Supramolecular self-templating

The self-assembling double-helical structure of DNA has provided the inspiration for a further area of supramolecular self-assembly, namely the use of metal ions to template the assembly of organic threads into... 

The principal motivation for studying these sugar-based microemulsion glasses came from the observation that water-oil-surfactant mixtures are extensively for nanomaterials synthesis with the central idea of switching dynamic self-assembly into chemically and mechanically stable supramolecular materials. Template polymerisations are classified as synergistic or transcriptive templating depending on whether the template itself participates in the reaction. 

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-... 

This method allows independent control over both the macropores, which are determined by the emulsion droplets in the first step of the process, and the mesopores, by the supramolecular self-assembly in the second step. Therefore, the two templating systems do not interfere vhth each other, and consequently the meso-and macro-structures can be optimized separately [21]. Inorganic oxides, such as silica, titania and zirconia, were obtained by this two-step process. The bimodal distribution of pores was characterized by highly ordered mesopores (5-10 nm) and by interconnected macropores (0.1 to 5 p,m). These materials possess high pore volumes (17 cm g ) and specific surface areas, as determined by the BET method applied to the nitrogen adsorption isotherm, of between 250 and 750 The... 

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

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... 

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... 

Organoclay materials with higher-order organization can also be prepared by template-directed methods involving self-assembled supramolecular structures. In this approach, preformed organic architectures in the form of tubes, fibers, hollow shells, gyroids, helicoids, and so on are transferred into hybrid materials exhibiting structural hierarchy, complex form and ordered mesoporosity [47-55]. For example,... 

---