Macromolecules dendritic

EDA and other alkylene amines react readily with acrylonitrile or acrylate esters. EDA reacts with acrylonitrile to give tetrakis(2-cyanoeth5i)-ethylenediamine which is reduced over Raney nickel to give tetralds(3-anainoprop5i)-ethyl-enediainine (52). With methyl acrylate and EDA under controlled conditions, a new class of starburst dendritic macromolecules forms (53,54). 

In 1996, Hawker and Frechet83 discussed a comparison between linear hyperbranched and dendritic macromolecules (Fig. 5.17) obtained with the same monomeric structure, 3,5-dihydroxybenzoic. The thermal properties (glass transition and thermal decomposition) were not affected by the architecture. 

Figure 5.18 Variation of intrinsic viscosity as function of molar mass for linear, hyper-branched, and dendritic macromolecules.

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

Remarkable concentration of the photon energy absorbed by aromatic dendritic scaffold toward the focal point (herein called antenna effects ) is one of the most distinct features of the dendritic macromolecules. Poly(benzyl ether) (PBE) dendron [1] has been studied most extensively as an efficient antenna dendron. Careful studies have revealed the crucial role of the symmetric dendritic structure for the antenna effect. 

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. 

Significant dendron shape distortion is required to accommodate the cylinder morphology in which the cylinder s diameter exceeds the diameter of the dendrons only by a factor of two. To allow formation of this geometry six single dendritic macromolecules have to assemble into a columnar... 

Initial efforts gave rise to well-characterized dendritic macromolecules, but applications remained limited because of the lack of specific functionalities. An exponential increase of publication volume observed for about 15 years testified the growing interest for dendrimers and has led to versatile and powerful iterative methodologies for systematically and expeditiously accessing complex dendritic structures. The perfect control of tridimensional parameters (size, shape, geometry) and the covalent introduction of functionalities in the core, the branches, or the high number extremities, or by physical encapsulation in the microenvironment created by cavities confer such desired properties as solubility, and hydrophilic/hydrophobic balance. Thus, creativity has allowed these structures to become integrated with nearly all contemporary scientific disciplines. 

C. J. Hawker and J. M. J. Frechet, Preparation of polymers with controlled molecular architecture. A new convergent approach to dendritic macromolecules, J. Am. Chem. Soc., 112 (1990) 7638-7647. 

Konno, K., Liu, M., and Frechet, J.M.J. (1999) Design of dendritic macromolecules containing folate or methotrexate residues. Bioconjug. Chem. 10, 1115-1121. 

Mourey, T.H., Turner, S.R., Rubenstein, M., Frechet, J.M.J., Hawker, C.J., and Wooley, K.L. (1992) Unique behavior of dendritic macromolecules Intrinsic viscosity of polyether dendrimers. Macromolecules 25, 2401-2406. 

Flory was the first to hypothesize concepts [28,52], which are now recognized to apply to statistical, or random hyperbranched polymers. However, the first purposeful experimental confirmation of dendritic topologies did not produce random hyperbranched polymers but rather the more precise, structure controlled, dendrimer architecture. This work was initiated nearly a decade before the first examples of random hyperbranched4 polymers were confirmed independently in publications by Odian/Tomalia [53] and Webster/Kim [54, 55] in 1988. At that time, Webster/Kim coined the popular term hyperbranched polymers that has been widely used to describe this type of dendritic macromolecules. 

Since the successful synthesis of dendritic macromolecules from low MW monomers [14a], research has also been performed in the area of dendritic polymers [14b, 15]. Dendritic polymers are obtained by attaching or growing several end-standing arms onto a central regular star polymer. This procedure is repeated in a generational manner, see Figure 3.3. 

This chapter describes the use of AFM as a methodology for characterizing dendritic macromolecules and their self-assembled films. Systematic AFM studies of the PAMAM dendrimers properties (e.g. their size, shape, rigidity, packing textures and molecular weight calculations) will be fully addressed in this chapter. 

The structural state of dendritic macromolecules at air-water (Langmuir mono-layers) and air-solid (adsorbed monolayers, self-assembled films and cast films) interfaces have been reviewed by Tsukruk [17]. Although this work summarizes various characterization techniques for dendritic films by AFM techniques, in this chapter, we will present recent progress on the characterization of the dendritic film surface morphologies. 

Spin-coating films of other compositionally different dendritic macromolecules such as carbosilane dendrimers and hyperbranched poly(styrene) were studied by Sheiko et al. [20-22] using tapping mode AFM. 

Unimolecular micelles are defined as a class of dendritic macromolecules, wherein an interior hydrophobic core is surrounded by a hydrophilic surface layer. These structures closely resemble the shape of classical micelles (shape,... 

The globular shape of dendritic macromolecules with a persistent nanosize and radius should allow easy separation or retention by ultra- or nanofiltration membranes. This concept of separating the catalysts from the product/substrate... 

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