Dendrimers macromolecules

S. Thayumanavan ( Thai ) obtained his B.Sc. and M.Sc. degrees from The American College, Madurai, India. He obtained his Ph.D. from the University of Illinois at Urbana-Champaign with Professor Peter Beak in 1996. After a postdoctoral stint with Professor Seth Marder at the California Institute of Technology, he started his independent career at Tulane University in 1999. His group moved to the University of Massachusetts at Amherst in 2003. He has been the winner of NSF-CAREER award, Cottrell Scholar award, and 3M Non-tenured Faculty awards. His research interests involve design and syntheses of macromolecules (dendrimers and polymers) to achieve controllable nanoscale assemblies that are of interest in chemistry, materials, and biology. 

A decade after the initial pioneering studies, dendrimer catalysis has developed into a highly varied and complex field of research. While much of the fascination is derived from the aesthetic appeal of dendrimers (as with other applications of this class of macromolecule), dendrimer catalysts have vindicated many of the utilitarian aspects of this research. This volume provides a comprehensive overview of the current state of the art. 

Villaraza, A.J.L., Bumb, A., Brechbiel, M.W. Macromolecules, Dendrimers, and Nanomaterials in Magnetic Resonance Imaging The Interplay between Size, Function, and Pharmacokinetics. Chem. Rev. 110(5), 2921-2959 (2010). doi 10.1021/Cr900232t... 

Dendrimers produced by divergent or convergent methods are nearly perfectly branched with great structural precision. However, the multistep synthesis of dendrimers can be expensive and time consuming. The treelike structure of dendrimers can be approached through a one-step synthetic methodology.31 The step-growth polymerization of ABx-type monomers, particularly AB2, results in a randomly branched macromolecule referred to as hyperbranch polymers. 

However, dendrimeric and hyperbranched polyesters are more soluble than the linear ones (respectively 1.05, 0.70, and 0.02 g/mL in acetone). The solution behavior has been investigated, and in the case of aromatic hyperbranched polyesters,84 a very low a-value of the Mark-Houvink-Sakurada equation 0/ = KMa) and low intrinsic viscosity were observed. Frechet presented a description of the intrinsic viscosity as a function of the molar mass85 for different architectures The hyperbranched macromolecules show a nonlinear variation for low molecular weight and a bell-shaped curve is observed in the case of dendrimers (Fig. 5.18). 

The field of synthetic enzyme models encompasses attempts to prepare enzymelike functional macromolecules by chemical synthesis [30]. One particularly relevant approach to such enzyme mimics concerns dendrimers, which are treelike synthetic macromolecules with a globular shape similar to a folded protein, and useful in a range of applications including catalysis [31]. Peptide dendrimers, which, like proteins, are composed of amino acids, are particularly well suited as mimics for proteins and enzymes [32]. These dendrimers can be prepared using combinatorial chemistry methods on solid support [33], similar to those used in the context of catalyst and ligand discovery programs in chemistry [34]. Peptide dendrimers used multivalency effects at the dendrimer surface to trigger cooperativity between amino acids, as has been observed in various esterase enzyme models [35]. 

Nonetheless, it was a fairly short step from octopus compounds to dendrimers, and the step was taken by Vogtle in the late 1970s when he attempted to use a cascade reaction to prepare a molecule of the dendrimer type that would now be considered a dendron rather than a fully developed dendrimer. It began with the addition of acrylonitrile to an anfine, followed by reduction of the nitrile to amine. This was followed by a further reaction with acrylonitrile, and the process was repeated several times to yield highly branched macromolecules. There were initially problems with the reduction step but these were overcome, and the preparation of these poly(propylene imine) dendrimers was later commercialized. 

Tomalia, D.A. et al. Dendritic macromolecules—Synthesis of starburst dendrimers, Macromolecules, 19, 2466-2468, 1986. 

The opto-electronic properties of branched structures have been an area of some interest for a number of years, especially as NLO and light-emitting materials [82]. In particular, the use of u-conjugated dendrimers (mono-disperse macromolecules [83]) has flourished for a number of reasons ... 

A way to narrow the MWD and to approach the structure of dendrimers is the addition of a small fraction of a/-functional initiator, to inimers [40,71]. In this process the obtainable degree of polymerization is limited by the ratio of inimer to initiator. It can be conducted in two ways (i) inimer molecules can be added so slowly to the initiator solution that they can only react with the initiator molecules or with the already formed macromolecules, but not with each other (semi-batch process). Thus, each macromolecule generated in such a process will contain one initiator core but no vinyl group. Then, the polydispersity index is quite low and decreases with / M /Mn l-i-l//. (ii) Alternatively, initiator and monomer molecules can be mixed instantaneously (batch process). Here, the normal SCVP process and the process shown above compete and both kinds of macromolecules will be formed. For this process the polydispersity index also decreases with/,but is higher than for the semi-batch process, M /Mn=Pn//. ... 

Dendrimer chemistry has taught us that these molecules create a nano-sized closed space that, presumably, is the origin of the specific physical properties of this class of materials. As the next stage of dendrimer chemistry, a macromolecule capable of creating such a space inside its molecule is proposed. To create the nano-sized space, porphyrin is considered to be the best candidate for the component molecules, because it has versatile properties associated with its expanded 7i-electron system and the incorporated metal. The resultant multi-detectable properties of porphyrin, that is, a number of its properties are detectable by many physical methods, may reveal the function of the nanometer-sized space. 

The maturity of dendrimer chemistry has led to confusion among researchers, because there are no specific research objectives in this field. It may be a good idea to design and synthesize a novel macromolecule, a non-dendrite-shaped molecule, keeping the concept of the dendrimer in mind. The nano-sized closed space inside the molecule is one of the key concepts for novel macromolecular chemistry. 

All the fullerene-containing dendrimers reported to date have been prepared with a Cgo core but never with fullerene units at their surface or with Cgg spheres in the dendritic branches. We have recently started a research program on the synthesis of dendrons substituted with fullerene moieties. These fulleroden-drons are interesting building blocks for the preparation of monodisperse fullerene-rich macromolecules. In addition, they are also amphiphilic compounds capable of forming stable Langmuir films at the air-water interface. 

This manuscript describes the dendritic macromolecules for optical and optoelectronic apph-cations, particularly stimulated emission, laser emission, and nonlinear optics. Dendrimers have been designed and synthesized for these applications based on simple concepts. A coreshell structure, through the encapsulation of active imits by dendritic branches, or a cone-shaped structure, through the step-by-step reactions of active imits, can provide particular benefits for the optical high-gain media and nonlinear optical materials. It also described experimental results that support the methods presented for designing and fabricating functionalized dendrimers for optoelectronic applications, and theoretical results that reveal the intermolecular electronic effect of the dendritic structure. 

Dendrimers, a relatively new class of macromolecules, differ from traditional Hnear, cross-Hnked, and branched polymers. The conventional way of introducing an active moiety into polymers is to Hnk it chemically into the polymeric backbone or a polymer branch. This synthetic approach results in a topologically complex material. Therefore, a significant effort has to be devoted to improve the structural complexities and functions of the polymers. 

The recent development of structurally controlled dendrimers has led to the development of a wide range of new functional macromolecules. These dendrimers were first applied in the fields of chemistry, including catalysis, pharmacology, and materials science [23-26]. More recently there have been several reports of dendrimers having electro active, photoactive, and recognition elements [27-34]. Important applications in photonics have recently been exploited, though the number of reports is still limited. 

Recently, highly branched macromolecular polyamidoamine dendrimers have been prepared with Co11 bound where the metal ions have additional exchangeable coordination sites.450 These macromolecules show a capacity for catalyzing the hydrolysis of phosphate esters, presumably via intermediate bound phosphoester species. 

The present volume gives a general and at the same time rather detailed review on main research developments in the field of dendrimers (oligomer and polymer) during the past several years, but also offers views and visions of the future - of what could soon be achieved in this area at the interface between small organic molecules and macromolecules (polymers). We are sure that the rapid development of fractal-shaped molecules will continue in academic institutes as well as in industry - there is still more to come. 

Moore et al. later reported [98] the design and synthesis of triarylamine based dendrimers. These fluorescent macromolecules exhibited reversible redox processes and their potential use in electro-optic film applications was envisioned. 

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