Synthesis of Gold Nanoparticles Using Fruit Waste
Hitesh Rajput1,2, Abhitosh Kedia1, a, Dimple Shah2, Krupali
Dobariya1, Aashi Naik1
1Department of Physics, Uka Tarsadia University, Bardoli,
Surat-394350, Gujarat, India
2Applied Physics Department, SVNIT, Surat, Gujarat, India.
a)[email protected] ; Tel: +91 8780357578
Abstract: In the present work we have utilized fruit extracts
(pomegranate, jack fruit) as an alternative, effectual, low-cost
and environment friendly green synthesis method to produce
well-defined geometries of gold nanoparticles at room temperature
(30 °C) having unique structural corelated optical property. The
phytochemicals present in the aqueous leaf or fruit extract acted
as a reducing agent and stabilization is also achieved with other
organic molecules. The generated AuNPs and were characterized by
Transmission electron microscopy (TEM), UV-Visible spectroscopy,
dynamic light scattering (DLS) and Zeta potential. Selected
electron area diffraction (SEAD) pattern showed the particles to be
crystalline in nature, with a face-centered cubic (fcc) structure.
The morphology and average size of particles were analyzed by TEM
measurements and DLS.
Keywords: Green synthesis, Metal nanoparticles, antibacterial
activities, TEM.
INTRODUCTION:
Notable growth in this upcoming technology has opened novel
elemental and applied frontiers, from the synthesis of nanoscale
materials to exploit their unique physicochemical properties in a
variety of areas such as health care, cosmetics, agriculture,
optics, biomedical science, chemical industries, electronic, space
industries, drug delivery, energy science, optoelectronics,
catalysis, and nonlinear optical devices [1,2].
In the size range of 1nm-100nm, the physical, chemical and
biological properties of the nanoparticles changes in essential
ways from the properties of both specific atoms/molecules and of
the corresponding bulk materials [2,3]. One of the important
aspects in the field of nanotechnology is the development of a more
consistent process for the synthesis of nano materials with wide
range of tunability in size and chemical composition. Strict
control over size, shape, and crystalline structure has inspired
the application of nanotechnology to numerous fields including
catalysis, medicine, and electronics, plasmonics, photonics, SPR,
SERS etc [4-6].
Physical approaches are much more expensive and most of chemical
approaches use some toxic substances, such as reducing agents
(sodium borohydrate) and further complication arises from the use
of potentially toxic surface capping agents such as (cetyl
tri-methyl ammonium bromide/chloride, tri-n-octylphosphineoxide)
during the process of particle formation and stabilization [7,8].
Currently there is a need to significantly reduce or completely
eliminate the use of toxic and environmentally damaging materials
in the synthesis of nanoparticles specially for their biological
applications. In the context of global efforts to minimize
dangerous waste, the continuously increasing demand of
nanomaterials ought to be accompanied by green synthesis methods.
Developing green chemistry-based techniques via biological systems
such plants, bacteria, fungus and similar organisms offer a
reliable and eco-friendly processes for the green synthesis of
nanoparticles [9,10].
Compared with other biogenic sources the use of plant or fruit
extracts for the synthesis of nanoparticles is relatively
straightforward where the biomolecules (phytochemicals) present in
plant extracts can act as both reducing agents and stabilizing
agents during the synthesis of nanoparticles [11,12]. The main
phytochemicals involved are terpenoids, carboxylic acids, flavones,
ketones, amides and aldehydes [13]. Flavones, organic acid, and
quinones are water-soluble phytochemicals that are responsible for
the immediate reduction of the ions.
The Gold nanoparticles have been found remarkable applications
in high sensitivity biomolecular detection, biolabeling, catalyst
in chemical reactions, antimicrobials and antibacterial materials
[14-16]. However, there is still need for economic commercially
viable as well as environmentally clean synthesis route to
synthesize the gold nanoparticles.
Below table 1 provides the list of gold nanoparticles
synthesized using various plant extract/organic waste.
TABLE 1: Green synthesis of gold nanoparticles by different
researchers using plant extracts:
Plants
Size(nm)
Types
Shape
References
Xanthium Strumarium
9.60-11.70
Leaves
Spherical
[15]
Ziziphus
-
Leaves
-
[16]
Mulberry
15-53
Leaves
Spherical
[17]
Garcinia mangostana
32.96±5.25
Fruit
Mostly spherical and some hexagonal and some triangular
[18]
Alternanthera sessilis
20-40
Leaves
Spherical
[19]
Studies have shown that source of the fruit extract can
significantly influence the formation of metal nanoparticles
[15-19]. This arises from different extracts having different
concentrations and combinations of biomolecules. Because of the
number of different biomolecules involved, the biological
reduction, formation and growth of nanoparticles is quite a complex
process [20]. Moreover, it is difficult to control over the
monodispersed morphology due to presence of various
biomolecules.
In our present work we have utilized punica granatum and
Artocarpus heterophyllus (fruit waste) as source of biomolecules at
room temperature for the synthesis of gold nanoparticles. UV-Vis
spectra is recorded indicates the formation of nanoparticles. The
size, shape and crystallinity of the prepared gold nanoparticles
were studied using transmission electron microscopy (TEM). The
formed nanoparticles are quite stable for the months and can be
used for biological applications.
MATERIALS AND METHOD:
Materials For Gold Nanoparticles:
Punica granatum and Artocarpus heterophyllus peel were collected
from Sardar Patel fruit market, Surat, India, Hydrochloauric acid
(HAuCl4.3H2O) was purchased from Sigma- Aldrich Chemicals.
Preparation Of The Extract:
Punica granatum and Artocarpus heterophyllus were individually
collected and washed several times with water to remove any debris
and dust particle and then sun dried to remove the lingering
moisture and grinded to form powder. 5g of fine powder along with
100 ml of millipore water was sonicated (40 KHz) for 20 min.
Further, the extract was filtered with Whatman no.1 filter paper
and stored at for further experiments.
Green Synthesis Gold Nanoparticles:
1 mM of HAuCl4.3H2O was added to 15 ml above prepared peel
extract separately at room temperature under stirring. The color
change of the reaction mixture indicated the formation of AuNps in
the reaction mixture further confirmed UV-Vis spectra of the
resulting colloidal solution of gold.
The solution thus obtained was centrifuged thrice at 8000 rpm
and washed with water and stored for further characterizations.
Characterizations Method:
Optical absorption measurements were carried out in all our
as-prepared nanoparticle solution samples in the wavelength range
of 300-1100nm using Thermo Scientific absorption spectrophotometer.
TEM samples were prepared by drying the threefold centrifuged
samples in water on carbon formvar coated copper grids and the
images were acquired using FE-Technai G2 system operated at an
accelerating voltage of 300kV. Particle surface charge and particle
size analysis carried out using Malvern Zetasizer (Nano-ZS 90). All
measurements were done at room temperature, unless otherwise
specified.
RESULT AND DISCUSSION:
Reduction of gold ions into gold nanoparticles from fruit waste
extracts was observed as a result of the color change. The
reduction of the metal ions occurring rapidly got complete within 2
hrs after addition of the metal ions to the fruit extract.
FIGURE 1 UV- Vis spectra of formed Gold nanoparticles in a)
Punica Granatum and b) Artocarpus heterophyllus over a period of
time indicating formation of stable nanostructures.
Single surface plasmon band centered, around 580 nm is clearly
visible in Punica Granatum (Fig. 1a) whereas the broad bands for
Artocarpus heterophyllus were observed in the range of 550-590 nm
as shown in Fig. 1b which is a foremost essential character of the
geometrical metal nanostructures. Single but little broad peak
(near to Guassian) in Punica Granatum indicated monodisperse
anisotropic nanoparticles but deviation form spherical geometry was
not high further in confirmation with the TEM images (Figure
2i).
Calculating the size distribution of nanoparticles from TEM
micrographs, we got the average size of around 50 to 70 nm in case
of Au nanoparticles obtained in Punica Granatum whereas quasi
spherical Au nanoparticles yet polydisperse in size (average size
22 nm) were obtained in Artocarpus heterophyllus (Fig. 2ii).
FIGURE 2: TEM images of formed Gold nanoparticles in 2i) Punica
Granatum and 2ii) Artocarpus heterophyllus along with size
distribution plot.
The size measured by the TEM analysis was in agreement with that
measured by DLS implying particle were well distributed in solution
and were stable. Average size obtained by DLS was 70 nm and 20 nm
in the case of Punica Granatum and Artocarpus heterophyllus
respectively (Figure 3).
FIGURE 3: DLS spectra of formed Gold nanoparticles in a) Punica
Granatum (with average size of 70 nm) and b) Artocarpus
heterophyllus (with average size of 20nm).
The metal particles were observed to be stable in solution even
after 6 months of their synthesis as seen from Fig. 1a & 1b. By
stability, we mean that there was no observable variation in the
optical properties of the nanoparticles solutions with time.
Further Zeta potential also provided key indication of the
stability of colloidal dispersions. Here, Figure 4a & 4b
illustrated the zeta potential of the biosynthesized AuNPs giving
sharp peak at -21.3 mV and -30.3 mV in Punica Granatum and
Artocarpus heterophyllus respectively. The negative value of zeta
potential confirmed that the surface of the NPs was negatively
charged in the dispersed medium and the repulsion among the
particles make them stable.
FIGURE 4: Zeta potential of Gold nanoparticles in a) Punica
Granatum and b) Artocarpus heterophyllus confirming stable
negatively charged nanoparticles.
From the selected area electron diffraction (SAED) pattern, we
also found the structural information of the particles (Figure 5).
Generally, by calculating the diameter of the different rings [21],
we got their respective d-spacing by using the formula:
(diameter/2) (mm, divided by 2 for 2 spot): (1/d1) (1/nm) = (mm,
the rule bare length): (1/nm).
FIGURE 5: Calculating the diameter of the different rings as
obtained from SEAD pattern in a) Punica Granatum b) Artocarpus
heterophyllus in order to obtain d- spacing.
By using this formula, we got d-spacing d1, d2 and d3 as shown
in table 2. Comparing this data to JCPDS standard data file
number-00-004-0784), we got crystalline planes (111), (220), (400)
and (200) respectively, and therefore we can conclude that AuNPs
have face centered cubic structure.
TABLE 2: d spacing calculated from above formula matches with
JCPDS standard data file number 00-004-0784 of Au indicating
crystalline FCC structure.
d1(nm)
hkl
d2(nm)
hkl
d3(nm)
hkl
Punica Granatum
1.0194
(400)
1.4423
(220)
2.3537
(111)
Artocarpus heterophyllus
1.4406
(220)
2.0426
(200)
2.3560
(111)
CONCLUSION:
In summary, the green synthesis method is eco-friendly, of low
cost and capable of producing AuNPs at room temperature. Herein,
Punica Granatum and Artocarpus heterophyllus extracts act as both
reducing and stabilizing agents in the formation of Au NPs. The
UV–Vis spectral studies confirmed the formation as well as
stability of formed Au NPs. The average particle size was
calculated by TEM along with DLS analysis and found to be 50-70 nm
and 15-25 nm respectively in Punica Granatum and Artocarpus
heterophyllus. Further bright spots obtained in SAED pattern
confirms the oriented crystallinity and FCC structure of the
as-formed gold nanostructures.
ACKNOWLEDGEMENTS:
Authors authors are grateful to Uka Tarsadia University for
materials characterization facilities and funding through
RPS-UTU/RPS/1262/2018
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