Common Dendrimer Types

Synthetic Overview of the Preparation of Common Dendrimer Types 121... 

The following Sections give a detailed account of the strategies most commonly used for synthesis of the various dendrimer types and the synthetic utility for targeted design of functional dendrimers is evaluated. 

Possible Mechanisms and Key Characteristics of Nanomaterials. A nanoparticle/nanomaterial is generally defined as a particle/ material having a physicochemical structure greater than typical atomic/molecular dimensions but at least one dimension smaller than lOOnm. It includes particles/ materials engineered or manufactured by humans on the nanoscale with specific physicochemical composition and structure to exploit properties and functions associated with its dimensions. Some of the common nanoparticle types are (1) carbon-based materials (e.g., nanotubes, fullerenes), (2) metal-based materials (e.g., nanogold, nanosilver, quantum dots, metal oxides), and (3) dendrimers (e.g., dendritic forms of ceramics). 

Two components are needed to construct a dendrimer a multifunctional core and an ABx monomer unit around which to build up the structure. The most commonly used types are polyamidoamine dendrimers (PAMAM), poly 2,2-bis(methylol)propionic acid (PBisMPA) dendrimers, polybenzyl ether dendrimers (PBzE), polymelamine (triazine) dendrimers, polypropyleneimine dendrimers (PPI), and polylysine dendrimers (PEL). PAMAM, PPI and PBisMPA are commercially available. PAMAM (left), PBisMPA (middle) and PPI (right) in Figure 2.7 are the most commonly employed structures in therapeutic applications these have been well characterised both in vitro and in vivo, and their toxicological properties have been evaluated. 

Dendrimers built around a metal complex as a core. These compounds can be considered metal complexes of ligands carrying dendritic substituents (Fig. 1 a). The most commonly used metal complex cores are porphyrin complexes, polypyridine complexes, and ferrocene-type compounds. 

The electroactive units in the dendrimers that we are going to discuss are the metal-based moieties. An important requirement for any kind of application is the chemical redox reversibility of such moieties. The most common metal complexes able to exhibit a chemically reversible redox behavior are ferrocene and its derivatives and the iron, ruthenium and osmium complexes of polypyridine ligands. Therefore it is not surprising that most of the investigated dendrimers contain such metal-based moieties. In the electrochemical window accessible in the usual solvents (around +2/-2V) ferrocene-type complexes undergo only one redox process, whereas iron, ruthenium and osmium polypyridine complexes undergo a metal-based oxidation process and at least three ligand-based reduction processes. 

Furthermore, to avoid the anticipated limitation upon the growth of this type of dendrimer, common when saccharides contain protecting groups, Jayaraman and Stoddart focused on synthesis of glycodendrimers wherein the saccharides were totally unprotected during construction.428... 

A common choice of crosslinker for this type of reaction is sulfo-SMCC, which has been used extensively for antibody conjugation (Chapter 20, Section 1.1). A better option for dendrimer conjugation is to use a similar crosslinker design, but one that contains a hydrophilic PEG spacer arm to promote dendrimer hydrophilicity after modification. Derivatization of an amine-dendrimer with a NHS-PEG-maleimide can create an intermediate that is coated with water-soluble PEG spacers. This modification helps to mask any potential for nonspecific interactions that the PAMAM surface may have, while providing terminal thiol-reactive maleimides for coupling ligands (Figure 7.10). 

The form factor term, P(q), contains information on the distribution of segments within a single dendrimer. Models can be used to fit the scattering from various types of particles, common ones being a Zimm function which describes scattering from a collection of units with a Gaussian distribution (equation (3a)), a... 

Like the currently popular area, called nanoscience , the field of supramolecular chemistry has rather hazy boundaries. Indeed, both areas now share much common ground in terms of the types of systems that are considered. From the beginning, electrochemistry, which provides a powerful complement to spectroscopic techniques, has played an important role in characterizing such systems and this very useful book goes considerably beyond the volume on this same topic by Kaifer and Gomez-Kaifer that was published about 10 years ago. Some of the classic supramolecular chemistry topics such as rotaxanes, catenanes, host-guest interactions, dendrimers, and self-assembled monolayers remain, but now with important extensions into the realms of fullerenes, carbon nanotubes, and biomolecules, like DNA. 

The most common functional templates are those of simple amino compounds 4, amino acids 5, and dipeptides 8 (Scheme 3). The simplest amino templates, the tris(ethylene amine) ammonia types 6, 7, and 9 first used in organic dendrimers, have only just begun to be applied in forming peptide dendrimers. Constrained and usual amino acids and heterocyclic compounds such as porphyrin 13, have also been reported.1691... 

Commercially available POPAM and PAMAM dendrimers (see Chapter 4) bearing terminal primary amino groups are currently the most commonly used divergently grown dendrimer structures, followed by poly(benzyl ether) den-drons or poly(benzyl ether) dendrimers (Frechet type) as representatives of con-vergently synthesised dendritic molecules. 

Peripheral ferrocenyl-functionalized dendrimers are in fact one of the most common type of metallodendrimers synthesized today. Due to the chemical and thermal stabilities of this kind of metallocene, formation of the intended dendrimer-supported metallocene complex can be performed in a single reaction step the metallocene fragment is introduced onto the surface of a (commercially available) dendrimer as the final construction step [56,57]. 

Dendrimers are hyperbranched polymers that emanate from a single core and ramify outward with each subsequent branching unit [1,2]. In the commonly employed divergent synthesis, dendrimers can be prepared through sequential, alternating reactions of two smaller units, one of which has a point of bifurcation. As is described elsewhere in this volume, several classes of dendrimers are known, including polypropyleneimine (PPI), polyamidoamine (PAMAM), and Frechet-type polyether dendrimers [1,2]. 

The electroactive units are the peripheral groups (Figure 2b). These dendrimers are functionalized on their surface, and all the units are equivalent. The most common units of this type are ferrocene and metal-polypyridine complexes. 

Since the pioneering studies reported by van Koten and coworkers in 1994 [20], dendrimers as catalyst supports have been attracting increasing attention. The metaUodendrimers and their catalytic applications have been frequently reported and reviewed [7-15]. As a novel type of soluble macromolecular support, dendrimers feature homogeneous reaction conditions (faster kinetics, accessibility of the metal site, and so on) and enable the application of common analytical techniques such as thin-layer chromatography (TLC) and nuclear magnetic resonance... 

Special attention is focused on dendrimers (see Sections 6-4 and 7-6), a new class of regular pol rmers characterized by a tree-type structure, generating from one center, by a great number of branching centers and by the absence of closed rings [83]. Sometimes they are called cascade polymers or polymers with controlled molecular architecture [84], Poly(amidoamine) or poly(propylene-amine) with a diaminobutane nucleus are commonly used for this purpose. In... 

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