Nanotube Molecular Wires as Chemical

Sensors
Sensing gas molecules is critical to environmental monitoring, control of
chemical processes, space missions, and agricultural and medical applications.
Upon exposure to gaseous molecules such as NO2 or NH3, the electrical
resistance of a semiconducting SWNT is found to dramatically increase or
decrease. This serves as the basis for nanotube molecular sensors.
The nanotube sensors exhibit a fast response and a substantially higher
sensitivity than that of existing solid-state sensors at room temperature. Sensor
reversibility is achieved by slow recovery under ambient conditions or by
heating to high temperatures.

CNT + Gas → CNTδe Gas δ+ or CNT δ+ Gas δe

Science, 287, 622-625, 2000

Dr. S. Paria, NITRKL Nanotechnology

However, it is currently difficult to obtain semiconducting SWNTs exclusively from as-grown
samples, which typically tend to be a mixture of both metallic and semiconducting nanotubes.
Even when nanotubes are directly grown on the platform by CVD, there is no control now for
the growth of semiconducting tubes selectively. This often results in additional processing steps
leading to fabrication complexity, low sensor yield, and poor reproducibility in sensor
performance.
Carbon Nanotube Tips: High-Resolution Probes for Imaging Biological Systems

The feature resolution obtained by AFM is determined

in large part by the size and shape of the probe tip used
for imaging. Commercially available probes consist of
microfabricated pyramids of Si or Si3N4 that have end
radii of curvature as small as 10 nm but are often much
larger. These tips place significant constraints on
potential lateral resolution, and furthermore, the
pyramidal shape restricts the ability of these tips to
access narrow and deep features. Recently, a potential
breakthrough in probe technology was achieved by
attaching MWNTs to the ends of Si tips.

Dr. S. Paria, NITRKL Nanotechnology

 Nanotube Nanotweezers

Micro Tweezer
Micrometer-scale electromechanical tweezers,
which represent basic microelectromechanical
systems, have been fabricated previously on silicon.
Tungsten deposition and subsequent processing
were used to produce tungsten arms 200 mm long
by 2.5 mm wide that could be closed by applying a
potential (V) of ~150 V and then opened again by
reducing V to zero. The potential difference
between the tungsten tweezer arms produces an (A) Schematic illustrating the deposition of two
attractive electrostatic force that can overcome the independent metal electrodes and the subsequent
attachment of carbon nanotubes to these electrodes.
elastic restoring force of the beams in closing the For fabrication of nanotube nanotweezers, free standing
tweezers. Smaller tweezers with single crystal electrically independent electrodes were deposited onto
silicon arms 30 mm long by 0.25 mm long, which tapered glass micropipettes, which can be routinely made
with end diameters of 100 nm. (C) shows that the MWNT
respond at a potential of 45 V, have also been made arms of the tweezer are about 4 mm long but only 50 nm
with conventional lithography and processing steps. in diameter.

Philip Kim and Charles M. Lieber, Science, 248, 2148-2150, 1999.

Dr. S. Paria, NITRKL Nanotechnology
The nanometer-diameter carbon nanotubes based robust nanotweezers are made and that can
be utilized for nanoscale manipulation and measurement. Carbon nanotubes are ideal materials
for nanoscale electromechanical devices because they exhibit remarkable mechanical toughness
and electrical conductivity.
The electromechanical response of nanotube nanotweezers was investigated by applying bias
voltages to the electrodes while simultaneously imaging the nanotube displacements. As the bias
voltage increased from 0 to 8.3 V. The ends of the tweezer arms bent closer to each other from
their relaxed position (at 0 V). The tweezer arms relaxed to the original position when the
applied voltage was removed, and this process could be repeated more than 10 times, producing
the same displacement each time within the optical microscope resolution limit. These results
demonstrate that the mechanical response is elastic and thus that neither the nanotubes nor the
nanotube-electrode junctions deform plastically. At 8.3 V, the distance between the tweezer ends
had decreased by about 50% of the initial value, and as the voltage was increased further to 8.5
V, the tweezer arms suddenly closed.
The nanotweezer arms typically remain closed after removal of the actuating voltage, because
the van der Waals interaction between tubes produces a second potential minimum at contact.

Dr. S. Paria, NITRKL Nanotechnology

The nanotweezers can, how-ever, be
readily opened by applying voltage of the
same polarity to both tweezer arms
relative to a nearby ground electrode.

2
1 πER 4
L
 d2y 
Gtot {y} = C{y}V 2 +
2 4 ∫  dx2  dx
0 

y(x) is the designate deflected distance of the tweezer

arm from the equilibrium position at x, where x is the
distance along a relaxed tweezer arm from the
electrode. The static equilibrium shape of tweezer y(x)
at bias voltage V is obtained by minimizing the free
energy Gtot{y}} with respect to y( x), where C{ y} is the
capacitance between the tweezer arms; and E, L, and R
are the Young’s modulus, length, and diameter of the
tweezer arm, respectively.
Calculated threshold voltage Vth 5 9.4 V, which is close
to the observed experimental value of 8.3 V.

Dr. S. Paria, NITRKL Nanotechnology

 Biosensors
Biosensors differ from classical chemical sensors in the following two ways:
(a)The sensing element consists of a biological material such as proteins (e.g., cell receptors,
enzymes, antibodies), oligo- or polynucleotides, microorganisms, or even whole biological
tissues
(b)The sensor is used to monitor biological processes or for the recognition of bio-molecules.

For in-vitro (technique of performing a given experiment in a controlled environment outside

of a living organism) biosensing, the sample solution (such as blood serum, urine, milk products
etc.) is dropped atop the biosensor, and the output signal gives information on the composition
of the solution.
By contrast, in-vivo biosensing addresses dynamic systems, aiming for instance to measure the
rate of uptake or efflux of relevant species or to estimate the spatial distribution of the
concentration of an analyte in a living organism.

CNTs have an outstanding ability to mediate fast electron-transfer kinetics for a wide range of
electroactive species, such as hydrogen peroxide or NADH. (Nicotinamide adinine
dinucleotide, active enzyme from vitamine B3. It plays an essential role in energy production in
cell) .
In addition, CNT chemical functionalization can be used to attach almost any desired chemical
species to them, which allows us, to enhance the solubility and biocompatibility of the tubes.

Dr. S. Paria, NITRKL Nanotechnology

 Suitability of CNTs for Biosensors
Several issues are important regarding nanomaterial/biosystems
(i) One of them is biocompatibility, especially for in-vivo applications of implantable
bioelectronic devices.
(ii) Another is specificity that requires biofunctionalization of nanomaterials for
recognition of only one type of target biomolecule in solution and rejection of others.
In order to use nanotubes for biosensors, as-grown nanotubes need to be purified to
remove amorphous carbon, substrate material such as Al2O3, and metal catalysts such as
Fe, Co, and Ni. Purification can be done using high-temperature annealing, plasma
treatment, or chemical methods.
Surface modification and functionalization can be performed to selectively immobilize
biological molecules. Functional groups such as carboxylic, hydroxyl, ketone, alcohol,
ester, amine, thiol, and fluorine can be created by wet and dry chemical modification
methods such as acid reflux and plasma treatment.
Compared with the sidewall, the ends of nanotubes are more reactive to strong acids
such as HNO3, H2SO4, KMnO4, K2Cr2O7 because of the presence of dangling bonds with
Stone-Wales defects.

Dr. S. Paria, NITRKL Nanotechnology

 Biofunctionalization
Methods for the immobilization of biological species to nanotubes can be separated into
covalent bonding and noncovalent bonding or physical adsorption. Once nanotubes are
oxidized and defects are created, moieties such as carboxylic groups and biomolecules
can be bonded covalently to the defect sites.

N-hydroxysulfosuccinimide = NHS
Attachment of DNA to a carbon nanotube: (a, b) NHS esters formed on carboxylated ends of
a nanotube and displaced by peptide nucleic acid (PNA); (c) hybridized DNA bound to PNA-
SWNT; (d, e) AFM images of PNA-SWNT structure
Dr. S. Paria, NITRKL Nanotechnology
Nature, 420, 761, 2002
 Enzyme-functionalized CNT electrodes

Electroanalytical techniques can provide information on chemical, biochemical, and physical

systems. Enzyme electrodes are this type.
Enzyme electrodes consist of two parts: a conductive part for electroanalytical purposes and a
specific enzyme layer that provides the selectivity. Enzymes provide biological affinity for a
particular substrate molecule and catalyze specific reactions of given substrates such as
glucose, lactate, cholesterol, urate, pyruvate, glutamate, insulin, amino acids, homocysteine,
organophosphate, nerve agents, and neurotransmitters.
In response to the presence of these analytes the enzymes generate hydrogen peroxide, which
can transfer electrons at a certain potential. there are a number of biomolecules and chemicals
that can be detected using enzyme biosensors.
On the down side, the sensitivity of enzyme biosensors is limited by interference effects from
uric acid, acetaminophen, ascorbic acid, paracetamol, and other chemicals. The interference
effects can be reduced by coating semipermeable membrane layers such as Nafion on the
electrode.
Now CNTs are providing the interface between the electrode surface and enzyme layers since
nanotubes have high electrical conductivity and enable individual tethering of the redox center
of enzymes, which minimizes surface fouling. The nanotube electrode provides
high sensitivity, a low detection limit, and a fast response.

Dr. S. Paria, NITRKL Nanotechnology

 The reconstitution of appoglucose oxidage, appo-
Gox, with the ferrocene-amino FAD (Flavin adenine
dinucleotide). Reconstitution of flavoenzyme on the
ends of the standing CNTs associated with
electrodes leads to electrical contacting of the
enzyme with the bulk electrodes surface.

Assembly of a SWCNT-based GOx electrode. A 2-thioethanol/cystamine (3:1

ratio) mixed monolayer was assembled on an Au electrode, followed by
coupling of SWCNTs to the surface in the presence of 1-ethyl-3-(3-
dimethylaminopropyl) carbodiimide hydrochloride (EDC). The amino
derivative of the FAD cofactor (1), was then covalently attached to the
carboxy groups at the SWCNT tips. In the last step, apo-GOx was
reconstituted on the FAD units.

Dr. S. Paria, NITRKL Nanotechnology

Specific and nonspecific binding: Functionalization of CNTs restricted nonspecific bindings
(NSB).
Ex. Streptanidin binding: The high density of nonspecifically adsorbed streptavidin (spots
along the lengths of nanotubes) points to high affinity of the proteins toward
nonfunctionalized nanotubes via hydrophobic interactions. The result also suggests that
streptavidin is an excellent system for investigating nanotube sidewall modification for
resisting NSB of proteins.

Figure (b) shows AFM image showing nonspecific

streptavidin binding is prevented by coating SWNTs with a
surfactant, Triton X-100, and a well-known protein
resistant polymer PEG
A variety of polymer coatings and self-assembled
monolayers have been used to prevent nonspecific binding
of proteins on surfaces for biosensor and biomedical device
applications. Among them, PEG is one of the most effective
and widely used.

Nano Lett., 2, 285-288, 2002

Dr. S. Paria, NITRKL Nanotechnology

PEG coated nanotubes exhibit certain degree of protein resistance, however, appreciable
adsorption of streptavidin was still observed, indicating that the coverage of PEG on
SWNT sidewalls is not complete or uniform. Triton X-100 can be adsorbed onto SWNTs
as a wetting layer to significantly enhance PEG adsorption on nanotubes.

.
.

Conventional electrochemical biosensors are based on either glassy carbon electrodes

(GCE) or metal electrodes (Au, Pt or Cu for example) for amperometric or voltammetric
analyte detection.

Dr. S. Paria, NITRKL Nanotechnology

 NTFET

Gate voltage (VG)

NTFET Detection of Antibody–Antigen Interactions

Biotin-streptavidin binding has been detected by changes in the device
characteristic.

Dr. S. Paria, NITRKL Nanotechnology

A polymeric functional
layer, which coats the
nanotube, is functionalized
with a molecular receptor,
biotin, a protein that
recognizes a biomolecule,
streptavidin.

Biotinylation reaction of the polymer layer

(PEI (polyethyleneimine) and PEG)

Nano Letter, 3, 459-463, 2003

Dr. S. Paria, NITRKL Nanotechnology
Atomic force microscopy image of the
polymer-coated and biotinylated NTFET
device after exposure to streptavidin
labeled with gold nanoparticles (10 nm in
diameter).
Light dots represent gold nanoparticles (10
nm), and thus indicate the presence of
streptavidin. Based on the image, it is
concluded that streptavidin is effectively
attached to the nanotubes, due to the
strong adsorption of the PEI polymer to
the sidewalls of the nanotubes.

Dr. S. Paria, NITRKL Nanotechnology

Figure shows a striking loss of source-drain
current for negative gate voltages after
exposure to streptavidin and consequent
streptavidin-biotin binding with little
evidence for the shift of the device
characteristic toward negative or positive
gate voltage.
The source-drain current dependence on the
gate voltage of the NTFET shows a
significant change upon the streptavidin
binding to the biotin-functionalized carbon
nanotube. The experiments reveal the
specific binding of streptavidin, which occurs
only at the biotinylated interface.

Dr. S. Paria, NITRKL Nanotechnology

Dr. S. Paria, NITRKL Nanotechnology
 Nanowire-based detection of single viruses

Concept of nanowire-based detection

of single viruses. Schematic
illustration showing two nanowire
devices, 1 and 2, in which the
nanowires are modified with different
antibody receptors. Specific binding
of a single virus to the receptors on
nanowire 2 produces a conductance
change. Right: Characteristics of the
surface charge of the virus only in
nanowire 2. When the virus unbinds
from the surface the conductance
returns to the baseline value

PNAS, 101, 14017-14022, 2004

Dr. S. Paria, NITRKL Nanotechnology