Gold(Au) Nanoparticles

• Motivation
• History
• Colloids
• Nucleation
• Growth
• Coagulation
• Procedure
• Properties
• Applications
• Some quacks still assert profound medicinal
properties
• Spherical nanoparticles can serve as biological
tags for tracking purposes
• The red color in stained glass windows is due to
colloidal gold
• Can be used for a new ultrasensitive and
selective detection scheme for DNA
• Gold nanorods can be bar-coded Au/Pt
• Alchemists believed Au sols might be the “elixir of life”
• Faraday researched many of the properties of colloidal
gold in the 1850’s.
• Mie’s theory of light scattering was developed to explain
the color of colloidal gold.
• Medical applications were developed that diagnosed
certain diseases based on the interaction of colloidal
gold and spinal fluids
• The first comprehensive investigation using the electron
microscope began in 1948 at Princeton University and
RCA Labs
• The color of the sol arises from a combination of absorption and
scattering of light and depends on particle size
• More specifically it is due to a resonance of the free electrons in
the metal particle. The light’s electromagnetic field causes them
to slosh back and forth (plasmon oscillations).
• At a characteristic frequency which depends of the size and the
metal, the sloshing is the most intense. This is the frequency
where plasmon oscillations are excited.
• The plasmon resonance is easily seen in the extinction spectrum
of the sol.
• A colloid is a homogeneous dispersion of particles in a solution
which are so small as to not settle out easily
• A sol is a specific type of colloid characterized as a solid dispersed
in a liquid
• The colloid is stabilized by electric charges on its surface due to
adsorbed ions. The charge causes the particles to repell each
other. The both the Gold and Silver sols used here have a negative
charge.
• The particles experience the constant buffeting of Brownian motion
which also helps to keep them in suspension.
• Formulation of Au nanoparticles is a three step process: nucleation,
growth, and coagulation
• Nucleation is the creation of nuclei upon which growth
can occur
• This is a redox reaction: oxidation of the citrate ion
produces the necessary reducing reagent for the gold:
acetone dicarboxylic acid
– The acetone dicarboxylic acid is the limiting reagent for
nucleation
• The formation of this molecule in the solution creates an
induction period before which no product can be seen
• The nature of the nucleation curve is evidence of an
autocatalytic reaction
– That is to say it has a rapid growth after the induction period
followed by a linear portion and then decay
 • A type of polymerization (complexation) occurs in which
the gold ions coordinate with acetone dicarboxylic acid
and join together
• When the “polymer,” or complex, reaches a critical mass
that is just greater its thermodynamic stability, reduction
to metallic gold occurs, yielding the nuclei
• Reduction is the rate determining step in the kinetics of
the reaction
• The less citrate in the mixture, the larger the particles will
be in size

OU NanoLab/NSF NUE/Bumm & Johnson

• Growth is the addition of more gold particles to
the existing nuclei
• The process of growth stops when all of the gold
is used
• The rate of growth is a first order in the gold
nuclei size
– Having the equation dD/dt = kD, where k is a
constant whose value is independent of particle
size
• Creation of the larger gold particles, such as 20 nm,
requires a coagulation of multiple (smaller) twins of
various shapes
• A conglomeration of multiple nuclei into particles can be
large enough to disturb the stability and fall out of the
colloid
• Control of the coagulation process during preparation
determines the size, structure, and size distribution of
the particle
• Once the preparation of the gold nanoparticles is
complete, the absence of coagulation insures its stability
• Bring to a boil 50 mL of 2.5×10-4 M chlorauric acid solution
• Add 0.16 to 1.0 mL of 34 mM sodium citrate solution to the
boiling solution while stirring
• After a minute will be faint blue and then darkening over 5
min to a brilliant red
• The size of the gold nanoparticles can be controlled by
varying the amount of sodium citrate solution. The above
procedure can grow controlled sizes from 147 nm (0.16 ml)
down to 16 nm (1.0 ml).
OU NanoLab/NSF NUE/Bumm & Johnson
 Optical & Electronic Properties of Gold Nanoparticles
• Gold nanoparticles’ interaction with light is strongly dictated by their
environment, size and physical dimensions. Oscillating electric fields
of a light ray propagating near a colloidal nanoparticle interact with
the free electrons causing a concerted oscillation of electron charge
that is in resonance with the frequency of visible light. These
resonant oscillations are known as surface plasmons. For small
(~30nm) monodisperse gold nanoparticles, the surface plasmon
resonance phenomenon causes an absorption of light in the blue-
green portion of the spectrum (~450 nm) while red light (~700 nm) is
reflected, yielding a rich red color. As particle size increases, the
wavelength of surface plasmon resonance related absorption shifts
to longer, redder wavelengths. Red light is then absorbed, and blue
light is reflected, yielding solutions with a pale blue or purple color

OU NanoLab/NSF NUE/Bumm & Johnson

 Contd...
• As particle size continues to
increase toward the bulk limit,
surface plasmon resonance
wavelengths move into the IR
portion of the spectrum and most
visible wavelengths are reflected,
giving the nanoparticles clear or
translucent color. The surface
plasmon resonance can be tuned
by varying the size or shape of the
nanoparticles, leading to particles
with tailored optical properties for
different applications.
•

OU NanoLab/NSF NUE/Bumm & Johnson

 Contd...
Colors of various sized monodispersed
gold nanoparticles
• This phenomenon is also seen when
excess salt is added to the gold
solution. The surface charge of the
gold nano particle becomes neutral,
causing nano particles to aggregate.
As a result, the solution color changes
from red to blue. To minimize
aggregation, the versatile surface
chemistry of gold nano particles allows
them to be coated with polymers, small
molecules, and biological recognition
molecules. This surface modification
enables gold nano particles to be used
extensively in chemical, biological,
engineering, and medical applications

OU NanoLab/NSF NUE/Bumm & Johnson

 Applications
• Electronics - Gold nanoparticles are designed for use as
conductors from printable inks to electronic chips.1 As the world of
electronics become smaller, nanoparticles are important
components in chip design. Nanoscale gold nanoparticles are being
used to connect resistors, conductors, and other elements of an
electronic chip.
• Photodynamic Therapy - Near-IR absorbing gold nanoparticles
(including gold nanoshells and nanorods) produce heat when
excited by light at wavelengths from 700 to 800 nm. This enables
these nanoparticles to eradicate targeted tumors.2 When light is
applied to a tumor containing gold nanoparticles, the particles
rapidly heat up, killing tumor cells in a treatment also known as
hyperthermia therapy.

Routray & Routray foundation

OU NanoLab/NSF NUE/Bumm & Johnson
 Contd...
• Therapeutic Agent Delivery - Therapeutic agents can also be
coated onto the surface of gold nanoparticles.3 The large surface
area-to-volume ratio of gold nanoparticles enables their surface to
be coated with hundreds of molecules (including therapeutics,
targeting agents, and anti-fouling polymers).
• Sensors - Gold nanoparticles are used in a variety of sensors. For
example, a colorimetric sensor based on gold nanoparticles can
identify if foods are suitable for consumption.4 Other methods, such
as surface enhanced Raman spectroscopy, exploit gold
nanoparticles as substrates to enable the measurement of
vibrational energies of chemical bonds. This strategy could also be
used for the detection of proteins, pollutants, and other molecules
label-free.
 Contd..
• Probes - Gold nanoparticles also scatter light and can produce an array of
interesting colors under dark-field microscopy. The scattered colors of gold
nanoparticles are currently used for biological imaging applications. Also,
gold nanoparticles are relatively dense, making them useful as probes for
transmission electron microscopy.
• Diagnostics - Gold nanoparticles are also used to detect biomarkers in the
diagnosis of heart diseases, cancers, and infectious agents. They are also
common in lateral flow immunoassays, a common household example
being the home pregnancy test.
• Catalysis - Gold nanoparticles are used as catalysts in a number of
chemical reactions. The surface of a gold nanoparticle can be used for
selective oxidation or in certain cases the surface can reduce a reaction
(nitrogen oxides). Gold nanoparticles are being developed for fuel cell
applications. These technologies would be useful in the automotive and
display industry.
Contd...