Nano Metal Oxides

What are metal oxides?

• Oxides, are a large and important class of chemical compounds in which oxygen is
combined with another element.
• Metal oxides are crystalline solids that contain a metal cation and an oxide anion.
They typically react with water to form bases or with acids to form salts.
• The alkali metal and alkaline earth metals form three different types of binary
oxygen compounds:
(1) oxides, containing oxide ions, O2−,
(2) peroxides, containing peroxide ions, O22−, which contain oxygen-oxygen
covalent single bonds, and
(3) superoxides, containing superoxide ions, O2−, which also have oxygen-oxygen
covalent bonds but with one fewer negative charge than peroxide ions.
Crystal structures of metal oxide nanoparticles (MON)
• A small variety of metal-oxide nanoparticles such as fumed silica and
TiO2 pigments have been produced as early as the mid-twentieth century.
However, it is in the last three decades that significant research efforts have been
made to develop production methods for metal-oxide nanoparticles.
• Metal and metal oxides nanoparticles exhibit different physiochemical properties
and are different than their native bulk compounds in several respects which
includes its surface, optical, thermal, and electrical properties.
• Metal oxide nanoparticles are manufactured by addition of oxidizing/precipitating
agents during their synthesis.
• Metal-oxide nanomaterials (MONs) are promising candidates in diverse areas of
chemistry, materials science, physics, and biotechnology.
• The unique electronic structure determines the conductor, semiconductor, and
insulator properties of nanomaterials.
• Transition metal ions typically possess unfilled d-shells, allowing for reactive
electronic transitions, wide band gaps, superior electrical characteristics, and high
dielectric constants.
• As a result, MONs have exceptional and adjustable optoelectronic, optical,
electrical, thermal, magnetic, catalytic, mechanical, and photochemical properties.
• Furthermore, MONs have a wide range of applications: sensors, fuel cells,
batteries, actuators, supercapacitors, optical devices, pyroelectrics, piezoelectrics,
ferroelectrics, and random access memory due to their exceptional shape and size,
which manifest distinctive physicochemical properties.
• Advantages such as high stability, simple preparation methods, excellent
engineering control over aspects ranging from size, shape, porosity, etc. and
cellular penetration capability, MONPs have grown into valuable materials for the
drug and health-related industry.
• Through the design and development of engineered MONPs, the limitations
imposed by their bulk counterparts could be finally overcome, allowing
researchers to make astounding breakthroughs in fields such as specific drug
delivery, bio-imaging, biomolecule sensors, etc.
• Moreover, due to their reduced size, metal oxide nanoparticles can interact on a
more in-depth level with various cellular structures compared to their bulk
counterparts, and, more importantly, they do not cause systemic toxicity due to
their highly improved biocompatibility.
• Currently, various types of MONPs are used in clinical practice as antibacterial
and wound healing dressings, biosensors and anticancer and image contrast
agents.
• Of these, zinc oxide NPs (ZnO NPs), cerium oxide NPs (CeO2 NPs), iron oxide
NPs (Fe2O3 NPs), silver oxide NPs (AgO NPs), magnesium oxide NPs (MgO
NPs), titanium oxide NPs (TiO2 NPs), nickel oxide NPs (NiO NPs), zirconium
oxide NPs (ZrO NPs) and cadmium oxide NPs (CdO NPs) are the most promising
candidates for biomedicine, with a considerable amount of research data available
in recent literature regarding their biological in vitro and in vivo activity.
ZnO
• ZnO NPs are a nontoxic, biocompatible biomaterial, with unique abilities that may
vary depending on their size, shape, orientation, morphology and aspect ratio.
They are widely used in commercial products such as sunscreens, ointments, food
packaging and everyday-care products.
• ZnO NPs exhibit a strong antibacterial effect, mainly attributed to their distinct
characteristics, that is also dependent on dose, time and synthesis method.
• Due to their inherent anticancer activity, ZnO NPs have been approved by the
FDA as a new and potent antitumor therapy. It is generally accepted that in
addition to the generation of high levels of reactive oxygen species (ROS), ZnO
NPs can exhibit a selective cytotoxic effect against cancer cells through the
induction of an impaired equilibrium of zinc-dependent protein activity.
• However, ZnO NPs were shown to induce toxic effects in different cells and
organisms, thereby requiring further studies meriting their therapeutic benefits
over the potential toxicological risk.
CeO2
• CeO2 NPs show unusual antioxidant properties and anticancer activity.
• The basis for CeO2 NPs activities lies in the thermodynamic efficiency of redox-
cycling between 3+ and 4+ states on their surface and their unusual ability to
absorb and release oxygen.
• It is worth noting that these NPs can also exhibit pro-oxidant effects at lower pH
values and high concentrations, and data found in the literature suggest that,
depending on their synthesis procedure, dosage and exposure time, they can
induce cytotoxic effects.
TiO2
• TiO2 NPs are prevailingly used in bone and tissue engineering due to their ability
to induce cell migration, adhesion, osseointegration, and wound healing.
• They also serve as an excellent antibacterial agent, playing an important role in
bacterial growth inhibition via ROS production in the presence of ultraviolet (UV)
light.
• Moreover, due to their ability to generate high levels of ROS, they also exhibit
anticancer activity.
 Fe2O3
• Fe2O3 NPs, can either be used as standalone agents (functionalized with other
bioactive molecules/agents), embedded in composites, or bound to different types
of cells.
• Generally, Fe2O3 NPs are mostly used as drug-delivery platforms for pro-
regenerative purposes or anticancer therapies, where the selectively targeted
release of an active drug is accomplished by either the use of specific binding
proteins or by the influence of external magnetic fields.
• In addition, various cells can be magnetically marked with these NPs, therefore
allowing for a non-invasive in vivo monitoring of the efficiency of a therapy.
Nanopolymers
• Nanopolymers in simple words are nanostructured polymers.
• The term polymer covers a large, diverse group of molecules, including
substances from proteins to high-strength kelvar fibres (plastic).
• A key feature that distinguishes polymers from other large molecules is the
repetition of units of atoms in their chains. This occurs during polymerisation, in
which many monomers come to form a polymer chain.
• Differing chain lengths occur because polymer chains terminate
during polymerisation after random intervals of chain lengthening.
• The attractive forces between polymer chains play a great role in determining
polymer properties. Because polymer chains are so long, these interchain forces
are amplified far beyond the attractions between conventional molecules.
• Polymers can be visualized as tangled spaghetti chains – pulling any one spaghetti
strand out is a lot harder the more tangled the chains are. These strong forces
typically result in high tensile strength and melting points.
Nanopolymer Composites
• Polymer nanocomposites (PNCs) may be defined as a mixture of two or more
materials, where the matrix is a polymer and the dispersed phase (nanofillers) has at
least one dimension smaller than 100 nm.
• It has been observed that the addition of low contents of these nanofillers into the
polymer can lead to improvements in their mechanical, thermal, barrier and
flammability properties, without affecting their processability.
• The ideal design of a nanocomposite involves individual nanoparticles
homogeneously dispersed in a matrix polymer.
• The reinforcing effect of filler is attributed to several factors, such as properties of
the polymer matrix, nature and type of nanofiller, concentration of polymer and
filler, particle aspect ratio, particle size, particle orientation and particle distribution.
• Various types of nanoparticles, such as clays, carbon nanotubes, graphene,
nanocellulose, and halloysite, have been used to obtain nanocomposites with
different polymers.
• Depending on the degree of separation of the
nanoparticles, three types of nanocomposite
morphologies are possible: conventional
composites (or microcomposites), intercalated
nanocomposites and exfoliated nanocomposites.
• When the polymer is unable to intercalate
between the silicate layers, a composite of
separate phases is obtained whose properties are
in the same range as those observed in traditional
composites.
• An intercalated structure, in which a single (and
sometimes more than one) extended polymer
chain is intercalated between the layers of the
silicate, results in a well-ordered multilayer
morphology with intercalated layers of polymer
and clay.
• When the silicate layers are completely and
uniformly dispersed in a continuous polymer
 Plastic:
• The industry works hard to resolve plastics’ environmental impact, boosting
recycling rates and lowering fossil fuel consumption; plastics producers are also
working hard to improve plastic performance.
• By altering the structure of polymer substances at the nanoscale, polymers can be
given new properties, such as added strength, crack resistance, thermal integrity, and
electroconductivity.
• Given that plastic already has so many uses, improving its performance and range of
properties even further, is certain to find new applications and open new markets for
plastic producers.
• One of the earliest industry to embrace using nanocomposites was the food
packaging sector, as nanotechnology researchers found that plastics could be
modified or have nanoparticles added to them which provided antibacterial
properties.
• Nanostructuring of polymers soon became an economically viable solution for
Applications of nanofibres
The nanofibres, hollow nanofibres, core-shell nanofibres, and nanorods or
nanotubes produced have a great potential for a broad range of applications
including homogeneous and heterogeneous catalysis, sensorics, filter applications,
and optoelectronics. Here we will just consider a limited set of applications related
to life science.
Tissue engineering
• This is mainly concerned with the replacement of tissues which has been
destroyed by sickness or accidents or other artificial means.
• The examples are skin, bone, cartilage, blood vessels, and may be even organs.
• This technique involves providing a scaffold on which cells are added and the
scaffold should provide favorable conditions for the growth of the same.
• Nanofibres have been found to provide very good conditions for the growth of
such cells, one of the reasons being that fibrillar structures are found on many
tissues which allow the cells to attach strongly to the fibers and grow along them.
Delivery from compartmented nanotubes
• Nano tubes are used for carrying drugs in general therapy and in tumor therapy in
particular. Their role is to protect the drugs from destruction in blood stream, to
control the delivery with a well-defined release kinetics, and in ideal cases, to
provide vector-targeting properties or release mechanism by external or internal
stimuli.
• Rod or tube-like, rather than nearly spherical, nanocarriers may offer additional
advantages in terms of drug delivery systems. Such drug carrier particles possess
additional choice of the axial ratio, the curvature, and the “all-sweeping”
hydrodynamic-related rotation, and they can be modified chemically at the
inner surface, the outer surface, and at the end planes in a very selective way.
• Nanotubes prepared with a responsive polymer attached to the tube opening allow
the control of access to and release from the tube. Furthermore, nanotubes can also
be prepared showing a gradient in its chemical composition along the length of the
tube.
Immobilization of Proteins
• Core shell fibers of nano particles with fluid cores and solid shells can be used to
entrap biological objects such as proteins, viruses or bacteria in conditions which
do not affect their functions. This effect can be used among others for biosensor
applications. For example Green Fluorescent Protein is immobilized in
nanostructured fibres providing large surface areas and short distances for the
analyte to approach the sensor protein.
• Biological objects of different complexity and synthetic objects carrying specific
functions can be incorporated into nanostructured polymer systems while keeping
their specific functions vital.
• Biosensors, tissue engineering, drug delivery, or enzymatic catalysis is just a few
of the possible examples.
Fig: Schematic illustration of polymer-enzyme hybrids synthesized through
different covalent-based methodologies.
Strategies (A–C) require the synthesis of a preformed polymer (grafting-
to approach) and (D) refers to the in situ synthesis of the enzyme-polymer hybrid
(grafting-from approach).
(A) Non-specific grafting of proteins, using polymers with a single reacting group
and proteins with several target residues.
(B) Multi-point strategy using polymers with multiple anchoring sites.
(C) Site-specific grafting using a biorthogonal approach.
(D) Grafting-from approach that entails the conjugation of the macroinitiator to the
protein and the subsequent in situ polymerization after the addition of the
monomers.
Carbon nano structures
• Carbon is a unique element that can form various compounds and structures on
both a macroscopic and nanoscopic scale.
• More than 95% of known chemical compounds can be classified as carbon-based
compounds. This is due to four valence electrons (2s and 2p), which participate in
the formation of a bond (single, double, and triple).
• In addition, carbon is able to bind to nearly all chemical elements generating an
unlimited variety of molecules and compounds. The resulting diversity of the final
compounds and nanostructures is accompanied by a vast range of different
chemical, physical, and biological properties.
Classification of carbon nano structures
Carbon nano allotropes and their applications
 Carbon nanotubes (CNT)
• CNT can be described as a sheet of graphene
rolled into a cylinder.
• Graphene is constructed from hexagonal
rings of carbon.
• CNT can have one layer or multiple layers.
• It can have caps at the ends making them
look like pills.
• CNT have diameters as small as 1 nm and
lengths up to several centimeters. Although,
like buckyballs, CNT are strong, they are not
brittle. They can be bent, and when released,
they will spring back to their original shape.
CNT have several properties that make them
useful: They are strong, elastic, lightweight,
and conduct heat and cold well.
• CNTs are composed of carbon atoms linked in hexagonal shapes, with each
carbon atom covalently bonded to three other carbon atoms. This bond forms
electron pairs between the atoms called shared pairs or bonding pairs. These pairs
maintain a balance of attractive and repulsive forces between the atoms that share
the electrons. This balance is referred to as covalent bonding.
• Carbon nanotubes are superstars when it comes to forming covalent bonds with
other atoms because of something called electronegativity. This changes the
chemical properties of the nanotube in a method called functionalization.
• Where buckyballs are round, nanotubes are cylinders. That shape makes them
more useful in applications which involve combining with other materials to
improve strength or electrical properties. Electrical properties of CNT are a result
of how hexagons are arranged around a nanotube structure. The electrical
resistance of carbon nanotubes can change when other molecules attach to them.
Structure and Morphology
• The bonding in carbon nanotubes is sp2, with each atom joined to three neighbors,
as in graphite.
• The tubes can therefore be considered as rolled-up graphene sheets (graphene is
an individual graphite layer)
• This bonding structure, which is stronger than the sp3 bonds found in diamond,
provides the molecules with their unique strength.
• Under high pressure, nanotubes can merge together, giving the possibility of
producing strong, unlimited length wires through high pressure nanotube linking.
Classification of carbon nanotubes
Carbon nanotubes are classified in following two types:
1. SWNT — Single walled carbon nanotubes
2. MWNT — Multi walled carbon nanotubes
Single-walled and Multi-walled Carbon Nanotubes
• CNT can occur as multiple concentric cylinders of carbon atoms, called multi-
walled carbon nanotubes (MWCNTs). CNT nanotubes that have only one cylinder
are called single-walled carbon nanotubes (SWCNTs). Both MWCT and SWCT
are used in composite materials such as those used in nanotube-polymer
composite blades used in windmills, or polymer-nanotube sensors activated when
electrical resistance changes to indicate stress.
• When MWCNTs are added to plastic they can increase electrical conductivity.
SWCNTs do an even better job in this application because they can be applied to
other materials than plastics. MWCNTs are longer than SWCNTs, and have a
higher ratio of width to height (called an aspect ratio). They are much stronger
than single walled carbon nanotubes (which are already strong in their own right).
Multi walled carbon nanotubes are therefore used in applications where high
mechanical strength is desirable. It’s also much easier to produce large quantities
of MWCNTs. The problems encountered in producing SWCNTs on a large scale is
reflected in their higher prices.
Comparison between SWNT and MWNT
 Properties of CNT
• The strongest and most flexible
molecular material because of C-C
covalent bonding and hexagonal
network architecture
• Strength to weight ratio ~500 times
greater than aluminium, steel, titanium
• Maximum strain ~10%; much higher
than any material
• Very high current-carrying capacity
• Other chemical groups can be attached
to the tip or sidewall (functionalization).
• CNT can be metallic or semiconducting,
depending on their diameter and atomic
arrangement.
 Carbon nanotube synthesis method
• Arc discharge method

• Chemical vapour deposition (CVD)

• Laser ablation
• The first method that was Arc discharge
discovered is referred to as “arc
discharge”.
• A spark that arcs in the space
between two graphite electrodes
when experiencing high voltage,
results in heat.
• This heat causes carbon in the
positive electrode to be changed
from a solid to a gas state.
• This then condenses on the
negative electrode as CNTs.
• With this approach a pulsed Laser ablation
laser vaporizes the carbon
from a graphite target.
• A portion of the vaporized
carbon forms into nanotubes
as it condenses.
• At this point, the addition of
metal catalyst particles makes
the process more effective.
• The majority of the nanotubes
produced by laser ablation are
SWCNTs.
Chemical Vapor deposition • This involves a hydrocarbon gas
which is the carbon source for
high-temperature decomposition
producing CNTs.
• This method provides bigger
yields and purer materials which
saves on the cost of purification.
• Purification can’t be avoided for
the arc discharge and laser
ablation methods.
• You can also produce SWCNTs
by CVD, but then you have to
carefully control various
conditions including
temperature, the hydrocarbon
source, the catalyst, and more.
Nanotube synthesis by CVD process
• Source of carbon atoms usually comes from an organic compound
• Mixed with a metal catalyst and insert gas
• Atomised and sprayed into reactor with temperatures ranging from 600C to
1200C.
• Pyrolysis of organic compound deposits carbon (as soot) and carbon nanotubes on
reactor wall (usually a tube constructed from quartz).
Sources of carbon for CVD
1. Typical organic/catalyst mixtures
• Xylene/ferrocene
• Toluene, benzene, xylene, mesitylene, n-hexane/ferrocene
• Ethylene and ethanol/Fe, Co, and Mo alloys

2. Typical carrier gases

• Argon
• Hydrogen
 Limitations of CNT
• Difficulty of mass production for industrial purposes.
• Solubility of CNTs in water
• The production of structurally and chemically reproducible batches of CNTs with
identical characteristics
• Difficulty in maintaining high quality and minimal impurities
Why functionalisation of CNTs?
• For biological and biomedical applications, the lack of solubility of carbon
nanotubes in aqueous media has been a major technical barrier.
• To overcome this problem the modification of the surface of CNT i.e.
functionalisation is done.
• With different molecules functionalisation is achieved by adsorption, electrostatic
interaction, or covalent bonding of different molecules and chemistries that render
them more hydrophilic.
• Through such modifications, the water solubility of CNT is improved and their
biocompatibility profile is completely transformed.
• Moreover, the aggregation of individual tubes through van der Waals forces are
also reduced by the functionalisation of their surface.
 Functionalisation of Carbon Nanotubes
A. Covalent defect-
group functionalization
B. Covalent sidewall
functionalization
C. Noncovalent with
surfactants
D. Noncovalent
exohedral polymers
E. Endohedral
functionalisation

In such functionalisation electrical and optical properties of CNTs are not damaged
or perturbed, but stability could be low.
Bio applications of CNT
 Bio-sensing

• Many spherical nano particles have been fabricated for biological applications.
• Nanotubes offer some advantages relative to other nanoparticles by the following
aspects:
1. Larger inner volumes — can be filled with chemical or biological species
2. Open mouths of nanotubes make the inner surface accessible
3. Distinct inner and outer surface can be modified separately
AFM tips
Carbon nanotubes as AFM (Atomic Force Microscopy) probe tips:
• Small diameter— maximum resolution
• Excellent chemical and mechanical robustness
• High aspect ratio
Use of a MWNT as AFM tip.
VGCF stands for Vapour
Grown Carbon Fibre.
At the centre of this fibre the
MWNT forms the tip
Molecular recognition AFM probe tips
Molecular-recognition AFM probe tips:
• Certain bio molecule is attached to the CNT tip
• This too is used to study the chemical forces between molecules— chemical force
microscopy
Hybridisation experiments (to make CNT based bio sensors)
 CNT based biosensors
• Probe molecule for a given target can be
attached to CNT tips for biosensor
development

• High specificity
• Direct, fast response
• High sensitivity
• Single molecule and cell signal capture and
detection w
Fabrication of genechip
Potential applications:
• Lab-on-a-chip applications
• Early cancer detection
• Infectious disease detection
• Environmental monitoring
• Pathogen detection
Single-walled carbon nanotubes for chemical sensors
• Every atom in a single-walled nanotube is on the surface and exposed to
environment.
• Charge transfer or small changes in the charge-environment of a nanotube can
cause drastic changes to its electrical properties
• Monitoring the change in conductivity forms the basis for sensing

Applications:
• Industrial toxic chemicals, safety
• Leak detection
Detecting bio molecular interactions using molecular
nanomechanics
Nanocantilever array
• The bio marker proteins are affinity-
bound to the cantilever and cause
them to deflect
• The deflections can be directly
observed with lasers
• Alternatively, the shift in resonant
frequencies caused by the binding
can be electronically detected.
• As for nanowire sensors, the
breakthrough potential in
nanocantilever technology is the
ability to sense a large number of
different proteins at the same time, in
real time.
CNTs for targeted drug delivery
• Anti-cancer drugs may be delivered more efficaciously with fewer systemic side-
effects using a “smart” nanotechnology platform than by conventional methods.
• Small-diameter semiconducting SWNTs represent one such promising platform,
due to their strong absorbance in the so called therapeutic infrared window
(between 700-1100 nm, depending on body tissue type)
CNT biosensors for cancer detection

• Folic acid functionalists

polydopamine coated CNT
for the electrochemical
detection of HeLa and HL60
cancer cells over-expressing
the folate receptor
Nanopore ion conductance
• Helps researchers detect errors in the genetic material that may lead to cancer
• Funnels DNA through, one strand at a time, resulting in more efficient DNA
sequencing
• Monitor shape and electrical proper of each base as they pass through the nano
pore
• Properties, which are unique to the bases allow the nanopore to help decipher
information encoded in the DNA.
Cellular internalisation of CNT via “nano needle”
mechanism vs endocytotic pathway
(A) Functionalized CNT rapidly
penetrates the cell membrane
directly to the nucleus, where it
releases the cargo (red circles).
(B) Functionalized CNT is
internalized in the cell by
endocytosis and delivered to the
endosome, which matures to a
lysosome. The accumulation into
the lysosome causes swelling and
rupture of the vesicle followed by
the release of the functionalized
CNT into the cytoplasm.
The cargo is then able to diffuse
through the cytoplasm.
Quantum Dots
• What are quantum dots?

• The methods of making quantum dots

• Working mechanism

• Applications of quantum dots

• Quantum dots are fluorescent semiconductor
particles with a typical diameter of 2–10 nm.
• They are so named because, due to their nanoscale
size, quantum effects play a significant part in their
light emitting properties.
• Quantum dots emit light via this mechanism: under
external stimulus, some of the electrons of the dot
material absorb sufficient energy to escape their
atomic orbit.
• This creates a conductance region in which the
electrons can move through the material, effectively
conducting electricity.
• As these electrons drop back into their atomic orbit,
energy is released in the form of light, the color of
which depends on the amount of energy released.
• Egs of quantum dots are CdSe, PbSe, PbTe, InP
 How to make a quantum dot?
• Quantum dots are sometimes referred to as artificial atoms, emphasising their
singularity, having bound, discrete electronic states, like naturally occurring atoms
or molecules.
• By coupling two or more such quantum dots an artificial molecule can be made,
exhibiting hybridisation even at room temperature.
• The electronic wave functions in quantum dots resembles the ones in real atoms.
Working mechanism of quantum dots
• When the quantum dots are illuminated by UV light, an electron in the quantum
dot can be excited to a state of higher energy.
• In the case of a semiconductimg quantum dot, this process corresponds to the
transition of an electron from the valence band to the conductance band.
• The excited electron then drop back into the valence band releasing its energy by
the emission of light (photoilluminance).
• The colour of that light depends on the energy difference between the conductance
band and the valence band.
Applications
Applications in Biotech
Medical imaging
• Quantum dots can be designed to bind to specific cell receptors.
• The photo below shows red blood cells, in which specific membrane proteins are
targeted and labelled with quantum dots. The number of purple features, which
indicate the nuclei of malaria parasites, increases as malaria development
progresses.
Cell imaging
• Quantum dots last longer in your system and are brighter than many organic dyes
and fluorescent proteins previously used to illuminate the interiors of cells.
• They also have the advantage or monitoring changes in cellular processes while
most high resolution techniques like only provide images of cellular processes
frozen at one moment. Quantum dots can be designed to bind to specific cell
receptors.
Cancer cell imaging
• These quantum dot scan be put
into single cells, or lots of cells, in
the tissue of living organisms.
• In future, it is planned to attach
specific antibodies to the quantum
dots— when injected into a body,
the quantum dots will find and
bind to cancer cells, and illuminate
them when they fluoresce.
Tenfold boost with quantum dots in ability to pinpoint
proteins in cancer cells
• This is a cell specimen used for two
rounds of testing.
• In the left panel, two biomarkers are
stained green and red, and on the right,
after the sample has been regenerated, the
same biomarkers are stained red and
green.
• This shows that the same tissue can be
used for multiple rounds of testing
without degrading the tissue sample.
Targeted drug delivery
• A drug molecule is attached to the quantum dots, which will then be able to
deliver the drug just to the cancer cells where it is needed.
• Current anti-cancer drugs tend to have a range of unpleasant side-effects, because
they affect the whole body, not just the cancer.