Fucntionalization of nano

materials
• Nanoscale materials : At least one dimension lies within the
nanometric range, i.e. in the range between one and several
hundreds of nanometers and shows quantum effect. Within this
length scale, the properties of matter are sufficiently different from
individual atoms or molecules and from bulk materials.
• Nanoscience : A new area of science, deals with the creation of
nano structures such as, nano particles, nano wires, nano tubes,
nano belts, nano rods, nano twizzer and nano springs and also
their unique properties like high surface-to-volume ratio, efficient
transport of electrons, optical excitation and their potential for
fabrication into high density nano scale devices including sensors,
electronics and optoelectronics.
• Nanotechnology :, This relates to the ability to build functional
devices based in the controlled assembly of nanoscale objects, for
specific technological applications.
 Why Functionalization ?
 Nanoparticles represent metastable clusters exhibiting the fundamental
property to aggregate. Thus, the stabilization of the nanoparticles against
aggregation is a fundamental pre-requisite in nanoparticle science and
technology.
 The association of ligands(capping agent) to growing nanoparticles can
control the dimensions and shapes of nanocrystals. Nanoengineering of
nanoparticle surfaces, eg. layer-by-layer deposition of organic modifiers,
allows fine control of the shell size and structure.
 To impart functional property so that the desired nano materials will be
suitable for particular application. Such surface functionalities may then
be used to link particles to surfaces or to inter-connect particles into
extended nanoscale architectures and functional systems.
 To modify the surface so that the resulting nano material can be
specifically useful for particular application
 The integration of chemical units of predesigned chemical functions such
as recognition sites, redox groups, or chromophore units, may yield hybrid
systems combining the unique features of nanoparticles with the tailored
properties of the molecular or macromolecular coatings. Such integrated
hybrid systems may yield new sensoric, photonic and electronic devices.
SYNTHESIS AND PROPERTIES OF MONOLAYER CAPPED
METAL NANOPARTICLES
Thiolate monolayers can assemble on different bulk surfaces
such as Au, Ag or Pt. The thiol monolayers are covalently
linked to the surfaces by the reaction of the metal surfaces
with the respective thiols and for some metals by the reaction
with disulfides. For gold surfaces, following mechanisms for
the formation of the Monolayers are experimentally
supported,as shown in Eq. (1 to 3) .
 As the upper gold surface includes an oxide sublayer, its
reduction by the thiol is suggested as a path for the formation
of the Au-thiolate bond, Eq. (1).
 Hydrogen evolution by the Au-mediated reduction of the
thiol protons could lead to the Au-thiolate bond, Eq. (2).
 The formation of the Au-thiolate bond in the presence of the
disulfide is a redox process where the gold surface is oxidized
by the disulfide and the disulfide bond is splitted, Eq. (3).
It is an exothermic process and associated with the release of 40-45 kcal/mol.
The monolayer reorganizes to a dense packing stabilized by Van der Waals or
Π interactions.

Ellipsometry, surface plasmon resonance (SPR), microgravimetric quartz

crystal microbalance, contact angle, XPS, FTIR, different scanning microscopy
techniques and electrochemical methods were applied to characterize these
monolayers. thiols and disulfides were employed as capping reagents for the
stabilization of different metal NP and for the surface derivatization of metal
NP with molecular functionalities.

Thiols and disulfides were employed as capping reagents for the stabilization
of different metal NP and for the surface derivatization of metal NP with
molecular functionalities.
 Functionalized Metal Nanoparticles in Organic Phases
• Synthesis of metal nanoparticles covered with a
hydrophobic monolayer of alkanethiols is usually a
two-phase system composed of aqueous and
nonaqueous solutions.
• A one-step method for the preparation of monolayer-
functionalized nanoparticles is developed by Schiffrin
et al.
• (a) In this method, ions are transferred from an
aqueous to a toluene solution using
tetraoctylammonium bromide as the phase transfer
reagent.
• (b) The gold is reduced with an aqueous solution of
borohydride in the presence of dodecanethiol as a
capping reagent, Eq (4 to 5).
On addition of the reducing agent NaBH4to the aqueous
phase, the organic phase changes color from orange to
deep brown within a few seconds indicating the formation
of Au nanoparticles protected with a self-assembled thiol
monolayer. HTEM photographs of the nanoparticles show
that they have diameters in the range 1-3 nm and a
maximum size distribution of 2.0-2.5 nm.
 Advantages

(i) It leads to a simple way for the direct synthesis of surface

functionalized nanoparticles.
(ii) Since the kinetics of the cluster growth is determined by
the surface coverage, cluster size can be controlled by the
reaction conditions and not by the metal ion reduction
kinetics, as is usually the case in condensed-phase colloidal
metal preparations.
(iii) These new hydrophobic metal clusters are of intrinsic
interest since in some respects, they behave like simple
chemical compounds; they can be precipitated, redissolved
and chromatographed without any apparent change in
properties.
 Effect of nature of thiol capping on the properties of
nano particles
• Solubility
Depending on the chemical nature of the thiol group
Alkanethiols with various chain lengths (C3 to C24)
soluble in variety of organic solvents. Thiol capping
provides solubility in non-polar organic solvents.
(C3 to C24) Hydrocarbon solvent
(Perfluorinated alkane ) Fluorocarbon media.
Arenethiol (phenethyl mercaptan,
benzylthiol, thiophenol, 4-thiocresol, and 2
naphthalenethiol) aromatic solvents.
Arrangement of alkane thiol

Smaller chain lengths relatively disordered, with large amounts of gauche defect.
The longer length alkanethiolates predominantly in the all-trans zigzag configuration.
However, even the long alkyl chains with a high degree of conformational order not
rigid, but instead undergo a dynamic process involving large-amplitude motion
about the chain axes. Molecular mobility increases towards the unbound ends
where there is a higher population of gauche conformers.

Stability

Alkane thiol capping molecules provide good protecting properties for the metal
cores.

Polydispersity

Arenethiol-protected Au NP have small cores of 2-3 nm less polydisperse than in

the case of the usual alkanethiolate-shell.

Speciality Properties

Thiol derivative containing a chromophore unit with a large dipole moment,

applied for capping of Au NP to introduce unique electronic properties.
Unsymmetrical disulfides having two distinct functional groups at the molecular
termini (X-R-SS-R-Y) offers the possibility of generating mixed self assembled
monolayers possessing a homogeneous distribution of functional groups.

Unsymmetrical disulfides possessing two distinct chain lengths (X-R-S-S-

R'-X) offers the possibility of generating nanoparticles designed with molecular
“roughness” which can be useful in manipulating the interactions between
nanoparticles by controlling the degree of interdigitation of the molecular tail.

Disulfides can be used to generate functionalized NP with terminal groups that are
incompatible with thiol anchor groups.

 The application of disulfide capping molecules with polymerizable moieties (1)

allows the formation of polymer shells around Au NP upon intraparticle
polymerization. Further etching of the Au cores results in the formation of
nanosize polymer capsules with small size dispersion.
Size control of Au NP by tuning the molecular cross section of capping
Disulfides . The use of a four-chained disulfide ligand resulted in
smaller and monodispersed gold nanoparticles compared to Au
nanoparticles capped with a conventional single chain alkanethiol.
Another method to the formation of thiol-derivatized NP refers to the acid-
facilitated transfer of hydrosol particles to a toluene layer containing a thiol.
The NP are produced by chemical reduction of the respective salts and
stabilized in the aqueous solution at a high pH value. When an organic layer
containing a capping thiol is added and on acidification of the aqueous
solution the NP are destabilized in the aqueous solution and moved to the
organic layer, yielding thiolate-functionalized metal nanoparticles in the
organic phase. The acid-facilitated transfer of hydrosol particles (Au, Pt and
Ag ) to a toluene layer containing a thiol produce NP of diameter 1-10 nm.
.

CH3
O
-
+ HS
Au (aq alkaline)
(organic)

+
H

Au CH3
S
(organic)
Characterization

Raman spectroscopy showed that the self-assembled monolayer is formed

by the covalent attachment of the sulfur atoms of the disulfide to the surface of gold shows
that the anchor group exists in the form of thiolate and not of disulfide R-SS-R. 13C NMR
shows that the anchor group exists in the form of thiolate, and not of disulfide R-SS-
R. FTIR-spectra suggests that the alkyl chains are highly ordered in the region near the
sulfur anchor-group.
Functionalized Metal Nanoparticles in Aqueous
Systems
While alkanethiolate self-assembled monolayers are nonpolar and the metal
nanoparticles capped with them are usually produced in two-phase
immiscible liquidliquid systems, highly polar ligands can yield water-soluble
metal nanoparticles that can be obtained directly in an aqueous phase. An
aqueous solution of a metal salt (e.g. in case of formation of AuNP) was
reacted with a reductant (e.g. in the presence of a water-soluble bifunctional
thiol yielding thiolate-capped AuNP directly in the aqueous solution.

mAuCl4- + nX-R-SH 4mCl - + (Au)m(S-R-X)n

 Type of polar Functional Group(X)
• Hydroxyl (OH)
• Carboxylic (COOH)
• Amino (NH2)
• Sulfonic (SO3H)
• Boronic acid (H2BO2)
• Phosphonic acid(H2PO3)
 OH C CH3
3
H2C
NH SO 3H

Na2S2O 3

OH C CH3
3

NaO 3S2 NH SO 3Na

1)HAuCl 4
2)NaBH4
3)HCl
Properties

Stability in a water solution depends on the extent of their hydrophilicity and the
charge state of the functional groups. Charging properties of the functionalized
metal nanoparticles were characterized by measuring their (–45.3 mV for
carboxylic-derivatized Au nanoparticles).

The charge of the dissociated head groups is pH dependent, allowing control on

the solubility of the nanoparticles. For example, NP-functionalized with amino
groups are soluble in acidic solutions, whereas carboxylic units provide solubility in
basic solutions. When pH change results in neutralization of the functional groups
of the shell layer, the nanoparticles loose the solubility and start to coagulate,
precipitate or adsorb at solid supports. Nanoparticles functionalized with sulfonic
acid units are well soluble in a broad pH range. Hydrogen bonding
between the nearest groups was found to be less efficient for the functionalized
nanoparticles than for planar monolayers, probably because of longer distances
between them at curved surfaces.

The increase of pH value results in dissociation of the carboxylic groups at the

particle surfaces thus resulting in the increase of the surface hydrophilicity, and
therefore the decrease of the advancing contact angle for a drop of water.
The interparticle H-bonding and their aggregation also show pH dependent
character. Titration of carboxylate-functionalized Au nanoparticles
with NaOH produced an increase in the intensity of the plasmon band at 550
Nm as shown in Figure (B). This behavior was attributed to the conversion of
groups, that provide effective H-bonding and aggregation, to groups that
provide repulsion and dissociation of the particle aggregates. The values of
pK corresponding to the transitions in the titration curves,
Amphoteric capping molecules that have basic groups (NH2/NH3+)and acidic
Groups (COOH/COO-) in addition to the thiol anchor groups (e.g. cysteine)
provide very efficient aggregation of the functional nanoparticles due to H-
bonding and electrostatic attraction. This aggregation process is temperature-
dependent and the particles can dissociate upon increase of the temperature
resulting in the absorbance decrease at 550 nm. However, this process is
reversible and a temperature decrease results in re-association of the
functionalized nanoparticles.
Chemical Reactivities of Functionalized Metal Nanoparticles and
their Stepwise Modifications
Mainly two type reaction (a) Ligand place Exchange Reacation

a) Ligand place Exchange Reaction

Ligand Exchange
Thiol-monolayers self-assembled on bulk Au electrodes can be
exchanged with other thiols. This is applicable to the formation of a
capping layer that may not be directly formed upon formation of the
nanoparticles.

Partial substitution of the primary capping molecules leads to a mixed

monolayer shell structure. Disulfides and oxidized sulfer species are
not involved in the reaction.
B ) Core metal Exchage
Au core edge and vertex sites are presumably more reactive than terrace
sites. The rate of place-exchange decreases as the chain length and/or
steric bulk of the initial protecting ligand shell is increased. Thiolate-capping
molecules can move from one metallic nanoparticle to another one that
has a bare unprotected surface. When negatively charged 4-
carboxythiophenol (4-CTP)-functionalized Au nanoparticles is mixed with
bare Ag nanoparticles, both particles were functionalized with the same, but
diluted capping monolayer after the interparticle thiolate-transfer reaction,
Transfer from the functionalized Ag nanoparticles to bare Au nanoparticles was
also possible.

(b) Reaction of the functional groups present at the terrace.

Functional groups on the outermost portion of the monolayer-functionalized

nanoparticles can undergo many synthetic transformations. Covalent binding of a
secondary modifier to functional groups of the primary capping molecules is a
powerful technique that allows the synthesis of very complex structures. For
example, p-mercaptophenol-capped Au nanoparticles were esterificated using
propionic anhydride.
more complex structures were obtained when Au nanoparticles
functionalized with tiopronin capping molecules were covalently
modified with N-methyl-N'-ethylamine-4,4’-bipyridinium by the
amide bond formation between the carboxylic group of tiopronin
and the amino group of the secondary modifier.

CH3 O CH3
H3C
NH + +
N
+
N
S
OH

CH3 O

NH
S + NH2
N +
N
SN2 Reaction

Nanoparticles functionalized with monolayers terminated with a Br-atom were

reacted with amines. In general, the rate of the reactions were found to be
dependent on the steric bulk of the incoming nucleophile (rates of n-propylamine
> isopropylamine > tert-butylamine) and on the relative chain lengths of
and surrounding alkanethiolate chains (rates of

It is surprising that even in the system where the active Br-atom is deeply
screened by the surrounding chains, the reaction proceeds with an observable
rate. This dramatically differs from a 2D-self- assembled monolayer at a Au
support, where the similar reaction is fully blocked. The higher chemical activity
of the monolayer at the nanoparticle surface originates from the curved surface,
which allows flexibility of the chains and allows access to the active sites of the
planar ligands.
CATALYTIC, ELECTROCHEMICAL AND PHOTOCHEMICAL
PROPERTIES OF FUNCTIONALIZED METAL NANOPARTICLES

• Catalytic Properties
Effectivity is due to :
• High surface-area of nanoparticles
• Particle morphology controlling the edge-step ratio

The reactions catalyzed by functionalized metallic

nanoparticles(mainly Rh, Pd, Pt, Ir, Os, Au) includes
isomerization
reductions of multiple bonds (C=C, C=O, N=O) & O2 , NO3-
hydroformylation
Fischer-Tropsch synthesis
cleavage of carboxylic acid ester
Gold is a poor catalyst in the bulk form where as shows high catalytic activity of
in the nano range e.g, CO oxidation. This oxidation reaction requires Au
nanoparticles less than 5 nm.

Preparation NP based catalyst

Catalytic nanoparticles embeded into polymer matrices act as immobilized
solid supports used as catalytic surfaces.

Self-assembly of thiol functionalized metal nanoparticles at a polymer-template

due to electrostatic interactions allows formation of stable catalytic aggregates
of desired size and shape.

Alternating adsorption of polyethyleneimine-metal ions, or complexes and

polyanions (e.g polyacrylic acid) results in the formation of multilayered
polyelectrolyte film. Postdeposition reduction of the metal ions by heating or
exposure yields composite films containing catalytically active Ag or Pt
nanoparticles.

Electrochemical reduction of metal ions included into a polyelectrolyte layer at

an electrode surface yields metallic species of various sizes and properties.
Novel monolayer-functionalized metal nanoparticles
could provide a unique opportunity for highly efficient
catalyst with precisely tunable activity and selectivity.
Weak temporary association of selected species with
functionalized nanoparticles could provide their
increased local concentration and thus enhanced
reactivity at the particle surfaces. This effect could be
used to develop nanosized catalytic centers with
selective activity. The shell-structure of the
functionalized nanoparticles could also provide a
favorable environment for a specific chemical route,
resulting in selectivity.
Metal nanoparticles capped with chiral molecules can lead to a new
type of enantioselective catalyst combining good selectivity control
and extraordinarily high activity and simple extraction. For example,
AU nanoparticles (2.5 nm) functionalized with alkanethiols that have
dihydroquinidine head groups. Dihydroxylation reactions were
performed at room temperature in t-butylalcohol/water with the
functionalized nanoparticles in the presence of and as oxidizers.
The dihydroxylation of proceeded in 80% yield and gave diol with an
enantiomeric excess of 90%
Another example of an enantioselective nano-sized catalyst includes Pt
nanoparticles (size from 1.5 nm to 4 nm depending on the Pt/capping
molecules ratio) capped with alkaloid dihydrocinchonidine.
 The functionalized Pt NP can catalyze hydrogenation of ethyl pyruvate.
enantioselectively.

The catalytic activity of the PVBCS-2 nanospheres for Heck reaction was
investigated using the model iodobenzene and methyl acrylate. The freshly
synthesized PVBCS-2 nano reaction of here exhibit a higher activity.

Catalyst synthesis is shown below..

 Electrochemical Properties of Functionalized Metal
Nanoparticles

Characteristics
• The electrochemical properties of nanoparticles could be significantly
different from those of the same bulk metal.
• The electrocatalytic activity of electrodes modified with metallic
nanoparticles depends on the size of the nanoparticles and it is similar to
the increase of an electrode catalytic activity upon roughening of an
electrode surface.
• The electrochemical properties of redox unit-functionalized nanoparticles
are unusual in comparison with free redox-molecules because they
transfer many redox equivalents under diffusional control to the
electrode/solution interface.
• The overpotential for electrochemical dioxygen reduction is significantly
decreased at electrode surfaces modified with Au or Pt nanoparticles
indicating the electrocatalytic process.
Electrochemical studies of redox-functionalized metal nanoparticles reveal
that all redox-units bound to the metal core are electrically contacted and
participate in the electrochemical process that can originate from internal
electrical conductivity of the metallic core and fast rotation of the
functionalized nanoparticles at the electrode surface. Thus, the redox-
functionalized nanoparticles can be considered as nanoelectrodes with a
modified surface.
(i) Shift in peak potential

The adsorption of redox-functionalized metal nanoparticles could be reversibly

controlled by their electrochemical reaction. For example, N-methyl-N'-
ethylamino-4,4’- bipyridinium (amino-viologen) was covalently linked to the
carboxylic groups of tiopronin-functionalized Au nanoparticles by amide bond
[Link] the viologen units carry two charges, the resulting functionalized
Au nanoparticles are soluble in water and can be studied in aqueous solution.
Figure shows cyclic voltammograms of functionalized Au nanoparticles (curve
a), and of a solution of free amino-viologen with the same concentration of the
viologen units (curve b). It can be seen that the vilogen units bound to the Au
nanoparticles show slightly positive-shifted redox potentials as a result of the
association that is typical for vilogen monolayers and a low peak current that
originates from the smaller diffusion coefficient of the nanoparticles.
 CH3 O

NH
S + NH2
N +
N
Electrochemistry of the redox-functionalized metal nanoparticles can be studied
after their association with a solid conductive support. For example,
Au nanoparticles were synthesized by the exchange reaction of
octanethiol-derivatized Au nanoparticles with in
solution. The Au nanoparticles were spontaneously
adsorbed on a flat Au electrode by simple dipping of the electrode into the
nanoparticle solution in The adsorbed Au nanoparticles
demonstrate well resolved reversible redox waves with and –1.29
V in
corresponding to and
redox transformations of the fullerene units, Figure curve (a). For
comparison, the 5 was directly chemisorbed onto a flat Au electrode yielding
a electrode. However, this electrode showed a poorly resolved cyclic
voltammogram with the peak potentials different from those of the
nanoparticle adsorbed at the Au electrode, Figure curve (b). The electrochemical
properties of redox-functionalized metal nanoparticles can be affected by their
association with ions or molecules. This suggests the application of redox-
functionalized metal nanoparticles for electrochemical sensing. For example,
alkylthiolate functionalized Au nanoparticles were reacted with a dendritic
ferrocene thiol derivative to yield ferrocene-functionalized Au nanoparticles by
thiol exchange.
(iii) Change of electrochemical characterixtics

Octylthiolate-covered Pd nanoparticles (3.8±0.8 nm) were prepared by

reduction of salt with in tetrahydrofuran (THF)
solution and capped in situ with monolayer. The functionalization
of the Pd nanoparticles with biferrocene units was performed by an
exchange reaction of the biferrocene thiol derivative with the octylthiolate-
capping monolayer in solution. Cyclic voltammograms of the biferrocene-
functionalized Pd nanoparticles were recorded on indium-tin oxide (ITO)
electrodes in solution. The first cyclic voltamograms showed two-
step one-electron waves at and 0.577 V corresponding to the
reversible oxidation of both ferrocene units bound to the solubilized Pd
nanoparticles. However, the peak currents were linearly dependent on the
applied potential scan rate, characteristic of electrochemistry of redox-
species adsorbed at the electrode surface. Consecutive potential scans
exhibited a gradual increase in the peak current and the voltammogram
slowly changed its shape to display one new redox wave between the two
original waves.
After the electrode was washed and immersed into a background solution, the
cyclic voltammogram still showed the same redox process. This behavior is
similar to the electropolymerization processes and can originate from an
electrochemically induced intra-molecular reaction of ferrocene units resulting
in their binding to the electrode surface. The electrochemical deposition of
ferrocenefunctionalized Pd nanoparticles yields a Pd layer with the thickness
controlled by the time of the electrochemical process and the electrochemical
properties quite different from the original ones (Fig A). The spectral
measurements performed upon the electrodeposition process also show the
increase of the Pd film thickness when the process progressed (Fig. B).
Similar oxidative electrodeposition processes were achieved for biferrocene-
functionalized Au nanoparticles and reductive electrodeposition was reported
for anthraquinone-functionalized Au nanoparticles.
Biferrocene thiol derivative
(iv) Fast electron transfer
Figure shows typical cyclic voltammograms at a stationary electrode (curve
a), and a RDE (curve b), in the presence of ferrocene-functionalized Au
nanoparticles. However, even in those systems that show diffusional type of
electrochemistry, “prewaves” and “postwaves” in the cyclic voltammograms
are sometimes observed as evidence of complications in the
redox processes possibly originating from the adsorption phenomena.
A cyclic voltammogram of the ferrocene-functionalized Au nanoparticles
solubilized in shows reversible electrochemistry for the ferrocene units. This
redox wave is decreased and finally disappeared upon titration of the particle
solution with while a new redox wave of the complex
appears at a potential less positive by 210 m V. An apparent association constant
for the ferrocene derivative and of 5200±1000 was derived from the
titration curves. Another kind of amidoferrocenyl alkylthiol ligands bound to Au
nanoparticles allowed specific sensing of and ions due to a
potential shift originating from the complex
formation between the ions and the ferrocene redox units. The redox potential of
the amidoferrocenyl group is sufficiently perturbed by the synergy between the
hydrogen bonding, electrostatic interaction and topology in the alkylthiol-Au
nanoparticles containing amidoferrocenyl ligands. Redox-functionalized metal
nanoparticles can behave as nanoelectrodes and can also be used for transporting
reduced or oxidized multi-electron equivalents. This allows their application for
electrocatalysis. For example, anthraquinone-functionalized Au nanoparticles were
used for the electrocatalytic reduction of 1, 1-dinitrocyclohexane,
Comparison of cyclic voltammograms corresponding to the
electrocatalytic process in the presence of the anthraquinone-
functionalized Au nanoparticles and molecular solution of the
anthraquinone, Figure, curves (1) and (2), respectively, show
comparable efficiencies of the electron transfer. Similar electron
transfer rate constants for the electrocatalytic process of both
systems were derived from rotating disk electrode
(RDE) experiments. This opens the way for the use of redox-
functionalized metal nanoparticles also as multi-electron
carriers in bioelectrocatalytic reactions.
 Photochemical Properties of Functionalized
Metal Nanoparticles
• For this purpose metal nanoparticles functionalized with pyrene, fluorescein,
Stilbene, porphyrin, azobenzene, and fullerene were synthesized.

Effects Observed
• Various chromophore-functionalized metal nanoparticles can demonstrate
efficient quenching of the photoexcited chromophore states with or without the
formation of photoseparated charges.

• Enhancement of lifetime of the photoexcited state.

Quenching Effect

Fullerene thiol emission is totally quenched when it is anchored on the Au

nanoparticles. This observation shows that the decay of singlet fullerene moieties is
affected by its binding to the particle. Time-resolved spectroscopy has shown that
energy transfer from the photoexcited singlet state of the fullerene to the Au core is
responsible for the efficient quenching of the fluorescence, Equation shows that the
photoinduced electron transfer mechanism does not contribute significantly.

Nanosized photochemical system involving pyrene (Py)-functionalized

nanoparticles was studied by time-resolved spectroscopy. It was seen that electron
transfer resulting in the formation of a photooxidized pyrene cation radical and
charged Au core. The fluorescence quenching is explained by the following equation.
Thiolate-capped Au nanoparticles are capable of holding charge in a quantized
fashion. This photoinduced charge separation between the Au nanocore and the
pyrene ligand is sustained for several microseconds before undergoing the
recombination.

The ability of functionalized Au nanoparticles to participate in photoinduced electron

transfer reactions, and the long lifetime of the photoseparated charges, suggests
that such systems could be used as nanosized photoreactive centers. Such
application of photoactive functionalized metal nanoparticles has been
demonstrated with photoinduced hydrogen evolution.
Supression of quenching

Fluorescent ligands bound to gold nanoparticles have shown suppression of

their quenching by the Au cores. In this context, porphyrin-functionalized Au
nanoparticles were studied in detail. Au nanoparticles (2.4±0.6 nm) were
synthesized in toluene by reduction of with in the presence of the porphyrin
disulfide derivative 6, yielding porphyrin-functionalized Au nanoparticles. The
Au nanoparticle coverage with the porphyrin units (109 porphyrin molecules
per particle) corresponds to 56% ratio between the porphyrin molecules and
Au atoms at the particle surface almost one order of magnitude higher than
that of a 2D-monolayer of the porphyrin. Electrochemical and spectral
properties of the porphyrin molecules bound to the Au nanoparticles are not
significantly different from those of the free porphyrin molecules in solution.
The most surprising and important result is that the lifetime of the excited
porphirin bound to the Au nanoparticle is similar to that of free porphyrin
molecules. Thus, there is no significant quenching of the porphyrin excited
state by the nanoparticle, whereas a bulk Au electrode effectively quenches
the fluorescence of a 2D-monolayer of the porphyrin self-assembled at a Au
surface.
The surface-binding properties of TOAB-capped gold nanoparticles and
functionalized organic molecules [1-aminomethylpyrene (Py–CH2NH2) and a
model compound 15N-labeled benzylamine (C6H5–CH2NH2)] (Scheme 1) were
followed using various spectroscopic techniques. The binding of 15N-labeled
benzylamine to gold nanoparticles was probed using 15N NMR spectroscopy and
two sets of signals were observed, one from the free molecule and the other from
the molecule complexed to Au nanoparticles . 1-Aminomethylpyrene is weakly
fluorescent when dissolved in an organic solvent such as tetrahydrofuran (THF) .
The low fluorescence yield of Py–CH2NH2 is attributed to the intramolecular
quenching of the singlet-excited state via an electron transfer from the
lone pair of the nitrogen to the pyrene moiety. However, Py–CH2NH2Au hybrid
nanoparticles, dissolved in THF, emit bright blue light upon UV excitation, with 30-
fold increase in the fluorescence quantum yield . Surface binding of the amine
group to gold nanoparticle suppresses the intramolecular photoinduced electron
transfer from the lone pair of the amine to pyrene and thereby increases the
efficiency of radiative deactivation of the singlet-excited state.
Surface-binding properties of TOAB-stabilized Au
nanoparticles
Application:

The ability of functionalized Au nanoparticles to participate in photoinduced electron

transfer reactions, and the long lifetime of the photoseparated charges, suggests that
such systems could be used as nanosized photoreactive centers. Such application of
photoactive functionalized metal nanoparticles has been demonstrated with
photoinduced hydrogen evolution.
•The high loading of the porphyrin at Au nanoparticles and its long-life fluorescence,
concludes that such a system is promising for light harvesting in
photoelectrochemical devices.
•Photoisomerizable molecules have been used extensively in photoswitchabe
systems in solutions and at [Link] nanoparticles were functionalized with an
azobenzene thiol derivative,. In order to study their photoizomerizable
features in solution Photoswitching was not observed in a single-component
monolayer of the azobenzene bound to Au nanoparticles, however, by increasing the
free volume available per azo unit by monolayer dilution with alkanethiol, reversible
photoisomerization between the cis- and trans-states was observed.
A tunnel junction is, in its simplest form, a thin insulating barrier between two
conducting electrodes. The following reasoning is for the case of tunnel
junctions with an insulating barrier between two normal conducting electrodes
(NIN junctions). According to the laws of classical electrodynamics, no current
can flow through an insulating barrier. According to the laws of
quantum mechanics, however, there is a nonvanishing (larger than zero)
probability for an electron on one side of the barrier to reach the other side
(see quantum tunnelling). When a bias voltage is applied, this means that
there will be a current flow. In first-order approximation, that is, neglecting
additional effects, the tunnelling current will be proportional to the bias
voltage. In electrical terms, the tunnel junction behaves as a resistor with a
constant resistance, also known as an ohmic resistor. The resistance
depends exponentially on the barrier thickness. Typical barrier thicknesses
are on the order of one to several nanometers. An arrangement of two
conductors with an insulating layer in between not only has a resistance, but
also a finite capacitance. The insulator is also called dielectric in this context,
the tunnel junction behaves as a capacitor.
Due to the discreteness of electrical charge, current flow through a
tunnel junction is a series of events in which exactly one electron
passes (tunnels) through the tunnel barrier (we neglect events in
which two electrons tunnel simultaneously). The tunnel junction
capacitor is charged with one elementary charge by the tunnelling
electron, causing a voltage buildup U = e / C, where e is the
elementary charge of 1.6×10-19 coulomb and C the capacitance of
the junction. If the capacitance is very small, the voltage buildup can
be large enough to prevent another electron from tunnelling. The
electrical current is then suppressed at low bias voltages and the
resistance of the device is no longer constant. The increase of the
differential resistance around zero bias is called the Coulomb
blockade.

A Coulomb staircase is a staircase-like current-voltage

characteristic resulting from Coulomb blockade effects.[1]
Coulomb staircase
 Functional Devices Based on Electronic Properties of
Metal Nanoparticles
Arrays
If metallic particles with a size of a few nanometers are arranged within ca.
1nm of each other, they build tunnel junctions with electrical capacitances
down to ca 10 -9 F. This allows controlled charge transport between the
particles by single electron tunneling (SET) events at room temperature,
which has been recognized to be a fundamental requirement for the
development of quantum electronics. Charging energy as well as capacitance
depends on the size of the metallic nanoparticles and the distances between
them. The charging energy (i.e. the energy barrier that has to be overcome
to
transfer a single electron from an initially neutral cluster to a neutral nearest
Neighboring cluster) is dependent of the inter-particle capacitance C, as
follows from Eq. Where e is the charge of electron.
The use of interparticle spacers can be valuable in controlling capacitance

For instance, while the close packing of the Pd561Phen36O20 0clusters gives
a capacitance of 4 X 10-18 F the insertion of 4,4'-diamino-l,2-
diphenylethane spacers decreases it down to 1.6 X 10-18 F. The electrical
conductivity and capacitance of nanostructured materials
have been studied using direct current (DC) measurements and
impedance spectroscopy. Cyclic voltammetry performed at a single Au-
nanoparticle contacted with an STM-tip has also been used to study single
electron transfer processes. The electrical conductivity and capacitance of
nanostructured materials have been studied using direct current (DC)
measurements and impedance spectroscopy. Cyclic voltammetry
performed at a single Au-nanoparticle contacted with an STM-tip has also
been used to study single electron transfer processes
SET devices range from a single conductive nanoparticle located between
two micro-electrodes or contacted with an STM-tip to 2D and 3D arrays.
Scanning tip-microscopy techniques can be used to observe SET-events
and even to build-up the respective devices. For example, scanning
tunneling spectroscopy (STS) has been applied for the observation of SET
effects on nanoparticle monolayers of Au55(Ph2C6H4SO3H)Cl2 contacted with
a tip, demonstrating “Coulomb staircase” behavior up to room temperature,
where the capacitance of the cluster/substrate junction was calculated to be
3.9 x 10 -19 F. Similar results were obtained applying STS to selfassembled
1.8 nm-gold nanoparticles on a dithiol-modified Au surface. A single particle
device was fabricated by AFM-assisted manipulation of a 20-nm sized Au
nanoparticle between two metallic leads. Two-dimensional lattices for SET
devices can be prepared by self-assembly techniques.
Single Electron Tunneling

SET devices can be used to construct circuits which process information by

manipulating individual electrons. SET devices are small, dissipate little power, and
can detect exquisitely small quantities of charge. The small size and low power
dissipation of SET circuits makes them potentially useful for the Information
Technology industry.
Layer-by-layer assembly has been used for the construction of metal-
insulator-nanoparticle-insulator-metal (MINIM) capacitors
which demonstrate single electron transfer steps in the i-V curve
(Coulomb staircase).
A gold substrate is primed with cysteamine. Insulating layers of α –
Zr(HPO4)2.H2O (α –PAH) and polyallylamine (PAH) hydrochloride
are adsorbed (terminating in cationic substance) until the desired
thickness was obtained (typically 30-100 Å) as measured by
ellipsometry. Subsequently, citrate-stabilized gold particles (ca. 2.5
nm) were immobilized on top of the insulating layer. The remaining
half of the double junction was constructed by simply reversing the
adsorption sequence described. For a junction thickness of 80 Å and
a particle radius of 1.25 nm, the capacitance of a double tunnel
junction device calculated from Eq (where μ0 is the vacuum
permittivity constant, μr is the dielectric constant of the insulator, r is
the particle radius, and L is the junction thickness 374) is 4.5 F. A
coulomb gap, e/C = 360 mV, should be observed at room
temperature since it is substantially higher than kT.
A typical i-V curve for such a MINIM-structure is shown in Figure . The high
impedance region is observed on both sides of 0 V and represents the average
charging potential (± e/2 C) of each particle at the double junction array by a single
electron. When enough energy is supplied to charge particles, electrons tunnel through
the junction, resulting in the square-law dependence of the current rise on either side of
the gap. Figure shows the i-V behavior of a device of similar thickness in the absence
of the gold particles. The linear curve typical for ohmic resistance is observed. In the
next generation of single-electron devices, “switchable” quantum dots and quantum
channels with correlated electrons will provide us with components orders of magnitude
smaller than classical electronic switches or semiconductor memory. This could result
in a new generation of computers, supersensitive electrometers, near-infrared
receivers and very simple miniature lasers.
A single electron transistor was constructed using alkanedithiol-stabilized
gold nanoparticles as tunnel junctions. Three Au-colloidal particles (10 nm) were
linked via 1,6-hexanedithiol, producing an Au-colloid-chain. The particle chain was
formed on a substrate with source, drain and gate electrodes defined by electron
beam lithography, Figure. The Au-colloid-chain bridged a 30 nm-gap between the
source and drain, forming a single electron transistor with a multi-tunnel junction in
the particle chain. Electron conduction through the chain exhibited a clear
Coulomb staircase and the periodic conductance oscillation as a function of gate
voltage. Gold nanoparticles capped with dissociating modifier molecules
(Au/galvinol) provided pH-adjustable resistance for single electron transfer
processes, even at only ca. 10 modifier molecules per Au-nanoparticle.
 A redox-switchable electron tunneling device was produced by covalent attachment of a
Au nanoparticle to a conductive support using N,N'- bipyridinium (18) as redox-active
bridging units, Figure . The nanoarchitecture embedded in an electrochemical cell allows
the reduction of the bipyridinium units to the respective cation-radical by means of the
bulk conductive support, and the reversible electrochemical oxidation of the cation-
radical to the original N,N'-bipyridinium. The oxidized bipyridinium bridge was found to
act as a barrier for electron tunneling from an STM tip to the electrode surface. The
reduction of the bipyridinium units results in the occupation of the LUMO energy level
and the formation of a hybrid electronic wave extending over the Au nanoparticle and the
molecular bridging unit. This reduces the tunneling barrier and a high tunneling current is
observed. Thus, by the cyclic reduction and oxidation of the redox units a gated
tunneling current switched between “ON” and “OFF” states is generated, respectively.
While single electron computing continues to be the ultimate goal of SET technology, its
most advanced practical application is currently the construction of a super-sensitive
electrometer. FET devices with nanoparticles in the gate have so far provided a charge
sensitivity of 600 pA per gate electron. This electrometer could be used as an extremely
sensitive tool for the detection of the redoxstate of a single molecule linked to the
nanoparticle, thus allowing determination of single molecule chemical reactions.
Quantum Cellular Automata (QCA) refers to any one of several models of
quantum computation, which have been devised in analogy to conventional
models of cellular automata introduced by von Neumann. It may also refer to
quantum dot cellular automata, which is a proposed physical implementation of
"classical" cellular automata by exploiting quantum mechanical phenomena.

The computation is considered to come about by parallel operation of multiple

computing devices, or cells. The cells are usually taken to be identical, finite-
dimensional quantum systems (e.g. each cell is a qubit)

Each cell has a neighborhood of other cells. Altogether these form a network of
cells, which is usually taken to be regular (e.g. the cells are arranged as a
lattice with or without periodic boundary conditions)

The evolution of all of the cells has a number of physics-like symmetries.

Locality is one: the next state of a cell depends only on its current state and that
of its neighbours. Homogeneity is another: the evolution acts the same
everywhere, and is independent of time.

The state space of the cells, and the operations performed on them, should be
motivated by principles of quantum mechanics.
Combining many SET elements together for the development of
computing devices remains challenging. It may not be an impossible
task to make electrical connections to a single nano-transistor, but
fabricating the billion-transistor network that is required for computing is
currently a far-off dream, Two independent approaches to contact many
SET-units have been suggested recently. The first approach involves
the simple combination of SET-units with well-developed FET-devices,
where a multi-gate FETdevice is used and each gate is associated with
a single SET-unit. The second, more novel approach is to forgo the
wires [Link] scheme, named quantum cellular automata
(QCA), is based on the electrostatic interactions present between cells
of connecting clusters.
In one possible design, the basic cell is a line of nanoclusters connected
by insulating material, Figure (A). An electric field polarizes the string to
give a “1” or “0” state, depending on the field direction. A similar design is
produced from square cells of nanoclusters carrying the polarization
states, Figure (B). Again, two states are possible depending upon the
direction of the applied field. In either design the cells can be connected in
various configurations to make more complex logic circuits. Figure (C)
illustrates how the cells can be connected to form a logic gate. The dark
and open circles correspond to one-electron rich and one-electron
deficient clusters, respectively. The signals in QCA are rapidly transferred
between interconnecting cells via electrostatic interactions at the speed of
light. Fast inter-cell interactions and the small size of each cell
(as low as ca. make the prospects of ultra-high density data storage and
processing excellent from this kind of device.
Functionalization of Carbon Nanotubes
 Carbon Nanotubes – A New Carbon Allotrope
• The small tubules consisted of concentrically
nested tube-like graphene structures, each
successive outer shell having a larger
diameter.

Idealized representations of different structures of defect-free and

opened carbon nanotubes. a Concentrical multi-walled carbon
nanotubes (MWCNT). b single-walled carbon nanotubes (SWCNT)
CNTs exhibit rather outstanding and unique mechanical and physical properties.

Depending on their structure, diameter and chirality (and thus on their

production), CNTs may be either metallic or semiconductors or super
conductors.

They have been shown to possess outstanding field emission properties.

• Functionalization of Carbon Nanotubes
CNTs in all their forms are difficult to disperse and dissolve in water and in
organic media, and they are extremely resistant to wetting. A suitable
functionalization of the nanotubes, i.e., the attachment of “chemical
functionalities” represents a strategy for overcoming these barriers.
Functionalization can improve solubility and processibility, and will allow
combinination of the unique properties of nanotubes with those of other
types of materials. Chemical bonds might be used to tailor the interaction
of the nanotube with other entities, such as a solvent, polymer and
biopolymer matrices and other nanotubes. A functionalized nanotube
might have mechanical or electrical properties that are different from
those of the unfunctionalized nanotube, and thus may be utilized for fine-
tuning the chemistry and physics of CNTs.
Different possibilities of the functionalization of SWCNTs

a Noncovalent exohedral functionalization with polymers.

b Defect-group functionalization.
c Noncovalent exohedral functionalization with molecules through Π-stacking.
d Sidewall functionalization.
e Endohedral functionalization
Covalent functionalization is based on covalent linkage of functional
entities onto the nanotube’s carbon scaffold. It can be performed at the
termini of the tubes or at their sidewalls. Direct covalent sidewall of
chemical transformations of defect sites already present. Defect sites can
be the open ends and holes in the sidewalls, terminated, for example, by
carboxylic groups, and pentagon and heptagon irregularities in the
hexagon graphene framework.
Oxygenated sites, formed through oxidative purification functionalization is
associated with a change of hybridization from sp2 to sp3 and a
simultanous loss of conjugation. Defect functionalization takes advantage,
have also to be considered as defects. A non-covalent functionalization is
mainly based on supramolecular complexation using various adsorption
forces, such as van der Waals’ and Π-stacking interactions. All these
functionalizations are exohedral derivatizations. A special case is the
endohedral functionalization of CNTs, i.e., the filling of the tubes with
atoms or small molecules.
 The Reactivity of Carbon Nanotubes

A perfect SWCNT without functional groups is a quasi-1D cylindrical aromatic

macromolecule and is thus expected to be fairly chemically inert. However, in
nonplanar conjugated organic molecules, two principal sources, namely
curvature- induced pyramidalization of the conjugated carbon atoms and Π-orbital
misalignment between adjacent pairs of conjugated carbon atoms, induce local
strain. л-orbital misalignment is likely to be the main source of strain in the CNTs.
Fullerenes are curved in two dimensions, 2D, whereas nanotubes are curved in
one dimension, 1D [Link] for a curved carbon structure of given radius, the
carbon atom network in a fullerene is more distorted than that in the
corresponding CNT. The more pyramidalized C-atoms of the end caps of closed
CNTs resemble a hemispherical fullerene and ensure that they are always more
reactive than the sidewalls, irrespective of the diameter of the CNT.
However,while the Π-orbital alignment in the fullerenes is almost perfect,
this is not the case for all the bonds in the CNTs.
Oxidative Purification – Carboxylation of CNTs

One of the most common functionalization techniques is the “oxidative purification”

of nanotubes by liquid-phase or gas-phase oxidation, introducing carboxylic groups
and some other oxygen-bearing functionalities such as hydroxy, carbonyl, ester and
nitro groups into the tubes. Oxidative treatment (“purification”) has been achieved
using boiling nitric acid, sulfuric acid or mixtures of both piranha” (sulfuric acid–
hydrogen peroxide) or gasous oxygen , ozone or air as oxidant at elevated
temperatures, or combinations of nitric acid and air oxidation.

Upon oxidative treatment the introduction of carboxylic groups and other

oxygen-bearing groups at the end of the tubes and at defect sites is promoted,
decorating the tubes with a somewhat indeterminate number of oxygenated
functionalities. However,mainly because of the large aspect ratio of CNTs,
considerable sidewall functionalization also takes place. The
oxidative treatment introduces defects on the nanotube surface , oxidizes
the CNTs (“hole-doping”), and produces impurity states at the Fermi level of
the tubes . In addition to purifying the raw material by removal of impurities,
oxidation can be used to cut (or “etch”), shorten and open the CNTs . Cutting and
shortening depends on the rate and extent of the reaction and gives rise to a new
length distribution which can be determined by transmission electron microscopy
(TEM). The cutting procedure will leave
SWCNTs with open and oxygenated [Link] occurrence, plurality and
degree of oxygenated functionalities have been determined
spectroscopically . Since reactivity is a function of curvature , the
oxidative stability also depends on the tubes’ diameter and on the
production process responsible for the tubes’ dimensions.

Section of an oxidized SWCNT, reflecting

terminal and sidewall oxidation
Since reactivity is a function of curvature , the oxidative stability also depends on the
tubes’. A direct relationship exists between diameter and reactivity. The smaller
diameter tubes are more rapidly air-oxidized than larger diameter tubes . This led to a
simple way to enrich largediameter SWCNTs by using a mixed, concentrated
H2SO4/HNO3 treatment.

Amidation – Formation of Carbon Nanotube-Acyl Amides

The introduction of carboxylic groups to nanotubes by oxidative procedures

gives access to a large number of functional exploitations by transformation
of the carboxylic functions, and provides anchor groups for further
modification. From carboxylic acids, carboxamides can be formed via
carboxylic acid chlorides and allow for the decoration of oxidized tubes with
aliphatic amines, aryl amines, amino acid derivatives, peptides, amino-
group-substituted dendrimers etc. as nucleophiles. The carboxylic groups
can be activated by conversion into acyl chloride groups with thionyl
chloride, and the acyl chlorides formed can be transformed to
carboxamides by amidation . Similarly, carboxamide nanotubes have been
prepared using di-cyclohexylcarbodiimide (DCC) as dehydrating agent and
allowing the direct coupling of amines and carboxylic functions under mild,
neutral conditions .
Schematic representation of oxidative etching (“cutting”) of SWCNTs followed by
treatment with thionyl chloride and subsequent amidation (a). For simplicity, the depiction
here as well as the following are not considering the nature and location of functionalities.
Only one functional group per tube end is shown. The oxidations also occur at defect sites
along the sidewalls, and other functionalities such as esters, quinones, and anhydrides
are also [Link] is shown as coupling reagent (b).
 HO -
N hydroxy succinimiide
N
O O
R
CH3 R
O +H3C N C N O
HO Carbodiimide O
O N O

R
O
HN
Selective thiolation may be used to make electrical
junctions between CNTs and metal electrodes or to position SWCNTs
relative to a noble metal surface by taking advantage of the strong thiol-
metal interactions.

Schematic diagram of the thiolization reaction of carboxyl-terminated

CNTs with cysteamine NH2CH2CH2SH (a) and of the assembling
structure of SWCNTs on gold (b)
a
 A gas-phase derivatization procedure was employed for direct
amidization of oxidized SWCNTs with simple aliphatic amines . In
some cases a minor amount of chemically formed amides in
addition to a larger portion of physisorbed amines were observed.
Full-length oxidatively purified SWCNTs were rendered soluble in
common organic solvents by non-covalent (zwitterionic)
functionalization in high yield . Of the SWCNT C-atoms, 4–8% can
be functionalized by octadecyl amine in this way.

Gas phase amidation of oxidatively purified SWCNT with

octadecylamin (ODA) to obtain zwitterionic functionalization
products
This acid–base reaction functionalization represents a simple route to
solubilizing SWCNTs. The ammonium cation can be readily exchanged by
other cations, and the ionic feature of the modified tube may allow
electrostatic interactions between SWCNTs and biological molecules.
From oxidized MWCNT-COOHs with a diameter of 10–30 nm, a glassy
carbon electrode (GCE) was fabricated. In the presence of the water-
soluble coupling reagent EDC, oligonucleotide probes with an amino
group at the 5’-phosphate end were covalently attached, to be used as a
DNA-biosensor . Nucleotide hybridization could be carried out by
exposure of the probe-containing electrode to its complementary DNA
sequence and detected with the redox intercalator daunomycin as an
indicator.

Schematic representation of the enhanced electrochemical detection of

DNA hybridization based on a MWCNT-COOH constructed DNA
biosensor. DPV Differential pulse voltammetry
Formation of Carbon Nanotube-Esters
Acyl-chloride-functionalized SWCNTs are also susceptible to reaction with
other nucleophiles, e.g., [Link] soluble ester-functionalized SWCNTs:SWCNT-
COO(CH2)17CH3, obtained by reaction with octadecylalcohol . Labelling of SWCNTs
with fluorescence probes was accomplished via esterification by oligomeric species
containing derivatized pyrenes, and the products were spectroscopically studied. The
fluorescence and fluorescence excitation results showed that the tethered pyrenes
form “intramolecular’’ excimers by Π-Π-interactions . The time-resolved fluorescence
results show that the pyrene monomer and excimer emissions are significantly
quenched by the attached SWCNTs. The quenching is explained in terms of a
mechanism in which CNTs serve as acceptors for excited-state energy transfers from
the tethered pyrene moieties.

Labelling of SWCNTs with fluorescence probes via esterification by derivatized

pyrenes and formation of “intertubulary’’ dimers and excimers by Π-Π-
interactions
Thiolation – Formation of SWCNT-CH2-SH by Modification of Oxidized
SWCNTs

Thiolation of CNTs by modification of carboxylated tubes

Schematic representation of the vertical view image of the thiolated CNTs with thiol groups at
both ends,binding to a gold surface.

A new type of bonding between the CNT and a noble metal surface was proposed by
the authors, involving a bow-type SWCNT with its two ends strongly attached to the
metal surface.
Halogenation of Carbon Nanotubes

Fluorination of Nanotubes

Extensive controlled and non-destructive sidewall fluorinations of

SWCNTs using elemental fluorine as the fluorinating agent, and similar
to that of the fluorination of fullerenes. “Fluorocarbon single-walled
nanotubes’’ (F-SWCNT) of approximately C2F product stoichiometries at
temperatures from 150 °C up to 500 °C were done .Attempts to produce
more highly fluorinated material at 500 °C resulted in the destruction
of the tubes. Depending on the reaction temperature, the degree of
fluorination of nanotubes from different origin varied from C3,9F to C1,9F,
as determined by XPS. Using iodine pentafluoride IF5, the highest
degree of fluorination could be achieved with a composition CF.

Schematic depiction of a sidewall-fluorinated SWCNT

The electrical conductivity of the functionalized material differed dramatically from
the SWCNTs: untreated SWCNTs were reported to have a resistance of 10–15
W,while fluorinated SWCNTs had a resistance of >20 MW. Fluorination may result
in modifying the electronic structures of the tubes to be either metallic or
semiconducting, depending on the coverage and method of fluorine application .
For fluorinated SWCNTs, evidence was shown for exfoliation of nanotube-ropes
and bundles into individual nanotubes.

Disadvantage
The high degree of fluorine atoms addition reflecting a great number of tube
defects and damage.

Advantages
The fluorotubes are very soluble and open new avenues to solution-phase
chemistry.
SWCNTs, once fluorinated, can serve as a staging point for a wide variety of
sidewall chemical functionalizations.
 By treating fluorinated tubes with strong nucleophiles such as Grignard
reagents, alkyl lithium reagents and metal alkoxides, the fluorine substituents were
replaced and derivatized products e.g., methyl-, butyl-, hexyl- and
methoxylnanotubes were formed . These reactions are thought to proceed via a
concerted, allylic displacement mechanism, as backside SN2 attack is not
possible, and the stability of a cationic SN1 intermediate is questionable.
 SWCNTs were found to be “cut” at the fluorinated sites during pyrolysis [126]. F-
SWCNTs seem to be a rather promising material, especially for the production of
composite materials.
Fluorinated SWCNTs have been employed as cathodes in
lithium electrochemical cells and are expected to be useful in other
applications .

Treatment of fluorinated tubes with strong nucleophiles and replacement of the

fluorine substituents, leading to derivatized methyl-,butyl-, hexyl- and methoxyl-
nanotubes as products (a). Removal of the covalently bound fluorine by treatment
with hydrazine (b).
By treatment with hydrazine or LiBH4/LiAlH4, the majority of the
covalently bound fluorine could be removed (Scheme 8, b) [117, 119, 124],
restoring most of the conductivity.
The chemical functionalization ofMWCNTs using electrolysis was described .
Electrolytical evolution of chlorine on an anode made from a foil of CNTs, the
halogen atoms were coupled to the nanotube lattice.

Hydrogenation of Carbon Nanotubes

Several methods for hydrogenation of SWCNTs have been described via
dissolved metal reduction.

Birch reduction of SWCNTs using lithium in diaminoethane . The

hydrogenated derivatives were thermally stable up to 450 °C,whilst above 450
°C a characteristic decomposition took place. Transmission electron
micrographs showed corrugation and disorder of the nanotube walls due to
hydrogenation and the formation of CH bonds was suggested. Hydrogenation
occurred even on the inner tubes of MWCNTs, as shown by the chemical
composition and the overall corrugation. Electrochemical hydrogenation of
open ended SWCNTs synthesized by CVD. Sheets of SWCNT bucky paper
were used as the negative electrode in an electrochemical cell containing an
aqueous solution of KOH as electrolyte. With laser Raman IR evidence and
the release of hydrogen by thermogravimetric measurements at 135 °C the
authors claimed to have incorporated up to 6 wt% of hydrogen into the tubes.
Addition of Radicals

The addition of perfluorinated alkyl radicals,obtained by photoinduction from

heptadecafluorooctyl iodide, to SWCNTs yielded perfluorooctyl-derivatized
CNTs (Scheme 9).No remarkable difference in the solubility of the fluoroalkyl
substituted nanotubes and the starting materials was observed.

Addition of heptadecafluorooctyl radicals obtained from photoinduction of

heptafluorooctyl Iodide .

Functionalization of SWCNTs and fluorinated F-SWCNTs with benzoyl (R=C6H5)

and lauroyl (R=C11H23) peroxides
Addition of Nucleophilic Carbenes

The reaction of a nucleophilic dipyridyl imidazolidene with the electrophilic SWCNT

p-system give zwitterionic polyadducts . Each covalently bound imidazolidene
addend bears a positive charge; one negative charge/addend is transferred to the
delocalized tube surface.

Sidewall functionalization by the addition of nucleophilic dipyridyl

imidazolidene to the electrophilic SWCNT p-system
Sidewall Functionalization Through Electrophilic Addition

Derivatization of SWCNTs through electrophilic addition of CHCl3 in the

presence of AlCl3 is reported. In addition, from hydrolysis of the so-
produced labile chlorinated intermediate species,hydroxy-functionalized
SWCNTs were obtained, the coupling of which with propionyl chloride led to
the corresponding ester SWCNT derivatives . The functionalities allowed not
only the identification of the structure of the modified tubes, but also
provided better solubility in organic solvents.

Electrophilic addition of CHCl3 to SWCNTs (i), followed by chlorine

substitution (ii) and esterification (iii), using i CHCl3,AlCl3; ii OH–,MeOH; iii
C2H5CO-Cl
 Carbene Addition

Dichlorocarbene addition to SWCNTs

Addition of Nitrenes

Sidewall functionalization of SWCNTs by the [2+1] cycloaddition of

alkoxycarbonyl nitrenes obtained from azides
 Sidewall Osmylation of Individual SWCNTs

a Reversible sidewall osmylation of SWCNT. b Electrical monitoring of the

resistance at the single tube level
Aryl Diazonium Chemistry – Electrochemical Functionalization –
Cathodic and Anodic Coupling

Reaction of SWCNTs with aryl diazonium compounds: electrochemical

reaction with preformed diazonium salts (a), and thermally promoted
reaction with in-situ generated diazonium compounds (b)
Solvent-free functionalization of carbon nanotubes performed with
various substituted anilines and isoamyl nitrite or NaNO2/acid. R can
be Cl,Br,NO2, CO2CH3, alkyl, OH, alkylhydroxy, oligoethylene
Electrochemical modification of SWCNTs. a Reductive coupling of p-
nitrophenyl diazonium salts to SWCNTs. b Oxidative coupling of
anilins to SWCNTs. The dotted lines mark positions of further linkages
that could be formed during the growth of a polymerized layer of phenyl
units on the SWCNTs
Noncovalent Exohedral Functionalization

The prospect of functionalizing the outer surface of CNTs in a noncovalent way

in order to preserve the extended p-network of the tubes is very attractive. In
the search for nondestructive purification methods, it has been shown that
nanotubes can be transferred to the aqueous phase through noncovalent
functionalization of surface-active molecules such as SDS or benzylalkonium chloride
.
•With the use of the surfactant Triton X-100, the surfaces of the CNTs
were changed from hydrophobic to [Link], the hydrophilic
surface of the CNT-Triton conjugate interacted with the hydrophilic surface of
enzyme, thus creating a water-soluble complex of the immobilized.

• Above the critical micellar concentration, SDS forms supramolecular structures

consisting of rolled-up halfcylinders on the nanotube’s surface .Depending on the
symmetry and the diameter of the CNT, rings, helices, or double helices were observed.
Immobilization of biomolecules on CNTs motivated the use of nanotubes as
potentially new types of biosensor materials . The electronic properties
of nanotubes coupled with the specific recognition properties of the immobilized
biosystems would indeed make for an ideal miniaturized sensor.
Different organizations of the SDS molecules on the surface of a CNT. a
Adsorbed perpendicular to the surface, forming a monolayer, b organized into half-
cylinders oriented parallel to the tube axis,and c half-cylinders oriented
perpendicular to the tube axis s.
Water-soluble SWCNTs via noncovalent sidewall functionalization with a
pyrene carrying ammonium ion

Sonication of solid SWCNTs in an aqueous solution of a pyrene-

carrying ammonium ion
Because of very effective p-stacking interactions of aromatic molecules strong
interactions with the graphitic sidewalls of SWCNTs may [Link] effect was
demonstrated in the aggregation with the bifunctional N-succinimidyl- 1-
pyrenebutanoate , irreversibly adsorbed onto the inherently hydrophobic surfaces of
the SWCNT. In these conjugates, the succinimidyl group could nucleophilically be
substituted with primary or secondary amino groups from proteins such as ferritin or
streptavidin and caused immobilization of the biopolymers on the tubes.
1-Pyrenebutanoic acid succinimidyl ester irreversibly adsorbed onto the
sidewall of a SWCNT via [Link] groups of a protein react with the
anchored succinimidyl ester to form amide bonds for protein immobilization.
p-stacking of 17-(1-pyrenyl)-13-oxa-heptadecanethiol (PHT) with SWCNTs
and self-assembling of gold nanoparticles from a colloid gold solution
The same p-stacking of SWCNTs with polyaromates in the self-assembling of gold
nanoparticles to soluble SWCNTs. 17-(1- pyrenyl)-13-oxa-heptadecanethiol (PHT)
was non-covalently bound onto the nanotubes’ surface by p-p-interactions and
subsequently treated with a colloid gold solution.A dense coverage of the
nanotubes’ surface was obtained by self-assembling of additional gold
nanoparticles
Endohedral Functionalization

The inner cavity of SWCNTs offers space for the storage of guest molecules
. For example, gold and platinum nanothreads have been created in
the capillaries of the tubes, by treating the SWCNTs with the corresponding
perchlorometallic acids at high temperatures. In some cases, the resulting
nanothreads are single crystals. The incorporation of fullerenes such as C60 or
metallofullerenes such as Sm@C82 are especially impressive examples
of the endohedral chemistry of SWCNTs, and may enable the creation
of new materials for molecular scale devices. This incorporation is executed at
defect sites localized at the ends or in the sidewalls. The encapsulated
fullerenes tend to form chains that are coupled by van der Waals forces. Such
arrays are sometimes called bucky peapods.
•Upon annealing, the encapsulated fullerenes coalesce in the interior of the
SWCNTs,which results in new, concentric, endohedral tubes with a diameter of 0.7
nm.

•The structures and energetics of several types of all-carbon peapods made

by C60 encapsulated inside SWCNTs were calculated, and the interactions between
the tubes and the C60 molecules revealed a minimal tube diameter for
exothermic encapsulation of 11.74 Å and a radial deformation of the C60 cage
as a linear function of the tube diameter. The activation energy for the
translation of isolated C60 molecules inside the tubes is very low. An isolated
fullerene C60 can diffuse freely inside the pod; the major factor controlling the
dynamics of molecular transport in the peapods is therefore the C60-C60 interaction.

•Small proteins have been entrapped in the inner hollow channel of opened
nanotubes by simple adsorption, thus forming natural nano test tubes .
Silicon
Sol-gel reaction

Si—C bonds have enhanced stability against hydrolysis in the

aqueous media usually used, which is not the case for many
metal–carbon bonds, so it is possible to easily incorporate a
large variety of organic groups in the network formed.
Principally R4–nSiXn compounds (n = 1–4, X = OR’, halogen)
are used as molecular precursors, in which the Si—X bond is
labile towards hydrolysis reactions forming unstable silanols
(Si—OH) that condensate leading to Si—O—Si bonds. In the
first steps of this reaction oligo- and polymers as well as
cyclics are formed subsequently resulting in colloids that
define the sol. Solid particles in the sol afterwards undergo
crosslinking reactions and form the gel.
Fundamental reaction steps in the sol–gel process based on tetrialkoxysilanes.
The process is catalyzed by acids or bases resulting in different reaction
mechanisms.

Differences in mechanism depending on the type of catalyst used in the

silicon-based sol–gel process.
The reaction is slowest at the isoelectric point of silica (between 2.5 and 4.5
depending on different parameters) and the speed increases rapidly on changing
the pH. The kinetics of the reaction depends on the pH, structure of the precursors
etc. Depending on the nature of the R group, the solubility of precursors changes.
Large R group slower down the reaction. The relative rates for the first hydrolysis
of alkoxysilanes reveal that MeO >> EtO > n-PrO > n-BuO. Most sol–gel chemistry
is performed with organotrimethoxysilanes and organotriethoxysilanes with the
later being favored for the lower toxicity of ethanol relative to methanol. As silanols
are less bulky than alkoxides, hydrolysis rates have generally been shown to
increase as alkoxide groups are lost. Conversely, siloxane bonds are bulky,
restricting access to the silicon centers.

[Link]-catalyzed reactions an open network structure is formed in the first steps of

the reaction leading to condensation of small clusters afterwards. Contrarily, the
base-catalyzed reaction leads to highly crosslinked sol particles already in the first
steps.
3. It is well known that the pH determines whether an acid or base-catalyzed
mechanism of hydrolysis and condensation is followed by alkoxysilanes. The
change over from acid to base-catalyzed mechanisms is marked by a minimum
in the reaction rate (Fig). For hydrolysis of alkoxysilanes this rate minimum
is at pH 7.
[Link] reactions observed under sol–gel polymerization of
organotrialkoxysilanes. Water producing condensation occurs when two silanols react.
Alcohol producing condensation occurs when a silanol reacts with a Methoxysilane.

[Link] transition from a sol to a gel is defined as the gelation point, which is
the point when links between the sol particles are formed to such an extent
that a solid material is obtained containing internal pores that incorporate
the released alcohol. However at this point the reaction has not finished,
but condensation reactions can go on for a long time until a final stage is
reached. This process is called ageing. During this reaction the material
shrinks and stiffens.
The precursors with hydrolytically stable Si—C bonds can also be used for co-
condensation reactions with tetraalkoxysilanes. In addition, organically
functionalized trialkoxysilanes can also be used for the formation of 3-D
networks alone forming so called silsesquioxanes (general formula R-SiO1.5)
materials. Generally a 3-D network can only be obtained if three or more
hydrolyzable bonds are present in a molecule. Two such bonds generally result
in linear products and one bond leads only to dimers or allows a modification of
a preformed network by the attachment to reactive groups on the surface of the
inorganic network.

Depending on the reaction conditions in the sol–gel process smaller species are
also formed in the organotrialkoxysilanebased sol–gel process, for example
cage structures or ladder-like polymers . Because of the stable Si—C bond the
organic unit can be included within the silica matrix without transformation.
There are only a few Si—C bonds that are not stable against hydrolysis, for
example the Si—C≡≡C bond where the Si—C bond can be cleaved by H2O if
fluoride ions are present. Some typical examples for trialkoxysilane compounds
used in the formation of hybrid materials . Usually the organic functionalizations
have a large influence on the properties of the final hybrid material. First of all
the degree of condensation of a hybrid material prepared by trialkoxysilanes is
generally smaller than in the case of tetraalkoxysilanes and thus the network
density is also reduced.
Different polysilsesquioxanes form from the hydrolysis and condensation of
organotrichlorosilane or organotrialkoxysilane monomers, RSiX3. The product
obtained depends on the monomer, its concentration, the pH of the solution,
the amount of water, type and amount of catalyst, the identity of the solvent,
and reaction temperature.
 Alternative Polymerization Chemistries

Polymerization leading to silsesquioxanes can also be accomplished by

generating silanols under anhydrous conditions.

Lewis acid-catalyzed condensation of chlorosilanes with alkoxysilanes to

afford siloxane bonds.

Reaction of chlorosilanes with dimethylsulfoxide to form siliconates that

condense with chlorosilanes to afford siloxane bonds.
Gelation of Polysilsesquioxanes
Forming polysilsesquioxane gels depends on the nature and
concentration of the monomer being used, the pH and to a lesser
extent, the amount of water and catalyst.

Since gelation occurs when macromolecules in the solution percolate

throughout the solution, the molecular weight of the building block can
have a pronounced effect on the relative ease of forming the required
network.

The organic groups in silsesquioxanes act as blocking agents to shield

one side of the monomer from reactions that would lead to bond
formation. The result is that a significant portion of siloxane bonds in
polysilsesquioxanes is located in siloxane rings. Furthermore, as
silanols are converted into siloxane bonds, the polysilsesquioxanes may
become sufficiently hydrophobic to induce phase separation
Gel forming silsesquioxane monomers, RSiX3
Effects of pH on Gelation

The pH-gelation time curve revealed gels formed rapidly under acidic
conditions (pH < 2) and basic conditions (pH > 11) and gels formed the
slowest at pH 5.

Graph of gelation time for silica gel (dashed line) and an alkyl substituted
silsesquioxane (solid line).
Properties of Polysilsesquioxane Gels
It is difficult to summarize the properties of polysilsesquioxanes because they
are as diverse as the different forms that can be synthesized and processed.
The thermal stability of polysilsesquioxanes can be as high as 500 °C, but
varies considerably depending on the but varies considerably depending on
the stability of the organic group. The most detrimental substitutents are
nucleophilic groups, such as amines which aid in the breaking of siloxane
bonds, particularly at higher temperatures.
The gels themselves vary from transparent, brittle, colorless monoliths, which
are nearly identical in appearance to silica gels, to fragile, opaque, white
monoliths, which are more reminiscent of Styrofoam®. As a rule the gels that
form the most readily, such as those from the hydrolysis and condensation of
CH3SiX3, ClCH2SiX3, or bridged monomers, are generally the most glass-
like. Those with more sterically bulky substituents, are usually white and
opaque.
Applications

The combination of organic and inorganic (siloxane) into a single building

block makes silsesquioxanes a useful material for many commercial
applications and for basic research into the creation of new polymers and
composites. Three reactive groups in the monomer and three siloxane bonds
to each repeat unit insures that silsesquioxanes can be formed in a wide range
of architectures, ranging from polyhedral oligosilsesquioxanes (POSS) to
macromolecular bridged silsesquioxanes composites.
The most important application for polysilsesquioxanes is for
surface modification to strengthen composites or to provide protection to sensitive
surfacs. Millions of kilograms of the disulfide-bridged silsesquioxane are used as
a silica-rubber coupling agent.
Large quantities of aminofunctionalized silsesquioxanes are used as coupling
agents for glassfilled Nylon and in protective coatings for metal surfaces.
Alkyl-silsesquioxanes solutions, kept at pH 4 to extend shelf-life, are used to
make glass windows hydrophobic and easier to see through in rain.
Methylsilsesquioxane formulations have been used to slow deterioration in
architectural stonework and protect against weathering.
Silsesquioxanes with long chain alkyl groups have been used to silylate and tailor
the surface characteristics the surface of stationary phases
in chromatographic columns.
An enormous amount of methyltrichlorosilane is burned to create fumed silica.
Dental composites based on POSS modified polymers may be the first of this new
class of materials to compete with engineering plastics and filled thermoplastics.