INDIAN INSTITUTE OF TECHNOLOGY ROORKEE

NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Biomedical Nanotechnology

Lec - 10
Carbon Nanotubes and its Bio-Applications

Dr. P. Gopinath
Department of Biotechnology
Indian Institute of Technology Roorkee

Hello everyone I welcome you all to the 10th lecture of this course. The 10th lecture is on carbon
nanotubes and its bio applications. In this lecture we are going to learn what carbon nanotubes
are and what is the difference between single walled nanotubes and multi walled nanotubes.
(Refer Slide Time: 00:31)

We are also going to learn about synthesis of carbon nanotubes and how to functionalize these
carbon nanotubes. We will also learn about various applications of carbon nanotubes.
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So let us see what carbon nanotubes are? The carbon nanotubes can be described as a sheet of
graphene rolled into a cylinder. See this animation. This is a graphene sheet rolled into
cylindrical shape, which are called as carbon nanotubes. Graphene is mainly made up of
hexagonal rings of carbon. Carbon nanotubes can have single layer or multiple layers of
graphene sheets. If it is having one layer that is called as single walled carbon nanotubes. If it is
having multiple layers, it is called as multi walled carbon nanotubes.

These carbon nanotubes can have caps at the ends so that we can load any therapeutic molecule
or any anti cancer drugs inside the carbon nanotubes which can be used for various therapeutic
applications.
(Refer Slide Time: 01:40)
The source of this graphene is from the graphite. If a single layer of graphene is rolled into a
tubular form, it is called as single walled carbon nanotubes. If multiple layers of graphene are
used, then that is called as multi walled carbon nanotubes.
(Refer Slide Time: 02:00)

Let us see the structure and morphology of carbon nanotubes. The bonding in the carbon
nanotubes is sp2 with each atom joined to 3 neighbors as in graphite. Therefore the tubes can be
considered as rolled up graphene sheets. This bonding structure is stronger than the sp3 bonds,
which are found in diamond. Under high pressure, these nanotubes can join together and form
nano wires.
(Refer Slide Time: 02:30)

Let us see the difference between the single walled carbon nanotubes (SWNT) and multi walled
carbon nanotubes (MWNT).
(Refer Slide Time: 02:38)
Single walled nanotubes has single layer of graphene and multi walled has multiple layers of
graphene. For synthesis, SWNT needs catalyst but MWNT can be produced without catalyst
also. Bulk syntheses of SWNT is difficult but in MWNT, bulk syntheses is easy. The purity of
SWNT is poor whereas purity of MWNT is high. SWNT will accumulate less in the body while
MWNT can accumulate more in the body. The selection of SWNT or MWNT depends on the
applications for which they are going to be used.
(Refer Slide Time: 03:22)

Let us see some of the properties of carbon nanotubes. Carbon nanotubes are strongest and most
flexible materials because of the presence of CC covalent bonding. It is 500 times stronger than
the aluminium and steel. The maximum strain it can withstand is more than 10% which is higher
than any other material. We can also add any kind of functional group, which is called as
functionalization.
(Refer Slide Time: 03:49)
Carbon nanotubes are 100 times stronger than stainless steel but six times lighter than them. It is
harder than the diamond. It has high current carrying capacity and high thermal stability.
Depending on the arrangements of the atoms, it can be metallic or it can be semiconducting.
(Refer Slide Time: 04:08)

Let us now see how to synthesis these carbon nanotubes. There are 3 approaches available to
make the carbon nanotubes- that is arc discharge, chemical vapor disposition and third one is
laser ablation.
(Refer Slide Time: 04:21)

In arc discharge method, you will connect two graphite rods to a power supply and place them a
few millimeters apart, which will make the carbon nanotubes. Here the yield will be around 30 to
90%. You will get short tubes with diameter of 1.4 nm in size. The advantages of this method
are that it is easy to produce SWNT with few structural defects so that it is good for
functionalization. We can also make multi walled nanotubes without any catalyst. It is not an
expensive method.
So the next method is chemical vapor disposition where a substrate is placed in an oven and
heated to 6000 C. Carbon bearing gas such as methane is slowly added to this. As the gas
decomposes, it produces carbon nanotubes. Here the gas enters the chamber at room temperature,
which means it is cooler than the reaction temperature. The gas is heated as it approaches the
substrate. The gas then react with the substrate or undergo chemical reaction in the reaction zone,
forming the deposited material. Here the gaseous products are then removed from the reaction
chamber. Here the yield will be around 20 to 100%. We can get long tubes of diameter 10 to 240
nm with this method. It is also easy to scale up to industrial production. The purity from this
method will be high. The typical carbon sources for this method are xylene or ferrocene. The
carrier gases like argon and hydrogen are used for making CNT using CVD method.
The next method is laser ablation. In laser ablation method, we will be applying the laser light to
the graphite target. This is kept in the furnace at 12000 Celsius in the presence of argon gas. The
laser light vaporizes the graphite target and produces the carbon nanotubes, which will be
collected in a water cooled collector. Here we will be applying laser light on graphite and it will
produce carbon nanotubes. The yield from this method will be around 70%. It is primarily used
for making single walled nanotubes. The advantages of this method are that it is a pure material,
so the reaction product is also pure. So we can used it for biological applications. However the
disadvantage is that it is little bit costly technique.
(Refer Slide Time: 05:55)

When this arc discharges, they will be having this graphite. The cathode and anode will be
connected and power will be applied. Then all the carbon nanotubes will be deposited.
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(Refer Slide Time: 07:37)

There are some limitations with CNT. The first thing is the difficulty for the mass production.
The second thing is the solubility of CNT in the water. It is also very difficult to produce uniform
CNT batch wise. Moreover, it is also difficult to maintain high quality of CNT with minimal
impurities.
(Refer Slide Time: 07:56)
So to overcome these difficulties, we have to functionalize the CNTs. For biological and
biomedical applications, the lack of solubility of carbon nanotubes in aqueous media has been a
major technical barrier. These carbon nanotubes aggregate through Van der Waals forces, which
can be overcome by functionalization. It will also increase the water solubility of CNT and also
improve the bio compatibility of CNT.
(Refer Slide Time: 08:27)
There are various approaches for functionalization. They are covalent defect group, covalent side
wall, third one is non covalent with surfactants and fourth one is non covalent exohedral
polymers. We can also perform endohedral functionalization. Let us see them all one by one.
(Refer Slide Time: 08:52)

Let us see endohedral functionalization. Here modification of CNT is done by putting

nanoparticles inside the tubes. We have to incubate the CNTs inside the suspension of solution
containing nanoparticles so that it can penetrate the tube’s internal side and stay inside the tube.
The endohedral functionalization here depends on the surface tension of the liquid and if the
surface tension of the liquid is more than 200, then the liquid can fill the nanotubes.
(Refer Slide Time: 09:19)
The exohedral functionalization is sub categorized into three main methods. The first one is
covalent exohedral functionalization, which means when you make the carbon nanotubes there
will be some defects, which are the best places for functionalization. Next one is covalent
exohedral functionalization. Here we can add the functional groups to the side walls of the
carbon nanotubes.
(Refer Slide Time: 09:45)
The third one is the non-covalent exohedral functionalization. Here you will be adding the
polymers or surfactants, which will be wrapping this CNT. By wrapping the polymer around the
CNT, there is a phenomena called Pi stacking.

What is Pi stacking? It is when the P orbitals of CNT and the functionalized group interact with
each other and cause less stability. In this type of functionalization, the electrical and the optical
properties of CNTs are not damaged. But the stability is quite low, okay.
(Refer Slide Time: 10:20)

Amidation and Fluorination are some other types of functionalization.

(Refer Slide Time: 10:28)
Amidation means addition of amide group. But we cannot add the amide group directly. First we
have to functionalize the carbon nanotubes with COOH, following which we can add the amide
group.
(Refer Slide Time: 10:38)

Similarly we can also add the fluorine group using Pentafluoride IF5.
(Refer Slide Time: 10:44)
This will add the fluorine group. So when you add the fluorine group, it increases the electrical
resistance. We can also substitute the fluorine with some other chemical group and use if for
various applications.
(Refer Slide Time: 10:58)

So let us see the various applications of carbon nanotubes. These carbon nanotubes are useful for
bio-imaging. It could be also useful for drug delivery applications.
(Refer Slide Time: 11:02)
We can also use it for bio-sensing and for therapeutic or theranostic applications. Let us see all of
them one by one.

(Refer Slide Time: 11:20)

For biological applications, the nanotubes offer some advantages related to nano particles by the
following aspects. The first thing is its larger inner volumes. The larger inner volumes can be
filled with chemical or biological species. It can be loaded with any kind of drugs or imaging
agents. The next advantage is the open mouths of nanotubes, which make the inner surface
accessible. And third one is their distinct inner and outer surfaces, which can be modified
separately.
(Refer Slide Time: 11:48)

Now, let us see how we can use the carbon nanotubes as AFM probe tips. The small diameter
and maximum resolution with its excellent chemical and mechanical robustness makes the
carbon nanotubes suitable for using as AFM probe tips.
(Refer Slide Time: 12:01)
So let us see how to make functional AFM tips. Certain bio molecules can be attached to the
CNT tip which is used to study the chemical forces between the molecules. So it is also called as
chemical force microscopy. If the tip is having COOH functional group and suppose your sample
is having NH2 group, then they can react and we can measure the force. So this is called as
chemical force microscopy.
(Refer Slide Time: 12:28)
Let us see the comparison between the microelectrode and nano electrode for sensor application.
In micro electrode the scale difference is very high because the molecules are in the range of
nano scale and the electrode is in the range of micro scale. Hence, the background noise will be
very high and so, we need more amount of target molecules for sensing the target molecule.
(Refer Slide Time: 12:52)

But when we use CNT tips for making a nano electrode for sensing application, it will reduce the
background noise because the nanotubes are in small scale in size. It can match exactly with the
target molecule because that is also in the range of nano scale. Because of this reason, the nano
tips are having high sensitivity.
(Refer Slide Time: 13:14)
Now, let us see how we can use it in hybridization experiments to make the CNT based sensors.
Here we will be adding single stranded DNA to the carbon nanotubes. The target single stranded
DNA will be taken from the serum of patients. When these two are put into the sensor, they will
combine and form a kind of bond. This is known as hybridization. Hence, if the patient’s DNA is
forming a bond with the probe DNA that means that person is having the particular disease.
(Refer Slide Time: 13:46)
So there will be a probe, single standard DNA and a target DNA. So when DNA from the
patient’s serum forms a bond with the probe DNA by hybridization, the electrical conductivity
property of the CNT will be changed, based on which the presence of a particular disease is
detected.
(Refer Slide Time: 14:30)

This biosensor has high specificity, very fast and gives direct response.
(Refer Slide Time: 14:46)
Based on these principles, we can make a genechip or lab on a chip.
(Refer Slide Time: 14:56)

Let us see an example for detecting cancer. We can have DNA probes for detecting multiple
types of cancer. For example, we can have separate DNA probes for lung cancer, breast cancer,
pancreatic cancer, brain tumor etc., we can have all these single standard DNA probes in a
microarray based chip. If the DNA from the patient’s serum forms hybridization only with the
lung cancer probe, which means the person is affected by lung cancer.

So instead of going through all the reactions, we can have all the things in a simple lab on a chip
concept. Based on this, we can easily identify the type of cancer that particular patient is having.
This method is highly sensitive and less time consuming. This will be useful for early detection
of cancer and other infectious diseases.
(Refer Slide Time: 16:29)
Let us now see how we can use single walled carbon nanotubes as a chemical sensor. Here every
atom in a single walled nanotube is on the surface and exposed to the environment. Hence, any
charge transfer or changes in the charge environment of a nanotube can cause drastic changes to
the electrical properties of these CNTs. Based on this principle, we can make a chemical sensor
which will be useful for detection of diseases and other application.
(Refer Slide Time: 16:53)
We will consider an example of how we can use this carbon nanotube based sensors for detecting
various diseases. We can have a kind of chip and a cantilever beam.
(Refer Slide Time: 17:18)

If the patient’s serum has more amount of a particular antigen, it comes and binds to the chip.
Now depending on the number of antigens, there will be deflection, which will be measured to
identify the particular disease. So if the patient’s serum has more amount of an antigen, then
there will be more amount of deflection. Based on this deflection, we can make a nano cantilever
based array for bio sensing application.
(Refer Slide Time: 17:29)
We can also use the carbon nanotubes for targeted drug delivery. Here you can see that the
carbon nanotube is loaded with a contrast agent. This contrast agent is used for imaging
applications. We can also use any anti-cancer drug for therapeutic applications. Antibodies can
be used along with these two agents for specific targeting of the carbon nanotubes to the cancer
cells. We can also add a functional group, which will give the CNT the property of
biocompatibility and increase the circulation time. Hence, this is called as multi-functional nano
particles or theranostic nano particles because it is having both contrast agent and as well as the
therapeutic agent.
(Refer Slide Time: 18:09)
Now let us see how to make CNT based biosensors for cancer detection.
(Refer Slide Time: 18:12)

Some of the cancer cells expresses a receptor for folic acid. So when carbon nanotubes with the
folic acid are made, these cells expressing the folic acid receptor can come and bind to the folic
acid. Based on this principle, we can make sensors for cancer detection. Here you can see that
this carbon atoms are coated with the folic acid. So these are folic acid functionalized
polydopamine coated carbon nanotubes could be useful for electrochemical detection of breast
cancer cells or Hela cells, which are expressing the folate receptor. We can also study the same
samples under the fluorescent microscope to confirm the expression of the folic acid receptor.
(Refer Slide Time: 19:41)

We can also use the carbon nanotubes for biomaterial applications. For example, in application
to spine interbody fusion material, a material call PEEK that is polyetheretherketone along with
multi walled carbon nanotubes is used. It possesses excellent mechanical property as well as
bone compatibility, which are useful for making various bio compatible materials for bone tissue
engineering.
(Refer Slide Time: 20:06)
Now, let us see how we can use this nano pore ion conductance for DNA sequencing. This will
help the researchers to detect errors in the genetic material, which may lead to cancer. In this,
you will be passing the DNA through small pores.
(Refer Slide Time: 20:16)

It will be similar to DNA sequencing and we can use the protein called α-hemolysin. The
drawback of this is that it is a toxic protein.

(Refer Slide Time: 20:32)

When you pass the single standard DNA through the carbon nanotubes, there will be a decay in
the current. This is the present scenario but in future researchers are trying to develop very
specific types of sensors so that when guanine passes through these carbon nanotubes, it will
have a specific kind of current decay, when adenine passes, it will produce a different kind of
current decay and so on. This way, we can easily sequence the DNA and will be also a low cost
DNA sequencing device.
(Refer Slide Time: 21:02)
We can also make carbon nanotubes based nano motors. It is like a nano scale motor, made up of
gold attached to a carbon nanotube. It spins in a particular direction due to electrical current. Let
us see how these carbon nanotubes are taken up by the cells.
(Refer Slide Time: 21:21)

There are two ways by which cells can take up these carbon nanotubes. One is nano needle
mechanism and the other one is endocytic pathway. In this nano needle mechanism, it will
directly inject the cells and it will release the drug. In endocytic pathway, the CNT will be
attached to the cell and endocytosis will happen. The CNTs will be enclosed in an endosome and
this endosome will combine with the lysosome and forms the endo-lysosome. When this
degrades, the drug molecules are released into the cytoplasm.
(Refer Slide Time: 21:56)
Now, let us see how to create a simple strain and chemical sensor using a pencil and paper.
Students from Northwestern University used pencil and paper to create functional sensor
devices. The graphene has very good conductive property. So when you draw a line on a piece of
paper with the pencil, the pencil shades numerous grapheme sheets.
(Refer Slide Time: 22:23)

So based on that we can make a strain or chemical sensor. If we make this kind of line on the
paper and if you curl the paper in one direction, it increases the conductivity. This is because the
graphene particles are compressed when curled. But when it is curled in the other direction, it
decreases the conductivity. This is a simple strain sensor.
(Refer Slide Time: 22:46)

In the second experiment, they have shown how we can use a bendable toy pencil for making
chemical sensors. Here, they have used a bendable toy pencil in which the graphite is mixed with
a polymer binder. When they create an electrode with this pencil, they found out that
conductivity was affected by the presence of volatile chemical vapors. Because the polymer
binder absorb the vapor and expands, the conductivity decreases. So we can use the simple paper
and pencil for making chemical sensors as well as the strain sensors.

As a summary of this lecture, we have learnt what is carbon nanotubes and how to synthesis
carbon nanotubes by various methods. We have also learnt how to functionalize the carbon
nanotubes and their bio applications. I will end my lecture here. I thank you all for listening, I
will see you in another interesting lecture.

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Indian Institute of Technology Roorkee
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