed at 1633, 1531, 1404, and of 374 nm which can be assigned to the intrinsic band-gap
871 cm 1 are due to the asymmetrical and symmetrical absorption of ZnO due to the electron transitions from the
stretching of the zinc carboxylate [32]. As shown in the FTIR valence band to the conduction band (O2p-Zn3d) [19,34].
traces, the spectral signatures of carboxylate impurities dis- In addition, this sharp peak shows that the particles are in
appear as the calcination temperature increases (600 1C). This nano-size, and the particle size distribution is narrow. It is
indicates the possibility of zinc carboxylate dissociation and clearly shown that the maximum peak in the absorbance
conversion to ZnO during the calcination process. For both of spectrum does not correspond to the true optical band gap of
Please cite this article as: M. Darroudi, et al., Green chemistry approach for the synthesis of ZnO nanopowders and their cytotoxic effects, Ceramics
International (2013), http://dx.doi.org/10.1016/j.ceramint.2013.09.032
4 M. Darroudi et al. / Ceramics International ] (]]]]) ]]]]]]
Fig. 7. Cell viability of neuro2A cells measured by the MTT assay. Cells were
incubated for 24 h with the indicated concentrations of the nanoparticles.
4. Conclusion
Please cite this article as: M. Darroudi, et al., Green chemistry approach for the synthesis of ZnO nanopowders and their cytotoxic effects, Ceramics
International (2013), http://dx.doi.org/10.1016/j.ceramint.2013.09.032
M. Darroudi et al. / Ceramics International ] (]]]]) ]]]]]] 5
Please cite this article as: M. Darroudi, et al., Green chemistry approach for the synthesis of ZnO nanopowders and their cytotoxic effects, Ceramics
International (2013), http://dx.doi.org/10.1016/j.ceramint.2013.09.032