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Journal of Industrial and Engineering Chemistry 20 (2014) 44734481

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry


journal homepage: www.elsevier.com/locate/jiec

One step green synthesis of hexagonal silver nanoparticles and


their biological activity
Samy M. Shaban a,*, Ismail Aiad a, Mohamed M. El-Sukkary a, E.A. Soliman b,
Moshira Y. El-Awady a
a
b

Petrochemical Department, Egyptian Petroleum Research Institute, Egypt


Faculty of Science, Ain Shams University, Cairo, Egypt

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).

of AgNPs using Sun light as reducing agent with assistance of the


used cationic surfactants in reduction process. The used surfactants
act as stabilizing agent for the synthesized AgNPs. AgNPs with
hexagonal shapes and others with spherical shapes were prepared in
short reaction time 5 min as maximum depending on the used
capping agents without using complicated systems and any other
intermediate steps.
2. Materials and methods
2.1. Chemicals
Silver nitrate (AgNO3, 99%), were provided from Sigma
Aldrich/Germany. The used cationic surfactants were prepared
according to reference [17]. All glassware was washed in a mixture
of distilled water and non-ionic detergent, followed by rinsing with
distilled water and ethanol for many times to get rid of any
remnants of non-ionic detergent then dried prior to use.
2.2. Synthesis
2.2.1. Preparation of cationic capping agents
The used cationic capping agents were reported [17].
The chemical structure of prepared capping agents showed in
Scheme 1.

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

Scheme 1. the chemical structure of prepared cationic capping agents.

2.2.2. Preparation of silver nanoparticles (AgNPs)


In situ, facile and green synthesis of silver nanoparticles was
prepared using sun light as reducing agent with assistance of
prepared surfactants [18].
In a typical experiment, 10 mL of 2 mM aqueous solution of
AgNO3 were mixed with 10 mL of 2 mM aqueous solution of
prepared cationic surfactants then the solution was irradiated with
sun light. It was noticed a very fast change in the color of the
solution to different colors like yellows with its different ranges in
a time of 5 min maximum depending on the used capping agents as
shown in Scheme 2.
2.3. Characterization techniques of silver nanoparticles
The formation of silver nanoparticles was conrmed by the
following instrumentations:
2.3.1. Transmission electron microscope (TEM)
A convenient way to produce good TEM samples is to use
copper grids. A copper grid pre-covered with a very thin
amorphous carbon lm. To investigate the prepared AgNPs using
TEM, small droplets of the liquid were placed on the carbon-coated
grid. A photographic plate of the transmission electron microscopy
employed on the present work to investigate the microstructure of
the prepared samples. Nanoparticle size was determined by using
TEM model Jeol JeM 2100 (Japan) (Egyptian Petroleum
Research Institute EPRI).
2.3.2. UVvisible spectroscopy
The photosynthesis of Ag nanoparticles was monitored periodically by a UVvisible spectrophotometer (Shimadzu, UV-2550,

[(Schem_2)TD$FIG]

Japan). For the analysis, 5 mL of 2 mM aqueous solution of silver


nitrate were mixed with 5 mL of 2 mM of the used cationic
surfactant then it irradiated by sun light, until color change, then the
sample was put in a cuvette for measurement.
2.3.3. Dynamic light scattering (DLS)
The hydrodynamic diameter and zeta potential of the same
solution which used in TEM, UVvis and EDX, was characterized
by dynamic light scattering (DLS) using a Malvern Zetasizer
Nano (Malvern Instruments Ltd., Worcestershire, UK). Each
DLS measurement was run in triplicate using automated,
optimal measurement time and laser attenuation settings. The
recorded correlation functions and measured particles mobilitys
were converted into size distributions and zeta potentials,
respectively, using the Malvern Dispersion Software (V5.10,
http://www.zetasizer.com/).
2.3.4. Energy dispersive X-ray (EDX) spectroscopy
The energy-dispersive X-ray (EDX) spectroscopy was recorded
with an EDX detector (Oxford LINKISIS 300) equipped on a
Transmission electron microscope (TEM, Hitachi S-520) operated
at 10 kV accelerating voltage.
2.3.5. Fourier transform infrared spectrometer (FTIR)
FT-IR spectra was recorded using the obtained solid cationic
surfactants capped silver nanoparticle after centrifugation and
washings to remove the unassociated organic molecules. Spectra
was recorded on an ATI Mattson Innity Series TM, Bench top 961
controlled by win rst TM V2.01 software (Egyptian Petroleum
Research Institute EPRI).

Scheme 2. In situ photo preparation of silver nanoparticles.

[(Fig._1)TD$IG]

S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481

4475

2.4. Biological activity


2.4.1. Biological activity against a wide range of bacteria and fungi
The antimicrobial activity of synthesized cationic surfactants
and their silver nanoform was measured against a wide range of
tested organisms comprising: (bacteria and fungi)
1. Source of microorganisms:
The different species of tested organisms were obtained from
the unit of operation development center, Egyptian petroleum
research institute.
2. The media
The following media used in the antimicrobial activity of
synthesized products, the bacterial species grow on nutrient
agar, while fungi mold grow on Czapeks dox agar.
(a) Nutrient agar
Nutrient agar consists of beef extract (3.0 g/l); peptone
(5.0 g/l), sodium chloride (3.0 g/l) and agar (20.0 g/l), then,
complete the volume to one liter, heated the mixture until the
boiling, and sterilize the media by autoclave.
(b) Czapeks Dox agar
Czapeks Dox agar consists of sucrose (20.0 g/l), sodium
nitrate (2.0 g/l), magnesium sulfate (0.5 g/l), potassium Chloride (0.5 g/l), ferrous sulfate (0.01 g/l) and agar (20.0 g/l), then,
complete the volume to one liter, heated the mixture until the
boiling, and sterilize the media by autoclave.
(c) Microorganisms
The used microorganisms were Gram-positive bacteria
(Bacillus pumilus and Micrococcus luteus), Gram-negative
bacteria (Pseudomonas aeuroginosa and Sarcina lutea) and
Fungi (Candida albicans and Penicillium chrysogenum).
An assay was made to determine the ability of an antibiotic to
kill or inhibit the growth of living microorganisms, the technique
that used is lter-paper disk-agar diffusion (Kirby-Bauer) [19].
1. Inoculate ask of melted agar medium with the organism to be
tested.
2. Pour this inoculated medium into a Petri dish.
3. After the agar has solidied, a multilobed disk that impregnated
with different antibiotics laid on top of agar.
4. The antibiotic in each lobe of disk diffuses into medium and if
the organism is sensitive to a particular antibiotic, no growth
occur in a large zone surrounding that lobe (clear zone).
5. The diameters of inhibition zones were measured after 2448 h
at 3537 8C (for bacteria) and 34 days at 2527 8C (for yeast
and fungi) of incubation at 28 8C.
6. Measure each clear zone and compare between them to
determine the antibiotic, which is more inhibitor.

3. Results and discussions


Aqueous solution of AgNO3 was reduced under exposure to sun
light as a gratis source of reducing agent with assistance of
prepared cationic surfactants. This technique is simple and
inexpensive without any surplus material. It was found that in
the presence of prepared cationic surfactants, an aqueous solution
of AgNO3 was reduced and color of solution was changed to
different colors like yellows with its different range, depending on
the used capping agent in a few minutes as 5 min maximum, as
indicated in Fig. 1 and shown in Scheme 2 .The color changes
implied the occurrence of Ag+ reduction to AgNPs [20]. In a control
experiment, when the sample (aqueous solution of silver nitrate
with capping agent) was stored in a vial wrapped with aluminum

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

The solvated electrons and H. atoms are strong reducing agents: E0


0
+
(H2 O=e
aqu ) = 2.87 V (SHE) and E (H /H) = 2.3 V (SHE) and can
reduce Ag+ ions to neutral Ag0 atoms:

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

3.2. Conrmation of silver nanoparticle formation


Stable silver nanoparticles were prepared. The shape and size
distribution were characterized using TEM, SAED, UV, DLS, EDX
and FTIR techniques as following
3.2.1. Transmission electron microscope (TEM) and selected area
electron diffraction (SAED)
The morphology of prepared silver nanoparticles (AgNPs) were
investigated by transmission electron microscope (TEM) Fig. 2 and
the selected area electron diffraction pattern (SAED) Fig. 3.
TEM photographs indicate that the nanosilver solution consist
of well dispersed agglomerates of spherical and cubic shapes
nanoparticles depending on the hydrophobic chain length of the
used capping agents. In this agglomeration, the formed nanoparticles are not fused, i.e. each particle keep a distance from
surrounding other particles and these distance increase by
increasing chain length, and this was conrmed also by zeta
potential values indicated in Table 2.
Fig. 2 shows TEM morphology of prepared silver nanoparticles
capped with C10Dim, C12Dim and C16Dim. AgNPs capped by
C10Dim have spherical shape some particles have hexagonal
shape, AgNPs capped by C12Dim have hexagonal shape while
AgNPs capped by C16Dim have spherical shape. We note also by
increasing the alkyl chain length of prepared capping agent the
dispersion between particles increase (aggregation decrease)
which conrmed by zeta potential values indicated in Table 2.
The selected area electron diffraction pattern of capped AgNPs
(SAED) is shown in Fig. 3. Where when the electron diffraction is
carried out on a limited number of crystals one observes some
spots of diffraction distributed on concentric circles [26], indicating that the prepared silver nanoparticles are polycrystalline [27].

3.2.2. UVvis spectroscopy


UVvis spectroscopy is quite sensitive to the formation of silver
nanoparticles due to surface plasmon excitation [28].
Fig. 4 shows absorption spectra of AgNPs capped by prepared
surfactants, which show absorption band at lmax 418, 412 and
420 nm for C10Dim, C12Dim and C16Dim, respectively which an
indication on formation silver nanoparticles, due to surface
plasmon resonance of colloidal silver nanoparticles [29,30]. Band
at lmax range from 290 to 306 nm characteristic for the used
capping agents, which matches with the band appeared for
aqueous solution of the used capping agents alone. It is known that
the amount and size of Ag nanoparticles are positively related with
the adsorption peak intensity and the lmax on the UVvis spectra
[3134], respectively.
From Fig. 4, there are increasing in the intensity (absorbance), of
the bands at lmax range from 412 to 420 nm with increasing
hydrophobic chain length of the used capping agent, which give
indication on increasing formation percent of silver nanoparticles.
For example, C10Dim, C12Dim and C16Dim have lmax at 418, 412
and 420 nm respectively with absorbance intensity 0.49, 0.79 and
0.89 respectively.
Fig. 4 shows very small shift in value of lmax of prepared silver
nanoparticles by increasing hydrophobic chain length of capping
agent, which indicate that the in situ photo-reduction using sun
light as reducing agent in the presence of the used capping agent,
give similar size distribution.
3.2.3. Dynamic light scattering (DLS)
Dynamic light scattering technique (DLS) was performed to
understand the size distribution of silver nanoparticles capped by
prepared cationic surfactants and their stability by zeta potential
values.

[(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

4477

Fig. 3. SAED image of prepared silver nanoparticles capped by (A) (C10Dim), (B) (C12Dim) and (C) (C16Dim).

Particle size distribution of silver nanoparticles in aqueous


solution of capping agents are listed in Table 1 and shown in Fig. 5.
which indicate that the in situ photo-reduction using sun light as
reducing agent in the presence of capping agent, give similar size
distribution, these results matches with data obtained from UVvis
spectroscopy as shown in Fig. 4.
Stability of nanoparticles is crucially important for many
applications and can be determined using zeta potential measurements [35]. Zeta potential is the net surface charge of the
nanoparticles when they are inside a solution. The fact that

[(Fig._4)TD$IG]

particles push each other and their agglomeration behavior


depends on large negative or positive zeta potential. The zeta
potential playing an important role limits in the stability of
solutions is +30 mV or 30 mV. To regard the particles as stable,
zeta potential should be either higher than +30 mV or lower than
30 mV [36].
By inspection data in Table 2, it was found that the zeta
potential values of prepared silver nanoparticle encapsulated by
the prepared cationic surfactants are greater than +30 mV, which
be indication on high stability of prepared silver nanoparticles
against agglomeration. High value of zeta potential indicate that
the surface charge on nano-silver is high so the electrostatic
repulsion between particles increase, keeping particles without
agglomeration and stable for long time. The acquired positive
charge of zeta potential is mainly due to the used capping agent is
cationic surfactant (carry positive charge) [37], while zeta
potential of silver nanoparticle prepared without using capping
agent and after irradiation to sun light for 1 month was 0.386 mV.
Also we found that zeta potential values of prepared silver
nanoparticles are positively related with hydrophobic chain length
of added capping agents, where by increase chain length of capping

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.

AgNPs capped by C10Dim


AgNPs capped by C12 Dim
AgNPs capped by C16Dim

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.

agent, zeta potential increase, which be indication on increasing


stability of prepared silver nanoparticle against agglomeration for
example zeta potential of prepared silver nanoparticle capped by
C10Dim, C12 Dim and C16 Dim are 34.1  10.4, 48.9  9.9 and
52  10.7 respectively.
3.2.4. Energy dispersive X-ray (EDX)
EDX spectroscopy results conrmed the signicant presence of
pure 100% silver with no other contaminants. The optical
absorption peak at 3 keV, is typical for the absorption of metallic
silver nanocrystallites due to surface plasmon resonance [38].
Fig. 6 shows the EDX analysis of the AgNPs capped by the
prepared cationic surfactants. The EDX spectrum showed a strong
and typical optical absorption peak at approximately 3 keV, which
was attributed to the SPR of the metallic Ag nanocrystals [38]. This
result indicated that AgNPs were formed in the reaction medium.
Beside of Ag there are others bands for C, O and Br elements peaks
which appeared due to the scattering caused by the compounds that
are bound to the surface of silver which indicating that the used
cationic surfactants act as capping agents for silver nanoparticles.

Table 2
Zeta Potential and conductivity of prepared silver nanoparticle by dynamic light
Scattering (DLS).
Capping agent

Zeta
potential (mV)

Conductivity
(mS/cm)

No capping and irradiation for 1 month


AgNPs Capped by C10Dim
AgNPs Capped by C12Dim
AgNPs Capped by C16Dim

0.386
34.1  10.4
48.9  9.95
52  10.7

1.64
0.183
0.169
0.152

3.2.5. FT-IR spectroscopy


FT-IR spectroscopy is used in order to understand the role of
prepared capping agent in the formation of silver nanoparticles
and the chemical environment of the nal product. In Fig. 7, all
bands around 2926, 2853, 1500 and 1642 cm1 indicating the
presence of capping agent with the nanoparticles. Bands at 2926
and 2853 cm1 corresponds to asymmetric and symmetric CH
stretching of alkyl chain of C12Dim. Band at 1642 cm1
correspond to Schiff base group (C5
5N). On comparing IR
bands of silver nanoparticles capped by surfactants in Fig. 7 with
IR bands of surfactant alone in Fig. 8, we notes that some bands
maxima are little blue shifted and some bands are also little red
shifted. These relatively small shifts are mostly due to the
constraint of the capping molecular motion, which presumably
resulted from the attachment on the nanoparticles surface [39].
Also we note increasing in the intensity of the band around
1375 cm1 by 5080% than band of capping agents alone, which
indicate presence co-ordination bond between CH2 of hydrophobic chain length of capping agent and silver nanoparticles
surface. This co-ordination bond enhance role of capping agents
chain lengths in shaping, sizing and distribution as indicated by
both transmission electron microscope, UVvis spectroscopy
and dynamic light scattering.
3.3. Evaluation of the synthesized surfactants as antibacterial and
antifungal
We evaluated the prepared cationic surfactants and their
capped form with silver nanoparticles as biocide against some
pathogenic Gram-positive (B. pumilus and M. luteus) and Gramnegative (P. aeuroginosa and S. lutea) bacteria and also, some

[(Fig._6)TD$IG]

S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481

4479

Fig. 6. EDX silver nanoparticles capped by prepared surfactants: (A) is C10Dim, (B) is C12Dim and (C) is C16Dim.

[(Fig._7)TD$IG]

pathogenic fungi (C. albicans and P. chrysogenum). The aim of the


formation silver nanoparticles capped by cationic compounds is to
increase their potency against microorganisms.
The results of antimicrobial activity are recorded in Table 3,
indicating that the synthesized compounds have antimicrobial
activity rang from a moderate to slight high effect on Gramnegative bacteria and from slight high to high on Gram- positive
bacteria and very high effect on fungi compared to the drug
reference used.
The biological activities of surfactants often show a non-linear
dependence on their chain length, where bactericides and
fungicide activity increase by increasing hydrophobic chain length

[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. 7. FTIR spectrum C12Dim capped silver nanoparticle.

[(Fig._8)TD$IG]

S.M. Shaban et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 44734481

4480

Fig. 8. IR spectrum of N-(3-((3,4-dimethoxybenzylidene)amino)propyl)-N,N-dimethyldodecan-1-ammonium (C12Dim).

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

solubility, they proposed that as the alkyl chain increases, lipid


solubility increases at a rate faster than the change in partition
coefcient (lipid/aqueous) theory. At these higher chain length,
partitioning is limited, making the concentration at the site of
action insufcient to have a signicant effect on the membrane of
the cell wall [46] and hence according to this theory the activity of
compounds should be ordered as follow C10? C12 ? C16 chain due
to increase lipid solubility from C10 to C16.
Other accounts attribute this cut-off to a decrease in perturbation of the membrane at higher chain lengths, proposing that the
longer alkyl chain molecules better mimic molecules in the lipid
bilayer, causing less of a disruption in the membrane [47].
Other theory based on critical micelle concentration (CMC), as
surfactants chain length increase, their tendency toward micelle
formation is greater, noted by the lower CMCs at higher chain
lengths. This tendency to form micelles becomes greater than the
tendency to move toward the interface (the membrane), and thus
the concentration at the action site becomes decreased, also, as the
size of the diffusing species increases from the size of a monomer
to that of micelles, their diffusibility and permeation abilities will
decrease, affecting their action on the microbial cell wall and hence
according to this theory the activity of compounds should be
ordered as follow C10? C12 ? C16.
Other theory based on surface and thermodynamic properties
surfactants which showed tendency of prepared compound

toward adsorption at the interfaces which facilitate their role of


adsorption at the bacterial cell membrane, where increasing
DGoads enhances the higher adsorptivity of prepared compound,
from previous thermodynamic results DGoads increase by increasing chain length [17], and hence according to this theory the
activity of compounds should be ordered as follow C16 ? C12 ? C10
chain.
From that we can conclude that factors effects on cut-off point
of homologous series of surfactants varying in chain length, are
solubility, critical micelle concentration, (CMC), size of diffusing
species and change in free energy of adsorption. Magnitude of
these factors determines when cut-off occurs, according to data in
Table 3, the cut-off was observed with surfactants with chain
length (C16) for all prepared compounds.
It was observed from data in Table 3, that biological activity
(inhibition zone) of silver nanoparticle in capsulated with prepared
cationic surfactants higher than corresponding prepared cationic
surfactant, this can be attributed to silver nanoparticle alone has
biological activity, so prepared surfactant capped silver nanoparticles have higher activity, this can be attributed to the higher
surface area of prepared nanoparticles and the acquired positive
charge of prepared silver nanoparticles (as indicated in zeta
potential values in Table 2) in addition positive charge of cationic
surfactants, where these positive charge facilitate adsorption at
negative cell wall membrane of bacteria.

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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