NANOTECHNOLOGY

DENDRIMERS

VARUNI.
A

B.TECH IT
 DENDRIMERS

ABSTRACT:

In recent years nanoscale science and technology have grown rapidly.

Nanochemistry, in particular, presents a unique approach to building devices
with a molecular-scale precision. Dendritic polymers are belonging to a
special class of macromolecules. They are called "Dendrimers." Similar to
linear polymers, they composed of a large number of monomer units that were
chemically linked together. Dendrimers are considered nanotechnology since
the size of a dendrimer molecule is typically in the nanometer range. Because
they are built up layer by layer and the properties of any individual layer can be
controlled through selection of the monomer, they are ideal building blocks in
nanochemistry for the creation of more complex three-dimensional
structures.The topics of interest include the synthesis, properties and
applications of dendrimers and the architecture of the dendritic molecules and
the properties they confer. Due to their unique physical and chemical properties,
dendrimers have wide ranges of potential applications. These include adhesives
and coatings, chemical sensors, medical diagnostics, drug-delivery systems,
high-performance polymers, catalysts, building blocks of supermolecules,
separation agents and many more.
 DENDRIMERS

1. INTRODUCTION:

Nanotechnology shortened to ‘Nanotech’ is the study of the control of

matter on an atomic or molecular scale. Generally Nanotechnology deals with
structures of the size 100 nanometers or smaller, and involves developing
materials or devices within that size. This paper deals with dendrimer molecule.
Dendrimers are considered nanotechnology since the size of a dendrimer
molecule is typically in the nanometer range. The first dendrimers were
synthesized divergently by Vögtle in 1978, by Denkewalter and coworkers at
Allied Corporation as polylysine dendrimers in 1981, by Tomalia at Dow
Chemical in 1983 and in 1985, and by Newkome in 1985. In 1990 a convergent
synthesis was introduced by Fréchet. Dendrimers then experienced an explosion
of scientific interest because of their unique molecular architecture . This
resulted in more than 5,000 scientific papers and patents published by the end of
2005.

1. WHAT ARE DENDRIMERS:

Dendrimers are large and complex molecules with very well-defined

chemical structures.From a polymer chemistry point of view, dendrimers are
nearly perfect monodisperse(basically meaning of a consistent size and
form)macromolecules with a regular and highly branched three-dimensional
architecure.They consist of three major architectural components: core,branches
and end groups.Dendrimers are considered nanotechnology since the size of a
dendrimer molecule is typically in the nanometer range.
1. STRUCTURE OF DENDRIMER:
Dendrimers have a globular configuration with monomer units
branching out from a center cord . The structure is highly defined and
organized. The number of branches increases exponentially extending from core
to the periphery. The branching would come to a stop when the steric hindrance
stopped any further growth. There are three distinct architectural components.
The multi-functionalized core (initiator core) forms the heart of the molecules;
all branches emanate from this core.

The monomers that attach to the core form the first branches (Tomalia
called them the First Generation). On the successive generations, two monomers
will attach to the ends of the monomers in the previous generation. At the
terminating generation, a terminal functional group is added to the tail of the
monomer.

1. SYNTHESIS OF DENDRIMERS:
Dendrimers are produced in an iterative sequence of reaction steps, in
which each additional iteration leads to a higher generation dendrimer. The
creation of dendrimers, using specifically-desingned chemical reactions, is one
of the best examples of controlled hierarchical synthesis, an approach that
allows the 'bottom-up' creation of complex systems.Each new layer creates a
new 'generation' with double the number of active sites(called end groups) and
approximately double the molecular weight of the previous generation. One of
the most appealing aspects of technologies based on dendrimers is that it is
relatively easy to control their size, composition and chemical reactivity very
precisely.

Dendrimers can be synthesised using one or more of the available approaches,

namely,
1. ‘Divergent’ dendrimer growth
1. ‘Convergent’ dendrimer growth
1. ‘Hypercores’ and ’Branched monomers’
1. ‘Double exponent’ and ’Mixed’ growth
1. Other accelerated growth techniques

1. DIVERGENT DENDRIMER GROWTH:

Divergent’ dendrimer growth: This name is derived from the manner in
which the dendrimer grows outwards from the core, diverging into space (Fig.
3). Starting from a reactive core, a generation is grown, and then the new
periphery of the molecule is activated for reaction with more monomers.

1. CONVERGENT DENDRIMER GROWTH:

 Convergent’ dendrimer growth: The convergent approach was developed
as a response to the pitfalls of divergent synthesis viz. nonconduciveness to
control growth and selective functionalisation. Convergent growth begins at
what will end up being the surface of the dendrimer, and works inwards by
gradually linking surface units together with more monomers (Fig. 4). In
contrast to divergent growth, only two simultaneous reactions are required for
any generation-adding step.

1. HYPERCORES AND BRANCHED MONOMERS:

These methods involve the pre-assembly of oligomeric species, which
can then be linked together to give higher yields of dendrimers in fewer steps

1. DOUBLE EXPONENTIAL AND MIXED GROWTH:

The most recent fundamental breakthrough in the practice of dendrimer
synthesis has come with the concept and implications of ’double exponential’
growth

Double exponential growth, similar to a rapid growth technique for linear

polymers, involves an AB2 monomer with orthogonal protecting groups for the
A and B functionalities. This approach allows the preparation of monomers for
both convergent and divergent growth from a single starting material. These two
products are reacted together to give an orthogonally protected trimer, which
may be used to repeat the growth process again.

1. CLASSIFICATION OF DENDRIMERS:

As such, there is no definite criterion on which dendrimers can be

classified. However, various classes of dendrimers reported in literature are
arbitrarily based upon their chemical structure and physical characteristics, as
under:
1. Poly (amido) amine (PAMAM) dendrimers: These are composed of
poly (amidoamine) segments, eg, Starburst (Dendritech Inc, USA)
dendrimers.
1. Polypropyleneimine (POPAM) dendrimers: These are also known as
dendritic boxes.
1. Tecto dendrimers: These are composed of a core dendrimer,
surrounded by dendrimers of several types, each type designed to
perform a function necessary for a smart therapeutic nanodevice.
Different components perform varied functions ranging from
diseased cell recognition, diagnosis of disease state, drug
delivery, reporting location to reporting outcome of therapy.

1. Multiligand dendrimers: In these dendrimers, the surface contains

multiple copies of a particular functional group. Depending upon the
functional group present on the surface, they are primarily of two types
i.e., peptide dendrimers, glycodendrimers.
1. Chiral dendrimers: The chirality in these dendrimers is based upon the
construction of 4 constitutionally different but chemically similar
branches to an achiral chore.
1. Hybrid dendritic linear polymers: These are hybrids (block or graft
copolymers) of dendritic and linear polymers.
1. Amphiphiic dendrimers: They are built with two-segregated sites of
chain end, half-electron donating and half-electron withdrawing.
1. Micellar dendrimers: These are unimolecular micelles of water-
soluble hyperbranched polyphenylenes.

1. PROPERTIES OF DENDRIMERS:
Most of the chemical properties of the molecule depend on types of
terminal groups. The physical properties of the molecules, such as solubility and
viscosity are also affected by the terminal groups.
Some of these dendrimers have diameters that are greater than ten
nanometers. The molecular weights range from about 50,000 to 200,000 g/mol.
The outer surface area of the molecule increases with the number of
generations. There is a significant of void space within the molecule. These
voids consist of channels and cavities4. These unique geometries give the
molecule special properties such as adhesiveness and ability to entrap foreign
molecules. The calculations of the molecular weight and other useful quantities
about the dendrimer molecules are presented in a paper by Tomalia
The number of terminal groups is easily calculated as follows:
Number of terminal groups = Nc (Nr)G
Where Nc is the number of branches at the core (core multiplicity); Nr is the
number of branches on each monomer unit (repeating unit multiplicity); G is the
number of generation. The degree of polymerization can be computed using
these quantities.

Degree of Polymerization =

Similarly, the molecular weight is given as

:
where Mc, Mr, and Mt are the molecular weight of the core, the repeating
monomer, and the terminal group respectively.
Theoretically, dendrimers are monodispersive. All molecules have the
exact process, same molecular weight and structure. Due to minor defect during
the synthesizing the polydispersity index is about 1.001. Polydispersity of
1.0007 for PAMAM has been reported. The intrinsic viscosity of dendrimers has
a peculiar behavior. It increases with increasing molecular weight (number of
generations). Contrary to linear polymers, the viscosity will reach a maximum
value then starts to decline. It is suggested that the space between the branches
is smaller in higher generation dendrimers than lower generation dendrimers.
The decline in viscosity is a consequence of prohibiting the interaction of the
outer branches between molecules at a higher generation. The glass transition
temperature (Tg) of dendrimers follows similar trend. It reaches to a maximum
Tg and levels off at higher molecular weights. This behavior is explained by the
absence of entanglement at higher molecular weights.
1. APPLICATIONS OF DENDRIMERS:
 1. MEDICAL APPLICATIONS :
Dendrimers are “stealth molecules” that have many potential
applications, including diagnostic and therapeutic applications. By customizing
and controlling dendrimer “architecture,” nanotechnologists are developing
dendrimers for drug delivery, diagnostic imaging and as carriers of genetic
material. Dendrimers can easily move across biological membranes and they
can store a wide range of metals, organic or inorganic molecules among their
branches. Companies developing these synthetic molecules claim that most
dendrimers don’t trigger the immune system when injected or used topically,
and have low cytotoxicity (that is, toxicity to cells). However, some forms of
dendrimers can induce clotting in the bloodstream - a potential concern for in
vivo applications.

1. MULTIVALENT DIAGNOSTICS FOR MRI:

The applications of gadolinium chelating poly (propylene imine)
dendrimers for Magnetic Resonance Imaging (MRI) are possible. Gadolinium-
based MRI contrast agents can be effective at a approximately 100-fold lower
concentration of Gadolinium ions in comparison to the concentration of Iodine
atoms required for CT imaging. Therefore, a number of dendrimer based
macromolecular MRI contrast agents of various sizes and properties prepared
employing relatively simple chemistry are readily available that can provide
sufficient contrast enhancement for various applications. Molecules up to 20 nm
in diameter behave differently in the body depending on their size. Even if these
molecules possess similar chemical properties, small changes in size can greatly
impact their pharmacokinetics. Changes in molecular size up to 15 nm in
diameter altered permeability across the vascular wall, excretion route, and
recognition by the reticuloendothelial system. Smaller sized polyamidoamine
(PAMAM) dendrimer-based contrast agents, i.e., less than 3 nm in diameter,
easily “leak” across the vascular wall resulting in rapid perfusion throughout the
body. Contrast agents of 3-6 nm in diameter were quickly excreted through the
kidney indicating these agents to be potentially suitable as functional renal
contrast agents. Contrast agents 7-12 nm in diameter were retained in
circulation and were better suited for use as blood pool contrast agents.
Hydrophobic variants of contrast agents formed with polypropylenimine
diaminobutane dendrimer cores quickly accumulated in the liver and potentially
have use as liver contrast agents. Larger hydrophilic agents have suitable
characteristics for lymphatic imaging. Finally, contrast agents conjugated with
either monoclonal antibodies or with avidin are able to function as tumor-
specific contrast agents and might also be employed as either

gadolinium neutron capture therapy or in conjunction with radioimmunotherapy.

1. GENE DELIVERY:

Key properties such as defined architecture and a high ratio of

multivalent surface moieties to molecular volume also make these nanoscaled
materials highly interesting for the development of synthetic (non-viral) vectors
for therapeutic nucleic acids. Rational development of such vectors requires the
link to be made between dendrimer structure and the morphology and
physicochemistry of the respective nucleic acid complexes and, furthermore, to
the biological performance of these systems at the cellular and systemic level.
Dendrimer-based transfection agents have become routine tools for many
molecular and cell biologists but therapeutic delivery of nucleic acids remains a
challenge. Perhaps the Dendrimers have unique molecular architectures and
properties that make them use in gene delivery. Of dendrimers most investigated
for drug delivery is the polyamidoamine (PAMAM) dendrimer. PAMAM
dendrimers are biocompatible, nonimmunogenic, water-soluble and possess
terminal-modifiable amine functional groups for binding various targeting or
guest molecules. The internal cavities of PAMAM dendrimers can host metals
or guest molecules because of the unique functional architecture, which contains
tertiary amines and amide linkages.

1. DRUG DELIVERY; AS A DRUG:

Dendrimers, a new class of candidate topical microbicides with activity

against herpes simplex virus (HSV) infection was investigated. Dendrimers can
have in vitro activity against HSV-1 and HSV-2. This activity generally required
that the compound be present at or before the time that cells were exposed to
virus. This suggested that the compounds might have utility as topical
microbicides. This was evaluated in a mouse model of genital HSV-2 infection
and represents the first demonstration that dendrimers are effective in an in vivo
setting. The studies were conducted with solutions of the dendrimers, and thus it
is probable that with an appropriate formulation designed for vaginal delivery,
efficacy could be improved. The prophylactic efficacy suggested that the
dendrimers might have potential as topical microbicides; products intended to
be applied to the vaginal or rectal mucosa to protect against sexually transmitted
infections.

1. ANTISEPTIC TREATMENT:

Another method of antiseptic treatment comprises forming a group of

dendrimers and securing a antimicrobial agent to each of the group of
dendrimers and bringing the group of dendrimers with the antimicrobial agent
secured thereto into a source of microbial activity in a fluid so that the fluid
must flow around the dendrimer containing the functional group. For example,
one may want to kill microbes in body fluids including blood by incorporation
the dendrimer with the antimicrobial agent into the fluid by running the blood
through a screen having a dendrimer with an antimicrobial agent secured to the
screen to thereby provide for on-the-go killing of microbes in the body fluid as
the blood flows through the screen.

1. INDUSTRIAL APPLICATIONS:
Dendrimers could also be used in coatings and materials, electronics and
photonics. A look at the patent assignees for dendrimer technology reveals the
wide range of potential applications - patents are assigned to chemical,
petroleum, tire, cosmetics and pharmaceutical companies, among others.

1. CATALYSIS:

The dendritic molecule has emerged as an attractive material in the field

of catalysis and various dendrimer catalysts have been applied not only to
catalytic reactions but also to non-catalytic ones such as nanoscale reactor
systems. In the field of catalysis, the hope is that dendrimer catalysts will retain
the benefits of homogeneous catalysts (high activity, high selectivity, good
reproducibility, accessibility of the metal site and so on), and unlike most other
polymeric species they will be readily recoverable after reaction. In principle,
dendrimer is one of the most promising candidates which can meet the needs for
an ideal catalyst: persistent and controllable nanoscale dimensions, chemically
reactive surface, favorable configurations in which all the active sites would
always be exposed towards the reaction mixture so that they are easily
accessible to migrating reactants, and soluble but can be easily recovered by
filtration. These properties, or some combination of them, are what makes
dendrimers so useful not only in catalytic applications but also in non-catalytic
ones such as nanoscale reactor systems. In particular, chiral dendrimers have
drawn much attention because the highly ordered structures of dendrimers are
considered to be suitable for realizing approximately the same chiral
environments. Dendrimers make themselves attractive in the design of
asymmetric catalysts by combining chirality or asymmetry with their highly
symmetrical nature. There are three types of chiral dendrimers according to
chiral active sites: 1. Focal point-functionalized chiral dendrimers; 2. Periphery-
functionalized chiral dendrimers; and 3. Core-functionalized chiral dendrimers.

1. ORGANOSILICANE COATINGS:

PAMAM dendrimers are the basis of poly (amidoamine) - organosilane

(PAMAMOS) coating technology. PAMAMOS coatings are tough, transparent,
flexible coatings, which have many of the same attributes of PAMAM
dendrimers in coating form. They are being investigated for applications in
microelectronics.

1. INKJET INKS AND TONERS:

PAMAM dendrimers, at low additive levels, dramatically improve water

resistance and adhesion of inks to a variety of porous or nonporous substrates
such as paper, glass, plastic, or metal. Their water and alcohol solubility permit
formulation of low viscous inks. These polymers exhibit Newtonian flow
behavior for shear stability in these formulations. In toners, they impart good
admix and flow characteristics, stable properties, and high image quality.

1. SENSORS:

Due to their organized structure ease of modification, and strong

adsorption behavior to a variety of substrates, PAMAM dendrimers can be used
to produce monolayers or stacked film layers, which can be used as sensors to
detect hazardous chemical vapors. A hydrogen peroxide biosensor based on
nano-Au/PAMAM dendrimer is also reported.

1. LIGHT HARVESTING:

Light harvesting is the trapping of energy via peripheral chromophores

and funneling to a central point where it is converted back into visible light. The
dendrimer possesses the properties that facilitate such a conversion. These
properties include its tree-like structure that acts as an energy gradient for the
funneling of energy. The large amount of absorbing units on the periphery, gives
the high probability of capture of light. The relatively short distance from the
periphery to the core allows for high efficiency energy transfer. The mechanism
begins with the periphery chromophore molecules capturing the energy of
photons from light. These photons excite the electrons in the molecules and
raise them from their ground state to their excited state. Interchromophore
energy transfer then occurs in one of two ways, Dexter excitation transfer, or
Forster excitation transfer. In Dexter excitation transfer the energy is transferred
through-bond electron exchange. This electron exchange requires a strong donor
to acceptor orbital overlap and is therefore a short-range interaction (<10 Å). In
Forster excitation transfer the energy is transferred through-space dipole-dipole
interaction. In this case, the donor to acceptor orbital overlap is not necessary,
allowing the chromophores to be separated by larger distances (10-100 Å).
Depending on the monomers used to synthesize the dendrimer that will affect
the energy transfer mechanism utilized. Using any of the above energy transfer
mechanisms, the energy is channeled to the core where it is converted into
visible light.

1. DENDRIMER FILM:

Frechet’s group at Cornell is working on polyether dendrimers films that

can isolate metal ions3. His target application is for signal amplification in fiber-
optic communication technology. Apparently, his dendrimer coatings on the
metal ions are able to prevent interference between ions when they excited by
light. Crooks and Well at A&M are exploring the possibilities of using
dendrimer films as sensitive interfaces for sensing applications16. The
dendrimers formed a thin monolayer film onto a gold surface. When it exposed
to volatile organic compounds, the film was able to capture the volatile
molecules. The contains of the film were then analyzed by a device called
surface acoustic wave mass balance. The functionalities on the periphery of the
dendrimer molecule could be modified to sense different organic compounds
selectivly16. Dendrimer films also serve as anti-corrosive coating on metal
surfaces. The film is able to trap corrosive agent in the dendritic cavities,
preventing any diffusion to the surface of the metal.

1. INTERPHASE APPLICATIONS:

As previously discussed, the convergent method is able to make

unsymmetrical dendrimers. This arrangement allows the dendrimers to form
monolayers at the gas-liquid interfaces or aqueous-organic interfaces.
Amphiphilic dendrimer are useful in forming interfacial liquid membranes for
stabilizing aqueous-organic emulsion One

.other application is to use dendrimer film to extract chemical compounds

between two phases. Dendrimers with carboxylate chain ends can form micelles
in water. Their hydrophobic interiors dissolve organic molecules that are
insoluble in water. They act like carrier for organic molecules in aqueous phase.
This arrangement holds promise for the development of organic chemistry in
aqueous medium. Hydrophilic dendrimers with hydrophobic functionalities on
the periphery form micelles in organic solvents. These types of dendrimers can
extract organic compound from the water phase to the organic phase5.
Dendrimers films also can use as purifiers. They can selectively permit
molecules to diffuse through the interface

1. DENDRIMERS IN PURIFICATION:

The present invention also comprises a method of disrupting microbe

proliferation securing an antimicrobial agent to a dendrimer, bringing the
dendrimer containing the antimicrobial agent into proximity of a fluid
containing microbes and maintain the dendrimer containing the antimicrobial
agent in the fluid to control microbial proliferation in the fluid.
In another method the dendrimer antimicrobial complex is placed
directly in the fluid to be treated without adhering the dendrimer antimicrobial
complex to a carrier. The dendrimer antimicrobial complex is useful in direct
treatment all types of fluids including body fluids, recreational fluids and
drinking fluids. As the dendrimers lacks any known appreciable toxicity the
incorporation and the presence of the dendrimers in fluids, even those which are
ingested by humans, is possible. In addition, the amount of measurable metal
ions present in the fluids that is sufficient to control microbes can actually be
less than the amount of measurable ions present with a conventional non-
dendrimer compounds that also yield metal ions. The greater efficacy of the
metal ions deliverable from a dendrimer as opposed to a non-dendrimer enables
the use of metal ions for antimicrobial purposes that might be effective in killing
microbes but could not be used because it requires antimicrobial levels in the
fluid that would exceed safe human levels.

Thus the present invention includes a method of disrupting microbe

proliferation securing a ion yielding material, such as a metal, to a dendrimer,
bringing the dendrimer containing an ion yielding material in ion
communication with a source of microbes in a fluid to control microbial
proliferation therein.

1. DENDRIMER AS A CARRIER:
The invention includes a method of killing bacteria in a body of water
applying a dendrimer containing a water purification material such as a
bactericide to a carrier, placing the carrier with the dendrimer by immersing the
carrier with the dendrimer containing the water purification material in a body
of water and allowing water to contact the dendrimer containing the water
purification material such as a bactericide to release the bactericide there from
to kill bacteria in the body of water. In this method the dendrimer can be
removed from the body of water after release of the water purification material
and a fresh water purification material is releasable secured to the dendrimer
followed by placing the dendrimer with the freshwater purification material
back into the body of water to continue the water purification thereof. While a
water purification material is attached to the dendrimer by ionic bonding
includes antimicrobial agents such as bactericides, other water purification
materials such as clarifiers or algaecides can also be secured to the dendrimer to
enable one to deliver the water purification materials to the fluids. If desired at
least two water purification materials such as two different antimicrobial agents
can be secured to the dendrimer to provide a wider range of effectiveness.

Thus the method of applying dendrimer containing a water purification

material can be placed in recreational waters such as found in a spa, a pool or a
hot tub. A use of the dendrimer with antimicrobial properties in drinkable fluids
such as fruit juices functions to rid the juices of harmful microbes.

1. OTHER APPLICATIONS:

There are also some others applications like: for cellular transport, as
artificial cells, for diagnostics and analysis, as protein / enzyme mimics or
modeling, for manufacture of artificial bones, for development of topical
microbicide creams; antimicrobial, antiviral (e.g. for use against HIV) and
antiparasitic agents, for biomedical coatings (e.g. for artificial joints), as
artificial antibodies and biomolecular binding agents, for carbon fibre coatings
and ultra thin films, as polymer and plastics additives (e.g. for lowering
viscosity, increasing stiffness, incorporating dyes, compatibilisers, etc.) for
creation of foams (i.e. synthetic zeolites or insulating material), as building
blocks for nanostructured materials, as dyes and paints, as industrial adhesives,
for manufacture of nanoscale batteries and lubricants, as decontamination
agents (trapping metal ions), for ultrafiltration, molecular electronics for data
storage, 3D optical materials, for light-harvesting systems, quantum dots, liquid
crystals, printed wire boards, etc.

1. CONCLUSION:
The special properties such as adhesiveness and ability to entrap
foreign molecules. Make dendrimers useful in various applications. Thus use
of dendrimers has been teeming in many fields. Due to its cost use of
dendrimers are limited but research are been carried out to produce dendrimers
at low cost and to use in many applications. One can synthesize with certain
molecular mass and structural conformation. The dendrimer topologies provide
many special properties such as in interphase applications and in nanoscale
reactors. The unique physical and chemical properties of dendrimers have
demonstrated great versatilities in variety of applications. . Dendrimers have
successfully been used in medicinal applications such as diagnostic tools and
eventually in drug delivery.