NANOCHEMISTRY

INTRODUCTION
➢ Hydrogen atom is 0.1 nm. Just ten hydrogen atoms
in a line make up nanometer.
➢ A water molecule is less than one nanometer.
➢ DNA width is 2 nm.
➢ Inside the computer, there are large number of tiny
switches and transistors that are only 100 nm’s
wide.
➢ A human hair is about 50,000 nm wide.
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Biological Nanomaterials in Nature

• Life begins at the
nanoscale
– Ion pumps move
potassium ions into and
sodium ions out of a cell
– Ribosomes translate RNA
sequences into proteins
– Viruses infect cells in
biological organisms and
reproduce in the host cell

Influenza virus
WHY NANOSCIENCE & NANOTECHNOLOGY?
➢ Typical sizes of atoms and molecules are in the 1 nm
to 100 nm range and researchers are working with
them for a long time. Can we call these atomic or
molecular chemistries as nanotechnologies?.
➢ No, because chemists were neither observing
dependencies of properties nor were suggesting
applications of these nanostructure into some
useful nanoscale devices.
➢ DEFINITION: Nanotechnology can be defined as
the application of science and scientific
knowledge, at the nanoscale, for industrial or
commercial objective.
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IS GOLD ALWAYS “GOLD”?

 Cutting down a cube of gold

 If you have a cube of pure
gold and cut it, what color
would the pieces be?
 Now you cut those pieces.
What color will each of the
pieces be?
 If you keep doing this -
cutting each block in half -
will the pieces of gold always
look “gold”?

Source: http://www.uwgb.edu/dutchs/GRAPHIC0/GEOMORPH/SurfaceVol0.gif
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Nanogold
• Well… strange things happen at
the small scale
– If you keep cutting until the gold
pieces are in the nanoscale range,
they don’t look gold anymore…
They look RED! 12 nm gold particles look red
– In fact, depending on size, they
can turn red, blue, yellow, and Other sizes are other colors
other colors
• Why?
– Different thicknesses of
materials reflect and absorb
light differently
Source: http://www.nano.uts.edu.au/pics/au_atoms.jpg
 NANOMATERIALS
➢ Nanomaterials are materials with dimensions and tolerances in the
range of 100 nm to 0.1 nm. They can be metals, ceramics,
polymeric materials or composite materials.
➢ Nanomaterials are biological, inorganic or organic structures
that, due to their small size, exhibit unique properties different
from those observed in bulk materials.
➢ Nanomaterials vary greatly in shape and composition.
➢ They specially help to improve products and applications. For
example,
 They provide higher stability in sports equipments. eg., carbon
nanotubes, fullerenes, nano clay, carbon and silica nanoparticles etc,
 Used for UV protection in sun blockers: ZnO and TiO2
nanoparticles
 Also used in self cleaning surfaces and fire protection etc.
 PREPARATION OF NANOMATERIALS
➢ Top down approach
❑ This methods starts with the bulk scale materials and then
scale them down to the nanometer level dimensions.
These involve physical breaking of the source material
through high energy processes like etching, mechanical
milling, laser ablation synthesis, arc discharge synthesis

➢ Bottom up approach
❑ This method starts with very small units, often individual
molecules or atoms and assembles, these building-block units
into larger hierarchical and controlled structures.
➢ Generally, a special and unique method is used to prepare a new
class of nanomaterial eg. Gase phase agglomeration.
➢ Fullerene can be made by vaporizing carbon within a gas
medium. (Chemical vapour deposition technique)
➢ Clay/polymer nanocomposites can be made by subjecting clay to
ion exchange and then mixing it with polymer melts.
 DIFFERENCE BETWEEN TOP-DOWN AND
BOTTOM-UP APPROACH
S. Top – down approach Bottom –up approach
No
1. In this approach, we begin In this approach, we start with
with a pattern generated on atoms or molecules and build up
a larger scale, then reduced to nanostructures.
to nanoscale.
2. This approach is expensive. This approach is less expensive.
3. This approach is slow and This approach is suitable for large
not suitable for large scale scale production.
production.
4. ▪Etching ▪Molecular self assembly
▪Mechanical grinding ▪Gas phase agglomeration
▪laser ablation synthesis ▪Chemical vapour deposition
▪arc discharge synthesis
 PROPERTIES OF NANOMATERIALS
 Nanoparticles are unique. This is because the physical
behaviour of particles changes from classical physics to
quantum physics with decreasing particle size to ≤ 100
nm.
 A nanoparticle with a radius of 2.5 nm and a density of
5 g/cm3 has a surface area of 240 m2/g when
assuming a spherical shape. However, their surface is
never exposed. The nanoparticles are always
agglomerated due to high energetic adhesive forces
close to the surface.
 By varying the particle size, properties like melting point,
solubility, colour, transparency and catalytic behaviour
changes. The physical and chemical behaviour also
changes due to varying the particle composition.
 Surface properties like dispersibility, conductivity,
catalytic behaviour and optical properties also alter.
Principal factors which cause the properties of nanomaterials
to differ significantly from other materials are:
➢ Small particle sizes ≤ 100 nm: As particle is reduced in
size, the number of atoms on surface increases as
compared to those in the interior, and so the number of
ordered electronic spins increases. A material composed
of nanoparticles or nano-crystallites would exhibit
magnetism and other properties derived from the
ordered spins, while a normal material having same
composition but conventional bigger size particles would not
exhibit such property.

➢ Increased relative surface area: The large proportion of

molecules or ions are located at the surface or grain
boundary as compared to interior of the grain
➢ Suppose radius of particle or grain = r
➢ Then the ratio of molecules or ion at the surface to the total
molecules in the grain ∝ 1/r
➢ Thus as the size of grain decreases the proportion of
molecules or ions at the grain boundary increases.
➢ Size distribution: Nanomaterials that have a wide particle
size distribution may exhibit unique properties. To exploit the
unique size-dependent properties, the nanomaterial must
be composed of monodisperse or nearly monodisperse
nanoparticles.
➢ Specific surface feature : Both size and surface feature is
resposible for unique properties of material. In
crystalline materials, the place where two faces come
together is known as edge and the places where three or
more faces come together is known as point. These edges
and points are often the location for pronounced catalytic
activity.
Crystalline nanoparticles contain enormous edges and
peaks. Thus catalytic activity of nanoparticles can be
maximized
 NANOSCALE MATERIALS
1. Carbon nanotubes (CNT)
Carbon nanotubes are sheets of graphite rolled up to make
a tube. They are about 0.4 nm in diameter. They can be
single-walled carbon nanotubes (SWCNT) or multi- walled
carbon nanotubes (MWCNT).
➢ Properties
i. They possess remarkable tensile strength.
ii. They can be insulating, semiconducting or conducting
depending on the way the graphite structure spirals around
the tube.
iii. They possess large surface area.
iv. They are thermally stable in vacuum upto 28000C.
v. They exhibit excellent electrical and mechanical
properties and capacity to carry an electric current
1000 times better than copper wires.
SINGLE-WALLED CARBON NANOTUBES (SWCNT) AND
MULTI- WALLED CARBON NANOTUBES (MWCNT)
.

Applications
➢ Carbon nanotubes are used as needles to bring active
agents into living cells. This process could be applied as a
new way to a therapy against cancer.
➢ The excellent electrical conductivity, heat transmission
capacity, heat stability, low density and high strength
makes them candidates for use as fillers in composite
materials for various applications like :
➢ Polymer LED
➢ Ultra-resistant materials for use as reinforcement fibers
➢ Electrical energy storage applications.
➢ Removal of pollutants by adsorption
 2. Fullerenes
➢ Fullerenes are a class of cage like carbon compounds
composed of fused, pentagonal and/or hexagonal sp2
carbon rings.
Properties
➢ They are insoluble in water.
➢ They exhibit excellent properties like excellent tensile
strength, and highest packing density.
➢ They possess cage like structure.
➢ They are impenetrable to all elements under normal
circumstances.

The first fullerene molecule to be discovered is

buckminsterfullerene(C60)
 .

Applications
➢ Fullerenes can be used as fillers.

➢ By the attachment of functional ligands to the carbon

cage or by trapping molecules inside the cage, they can
be potentially used as drug deliverers.
➢ The trapping of lanthanide metals inside the cage of
fullerene could enable the application as tracer molecules.
➢ They are impervious to lasers, allowing for defence in
warfare.
➢ They have been shown to be useful at fighting the HIV
and other viruses. Water soluble fullerenes developed
recently have anti-viral properties.
3. Nano-metals
Nanometals can be broadly sub-divided into two categories:
➢ Nanopowders of noble metals (Ag, Au, Pt, Pd).
➢ Bulk nano-structured metals and powders (like Ti, Ti-Al, Mg-
Ni, Al-Mg alloy etc.)
Properties
➢ Nanopowders possess high specific surface areas. They
exhibit soft magnetic properties and new deformation
mechanisms.
➢ When the nanopowders are suspended in a fluid or another
material, the most important property is the high
contribution of surfaces of the particle to the properties
of the function they are embedded in.
➢ This results in a high material activity, which could be used
as a catalyst or as source of ions for antibacterial and
antimicrobial properties.
.

Applications:
➢ Construction

➢ Catalysis

➢ Electronics

➢ Environment protection

➢ Power transmission

➢ Telecommunications

➢ Energy storage

➢ Information technology

➢ Medicine
4. Biological Nanomaterials
➢ These are materials of biological origin that are used for
nanotechnological applications.
➢ These materials mainly consist of biological molecules and
have been chosen or designed for a certain application that relies
on a nanoscale feature. For e.g., proteins, nucleic acids, lipids,
hormones, vitamins etc.
Properties:
➢ Self assembling properties
➢ Specific molecular recognition
Applications:
1 Drug delivery
2 Sensors
3 Memory devices
4 Specific filtration
5 Arrays (chips) for large scale protein or DNA screening
IMPORTANT APPLICATIONS OF NANOTECHNOLOGY

1. Smart materials
➢ Smart materials refers to any material engineered at
the nanoscale to perform a specific task.
➢ Eg., Photorefractive polymers have structures which
contain mobile electronic charges, almost like metals.
➢ They are of major interest as information storage devices
whose storage density can far exceed in comparison to
presently available magnetic storage structures.
2. Sensors
➢ Sensors are capable of responding in a recognizable way to
the presence of something we wish to detect. They indicate
the presence of particular molecules or biological structures,
as well as the amounts that are present.
i. Synthetic nanoscale sensors.
i. Electromagnetic sensors: They are sensors for
electromagnetic radiation.
ii. Biosensors: Biosensors are sensors for biological entities
like proteins, drugs, glucose etc. For e.g., DNA sensing: Lab-
on-a-chip concept:- Several screening sensors are
included on a chip for instant recognition of viral or bacterial
DNA associated with several diseases found in the body.
Such chips can also be used to sense the presence of
natural or artificial toxic species in water supplies ,
atmosphere etc.
3. Biomedical Applications
1. Drugs:
➢ Nanosize molecular drug are individual molecules that work
by interacting specifically with biological targets like DNA or
proteins within the body.
2. Drug delivery:
➢ Drug molecules can be encapsulated within nanoscale
cavities inside polymers. Then this polymer is swallowed as
part of a tablet.
➢ Within the specific place in the body, as the polymeric
structure opens up, the enclosed drug is released.
➢ This method has potential to continuously deliver the drug
smoothly over an extended period of time.
3. Photodynamic therapy:
➢ Molecular nanodot particle or a nanoshell is
placed within the body and is illuminated with
light from the outside using laser. The light is
absorbed by this particle and heats it. The heat is
released only where the particles are and where
the light is shined so it is a directed therapy.
➢ Light produces chemically reactive excited oxygen
molecules with some particular nanodots/
nanoshells. These oxygen molecules chemically
react and destroy tumors next to them.
➢ This therapy is directed and does not leave a toxic
trail of highly aggressive and reactive molecules
in the body as in Chemotherapy.
 4. Optics and Electronics
▪ Light production: In LEDs, the oppositely charged electrical
carriers recombine to form a neutral excited state, which then
loses its energy by light emission. LEDs are being used in
extremely high-resolution displays, cellular phone displays, full
room lighting, dashboard controls on automobiles, military vision
systems etc.
▪ Transmission using fibre optics: The structure of the fibre-
optic cable is quite complex. The inner fibre should be free from
in-homogeneities, cracks, impurities to minimize scattering or
destruction of signal during its propagation over thousand of
miles requiring external amplifiers or repeaters. The inner fibre is
doped with nano-structures to recover diminishing signals.
▪ Memory devices: In hard-disc memories, the bits of
information (0 and 1) are stored in magnetic nanodots.
When one bit of information is stored in one magnetic
nanodot and nanodots are spaced by distances equal to
ten times their own sizes, then it is possible to easily
store one lakh copies of Encyclopaedia Britannica on
a single page of this book.
In optical memory devices like CDs and DVDs
photorefractive nano-materials are used.

▪ Molecular Electronics : Transistors are the heart of

digital computing. Using nanotechnology, individual
molecules can act as field effect transistors. Their sizes
are 100 times smaller than currently available silicon
based transistors.
 APPLICATION OF NANOTECHNOLOGY TO FOOD
SCIENCE
The potential application of nanotechnology to food science and
technology are
➢ Food packaging: Nanocomposites packages are lighter,
biodegradable, and they have enhanced thermal stability,
mechanical strength, conductivity and gas barrier
properties.

➢ Scientists have developed ‘smart packages’ using

nanoscience. These smart packages have oxygen sensors
which are composed of ink that contains nano-particles of
titanium dioxide. The nanoparticles become sensitive to
oxygen levels once they are exposed to UV, changing colour as
oxygen levels are altered. Thus, they provide an indication of
the integrity of the product package during storage.
 .

➢ Food safety: The presence of microbial and chemical

contamination can be detected using nanosensors.

➢ Agriculture: By linking nanosensors with the global

positioning system (GPS), it is possible to do real-time
monitoring of field and crop conditions. This approach
allows farmers to more precisely manage their crops for
increased production and decreased costs and waste.
➢ Herbicide and pesticide researchers are trying to use
nanoparticles so as to allow for the improved incorporation
of active ingredients and nanoemulsions to ensure more
uniform suspensions of active ingredients.
 APPLICATION OF NANOTECHNOLOGY TO ENERGY
RESOURCES
The most important applications of nanotechnology related to
energy are:
➢ Storage, conversion, manufacturing improvements by reducing
materials and process rates, energy saving and enhanced
renewable energy sources.
Nanotechnology helps in the reduction of energy consumption
➢ By providing better insulation systems

➢ By the use of more efficient lighting or combustion systems

➢ By the use of lighter and stronger materials in the transportation

sector.
Conventional light bulbs only convert approximately 5% of
electrical energy into light. LEDs or quantum caged atoms
(QCAs) could lead to a strong reduction of energy consumption
for illumination.
 .

Nanotechnology helps in increasing the efficiency of energy

production
➢ Solar cells have layers of different semiconductors stacked together
to absorb light at different energies. Commercially available best
solar cells have about 40% efficiency. Nanotechnology could
help increase the efficiency of light conversion by using
nanostructures with a continuum of band gaps.
Nanotechnology helps in using more eco-friendly energy systems
➢ In fuel cells, the most prominent nanostructured materials is the
catalyst. It consists of carbon supported noble metal particles with
diameter of 1-5 nm.
➢ It is also possible to reduce combustion engine pollutants by
using nanoporous filters. They clean the exhaust mechanically, by
catalytic converters based on nanoscale noble metal particles or by
catalytic coatings on cylinder walls and catalytic nanoparticles as
additives for fuels.