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Silver nanoparticle

Electron micrograph of silver manoparticles

Silver nanoparticles are nanoparticles of


silver of between 1 nm and 100 nm in
size.[1] While frequently described as being
'silver' some are composed of a large
percentage of silver oxide due to their
large ratio of surface-to-bulk silver atoms.
Numerous shapes of nanoparticles can be
constructed depending on the application
at hand. Commonly used are spherical
silver nanoparticles but diamond,
octagonal and thin sheets are also
popular.[1]

Their extremely large surface area permits


the coordination of a vast number of
ligands. The properties of silver
nanoparticles applicable to human
treatments are under investigation in
laboratory and animal studies, assessing
potential efficacy, toxicity, and costs.

Synthetic methods
Wet chemistry

The most common methods for


nanoparticle synthesis fall under the
category of wet chemistry, or the
nucleation of particles within a solution.
This nucleation occurs when a silver ion
complex, usually AgNO3 or AgClO4, is
reduced to colloidal silver in the presence
of a reducing agent. When the
concentration increases enough, dissolved
metallic silver ions bind together to form a
stable surface. The surface is
energetically unfavorable when the cluster
is small, because the energy gained by
decreasing the concentration of dissolved
particles is not as high as the energy lost
from creating a new surface.[2] When the
cluster reaches a certain size, known as
the critical radius, it becomes energetically
favorable, and thus stable enough to
continue to grow. This nucleus then
remains in the system and grows as more
silver atoms diffuse through the solution
and attach to the surface[3] When the
dissolved concentration of atomic silver
decreases enough, it is no longer possible
for enough atoms to bind together to form
a stable nucleus. At this nucleation
threshold, new nanoparticles stop being
formed, and the remaining dissolved silver
is absorbed by diffusion into the growing
nanoparticles in the solution.

As the particles grow, other molecules in


the solution diffuse and attach to the
surface. This process stabilizes the
surface energy of the particle and blocks
new silver ions from reaching the surface.
The attachment of these
capping/stabilizing agents slows and
eventually stops the growth of the
particle.[4] The most common capping
ligands are trisodium citrate and
polyvinylpyrrolidone (PVP), but many
others are also used in varying conditions
to synthesize particles with particular
sizes, shapes, and surface properties.[5]

There are many different wet synthesis


methods, including the use of reducing
sugars, citrate reduction, reduction via
sodium borohydride,[6] the silver mirror
reaction,[7] the polyol process,[8] seed-
mediated growth,[9] and light-mediated
growth.[10] Each of these methods, or a
combination of methods, will offer
differing degrees of control over the size
distribution as well as distributions of
geometric arrangements of the
nanoparticle.[11]

A new, very promising wet-chemical


technique was found by Elsupikhe et al.
(2015).[12] They have developed a green
ultrasonically-assisted synthesis. Under
ultrasound treatment, silver nanoparticles
(AgNP) are synthesized with κ-
carrageenan as a natural stabilizer. The
reaction is performed at ambient
temperature and produces silver
nanoparticles with fcc crystal structure
without impurities. The concentration of κ-
carrageenan is used to influence particle
size distribution of the AgNPs.[13]
Monosaccharide reduction

There are many ways silver nanoparticles


can be synthesized; one method is through
monosaccharides. This includes glucose,
fructose, maltose, maltodextrin, etc. but
not sucrose. It is also a simple method to
reduce silver ions back to silver
nanoparticles as it usually involves a one-
step process.[14] There have been methods
that indicated that these reducing sugars
are essential to the formation of silver
nanoparticles. Many studies indicated that
this method of green synthesis,
specifically using Cacumen platycladi
extract, enabled the reduction of silver.
Additionally, the size of the nanoparticle
could be controlled depending on the
concentration of the extract. The studies
indicate that the higher concentrations
correlated to an increased number of
nanoparticles.[14] Smaller nanoparticles
were formed at high pH levels due to the
concentration of the monosaccharides.

Another method of silver nanoparticle


synthesis includes the use of reducing
sugars with alkali starch and silver nitrate.
The reducing sugars have free aldehyde
and ketone groups, which enable them to
be oxidized into gluconate.[15] The
monosaccharide must have a free ketone
group because in order to act as a
reducing agent it first undergoes
tautomerization. In addition, if the
aldehydes are bound, it will be stuck in
cyclic form and cannot act as a reducing
agent. For example, glucose has an
aldehyde functional group that is able to
reduce silver cations to silver atoms and is
then oxidized to gluconic acid.[16] The
reaction for the sugars to be oxidized
occurs in aqueous solutions. The capping
agent is also not present when heated.

Citrate reduction
An early, and very common, method for
synthesizing silver nanoparticles is citrate
reduction. This method was first recorded
by M. C. Lea, who successfully produced a
citrate-stabilized silver colloid in 1889.[17]
Citrate reduction involves the reduction of
a silver source particle, usually AgNO3 or
AgClO4, to colloidal silver using trisodium
citrate, Na3C6H5O7.[18] The synthesis is
usually performed at an elevated
temperature (~100 °C) to maximize the
monodispersity (uniformity in both size
and shape) of the particle. In this method,
the citrate ion traditionally acts as both the
reducing agent and the capping ligand,[18]
making it a useful process for AgNP
production due to its relative ease and
short reaction time. However, the silver
particles formed may exhibit broad size
distributions and form several different
particle geometries simultaneously.[17] The
addition of stronger reducing agents to the
reaction is often used to synthesize
particles of a more uniform size and
shape.[18]

Reduction via sodium borohydride

The synthesis of silver nanoparticles by


sodium borohydride (NaBH4) reduction
occurs by the following reaction:[19]
Ag+ + BH4− + 3 H2O → Ag0 +B(OH)3 +3.5
H2

The reduced metal atoms will form


nanoparticle nuclei. Overall, this process is
similar to the above reduction method
using citrate. The benefit of using sodium
borohydride is increased monodispersity
of the final particle population. The reason
for the increased monodispersity when
using NaBH4 is that it is a stronger
reducing agent than citrate. The impact of
reducing agent strength can be seen by
inspecting a LaMer diagram which
describes the nucleation and growth of
nanoparticles.[20]
When silver nitrate (AgNO3) is reduced by
a weak reducing agent like citrate, the
reduction rate is lower which means that
new nuclei are forming and old nuclei are
growing concurrently. This is the reason
that the citrate reaction has low
monodispersity. Because NaBH4 is a much
stronger reducing agent, the concentration
of silver nitrate is reduced rapidly which
shortens the time during which new nuclei
form and grow concurrently yielding a
monodispersed population of silver
nanoparticles.

Particles formed by reduction must have


their surfaces stabilized to prevent
undesirable particle agglomeration (when
multiple particles bond together), growth,
or coarsening. The driving force for these
phenomena is the minimization of surface
energy (nanoparticles have a large surface
to volume ratio). This tendency to reduce
surface energy in the system can be
counteracted by adding species which will
adsorb to the surface of the nanoparticles
and lowers the activity of the particle
surface thus preventing particle
agglomeration according to the DLVO
theory and preventing growth by
occupying attachment sites for metal
atoms. Chemical species that adsorb to
the surface of nanoparticles are called
ligands. Some of these surface stabilizing
species are: NaBH4 in large amounts,[19]
poly(vinyl pyrrolidone) (PVP),[21] sodium
dodecyl sulfate (SDS),[19][21] and/or
dodecane thiol.[22]

Once the particles have been formed in


solution they must be separated and
collected. There are several general
methods to remove nanoparticles from
solution, including evaporating the solvent
phase[22] or the addition of chemicals to
the solution that lower the solubility of the
nanoparticles in the solution.[23] Both
methods force the precipitation of the
nanoparticles.
Polyol process

The polyol process is a particularly useful


method because it yields a high degree of
control over both the size and geometry of
the resulting nanoparticles. In general, the
polyol synthesis begins with the heating of
a polyol compound such as ethylene
glycol, 1,5-pentanediol, or 1,2-propylene
glycol7. An Ag+ species and a capping
agent are added (although the polyol itself
is also often the capping agent). The Ag+
species is then reduced by the polyol to
colloidal nanoparticles.[24] The polyol
process is highly sensitive to reaction
conditions such as temperature, chemical
environment, and concentration of
substrates.[25][26] Therefore, by changing
these variables, various sizes and
geometries can be selected for such as
quasi-spheres, pyramids, spheres, and
wires.[11] Further study has examined the
mechanism for this process as well as
resulting geometries under various
reaction conditions in greater detail.[8][27]

Seed-mediated growth

Seed-mediated growth is a synthetic


method in which small, stable nuclei are
grown in a separate chemical environment
to a desired size and shape. Seed-
mediated methods consist of two different
stages: nucleation and growth. Variation
of certain factors in the synthesis (e.g.
ligand, nucleation time, reducing agent,
etc.),[28] can control the final size and
shape of nanoparticles, making seed-
mediated growth a popular synthetic
approach to controlling morphology of
nanoparticles.

The nucleation stage of seed-mediated


growth consists of the reduction of metal
ions in a precursor to metal atoms. In
order to control the size distribution of the
seeds, the period of nucleation should be
made short for monodispersity. The LaMer
model illustrates this concept.[29] Seeds
typically consist small nanoparticles,
stabilized by a ligand. Ligands are small,
usually organic molecules that bind to the
surface of particles, preventing seeds
from further growth. Ligands are
necessary as they increase the energy
barrier of coagulation, preventing
agglomeration. The balance between
attractive and repulsive forces within
colloidal solutions can be modeled by
DLVO theory.[30] Ligand binding affinity,
and selectivity can be used to control
shape and growth. For seed synthesis, a
ligand with medium to low binding affinity
should be chosen as to allow for exchange
during growth phase.

The growth of nanoseeds involves placing


the seeds into a growth solution. The
growth solution requires a low
concentration of a metal precursor, ligands
that will readily exchange with preexisting
seed ligands, and a weak or very low
concentration of reducing agent. The
reducing agent must not be strong enough
to reduce metal precursor in the growth
solution in the absence of seeds.
Otherwise, the growth solution will form
new nucleation sites instead of growing on
preexisting ones (seeds).[31] Growth is the
result of the competition between surface
energy (which increases unfavorably with
growth) and bulk energy (which decreases
favorably with growth). The balance
between the energetics of growth and
dissolution is the reason for uniform
growth only on preexisting seeds (and no
new nucleation).[32] Growth occurs by the
addition of metal atoms from the growth
solution to the seeds, and ligand exchange
between the growth ligands (which have a
higher bonding affinity) and the seed
ligands.[33]

Range and direction of growth can be


controlled by nanoseed, concentration of
metal precursor, ligand, and reaction
conditions (heat, pressure, etc.).[34]
Controlling stoichiometric conditions of
growth solution controls ultimate size of
particle. For example, a low concentration
of metal seeds to metal precursor in the
growth solution will produce larger
particles. Capping agent has been shown
to control direction of growth and thereby
shape. Ligands can have varying affinities
for binding across a particle. Differential
binding within a particle can result in
dissimilar growth across particle. This
produces anisotropic particles with
nonspherical shapes including prisms,
cubes, and rods.[35][36]
Light-mediated growth

Light-mediated syntheses have also been


explored where light can promote
formation of various silver nanoparticle
morphologies.[10][37]

Silver mirror reaction

The silver mirror reaction involves the


conversion of silver nitrate to Ag(NH3)OH.
Ag(NH3)OH is subsequently reduced into
colloidal silver using an aldehyde
containing molecule such as a sugar. The
silver mirror reaction is as follows:
2(Ag(NH3)2)+ + RCHO + 2OH− → RCOOH
+ 2Ag + 4NH3.[38]

The size and shape of the nanoparticles


produced are difficult to control and often
have wide distributions.[39] However, this
method is often used to apply thin
coatings of silver particles onto surfaces
and further study into producing more
uniformly sized nanoparticles is being
done.[39]

Ion implantation

Ion implantation has been used to create


silver nanoparticles embedded in glass,
polyurethane, silicone, polyethylene, and
poly(methyl methacrylate). Particles are
embedded in the substrate by means of
bombardment at high accelerating
voltages. At a fixed current density of the
ion beam up to a certain value, the size of
the embedded silver nanoparticles has
been found to be monodisperse within the
population,[40] after which only an increase
in the ion concentration is observed. A
further increase in the ion beam dose has
been found to reduce both the
nanoparticle size and density in the target
substrate, whereas an ion beam operating
at a high accelerating voltage with a
gradually increasing current density has
been found to result in a gradual increase
in the nanoparticle size. There are a few
competing mechanisms which may result
in the decrease in nanoparticle size;
destruction of NPs upon collision,
sputtering of the sample surface, particle
fusion upon heating and dissociation.[40]

The formation of embedded nanoparticles


is complex, and all of the controlling
parameters and factors have not yet been
investigated. Computer simulation is still
difficult as it involves processes of
diffusion and clustering, however it can be
broken down into a few different sub-
processes such as implantation, diffusion,
and growth. Upon implantation, silver ions
will reach different depths within the
substrate which approaches a Gaussian
distribution with the mean centered at X
depth. High temperature conditions during
the initial stages of implantation will
increase the impurity diffusion in the
substrate and as a result limit the
impinging ion saturation, which is required
for nanoparticle nucleation.[41] Both the
implant temperature and ion beam current
density are crucial to control in order to
obtain a monodisperse nanoparticle size
and depth distribution. A low current
density may be used to counter the
thermal agitation from the ion beam and a
buildup of surface charge. After
implantation on the surface, the beam
currents may be raised as the surface
conductivity will increase.[41] The rate at
which impurities diffuse drops quickly
after the formation of the nanoparticles,
which act as a mobile ion trap. This
suggests that the beginning of the
implantation process is critical for control
of the spacing and depth of the resulting
nanoparticles, as well as control of the
substrate temperature and ion beam
density. The presence and nature of these
particles can be analyzed using numerous
spectroscopy and microscopy
instruments.[41] Nanoparticles synthesized
in the substrate exhibit surface plasmon
resonances as evidenced by characteristic
absorption bands; these features undergo
spectral shifts depending on the
nanoparticle size and surface
asperities,[40] however the optical
properties also strongly depend on the
substrate material of the composite.

Biological synthesis

The biological synthesis of nanoparticles


has provided a means for improved
techniques compared to the traditional
methods that call for the use of harmful
reducing agents like sodium borohydride.
Many of these methods could improve
their environmental footprint by replacing
these relatively strong reducing agents.
The problems with the chemical
production of silver nanoparticles is
usually involves high cost and the
longevity of the particles is short lived due
to aggregation. The harshness of standard
chemical methods has sparked the use of
using biological organisms to reduce silver
ions in solution into colloidal
nanoparticles.[42][43]

In addition, precise control over shape and


size is vital during nanoparticle synthesis
since the NPs therapeutic properties are
intimately dependent on such factors.[44]
Hence, the primary focus of research in
biogenic synthesis is in developing
methods that consistently reproduce NPs
with precise properties.[45][46]

Fungi and bacteria

A general representation of the synthesis and


applications of biogenically synthesized silver
nanoparticles using plant extract.
Bacterial and fungal synthesis of
nanoparticles is practical because
bacteria and fungi are easy to handle and
can be modified genetically with ease.
This provides a means to develop
biomolecules that can synthesize AgNPs
of varying shapes and sizes in high yield,
which is at the forefront of current
challenges in nanoparticle synthesis.
Fungal strains such as Verticillium and
bacterial strains such as K. pneumoniae
can be used in the synthesis of silver
nanoparticles.[47] When the
fungus/bacteria is added to solution,
protein biomass is released into the
solution.[47] Electron donating residues
such as tryptophan and tyrosine reduce
silver ions in solution contributed by silver
nitrate.[47] These methods have been
found to effectively create stable
monodisperse nanoparticles without the
use of harmful reducing agents.

A method has been found of reducing


silver ions by the introduction of the
fungus Fusarium oxysporum. The
nanoparticles formed in this method have
a size range between 5 and 15 nm and
consist of silver hydrosol. The reduction of
the silver nanoparticles is thought to come
from an enzymatic process and silver
nanoparticles produced are extremely
stable due to interactions with proteins
that are excreted by the fungi.

Bacterium found in silver mines,


Pseudomonas stutzeri AG259, were able
to construct silver particles in the shapes
of triangles and hexagons. The size of
these nanoparticles had a large range in
size and some of them reached sizes
larger than the usual nanoscale with a size
of 200 nm. The silver nanoparticles were
found in the organic matrix of the
bacteria.[48]

Lactic acid producing bacteria have been


used to produce silver nanoparticles. The
bacteria Lactobacillus spp., Pediococcus
pentosaceus, Enteroccus faeciumI, and
Lactococcus garvieae have been found to
be able to reduce silver ions into silver
nanoparticles. The production of the
nanoparticles takes place in the cell from
the interactions between the silver ions
and the organic compounds of the cell. It
was found that the bacterium
Lactobacillus fermentum created the
smallest silver nanoparticles with an
average size of 11.2 nm. It was also found
that this bacterium produced the
nanoparticles with the smallest size
distribution and the nanoparticles were
found mostly on the outside of the cells. It
was also found that there was an increase
in the pH increased the rate of which the
nanoparticles were produced and the
amount of particles produced.[49]

Plants

The reduction of silver ions into silver


nanoparticles has also been achieved
using geranium leaves. It has been found
that adding geranium leaf extract to silver
nitrate solutions causes their silver ions to
be quickly reduced and that the
nanoparticles produced are particularly
stable. The silver nanoparticles produced
in solution had a size range between 16
and 40 nm.[48]

In another study different plant leaf


extracts were used to reduce silver ions. It
was found that out of Camellia sinensis
(green tea), pine, persimmon, ginko,
magnolia, and platanus that the magnolia
leaf extract was the best at creating silver
nanoparticles. This method created
particles with a disperse size range of 15
to 500 nm, but it was also found that the
particle size could be controlled by varying
the reaction temperature. The speed at
which the ions were reduced by the
magnolia leaf extract was comparable to
those of using chemicals to reduce.[42][50]

The use of plants, microbes, and fungi in


the production of silver nanoparticles is
leading the way to more environmentally
sound production of silver
nanoparticles.[43]

A green method is available for


synthesizing silver nanoparticles using
Amaranthus gangeticus Linn leaf
extract.[51]

Products and functionalization


Synthetic protocols for silver nanoparticle
production can be modified to produce
silver nanoparticles with non-spherical
geometries and also to functionalize
nanoparticles with different materials,
such as silica. Creating silver
nanoparticles of different shapes and
surface coatings allows for greater control
over their size-specific properties.

Anisotropic structures

Silver nanoparticles can be synthesized in


a variety of non-spherical (anisotropic)
shapes. Because silver, like other noble
metals, exhibits a size and shape
dependent optical effect known as
localized surface plasmon resonance
(LSPR) at the nanoscale, the ability to
synthesize Ag nanoparticles in different
shapes vastly increases the ability to tune
their optical behavior. For example, the
wavelength at which LSPR occurs for a
nanoparticle of one morphology (e.g. a
sphere) will be different if that sphere is
changed into a different shape. This shape
dependence allows a silver nanoparticle to
experience optical enhancement at a
range of different wavelengths, even by
keeping the size relatively constant, just by
changing its shape. The applications of
this shape-exploited expansion of optical
behavior range from developing more
sensitive biosensors to increasing the
longevity of textiles.[52][53]

Triangular nanoprisms

Triangular shaped nanoparticles are a


canonical type of anisotropic morphology
studied for both gold and silver.[54]

Though many different techniques for


silver nanoprism synthesis exist, several
methods employ a seed-mediated
approach, which involves first synthesizing
small (3-5 nm diameter) silver
nanoparticles that offer a template for
shape-directed growth into triangular
nanostructures.[55]

The silver seeds are synthesized by mixing


silver nitrate and sodium citrate in
aqueous solution and then rapidly adding
sodium borohydride. Additional silver
nitrate is added to the seed solution at low
temperature, and the prisms are grown by
slowly reducing the excess silver nitrate
using ascorbic acid.[6]

With the seed-mediated approach to silver


nanoprism synthesis, selectivity of one
shape over another can in part be
controlled by the capping ligand. Using
essentially the same procedure above but
changing citrate to poly (vinyl pyrrolidone)
(PVP) yields cube and rod-shaped
nanostructures instead of triangular
nanoprisms.[56]

In addition to the seed mediated


technique, silver nanoprisms can also be
synthesized using a photo-mediated
approach, in which preexisting spherical
silver nanoparticles are transformed into
triangular nanoprisms simply by exposing
the reaction mixture to high intensities of
light.[57]

Nanocubes
Silver nanocubes can be synthesized using
ethylene glycol as a reducing agent and
PVP as a capping agent, in a polyol
synthesis reaction (vide supra). A typical
synthesis using these reagents involves
adding fresh silver nitrate and PVP to a
solution of ethylene glycol heated at
140 °C.[58]

This procedure can actually be modified to


produce another anisotropic silver
nanostructure, nanowires, by just allowing
the silver nitrate solution to age before
using it in the synthesis. By allowing the
silver nitrate solution to age, the initial
nanostructure formed during the synthesis
is slightly different than that obtained with
fresh silver nitrate, which influences the
growth process, and therefore, the
morphology of the final product.[58]

Coating with silica

General procedure for coating colloid particles in silica.


First PVP is absorbed onto the colloidal surface. These
particles are put into a solution of ammonia in ethanol.
the particle then begins to grow by addition of Si(OEt)4.
Electron micrograph of core-shell nanoparticles, which

comprise dark silver cores and light silica shells

In this method, polyvinylpyrrolidone (PVP)


is dissolved in water by sonication and
mixed with silver colloid particles.[1] Active
stirring ensures the PVP has adsorbed to
the nanoparticle surface.[1] Centrifuging
separates the PVP coated nanoparticles
which are then transferred to a solution of
ethanol to be centrifuged further and
placed in a solution of ammonia, ethanol
and Si(OEt4) (TES).[1] Stirring for twelve
hours results in the silica shell being
formed consisting of a surrounding layer
of silicon oxide with an ether linkage
available to add functionality.[1] Varying the
amount of TES allows for different
thicknesses of shells formed.[1] This
technique is popular due to the ability to
add a variety of functionality to the
exposed silica surface.

Metrology
A number of reference materials are
available for silver nanoparticles.[59] NIST
RM 8017 contains 75 nm silver
nanoparticles embedded in a cake of the
polymer polyvinylpyrrolidone to stabilize
them against oxidation for a long shelf life.
They have reference values for mean
particle size using dynamic light
scattering, ultra-small-angle X-ray
scattering, atomic force microscopy, and
transmission electron microscopy; and
size distribution reference values for the
latter two methods.[60][61] The BAM-N001
certified reference material contains silver
nanoparticles with a specified size
distribution with a number-weighted
median size of 12.6 nm measured by
small-angle X-ray scattering and
transmission electron microscopy.[62]

Use
Catalysis

Using silver nanoparticles for catalysis


has been gaining attention in recent years.
Although the most common applications
are for medicinal or antibacterial purposes,
silver nanoparticles have been
demonstrated to show catalytic redox
properties for dyes, benzene, carbon
monoxide, and likely other compounds.
NOTE: This paragraph is a general
description of nanoparticle properties for
catalysis; it is not exclusive to silver
nanoparticles. The size of a nanoparticle
greatly determines the properties that it
exhibits due to various quantum effects.
Additionally, the chemical environment of
the nanoparticle plays a large role on the
catalytic properties. With this in mind, it is
important to note that heterogeneous
catalysis takes place by adsorption of the
reactant species to the catalytic substrate.
When polymers, complex ligands, or
surfactants are used to prevent
coalescence of the nanoparticles, the
catalytic ability is frequently hindered due
to reduced adsorption ability.[63] However,
these compounds can also be used in
such a way that the chemical environment
enhances the catalytic ability.

Supported on silica spheres –


reduction of dyes

Silver nanoparticles have been


synthesized on a support of inert silica
spheres.[63] The support plays virtually no
role in the catalytic ability and serves as a
method of preventing coalescence of the
silver nanoparticles in colloidal solution.
Thus, the silver nanoparticles were
stabilized and it was possible to
demonstrate the ability of them to serve as
an electron relay for the reduction of dyes
by sodium borohydride.[63] Without the
silver nanoparticle catalyst, virtually no
reaction occurs between sodium
borohydride and the various dyes:
methylene blue, eosin, and rose bengal.

Mesoporous aerogel – selective


oxidation of benzene

Silver nanoparticles supported on aerogel


are advantageous due to the higher
number of active sites.[64] The highest
selectivity for oxidation of benzene to
phenol was observed at low weight
percent of silver in the aerogel matrix (1%
Ag). This better selectivity is believed to be
a result of the higher monodispersity
within the aerogel matrix of the 1% Ag
sample. Each weight percent solution
formed different sized particles with a
different width of size range.[64]

Silver alloy – synergistic oxidation


of carbon monoxide

Au-Ag alloy nanoparticles have been


shown to have a synergistic effect on the
oxidation of carbon monoxide (CO).[65] On
its own, each pure-metal nanoparticle
shows very poor catalytic activity for CO
oxidation; together, the catalytic properties
are greatly enhanced. It is proposed that
the gold acts as a strong binding agent for
the oxygen atom and the silver serves as a
strong oxidizing catalyst, although the
exact mechanism is still not completely
understood. When synthesized in an
Au/Ag ratio from 3:1 to 10:1, the alloyed
nanoparticles showed complete
conversion when 1% CO was fed in air at
ambient temperature.[65] The size of the
alloyed particles did not play a big role in
the catalytic ability. It is well known that
gold nanoparticles only show catalytic
properties for CO when they are ~3 nm in
size, but alloyed particles up to 30 nm
demonstrated excellent catalytic activity –
catalytic activity better than that of gold
nanoparticles on active support such as
TiO2, Fe2O3, etc.[65]

Light-enhanced

Plasmonic effects have been studied quite


extensively. Until recently, there have not
been studies investigating the oxidative
catalytic enhancement of a nanostructure
via excitation of its surface plasmon
resonance. The defining feature for
enhancing the oxidative catalytic ability
has been identified as the ability to convert
a beam of light into the form of energetic
electrons that can be transferred to
adsorbed molecules.[66] The implication of
such a feature is that photochemical
reactions can be driven by low-intensity
continuous light can be coupled with
thermal energy.

The coupling of low-intensity continuous


light and thermal energy has been
performed with silver nanocubes. The
important feature of silver nanostructures
that are enabling for photocatalysis is their
nature to create resonant surface
plasmons from light in the visible range.[66]

The addition of light enhancement enabled


the particles to perform to the same
degree as particles that were heated up to
40 K greater.[66] This is a profound finding
when noting that a reduction in
temperature of 25 K can increase the
catalyst lifetime by nearly tenfold, when
comparing the photothermal and thermal
process.[66]

Biological research

Researchers have explored the use of


silver nanoparticles as carriers for
delivering various payloads such as small
drug molecules or large biomolecules to
specific targets. Once the AgNP has had
sufficient time to reach its target, release
of the payload could potentially be
triggered by an internal or external
stimulus. The targeting and accumulation
of nanoparticles may provide high payload
concentrations at specific target sites and
could minimize side effects.[67]

Chemotherapy

The introduction of nanotechnology into


medicine is expected to advance
diagnostic cancer imaging and the
standards for therapeutic drug design.[68]
Nanotechnology may uncover insight
about the structure, function and
organizational level of the biosystem at
the nanoscale.[69]
Silver nanoparticles can undergo coating
techniques that offer a uniform
functionalized surface to which substrates
can be added. When the nanoparticle is
coated, for example, in silica the surface
exists as silicic acid. Substrates can thus
be added through stable ether and ester
linkages that are not degraded
immediately by natural metabolic
enzymes.[70][71] Recent chemotherapeutic
applications have designed anti cancer
drugs with a photo cleavable linker,[72]
such as an ortho-nitrobenzyl bridge,
attaching it to the substrate on the
nanoparticle surface.[70] The low toxicity
nanoparticle complex can remain viable
under metabolic attack for the time
necessary to be distributed throughout the
bodies systems.[70] If a cancerous tumor is
being targeted for treatment, ultraviolet
light can be introduced over the tumor
region.[70] The electromagnetic energy of
the light causes the photo responsive
linker to break between the drug and the
nanoparticle substrate.[70] The drug is now
cleaved and released in an unaltered
active form to act on the cancerous tumor
cells.[70] Advantages anticipated for this
method is that the drug is transported
without highly toxic compounds, the drug
is released without harmful radiation or
relying on a specific chemical reaction to
occur and the drug can be selectively
released at a target tissue.[70][71]

A second approach is to attach a


chemotherapeutic drug directly to the
functionalized surface of the silver
nanoparticle combined with a nucelophilic
species to undergo a displacement
reaction. For example, once the
nanoparticle drug complex enters or is in
the vicinity of the target tissue or cells, a
glutathione monoester can be
administered to the site.[73][74] The
nucleophilic ester oxygen will attach to the
functionalized surface of the nanoparticle
through a new ester linkage while the drug
is released to its surroundings.[73][74] The
drug is now active and can exert its
biological function on the cells immediate
to its surroundings limiting non-desirable
interactions with other tissues.[73][74]

Multiple drug resistance

A major cause for the ineffectiveness of


current chemotherapy treatments is
multiple drug resistance which can arise
from several mechanisms.[75]

Nanoparticles can provide a means to


overcome MDR. In general, when using a
targeting agent to deliver nanocarriers to
cancer cells, it is imperative that the agent
binds with high selectivity to molecules
that are uniquely expressed on the cell
surface. Hence NPs can be designed with
proteins that specifically detect drug
resistant cells with overexpressed
transporter proteins on their surface.[76] A
pitfall of the commonly used nano-drug
delivery systems is that free drugs that are
released from the nanocarriers into the
cytosol get exposed to the MDR
transporters once again, and are exported.
To solve this, 8 nm nanocrystalline silver
particles were modified by the addition of
trans-activating transcriptional activator
(TAT), derived from the HIV-1 virus, which
acts as a cell penetrating peptide
(CPP).[77] Generally, AgNP effectiveness is
limited due to the lack of efficient cellular
uptake; however, CPP-modification has
become one of the most efficient methods
for improving intracellular delivery of
nanoparticles. Once ingested, the export
of the AgNP is prevented based on a size
exclusion. The concept is simple: the
nanoparticles are too large to be effluxed
by the MDR transporters, because the
efflux function is strictly subjected to the
size of its substrates, which is generally
limited to a range of 300-2000 Da. Thereby
the nanoparticulates remain insusceptible
to the efflux, providing a means to
accumulate in high concentrations.

Antimicrobial

Introduction of silver into bacterial cells


induces a high degree of structural and
morphological changes, which can lead to
cell death. As the silver nano particles
come in contact with the bacteria, they
adhere to the cell wall and cell
membrane.[78] Once bound, some of the
silver passes through to the inside, and
interacts with phosphate-containing
compounds like DNA and RNA, while
another portion adheres to the sulphur-
containing proteins on the membrane.[78]
The silver-sulphur interactions at the
membrane cause the cell wall to undergo
structural changes, like the formation of
pits and pores.[79] Through these pores,
cellular components are released into the
extracellular fluid, simply due to the
osmotic difference. Within the cell, the
integration of silver creates a low
molecular weight region where the DNA
then condenses.[79] Having DNA in a
condensed state inhibits the cell’s
replication proteins contact with the DNA.
Thus the introduction of silver
nanoparticles inhibits replication and is
sufficient to cause the death of the cell.
Further increasing their effect, when silver
comes in contact with fluids, it tends to
ionize which increases the nanoparticles
bactericidal activity.[79] This has been
correlated to the suppression of enzymes
and inhibited expression of proteins that
relate to the cell’s ability to produce ATP.[80]

Although it varies for every type of cell


proposed, as their cell membrane
composition varies greatly, It has been
seen that in general, silver nano particles
with an average size of 10 nm or less
show electronic effects that greatly
increase their bactericidal activity.[81] This
could also be partly due to the fact that as
particle size decreases, reactivity
increases due to the surface area to
volume ratio increasing.

It has been noted that the introduction of


silver nano particles has shown to have
synergistic activity with common
antibiotics already used today, such as;
penicillin G, ampicillin, erythromycin,
clindamycin, and vancomycin against E.
coli and S. aureus.[82]

Silver nanoparticles can prevent bacteria


from growing on or adhering to the
surface. This can be especially useful in
surgical settings where all surfaces in
contact with the patient must be sterile.
Silver nanoparticles can be incorporated
on many types of surfaces including
metals, plastic, and glass.[83] In medical
equipment, it has been shown that silver
nano particles lower the bacterial count on
devices used compared to old techniques.
However, the problem arises when the
procedure is over and a new one must be
done. In the process of washing the
instruments a large portion of the silver
nano particles become less effective due
to the loss of silver ions. They are more
commonly used in skin grafts for burn
victims as the silver nano particles
embedded with the graft provide better
antimicrobial activity and result in
significantly less scarring of the
victim.These new applications are direct
decedents of older practices that used
silver nitrate to treat conditions such as
skin ulcers. Now, silver nanoparticles are
used in bandages and patches to help heal
certain burns and wounds.[84]

They also show promising application as


water treatment method to form clean
potable water.[85] This doesn’t sound like
much, but water contains numerous
diseases and some parts of the world do
not have the luxury of clean water, or any
at all. It wasn’t new to use silver for
removing microbes, but this experiment
used the carbonate in water to make
microbes even more vulnerable to silver.[86]
First the scientists of the experiment use
the nanopaticles to remove certain
pesticides from the water, ones that prove
fatal to people if ingested. Several other
tests have shown that the silver
nanoparticles were capable of removing
certain ions in water as well, like iron, lead,
and arsenic. But that is not the only reason
why the silver nanoparticles are so
appealing, they do not require any external
force (no electricity of hydrolics) for the
reaction to occur.[87]
Consumer Goods

Household applications

There are instances in which silver


nanoparticles and colloidal silver are used
in consumer goods. Samsung for example
claimed that the use of silver
nanoparticles in washing machines would
help to sterilize clothes and water during
the washing and rinsing functions, and
allow clothes to be cleaned without the
need for hot water.[88] The nanoparticles in
these appliances are synthesized using
electrolysis. Through electrolysis, silver is
extracted from metal plates and then
turned into silver nanoparticles by a
reduction agent.[89] This method avoids
the drying, cleaning and re-dispersion
processes, which are generally required
with alternative colloidal synthesis
methods.[89] Importantly, the electrolysis
strategy also decreases the production
cost of Ag nanoparticles, making these
washing machines more affordable to
manufacture.[90] Samsung has described
the system:

[A] grapefruit-sized device


alongside the [washer] tub uses
electrical currents to nanoshave
two silver plates the size of large
chewing gum sticks. Resulting in
positively charged silver atoms-
silver ions (Ag+)-are injected into
the tub during the wash cycle.[90]

Samsung’s description of the Ag


nanoparticle generating process seems to
contradict its advertisement of silver
nanoparticles. Instead, the statement
indicates that laundry cycles.[89][90] When
clothes are run through the cycle, the
intended mode of action is that bacteria
contained in the water are sterilized as
they interact with the silver present in the
washing tub.[88][90] As a result, these
washing machines can provide
antibacterial and sterilization benefits on
top of conventional washing methods.
Samsung has commented on the lifetime
of these silver-containing washing
machines. The electrolysis of silver
generates over 400 billion silver ions
during each wash cycle. Given the size of
the silver source (two “gum-sized” plate of
Ag), Samsung estimates that these plates
can last up to 3000 wash cycles.[90]

These plans by Samsung were not


overlooked by regulatory agencies.
Agencies investigating nanoparticle use
include but are not limited to: the U.S. FDA,
U.S. EPA, SIAA of Japan, and Korea's
Testing and Research Institute for
Chemical Industry and FITI Testing &
Research Institute.[88] These various
agencies plan to regulate silver
nanoparticles in appliances.[88] These
washing machines are some of the first
cases in which the EPA has sought to
regulate nanoparticles in consumer goods.
Samsung stated that the silver gets
washed away in the sewer and regulatory
agencies worry over what that means for
wastewater treatment streams.[90]
Currently, the EPA classifies silver
nanoparticles as pesticides due to their
use as antimicrobial agents in wastewater
purification.[88] The washing machines
being developed by Samsung do contain a
pesticide and have to be registered and
tested for safety under the law, particularly
the US Federal insecticide, fungicide and
rodenticide act.[88] The difficulty, however
behind regulating nanotechnology in this
manner is that there is no distinct way to
measure toxicity.[88]

Health and safety


Although silver nanoparticles are widely
used in a variety of commercial products,
there has only recently been a major effort
to study their effects on human health.
There have been several studies that
describe the in vitro toxicity of silver
nanoparticles to a variety of different
organs, including the lung, liver, skin, brain,
and reproductive organs.[91] The
mechanism of the toxicity of silver
nanoparticles to human cells appears to
be derived from oxidative stress and
inflammation that is caused by the
generation of reactive oxygen species
(ROS) stimulated by either the Ag NPs, Ag
ions, or both.[92][93][94][95][96] For example,
Park et al. showed that exposure of a
mouse peritoneal macrophage cell line
(RAW267.7) to silver nanoparticles
decreased the cell viability in a
concentration- and time-dependent
manner.[95] They further showed that the
intracellular reduced glutathionine (GSH),
which is a ROS scavenger, decreased to
81.4% of the control group of silver
nanoparticles at 1.6 ppm.[95]

Modes of toxicity

Since silver nanoparticles undergo


dissolution releasing silver ions,[97] which
is well-documented to have toxic
effects,[96][97][98] there have been several
studies that have been conducted to
determine whether the toxicity of silver
nanoparticles is derived from the release
of silver ions or from the nanoparticle
itself. Several studies suggest that the
toxicity of silver nanoparticles is attributed
to their release of silver ions in cells as
both silver nanoparticles and silver ions
have been reported to have similar
cytotoxicity.[94][95][99][100] For example, In
some cases it is reported that silver
nanoparticles facilitate the release of toxic
free silver ions in cells via a "Trojan-horse
type mechanism," where the particle enters
cells and is then ionized within the cell.[95]
However, there have been reports that
suggest that a combination of silver
nanoparticles and ions is responsible for
the toxic effect of silver nanoparticles.
Navarro et al. using cysteine ligands as a
tool to measure the concentration of free
silver in solution, determined that although
initially silver ions were 18 times more
likely to inhibit the photosynthesis of an
algae, Chlamydomanas reinhardtii, but
after 2 hours of incubation it was revealed
that the algae containing silver
nanoparticles were more toxic than just
silver ions alone.[101] Furthermore, there
are studies that suggest that silver
nanoparticles induce toxicity independent
of free silver ions.[96][102][103] For example,
Asharani et al. compared phenotypic
defects observed in zebrafish treated with
silver nanoparticles and silver ions and
determined that the phenotypic defects
observed with silver nanoparticle
treatment was not observed with silver
ion-treated embryos, suggesting that the
toxicity of silver nanoparticles are
independent of silver ions.[103]

Protein channels and nuclear membrane


pores can often be in the size range of
9 nm to 10 nm in diameter.[96] Small silver
nanoparticles constructed of this size
have the ability to not only pass through
the membrane to interact with internal
structures but also to be become lodged
within the membrane.[96] Silver
nanoparticle depositions in the membrane
can impact regulation of solutes,
exchange of proteins and cell
recognition.[96] Exposure to silver
nanoparticles has been associated with
"inflammatory, oxidative, genotoxic, and
cytotoxic consequences"; the silver
particulates primarily accumulate in the
liver.[104] but have also been shown to be
toxic in other organs including the
brain.[105] Nano-silver applied to tissue-
cultured human cells leads to the
formation of free radicals, raising
concerns of potential health risks.[106]
Allergic reaction: There have been
several studies conducted that show a
precedence for allerginicity of silver
nanoparticles.[107][108]
Argyria and staining: Ingested silver or
silver compounds, including colloidal
silver, can cause a condition called
argyria, a discoloration of the skin and
organs.In 2006, there was a case study
of a 17-year-old man, who sustained
burns to 30% of his body, and
experienced a temporary bluish-grey hue
after several days of treatment with
Acticoat, a brand of wound dressing
containing silver nanoparticles.[109]
Argyria is the deposition of silver in deep
tissues, a condition that cannot happen
on a temporary basis, raising the
question of whether the cause of the
man’s discoloration was argyria or even
a result of the silver treatment.[110] Silver
dressings are known to cause a
"transient discoloration" that dissipates
in 2–14 days, but not a permanent
discoloration.[111]
Silzone heart valve: St. Jude Medical
released a mechanical heart valve with a
silver coated sewing cuff (coated using
ion beam-assisted deposition) in
1997.[112] The valve was designed to
reduce the instances of endocarditis.
The valve was approved for sale in
Canada, Europe, the United States, and
most other markets around the world. In
a post-commercialization study,
researchers showed that the valve
prevented tissue ingrowth, created
paravalvular leakage, valve loosening,
and in the worst cases explantation.
After 3 years on the market and 36,000
implants, St. Jude discontinued and
voluntarily recalled the valve.

See also
Oxidative dissolution of silver
nanoparticles
Environmental impact of silver
nanoparticles
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