BATANGAS STATE UNIVERSITY

College of Engineering, Architecture, Fine Arts

Gov. Pablo Borbon Campus II, Alangilan, Batangas City, Philippines 4200

www.batstate-u.edu.ph Telefax: (043) 300-4404 locs. 106-118

CHEMICAL AND FOOD ENGINEERING DEPARTMENT

ChEE 401 - ChE Elective 1

Alib, Lhester
Balmes, Lyka
Dapul, Lara May
Delmo, Shara Jane
Guillano, Justin
Lubay, Kathleen Mae

ChE 4302

Dr. Sicily B. Tiu

March 2017
MONOLAYER-PROTECTED METAL NANOPARTICLES

INTRODUCTION
In 1857, Faraday made a colloidal gold by reducing the aqueous
solution of AuCl4- with phosphorus in CS2.
Citrate reduction method of Turkevitch is the most popular where a
solution of the gold or silver salt (typically 1mM) is boiled with a higher
concentration (typically 1M) of sodium citrate for a few minutes. This
results to formation of metal colloids of 10-50nm diameter. The
stability of this solution is due to an electrical double layer surrounding
the metal surface and is stable as long as the conditions are not
altered greatly.
The 3D monolayers or monolayer-protected metal clusters (MPCs)
belong to a category of materials wherein the constituting monolayer-
protected clusters or nanoparticles behave like molecules.

METHOD OF PREPARATION

Fig.1 Burst Method of Preparing Monolayer-Protected Clusters

Burst, et al. combined the two-phase method of Faraday and the
technique of phase transfer catalysis. They prepared
dodecanethiol-protected gold nanoparticles 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 then reduced in the presence of
the surfactant, octadecanethiol using NaBH4 as the reducing
agent.

Overall reaction:
AuCl4-(aq) + N(C8H17)4+ (toluene) N(C8H17)4+ AuCl4-(toluene)
m AuCl4-(toluene) + nC12H25SH(touluene) + 3me- (Aum)
(C12H25S)n(toluene) +4mCl-1(aq)
 CHARACTERIZATION
Characterization of Self-Assembled Monolayers (SAMs)
1. UV/vis spectroscopy has been used to characterize the core of the
material.
2. High resolution transmission microscopy- showed FCC packing of
atoms in the gold core with a mixture of particle shapes with
predominantly truncated octahedral, cuboctahedral and icosahedral
structures at lattice resolution on size-selected gold
nanocrystallites.
3. X-ray photoelctron spectroscopy- used to find out the oxidation
state of gold in the material.
4. IR spectroscopy- a powerful tool used to study the structure of the
adsorbate on the metal surface.
5. 13C NMR spectra of alkaline thiol- stabilized clusters for three
different alkyl chain lengths showed that the peak narrows down as
the distance of the carbon from gold surface increases.

MPCs display current due to double layer charging of the metal core.
This is due to the extremely small sub-atto Farrad capacitance of MPCs. The
double layer charging occurs as a series of one electron, approximately
evenly spaced, current peaks as shown in the figure below.

Fig.2 Differential Pulse Voltammetry of 0.1 nM C6MPCs in CH2Cl2

FUNCTIONALIZED METAL NANOPARTICLES
The synthesis of functionalized nanomaterials has been receiving
considerable attention during the past few years. Functionalization can either
be through a ligand exchange reaction or using modified thiol as the capping
agent in the Burst method.
Fig.3 Various photoactive molecules attached to the surface of gold using the
thiol end group and such structures

Fig.4 Reversible binding of amino acids with spiropyran capped gold

nanoparticles
 Fig.5 Gold nanoparticles-assisted enhancement of fluorescence in pyrene
methyl amine. Due to the attachment of nitrogen onto the nanoparticles,
conjugation between lone pair on nitrogen and the pyrene is blocked.
APPLICATIONS
Due to very high extinction coefficients of gold nanoparticles and its
color change during the transition of nanoparticles from the dispersed to
aggregate state is quite evident, coupling of nanoparticles with ionophores
gives better sensors.

Fig.6 Sensing of potassium ion by crown ether functionalized gold

nanoparticles
 Fig.7 Shows the Li+ ion assisted aggregation of gold nanoparticles

Fig.8 Structure of ligand used in Fig.7

Fig.9 TEM picture of the aggregate

Fig.10 Ion-assisted chelation for the detection of heavy metals

SUPERLATTICES
Superlattice is a periodic, synthetic multi-layer, wherein a unit cell,
consisting of successive layers that are chemically different from their
adjacent neighbors, is repeated. They are characterized by their double
periodicity in the structure, periodicity of atoms in the angstrom level, and
periodicity of nanocrystals in the nanometer.

Fig.11 Temperature sensor based on gel-coated nanoparticles

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 as shown in
the figure below.

Fig.12 Potential energy-distance curve showing the resultant interaction

energy
Monodispersity is another important factor that controls the formation
of superlattice. Size selective separation is requiredto make monodisperse
particles. The method developed by Murray, et al., 1993, facilitates the
synthesis of monodisperse particles.
Method by Murray, et al., 1993- metal-organic precursors are injected
into a hot solution containing co-ordinating ligands like trioctyl phosphine.
When a drop of solution of monolayer-protected cluster in a volatile
organic solvent is placed on a plane surface and allowed to evaporate under
controlled conditions, the particle starts coming closer, the individual
nanocrystals start nucleating and the crystals starts growing. This is followed
by annealing process which results in the formation of superlattices.
 In hydrophobically-modified SAMs, hard sphere repulsion and the van
der Waals forces assist the formation of superlattices.

Fig.13 Pictorial representation of a superlattice

Formation of a superlattice is easy if the surface of the nanoparticle is
modified with thiols with the terminal group capable of forming hydrogen
bonds.
Kimura- observed the hydrogen bond-meditated formation of
superlattices in mercaptosuccinic acid modified gold nanoparticles.
Digestive ripening - is another way of making superlattice.
- Already prepared nanoparticles are refluxed in a
solvent with ligands capable of acting as digestive
ripening agents (thiols, amines, alcohols, alkanes, and
silanes). Thiols are found to be the best ripening
agents.

Fig.14 TEM images taken at each step during the preparation of superlattice
 Superlattices result from collective interactions, which is different from
individual nanocrystals. One of the interesting phenomena observed in a
superlattice is the metal-insulator transition.

CORE-SHELL NANOPARTICLES
Core shell nanoparticles are hybrid systems. They have a core and a
shell. Various cores and diverse shells are available. The cores and shells can
have distinct attributes such as metallicity, semiconductivity, magnetism,
etc.

INTRODUCTION
One of the fascinating characteristics of nanomaterials is that their
properties are dependent on size, shape, composition and structural order.
Core-shell nanoparticles, ie. particles with a well-defined core and a shell
both in the nanometer range, have demanding applications in
pharmaceuticals, chemical engineering, biology optics, drug delivery and
many other related areas in addition to chemistry.
For the past decades, there is a widespread research on core-shell
colloidal nanoparticles. Some examples are composite coatings which are
used in sensors, nanoelectronics, catalysis and pharmaceuticals.
The term used to describe the synthesis of core-shell partcles with
well-defined morphologies and tailored properties is called particle
engineering. This is achieved by encapsulating the nanometal core with the
shell material. The shell protection imparts certain functional properties to
the nanomaterial including: (1) monosdispersity in size (2) core and shell
processibility, (3) solubility and stability, (4) ease of self-assembly, and (5)
applications in nanoscale optic, nanoelectonics, as well as in magnetic,
catalytic, chemical and biological fields. Shell protection is absolutely
necessary for the following important reasons: (a) the shell can alter the
surface charge, reactivity and functionality of the metal core thereby
enhancing the stability and dispersibility of colloidal materials : (b) by
choosing a suitable shell-forming material, we can incorporate magnetic,
optical and catalytic properties into the composite material; (c) encasing the
metal core in a shell invariably protects it from physical and chemical
changes; and (d) core-shells exhibit improved physical and chemical
characteristics as compared to their single component counterparts.
9.2 TYPES OF SYSTEMS
9.2.1 METAL- METAL OXIDE CORE- SHELL NANOPARTICLES
Nanosized metal clusters have intense colour, which can be tuned by
varying the size of the clusters. One of the major problems associated with
their handling id their vulnerability to aggregation. To avoid this, various
methodologies have been developed, with the most notable one being
coating them with silica, titania, zirconia and manghemite. Liz- marzan et al.
have developed a synthetic procedure to prepare silica-coated nanosized
metal clusters, and the same methodology has been applied to various
metals like Au, Ag and CdS.
The methodology uses 3-aminopropyl trimethoxy silane (APS), the
silane coupling agent, which can bind to the nanoparticles surface and can
also function as an anchor point for the chemical deposition of active silica
(Sio32-).
An aqueous dispersion of citrate-capped Au nanoparticles has been
treated with amino propyl trimethoxy silane (APS). A thin layer of active silica
is deposited onto the activated surface of Au clusters, which are thereby
stabilized and can be transferred to ethyl alcohol. After transfer into the
ethanol medium, the silica shell can be grown on it by using the standard
Stober procedure. The thickness of the silica shell can be adjusted by using
this method and can be varied from 10-83 nm. The absorption characteristics
are tunable according to the shell thickness.
Compatibility between the metal core and the inorganic shell forming
materials is also a prerequisite for obtaining uniform coatings with
aggregation.
A recent study extended the methodology to the syntheses of ZrO2
and TiO2 coated Au and Ag nanoparticles through a one step synthesis.
The synthetic insertion of Au nanoparticles into the mesoporous silica
was demonstrated by Konya, et al. using the mesoporous silica materials
MSM 41 and MCm -48.
Another important process for the development of metal-metal oxide
core-shell nanoparticle was used by Teng, et al. Robust Pt-manganese
(Fe2O3) core-shell nano particles were synthesized by a one-pot method
involving the reduction of platinum acetylacetonate in octyl ether-yielding Pt
nanoparticles. Layers of iron oxide were subsequently deposited on their
surface as a result of the thermal decomposition of iron pentacarbonyl.
Examples of Core Shell Nanoparticles:

Fig.1.1 Faradays Gold. A sample flask containing a

sample of a gold colloid made by Michael Faraday in
1857. A gold colloid is a suspension of microscopic
particles of metallic gold in water. He used phosphorus
to reduce a solution of gold chloride, as the metal
precipitates out it forms particles of the order 100
nanometres in diameter. The colour of the colloid is
determined by the particle size.

Fig 1.2. Lycurgus Cup. The glass chalice,

known as the Lycurgus Cup because it
bears a scene involving King Lycurgus of
Thrace, appears jade green when lit from
the front but blood-red when lit from
behinda property that puzzled scientists
for decades after the museum acquired the
cup in the 1950s. The mystery wasnt
solved until 1990, when researchers in
England scrutinized broken fragments under a microscope and discovered
that the Roman artisans were nanotechnology pioneers: Theyd impregnated
the glass with particles of silver and gold, ground down until they were as
small as 50 nanometers in diameter, less than one-thousandth the size of a
grain of table salt. The ancient nanotech works something like this: When hit
with light, electrons belonging to the metal flecks vibrate in ways that alter
the color depending on the observers position.

Fig 1.3. Quantum Corral. In 1993 D. Eigler and his collaborators created a
so-called "quantum corral" by placing 48 iron atoms in a circle on a copper
 surface and thus demonstrated a shining
example of forming nano-objects through
the manipulation of individual atoms with
the use of scanning tunnelling microscopy
(STM). A quantum corral acts as a two-
dimensional cylindrical quantum well
confining surface state electrons. Circular
waves observed inside the corral in the STM
image are standing waves of electron
density, whose existence is predicted by
Schrodinger's equation for those boundary
conditions. The possibility of building quantum corrals of various shapes
(triangular, rectangular, hexagonal, etc.) was shown. Using an elliptical ring
of cobalt atoms on a copper surface, the researchers demonstrated the
effect of "quantum mirage": when a cobalt atom was placed at one focus of
the ellipse, a mirage of the atom appeared in the STM image at the other
focus. Moreover, the electronic properties of the two-dimensional electron
gas surrounding both foci were similar, even though the cobalt atom was
only present at one focus.
Fig 1.4. Raman. Since Raman spectroscopy is a
nondestructive method, it is commonly used in
characterization of the structure and quality of
synthesized diamond films
Fig 11.6 Target selective fluorescent and TEM imaging of PML bodies on cell
nucleus using 10nm Gold and 10-15 nm CdSe nanocrystal. A and D are
fluorescence image of HEp-2 PML I cells labeled with 10 nm gold and CdSe
particles. B and E are the TEM images of the marked areas given in Fig A and
D, respectively C and F are enlarged views of B and E.

High resolution optical images of SiHa cells

labeled with anti-EGFR/gold conjugate. Non-
specific labeling using gold conjugates with BSA is
shown in E and F. Laser scanning confocal
reflectance (A C and E) and combined with
confocal reflectance/transmittance (B D and F).
(40X objective). Scattering from gold conjugates is
false-colored in red. On A and B focal plane is at
the top of the cells. C and D on middle cross-
section.
Scheme 11.3: This scheme represents an immunoassay based on target
selective surface-enhanced Raman scattering (SERS) probe.
Scheme 12.3: Some of the methods of template-assisted organization of
nano particles.

Scheme 12.5: The working of an electronic nose. The diffused colors

represent different gases while the solid colors represent the various nano
particles that are sensitive to specific gas molecules. The gases thus
adsorbed on the films might be removed by suitably heating the array, thus
making repeated use of the system possible.
Scheme 12.7: Cartoon representation of fabrication protocol of a nanofiber as
a probe for biological sensing and imaging. As the optical fiber is withdrawn
from the HF solution, surface tension causes the HF to initially rise along the
organic cladding. Slow draining of HF from there causes a nanotip to be
formed, after which the organic cladding is removed by treating with a
suitable solvent.

Scheme 12.9 Proposed structure of a smart dust multifunctional sensor.

HRTEM images of Ag@ZrO2 core-shell nanoparticles functionalized with a
stearate monolayer. From Nair et. al.

Bimetallic Core-shell Nanoparticles

Various bimetallic core-shell nanoparticles have been synthesized in
the recent past because of their renewed interest in catalysis. Henglein
synthesized core-shell alloys of Au-Pt through the simultaneous reduction of
chloroauric acid and chloroplatinic acid.

Semiconductor Core-shell Nano particles

Semiconductor nanocrystal exhibit interesting size-dependent optical
properties because of the confinement of electronic wavefunctions. Control
of their surface is the key to highly luminescent nanocrystal. This is because
of the presence of a large number of surface defects arising from
nonstoichiometry, unsaturated bonds. Over coating of nanocrystallites with
higher band gap inorganic materials has been shown to increase the photo
luminescence quantum yields due to the passivation of surface non-
radioactive recombination sites.
Polymer-coated Core-shell Nanoparticles
Polymer-coated core-shell nanoparticles have interesting applications
ranging from catalysis to industry in making additives, paints and pigments
and a host of other materials. The synthetic methodologies adopted for
polymer capping of nanoparticles are of two main classes, namely: (a)
polymerization at the nanoparticle surface, (b) adsorption of pre-formed
polymer onto the nanoparticle cores.
 Fig 9.9: TEM of LbL assembled polystyrene-capped Au nanoparticles.

Characterization
X-ray Diffraction (XRD)
Power X-ray diffraction is one of the powerful techniques for the
characterization of core-shell nanoparticles.
In case of materials where the core and the shell are crystalline,
diffraction patterns from the prominent lattice planes can be seen in
the diffractograms.

Optical Spectroscopy

Optical spectroscopy is another very important tool used for the

characterization of nanomaterials.
All the nanostructured materials exhibit unique and complex optical
properties.
Plasmons-electromagnetic resonance resulting from the collective
oscillations of conduction band electrons.
The resonance frequency mainly depends on the restoring force.
Zeta Potential
Zeta potential or electrokinetic potential is the potential at which the
fixed part of the double layer along with a part of the mobile layer
moves towards an electrode.
It can also be defined as the potential at the shear plane of the particle
when it moves in the medium.
The measure of zeta potential throws a light on the stability of
colloidal/nanoparticles solutions. If all particles in a suspension have
large negative or positive zeta values, then they will repel each other
and there will not be any tendency to flocculate.
If particles have low zeta potential values, then there is no force to
prevent the particles from coagulating.
The greater the zeta potential, the greater will be the stability.
The zeta potential is traditionally measured by using the micro
electrophoresis method. Microelectrophoresis is a technique based on
light scattering by particles.

Zeta potential depends on a number of parameters like:

Surface charges
Ions adsorbed at the interfaces
Nature and composition of the surrounding medium

Zeta potential is calculated according to Smoluchowskis Formula

Properties
Electrochemistry
The shells in core-shell nanoparticles are porous and hence permit
electron transport through them
The porosity of core-shell nanoparticles was extensively
investigated by using cyclic voltammetry and absorption
spectroscopy.
Optical Properties
Optical properties of nanoparticles

The optical interaction induces a dipole moment that oscillates

coherently at the frequency of the incident wave.
The frequency of this oscillation depends on the:
Electron density
Effective mass
Shape and size of the charge undergoing oscillation
The collective oscillation of the free conduction electrons is called
plasmon resonance of the particle and is schematically depicted by:

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.

A dispersion diagram showing the conditions of surface Plasmon resonance

as a function of wavelength of the incident light is shown in:
FIGUREEEEEEE 9.13
Optical properties of core-shell nanoparticles

The optical characteristics of core-shell nanoparticles can be explained

on the basis of the modified Mies theory, which considers the
scattering of light from spheres coated with a homogeneous layer of
uniform thickness.
For nanometer-sized objects of core-shell nanoparticles considered
here, the particles may be described as dipole oscillators.
 The degree of scattering by the shell layer can be controlled by
altering the refractive index of the solvent. This means that even if the
particles are grown to micron size by silica deposition, the sol can still
exhibit the optical properties of the nanoparticles cores.

Optical Non-Linearity

Organic non-linear optical materials can be used for high density data
storage, phase conjugation, holography, and spatial light modulation.
Among the non-linear optical applications, optical limiting has been the
most promising.
A non-linear absorption wherein the materials absorbance increases
with the intensity of the incident light is obviously useful for optical
limiting. One mechanism that has been particularly useful for optical
limiting is two-photon absorption.

Applications
Biological Applications
Magnetic core-shell particles are used in clinical applications and
biotechnology, as the shells can be made biocompatible. They also find
extensive uses in:
The transportation of drugs to the sites of diseases
Functions as magnetic carriers for the isolation of blood cells and
antibodies

Magnetism of Core-shell Nanoparticles

The magnetism of core-shell nanoparticles can be tuned by varying the
shell thickness
The Fe58Pt42/Fe3O4 core shell nanoparticles are ferromagnetic at low
temp but super-paramagnetic at room temperature. Such materials
find application in:
Ultra high density magnetic storage
Biological labeling
Detection and drug delivery
The super paramagnetism of -Fe2O3 nanoparticles has been utilized in
making facile recyclable catalysts in Suzuki cross-coupling reactions.
Magnetic nanoparticles are used in various areas such as:
Bearings
Seals
Lubricants
Heat carriers
 Printing
Recording
Polishing media
MRI
Drug delivery
Biological separations
Therapy
Magnetic nanoparticles are being tested as contrast-enhancing agents
for cancer imaging and therapy.

Catalysis

Catalysis by core-shell nanoparticles is a very important, active and

emerging area, which can have a tremendous impact in the chemical
industry, pharmaceutical products and the fuel sector.
More than 90% of all industrial processes are catalytically controlled.

9.5.4 Sensing
The most important challenge in the field of chemical/biological sensors is
the rational design of materials with high sensitivity and selectivity.
Nanostructured materials provide challenging opportunities for adressing
problems because of their new and unique interparticle spatial and chemical
properties that can be fine-tuned with various parameters. The sensing
properties are highly dependent on several design parameters such as
particle size, interparticle distances and the dielectric constant of
the surrounding medium.
Sensors in the field of biology are in great demand now because of
their potential uses in detecting the mutations of genes.
Biosensor technologies for DNA are also in great demand because of
the sensitivity and selectivity they offer.
The construction of nanoarrays on the basis of design parameters
facilitates real-world sensing applications like detection of toxic gases,
explosives and toxins.
Alternative laver-by-laver assemblies of core-shell nanostructured
materials have found interesting new applications in sensors and
actuators on a wide scale.
Dye-embedded core-shell nanoparticles with surface Raman
enhancement are excellent spectroscopic tags for detection protocols.

Core-shell nanoparticles
Metallic core-optical enhancer
 Reporter molecule-spectroscopic tag
Inert shell-stabilization and conjugation

9.5.5 Chemical Reactivity

The chemical reactivity of core-shell nanoparticles is fascinating
because they are excellent substrates for the conduct of C-C coupling
reactions. Their specific chemistry leads to the metal core getting leached
away by suitable molecules and thereby results in oxide shells or oxide
nanobubbles. The most widely studied core-shell nanosystems in this
category are Ag@TiO2, Au@TiO2, Ag@ZrO2, Au@ZrO2 and Au@SiO2.
9.5.6 Optical Limiting
Optical sensors are important, for the light-sensitive devices that are
used in the detection of light. A proper protective device is essential for
protecting the sensor at high light intensities. Nanomaterials constitute one
of the best optical limiters so far. The presence of inert shells around the
core of nanoparticle protects them from higher laser powers. Core-shell
nanomaterials are very good optical limiters and the most prominent
mechanism observed for optical limiting is non-linear scattering. They are
revealed by Z-scan experiments. The z-scan technique is a method by
which the sample is scanned along an axis (z-axis) while the laser is focused
on it by lens.

Chapter 10-NANOSHELLS
Nanoshells are important from the point of view of cancer therapy
and spectroscopic applications. Their method of synthesis is quite simple and
includes one-step and two-step approaches. Silica nanoshells are used
mainly in the field of molecular encapsulation while metal nanoshells are
used for cancer therapy. Principal tools for their characterization are
absorption spectroscopy, fluorescence spectroscopy and
transmission electron spectroscopy.
0.1 Introduction
Nanoparticles are stabilized by different types of ligands such as
organic molecules, polymers, surfactants, etc. Nanoparticles, whose surface
is passivated by a shell with its own distinct properties other than the core,
are called core-shell particles. Such coatings not only stabilize colloidal
dispersions but also allow modification and tailoring of the particle
properties.
 Nano-sized objects which have only the shell and are devoid of the
core, are called nanoshells sometimes called as nanocapsules and
nanobubbbles. Nanoparticles of metallic, semiconducting, and magnetic
materials have recently generated interest in terms of research because of
their potential uses in optoelectronics, reprography, catalysis, chemical and
biological sensing, etc. Among the metallic particles, the study of colloidal
gold particles particularly stands out.
Nanoshells which are obtained in the case of oxide nanoshells have
diameters in the range of 10-20 nm. In the case of metal nanoshells like
gold and silica shell, the thickness of the shell can be up to around 20 nm.
10.2 Types of Nanoshells
It is possible to obtain nanoshells by surface precipitation of inorganic
molecular precursors on particles and removal of the core by thermal or
chemical means.

10.2.1 Oxide 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 spectroscopy.
Holllow silica nanoshells

Has certain advantages when used as a protecting agent

Chemically inert, does not affect reactions taking place at the core
Optically transparent
Useful in the study of the photochemistry of molecules, mainly
fluorophores

Zirconia nanoshells
Form the point of view of catalysis and sensing
Made from core-shell particles synthesized by two-step or one-step
routes

Synthesis of core-shell particles

1 Two-step synthesis. The first step is to synthesis of the core-
shell particles. Silver nanoclusters are made first as in the case
of monolayer protected clusters. The monolayer made has a
carboxyl functionality. The method used is called the Brust
method.
 2 One-pot synthesis. In this method of making core-shell
nanoparticles, the method adopted is the reduction of noble
metals by dimethlyformamide in the presence of oxide forming
precursors. It is possible to make silver- and gold-covered
zirconia as well as titania in this manner.

Titania nanoshells
Can also be prepared by the dissolution of the cores of Ag@TiO 2
nanoparticles using ammonia solution
The shells have diameters of 10-30 nm and thicknesses of 3-5 nm.
Has applications in the biomedical field

Zinc oxide nanoshell having silica core

Simultaneous introduction of triethanolamine and Zn(Ac)2 into the SiO2
ethanol dispersion yields this composite.

10.2.2 Metal Nanoshells

Metal nanoshells are different from oxide nanoshells in their structure,
which has a dielectric core made of silica.
Gold nanoshells

Its properties can be tuned to scatter or adsorb light over a broad

spectral range.
Have sensitivity in the subnanogram per mL range within 10-30 min
Have large cross-section as compared to the conventional near-IR (NIR)
dyes
Also show improved photostability
The gold surface can be used to anchor different molecules.
The gold surface is generally considered to be biocompatible.

Silver nanoshells
In another method, the seed growth approach was used to prepare
silver nanoshells on silica nanoparticles.
Optical properties can also be changed
A silver colloid is expected to have a stronger and sharper plasmon
resonance than gold.
The plasmon resonance appears at a shorter wavelength than that of
gold.
Preparation of a silver nanoshell on a silica shell
1 The silica sphere core is treated with an amine terminated surface
silanizing agent.
2 Growth of a silver nanoshell over layer.
3 Growth of silver particles.
Nanoshells From Liposomes
Liposomes

covered with silica - nonporous in nature

are very sensitive to parameters such as pH and ionic strength, and
also to the presence of the organic solvents in the reaction mixture.
can be used in the case of drug delivery
are biological systems and biodegradable
Synthesis of Liposomes Covered with Silica (Bangham)
1 L dipalmitoylophosphatdylcholine was dissolved in chloroform.
2 Solvent was removed, a buffer solution was added and a 10 mg ml-1
lipid suspension was made.
3 The suspension was then extruded above the transition temperature of
the lipids (41oC) using an extruder having polycarbonate membranes.
(Quasi-Elastic Light Scattering (QELS) measurements, 108 nm)
a QELS allows one to study the dynamics if a system real-time
4 The silica is grown by adding tetraethylorthosilane to the diluted
suspension of liposomes at room temperature with stirring.
5 Addition of the NaF (4% molar ratio with respect to TEOS).
6 Stirred for 48 hours and dried at 40oC to obtain silica covered
liposomes.
Properties
Reactions inside the Silica Nanoshell
Colloidal Alloy Formation Inside Silica Shells
It is found that the silver core-shell silica particle can be
converted to gold core via oxidation with AuCl-4.
Silica shell
Porous in nature and also catalytically active even though the
core is separated by a shell.
The shell acts as a selective membrane which controls the
rate of the chemical reaction with the metal core.
 The rate can be controlled by varying the thickness of the
silica shell.
Formation of Carbon Onions inside Silica Nanoshells
Nanoshells can be formed from Au@SiO2 by leaching gold using
carbon tetrachloride. It is found out that the amorphous carbon
produced in the leaching process gives rise to carbon onions
inside the shell.
Incorporation of Molecules Inside the Nanoshells
Nanoscopic containers

Used for controlling the environment of the molecule

Nanoshells

Can be used as carriers of molecules

Helps protect the molecule from unwanted chemical reactions
Can be used for drug delivery as well as studying
photochemistry
Cavity

Provides rigid environment for adsorbed molecules

Incorporation of Dye Molecules Inside Silica Nanoshells
Steps to incorporate any molecule
1 Functionalize the molecule to have an amino or
thiocynato group.
2 Add the functionalized molecule together with the
aminopropylsilane.
3 Do further polymerization using tetramethyl
orthosilicate.
4 Allow further shell growth in ethanolic medium.
Aminopropylsilane
Precursor for shell formation
Fluorescein Isothiocyante@SiO2
Self-quenching occurs due to decrease in the quantum yield of
the encapsulated dye.
Decreases porosity of the nanoshell.
Takes more time for mineralization using cyanide ion when
shell has the dye.
Fluorescein Isothiocyante
 Very important dye molecule, with applications in the field of
protein labeling
Undergoes photobleaching very fast

Modification of Silica Shell for Immunoassays

The success of targeted drug delivery depends upon two facts:

Attachment of antibody to the silica surface

The ability of the antibodies to bind their specific antigen
while they are attached to the shell.
Characterization
Transmission Electron Microscopy

It is main technique used for the characterization of nanoshells as can

see the nano structures.
Optical Spectroscopy
In case of Monitored
Silica nanoshells formed by leaching Disappearance of plasmon peak
of gold or other nanometal core characteristic
Shells incorporated by molecules Absorption characteristics
Metal nanoshells Formation

Fluorescence Spectroscopy
Used to characterize nanoshells
Emission spectrum of the incorporated molecule can be used for
characterization
Cyclic Voltammetry

Provide valuable information on the molecules present inside the

nanoshell, thus probing the shell indirectly
Used in looking for the reactions taking place inside the nanoshell
Infrared Spectrocopy
Provides information about the kind of linkages present in nanoshells
Applications
 Electrochemical dopamine sensing using an LbL of TiO2
Gold Nanoshells for Blood Immunoassay and Cancer Detection and
Therapy
Gold Nanoshells for Enhancing the Raman Scattering