Dendrimers core units

The degree of branching can be regarded as the ratio of branched units in the polymer to those in a perfect dendrimer. Thus, the hmiting values are DB=0 for hnear polymers and DB=1 for a perfect dendrimer. Various definitions of DB have been given. If we do not take into account the vinyl group or initiator unit (the core unit ), the DB is defined as... 

Host-guest systems made from dendritic materials have potential in the areas of membrane transport and drug delivery [68, 84, 85]. In a recent report [136] Tomalia and coworkers investigated structural aspects of a series of PAM AM bolaamphiphiles (e.g., 50) with a hydrophobic diamino do decane core unit. Fluorescence emission of added dye (nile red) was significantly enhanced in an aqueous medium in the presence of 50 unlike the cases when 51 and 52 were added (Fig. 23). Addition of anion surfactants to this mixture generated supramolecular assemblies which enhanced their ability (ca.by 10-fold) to accommodate nile red (53). Further increase in emission was noted by decreasing the pH from the normal value of 11 for PAMAM dendrimers to 7. At lower pH values the... 

In our group, several dendrimers based on ( R)-3-hydroxybutanoic acid (HB) have been prepared [56-58]. The dendrimers were synthesized by the convergent strategy. Trimesic acid has been used as core unit and the benzyl esters of the dimer and the tetramer of HB as elongation units. In such a way dendrimers of 1st and 2nd generation (27-30) have been constructed (Fig. 13). Since poly(.R)-3-hydroxybutanoic acid (PHB) is known to be biodegradable [59, 60] the stability of the dendrimers 27-30 was tested in the presence of PHB-de-... 

At the beginning of investigations on chiral dendrimers in our own group was the question of how to synthesize chiral, non-racemic derivatives of tris(hydroxymethyl)-methane [82], which we wanted to use as dendrimer center pieces. We have developed efficient diastereoselective syntheses of such triols [83-85] from ( R)-3-hydroxybutanoic acid, readily available from the biopolymer PHB [59,60] (cf. Sect. 2.4). To this end, the acid is converted to the dioxanone 52 [86, 87], from which various alkylation products and different aldol adducts of type 53 were obtained selectively, via the enolate (Fig. 20). These compounds have been reduced to give a variety of enantiopure chiral building blocks for dendrimers, such as the core unit 54, triply branching units 55a and 55b or doubly branching unit 56 [1,88]. 

The same research group extended their studies, proposing a systematic investigation of the core activities for different carbohydrate densities during biosensing processes.279 Three new mannosylated dendrimers with a Ru(bipy)3 core unit were synthesized, and the influence of the number and size of dendritic branches on the rate of electron and energy transfer, as well as the lectin-biosensing abilities (Scheme 41),... 

Figure 1. General subdivision of dendrimers into core unit, branching units, and end groups.

Figure 11. The implications for the total yield, assuming an idealized dend-rimer functionalization for the example of a dendrimer with AB2-branching and bifunctional core unit (G = generation).

A first generation poly(amido amine) dendrimer has been functionalized with three calyx[4]arenes, each carrying a pyrene fluorophore (4) [30]. In acetonitrile solution the emission spectrum shows both the monomer and the excimer emission band, typical of the pyrene chromophore. Upon addition of Al3+ as perchlorate salt, a decrease in the excimer emission and a consequent revival of the monomer emission is observed. This can be interpreted as a change in the dendrimer structure and flexibility upon metal ion complexation that inhibits close proximity of pyrenyl units, thus decreasing the excimer formation probability. 1H NMR studies of dendrimer 4 revealed marked differences upon Al3+ addition only in the chemical shifts of the CH2 protons linked to the central amine group, demonstrating that the metal ion is coordinated by the dendrimer core. MALDI-TOF experiments gave evidence of a 1 1 complex. Similar results have been obtained for In3+, while other cations such as Ag+, Cd2+, and Zn2+ do not affect the luminescence properties of... 

As the name impHes, the core unit, or focal point group, is located at the center of the dendritic macromolecule and, as such, constitutes only a small proportion of the overall dendrimer structure. However the role of functional groups at the central core can have a profound effect on a number of physical properties and be extremely useful in investigating the structure of dendrimers. The central role played by the focal point group in the success of the convergent growth approach has also been well documented in the above discussions. 

Our choice was the two series of dendritic polymers 5 and 6, depicted in Figure 4, which have all their open-shell centers (or trivalent carbon atoms) sterically shielded by an encapsulation with six bulky chlorine atoms in order to increase their life expectancies and thermal and chemical stabilities. Indeed, it is very well known that the monoradical counterpart of both series of polyradicals, the perchlo-rotriphenyl methyl radical, shows an astonishing thermal and chemical stability for which the term of inert free radical was coined. The series of dendrimer polymers 5 and 6 differ in the nature and multiplicity (or branching) of their central core unit, N, as well as in their branch-juncture multiplicities, N Thus, series 5 has a hyperbranched topology with = 3 and = 4, while dendrimer series 6 has a lower level of branching with = 3 and = 2, and the topology of a three-coordinated Cayley tree. 

Pyridine-based ligands which have been used for dendrimers are 2,2-bipyridine (bpy) 17,2,3-bis(2-pyridyl)pyrazine (2,3-dpp) 18 and its monomethylated salt 19, and 2,2 6, 2"-terpyridine 20. Their transition metal complexes possessing dendritic structures were first reported in the collaborative work of Denti, Campagne, and Balzani whose divergent synthetic strategy has led to systems containing 22 ruthenium centers. - The core unit is [Ru(2,3-dpp)3] 21 which contains three... 

Such units, together with methyl derivatives of ferrocene and cyclopentadienyl (r 6-arene)-iron(II), [FeCp(r 6-arene)]+, have been extensively used as dendrimer peripheral units, but examples of dendrimers containing metallocene residues both as a core and as terminal units and as a core are also reported.5a,b 17... 

The oligo- or multi-functional core unit also plays a role in determining the space occupied by a dendrimer. The core itself can exercise a function, as demonstrated by metallodendrimers (see Section 4.1.11), in which the metal ion core in a supramolecular or coordinatively constructed architecture coordinates with the surrounding branching units - and in this way can influence catalytic and photochemical processes. 

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