Unit -III

2 MARKS:

1. Define Nano-chemistry.
Nanochemistry is a scientific branch that deals with the synthesis, analysis and
structure of the chemical compounds at the nanoscale.

2. Write the classifications of nanomaterials based on their shape.

 Nanomaterials are defined as the materials having a size of roughly 1 to
100 nanometers. They may be in the form of particles, tubes, rods or
fibers.
 Based on their sizes and shapes, they can be divided into the following
types.
Nanospheres, nanotubes, nanorods, nanofibers, nanofilms etc…

3. How are nanomaterials classified based on their dimension?

Based on their dimensions, nanomaterials are classified as follows;
 Zero dimensional nanomaterials.
 One dimensional nanomaterials.
 Two dimensional nanomaterials.
 Three dimensional nanomaterials.

4. What is magic number?

Magic number is the number of atoms present in the clusters of criticle sizes
with higher stability.

5. Write about the various steps involved in synthesis of CVD.

 Transport and adsorption of gaseous reactants on the surface.
 Occurrence of the catalyzed reaction on the surface.
 Diffusion and nucleation of product on the growth sites.
 Desorption of product away from the surface.

6. Define size effect.

 Size effect constitutes a peculiar and fascinating aspect of
nanomaterials.
 The effect determined by the size pertain to the evolution of structural,
thermodynamic, electronic, spectroscopic, electromagnetic and
chemical features of these systems with changing size.
 7. Write the electrical properties of nanomaterials.
 The electrical conductivity decreases in reduced dimension but
increases in nanocomposites.
 The electric resistance increases in metal nanoparticles.

8. What is meant by laser ablation?

 Laser ablation is the process of removing material from a solid
substance.
 Also known for the process of removing material from a solid (or
occasionally liquid) surface by irradiating it with a laser beam.

9. Write any four nanomaterials.

 Carbon-based nanomaterials
 Metal-based nanomaterials
 Dendrimers
 Nanocomposites

10. Differentiate quantum well and quantum dot.

Quantum Well Quantum Dot

It is a two-dimensional system It is a zero-dimensional system
The electrons can move in two The electron movements are restricted in entire
directions and restricted in one three directions
direction

13 MARKS :

1.Write detail notes on properties of nanomaterials including size dependent

properties.

SIZE DEPENDENT PROPERTIES OF NANO MATERIALS

 The nano materials have different properties when compared to bulk due to
the following reasons
 Large surface area can make nano materials more chemically reactive and
affect their strength or electrical properties.
 Quantum effects can begin to dominate the behavior of matter at nanoscale,
which affects several properties such as melting point, bolling point, band
gap,optical properties, mechanical properties and magnetic properties.
  Nanomaterials are composed of grains resulting a significant Increase in the
volume fraction of grain boundaries or Interfaces, resulting defect
configurations.
 Hence the mechanical and chemical properties of nanomaterials are
significantly altered due to defect dynamics.
 The elastic property of nanomaterials are different from that of bulk alloys
due to the presence of increased fraction of defects.

Example

 Nanocrystalline ceramics are tougher and stronger than those with coarse
grains
 Nano-sized metals exhibit significant decreases in toughness and yield
strength increases.

1. Thermal properties (Melting points).

 Nano-materials have a significantly lower melting point or phase transition

temperature than bulk materials. This is due to
I. reduced lattice spacing between atoms.
II. due to huge fraction of surface atoms in the total amount of atoms.
 Nano crystal size decreases → surface energy increases →Melting point
decreases

Example:- Melting point of 3nm CdSe - 700K, Bulk CdSe--1678 K.

2. Optical properties (absorption and scattering of light)

 Nano materials exhibit different optical properties due to quantum

confinement of electrons within the nano particles increases the energy level
spacing.
 Optical properties depend on size, shape, surface characteristics, interaction
with surrounding environment etc.
 Example:
Bulk gold-yellow in colour.
 Nano gold can be orange (80nm) red (20nm) or purple depending on particle
size.

 The optical absorption peak of a semiconductor nana particles shifts to a

short, wavelength, due to an increased band gap.
  The colour of metallic nano particles may change with their sizes due to
surface plasma resonance.

3. Magnetic properties

 Magnetic properties of nano particles are different from that of the bulk
materials. Ferro-magnetic behavior of bulk materials disappear, when the
particle size is reduced and transfer to super- para magnetic.
 This is due to the huge surface area.

Example:

Material Bulk Nanoscale

Fe , Co and Ni Ferromagnetic Super paramagnetism

Na , K Paramagnetic Ferromagnetic

4. Mechanical properties

 The nano materials have less defects compared to bulk materials, which
increases the mechanical strength.
 As nano- materials are stronger, harder and more wear resistant and
corrosion resistant, they are used in spark plugs
 Example:
Nano-crystalline carbides are much stronger, harder and wear
resistant, which are used in micro drills.

5. Electrical properties

 Electrical conductivity decreases with a reduced dimension due to increased

surface scattering. However, it can be increased, due to better ordering in
micro-structure
 Nano-crystalline materials are used as very good separator plates in batteries,
because they can hold more energy than the bulk materials.

 Example:
 Nickel-metal hydride batteries made of nanocrystalline nickel and
metal hydride, require far less frequent recharging and last much longer.

2.What are nanorods and nanowires? Give its applications.

Nanorods
 Nanorod is two dimensional cylindrical solid material having an aspect ratio
i.e., length to width ratio less than 20.
 Example:
Zinc oxide, Cadmium sulphide, Gallium nitride nano rods.
Synthesis of nanorods:
 Nano-rods are produced by direct chemical synthesis.
 A combination of ligands act as shape control agents and bond to different
facets of the nano-rods with different strength.
 This allows different nanorods to grow at different rates producing an
elongated objects.
 Many of the above nanorods are not manufactured due to lack of commercial
demand.

Properties of nanorods :
1. Nanorods are two-dimensional materials.
2. It exhibits optical and electrical properties

Applications of nanorods :

1. Nanorods find application in display technologies.

2. It is also used in the manufacturing of micro mechanical switches.

3. Nanorods are used in an applied electric field, micro electro mechanical systems,
etc..

4 Nanorods along with noble metal nanoparticles function as theragnostic agents.

5. They are used in energy harvesting and light emitting devices.

6. Nanorods have used as cancer therapeutics.

Nanowires

 Nanowire is two dimensional cylindrical solid material having an aspect ratio

ie., length to width ratio greater than 20.
 Diameter of the nanowire ranges from 10 - 100 nm.

Example: Different types of nanowires

S.NO Types of nanowires Examples

1. Metallic nanowires Au , Ni , Pt

2. Nanowires of semiconductors InP , Si , GaN

3. Nanowires of insulators SiO2 , TiO2

4. Molecular nanowires DNA

Synthesis of nanowires

1. Template-assisted synthesis :

 Template assisted synthesis of nanowires is a simple way to fabricate

nanostructures.
 These templates contain very small cylindrical pores or voids within the host
material and the empty spaces are filled with the chosen material to form
nanowires.

2. VLS (Vapour Liquid Solid) method :

 It involves the absorption of the source material from the gas phase into a
liquid phase of catalyst.

 Upon supersaturation of the liquid alloy, a nucleation event generates a solid

precipitate of the source material.
  This seed serves as a preferred site for further deposition of material at the
interface of the liquid droplet, promoting the elongation of the seed into a
nanowire.

Properties of nanowires :

1. Nanowires are two-dimensional material.

2. Conductivity of a nanowire is less than that of the corresponding bulk materials.

3. It exhibits distinct optical, chemical, thermal and electrical properties due to this
large surface area.

4. Silicon nanowires show strong photoluminescence characteristics.

Uses of nanowires :

1. Nanowires are used for enhancing mechanical properties of composites.

2. It is also used to prepare active electronic components such as p-n junction and
logic gates.

3. Semiconductor nanowire crossings are expected to play a important role in future

of digital computing.

4. Nanowires find applications in high-density data storage either as magnetic read

heads or as patterned storage media.

5. Nanowires replace conventional copper wires used in computers, televisions.

6. It is also used to link tiny components into very small circuits.

3.Differentiate between bulk materials, nanomaterials and molecules.

PROPERTY ATOMS/ NANOMATERIALS BULK MATERIALS
MOLECULES

Size Few angstrom(10^- Nanometres (10^-9 Microns to higher

10 m) m) (10^-6 m)

No.of One atom to few / Few atoms to several Infinite / of the order of
constituent many atoms thousand of atoms Avogadro number
particles
Electronic confined confined Not
structure confined(continuous)

Mechanical NA Properties depend on Properties independent

properties particle size of particle size

Wave applicable applicable Applicable to limited

nature extend

Random present present Not present

motion

Stability stable Can be stable or Stable

unstable depending
on surface energy
Geometric Well - defined Well – defined Crystal structure
structure structure and structure and
predictable predictable
Interaction Chemical forces Strong interactions at Interactions include
the nanoscale bulk forces like gravity

Conductivity - Enhanced thermal May vary across the

and electrical material
conductivity at the
 nanoscale
Phase Changes in state Nanoscale materials Based on temperature
transitions common may exhibit unique and pressure.
phase transitions
Applications Studied in chemistry Diverse applications in Wide range from
and biology medicine , construction to
electronics , catalysis electronics
Example NaCl , CO2 Carbon nanotube Gold bar , silver bar

4. Explain the synthesis of carbon nanotube by pyrolysis and carbon arc method.
Give the properties and applications of carbon nanotubes.

Synthesis of Carbon Nanotubes by Pyrolysis Method:

1. Precursor Selection:
Choose a carbon-containing precursor, often a hydrocarbon gas like methane or
ethylene, as the starting material.

2. Thermal Decomposition:
 Subject the precursor to high temperatures in a controlled environment,
typically using a furnace.
 Thermal decomposition of the precursor leads to the formation of carbon
nanotubes.

3. Reaction Conditions:
 Adjust reaction parameters such as temperature, pressure, and gas
composition to control nanotube characteristics.
 Fine-tune conditions to achieve the desired properties of the synthesized
carbon nanotubes.
Synthesis of Carbon Nanotubes by Carbon Arc Method:
1. Electrode Setup:
 Create an electric arc between two carbon electrodes, often made of graphite,
in an inert atmosphere.
 The electric arc vaporizes the carbon electrodes, producing a vapour phase of
carbonaceous material.

2. Nanotube Formation:
 Carbonaceous material condenses to form carbon nanotubes as the vapour
cools down.
 Catalyst particles may be introduced to facilitate and control the nanotube
growth.

3. Control over Characteristics:

 Manipulate the arc conditions to achieve control over the length and diameter
of the carbon nanotubes.
 Fine-tune parameters to tailor the nanotubes for specific applications.

Properties of CNTs :
1. CNTs are very strong, withstand extreme strain in tension and posses elastic
flexibility.
2. The atoms in a nano-tube are continuously vibrating back and forth.

3. It is highly conducting and behaves like metallic or semiconducting materials.

4. It has very high thermal conductivity and kinetic properties.

Uses of CNTs :
1. It is used in battery technology and in industries as catalyst.
2. It is also used as light weight shielding materials for protecting electronic
equipments.
3. CNTs are used effectively inside the body for drug delivery.
4. It is used in composites, ICs.
5. It also acts as an efficient catalysts for some chemical reactions.

6. It acts as a very good biosensor. Due to its chemical inertness carbon nanotubes
are used to detect many molecules present in the blood.
7. It is also used in water softening process as a filter.

5.Discuss the chemical vapour deposition method and laser ablation techniques for
the synthesis of nanoparticles.

Chemical Vapour Deposition (CVD) :

 This process involves conversion of gaseous molecules into solid
nanomaterials in the form of tubes, wires or thin films.
 First the solid materials are converted into gaseous molecules and then
deposited as nanomaterials.
 The CVD reactor consists of a higher temperature vacuum furnace maintained
at inert atmosphere.
 The solid substrate containing catalyst like nickel, cobalt, iron supported on a
substrate material like, silica, quarts is kept inside the furnace.
 The hydrocarbons such as ethylene, acetylene and nitrogen cylinders are
connected to the furnace.
 Carbon atoms, produced by the decomposition at 1000°C, condense on the
cooler surface of the catalyst.
 As this process is continuous, CNT is produced continuously.
1. Hot-wall CVD

Hot wall CVD reactors are usually tubular in form. Heating is done by surrounding the
reactor with resistance elements.

2. Cold-wall CVD

In cold-wall CVD reactors, substrates are directly heated inductively while chamber
walls are air (or) water cooled.

Advantages of CVD

1. Nanomaterials, produced by this method, are highly pure.

2. It is economical.

3. Nanomaterials, produced by this method, are defect free.

4. As it is simple experiment, mass production in industry can be done without major

difficulties.

Laser ablation

 In laser ablation technique, high-power laser pulse is used to evaporate the

material from the target.
 The stoichiometry of the material is protected in the interaction.
 The total mass ablated from the target per laser pulse is referred to as the
ablation rate.
  This method involves vapourisation of target material containing small
amount of catalyst (nickel or cobalt) by passing an intense pulsed laser beam
at a higher temperature to about 120°C in a quartz tube reactor.
 Simultaneously, an inert gas such as argon, helium is allowed to pass into the
reactor to sweep the evaporated particles from the furnace to the colder
collector.

Uses:

1. Nanotubes having a diameter of 10 to 20 nm and 100 µm can be produced by this

method.

2. Ceramic particles and coating can be produced.

3. Other materials like silicon, carbon can also be converted into nanoparticles by this
method.

Advantages of laser ablation:

1. It is very easy to operate.

2. The amount of heat required is less.

3. It is eco-friendly method because no solvent is used.

4. The product, obtained by this method, is stable.

5. This process is economical.

6.Compare solvothermal thermolysis method and hydrothermal thermolysis

method.
A) Solvothermal synthesis

 A "solvothermal reaction can be defined as a chemical reaction (or a

transformation) between precursor(s) in a solvent (in a close system) at a
temperature higher than the boiling temperature of this solvent and under
high pressure".
  The Solvothermal method is identical to the hydrothermal method except that
a variety of solvents other than water can be used for this process.
 This method has been found to be a versatile route for the synthesis of a wide
variety of nanoparticles with narrow size distributions, particularly when
organic solvents with high boiling points are chosen.
 It is a method for preparing a variety of materials such as metals,
semiconductors, ceramics, and polymers.
 Solovothermal are usually thick walled steel cylinders with hermetic seal
which must withstand high temperature and pressure for prolonged periods
of times.
 The autoclave material must be inert with respect to the solovent.
 The closure is the most important element of the autoclave.
 To prevent corroding of the internal cavity of the autoclave, prodective inserts
are genrally used.
 These may have the same shape of the autoclave and fit in the internal cavity.
 Inserts may be made up of carbon free iron, glass or quarts, copper or Teflon
depending on the temperature and material used.
 The process involves the use of a non-aqueous solvent under moderate to
high pressure (typically between 1 atm and 10,000 atm) and temperature
(typically between 100 °C and 1000 °C) that Facilitates the interaction
between reactants during synthesis.
 High temperature and pressure facilitates the dissolution of the reactants and
products are generally obtained in the nanocrystalline form.
 It is then washed and then dried.
 Example - 1:- Nano crystal of CdSe have been prepared by reacting cadmium
stereate with selenium powder using toluene as solvent, tetrahydro
phenolphthalein as reducing agent.

 Example - 2:- Cadmium oxalate and chalcogens undergo reaction in presence

of pyridine as solvent to produce cadmium nanoparticle.

E = Chalcogenide( S,Se, Te)

Advantages:
  Relatively easy and cheap method.
 Products obtained are in crystalline form. So no purification required.
 Can be used for preparing nanomaterials of different morphology (powder,
rod, wire, tube, single crystals and nanocrystals).
 Precise control over the size, shape distribution and crystallinity of
nanoparticles by varying experimental conditions.
 Variety of organic solvents can be used as it helps the dispersion
nanocrystallites and may stabilize some metastable phases.

Disadvantages:

 Inability to monitor crystals in the process of their growth.

 The need to expensive autoclave.
 Safety issues during the reaction process.

Applications:

 Various kind of Nano structures can be center sized of through solvothermal

approaches including medal oxides carbonaceous Nano Structures and etc.,
 This method can also be used produce zeolite, nano wires, carbon nanotubes.

B)Hydrothermal synthesis:

 Hydrothermal synthesis is carried out in an autoclave under autogenous (high)

pressure and below the supercritical temperature of water (374 °C).
 These conditions are favorable for the crystallization of products.
  pH of the medium tobe maintained, pH is generally made alkaline to increase
the solubility of the reactants.
 Example-Synthesis of ZnO nanoparticles
 This process is carried out in teflon lined sealed stainless steel autoclave at the
temperature range of 100 - 200 °C for 6 - 12 hrs under autogenous pressure.
 The stock solution of Zn(CH₃COO)₂ . H₂O (0.1M) was prepared in 50ml
methanol under stirring.
 25 ml of NaOH(0.2-0.5M) solution prepared in methanol was added to
maintain pH (8-11), Finally at the end of the reaction white ZnO nano particles
are formed.

 Metal oxides, Carbon nanotubes etc. can be prepared this way.

Advantages

 Solvent used is water.

 Rate of the reaction is much faster at high temperature and pressure.
 Ability to synthesize large crystals of high quality.
 Reagents and solvents can be regenerated.
 Used to prepare nanomaterials of different morphology (powder, rod, wire,
tube, single crystals and nanocrystals).

Disadvantages:

 High cost of equipment.

 Sometimes, it is difficult to predict the morphology of the product.

7.Enlist the differences between top-down approach and bottom-up approach.

S.NO TOP- DOWN APPROACH BOTTOM – UP APPROACH

1. Top – down approach refers to slicing Bottom – up approach refers to the

or successive cutting of a bulk material buildup of materials from the bottom ,
to get a nano sized particles i.e atom by atom or molecule by
molecule.

Atom by atom deposition leads to

formation of self – assembly of atoms/
molecules and clusters.

These clusters come together to form

self – assembled monolayers on the
surface of the substrate.

2. The starting material is solid state The starting material is either gaseous
state or liquid state of matter

3. Physical processing method: Physical and Chemical processing

method:
Mechanical methods: cutting, etching,
grinding, Ball milling Physical technique:

Lithographic techniques: Photo Physical vapour Deposition(PVD):

lithography, Electron bean involves condensation of vapour
lithography phase species

-Evaporation

-Sputtering

-Plasma Arcing

-Laser ablation

Chemical techniques:

Chemical Vapour Deposition(CVD):

 involves the deposition of vapour phase
of reaction species

Self-assembled monolayer:
Electrolytic deposition, Sol-gel method ,
pyrolysis.

4. Advantages: Advantages:
✓ Large scale production: ✓ Ultrafine nanoparticles, nanoshells,
deposition over a large substrate is nanotubes can be prepared
possible
✓ Deposition parameters can be
✓ Chemical purification is not required controlled

✓Narrow size distribution is possible(1-

20nm)

✓Chepeast technique

5. Disadvantages Disadvantages

Yields:  Large scale production is difficult

 Broad size distribution (10-  Chemical purification of

1000nm) nanoparticles is required

 Control over deposition

parameters is difficult to
achieve.

 Varied particle shapes or

geometry

Impurities: stresses, defects and

imperfections get introduced

✓ Expensive technique

Limitations: Limitations:
6. Limited precision at the nanoscale; Challenging to scale up for mass
 difficult for very small structures. production; can be time – consuming
and complex.

Applications: Applications:
7.
Nanotechnology , nanomedicine ,
Semiconductor industry , large– scale
material science and nanoelectronics.
manufacturing.

Example:
8. Example:
Self – assembly, molecular beam
Lithography , etching , grinding or epitaxy, sol – gel synthesis or atomic
layer deposition.
milling processes.

8. Discuss how the nanomaterials are prepared by using precipitation method.

Precipitation

 Generally nano-particles are synthesised by the precipitation reaction

between the reactants in presence of water soluble inorganic stabilizing
agent.

Examples

1. Precipitation of BaSO4 Nano-particles

 10 gm of sodium hexameta-phosphate (stabilizing agent) was dissolved in 80

ml of distilled water in 250 ml beaker with constant stirring.
 Then 10 ml of 1M sodium sulphate solution was added followed by 10 ml of
1M Ba(NO3)2 solution.
 The resulting solution was stirred for 1 hr.
 Precipitation occurs slowly.

 The resulting precipitate was then centrifuged, washed with distilled water
and vacuum dried.
Note : In the absence of stabilizing agent, Bulk BaSO4 is obtained.

2. Precipitation by reduction

 Reduction of metal salt to the corresponding metal atoms.

 These atoms act as nucleation centres leading to formation of atomic clusters.
 These clusters are surrounded by stabilizing molecule that prevent the atoms
agglomerating.
 Example

Nanoparticles of molybdenum can be produced from MoCl₂ in toluene

solution using NaBH (C2H5)3 as a reducing agents at room
temperature.

9.Explain the source, synthesis and properties of nanoclusters.

Nanoclusters

 Nanoclusters are fine aggregates of atoms or molecules .

 The size of which ranges from 0.1 to 10 nm.
 Of all the nano materials, nanoclusters are the smallest sized nano materials
because of their close packing arrangement of atoms.
 Example:
CdS, ZnO, etc.,

 All the atoms, in nanocluster, are bound by forces like metallic, covalent, ionic,
hydrogen bond or Vander Waals forces of attraction.
  Clusters of certain critical size are more stable than others.
 Nanoclusters consisting of up to a couple of hundred atoms, but larger
aggregates, containing 10^3 or more atoms, are called nanoparticles.

Magic number

 Magic number is the number of atoms present in the clusters of criticle sizes
with higher stability.
 Different types of nanoclusters can be distinguished from the nature of forces
present between atoms.
 Generally clusters containing transition metal atom have unique chemical,
electronic and magnetic properties.
 These properties vary with the number of constituent atoms, the type of
element and the net charge on the cluster.

Production of Nanoclusters

 Nanoclusters can be produced from atomic or molecular constituents or from

the bulk materials either by bottom up process or top down process.

Fig. 10 . 1 : Production of nanoclusters from atoms or molecules or from bulk

materials.

Properties of nanoclusters
1. Atomic clusters or molecular clusters are formed by the nucleation of atoms or
molecules respectively.

2. The reactivity of nanoclusters are decreased due to their decrease in size.

3. The melting point of nanoclusters are lower than the bulk materials due to high
surface to volume ratio.

4. The electronic structure of the nanocluster is more confined than the bulk
materials.

Applications of nanocluster:

1. Nanoclusters are used as catalysts in many reactions.

2. It is used in nano based chemical sensors.

3. It is also used as a light emitting diode in quantum computers.

10.Explain the application of gold nanoparticles in medicine.

Gold Nanoparticles in Medicine

 Gold nanoparticles and its compounds are rapidly adsorbed following
intramuscular injection.
 The gold is widely distributed in body tissues with the highest concentrations
being found in the reticuloendothelial system.
 Binding of gold from orally administered gold to red blood cells is higher than
in injectable gold.
 Gold accumulates in inflamed joints, where high level persists for at least 20
days following injection.
 Although gold is excreted primarily in the urine, the bulk of injected gold is
retained.

Examples
(i) Nanoparticles of Gold Sodium thiomalate:
Nanoparticles of Gold Sodium thiomalate, the gold content is 50%, is administered
intramuscularly because it is not absorbed on oral administration and is bound to
plasma proteins. It is indicated in the treatment of active adult and juvenile
rheumatoid arthritis.

(i) Aurothioglucose:
Aurothioglucose containing 50% gold content, is highly protein bound (95%).
It is used for the adjunctive treatment of adult and juvenile rheumatoid arthritis.

(iii) Auranofin:
Auranofin, gold content is 29%, is the first orally effective gold compound used to
treat rheumatoid arthritis.
Daily oral dose produce a rapid increase in kidney and blood gold levels.

1. Nucleic acid and protein analysis

(1) Bio-Barcode assay

 Another analytical technique, which results in high sensitivity without the
need for target amplification for the analysis of nucleic acid and protein is the
Bio-Barcode assay.
 Bio-Barcode assay uses both the gold nanoparticles and magnetic
microparticles. When it is exposed to the target analyte, (DNA), both gold
nanoparticles and magnetic microparticles bind to the analyte creating
complexes of gold nanoparticle - analyte - magnetic microparticle.
 This complexes are separated washed, dehybridized and released from the
gold nanoparticles into solution.

(ii) Aptamer-conjugated gold nanoparticles:

  Aptamer-conjugated gold nanoparticles bind desired protein targets forming
gold-tagged proteins for subsequent analysis.
 The bound gold nanoparticles are enlarged in catalytic solution of gold
chloride resulting in higher absorbance at 540 and 650 nm as the size of gold
nanoparticles increases.

Example
 Thrombin as target protein as shown in Fig 8.15. A greater concentration of
protein binds more aptamer – gold nanoparticle conjugates, which provides
greater surface density for catalytic solution to deposit more gold.
 The observed absorbance is a function of protein concentration.
 If the absorbance is more the concentration of protein is more.

2. Gold nanoparticles as sensors

 Gold nanoparticles have very high extinction coefficients, and the color
change during the transition of nanoparticles from the dispersed to the
aggregate state.
 Hence the coupling of nanoparticles with ionophores shows better sensors.
 The sensing of a particular ion by the ionophores can be seen as a colour
change.

Example 1 -> Detection of K+ ions.

 Crown ethers in combination with gold nanoparticles are used as K+ ion
 sensor.
 K+ ion has the ability to form 1:2 adducts with crown ethers attached to
adjacent nanoparticles, this results in aggregation and the colour changes
from dark brown to purple.

Example 2 -> Detection of toxic heavy metal ions

(Pb2+ , Hg2+ , Cd2+)
 Toxic heavy metal ions such as lead, cadmium and mercury can be detected
from the human body by using gold nanoparticles.
 In the presence of metal ions, gold nanoparticles aggregate through chelation
of the ions with the carboxyl group on adjacent nanoparticles.
 This chelation process changes the colour of the solution.

3. Gold Nanoshells for blood immunoassay

 For usual blood immunoassays, optical tests are carried out at visible
wavelengths.
 Since the whole procedure takes long time and several unwanted materials to
be removed , gold nanoshells are used.

 Gold nanoshells are conjugated with antibodies which act as recognition sites
for a specific analyte.
  The analyte causes the formation of dimers, which causes fast absorption and
determine the presence of the molecule, avoiding the purification step.

4. Gold nanoshells for cancer detection and therapy

 Optical properties of the gold nanoshells can be utilised for both imaging and
therapy.
 Selective accumulation of the nanoshells can be used to image the tumor by
using the high permeability and retention properties of the cancer cells.

 After the therapy, it is also found that the cancer cells, treated with gold
nanoshells, are dead.
 This effect was not observed in the case of non-cancer cells.

5. Targeted drug delivery using gold nanoparticles

 Targeted drug delivery means the slow and selective release of drugs to the
targeted organs.
 Nanoparticles are 100-1000 times smaller than human cells.
 We can fabricate the desired nano-sized drug delivery vehicle having the
required properties.

------------ Another part --------- choose the correct answer ------------

1. Diagnostic Imaging:
  Gold nanoparticles serve as effective contrast agents in medical imaging
techniques.
 Also in enhancing resolution methods like CT scans.

2. Biosensing:
 Gold nanoparticles are employed in biosensors for detecting biomarkers and
pathogens.
 They are also employed in biosensors for providing sensitive and specific
diagnostic tools.

3. Gene Delivery:
 Gold nanoparticles can be engineered to deliver genetic material, facilitating
gene therapy for treating genetic disorders .
 Enhance the efficiency of gene transfer to targeted cells.

4. Dental Applications:
 Used in dental materials and treatments.
 Enhance dental restorations and antibacterial properties.

5.Wound Healing:
 Antimicrobial properties aid in faster wound healing.
 Assist in tissue regeneration and reduce inflammation.

6. Neurological Treatment:
 Potential for delivering drugs across the blood-brain barrier.
 Improves treatments for neurological disorders.

7. Targeted Drug Delivery:

 Direct delivery of drugs to specific cells or tissues.
  Enhances drug efficacy while reducing side effects.

8. Antibacterial Applications:
 Utilized in antibacterial coatings for medical devices.
 Prevents infections and improves device safety.

9. Glucose Monitoring:
 Utilized in developing glucose sensors for accurate measurements.
 Binding to glucose molecules for sensitive monitoring.

10.Photodynamic Therapy:
 Combined with photosensitive compounds for therapy.
 Selective killing of cancer cells or pathogens.

11.Tissue Engineering:
 Assists in creating scaffolds for tissue regeneration.
 Enhances the growth and regeneration of tissues.

12.Bone Regeneration:
 Aid in bone regeneration and repair.
 Improve healing in bone-related injuries or diseases.

13.HIV Therapy:
 Investigated for potential use in HIV treatment strategies.
 Target viral reservoirs or aid in drug delivery to infected cells.

15 MARKS:
1.Explain the application of carbon nanotube in fuel cell with a neat diagram.
Applications of Carbon Nanotubes
 Due to the unusual and unique properties of CNTs, they find potential
applications in the following field.

1. CNT in Fuel Cells

Carbon nanotubes play an important role in the applications of battery technology
because some charge carriers can be successfully stored inside the nanotubes.

Example:
Lithium atom
 Lithium atom, which is a very good charge carrier in some batteries, can be
stored inside the carbon nanotubes.

 It has been estimated that one lithium atom can be stored for every six carbon
of the tube.

Hydrogen
 Hydrogen can also be stored in the carbon nanotubes, which may be used for
the development of fuel cells as sources of electrical energy for future
automobiles.

Description of the fuel cell

 A fuel cell containing carbon nanotubes, consists of two electrodes.

 Anode (negative electrode), in the form of plate or paper, consists of single-

walled nanotube (SWNT) and the counter electrode cathode (positive
 electrode) consists of Ni(OH)2.
 Both the electrodes are separated by a special electrolyte, KOH solution,
which allows only the hydrogen ions (H+) but not the electrons to pass
through it.

Working
 Hydrogen gas is passed to the anode, where it is ionized.
 The liberated electrons travel through an external circuit wire to the cathode,
where electrons, hydrogen, and oxygen combine to form water.
 The water of the electrolyte is decomposed in to positive hydrogen ions (H+)
that are attracted to the negative SWNT electrode.
  This system needs a source of hydrogen, which can be stored inside the
carbon nanotubes.
 It has been estimated that the carbon nanotubes need to hold 6.5% hydrogen
by weight for useful in this application.
 But at present only about 4% hydrogen by weight has been successfully put
inside the carbon nanotubes.
 The efficient method to put hydrogen into the carbon nanotubes employs the
electrochemical cell shown in the figure.
 The presence of hydrogen, bonded to the tubes, is indicated by a decrease in
the intensity of a Raman-active vibration as shown in the figure 8.14 , which
shows the intensity of the peak before and after the material is subjected to
the electrochemical process.

2.Explain the various applications of nanomaterials.

 Nano-technology finds significant impact on all most all the industries and all
areas of society.
  Since nano-materials possess unique beneficial chemical, physical and
mechanical properties, they can be used for a wide variety of applications.

MEDICINE
1.Nano drugs
 Nano materials are used as nano drugs for the cancer and TB therapy.

2. Laboratories on a chip
 Nano technology is used in the production of laboratories on a chip.

3. Nano-medibots
 Nanoparticles function as nano-medibots that release anti-cancer drug and
treat cancer.

4. Gold-coated nanoshells
 It converts light into heat, enabling the destruction of tumours.

5. Gold nanoparticles as sensors

 Gold nanoparticles undergo colour change during the transition of
nanoparticles.

6. Protein analysis
Protein analysis can also be done using nanomaterials.

7. Gold nanoshells for blood Immuno assay

Gold nano shells are used for blood immuno assay.
8. Gold nano shells in imaging
Optical properties of the gold nano shells are utilized for both imaging and therapy.

9. Targeted drug delivery using gold nanoparticles

It involves slow and selective release of drugs to the targeted organs.

10. Repairing work

Nano technology is used to partially repair neurological damage.

INDUSTRIES
1. As Catalyst
 It depends on the surface area of the material.
 As nano-particles have an appreciable fraction of their atom at the surface, its
catalytic activity is good.
 Example
Bulk gold is chemically inert, where as gold nano-particles have excellent
catalytic property.

2. In water purification
 Nano-filtration makes use of nano-porous membranes having pores smaller
than 10 nm.
 Dissolved solids and colour producing organic compounds can be filtered very
easily from water.
 Magnetic nano-particles are effective in removing heavy metal contamination
from waste water.
3. In fabric Industry
 The production of smart-clothing is possible by putting a nano-coating on the
fabric.
(i) Embedding of nano-particles on fabric makes them stain repellent.
(ii) Socks with embedded silver nano-particles fills all the bacteria and makes it
odour free.

4. In Automobiles
(i) Incorporation of small amount of nano-particles in car bumpers can make
them stronger than steel.
(ii) Specially designed nano-particles are used as fuel additive to lower
consumption in vehicles.

5. In food industry
 The inclusion of nano-particles in food contact materials can be used to
generate novel type of packing materials and containers.

6. In energy sector
 In solar power, nano-technology reduces the cost of photovoltaic cells by 10
to 100 times.

ELECTRONICS
1. Quantum wires are found to have high electrical conductivity.
2. The integrated memory circuits have been found to be effective devices.
3. A transistor, called NOMFET, (Nano particle organic memory field effect transistor)
is created by combining gold nanoparticles with organic molecules.
4. Nano wires are used to build transistors without p-n junctions.
5. Nano radios are the other important devices, using carbon nanotubes.
6. MOSFET (Metal Oxide Semi conductor Field Effect Transistor), performs both as
switches and as amplifiers.

BIO-MATERIALS (BIOLOGY)
1. Nano materials are used as bone cement and bone plates in hospitals.
2. It is also used as a material for joint replacements.
3. Nano technology is being used to develop miniature video camera attached to a
blind person's glasses.
4. Nano materials are also used in the manufacture of some components like heart
valves and contact lenses.
5. Nano materials are also used in dental implants and breast implants.
6. CNTs are used as light weight shielding materials for protecting electronic
equipments against electromagnetic radiation.

3.Explain the principle, construction and working of scanning electron microscopy

(SEM) with a neat diagram.
Scanning Electron Microscope
 Scanning electron microscope is an improved model of an electron
microscope.
 SEM is used to study the three dimensional image of the specimen.

Principle:
 When the accelerated primary electrons strikes the sample, it produces
secondary electrons.
 These secondary electrons are collected by a positive charged electron
detector which in turn gives a 3- dimensional image of the sample.
Construction:
 It consists of an electron gun to produce high energy electron beam.
 A magnetic condensing lens is used to condense the electron beam and a
scanning coil is arranged in-between magnetic condensing lens and the
sample.
 The electron detector (Scintillator) is used to collect the secondary electrons
and can be converted into electrical signal.
 These signals can be fed into CRO through video amplifier as shown.
Working:
 Stream of electrons are produced by the electron gun and these primary
electrons are accelerated by the grid and anode.
 These accelerated primary electrons are made to be incident on the sample
through condensing lenses and scanning coil.
 These high speed primary electrons on falling over the sample produce low
energy secondary electrons.
 The collection of secondary electrons is very difficult and hence a high voltage
is applied to the collector.
  These collected electrons produce scintillations on to the photo multiplier
tube are converted into electrical signals.
 These signals are amplified by the video amplifier and are fed to the CRO.
 By similar procedure the electron beam scans from left to right and the whole
picture of the sample is obtained in the CRO screen.

Difference between SEM and TEM

S.NO SEM TEM

1. Type of electrons Scattered , scanning Transmitted electrons

electrons
2. High tension ~1 – 30 kV ~60 -300kV

3. Specimen thickness any Typically <150 nm

4. Type of info 3D image of surface 2D projection image of inner

structure.
5. Max . magnification Up to ~ 1 – 2 million More than 50 million times.
times
6. Max . Field of view large limited
(FOV)
7. Image formation Electrons are capture and Direct imaging on fluorescent
counted by detectors , screen or PC screen with CCD
image on PC screen
8. Operation Little or no sample Laborious sample preparation,
preparation , easy to use trained users required.
4.Write the principle, working and application of STM.
Scanning Tunneling Microscope (STM)

 In 1981 Gerd Binning and Heinrich Rohrer developed the scanning microscope
(STM) significantly superior tool for observing surface atom by atom.
 STM is the highest resolution imaging and nano fabrication technique
available.
 It depends on quantum tunneling of electron from sharp metal tip to a
conducting surface.

Principle

 The basic principle used in Scanning Tunneling Microscope (STM) is the

tunneling of electron between the Sharpe metallic tip of the probe and
surface of the sample.
 STM has a metal needle that scans a sample by moving back and forth and
gathering information about the curvature of the surface.
 It follows the smallest changes in the contours of a sample.
 The needle does not touch the sample, however,but stays about the width of
two atoms about it.

Instrumentation

 A schematic of STM is shown in figure. It has the following components.

 Piezo electric tube with the tip and electrode.
 Capable of moving in X,Y, Z direction.
 Fine needle tip for scanning the sample surface.
 A macro scale image of an etched tungsten STM tip is shown in figure.
 Tip is affixed to the piezoelectric tube in order to control it position and
movement on an atomic scale.
 Piezoelectric materials exhibit an elongation or contraction along their length
when an electric field is applied.
Working

 The tip is mechanically connected to the scanner, an XYZ positioning device.

 The sharp metal needle is brought close to the surface to be imaged.
 The distance is of the order of a few angstroms.
 A bias voltage is applied between the sample and the tip.
 When the needle is at a potential with respect to the surface, electrons can
tunnel through the gap and set up a small tunneling current in the needle.
 This feeble tunneling current is amplified and measured.
 With the help of the tunneling current the feedback electronics keeps the
distance between tip and sample constant.
 The sensitivity of the STM is so large that electronic corrugation of the surface
atoms and the electron distributions around them can be detected.

Applications of STM

1. The STM shows the positions of atoms more preciously.

2. STMs are versatile.
3. STMs give the 3 dimensional profile of a surface, which allows researchers to
examine a multitude of characteristics, including roughness, surface defects
and molecule size.
 4. STM is used in study of structure, growth, morphology, electronic structure,
thin films and nano structures.
5. Lateral resolution of 0.1nm to 0.01nm of resolution in depth can be achieved.

Disadvantages

1. It is very expensive
2. It needs specific training to operate effectively.
3. A single dust particle could damage the needle.
4. A small vibration, even a sound, could smash the tip and sample together.