Chemical synthesis of nanomaterials:

Wet reduction:

Chemical reduction or wet reduction is the most frequently applied method for the
preparation of silver and gold nanoparticles as stable, colloidal dispersions in water or
organic solvents.

Commonly used reducing agents are sodium borohydride (NaBH4), hydrazine hydrate NH2-
NH2.H2O), sodium citrate and lithium aluminium hydride (LiAlH4).

Commonly used capping or stabilizing agents are sodium dodecyl sulphate (SDS), Sodium
citrate, poly vinyl pyrrolidone (PVP), poly vinyl alcohol (PVA), cellulose and all classes of
surfactants (anionic, cationic, neutral and zwitterionic).

The reduction of silver ions (Ag+) in aqueous solution generally yields colloidal silver with
particle diameters of several nanometers. A silver ion complex is reduced to colloidal silver
in the presence of a reducing agent, which oxidizes and gives back the missing electron, so
that the silver ion is reduced back to its metallic state. The newly formed silver nanoparticles
can then also be stabilized with a stabilizing/capping agent, which stabilizes the energy of the
surface of the newly formed nanoparticle to prevent them from aggregate to larger
particles. Silver nanoparticles are ultra fine particles of silver. They are ten to a hundred
nanometers large, and differ from the bulk silver as they have different colors such as yellow,
as opposed to the silver.

Gold nanoparticles (AuNPs) were synthesized using HAuCl4 as a precursor following the
renowned Turkevich method (trisodium citrate dihydrate - Na3C6H5O7.2H2O as reducing
agent) and an ecofriendly route using amino acids as reducing and capping agent.

Briefly, 0.5 mM reducing agent (trisodium citrate dihyrate/amino acid) was added to boiling
aqueous solution of HAuCl4 at a constant flow rate. Preheating of the solution not only
decreases the reaction time but also helps in controlling the distribution of nanoparticles. The

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resulting solution turned from yellow to light yellow and then to colorless in 5 min. The
change in color of the HAuCl4 solution is attributed to the rapid reduction of Au3+ to Au+ by
electrons donated by the reducing agent (trisodium citrate/amino acid). After few minutes, the
color of the yellow solution turned to pale red indicating the commencement of colloidal gold
formation. Solution was continuously stirred while the heating was on till it turned bright red
and then growth of nanoparticles was arrested by sudden change in temperature using an ice
bath. Quenching of the solution was followed by sonication for 15 minutes in an
ultrasonicator water bath. The mixture was then dried to room temperature and the colloidal
red solution of gold nanospheres was centrifuged at 12,000 rpm for 20 minutes.

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Sol-gel method:

Sol-gel method is a wet chemical technique involves the evolution of inorganic nanoparticles
through the formation of a colloidal suspension (sol) and gelation of the sol to form a network
in a continuous liquid phase (gel).

Metal alkoxides and metal chlorides are typical precursors. They undergo hydrolysis and
polycondensation reactions to form a colloid, a system composed of nanoparticles dispersed
in a solvent. The sol evolves then towards the formation of an inorganic continuous network
containing a liquid phase (gel).

Synthesis by sol-gel involves the hydrolysis of precursors, condensation followed by

polycondensation to form particles, gelation and drying process by various routes. Precursors
(starting chemicals) are to be chosen such that they have a tendency to form gels.

Sol-gel synthesis may be used to prepare materials with a variety of shapes, such as porous
structures, thin fibers, dense powders and thin films.

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Addition of H2O to Ti(OPr)4 instantaneously precipitate Ti(OH)4. TiO2 nanoparticles will be
used in the fabrication of solar cells and medical applications.

Precipitation method:

Hydroxyapatite [Ca10(PO4)6(OH)2, HA] has been employed to produce substitute materials

for the hard tissue implantation due to its excellent biocompatibility and osteoconductivity as
well as close similarity to the human bone structure. (70 % of bone is hydroxyl apatite and
found in teeth and bone).
Ca(NO3)2.4H2O and (NH4)2HPO4 were dissolved in deionized water separately. The
pH of each aqueous solution was adjusted to 11 by using NH4OH solution. The dropwise
addition of Ca(NO3)2 aqueous solution to vigorously stirred (NH4)2HPO4 solution at room
temperature for about 1h produced a milky and somewhat gelatinous precipitate which was
then stirred for 1h. Then the reflux process was employed at 100°C for 1h followed by ageing
for 24h. It was then washed and filtered.

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Hydroxy apatite is commonly used as a filler to replace amputated bone or as a coating to
promote bone growth into prosthetic implants. Modern implants like lip replacement, dental
implants and bone implants are coated with hydroxyl apatite to promote osseointegration.

DNA directed self-assembly of Au nanoparticles:

The assembly of nanoparticles into ordered architectures is a potential route to achieve

further construction and miniaturization of electronic and optical devices such as molecular
imaging, nanoelectronics and nanobiosensors.

Self-assembly is a phenomenon where the components of a system assemble themselves to

form a larger functional unit. This spontaneous organization can be due to direct specific
interaction and/or indirectly through their environment.

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Medical field:

Application of gold nanoparticles (AuNP) based anti-cancer agents:

Platinum based anti-cancer drugs cisplatin, carboxyplatin and oxaliplatin are important
components of chemotherapy but are limited by severe close-limiting side effects (overdosing
and non-targeted delivery) and the ability to tumors to develop resistance rapidly. These
drugs also affect rapidly developing healthy cells as well.

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The above drugs can be improved through the use of drug delivery vehicles (such as Au
Nanoparticles, 20-100 nm) that are able to target cancer cells only (not the healthy cells).

H
O N
S S
Pt
Au
Nanoparticle
N
O H
Drug delivery S S
agent

Anti cancer drug  

Drug is attached to Au nanoparticles for improved/targeted drug delivery and slow release of drug.

FeCo and FePt nanoparticles as MRI contrast agents:

Contrast agents: MRI contrast agents are a group of contrasting media to improve the
visibility of internal body structures in magnetic resonance imaging. The most commonly
used contrast agents are iron-cobalt, iron-platinum nanoparticles and gadolinium-based
agents.

In MRI scanners, the body is exposed to a very strong magnetic field causing
primarily the hydrogen nuclei (spins) of water in tissues to be polarized in the direction of the
magnetic field and difference in spin energy levels are created. When radiofrequency is
applied, each proton absorbs the radiofrequency (a particular frequency) corresponding to the
energy difference in their spin levels. This absorption of RF causes a signal. Each proton
undergoes change in spin on absorption of RF and then return to its original state. This
returning time is called T1 relaxation time. Water protons in different tissues have different T1
values, which is one of the main sources of contrast in MR images. The contrast agent usually
shortens the value of T1 of water protons thereby altering the contrast in the image.

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Electronic industry:

ZnO and Fe3O4 based memristors:

A memristor is an electrical component that limits or regulates the flow of electrical current
in a circuit and remembers the amount of charge that has previously flowed through
it. Memristors are important because they are non-volatile, meaning that they retain memory
without power.

Memristor = Memory + Resistor

Like resistor, capacitor and inductor, memristor is an electronic component. Memristor is

known as “memory resistor”. That means, the resistance of a memristor is not a fixed value
(unlike resistor) but changes according to the current passes. It also means once the power is
cut-off, the memristor retains (memorises) the resistance value present by the time the power
was cut-off.

In terms of its function, it works like a transistor (switch) i.e., the direction of flow of current
is maximum in one direction and minimum in the opposite direction.

Various metal oxide nanomaterials such as ZnO, Fe3O4, WO3, Ir2O3, TiO2 etc., are used for
the fabrication of memristors.

A memristor is often compared to an imaginary pipe that carries water. When the water flows in one direction,
the pipe's diameter expands and allows the water to flow faster -- but when the water flows in the opposite
direction, the pipe's diameter contracts and slows the water's flow down. If the water is shut off, the pipe retains
its diameter until the water is turned back on. To continue the analogy, when a memristor's power is shut off, the

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memristor retains its resistance value. This would mean that if power to a computer was cut off with a hard shut
down, all the applications and documents that were open before the shut down would still be right there on the
screen when the computer was restarted.

Construction of ZnO memristor:

ZnO1-x ZnO

Doped Undoped

Pt electrode
Pt electrode

This region contains This region has relatively high

slightly depleted oxygen electrical resistance
(Region with lower resistance)  

When a voltage is applied across the platinum electrodes, oxygen atoms in the material
diffuse left or right, depending on the polarity of the voltage, which makes the material
thinner or thicker, thus causing a change in resistance (adding more oxygen atoms makes the
material thicker because you're adding more material, and vice versa: removing oxygen
makes the material thinner. Remember, at nanoscales even a small change in thickness can
result in a dramatic resistance change).

Memristors are going to replace transistor based RAM existing in the current computers. In
the current RAM (transistor), if the power goes before saving data, the data is lost; whereas
memristors can retain data as a resistance (i.e., via memory) and when power resumes, the
data can be recovered. That means, transistor stores data by electron charge, whereas
memristor stores data as resistance state. Memristors are used as a switch, as a non-volatile
memory and for making booting-free computers.

ZnO/PbS based quantum dot solar cells:

Quantum dots are crystalline nanoparticles of semiconductor materials ranges from 2-10 nm
in diameter. Due to their small size, the electrons in quantum dots are confined in a small
space (quantum box).

The electronic properties of quantum dots are intermediate between those of bulk
semiconductors and of discrete molecules closely related to their size and shape. This allows
properties such as the band gap, emission colour, and absorption spectrum to be highly
tuneable, as the size distribution of quantum dots can be controlled during fabrication. For

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example, in fluorescent dye applications, the frequency of emitted light increases as the size
of the quantum dot decreases, shifting the colour of the emitted light from red to violet.

Quantum dots find applications in transistors, solar cells, LED’s and diode lasers.

Quantum dots (Q.D) are leading candidate materials for third generation solar cells (as a
follow-up to silicon and thin-film solar cells).

Unlike silicon, QD’s can generate more than one electron/hole pair or exciton per colliding
photon. Hence, QD’s have the potential to double the sunlight to energy conversion
efficiency.

Theoretical calculations show that the maximum conversion efficiency of first and
second generation solar cells is 31 %, whereas quantum dots have up to 66 %. These third
generation quantum dot solar cells are currently under intense study, particularly on how to
split the electron/hole pairs created by quantum dots and collect these with high efficiency.
(Practical efficiency of these cells at present is only 4.4%).

C60 in cosmetics:

Fullerene (C60) dissolved at a concentration of around 200 ppm in squalene (a hydrocarbon

oil prepared from olive oil) is used as a active ingredient for wrinkle care cosmetics. It is
claimed by the cosmetics manufacturers C60 has anti-oxidant characteristics (i.e., free-radical
scavenging........free radicals that cause ageing) and is highly effective for treating facial
wrinkles and even preventing cancer.

The actual anti-ageing properties of C60 and its impact on its discharge into
environment (through face wash) are yet to be verified.

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Water purificatioon using silvver nanopaarticles (Ag
g NP’s):

The annti-microbial propertiess of silver have been known alll around thhe world fo
or many
centuriees. Silver doollars used to put in to milk bottlees to keep milk
m fresh; w
water tanks of ships
and airpplanes are “silvered”
“ to render waater potablee for monthhs and even water bottlles were
coated with silverr to discourrage contam
mination off water by microbes. In fact, neew born
childrenn were adm
ministered drops
d of aqq. silver nittrate to eyees to preveent transmisssion of
Neisserria gonorrhooea from inffected mothher, during 1884.
1

Once antibiiotics were discovered, the use off silver as a bacterial

b aggent decreassed. Due
to increeasing antibbiotics resisttance, theree has recenttly been a reenewed inteerest in silv
ver as an
antibactterial agent..

Owing to thhe increasedd specific suurface area of silver naanoparticless, they are currently
c
used to purify drinnking waterr. Papers orr porous po
olymer mem
mbranes em
mbedded witth silver
nanoparrticles are used to filter raw water. Any
A bacteriia, that paasses throu
ugh the
membraane/paper gets
g destroyeed (within few
f minutess) and safe drinking
d waater is obtain
ned.

It has been
b reporteed that the silver nanooparticles ‘sslowly ionisses’ (as Ag+) and enters water
and thiss Ag+ enterss the cells of
o the bacterria, disruptss the hydroggen bonds inn DNA and
d thereby
denaturres DNA moolecule, whhich results in
i the destru
uction of microbes.
m At the same tiime, any
A + ions prresent in waater is foundd to be safee to drink annd do not caause any daamage to
excess Ag
the hum
man body ceells.

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Construction Enggineering:

TiO2 baased self-clleaning glasss:

In recennt days, glaasses used inn multi-storried buildin

ngs and in several
s dom
mestic and in
ndustrial
use as windows or
o ceiling materials
m have self-cleeaning capaabilities. Thhis is achieeved by
giving a thin coatiing of TiO2 nanomaterrial on one side of the glass which is exposeed to the
surrounndings. The TiO2 coatinng is transparent and hence
h doesn’t decrease the visibilitty of the
glass. The
T TiO2 material
m is known
k for itts excellentt photocatallytic activityy. Thereforre, when
any dust particle falls on thhe glass, byy make usee of UV ligght from S
Sun light, th
he TiO2
nanoparrticles breakks down thhe dust partiicles into CO
C 2 and waater (photo-ooxidation products)
or as sm
maller sizedd particles. TiO2 is higghly hydrophilic (unlikke glass whiich is hydro
ophobic)
and when rain fallss on the TiO
O2 coated glass,
g it com
mpletely wasshes away aany leftoverr broken
dust parrticles and hence
h the gllass surfacee always loo
oks clean.

In fact, the difference betweeen ordinary glass and TiO

T 2 coatedd glass is phhenomenal in
i terms
of its cleanliness and
a visibilitty. These TiO
T 2 coating
gs are said to be veryy cost effecttive and
complettely saves the
t cost of cleaning glass surfacees which iss done at leeast once in
n a year.
Most im
mportantly, in a multi-sstoried buildings the glass surfacee cleaning bby humans involves
i
risk duee to height, which becoomes unneceessary when
n self-cleaning glasses are installed.

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