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In this section, the most essential principles and concepts relevant to the study
of nanomaterials to demonstrate ULO2d will be reviewed. Please refer to these
definitions in case you will encounter difficulty in the in understanding educational
concepts.
Bottom-up Approach includes the miniaturization of materials components (up to
atomic level) with further selfassembly process leading to the
formation of nanostructures
Buckminsterfullerene also known as buckyball, is a spherical close- caged structure
made of sixty sp2 carbons it has a highly symmetrical structure
which give it its electronic properties
Carbon nanotubes are tubes made of carbon with diameters typically measured
in nanometers; often refer to single-wall carbon
nanotubes (SWCNTs) with diameters in the range of a
nanometer.
Dendrimers are highly branched, star-shaped macromolecules with
nanometer-scale dimensions
Engineered materials with sizes 1 to 100 nanometers and are intentionally
nanomaterials produced for specific product application
Fullerene an allotrope of carbon whose molecule consists of carbon
atoms connected by single and double bonds so as to form a
closed or partially closed mesh, with fused rings of five to seven
atoms. The molecule may be a hollow sphere, ellipsoid, tube,
or many other shapes and sizes.
Graphene a carbon-based nanomaterial derived from graphite through
exfoliation
Nanocomposites are materials that incorporate nanosized particles into a matrix
of standard material. The result of the addition of nanoparticles
is a drastic improvement in properties that can include
mechanical strength, toughness and electrical or thermal
conductivity.
Nanomaterials materials that have structural components smaller than 1
micrometer in at least one dimension
Nanoparticles particles with at least one dimension smaller than 1 micron and
potentially as small as atomic and molecular length scales
(~0.2 nm)
Nanotechnology the design, synthesis, and application of materials and devices
whose size and shape have been engineered at the nanoscale
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Nanomaterials are any material with any external dimension in the nanoscale
which ranges from 1-100 nanometers or internal or surface structure are in nanoscale
(IOS, 2015). Moreover, the European Commission (2011) defined a nanomaterial as
any natural, incidental or manufactured material containing particles in an unbound
state or as an aggregate where 50% or more of the particles’ size extends from 1-100
nm.
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Figure 1. Conceptual free-energy landscape for the formation and interactions that
define the typical state of nanomaterials in the environment.
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Engineered Nanoparticles
From its name, carbon- based nanomaterials are composed mostly of carbon
which may form hollow spheres, ellipsoids or tubes. Spherical and ellipsoidal carbon
nanomaterials are generally called fullerenes whereas cylindrical ones are called
nanotubes. These particles are best used in improved films and coatings, stronger and
lighter materials and electronics application.
Carbon Nanotubes
It is referred as the most widely used CBN. It is known for its tunable physical
properties such as diameter, length, surface functionalization and chirality. It is
produced through arc discharge or chemical water deposition of graphite. Carbon
nanotubes have cylindrical carbon structure and wide range of electrical and optical
properties (Saito, et al, 1998).
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Graphene
Graphene is the latest CBN to burst into the scene. It is derived from graphite
through exfoliation, a method introduced by Geim and Novoselov (2007). In addition,
graphene is extraordinarily strong and is famed as the strongest material ever known
and tested. It is supernaturally light and electrically super conductive (Science 321,
385 and Changu, 2008).
Figure 3. Graphene
Fullerenes
Buckminsterfullerene
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Figure 4. Buckyball
Iron oxide is one of the three main oxides of iron. It is a reddish brown, inorganic
and is paramagnetic in nature delivery and imaging, molecular and cellular tracking,
detection of cancer, diabetes, etc. Superparamagnetic iron oxide nanoparticles are
known for their magnetic properties and biocompatibility. Due to these properties, iron
oxide nanoparticles are used in biomedical applications such as for enhanced
resolution content agents for magnetic resonance imaging (MRI). (Morales, et al,
2003)
❖ Dendrimers
Dendrimers are nanosized polymers built from branched units. Their surfaces
have numerous chains which can be tailored to perform a specific chemical function.
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Moreover, this is also the reason for being useful in catalysis. They may also be used
for drug delivery due to its interior cavities which other molecules could be placed. This
is particular for three-dimensional dendrimers.
Polyamidoamine (PAMAM)
Peptide Dendrimers
These are dendrimers which held amino acid as branching or interior units.
Diagnostic purposes and vaccine delivery are some of its applications (Yasukawa, et
al, 2008).
Multilingual Dendrimers
❖ Nanocomposites
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Ceramic-Matrix Nanocomposite
Metal-Matrix Nanocomposites
Polymer-Matrix Nanocomposites
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Materials in the nanometer size are in demand for production for the past years. It is
used in a broad variety of applications. So as years continue to pass by, so is the
production of nanomaterials. Its production rate continues to immerse that almost all
materials were made after it. It has been compromising many products and is used in
various technologies. For example, the Carbon Black, has been used in tires since
1930 and as of now it is still being used by companies to produce tires. Moreover,
most nanoproducts are required to be processed through a series of production that
inhabits a precisely defined, narrow range of particle sizes (monodispersity) to attain
a result.
The said series of processes are used to produce diverse nanoparticles,
coatings, dispersions or composites that are needed to make an engineered
nanomaterial. This production involves a thorough defined production and reaction
conditions for obtaining such size-dependent particle features. Particle size, chemical
composition, crystallinity and shape can be controlled by temperature, pH-value,
concentration, chemical composition, surface modifications and process control.
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B. Laser Ablation
Laser ablation has been studied for various applications in the late 1963 but
has been employed for synthesizing nanomaterials in the mid 1990s. Laser ablation
means the removal of materials from a surface by means of laser irradiation. The word
“Laser ablation” is used to emphasize the non-equilibrium vapor or plasma conditions
that is created at the surface by laser pulse, to distinguish from “laser evaporation,”
which is heating and evaporation of material in condition of thermodynamic
equilibrium. Briefly, there are two essential parts in the laser ablation device: a pulsed
laser (CO2 laser, Nd-YAG laser, ArFexcimer laser, or XeClexcimer laser) and an
ablation chamber. The high power of the laser beam induces large light absorption on
the surface of target, which makes temperature of the absorbing material increase
rapidly.
As a result, the material on the surface of target vaporizes into laser plume. In
some cases, the vaporized materials condensate into cluster and particle without any
chemical reaction. In some other cases, the vaporized material reacts with introduced
reactants to form new materials. The condensed particle will be either deposited on a
substrate or collected through a filter system consisting of a glass fiber mesh. Then,
the collected nanoparticle can be coated on a substrate through drop-coating or
screen-printing process. (Cao, 2007).
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Pyrolysis
• Solvothermal Reaction
Solvothermal Reaction is a method for preparing engineered nanomaterials such as
nanobots and nanorods. A liquid phase synthesis that involves the use of solvent
under moderate to high pressure typically between 1 atm and 10,000 atm and
temperature typically between 100 °C and 1000 °C that is responsible for the
interaction of precursors during synthesis. The formation of nanocrystal is controlled
by manipulating the solvent supersaturation, chemical of interest concentration, and
kinetic control. This method can be used to prepare thermodynamically stable and
metastable states including novel materials that cannot be easily formed from other
synthetic routes. Over the last decade, a majority (~80%) of the literature concerning
solvothermal synthesis has focused on nanocrystals. If water is used as the solvent,
the method is called “hydrothermal synthesis.” The synthesis under hydrothermal
conditions is usually performed below the supercritical temperature of water (374 °C).
The process can be used to prepare much geometry including thin films, bulk powders,
single crystals, and nanocrystals to produce engineered nanomaterials (Zabara,
2016).
• Sol-Gel
A well-established colloidal chemistry technology, which offers possibility to
produce variety of nanomaterials with novel, predefined characteristics in a simple
process at a low cost. The term “sol” originated from the name of a colloidal solution
made of solid particles few hundred nm in diameter, suspended in a liquid phase, while
the gel refers to the solid macromolecule immersed in a solvent. Sol-gel process
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consists in the chemical transformation of a liquid (the sol) into a gel state and with
subsequent post-treatment and transition into solid oxide material. The main benefits
of sol–gel processing are the high purity and uniform nanostructure achievable at low
temperatures (Zabara, 2016).
Graphene can be used as energy storage and it is being studied and developed
to be used in manufacture of super capacitors which are able to be charged very
quickly. Also it can be able to store a large amount of electricity. Graphene – enhanced
lithium ion batteries could be used in much higher energy usage application such as
electricity powered vehicles, smart phones, laptops, and tablets PCs but at significant
lower level of size and weight (La Fuente, n.d.).
Fullerenes belong to the class of inorganic molecules and show wide availability
due to their small size and biological activity. The fullerene core is hydrophobic and
the functional group is attached to its core. By attaching hydrophilic moieties, fullerene
become water-soluble and capable of carrying drugs and gene for the cellular delivery.
Derivatized fullerene can cross the cell membrane and bind to the mitochondria
(Folley, 2002).
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Quantum dots can be used for producing images of cancer tumors and it is
used to evaluate the performance of cancer treatments. Also, it is used to produce
miniature laser to be used in communication devices. The advantage of this laser is
its high speed data transfer with low power consumption. Quantum dots can be used
in computer or TV displays. Using quantum dot display should be thinner, lower than
current displays as well as able to be flexible.
Large surface area to volume ratio of gold nanoparticles enables their surface
to be coated with hundreds of molecules including therapeutics, targeting agents, and
anti-fouling polymers. Also, in DNA combined assembly, gold particles are used as
efficient gene transfection tools.
Dendrimers
Types of Composites
The other example is metal matrix nanocomposites. With the use of carbon
nanotube, they can be used in different industries, such as in sports: badminton, tennis
racket and light weight bicycle; aerospace: landing gears and aircraft brakes;
automobile: gears, break shoes, piston rings and cylinder liners.
Self-Help: You can also refer to the sources below to help you
further understand the lesson.
Let’s Check
1. What is nanotechnology?
2. What are engineered nanomaterials? Give examples and discuss each.
3. What analytical techniques are used to characterize nanomaterials?
Let’s Analyze
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In a Nutshell
Keywords Index
Bottom-up Buckminsterfullerene
Approach
Fullerene Graphene
Engineered Nanocomposites
nanomaterials
Nanoparticles Nanomaterials
Carbon Nanotechnology
nanotubes
Dendrimers Top-down Approach
References
Araújo, R., Santos, S., Igne Ferreira, E., & Giarolla, J. (2018). New Advances in
General Biomedical Applications of PAMAM Dendrimers. Molecules, 23(11),
2849. doi:10.3390/molecules23112849
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Folley, S., et.al. (2002). Cellular localization of a water soluble fullerene derivative.
Biochem Biophys Res Commun
Geim, A.K; Novoselov, K.S. (2007). The rise of graphene. Nat Mater. 6: 183-189
Hermanson, Greg T. (2008). “7”. Bioconjugate techniques (2nd ed). Academic Press
of Elsevier: London.
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Kruis, F.E, et al. (1998). Synthesis of nanoparticles in the gas phase for electronic,
optical and magnetic applications.
Link, et al. (1999). Simulation of the optical absorption spectra of gold nanorods as a
function of their aspect ratio and the effect of the medium dielectric constant.
Morales, et al. (2003). Contrast agent for MRI based on iron oxide nanoparticles
prepared by laser pyrolysis.
Murphy, CJ, et al. (2008), Gold nanoparticles biology: beyond toxicity to cellular
imaging
National Institute for Occupational Safety and Health. (2018). Protecting workers
during the handling of nanomaterials.
Sampathkumar, SG., Yarema, KJ. (2007). Nanomaterials for Cancer Diagnosis and
Theraphy. Nanotechnologies for the Life Sciences. Volume 6: pp 1-47.
Science 321, 385 (2008); Changu, Lee, et al. Measurement of the elastic properties
and intrinsic strength of monolayer graphene.
Science Daily. (2018). Fullerenes. Britannica Encyclopedia.
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Yasukawa, et al. (2004). Drug Delivery Systems for vitro Retinal Diseases. Progress
in Retinal and Eye Research
Zabara, M., (2016) “Metallic Nanoparticles, part II (Top- Down and Bottom-Up)”
Retrieved from: https://nanografi.com/blog/metallic-nanoparticles-part-ii-top-
down-and-bottom up/
Course Schedule
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