Aggregates dendrimers

In general, dendrimers show sharp M+ signals at the expected values. This confirms the overall dendrimer structure. Mass spectra may be complicated by the presence of small peaks corresponding to two- or three-molecule aggregates bearing a single charge and this phenomenon is... 

The use of ordered supramolecular assemblies, such as micelles, monolayers, vesicles, inverted micelles, and lyotropic liquid crystalline systems, allows for the controlled nucleation of inorganic materials on molecular templates with well-defined structure and surface chemistry. Poly(propyleneimine) dendrimers modified with long aliphatic chains are a new class of amphiphiles which display a variety of aggregation states due to their conformational flexibility [38]. In the presence of octadecylamine, poly(propyleneimine) dendrimers modified with long alkyl chains self-assemble to form remarkably rigid and well-defined aggregates. When the aggregate dispersion was injected into a supersaturated... 

The geometry and surface chemistry of the dendrimer assemblies can be varied through the addition of surfactants. These dendrimer/surfactant aggregates can be tuned to template the formation of the different phases of calcium carbonate [40]. In combination with hexadecyltrimethylammonium bromide (CTAB), small spherical aggregates were formed that induce the formation of vaterite. Over a period of five days, the vaterite was transformed into calcite. The use of the negatively charged surfactant, sodium dodecylsulfonate (SDS), result-... 

We have found that dendrimers can be used to encapsulate active moieties, thereby preventing them from interacting. This passivation effect limits inter-molecular interactions such as self-aggregation and molecular clustering. We also found that dendrimers can be made dipolar. This asymmetry in molecular orientation enables dendrimers to be used in NLO. In this chapter we describe our application of dendrimers to lasers and NLO. 

The UV-visible spectra of the H- and nifro-azobenzene dendrimers in chloroform solution showed strong absorption bands within the visible region due to the transitions of azobenzene chromophores (Table 2). Because of the stronger delocalization of n-electrons in nitro-azobenzene, the maximum absorption band is at a longer wavelength compared with that for H-azoben-zene. There was little spectral shift of the absorption maximum for dendrimers with different numbers of azobenzene units, indicating that dendrimers did not form any special intermolecular aggregates. 

Hellmann, J., Hamano, M., Karthaus, O., Ijiro, K., Shimomura, M. and Irie, M. (1998) Aggregation of dendrimers with a photochromic dithienylethene core group on the mica surface - atomic force microscopic imaging. Jpn. J. Appl. Phys., 37, L816-L819. 

Meijer et al. [135] further studied aggregation phenomena of amphiphilic copolymers obtained by modifying the termini of the dendrimer units of the above series with carboxylic acid groups (49). TEM experiments indicated that all block copolymers formed large aggregates except third generation copolymer which formed worm-like micelles. 

Complexation of gold ions, [Au(I)], with peripheral phosphine groups of a P-based dendrimer was reported by Majoral et al. [185]. Transmission electron microscopy (TEM) was used to analyze the large aggregates formed by the dendritic gold complexes and a direct correlation was observed between the size of the particles and the dendrimer generation number. In a recent report [186], Majoral et al. further demonstrated that up to 48 diphosphino groups could be anchored to the surface of dendrimers and various dendritic metal-complexes... 

This chapter draws a comprehensive picture of what has been done in the field of dendrimers with polymeric cores putting emphasis first on synthetic issues and then on experiments investigating the aggregation behavior of these intruiging macromolecules both in the solid state and on surfaces. Additionally, experiments will be described which show that some of these dendrimers can be considered cylindrical molecular objects. The macromolecules treated in this chapter may be considered as either dendrimers with polymeric core or alternatively dendronized polymers (or polymers with appendent dendrons) depending on whether one sees them from the vantage point of an organic or macromolecular chemist. 

Two fractions of atactic polystyrene dendrimer derived from monomer 12(G-2) were investigated by GPC and LS under conditions where no aggregation occurs. Whereas GPC gave Mw=82,000 and Mw= 600,000, LS furnished... 

Testing of G-l, G-2, and G-3 dendrimers in this application provided insight into the density of surface modification needed to passivate completely the particles and prevent aggregation. The G-l dendron was insufficient in this regard, but both the G-2 and G-3 dendron were big enough to create a surface barrier, which resulted in excellent colloidal stability of the particles in solution. 

As the dendrimer concentration is lowered to 0.001% w/w, the cast G4 film is no longer uniform and flat. Individual dendrimer molecules are not seen, but instead the dendrimers aggregate to produce a patchy film, Figure 12.4(b). 

Scheme 5 Aggregates formed between DTAB and a PAMAM dendrimer...

---