Aqueous dendrimer

Ramamurthy and Jayaraman employed the cavity of poly(aIkyl aryl ether) dendrimers of the third generation with various n-alkyl linker (ethyl to n-pentyl) connecting the branch points (C2G3-C5G3) for photochemical isomerizations of azobenzene and stilbene. Isomerization was carried out in aqueous dendrimer solutions. Irradiation of solutions for 6 h furnished products. The results of isomerization of stilbene in the presence of various dendrimer solutions and in... 

TABLE 6.3 Isomerization of (rans-Stilbene in Aqueous Dendrimer Solutions and in EtOH... 

An interesting case in the perspective of artificial enzymes for enantioselective synthesis is the recently described peptide dendrimer aldolases [36]. These dendrimers utilize the enamine type I aldolase mechanism, which is found in natural aldolases [37] and antibodies [21].These aldolase dendrimers, for example, L2Dl,have multiple N-terminal proline residues as found in catalytic aldolase peptides [38], and display catalytic activity in aqueous medium under conditions where the small molecule catalysts are inactive (Figure 3.8). As most enzyme models, these dendrimers remain very far from natural enzymes in terms ofboth activity and selectivity, and at present should only be considered in the perspective of fundamental studies. 

Dendrimers can be designed to have a hydrophobic interior and a hydrophilic periphery. This gives them properties that are similar to those of conventional surfactants, and they can solubilize hydrophobic substances such as pyridine in aqueous solution by including them as guest molecules. They are therefore effectively mimolecular micelles. 

Naka K (2003) Effect of Dendrimers on the Crystallization of Calcium Carbonate in Aqueous Solution. 228 141-158... 

Smith DK, Diederich F (2000) Supramolecular Dendrimer Chemistry - A Journey Through the Branched Architecture. 210 183-227 Stec WJ, see Guga P (2002) 220 169-200 Steudel R (2003) Aqueous Sulfur Sols. 230 153-166 Steudel R (2003) Liquid Sulfur. 230 80-116... 

As an extension of this work,Kaifer et al. prepared a series of PPI dendrimers (G-l-G-4) functionalized with cobaltocenium at the periphery [48] and studied their electrochemical behavior and binding interactions with P-CD. While the positively charged cobaltocenium-terminated dendrimer 27G-1 is not com-plexed by P-CD in aqueous media, electrochemical reduction of the dendrimer in the presence of excess P-CD triggers the formation of a multisite inclusion complex with this host to provide pseudorotaxane-terminated dendrimer 28G-1 (Fig. 10). Similar electrochemical and binding behavior toward P-CD was observed for the G-2 and G-3 dendrimers. However, the resulting multisite inclu-... 

Also, from the dendrimer point of view, the introduction of mechanical bonds to dendrimers has an enormous potential to alter the properties of dendrimers in a controlled way. For example, in the synthesis of a Type II rotaxane dendrimers, the wheel components are introduced to the terminal groups of the dendrimers. This can improve the solubility of dendrimer in organic and/or aqueous media due to the formation of complexes soluble in such solvents. 

Crystallization of CaCOj is highly dependent on nucleation condition. The precipitation of CaCOj in the absence or the presence of the G4.5 PAMAM dendrimer was carried out by a carbonate diffusion method similar to the method described by Addadi et al. [35]. A solution of the dendrimer with calcium chloride in 200 ml of distilled water was adjusted to pH 8.5 with aqueous NHj, and then placed in a closed desiccator containing crushed ammonium carbonate (Fig. 5). Carbon dioxide was introduced to the solution via vapor diffusion. The critical point of the appearance in the turbidity of the solution was observed at around 5 min. These solutions were kept at 30 °C under N2 for one day. The crys-... 

Dendritic hosts can be used in aqueous solution to encapsulate water-soluble fluorescent probes. Changes in the photophysical properties of these encapsulated probes are useful to understand the properties of the microenvironment created by the dendritic interior. For example, adamantyl-terminated poly(pro-pylene amine) dendrimers from the first to the fifth generation (36 represents the third generation) can be dissolved in water at pH<7 in the presence of -cyclodextrin because of encapsulation of the hydrophobic adamantyl residue inside the /1-cyclodextrin cavity and the presence of protonated tertiary amine units inside the dendrimer [72]. Under these experimental conditions, 8-anifi-... 

Dendrimers containing a polar surface and an apolar interior can work as hosts of hydrophobic fluorescent probes in aqueous environment. In particular. 

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... 

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