Supramolecular templating

Finally, it needs to be mentioned that the mechanisms of supramolecular self-assembly apply to many systems more complex than simple surfactants and amphiphilic block copolymers. Supramolecular self-assembly and pattern formation is one of the crucial principles in nature and gives rise to hierarchical structure ranging from the length scale of a few nanometers to the macroscopic domain. The generation of intricate and very regular structures by templating supramolecularly self-assembled structures in the shape of LLC phases has proven extremely successful. Therefore, the utilization of the more complex systems found in nature (e.g. protein assemblies in viruses) is at the hands of mod-... 

Scheme 8 Templated supramolecular synthesis of a three-component dendrimer [X = B(Ph(CF3)2)4]. ...

Hong, J.S., Vreeland, W.N., Lacerda, S.H., Locascio,L.E.,Gaitan, M.,andRaghavan,S.R. 2008. Liposome-templated supramolecular assembly of responsive alginate nanogels. Langmuir 2d 4092-4096. 

Guo J, Yang J, Liu Y, Ma J (2013) Two new polyoxometalate-templated supramolecular compounds constructed by a new tridentate ligand 2,4,6-tris[l-(4-oxidroxypyridinium)-yhnethylj-mesitylene. Inorg Chim Acta 400 51-58... 

Template effect and incapsulation in macroheterocyclic supramolecular systems 97T15911. 

Sauvage, J. P. and Hosseine, M. W., Eds., Comprehensive Supramolecular Chemistry, Volume 9 Templating, Self-Assembly, and Self-Organization, Pergamon, Oxford, 1999. 

Albrecht M (2004) Supramolecular Templating in the Formation of Helicates. 248 105-139 Ando T, Inomata S-I, Yamamoto M (2004) Lepidopteran Sex Pheromones. 239 51-96 Angyal SJ (2001) The Lobry de Bruyn-Alberda van Ekenstein Transformation and Related Reactions. 215 1-14... 

The use of DNA hybridization just described opens up a novel, uncomplicated, yet powerful strategy for supramolecular synthesis Many different devices are connected to a distinct sequence codon and are subsequently organized on a suitable template strand. The utilization of appropriate nucleic acid scaffolds should even allow the fabrication of highly complex supramolecular structures by means of a modular construction kit. For approximately 20 years, the work of Seeman and coworkers [8,27] have been engaged in the rational construction of ID, 2D, and 3D DNA frameworks. They use branched DNA... 

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... 

Switching the roles of the zinc porphyrin template and N-donor adapter provides an alternative mode for the supramolecular construction of biden-tate ligands (Scheme 32). Complex 26 derived from mixing three equivalents of template 24 with two equivalents of monodentate phosphite ligands 23 furnished a rhodium catalyst which displayed good regioselectivity toward... 

One of the most successful approaches to the synthesis of metalla-supramolecular systems has been by templated self-assembly processes. Most of the templating agents used by synthetic chemists are either cationic or neutral species. Anions, on the other hand, have only fairly recently been successfully utilized as templates. The new metalla-macrocycles [Pd2Ni2(atu)4(PPh3)4X]3+ (atu = deprotonated amidinothiourea, X = C1, Br, I) have been prepared using anion templated syntheses. Only in the presence of each of these three halides are the metalla-macrocycles... 

Sauvage, J.-P. Dietrich-Buchecker, C. O. Chambron, J.-C. Transition metals as assembling and templating species synthesis of catenanes and molecular knots. In Comprehensive Supramolecular Chemistry, Sauvage, J.-P. Hosseini, M.W., Ed., Publisher Elsevier, Oxford, UK 1996 Vol. 2, p 43. 

Other supramolecular structures such as catenanes and rotaxanes can be formed using zinc as a template ion for example, a benzylic imine catenate formed by Leigh et a/.288 The reversible five-component assembly of a [2]catenane from a chiral metallomacrocycle and a dinaphtho-crown ether has been achieved. Zinc is used as the metal component and drives assembly via the coordination to a bipyridyl unit 7r interactions between the aromatic components are also... 

Macrocyclic complexes of zinc have inspired interest in varied areas such as supramolecular and biomimetic chemistry including hydrolysis enzymes, such as phosphatases and esterases, and also for the fluorescent detection of zinc. The polyaza macrocycles and their A--functionalized derivatives are particularly well represented. An important aspect of macrocycle synthesis is the use of metal templates to form the ligand. Examples of zinc as a template ion will be discussed where relevant. 

Hawthorne and co-workers have also produced a series of macrocyclic Lewis acid hosts called mercuracarborands (156, 157, and 158) (Fig. 84) with structures incorporating electron-withdrawing icosahedral carboranes and electrophilic mercury centers. They were synthesized by a kinetic halide ion template effect that afforded tetrameric cycles or cyclic trimers in the presence or absence of halide ion templates, respectively.163 These complexes, which can bind a variety of electron-rich guests, are ideal for catalytic and ion-sensing applications, as well as for the assembly of supramolecular architectures. 

Reference [33] describes recent progress on cyanine probes that bind noncova-lently to DNA, with a special emphasis on the relationship between the dye structure and the DNA binding mode. Some of the featured dyes form well-defined helical aggregates using DNA as a template. This reference also includes spectroscopic data for characterizing these supramolecular assemblies as well as the monomeric complexes. 

Many of the materials currently under development draw their inspiration from structures found in nature. That is, by mimicking the supramolecular architecture of natural materials, one can prepare complex materials capable of highly sophisticated functions. An important aspect of this work involves the selection of microorganism templates (e.g., diatomite) based on specific porous structures that may benefit targeted applications. 

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