Templating dendrimer templation

Perrier RJ (2001) Direct Conversion of 5,6-Unsaturated Hexopyranosyl Compounds to Functionalized Glycohexanones. 215 277-291 Frey H, Schlenk C (2000) Silicon-Based Dendrimers. 210 69-129 Forster S (2003) Amphiphilic Block Copolymers for Templating Applications. 226 1-28 Frullano L, Rohovec J, Peters JA, Geraldes CFGC (2002) Structures of MRI Contrast Agents in Solution. 221 25-60... 

Template effects have been used in rotaxane synthesis to direct threading of the axle through the wheel. Since macrocycHc compounds such as cyclodextrins, crown ethers, cyclophanes, and cucurbiturils form stable complexes with specific guest molecules, they have been widely used in the templated synthesis of rotax-anes as ring (wheel) components. Here, we briefly discuss macrocycles used in the synthesis of rotaxane dendrimers and their important features. 

In this review, we tried to cover all the supramolecular species that maybe classified as rotaxane dendrimers. We classified them by their structures - where in dendrimer rotaxane-hke features are introduced. Several different types of macrocycles have been employed as a ring component in the templated synthesis of rotaxane dendrimers. While the synthesis of Type I and II rotaxanes dendrimers is relatively straightforward, that of well-defined Type III rotaxane dendrimers, particularly those of second and higher generations, is still challenging. 

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-... 

Spherical vaterite crystals were obtained with 4-mercaptobenzoic acid protected gold nanoparticles as the nucleation template by the carbonate diffusion method [51]. The crystallization of calcium carbonate in the absence of the 4-MBA capped gold nanoparticles resulted in calcite crystals. This indicates that the polymorphs of CaCOj were controlled by the acid-terminated gold nanoparticles. This result indicates that the rigid carboxylic acid structures can play a role in initiating the nucleation of vaterite as in the case of the G4.5 PAMAM dendrimer described above. 

Knecht, M.R. and Wright, D.W. (2004) Amine-terminated dendrimers as biomimetic templates for silica nanospheres formation. Langmuir, 20, 4728-4732. 

Scheme 9.4 Schematic of metal nanoparticles synthesis within dendrimer templates. (Reprinted from [54] copyright 2002, Marcel Dekker.)...

Controlling the size, shape and ordering of synthetic organic materials at the macromolecular and supramolecular levels is an important objective in chemistry. Such control may be used to improve specific advanced material properties. Initial efforts to control dendrimer shapes involved the use of appropriately shaped core templates upon which to amplify dendritic shells to produce either dendrimer spheroids or cylinders (rods). The first examples of covalent dendrimer rods were reported by Tomalia et al. [43] and Schluter et al. [44], These examples involved the reiterative growth of dendritic shells around a preformed linear polymeric backbone or the polymerization of a dendronized monomer to produce cylinders possessing substantial aspect ratios (i.e. 15-100) as observed by TEM and AFM. These architectural copolymers consisting of linear random... 

Figure 16.17 Amine-terminated polypropylene imine) dendrimers act as tridentate ligands for the complexation of transition metals [217] (a), and can function as templates for the assembly of Troger s base dizinc(ll) bis-porphyrin molecules, (b) [218]...

Recently, two new approaches for the preparation of metallodendritic catalysts were described. The first one involves the use of PAMAM dendrimers [11] as both template and stabilizer of metal ions. The cavities of these dendrimers can serve as host type nano-reactors for metal ion guests. This strategy is referred to as reactive encapsulation . The concept was first elegantly demonstrated by... 

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