One Step Green Synthesis of Hexagonal Silver Nanoparticles and Their Biological Activity
One Step Green Synthesis of Hexagonal Silver Nanoparticles and Their Biological Activity
One Step Green Synthesis of Hexagonal Silver Nanoparticles and Their Biological Activity
A R T I C L E I N F O
Article history:
Received 19 January 2014
Accepted 6 February 2014
Available online 14 February 2014
Keywords:
Photosynthesis
Hexaonal shapes
Zetapotential
Biological activity
A B S T R A C T
Hexagonal and spherical silver nanoparticles were prepared by in situ and green synthesis using sun
light as reducing agent with assistance newly prepared cationic surfactant which act also as capping
agents. The silver nanoparticles formation was investigated using UVvis spectrophotometer,
transmission electron microscope (TEM), dynamic light scattering (DLS), energy dispersive X-ray
(EDX) and FTIR. The results showed formation uniform, well arrangement hexagonal and spherical
shapes. Increasing hydrophobic chain length increase the stability and amount of AgNPS. Both prepared
surfactants and surfactants capping silver nanoparticles showed high antimicrobial activity against
Gram-positive and Gram-negative bacteria.
2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.
1. Introduction
Nanotechnology is a eld of applied science, focused on the
design, synthesis, characterization and application of materials
and devices on the Nano scale, many techniques of synthesizing
silver nanoparticles (AgNPs) have been investigated. Some of them
are chemical reduction [1], electrochemical [2], photochemical
reduction [3], microwave [4] microemulsion [5,6] and UVirradiation [7], and. Nowadays special focus on green chemistry
by researchers because of increasing awareness about the
environment. Utilization of nontoxic chemicals, environmentally
benign solvents and renewable materials are some of the key
issues that merit important consideration in a green synthesis
strategy [8,9]. Silver nano-particles have attracted considerable
attention because of their potential applications in various elds
such as environmental friendly antimicrobial coatings [10],
oxidative catalysis [11], nano electronics (single-electron transistors, electrical connects) [12], conductive coatings [13], biosensors
[14,15], antibacterial activity [16].
The aim of the present work is to develop a simple and effective
one-pot green approach toward the rapid synthesis and stabilization
* Corresponding author. Tel.: +20 127 679 2188; fax: +20 222 747 433.
E-mail address: samyshaban@yahoo.com (S.M. Shaban).
http://dx.doi.org/10.1016/j.jiec.2014.02.019
1226-086X/ 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
[(Schem_1)TD$FIG]
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S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481
[(Schem_2)TD$FIG]
[(Fig._1)TD$IG]
S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481
4475
Fig. 1. Colors(For interpretation of the references to color in this gure legend, the
reader is referred to the web version of the article.) of prepared colloidal silver
nanoparticles with different capping agents.
foil to exclude light, the solution did not change color or form any
solid precipitate over longer period. When the silver nitrate
solution exposed to sun light without capping agent, after long
time exceed 2 months we notes very slight change in color with
very small precipitate on wall of glass vial.
3.1. Formation mechanism of silver nanoparticles
For the synthesis of AgNPs, the generally accepted mechanism
suggests a two-step process, i.e. atom formation and then
polymerization of the atoms. In the rst step, a portion of metal
ions in a solution reduced by a suitable reducing agent. The atoms
thus produced act as nucleation centers and catalyze the reduction
of the remaining metal ions present in the bulk solution.
Subsequently, the atoms coalesce leading to the formation of
metal clusters. The process stabilized by the interaction with the
prepared capping agent so preventing further coalescence and
aggregation [21,22].
When aqueous solutions subject to sun light irradiation (gradiolysis), it produces the following species [23]:
H2 O ! e
aqu ;
H 3 O ;
H2 ; H; OH;
H 2 O2
0
Ag e
aqu ! Ag
The reduction of Ag+ ions is the main process for the formation of
nanoparticles under g-radiolysis. So both oxidizing OH radicals
and H produced in radiolysis of water should be scavenged and it
can be done efciently by capping agents to produce H2O, H2 and
organic radical.
Since the electrochemical potential of the organic radical is
more positive than that of the Ag+/Ag0 system [24], reaction of
organic radical obtained from capping agent with Ag+ ions is
relatively slow. Thus, during the process of irradiation, Ag+ ions are
primarily reduced by solvated electrons and give rise to Ag0. The
growth of silver nanoparticles by reduction of Ag+ to Ag0 is
stepwise [25]. These neutral Ag0 atoms at rst dimerize when they
encounter or associate with the excess Ag+ ions trapped in the
individual loops of capping agent.
From the above results, we can conclude that sun light act as
reducing agent in the presence of prepared cationic surfactants,
theses surfactants facilitating and increasing rate of silver
nanoparticles formation in addition their role as capping agent.
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S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481
[(Fig._2)TD$IG]
Fig. 2. TEM image of prepared silver nanoparticle capped by (A) (C10Dim), (B) (C12Dim) and (C) (C16Dim).
[(Fig._3)TD$IG]
S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481
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Fig. 3. SAED image of prepared silver nanoparticles capped by (A) (C10Dim), (B) (C12Dim) and (C) (C16Dim).
[(Fig._4)TD$IG]
Table 1
Size distribution of prepared silver nanoparticles using prepared capping agents.
Capping agent
Distribution range
Maximum
distribution range
Size
Number (%)
Size (nm)
Number (%)
97
98.3
97.2
1538
2138
2144
92.2
87.4
91.6
(nm)
Fig. 4. UV spectra of prepared silver nanoparticles using C10Bn, C12Bn and C16Bn as
capping agent.
1550
1850
1850
[(Fig._5)TD$IG]
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S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481
Fig. 5. Size distribution of silver nanoparticles using prepared capping agents determined by DLS.
Table 2
Zeta Potential and conductivity of prepared silver nanoparticle by dynamic light
Scattering (DLS).
Capping agent
Zeta
potential (mV)
Conductivity
(mS/cm)
0.386
34.1 10.4
48.9 9.95
52 10.7
1.64
0.183
0.169
0.152
[(Fig._6)TD$IG]
S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481
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Fig. 6. EDX silver nanoparticles capped by prepared surfactants: (A) is C10Dim, (B) is C12Dim and (C) is C16Dim.
[(Fig._7)TD$IG]
[40], in our work the optimal alkyl chain length has been noted to
be twelve carbon atoms, which has the maximum inhibition zone
where compounds with twelve carbon chain higher than these
with ten carbon atoms chain which higher than these of sixteen
carbon atoms. These results are agreement with results obtained
before [4044], this behavior known by cut-off effect which
observed for the rst time more than 70 years ago, in which the
activity increases progressively in a homologous series of
compounds, with increasing chain length up to a critical point,
beyond which the activity decreases [45].
Several theories have been postulated as to why this cut-off
effect occurs, rst have associated this cutoff with a limit in
[(Fig._8)TD$IG]
S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481
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Table 3
Antimicrobial activity of synthesized surfactants and their nano form against pathogenic bacteria and fungi.
Inhibition zone diameter (mm)
Pseudomonas aeuroginosa
Sarcina lutea
Bacillus pumilus
Micrococcus luteus
Candida albicans
Penicillium chrysogenum
Erythromycin
30
44
32
32
Metronidazole
27
25
C10Dim
C12Dim
C16Dim
AgNPs capped by C10Dim
AgNPs capped by C12Dim
AgNPs capped by C16Dim
13
16
15
16
17
16
29
37
24
29
38
26
17
18
16
23
24
17
22
31
22
25
32
22
24
28
23
27
36
24
17
19
16
25
29
25
S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481
4. Conclusion
From the obtained results, we can conclude:
In situ, facile and green synthesis of silver nano particles were
developed using sun light as reducing agent with assistance of
prepared surfactants.
The prepared surfactants act as capping agents (DLS, EDX and
FTIR).
Increasing hydrophobic chain length of the capping agents, the
stability of prepared AgNPs increase.
Increasing hydrophobic chain length of the capping agents, the
amount of AgNPs increase (Increasing absorbance in UVvis
spectra).
Hexagonal AgNPs were prepared.
The silver nanoparticles increase the biological activity of the
capping agents.
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