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INTRODUCTION
1857 - Faraday made colloidal gold by reducing the aqueous solution of AuCl 4- with
phosphorus in CS2.
Citrate reduction method of Turkevitch most popular method for the synthesis of
colloidal gold particles.
CITRATE REDUCTION METHOD OF TURKEVITCH
A solution of gold or silver salt (typically 1Mm) IS boiled with a higher
concentration (typically 1 M) of sodium citrate for a few minutes. This results in the
formation of metal colloids of 10-50nm diameter, and the size can be varied by altering
synthetic parameters. This colloidal solution is stable for several months (the gold colloid
is much more stable than that of silver). Here the stability is due to an electrical double
layer surrounding the metal surface. This later is dynamic and the colloid is stable as
long as the conditions are not altered greatly. For example, if we precipitate the colloid,
the material cannot be re-dispersed. Precipitation leads to aggregation as the stabilizing
ionic layer is easily disturbed. A stable colloidal particle which can be precipitated, dried
and re-dispersed, or in effect one that has similar characteristics as a molecule,
generated interest for a long time. The 3D monolayer or monolayer-protected metal
clusters (MPCs) belong to this category of materials. They are molecular materials,
wherein the constituting mono-layer-protected cluster or nanoparticles behave like
molecules. 3D is used to distinguish these from the corresponding 2D monolayers,
which are grown on planar surfaces.
METHOD OF PRECIPITATION
By combining this two-phase method of Faraday and the technique of phase transfer
catalysis prepared dodecanethiol-protected gold nanoparticle with a core size in the
range 1-3 nm. AuCl4- was transferred to toluene using tetra octyl ammonium bromide as
the phase transfer agent. The phase-transferred Au3+ is the presence of the surfactant,
octanedecanethiol using NaBH4 as the reducing agent.
( toluene )
+ AuC l 4
+ ( toluene ) N (C8 H 17)4
AuC l 4aq + N (C 8 H 17)4
C 12 H 25 S n ( toluene ) + 4 mC l 1(aq)
( A um )
( toluene ) +n C12 H 25 SH ( toluene )+3 m e
mAuC l 4
The material formed is dark brown powder with a wacy texture which is reffered to as
Au@DDT, the @ symbolism means that the DDt covers the Au ( DDT is dodecane thiol,
C12H25SH).
The Material is redispersible in common organic solvents and can be purified by gel
filtration chromatography wooth separanose 6B/toluene. The size of the gold core can
be controlled by varying metal ion ligand ratio. A large thiol/gold ration leads to the
formation of smaller nanoparticles. Various ligands other than thiols have been used to
prepare 3D SAMs.
CHARACTERIZATION
2
2 N e
the equation p = m , where N is the free electron, e is the electron charge and m
is its effective mass. Mie explained this phenomenon by solving Maxwells equation for
the absorption and scattering of the electromagnetic radiation by spherical particles.
The plasmon absorption band is characteristic of the size and shape if nanoclusters.
Anisotropic particles such as metal nanorods as show the presence of two plasmon
features, namely transverse, due to the coherent oscillation along the short axis, and
the longitudinal due to the oscillation along the long axis. The intensity of the
longitudinal plasmon band is large and its position varies with the length of the rod.
Techniques used to derive information on the structure of the metal core:
1. TEM
2. XRD
3. ADM
4. STM
5. Etc.
High resolution transmission electron microscopy at lattice resolution on size-selected
gold Nano crystallites showed FCC packing of atoms in the gold core with a mixture of
particle shapes with predominantly truncated octahedral, cuboctahedral and icosahedral
structures. Octahedral core with have 8 (111) planes and the six corners will be
truncated by (100) planes. The high radius of curvature of the core suggest that the
monolayer chain density decreases as we move away from the metal core. Thus the
terminal methyl groups have enough orientation freedom. This is again supported by the
fact that the hydrodynamic radius of the metal nanoparticle is lower than that calculated
by assuming the monolayer to be straight chain.
TEM gives the mean diameter (d) of the particles which can be used to calculate the
3
d
mean number of atoms (N) in the core using the relationship N Au=
4 ()
2 .
V Au
X-ray photoelectron spectroscopy has been used to find out the oxidation state of
gold in the material.
IR Spectroscopy is a powerful tool used to study the structure of the adsorbate on the
metal surface.
C NMR Spectra of alkane hiol stabilized clusters for three different alkyl chain length
shied that the oeek narrows down as the distance of the carbon from the gold surface
increases.
MPCs display current to double layer charging of the metal core. This is due to small
sub-atto Farad capacitance of MPCs. The double layer charging occurs as a series of
one electron approximately evenly spaced.
*One can charge the core of the MPCs electrochemically in a solvent in the presence of
a supporting electrolyte. The solvent is then removed and the supporting electrolyte is
washed away. Such positively or negatively charged MPCs can act as oxidizing as well
as reducing agents.
Ligand exchange reactions on electrochemically charged MPCs, they found that the rate
as well as the extent of exchange increased with an increase in the positive charge on
the core. Mixing MPCs with different core charges results in the transfer of electrons
between the MPCs resulting in a solution with a potential determined by the
stoichiometry of the mixture and Nernst equation.
The DSC of the alknethiol-capped gold nanoparticles with alkane thiols with chain
lengths carrying from C12 to C20 are shown in Fig. 8.4. The broad endotherm is caused
by the order-disorder transition associated with the hydrocarbon chain. The transition
temperature as well as the transmission enthalpy increased with the chain length. Alkyl
chains below 12 carbons do not show the melting of the hydrocarbon chain. Apart from
this, another melting is observed above 100C This is due to the small fraction of the
superlattice present in the sample.
The enthalphy of the super lattice melting can be very high due to the high cohesive
energy of such systems. As one can see from the cartoon structure of the superlattice in
Fig. 8.5, the ordered portion of the alkyl chain can be either at the end or in between the
two clusters.
APPLICATIONS
Gold nanoparticles have very high extinction coefficients, and the color change during
the transition of nanoparticles from the dispersed to the aggregate state is quite
evidence. Hence, coupling of nanoparticles with ionosphere gives better sensors.
Crown ethers in combination with gold nanoparticles have been used as K+ ion
sensor. K+ has the ability to form 1:2 adducts with crown ethers attached to the adjacent
nanoparticles. This results in aggregation and the color changes from dark brown to
purple.
Used to detect toxic heavy metal ions such as lead, cadmium and mercury
In the presence of metal ions, gold nanoparticles aggregate through chelation of the
ions with the carboxyl group on adjacent nanoparticles. This ion templated chelation process
changes the color of the solution. It also changes the Rayleigh scattering response from the
medium. This chelation can be reversed through the addition of a strong metal ion chelator
such as EDTA.
SUPERLATTICES
Superlattice
A periodic, synthetic multi-layer, wherein a unit cell, consisting of successive layers
that are chemically different from their adjacent neighbors, is repeated
Characterized by their double periodicity in the structure, periodicity of atoms in the
angstrom level, and periodicity of nanocrystals in the nanometer level
How superlattice is form?
In order to allow the superlattice formation to occur, the van der Waals
interaction between particles should
be sufficiently strong to create a
secondary minimum M2 in the
potential energy-distance curve.
Figure 3 Potential energy-distance curve showing the resultant interaction energy (iii) due to
contibution from attractive (i) as well as replusive force (ii)
*M2 refers to the shallow minimum which can lead to the particles associated reversibly
Monodispersity
Annealing Process
In hydrophobically-modified SAMS, hard sphere repulsion and van der Waals forces
assist the formation of superlattices. The self-organization of monolayers leads to an
assembly of the chains on the crystal planes of the nanocrystals. Such assemblies of
adjacent clusters can interact, forming a well-organized superlattice structure.
In this method, the already prepared nanoparticles are refluxed in a solvent with
ligands capable of acting as digestive
ripening agents. This includes thiols,
amines, alcohol, alkanes and silanes.
Figure 8 TEM images taken at each step during the preparation of superlattice
Particle Engineering
Term used to describe the synthesis of core-shell particles with well-defined
morphologies and tailored properties
Achieved by encapsulating the nanomaterial core within the shell of a preferred
material, or by coating the nanoparticle core with the shell material
4. Ease of self-assembly
o The shell can alter the surface charge, reactivity and functionality of the metal
core thereby enhancing the stability and dispersibility of the colloidal materials
o By choosing a suitable shell-forming material, we can incorporate magnetic,
optical and catalytic properties into the composite material
o Encasing the metal core in a shell invariably protects it from physical and
chemical changes
OPTICAL PROPERTIES
The dipole plasmon frequency is related to the dielectric constant of the metal.
The frequency dependent dielectric constant of a bulk metal (w) is measurable
In electrostatic theory when the incident electric field of the radiation interacts with
the electrons, we get a net field due to the applied field and its induced field. This
field in reality is a radiating one and contributes to extinction and Rayleigh
scattering by the particle. The strength of extinction and scattering can be given
in terms of their efficiencies.
QExt =4 x Imgd
Extinction efficiency,
8 4 2
Scattering Efficiency,
Q Scat = x |gd|
3
where:
x=( 2 R m ) /( )
gd =( c m) /( c +2 m ) , c and
m are dielectric constants of the
R= particle radius
I m= imaginary part
2
The efficiency = cross section / area ( R )
In the intrinsic regime, for particles less than 10 nm in diameter, the dielectric
function itself changes with size.
Mies theory
Qext =4 x I m
[ ( s m )( c +2 s ) +(1g)( c s)( m2 s)
( s +2 s ) ( c +2 s ) +(1g)( s +2 m )( c s) ]
where:
c= core
s= shell
The color of the core-shell solutions of nanoparticles changes by varying the shell
thickness.
Figure 9 The absorption spectra of Au@SiO2 colloids as a function of solvent refractive index
(top figures) ang Ag@TiO2 (bottom A) and Ag@ZrO2 (bottom B) as a function of increasing core
dimension, a-d (A) and increasing shell thickness, a-d (B)
The transmitted and reflected colors of thin film of Au@SiO2 colloids as a function of
silica shell thickness are shown below.
Optical Non-Linearity
Organic non-linear optical materials can be used for high density data storage,
phase conjugation, holography and spatial light modulation.
Optical limiting has been the most promising among the non-linear optical
applications. Optical Limiters have a transmission that varies with the intensity of
light. One mechanism that has been particularly useful for optical limiting is two-
photon absorption and is shown by most of the materials.
The most important difficulty with the usage of common optical limiters is their low
damage threshold, that is the material themselves get damaged under the impact
of high intensity laser pulses.
Studies have shown the protected nanoparticles of silver, gold and Pd are good
optical limiters in the nanosecond regime.
TYPES OF SYSTEMS
CHARACTERIZATION
2. Optical Spectroscopy
3. Zeta Potential
PROPERTIES
1. Electrochemistry
The shells in core-shell nanoparticles are porous and hence permit electron
transport through them.
APPLICATIONS
Biological Applications
Sensing
Chemical Reactivity
Optimal Limiting
Optical sensors are important, for the light-sensitive devices that are used in the
detection of light. However, they may be susceptible to damage if exposed to a high
intensity of light, especially as in the case of a laser. Therefore, a proper protective
device is essential for protecting the sensor at high light intensities. Nanomaterials
constitute one of the best optical limiters discovered so far. The optical limiting
mechanisms of carbon nanotubes, carbon nanoparticles and carbon black suspensions
have already been studied in detail. The biggest problem with bare nanoparticles is that
they are prone to laser-induced damage at higher laser fluencies. Therefore, the
relevance of core-shell nanomaterials for this purpose has been considered as an
alternative. The presence of inert shells around the core of nanoparticle protects them
from higher laser powers.
NANOSHELLS
Introduction
Types of Nanoshells
A. Oxide Nanoshells
This group includes silica, titania and zirconia nanoshells. The unique feature of
this group is that they have a hollow core and a covering made of oxide. Their main
applications are in the fields of encapsulation of molecules and in spectroscopy.
Zirconia nanoshells
1. Two-step synthesis
The core shell particles which are synthesized by the above methods are
subjected to different reactions which result in nanoshells. For getting nanoshells, 4 ml of
the core-shell particle dispersion was mixed with 1 ml each of CCl 4 or benzyl chloride
separately. The reaction took place a period of several hours and the solution turned
colorless. Silver ions were leached out and precipitated as AgCl during the reaction.
Titania nanoshells
Titania nanoshells can also be prepared by the dissolution of the core of
Ag@TiO2 nanoparticles by using ammonia solution.
Almost the same method that was used for the synthesis of zinc oxide covered silica
which is photoluminescent.
B. Metal Nanoshells
Metal nanoshells are different from oxide nanoshells in their structure, which has
a dielectric core made of silica. The main advantage of such a system is that the optical
properties can be tuned by changing the thickness of the shell. Among this group, gold
nanoshells find application in the field of cancer therapy.
Gold nanoshells
The novelty of this material is that its properties can be tuned to scatter or
adsorb light over a broad spectral range including the near IR, a wavelength region
that provides maximal penetration of light through the tissue. This property offers the
opportunity to design nanoshells which can be used for diagnostic and therapeutic
applications and also can be used to monitor dierent analytes such as
immunoglobulin in blood, saline, etc. This system is found to have sensitivity in the
subnanogram per mL range within 10-30 min. Gold nanoshells have many
advantages over silica nanoshells. Apart from the fact that their optical properties,
especially absorption, can be tuned as a function of the thickness of the gold layer,
they have large optical cross section as compared to the conventional near-IR (NIR)
dyes.
Silver nanoshell
In another method, the seed growth approach was used to prepare to silver
nanoshells on silica nanoparticles. In this case also, the optical properties could be
changed by changing the thickness of the shell. Since its Mie resonance occurs at
energies distinct from any bulk interband transition, a silver colloid is expected to
have a stronger and sharper plasmon resonance than gold. Another advantage of a
silver colloid is that the plasmon resonance of a solid silver nanoparticle appears at a
shorter wavelength than that of gold.
PROPERTIES
Reactions like colloidal alloy formation are possible inside the silica shell. It is
found that the core of the core-shell silica particle can be converted to gold core via
oxidation with AuCl4-.
These processes are taking place because the silica shell is porous in nature
and also catalytically active; even though the core is separated by a shell. Thus the
shell acts as a selective membrane which controls the rate of the chemical
reactions with metal cores.
Since most of these nanoshells are used as containers for molecules, they
can also be used for drug delivery as well as for studying the photochemistry of
these molecules.
Fluorescein Isothiocyanate@SiO2
Fluorescein isothiocyanate is a very important dye molecule, with application
in the field of protein labeling. But one disadvantage of this dye is that it undergoes
photobleaching very fast.
It was found that the incorporation of this dye on the shell surface decreases
the porosity of the nanoshell. It takes more time for mineralization using cyanide ion
when the shell has the dye.
Optical Spectroscopy
There are many methods by which one can use optical spectroscopy to
characterize nanoshells:
In the case of silica nanoshells formed by the leaching of gold or other nanometal
core, it is possible to monitor the disappearance of the plasmon peak characteristic of it.
In the case of shells incorporated with molecules, it is possible to get the absorption
characteristics of that molecule from absorption spectroscopy.
Fluorescence Spectroscopy
Fluorescence spectroscopy is used to characterize nanoshells. The emission
spectrum of the incorporated molecule can be used for its characterization.
Cyclic Voltammetry
It is a very useful tool in cases where one is looking in the reactions taking place
inside the nanoshell.
Infrared Spectroscopy
Infrared spectroscopy provides information about the kind of linkages present in
nanoshells.
APPLICATIONS
Gold Nanoshells for Blood Immunoassay and Cancer Detection and Therapy
Since these nanoshells have a large optical scattering cross section, they can be
used as potential contrasting agents for photonics-based imaging modalities. Among the
methods, reflectance confocal miscroscopy (RCM) and optical coherence tomography
(OCT), which facilitate early cancer detection are important.