VARUNI. A B.TECH IT
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.
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.
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
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. 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 watersoluble 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:
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. Gadoliniumbased 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 tumorspecific 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.
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.
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. Peripheryfunctionalized 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.
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 fiberoptic 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.
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 nondendrimer 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.
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.