Antipyrine cationic surfactants capping silver nanoparticles as potent antimicrobial agents against pathogenic bacteria and fungi

Article abstract of DOI:10.1016/j.molliq.2017.08.072

Development of effective anti-microbial agents has been hindered by the emergence of bacterial strains with multi-drug resistance. In this article, we report an efficient synthesis of silver nanoparticle (AgNP) by capping with a synthetic cationic surfact

Full text of DOI:10.1016/j.molliq.2017.08.072

Journal of Molecular Liquids 243 (2017) 572–583
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Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Antipyrine cationic surfactants capping silver nanoparticles as potent
antimicrobial agents against pathogenic bacteria and fungi
I. Aiad a, Magda I. Marzouk b, Soheir A. Shaker b, Nagwa E. Ebrahim c, Ali A. Abd-Elaal a, Salah M. Tawfik a,
⁎
a
Department of Petrochemicals, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
Department of Chemistry, Faculty of Science, Ain Shams University, Cairo, Egypt
b
c
Environmental Affairs Agency, Cairo, Egypt
a r t i c l e i n f o
a b s t r a c t
Article history:
Development of effective anti-microbial agents has been hindered by the emergence of bacterial strains with
multi-drug resistance. In this article, we report an efficient synthesis of silver nanoparticle (AgNP) by capping
with a synthetic cationic surfactants-based antipyrine. The synthesized antipyrine cationic surfactants were char-
acterized by FT-IR and 1H NMR and their AgNPs were also delineated by TEM, DLS and UV–vis techniques. These
AgNPs-capped cationic surfactants have average particle size of ~15–30 nm. These surfactants could self-assem-
ble to form micelles in an aqueous medium and the critical micelle concentration (CMC) values as well as the sur-
face parameters were determined at 20, 40 and 60 °C. The synthesized antipyrine cationic surfactants and their
AgNPs were tested against growth of both Gram positive (Bacillus subtilis and Staphyl. aureus) and Gram negative
(Pseudomonas aeruginosa and E. coli.) bacterial strains as well as fungi (Candida albicans and Aspergillus niger). It
was found that the AgNPs significantly enhanced the antimicrobial activities of the synthesized antipyrine cation-
ic surfactants. A strong structure-activity relationship was observed as a function of AgNPs functionality; provid-
ing guidance to activity prediction and rational design of effective antimicrobial nanoparticles. We propose that
the antipyrine cationic surfactants-capped AgNPs can have potential bio-medical application against pathogenic
bacteria.
Received 29 March 2017
Received in revised form 9 June 2017
Accepted 18 August 2017
Available online 24 August 2017
Keywords:
Silver nanoparticles
Antipyrine cationic surfactants
CMC
Antimicrobial
E. coli.
Structure-activity
© 2017 Elsevier B.V. All rights reserved.
1. Introduction
features, NPs have been conjugated with known antibiotics to combat
bacteria. The antibiotic moleculescan be infused with NPs via non cova-
Infection diseases induced by pathogenic bacteria continue to be one
of the greatest health problems worldwide. There has been constant de-
crease in effectiveness of antibiotics mainly due to unregulated use of
antibiotics, leading to the development of multi-drug-resistant bacterial
strains [1,2]. Additionally, the significant and continuous decrease in the
number of approved antibiotics in the past decade has contributed to
the increasingly threatening situation [3] that has resulted in an urgent
need for the discovery of novel antibacterials and treatment strategies
[4]. There are a number of actively pursued strategies, including
searching for new antimicrobials from natural products, modification
of existing antibiotic classes, and the development of antimicrobial sur-
factants [5]. Nanoparticles (NPs) provide versatile platforms for thera-
peutic applications based on their physical properties [6,7]. For
example, NP size range is commensurate with biomolecular and bacte-
rial cellular systems, providing additional interactions to small molecule
antibiotics [8]. The high surface to volume ratio allows incorporation of
abundant functional ligands, enabling multivalencyon NP surface to en-
hance interactions to target bacteria. Utilizing these characteristic
lent interactions [9]or incorporated on NPs via covalent bonds [10,11].
Both methods have been reported for enhanced activity against bacte-
ria. The improved performance is proposed to result from polyvalent ef-
fect of concentrated antibiotics on the NP surface as well as enhanced
internalization of antibiotics by NPs. Yet the dependence on existing an-
tibiotics in these approaches may not be able to delay the onset of ac-
quired resistance. The capping surfactants on NP surface can provide
direct multivalent interactions to biological molecules, allowing NPs to
be exploited as self-therapeutic agents [12–14].
In-spite of the fact, that silver has been utilized from time immemo-
rial. In current years, it has been employed more extensively for numer-
ous biomedical [15], and industrial [16] applications as it shows
fantastic antimicrobial properties against an extensive variety of bacte-
ria and fungi [17]. It is known that silver ions accomplish noteworthy
decreases in microbial growth at very low concentrations, and despite
the fact that the mechanism that causes this impact have not been total-
ly illustrated yet, some researchers have attributed the cytotoxicity of
silver to a few conceivable mechanisms, including the production of a
lot of free radicals affecting high oxidative stress, the disturbance of
cell layer integrity, or protein or DNA binding and damage to genetic
material [18,19]. Recently, the biocidal properties of silver compounds
⁎
Corresponding author.
E-mail address: salahtwfk85@yahoo.com (S.M. Tawfik).
http://dx.doi.org/10.1016/j.molliq.2017.08.072
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I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
573
have been upgraded through nanotechnology by means silver nanopar-
ticles (AgNPs) which has allowed the size of AgNPs to be modularly and
accurately reproduced in order to improve the stability of the colloidal
emulsions as well as a controlled release of the AgNPs, obtaining a
long-term antimicrobial activity and reducing unwished potential ef-
fects, among others [20,21].
2.2.2. Synthesis of antipyrine cationic Schiff bases surfactant (APB8,
APB12&APB16) and (APC8, APC12&APC16)
The antipyrine cationic Schiff bases surfactant were synthesized ac-
cording to the following strategy. Typically, The synthesized Schiff
bases (APB and APC) (5 mmol) were refluxed separately in presence
of 5 mmol of the alkylbromide (octyl, dodecyl and hexadecyl bromide)
individually in 50 mL of ethanol as a solvent and few drops of pipiredine
as a catalyst for 24 h. After the reaction was completed, the reaction so-
lution was concentrated to 5 mL. The residue was poured into 200 mL of
absolute diethyl ether under stirring and then filtered. The precipitate
was filtered, washed with absolute diethyl ether and dried to give
APB8 (yield 82%), APB12 (yield 83.5%), APB16 (yield 89.5%), APC8
(yield 88%), APC12 (yield 91.5%), and APC16 (yield 92.3%) (Scheme 1).
Schiff bases of 4-aminoantipyrine are known for their variety of ap-
plications in the area of catalysis [22,23], clinical applications [24], and
pharmacology [25]. New kinds of chemo-therapeutic agents containing
Schiff bases have gained significant attention among biochemists and of
those aminopyrines are commonly administered intravenously to de-
tect liver disease in clinical treatment. The most spectacular advances
in medicinal chemistry have been made when heterocyclic compounds
played an important role in regulating biological activities. Heterocyclic
moieties can be found in a large number of compounds which display
biological activity. Antipyrine (N-heterocyclic compound) and its deriv-
atives exhibit a wide range of biological activities and applications [26–
27]. Antipyrine is a marker in the study of transfer and bio transforma-
tions of drugs in the human body [28] antipyrine metabolites are report-
ed to show a positive correlation with plasma fibronectin level in
monitoring patients with chronic liver illness (HBC, HCV and alcohol-re-
lated disease) [29]. Quaternary ammonium salts compound display an-
timicrobial activity against gram positive and negative bacteria, yeast
and fungi. Most of quaternary ammonium salts have positive nitrogen
atoms in their chemical structure. Nitrogen atom is hetero atom and
carrier positive charge which lead to enhance the antimicrobial activity
[30]. Several works deal with the synthesis of different cationic surfac-
tant compounds and studied the relationship between surface activity
and antimicrobial activity against wide strain of pathogenic bacteria,
fungi and yeast [31–33]. In this work, we synthesized a series of antipy-
rine Schiff base cationic surfactants and their silver nanoparticles
(AgNPs) as an antimicrobial agent. The structure-activity relationship
of the synthesized surfactants capped AgNPs revealed that antimicrobial
properties can be tailored through surface hydrophobicity, providinga
new aspect to design antimicrobial nanomaterials. On the basis of
these studies, we focused on the most potent of novel synthesized anti-
pyrine surfactants candidate and enhance their potential by capping
with AgNPs. The result showed inhibited growth of multiple strains of
pathogens bacteria and fungi.
2.2.3. Preparation of the nanostructure of synthesized antipyrine cationic
surfactants with silver nanoparticles
The chemical reduction method was used to prepare silver nanopar-
ticles solution. All solutions of reacting materials were prepared in
bi-distilled water. In a typical experiment 50 mL of AgNO3 solution
(1 × 10−3 M) was boiled, then 5 mL of 1% trisodium citrate was added
drop wise under vigorous stirring until the color changed to pale yellow.
Then, heating stopped and the reaction cooled to room temperature [35].
Solutions of each prepared antipyrine cationic surfactants (APB8,
APB12&APB16) and (APC8, APC12& APC16) (5 mL/5 × 10−2 M) were
added drop wise during 15 min to 20 mL silver nanoparticles solution.
Mixture solutions stirred continuously for 24 h until the color change.
The resulting solutions with final concentration (1 × 10−2 M) labeled
surfactants (APB8Ag, APB12Ag&APB16Ag) and (APC8Ag, APC12Ag&
APC16Ag) were used for UV–vis absorption spectroscopy, transmission
electron microscope (TEM) analysis dynamic light scattering (DLS) and
for surface parameters measurements.
2.3. Characterization
The chemical structures of the synthesized antipyrine cationic sur-
factants were confirmed using FTIR and 1H NMR spectroscopy. The
FTIR analysis was done in Egyptian Petroleum Research Institute using
ATI Mattsonm Infinity Series™, Bench top 961 controlled by Win
First™ V2.01 Software while 1HNMR was done in National Research
Center using GEMINI 200 (1H 300 MHz) in CDCl3·The UV–vis measure-
ments for the solution of AgNPs and solutions of the nanostructure of
the synthesized antipyrine cationic surfactants with AgNPs were carried
out by UV–vis photometer. Transmission Electron Microscope (TEM)
used to investigate the nanostructure of the prepared samples. A conve-
nient way to produce good TEM samples is to use copper grids. A copper
grid pre-covered with a very thin amorphous carbon film. To investigate
the prepared AgNPs, the nanostructure of synthesized antipyrine cat-
ionic surfactants with AgNPs using TEM, small droplets of the liquid
was placed on the carbon-coated grid. A photographicplate of the high
resolution transmission electron microscopy (Type JEOL JEM-2100 op-
erating at 200 kV attached to a CCD camera). Dynamic light scattering
(DLS) was used to determine the hydrodynamic diameter of the same
solution which used in TEM, and UV–vis using a Malvern Zetasizer
Nano (Malvern Instruments Ltd., Worcestershire, UK). Each DLS mea-
surement was run in triplicate using automated, optimal measurement
time and laser attenuation settings. The recorded correlation functions
and measured particles mobility's were converted into size distribu-
tions, using the Malvern Dispersion Software (V5.10, http://www.
zetasizer.com/).
2. Materials and methods
2.1. Chemicals
4-aminoantipyrine (97%), Benzaldehyde (99.5%), chlorobenzal
dehyde (97%), octyl bromide (98%), dodecylbromide(98%), hexadecylb
romide(98%), silver nitrate (AgNO3, 99%),and trisodiumcitrate (99%)
were analytical grade chemicals were obtained from Aldrich chemical
Company. All the reagents were analytical grade and used as received
without further purification.
2.2. Synthesis
2.2.1. Synthesis of 4-aminoantipyrine Schiff bases (APB) and (APC)
The 4-aminoantipyrine Schiff bases were synthesized according to
the following strategy. Typically, 4-aminoantipyrine (2.03 g, 10 mmol)
was refluxed with benzaldehyde (1.06 g, 10 mmol) or
chlorobenzaldehyde (1.40 g, 10 mmol) for 12 h in presence of ethanol
(50 mL) as a solvent. After removal of the solvent under vacuum, the
residue was extracted with methylene chloride and washed with
water several times. The organic phase was dried over MgSO4 and fil-
tered, and, upon removal of the solvent, an analytically pure bright yel-
low crystalline solid was obtained APB and APCin 89 and 92% yield,
respectively (Scheme 1) [34].
2.4. Surface tension measurements
The surface activity of the synthesized antipyrine Schiff base
cationic surfactants and their nanostructures with AgNPs were deter-
mined from surface tension data and surface tension was measured by
the platinum ring method using a Kruss K6 tensiometer. The surface

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I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
Scheme 1. Synthetic route of synthesized cationic surfactants derived from antipyrine.
tension measurements were carried out with a concentration range
of 1 × 10−2–1 × 10−8 M/L at 20, 40 and 60 °C. The solutions were placed
in a clean cup made from Teflon with a diameter of28 mm, and the sur-
face tension measurements started after2 h to ensure solution interface
stabilization and surfactants molecules adsorption at the water/air
interface. The surface tension values were considered as an average of
three replicates [36].
2.4.1. Antimicrobial test
Synthesized antipyrine cationic surfactants (APB8, APB12 &APB16)
and (APC8, APC12 & APC16) and their nanostructures (APB8Ag,
APB12Ag&APB16Ag) and (APC8Ag, APC12Ag& APC16Ag) were
screened for their antimicrobial activity against a wide range of patho-
genic bacteria and fungi using well diffusion method [37,38] and eryth-
romycin/metronidazole was taken as a reference [39]. The different
species of tested organisms, Gram-positive bacteria (Bacillus subtilis
and Staphylococcus aureus), Gram- negative bacteria, (Escherichia coli
and Pseudomonas aeruginosa) and Fungi (Candida albicans and
Asperigllusniger) were obtained from the unit of operation development
center, Egyptian Petroleum Research Institute, Cairo, Egypt.
The following media used in the antimicrobial activity of synthesized
compounds, the bacterial species grow on nutrient agar, while fungi
mold grow on Czapek'sdoxagar. Nutrient agar consists of Beef extract
(3.0 g/L); Peptone (5.0 g/L), Sodium chloride (3.0 g/L) and Agar
Fig. 1. FTIR spectra of antipyrine Schiff base cationic surfactants.

I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
575
(20.0 g/L), then, completes the volume to 1 L, heated the mixture until
the boiling, and sterilizes the media by autoclave. While, Czapek's 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 1 L, heated the mix-
ture until the boiling, and sterilize the media by autoclave [40].
An assay is made to determine the ability of an antibiotic to kill or in-
hibit the growth of living microorganisms, the technique which used
is:Filter-paper disc-agar diffusion (Kirby-Bauer) [41]. The bacterial and
fungal strains were cultured according to the standards of the National
Committee for Clinical Laboratory. The diameters of inhibition zones
were measured after 24–48 h at 35-37 °C (for bacteria) and 3–4 days
Fig. 2. 1H‐ NMR spectra of antipyrine Schiff base cationic surfactants.

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I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
at 25–27 °C (for yeast and fungi) of incubation at 28 °C, with subsequent
filtering to remove mycelia fragments before the solution containing the
spores was used for inoculation.
was established by TEM and DLS studies. TEM was used to study the
size and morphology of the nanostructure of antipyrine cationic surfac-
tants and their AgNPs. Fig. 4 shows the TEM micrograph and particles
size distribution of the synthesized nanostructure of antipyrine cationic
surfactants with silver nanoparticles APB8Ag, APB12Ag&APB16Ag and
APC8Ag, APC12Ag& APC16Ag. TEM images show the spherical silver
nanoparticles with a corona of the cationic surfactant ligands, which re-
lated to the self-assembling of the surfactant molecules on the silver
nanoparticles. The TEM images showed good dispersion of silver nano-
particles due to interaction with the cationic surfactant molecules with-
out aggregation was observed. While DLS analyses indicated number
average hydrodynamic diameters of silver nanoparticles in the presence
of APB8, APB12 and APB16 are 30, 28 and 17 nm and APC8, APC12 and
APC16 are 25, 20 and 15 nm, respectively (Table 1). By data inspection,
the increasing in the hydrophobic alkyl chains length result in smaller
particle size and more dispersed. Cationic surfactant has positively
charge head group, which leads to a stronger interaction with the nano-
particles, the hydrophobic chain length form a steric hindrance around
the nanoparticles, and therefore it can protect the nanoparticles from
aggregation and act as a better stabilizer. The effect of hydrophobic
chain length of the surfactants on the stabilization of AgNPs was ob-
served from UV–vis, TEM, DLS results where the surface aggregates
capped on silver surface should provide more effective stabilization
with increasing the hydrophobic chain length. The results demonstrate
stability of the nanostructure formation of the synthesized antipyrine
cationic surfactants with silver nanoparticles AgNPs.
For preparation of discs and inoculation, 1.0 mL of inocula were
added to 50 mL of agar media (40 °C) and mixed. The agar was poured
into 120 mm Petri dishes and allowed to cool to room temperature.
Wells (6 mm in diameter) were cut in the agar plates using proper ster-
ile tubes. Then, filled up to the surface of agar with 0.1 mL solution of the
synthesized compounds consists of1mg surfactants in 1 mL of DMSO
(DMSO has negligible influence on the growth of the microorganisms).
The plates were left on a leveled surface, incubated for 24 h at 30 °C for
bacteria and then the diameter of the inhibition zones was measured.
The inhibition zone is formed by these compounds against the particu-
lar test microorganisms determined the biocidal activity of the synthetic
compounds. The mean value for three replicates was used to calculate
the zone of growth inhibition of each sample [42].
3. Results and discussion
3.1. Characterization of the synthesized antipyrine cationic surfactants
The characterization of (APB8, APB12 &APB16) and (APC8, APC12 &
APC16) was performed by FT-IR and 1H NMR spectra. The FT-IR spectra
(Fig. 1), Band was appeared at 3057 cm−1 due to the HC_CH stretching
in the aromatic benzene ring. The two peaks at 2925 and 2855 cm−1 can
be assigned to the asymmetric and symmetric stretching vibrations of
amethylene group, respectively, which exists in the long alkyl chain of
the alkyl halide. Band at 1650 cm−1 corresponding to the stretching vi-
bration of the HC_N, suggesting the formation of Schiff base group.
Peaks at1605, 1570 and 1460 cm−1 are associated with the phenyl
ring. Peak at 1380 cm−1was assigned to (CH2)n bending of long alkyl
chain. Peak at 1082 cm−1was assigned to C–N+ of quaternary ammoni-
um salt, peaks at 720–830 cm−1was assigned to aromatic substation
in phenyl ring. FT-IR spectra confirmed the expected functional groups
in the synthesized cationic surfactants. 1H NMR spectra of the synthe-
sized antipyrine Schiff base cationic surfactants in CDCl3 (Fig. 2),
showed signals at: phenyl as multiplet at 6.9–7.8 ppm, =C–CH3 at
2.4 ppm, −N–CH3 at 3.5 ppm and –CH = N– protons at 9.5–10 ppm.
The peaks from 0.82 to 1.77 ppm is attributable to the (CH2)n
group present in the long alkyl chain. The only difference between the
signals of these compounds was the signal intensity of methylene pro-
ton (m, nH, +NCH2 (CH2)nCH2CH3), where the intensity of this signal
was increased by increasing the methylene groups (chain length) of
the prepared compounds.
3.2. Characterization nanostructure of antipyrine cationic surfactants
Effective surface modification of AgNPs by using antipyrine cationic
surfactants was evidenced by UV–vis, TEM, and DLS. The UV–vis data of
the prepared AgNPs solution and the solutions of the nanostructures of
the antipyrine cationic surfactants assembled on the AgNPs (APB8Ag,
APB12Ag&APB16Ag) and (APC8Ag, APC12Ag& APC16Ag). The silver
nanoparticles have a peak absorbance at 419 nm due to surface plasmon
absorption of metal clusters as shown in Fig. 3a, b. The UV–vis absorp-
tion spectra of the AgNPs changed after addition of the synthesized an-
tipyrine cationic surfactants to the AgNPs solution as shown in Fig. 3a,b.
In the prepared samples APB8Ag, APB12Ag&APB16Ag and APC8Ag,
APC12Ag& APC16Ag the characteristic band at 419 nm is disappeared
which confirmed that the silver nanoparticles successfully attached to
the antipyrine cationic surfactant structure. Disappearing of the surface
plasmonic band of silver nanoparticles attributed to adsorption of anti-
pyrine molecules with Br− attached to the Ag surfaces, and the antipy-
rine surfactant's head groups surrounded the Br− layer by electrostatic
interactions. Thus, the hydrophobic tails would point outward, which
change the surface Plasmon resonance resulting in peak fade [43]. Fur-
ther evidence of the formation of antipyrine surfactants capped AgNPs
Fig. 3. UV Spectra of the nanostructure of synthesized cationic surfactants derived from
antipyrine with silver nanoparticles.

I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
577
Stability of nanoparticles is crucially important for many applica-
3.3. Surface properties
tions and can be determined using zeta potential measurements [44].
Zeta potential is the net surface charge of the nanoparticles when they
are inside a solution. The zeta potential playing an important role limits
in the stability of solutions is +30 mV or −30 mV. To regard the parti-
cles as stable, zeta potential should be either higher than +30 mV or
lower than −30 mV [45]. By inspection data in Table 1, it was found
that the zeta potential values of prepared silver nanoparticle encapsu-
lated by the synthesized cationic surfactants are greater than
+30 mV, which be indication on high stability of the synthesized silver
nanoparticles against agglomeration. High values of zeta potential indi-
cate that the surface charge on nano silver is high so the electrostatic re-
pulsion 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 stabilizing agent is cationic
surfactant (carry positive charge on head group) [43]. Also we found
that zeta potential values of synthesized silver nanoparticles are posi-
tively related with hydrophobic chain length of added stabilizing
agent, where by increase chain length of stabilizing agent, zeta potential
increase, so electrostatic repulsion between particles will increase
which be indication on increasing stability of synthesized silver
nanoparticle against agglomeration for example zeta potential of
synthesized silver nanoparticle stabilized using APB8, APB12 and
APB16 are +31, +34, and +40 mv, respectively.
The critical micelle concentration of surfactant is an important value
that can be obtained from surface tension concentration profile of the
surfactants in aqueous solutions. The critical micelle concentration
values of the synthesized antipyrine cationic surfactants (APB8, APB12
&APB16 and APC8, APC12 & APC16) and their silver nanoparticles
(APB8Ag, APB12Ag&APB16Ag and APC8Ag, APC12Ag& APC16Ag) were
extracted from Fig. 5 and recorded in Table 2. It seems that the critical
micelle concentration values are reduced by increasing the alkyl chain
length, Fig. 5. The micellization process is accompanied by saturation
of surfactant solution interface with surfactant molecules. Adsorption
of the synthesized surfactants at air/solution interface is occurred due
to two forces. The first is the attraction force between surfactants and
water molecules, and the second is repulsion force between phenyl
groups and water molecules. The first force increases the tendency of
surfactant molecules to locate in the bulk of their solution, while the
second increases their presence at the air/water interface [46–48].
Also, increasing hydrophobic chain length lead to destroying the
water structure by the hydrophobicity, hence the free energy of the sys-
tem increase which force the surfactant monomer aggregate in clusters
and/or migrate to the interface to decrease. Hence, the hydrophobicity
enhances the affinity of the surfactants to form micelle in lower concen-
tration. For instance, the CMC values of the synthesized antipyrine
Fig. 4. TEM images and DLS of the nanostructure of synthesized cationic surfactants derived from antipyrine with silver nanoparticles.

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I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
Table 1
cationic surfactants APB8, APB12 &APB16 and APC8, APC12 & APC16at
20 °C, equal to 3.55, 1.78, 1.58 and 2.15, 2.24, 1.78 mM, respectively
(Table 2). Furthermore, their nanostructures have a decreasing effect
on the CMC values upon increasing the hydrophobic chain length, for
example, the CMC values of APB8Ag, APB12Ag&APB16Ag and APC8Ag,
APC12Ag& APC16Ag at 20 °C, equal to 2.24, 1.99, 1.12 and 2.16, 1.80,
1.60 mM, respectively (Table 2). By inspection data in Table 2, and
Fig. 5, we observed that the critical micelle concentration (CMC) of the
synthesized antipyrine cationic surfactants and their AgNPs also de-
crease upon raising the solution temperature. This may be due to the ef-
fect of decreasing the hydration around the hydrophilic head of the
synthesized surfactants is a dominant than the disruption of water
Size and Zeta potential of silver nanoparticles using synthesized cationic surfactants.
Compound
Size
(r·nm)
Zeta potential (mv)
APB8Ag
30
28
17
25
20
15
31
34
40
32
39
45
APB12Ag
APB16Ag
APC8Ag
APC12Ag
APC16Ag
Fig. 5. Surface tension of the synthesized cationic surfactants derived from antipyrine and their nanostructure with silver nanoparticles.

I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
579
structure around the hydrocarbon tail; hence, the synthesized surfac-
tants favor micellization process and consequently the CMC decreases
[49]. For example, the CMC of the synthesizedAPB8 surfactant was
3.55, 3.16 and 1.41 mM and it is nanostructure APB8Ag was 2.24, 1.58
and 1.25 mM at 20, 40 and 60 °C, respectively.
The effectiveness values (πcmc) are the depression in surface tension
values of surfactant in their aqueous solutions at the critical micelle con-
centration compared to that of distilled water and can be calculated ac-
cording to Eq. (1) as follows [50]:
at the interface hence in the amount of accumulated surfactants on the
interface decrease. The smallest area Amin (125A2) at the air–water in-
terface was obtained for APB8 surfactant which had eight repeated
methylene groups. Increasing the repeated methylene groups to 16 in-
creases the area occupied by surfactant molecules at their aqueous solu-
tion interface to 141A2 at 20 °C, while their Γmax equal to 1.29 and 1.18
(×10−10 mol·cm−2) respectively.
The suggested explanation for that trend is that the longer hydrocar-
bon chains are more prone to bend and curl hence the area occupied by
the surfactant unimer become larger and on this basis the amount of the
accumulated surfactants at the interface decreases (Γmax decrease).
The temperature effect on the (Amin) and (Γmax) were shown in
Table 2. The data showed that upon elevating the solution temperature,
the Amin increase while Γmax decrease. For example, the Amin of the sur-
factants APB8 equals to 125, 148 and 165 A2 at 20, 40 and 60°C respec-
πCMC ¼ γo−γCMC
ð1Þ
where γo is the surface tension of bi-distilled water (71.8 mN/m) at
25 °C, γcmc is the surface tension of aqueous surfactant solution at crit-
ical micelle concentration. Effectiveness is a useful surface active pa-
rameter and can be used to compare between the surface activities of
two or more surfactants within the same series, i.e., surfactants have
same function groups. Larger πcmc value of aqueous surfactant solution
indicates its higher surface activity than aqueous surfactant solution
with smaller πcmc value [51]. And from the data in Table 2 is clear that
the πcmc values of the antipyrine cationic surfactants and their silver
nanoparticles are increases with increasing the alkyl chain length
from 8 to 16 carbon atom in their aqueous solutions and decreases
with increasing temperature. Hence, the synthesized surfactants
APB16, APB16Ag, APC16, and APC16Ag are the most effectiveness
each in his category, APB16 and APC16 derivatives are more surface ac-
tive then APB8 and APC8 derivative.
The efficiency values (Pc20) are the logarithm values of surfactant
concentration at which the surface tension of aqueous surfactant
solutions reduced by 20mNm−1. Pc20 value measures the efficiency of
surfactant adsorption air–water interface. Pc20 value is useful in com-
parison between two or more surfactants of different types (i.e., anionic,
cationic or nonionic). Larger Pc20 values indicate higher tendency of
surfactant molecules to adsorb at air–water interface [52]. The efficiency
values of the synthesized cationic surfactants are shown in Table 2. The
efficiency, PC20 increases with increasing the temperature of the solu-
tion from 20, 40 up 60 °C. Increasing the hydrophobic chains increases
the hydrophobicity of the molecules, hence water–hydrophobe interac-
tions increase which decreases the surface tension, followed by an in-
crease in the efficiencyPc20 (Table 2). This trend due to increasing the
solution hydrophobicity, therefore the rate of migration of the surfac-
tant monomer to the interface increase, leading to more reduction in
the surface tension at lower concentration.
tively, while its Γmax equal to 129, 1.12 and 0.95 (×10−10 mol·cm−2
)
respectively. The decrease of amount of accumulated surfactants on
the interface can be ascribed to decreasing the hydration around the hy-
drophilic head, which enhance the micellization process; hence, the sur-
factant population at the interface decreases. Increasing the Amin of the
synthesized antipyrine cationic upon elevation their solution tempera-
ture returns to increasing the activation energy of the molecules,
which increases the repulsion force between the hydrocarbon chains
and aqueous solution and consequently the surfactants unimers orient-
ed horizontally at the air/solution interface so Amin increased. It was no-
ticed from Fig. 5 that the nanostructure of these surfactants with AgNPs
cause more reduction in surface tension than the individual surfactants.
This is related to that the ability of the nanoparticles to adsorb at inter-
face and decrease the surface tension.
Table 2
Surface parameters of antipyrine derived schiff base cationic surfactants and their nano-
structure at 20, 40 and 60 °C.
Compound T, °C CMC, πcmc
,
Pc20
M
,
Γ
max×10−10
,
Amin,
mM
mN−1 m−1
mol·cm−2
A2 molecule−1
APB8
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
3.55
3.16
1.41
1.78
1.41
1.12
1.58
1.25
0.89
2.51
1.78
1.25
2.24
1.58
1.12
1.78
1.00
0.79
2.24
1.58
1.25
1.29
1.21
1.12
30.0
29.0
27.0
37.5
36.0
32.5
46.0
37.5
35.0
35.0
33.0
32.0
36.5
35.0
32.5
40.0
37.0
33.0
35.0
32.5
27.5
36.5
34.0
32.0
3.5
4.3
4.6
3.8
4.5
4.9
4.8
5.1
5.5
3.4
4.1
4.6
4.7
5.4
6.4
5.0
6.1
6.5
4.9
5.0
5.5
5.3
5.7
5.9
5.6
6.5
6.8
5.3
5.5
5.7
5.9
6.4
6.8
6.3
6.6
6.9
1.29
1.12
0.95
1.28
1.08
0.91
1.18
0.98
0.90
1.34
1.22
1.15
1.19
1.08
0.87
1.00
0.88
0.77
1.32
1.05
0.94
1.21
1.04
0.93
1.19
1.02
0.90
1.36
1.08
1.01
1.10
0.99
0.86
1.04
0.91
0.81
125
148
165
129
153
174
141
168
182
124
136
144
138
152
190
165
189
214
126
158
176
139
159
179
137
163
184
121
153
164
150
167
193
160
182
205
APB12
APB16
The maximum surface excess (Γmax) is defined as the maximum con-
centration can be reached by surfactant at air–aqueous solution inter-
face before the micellization occurred.
in the bulk. The maximum surface excess values of the synthesized
nonionic surfactants were calculated using the modified form of
Gibb's-Duhem according to Eq. (2) as follows [53]:
APC8
APC12
APC16
Γmax ¼ 1=2:303 nRT ð∂γ=∂ log CÞ
ð2Þ
APB8Ag
APB12Ag
APB16Ag
APC8Ag
APC12Ag
APC16Ag
where dγ/dlog C is the slope of the surface tension profile in the steeper
region, R is the universal gas constant and T is the absolute temperature.
The area per surfactant molecule (Amin) or the average area occupied
by each surfactant molecule at the air–water interface is calculated ac-
cording to Eq. (3) [54] as follows:
1. 12 40.0
1.00
1.00
2.16
2.24
1.78
1.80
1.30
1.00
1.60
1.30
1.00
36.0
32.5
35.0
32.0
30.0
35.5
33.0
32.0
36.5
35.0
32.5
Amin ¼ 1014=NAΓmax
ð3Þ
where NA is Avogadro's number and Γmax is the maximum surface ex-
cess at constant temperature.
The calculated Γmax and Amin values of the synthesized antipyrine
cationic surfactants and their nanostructures were listed in Table 2.
The data in Table 2, revealed that both Γmax and Amin were hydrophobic
dependent. Increase the hydrocarbon chain length of the synthesized
surfactants followed by increasing the area occupied by each surfactant

580
I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
The surface parameters including effectiveness, efficiency, maxi-
−ΔS °
¼ ΔG °mic=ΔT
ð6Þ
mic
mum surface excess and minimum surface area of the synthesized sur-
factants determine their ability towards adsorption at the different
interfaces. Higher effectiveness and efficiency and maximum surface
excess values and lower minimum surface area indicate high tendency
of surfactants molecules at the different interfaces (air–water, oil–
water, solid–water interfaces). The high tendency of surfactants to-
wards adsorption at the various interfaces increases their applicability
in several applications and mainly as antimicrobial agent.
It was noticed from Fig. 5 that the nanostructure of these surfactants
with AgNPs cause more reduction in surface tension than the individual
surfactants. This is related to that the ability of the nanoparticles to ad-
sorb at interface and decrease the surface tension. Also, the critical mi-
celle concentration values are lower than that of individual surfactants
the effectiveness values increase as the alkyl chain increase and these
values also increase with the synthesized surfactants as shown in
Table 2.
−ΔS ° ¼ ΔG °ads=ΔT
ð7Þ
ð8Þ
ð9Þ
ads
ΔH °
¼ ΔG °mic þ TΔS °
mic
ΔH ° ¼ ΔG °ads þ TΔS °
ads
where R is the universal gas constant (8.314 J mol−1 K−1), T the abso-
lute temperature, πCMC is the effectiveness and Amin is the minimum
surface area.
Negative values of both micellization and adsorption for the synthe-
sized cationic surfactants and their nanostructures indicate that the ad-
sorption and micellization are spontaneous processes. On analyzing the
data in Table 3, we reveal that upon raising the solution temperature,
the both ΔG°ads and ΔG°mic increase in the negative direction. The
ΔG°mic of the synthesized surfactants APB8 was −13.74, −14.98
and −18.18 kJ/mol at 20, 40 and 60 °C respectively and its ΔG°ads was
−17.64, −18.33 and −22.06 kJ/mol at 20, 40 and 60 °C respectively.
The Free energies of adsorption and micellazation become more negative
with increasing hydrophobic side chain. However, the adsorption process
is more prefer than micellazation process due to high negativity of free
energies and governed by the thermodynamic aspect. On rising the tem-
perature from 20 to 60 °C the negativity of free energy are increased due
to the stability of the adsorbed and micellized surfactant molecules than
the freely dispersed in the aqueous phase as showed in Table 3.
Entropy changes of micellization (ΔSmic) are low values which point
to the ordering of the synthesized cationic surfactants molecules partic-
ipated in the micellar phase. Ordering of the molecules evident their
3.4. Micellization and adsorption thermodynamics
The standard free energy, entropy and enthalpy of micellazation and
adsorption for the synthesized cationic surfactant were calculated ac-
cording to Gibbs equations at 20, 40 and 60 °C [53], and data are sum-
marized in Table 3:
ΔG °
¼ 2:303RTlogCMC
ð4Þ
ð5Þ
mic
ΔG ° ¼ ΔG ° −ð0:06πCMCAminÞ
ads
mic
Table 3
Thermodynamic parameters of antipyrine derived cationic surfactants and their nanostructure at 20, 40 and 60 °C.
Compound
T, °K
ΔGads
kJ/mol
,
ΔGmic
kJ/mol
,
ΔSads
,
ΔSmic
,
ΔHads
,
ΔHmic,
kJ·mol−1 K−1
kJ·mol−1 K−1
Kcal·mol−1
Kcal·mol−1
APB8
293
313
333
293
313
333
293
313
333
293
313
333
293
313
333
293
313
333
293
313
333
293
313
333
293
313
333
293
313
333
293
313
333
293
313
333
−17.64
−18.33
−22.06
−17.74
−20.02
−21.78
−18.63
−20.72
−22.85
−17.57
−19.34
−21.33
−17.91
−19.81
−22.24
−19.30
−22.18
−24.03
−18.22
−20.23
−21.94
−17.92
−20.32
−22.31
−16.44
−21.16
−22.17
−17.32
−19.40
−21.53
−18.79
−21.02
−22.61
−18.27
−20.44
−22.33
−13.74
−14.98
−18.18
−15.43
−17.08
−18.81
−15.72
−17.40
−19.45
−14.59
−16.48
−18.51
−14.87
−16.79
−18.81
−15.43
−17.98
−19.78
−14.87
−16.79
−18.51
−15.15
−17.08
−18.81
−16.55
−17.98
−19.13
−14.03
−15.88
−17.53
−15.43
−17.40
−19.13
−15.72
−17.40
−19.13
–
–
–
–
–
–
−0.046
−0.249
–
−0.152
−0.117
–
−0.139
−0.142
–
−0.118
−0.133
–
−0.127
−0.161
–
−0.192
−0.124
–
−0.134
−0.114
–
−0.160
−0.132
–
−0.114
−0.067
–
−0.149
−0.106
–
−0.149
−0.106
–
−0.144
−0.126
−0.083
−0.213
–
−0.111
−0.115
–
−0.112
−0.137
–
−0.126
−0.135
–
−0.128
−0.135
–
−0.170
−0.120
–
−0.128
−0.115
–
−0.129
−0.115
–
−0.095
−0.077
–
−0.124
−0.110
–
−0.132
−0.115
–
−0.112
−0.115
−105.03
–
–
−60.78
–
–
−70.28
–
–
−65.49
–
–
−75.96
–
–
−65.18
–
–
−60.07
–
–
−66.37
–
–
−89.04
–
–
−57.20
–
–
−65.01
–
–
−63.61
–
–
−63.78
–
–
−59.78
–
–
−56.73
–
–
−57.20
–
–
APB12
APB16
APC8
APC12
APC16
APB8Ag
APB12Ag
APB16Ag
APC8Ag
APC12Ag
APC16Ag
−44.49
–
–
−68.77
–
–
−57.94
–
–
−44.63
–
–
−54.19
–
–
−57.53
–
–
−64.39
−57.53

I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
581
Table 4
Antimicrobial activity of the synthesized antipyrine derived cationic surfactants against pathogenic bacteria and fungi.
Samples
Inhibition zone diameter (mm/mg sample)
Bacillus subtilis
Staphylococcus
Aureus
Escherichia
coli
Pseudomonas aeruginosa
Candida albicans
Asperigllus
niger
Reference
APB8
APB12
APB16
APC8
[32]
13
14
16
13
[34]
-ve
15
17
16
[35]
-ve
-ve
15
14
15
[38]
-ve
-ve
13
14
14
[26]
-ve
-ve
15
16
16
[29]
15
15
17
-ve
17
APC12
APC16
-ve
17
17
19
16
15
17
20
compactness at which the hydrophobic alkyl chains are coiled in the mi-
cellar core in high compatibility, and the hydrophilic head positive ni-
trogen group direct to the water phase. That arrangement decreases
the repulsion in the surfactant-aqueous phase system and leads to sta-
bilization for the formed micelles. The sequence of the enthalpy changes
(ΔH°ads/mic) in Table 3 shows the both the micellization and adsorption
processes indicate the thermodynamic predominance of the adsorption
process than the micellization process for the synthesized surfactants.
3.5. Effect of silver nanoparticles on the surface parameters behavior
The synthesized silver nanoparticles have a negative charge in their
solution. The synthesized cationic surfactant carries positive charge, so
the synthesized can self-assemble on the silver nanoparticles. The
adsorbed monolayer from the synthesized cationic surfactant would neu-
tralize the negative charge on the synthesized Ag NPs. I n light of these
types of interactions, the surface charge around the hydrophilic head of
Ag NPs-Surfactant diminish because of neutralization, therefore the hy-
dration around the hydrophilic group decrease, so the nanoparticles-sur-
factant have a tendency to migrate to the interface and/or aggregates in
micelles to decrease the energy of the system [54]. In other means, the hy-
drophobicity of the silver nanoparticles-cationic surfactants colloid
higher than the hydrophobicity of the cationic surfactants alone and so
the Ag NPs- surfactants colloid has a higher propensity to migrate to the
interface or aggregate in micelle as it appears from the experimental re-
sults which complied in Table 2. The CMC of Ag NPs- surfactant colloid
is lower than the synthesized surfactants at all the tested temperature
(Table 2). The CMCs of the APB8, APB12 and APB16 were 3.55, 1.41 and
1.25 mM at 20 °C respectively, while for APB8Ag, APB12Ag and
APB16Ag it equals 2.24, 1.25 and 1.12 mM respectively (Table 2).
As a result of electrostatic interaction between the surfactant head
and silver nanoparticles in the synthesized nanoparticles, occur charge
neutralization around the hydrophilic head of the surfactants and con-
sequently the binding force between the surfactants head and their
counter ions decrease. In addition to the neutralization of the surface
charge around the surfactant hydrophilic head of the nanostructured
system, hence the hydrophobicity increase, and consequently the mi-
gration to the interface increase. So the maximum surfactant concentra-
tion at surface increase (Γmax) making the surfactants less prone to bend
and so Amin decrease compared to surfactant alone.
As just discussed, the hydrophobicity of the synthesized silver nano-
structured-cationic cationic surfactant colloid higher than that of surfac-
tant alone because of surface charge neutralization. From that, the
energy of the nanostructured system will be higher because of
destroying the water structure; hence, their propensity to migrate to
the interface or aggregate in micelle (for decreasing the system energy)
will be higher as it appears from the experimental results, which com-
plied in Table 3. The change in the free energy of adsorption of the syn-
thesized nanostructure (ΔG°ads) APB8Ag, APB12Ag and APB16Ag equal
to −18.22, − 17.92 and −16.44 kJ·mol − 1, respectively at 20 °C
while for the synthesized surfactant equal to −17.64, − 17.74
1
and – 18.63 kJ·mol− for the surfactant APB8, APB12 and APB16
Fig. 6. Antimicrobial activity of the synthesized cationic surfactants derived from
respectively.
antipyrine (a) and their nanostructure with silver nanoparticles (b).

582
I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
Table 5
Antimicrobial activity of the synthesized antipyrine derived cationic surfactants capped silver nanoparticles against pathogenic bacteria and fungi.
Samples
Inhibition zone diameter (mm/mg sample)
Bacillus subtilis
Staphylococcus
Aureus
Escherichia
coli
Pseudomonas aeruginosa
Candida albicans
Asperigllus
niger
Reference
APB8Ag
APB12Ag
APB16Ag
APC8Ag
[32]
16
19
21
18
22
26
[34]
17
21
22
19
21
22
[35]
13
17
19
18
20
27
[38]
13
15
20
19
23
30
[26]
16
18
23
18
22
23
[29]
12
16
20
15
24
25
APC12Ag
APC16Ag
3.6. Biological activities
herbicides. This gave a great impetus to the search for potential pharma-
cologically active drugs carrying pyrazole substituents. Pyrazolyl
pyrazoline derivatives were found to possess therapeutic activities
such as antiinflammatory [57], antiallergic [58], antidiabetic [59], car-
diovascular [60] and antimicrobial [61]. The efficiency of the pyrazole
derivatives was increased by the introducing charged center in its struc-
ture either as cationic center (pyrazolium) or anionic center (carboxyl-
ate, sulfate…).
Heterocyclic compounds are considered the most effective active
matters in about 70% of the drugs, especially the antibacterial and anti-
fungal medications. These heterocyclic compounds are varied between
five or six membered rings or even fused rings. One of these heterocyclic
derivatives is the pyrazole derivatives which remain of great interest
due to the wide applications of such heterocyclic compounds in
the pharmaceutical and agrochemical industry. Pyrazole derivatives
were reported to possess significant antibacterial [55], monoamine ox-
idase inhibitory activities [56] insecticidal, anticancer, anti-HIV and
Antibacterial activities (zone of growth inhibition) of the synthe-
sized cationic surfactants are shown in Table 4, Fig. 6a. Obtained data in-
dicate high antimicrobial activity of the synthesized surfactants
Fig. 7. Schematic representation of possible mechanism of antimicrobial activity of the synthesized cationic surfactants.

I. Aiad et al. / Journal of Molecular Liquids 243 (2017) 572–583
[4] A.J. Alanis, Arch. Med. Res. 36 (2005) 697–705.
583
compared to the standard against Gram-positive bacteria (Bacillus
subtilis and Staphyl. aureus), Gram- negative bacteria (Pseudomonas
aeruginosa and E. coli.) and Fungi (Candida albicans and Aspergillus
niger). By inspection the data in Table 4 we found that the synthesized
surfactants have good antimicrobial activity against gram negative bac-
teria, gram positive bacteria and fungi compared to the drug reference
used. The antimicrobial activity of these compounds strongly related
to the presence of the heteroatoms, cationic charge, Schiff base moiety,
and hydrophobic long chain in their chemical structures. Table 4 repre-
sents the effect of hydrophobic chain length on the antimicrobial activ-
ities of the synthesized Schiff bases surfactants. It is clear that the
hydrophobic chain length has an increment role on the biological activ-
ities of the cationic compounds. Increasing the hydrophobic chain
length from octyl to hexadecyl chain increases the biological activity
considerably. The maximum inhibition efficiency was corresponding
to the hexadecyl derivatives (APB16 and APC16), while the lowest
was obtained by using octyl derivatives (APB8 and APC8). That was at-
tributed to the adsorption tendency of the different antipyrine-Schiff
base cationic derivatives at the interfaces as reflected from the surface
activity data, Table 3. Longer chain length decreases the interfacial ten-
sion values which consequently indicate the adsorption of the mole-
cules at the interfaces. On the contrary, surfactants having shorter
hydrophobic chains had higher interfacial tension values which repre-
sented their lower tendency towards adsorption at the interfaces [62].
Antibacterial activities of the synthesized cationic surfactants
capped silver nanoparticles are shown in Table 5, Fig. 6b. The data re-
vealed that the synthesized surfactants capped silver nanoparticles
(APB8Ag, APB12Ag&APB16Ag and APC8Ag, APC12Ag& APC16Ag) have
enhancement in the antimicrobial activity compared to that of the par-
ent surfactants (APB8, APB12&APB16 and APC8, APC12& APC16). The
silver nanoparticles show efficient antimicrobial property compared to
other salts due to their extremely large surface area, which provides
better contact with microorganisms. There are several suggested mech-
anisms describing the bacterial inhibition by AgNPs reported in works of
literature [63,64]. (i) Adhesion of NPs to the bacteria surface, altering
the membrane properties; (ii) AgNPs penetrating inside the bacterial
cell, resulting in DNA damage; (iii) Reactive Oxygen Species (ROS) can
be generated outside the cell, in medium, or inside the cell, also as a con-
sequence of cell damage/disruption; (iv) Disruption of transmembrane
electrochemical gradient leading to reduced intracellular ATP levels.
These can be considered as the mechanism of the antimicrobial activity
of AgNPs (Fig. 7).
[5] K.M.G. O'Connell, J.T. Hodgkinson, H.F. Sore, M. Welch, G.P.C. Salmond, D.R. Spring,
Angew. Chem. Int. Ed. 52 (2013) 10706–10733.
[6] M. De, P.S. Ghosh, V.M. Rotello, Adv. Mater. 20 (2008) 4225–4241.
[7] D. Peer, J.M. Karp, S. Hong, O.C. Farokhzad, R. Margalit, R. Langer, Nat. Nanotechnol. 2
(2007) 751–760.
[8] F.X. Redl, C.T. Black, G.C. Papaefthymiou, R.L. Sandstrom, M. Yin, H. Zeng, C.B.
Murray, S.P. O'Brien, J. Am. Chem. Soc. 126 (2004) 14583–14599.
[9] A. Ahangari, M. Salouti, Z. Heidari, A.R. Kazemizadeh, A.A. Safari, Drug Deliv. 20
(2013) 34–39.
[10] H. Gu, P.L. Ho, E. Tong, L. Wang, B. Xu, Nano Lett. 3 (2003) 1261–1263.
[11] A. Rai, A. Prabhune, C.C. Perry, J. Mater. Chem. 20 (2010) 6789–6798.
[12] R.R. Arvizo, S. Saha, E. Wang, J.D. Robertson, R. Bhattacharya, P. Mukherjee, Proc.
Natl. Acad. Sci. 110 (2013) 6700–6705.
[13] Y. Zhao, Y. Tian, Y. Cui, W. Liu, W. Ma, X. Jiang, J. Am. Chem. Soc. 132 (2010)
12349–12356.
[14] J. Bresee, K.E. Maier, A.E. Boncella, C. Melander, D.L. Feldheim, Small 7 (2011)
2027–2031.
[15] J.-H. Park, L. Gu, G. von Maltzahn, E. Ruoslahti, S.N. Bhatia, M.J. Sailor, Nat. Mater. 8
(2009) 331–336.
[16] H.J. Lee, S.Y. Yeo, S.H. Jeong, J. Mater. Sci. 38 (2003) 2199–2204.
[17] G. Zhao, S.E. Stevens, Biometals 11 (1998) 27–32.
[18] E. Bressan, L. Ferroni, C. Gardin, C. Rigo, M. Stocchero, V. Vindigni, W. Cairns, B.
Zavan, Int. J. Dent. 2013 (2013) 312747.
[19] S. Phrabhu, E.K. Poulose, Int. Nano Lett. 2 (2012) 32.
[20] V. Sambhy, A. Sen, Chem. Today 26 (2008) 316–318.
[21] S. Egger, R.P. Lehmann, M.J. Height, M.J. Loessner, M. Schuppler, Appl. Environ.
Microbiol. 75 (2009) 2973–2976.
[22] K. Bernardo, S. Leppard, A. Robert, G.F. Commenges, B. Dehan, M. Meunier, Inorg.
Chem. 35 (1996) 387.
[23] T. Punniyamurthy, S.J.S. Kalra, J. Iqbal, Tetrahedron Lett. 36 (1995) 8497.
[24] D. Chiaramonte, J.M. Steiner, J.D. Broussard, K. Baer, S.E.M. Gumminger, Moeller, D.A.
Williams, R. Shumway, N. Can, J. Vet. Res. 67 (2003) 183.
[25] J. Hosler, C. Tschanz, C.E. Hignite, D.L. Azarnoff, J. Invest. Dermatol. 74 (1980) 51.
[26] K.Z. Ismail, A. El-Dissouky, A.Z. Shehada, Polyhedron 16 (2009) 2909.
[27] A.M. Farghaly, A. Hozza, Pharmazie 35 (1980) 596.
[28] A. Pastrakuljic, R.N. Patel, S. Kumar, K.B. Pandeya, J. Inorg. Biochem. 89 (2002) 61.
[29] A. Grieco, A. Matera, P. Di-Rocco, S. Marcoccia, A. Giancaterini, B. Alfei, G. Addolorato,
F. Varlese, G. Gasbarrini, Heparogastroenterology 45 (1998) 1731.
[30] S.M. Shaban, S. Atef, S.M. Tawfik, A. Abd-Elaal, A. Ismail, J. Ind. Eng. Chem. 19 (2013)
2004.
[31] N.A. Negm, Y.M. Elkholy, F.M. Ghuiba, M.K. Zahran, S.A. Mahmoud, S.M. Tawfik, J.
Dispers. Sci. Technol. 32 (2011) 512.
[32] N.A. Negm, A.A. Ismail, S.M. Tawfik, J. Surfactant Deterg. 13 (2010) 503.
[33] I. Aiad, S.M. Tawfik, A. Abd-Elaal, M. El-Shafie, J. Surfactant Deterg. 17 (2014) 391.
[34] N.A. Negm, F.M. Ghuiba, S.M. Tawfik, Corros. Sci. 53 (2011) 3566.
[35] A.A. Abd-Elaal, S.M. Tawfik, S.M. Shaban, Appl. Surf. Sci. 342 (2015) 14.
[36] N.A. Negm, F.M. Ghuiba, S.A. Mahmoud, S.M. Tawfik, Eng. Life Sci. 11 (2011) 496.
[37] G.H. Sayed, F.M. Ghuiba, M.I. Abdou, E.A. Badr, S.M. Tawfik, N.A. Negm, Colloids Surf.
A Physicochem. Eng. Asp. 393 (2012) 96–104.
[38] R.E. Cooper, Analytical Microbiology, Academic Press, New York and London, 1972.
[39] National Committee for Clinical Laboratory Standards, Methods for Dilution Antimi-
crobial Susceptibility Tests for Bacteria that Grow Aerobically. Approved Standard
M7-A4, National Committee for Clinical Laboratory Standards, Wayne, 1997.
[40] S.S. Shah, M.S. Khan, H. Ullah, M.A. Awan, J. Colloid Interface Sci. 186 (1997) 382–389.
[41] D.N. Muanza, B.W. Kim, K.L. Euler, L. Williams, Inter. J. Pharm. 32 (1994) 337–345.
[42] N.A. Negm, I.A. Aiad, S.M. Tawfik, J. Surfactant Deterg. 13 (2010) 503–508.
[43] S.M. Shaban, A.A. Abd-Elaal, Mater. Sci. Eng. C 76 (2017) 871–885.
[44] Y. Zhang, M. Yang, N.G. Portney, D. Cui, G. Budak, E. Ozbay, M. Ozkan, C.S. Ozkan,
Biomed. Microdevices 10 (2008) 321.
4. Conclusion
In this work we have successfully synthesized new antimicrobial
agents based on antipyrine derived cationic surfactants and silver nano-
particles. Results from UV–Vis, TEM and DLS show the monodisperse
particle size distribution of nanoparticle. These surfactants could self-as-
semble to form micelles in an aqueous medium and the critical micelle
concentration (CMC) values as well as the surface parameters were de-
termined. The results proved the ability of synthesized cationic surfac-
tant for stabilization of the synthesized AgNPs. The synthesized AgNPs
have an effect on the surface and thermodynamic behavior of the syn-
thesized cationic surfactants. Combination of AgNPS.
[45] J. Ho, M.K. Danquah, H. Wang, G.M. Forde, J. Chem. Technol. Biotechnol. 83 (2008) 351.
[46] N.A. Negm, S.M. Tawfik, A.A. Abd-Elaal, J. Ind. Eng. Chem. 21 (2015) 1051–1057.
[47] T. Farıas, L.C. de Menorval, J. Zajac, A. Rivera, J. Colloid. Interface Sci. 363 (2011) 465.
[48] T. Farıas, L.C. de Menorval, J. Zajac, A. Rivera, Colloids Surf. A Physicochem. Eng. Asp.
345 (2009) 51.
[49] L. Pei, Z. Cai, Z. Song, X. Zhu, S. Shang, J. Surfactant Deterg. (2013)http://dx.doi.org/
10.1007/s11743-013-1490-0.
[50] N.A. Negm, S.M. Tawfik, Chem. Today J. 30 (2012) 5.
[51] S.M. Tawfik, A. Sayed, I. Aiad, J. Surfactant Deterg. 15 (2012) 577.
[52] N.A. Negm, F. Ahmed, S.M. Tawfik, M. Ahmad, H.H. Hefni, A.K. Manal, J. Surfactant
Deterg. 16 (2013) 333.
[53] M.J. Rosen, J.H. Mathias, L. Davenport, Langmuir 15 (1999) 7340.
[54] Samy M. Shaban, Ali A. Abd-Elaal, Mater. Sci. Eng. C 76 (2017) 871–885.
[55] M. Zhou, X. Zhong, J. Zhao, X. Wang, J. Surfactant Deterg. 16 (2013) 285.
[56] J. Dey, A. Mohanty, S. Roy, D. Khatua, J. Chromatogr. A 1048 (2004) 127.
[57] J. Panda, S.V. Srinivas, M.E. Rao, J. Indian Chem. Soc. 79 (2002) 770.
[58] S.K.W. Lee, C.K. Wong, R.Y.T. Sung, T.F. Leung, K.P. Fung, P.C. Leung, C.W.K. Lam, J.
Ethnopharmacol. 103 (2006) 406.
with the surfactants leads to decreasing the critical micelle concen-
tration surfactant compared to surfactants alone without AgNPs. It
was concluded that the AgNPs enhanced significantly biocidal activities
of the synthesized antipyrine cationic surfactants.
[59] O. Zolk, Clin. Pharmacol. Ther. 86 (2009) 595.
[60] F. Palm, M.L. Onozato, Z. Luo, C.S. Wilcox, Am. J. Physiol. Heart Circ. Physiol. 293
(2007) 3227.
References
[61] C. Campanac, L. Pineau, A. Payard, G. Baziard-Mouysset, C. Roques, Antimicrob.
Agents Chemother. 46 (2002) 1469.
[62] M. Ganzle, Appl. Microbiol. Biotechnol. 64 (3) (2004) 326.
[63] I. Chernomordik, M.M. Kozlov, J. Zimmerberg, J. Membr. Biol. 146 (1) (1995).
[64] J. Liu, D.A. Sonshine, S. Shervani, R.H. Hurt, ACS Nano 4 (2010) 6903–6913.
[1] R.R. Arvizo, S. Bhattacharyya, R.A. Kudgus, K. Giri, R. Bhattacharya, P. Mukherjee,
Chem. Soc. Rev. 41 (2012) 2943–2970.
[2] S.B. Levy, B. Marshall, Nat. Med. (2004).
[3] B. Spellberg, J.H. Powers, E.P. Brass, L.G. Miller, J.J.E. Edwards, Clin. Infect. Dis. 38
(2004) 1279–1286.