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Review Article
Role of Surfactants in Nanotechnology and Their Applications
ABSTRACT
The Main goal of surfactants in the formation of nanoparticles is due to its high
Keywords
effect on the dispersion. Nano-emulsions, as non-equilibrium systems, present
Nanoparticles; characteristics and properties which depend not only on composition but also on
nano- the preparation method. Although interest in nano-emulsions was developed since
about 20 years ago, mainly for nanoparticle preparation, it is in the last years that
emulsions;
direct applications of nano-emulsions in consumer products are being developed,
pharmacy ,
mainly in pharmacy, drugs, personal care, health care, agrochemicals and
drugs,
cosmetics. These recent applications have made that studies on optimization
agrochemicals
methods for nano-emulsion preparation be a requirement. This review is focused on
and cosmetics.
the most recent literature on developments of nano-emulsions as final application
products and on the optimization of their preparation.
Introduction
Surfactants are characterized by the Surfactants can be categorized according
essential features that we saw in sodium to the charge present in the hydrophilic
oleate. A surfactant molecule has a portion of the molecule (after dissociation
hydrophilic (water-loving) head and a long in aqueous solution):
hydrophobic (water-hating or oil-loving) o Anionic surfactants
tail. For this reason, we often describe o Nonionic surfactants
surfactants is being amphiphilic molecules o Cationic surfactants
- they love everything. o Amphoteric surfactants
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Figure.2 Microemulsion droplet radius and silver nanoparticle radius obtained by Reaction
in microemulsion using different combinations (molar ratio Indicated) of the alcohol
ethoxylate Brij 30 and the anionic surfactant AOT.
Figure.3 TEM images of (a) precursor and the samples prepared by hydrothermal treatment
for (b) 45, (c) 60, and (d) 75 min. Reaction temperature: 160 C. The inset in c is the SAED
pattern of a single nanosheet.
Figure.4 TEM images of products synthesized with different amounts of SDBS: (a) 0.0, (b)
0.05, (c) 0.10, and (d) 0.15 g. The top inset in a is the SAED pattern, and the lower one is a
low-resolution TEM imag
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There are other commonly preferred al., 2002; Patarin et al., 2002; Palmqvist,
milling methods used by different 2003).
researchers includes dry milling and ball
milling techniques (Philip, 2001). When nanoparticles are incorporated in
In vapor-phase synthesis of nanoparticles, compositions, a release of the active
the formation of nanoparticles takes place agents into the composition frequently
in gas phase. In this synthesis technique takes place. In the particular case of
the condensation of atoms and molecules nanocapsules, when they are incorporated
is carried out. The vapor phase synthesis is in a composition containing an oily phase,
not new and many multinational such as for example emulsions, the active
companies have been using flame reactors agents encapsulated in the oily core
for decades for producing large quantities migrate to the oily phase of the
of nanoparticles. The flame reactors were composition. This premature release of the
used for forming various nanoparticles active agents into the composition makes
such as carbon black and titanium dioxide. their encapsulation in nanoparticles
The last and most advanced technique is ineffective.
known as inert gas condensation.
Although the technique is costly, it is Preparation of Nanoparticles using
considered as a controlled process as by Surfactants
this method the exact shape and size of the
nanoparticle can be synthesized. In inert The synthesis procedure for the
gas condensation technique, the preparation of metal nanoparticles from
nanoparticle as soon as they formed water-in oil microemulsions is simple.
rapidly collides with inert gas in a low- Two microemulsions are formulated, one
pressure environment and thus smaller and with a metal salt or a metal complex
controlled nanoparticles are formed(Philip, dissolved in the water pools and one with
2001). a reducing agent, such as sodium
borohydride or hydrazine. The reaction
Synthesis of inorganic materials with leading to the solid materials, such as a
nanosized dimensions can take advantage reduction of a metal salt to the metal. The
of the ability of surfactants to self- overall kinetics of the system are usually
assemble into well-delined structures. such that the particles cease to grow when
These structures are used as a kind of they have reached a size comparable with
template for the synthesis. This approach the size of starting microemulsion. Thus,
of nanomaterials preparation has triggered for systems involving fast reaction steps
substantial interest both in the surface within the droplets, the overall reaction
chemistry and the materials chemistry kinetics are mainly governed by transport
community. The accuracy and of species through the hydrocarbon
reproducibility of the self-assembly domain and by droplet fusion,which
process has been seen as means of governs the size and the size distribution
achieving control of materials architecture of the nanoparticles. The water droplets of
on the nanometer scale. This is a the starting water in-oil microemulsion
biomimctic approach: a wide variety of should not be seen as a mold that is being
biological structural materials are made by filled with product during the course of the
a templating process with the use of reaction. After completed reaction, a fine
surface active compounds (Holmberg et suspension of nanoparticles can be
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obtained and this suspension coexists with droplet radius and silver nanoparticle
a microemulsion consisting of water radius obtained by reaction in
droplets in oil. The inorganic nanoparticles microemulsions using different
are most likely surrounded by a water combinations (Figure 2) of the alcohol
film, and both the particles and the water ethoxylate Brij 30 and the anionic
droplets will be stabilized by a monolayer surfactant AOT. The results support that
of surfactant. The surfactants will direct larger microemulsion droplets have a
the polar head group into the water and the tendency to give larger particles and the
hydrophobic tails will be oriented into the study shows that the starting droplet size
continuous hydrocarbon domain. The influences the size of the formed
process is illustrated in Figure (1.a) nanoparticles even though the actual sizes
(Boutonnet et al., 1991). are different (Andersson et al., 2005).
Alternatively, one may mix three The metal nanoparticles formed in the
microemulsions, one containing a salt of microemulsion-based synthesis are not
the first metal, one containing a salt of the always spherical. On preparation of copper
second metal, and one containing the nanoparticles from microemulsions with
reducing agent. As an example, mixed varying internal structures (Lisiecki et al.,
platinum-palladium nanoparticles in the 2000; Pileni, 2001). Reaction in a
size range of 5-40 nm can be prepared by microemulsion consisting of spherical
mixing a nonionic surfactant-based water droplets gave spherical particles.
microemulsion containing both platinum Reaction in a microemulsion consisting of
and palladium salts in the water pools with interconnected water cylinders yielded
a hydrazine-containing microemulsion cylindrical copper nanocrystals (together
(Yashima et al., 2003). a bimetallic with some spherical particles). Finally,
particle is shown in Figure (1.b). reaction in a complex system consisting of
a water in-oil microemulsion coexisting
Interestingly, Wu, Chen, and Huang with a lamellar phase gave a mixture of
(2001) found, in contrast, strong particles with different shapes:
indications that their synthesis which was spheres,cylinders,flat objects,etc. An
based on sodium bis (2-ethylhexyl) excellent example of this is again the
sulfosuccinate (AOT) as surfactant and formation of coppernanocrystals made
hydrazine as reducing agent,resulted in Pt- from copper bis (2-ethylhexyl)
Pd alloy particles. The reason for this sulfosuccinate (AOT) with sodium as
difference is not clear, but the results counter ion exchanged by the divalent
indicate the importance of suitable cuprous ion (Pileni, 2003; Filankembo A.
surfactant-metal ion interactions for the and Pileni, 2000).
formation of crystalline alloy
nanoparticles in microemulsions. Yu and Kudo (2005) had synthesized
bimetal (BiVO4 ) nanofibers with an
The microemulsions of interest for the average diameter of 100 nm and lengths of
synthesis of inorganic nanoparticles are of up to several micrometers by a surfactant-
water-in-oil type that is, they consist of assisted hydrothermal synthesis using
small water droplets , surrounded by a cetyltrimethylammonium bromide
monolayer of surfactants and dispersed in (CTAB), which proved to be an effective
a continuous oil domain. Microemulsion route to control the phase structure and
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Figure.7 Schematic illustration of how a surfactant liquid crystal is first solidified and then
transformed into a mesoporous material by removal of the surfactant.Surfactant removal can
be made either by washing or by calcinations.
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sodium dodecyl sulfate while keeping the with cubic geometry. Nonionic surfactant,
concentration of copper dodecyl sulfate in particular block copolymers made up of
constant, gave smaller particles, most hydrophilic polyoxyethylene segments and
likely as a result of fewer Cu (II) ions per hydrophilic polyoxypropylene segments
micelle. (Figure 7).
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Figure.8 TEM micrographs of mesoporous titania with incorporated silver. The left picture
shows a bright field (BF) micrographs of the highly ordered mesoporous cubic structure of
titania. The dark spots are silver particles situated within the titania. The right picture shows
a dark field (DF) micrographs taken on mesoporous cubic titania. Here the bright spots ara
titania crystallites and the very dark spots are silver.
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The synthesized iron particles without ranging from 1.1 to 1.9 x 10(6) g/mol
surfactant are flocculated to be clusters of could easily be obtained for all three
20-50 nm. In the case of using 0.0425M systems investigated. For both
surfactant, the obtained particles are cationic/cationic and anionic/anionic
almost sphere. While oleylamine surfactant systems, the number of PS
concentration was added up to 0.085M, particles per milliliter of latex (Np)
several iron nuclei are agglomerated generated in the very early stage of O/W'
together regularly. It is confirmed that the microemulsion remained rather constant
synthesized iron particles are amorphous, throughout the polymerization. This was
but the surface of the particles is easily controlled by using only 1 wt% of mixed
oxidized and to be spinel structured iron surfactants and the continuous addition of
oxide by HRTEM. a small amount of styrene. The present
polymerization method allows one to
On the other hand , Lai JI,etal.(2005) synthesize nanoparticles of PS or other
controlled the size of magnetic polymers of high polymer/surfactant
nanoparticles by adjusting the weight ratios at some particle sizes that are
surfactant/solvent ratio. Gamma-Fe2O3 unable to achieve them with a single type
nanoparticles of 5.6 and 12.7, and Fe(0) of surfactant.
nanoparticles of 22.3 nm in diameter were
prepared, all having spherical shape and While Woo J. K., etal. (2008) were
uniform size as confirmed by TEM. prepared polypyrrole nanoparticles by
Mossbauer spectra confirmed Fe3+ for the emulsion polymerization, and the surface
5.6 and 12.7 nm particles and Fe(3+) and charge of PPy nanoparticles was
Fe(0) for 22.3 nm particles, in good controlled by the mixed surfactant system
agreement with synchrotron XRD patterns. of dodecylbenzene sulfonic acid and
isooctylphenyl ether. The shape and size
Xu XJ, etal. (2003) have been of nanoparticles prepared could be
successfully synthesized nanosized controlled by changing concentration of
polystyrene (PS) latexes stabilized by the surfactant. In addition, it was confirmed
mixture of cationic/cationic, that the nanoparticles with good
anionic/anionic, or anionic/cationic conductivity could be obtained by this
surfactants of various types with high preparation method. Consequently, well
weight ratios of PS to surfactant (ca. 10:1) dispersed PPy nanoparticles with 60-100
by a semicontinuous microemulsion nm in diameter with cubic shape were
polymerization process. For cationic or obtained.
anionic systems, spherical latex particles
with a weight-averaged diameter (Dw) The barium compound nanoparticles were
ranging from about 22 to 53 nm were synthesized using the microemulsion
nearly linearly dependent on the weight formed by AOT as an anionic surfactant
ratio of the mixed surfactants with similar and iso-octane as an organic solvent.
charges. Their particle size distributions Chromate, sulfate, or carbonate-containing
were rather uniform (Dw/Dn < 1.20). For microemulsion solution and Ba(AOT)2
a system with oppositely charged reverse micelle solution were mixed. After
surfactants at nonequimolar ratios, it could a few days, the morphology of the product
produce stable PS particles up to 94 nm in material was observed using TEM. Then,
diameter. High molar masses (Mw) of PS bundle of the nanowire, chain structure of
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events and limits the growth of the nanotubes, but may prove toxic to cells
particles is understood in general when used as non-viral transporters for
qualitative terms. The steric bulk of the biomolecules including DNA, siRNA and
surfactants provides a physical barrier that proteins for therapeutic purposes.
prevents the metal surfaces from
contacting each other directly. They can The nanotubes were purified without
also change the surface charge of a cluster metallic catalyst particles and amorphous
and thus change its stability toward carbons. Both catalyst particles and
aggregation (Azzam et al., 2009). amorphous carbon have been
demonstrated to influence cell viability.
Role of surfactants in carbon nanotube The experiments show that the toxicity of
toxicity: nanotube conjugates appears to be
controlled by the specific molecules
Synthesized carbon nanotubes, especially attached on the nanotube surfaces. This
single-walled carbon nanotubes means, one criteria whether nanotubes are
(SWCNTs), are in the form of bundles toxic or not depends on how the nanotubes
with other impurities such as catalyst are purified and dispersed as well as the
particles and amorphous carbon debris. In surface cargos that they may carry. Our
order to be useful for many types of experiments also demonstrate that, in
applications, for instance in nanoelectronic contrast to SDS and SDBS, SC is an
devices or biomedical applications, environmental-friendly reagent to be used
SWCNTs need to be purified and for dispersion and purification of
dispersed into individual nanotubes. One nanotubes.
method to do this is by surfactant
stabilization of the hydrophobic nanotube In the preparation and processing of
surface, which overcomes the van der nanocomposites, where carbon nanotubes
Waals forces among the nanotubes and (CNTs) are introduced into polymeric
results in suspensions of individual matrices as a reinforcing filler, microscale
SWCNTs. (Guobin et al., 2009). Several aggregation of the CNTs is a major issue.
commercial surfactants, such as sodium
dodecyl sulfate (SDS), sodium cholate
(SC) and sodium dodecylbenzene Researchers at The Hebrew University of
sulfonate (SDBS) have been demonstrated Jerusalem and the Weizmann Institute of
to efficiently disperse bundled single- Science in Israel have analyzed the effect
walled carbon nanotubes into aqueous of surfactants, as well as surface oxidation
suspensions of individual nanotubes. and functionalization, on the dispersion of
However, there has been no systematic surface-modified multiwalled CNTs in
study on the toxicity of nanotube polymers .
conjugates with the extensively-used SDS,
SDBS, and SC surfactants. It is critical to Due to the vast number of combinations of
understand the cytotoxicity of the polymers and mixing conditions, it would
nanotube-surfactant conjugates since these be beneficial to have a handy set of
reagents are increasingly being used in guidelines to help select the optimum
industry and laboratories. The toxicity of a mixing variables, says Gad Marom of
surfactant may not only cause health The Hebrew University. The researchers
issues for those working with carbon suggest general guidelines to produce
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nanoparticles are nearly the same and that surfactant showed higher degradation than
indicates the anticancer activity of the that with a cationic surfactant.
loaded Cu (II)-CTAB nano compound is
higher four folds than the free Cu (II)- Future work
CTAB.
Application of surfactant nanoparticles
Electrochemical behaviour of carbon as stationary phases in gas
steel in acid chloride solution in the chromatography
presence of dodecyl cysteine
hydrochloride self-assembled on gold Characterizes
Nanoparticles Surfactants and polymeric surfactant
nanoparticles are promising to be good
The maximum inhibition efficiency adsorbants and can be used as stationary
approached 76.6% in the presence of 175 phases in GC packed and capillary
ppm of dodecyl cysteine and 90.8% in the columns. May be due to their specific
presence of the same concentration of characteristics and it can gives good
dodecyl cysteine hydrochloride self- resolution for solving some petroleum
assembled on gold nanoparticles. problems such as separation of isomers
(xylenes,cresol and other compound which
Characterization of Cobalt Oxide have the same boiling point and same
Nanocatalysts Prepared by molecular weight ), and separation of
Microemulsion with different macromolecules (compounds of high
Surfactants, Reduction by Hydrazine molecular weight).
and Mechanochemical Method
Nanocomposite thin film coatings.
Cobalt oxide(Co3O4) nanoparticles were Characterizes
prepared by different techniques and the
results revealed that all samples obtained Corrosion usually takes place and
from different methods were nanosized degrades material surfaces based on
particles. environmental chemistry.
Preparation of Ni- and Cu-Oxide These include surface treatment methods,
Nanocatalysts by Microemulsion nanocomposite thin film coatings, the
Method using Surfactant and Their corrosion performance of materials is
Characterization significantly improved as compared to
materials processed using conventional
The decomposition of hydrogen peroxide methods.
over Ni- and Cu-Oxide Nanocatalysts
showed that they have obviously higher Nanotechnology The Next Revolution
catalytic activities as compared with nickel For Wastewater Treatment (TNT
oxide and copper oxide prepared by the Contaminants)
conventional precipitation method.
At present there are clear opportunities for
Alkaline Hydrolysis of TNT in Micellar nanoscience and nanotechnology in
System (Sanaa M.Soliman , 2010) industry. Some applications can be
anticipated and can result in targeted
Alkaline hydrolysis of TNT using mixture advances in technology. However, new
of nonionic surfactant micelles and anionic scientific advances usually lead to new
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technological innovations that might not Chavanpatil M., Khdair A. and Panyam J, Pharm
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