Design, functionalized nanoscopic

Design of Assemblies of Functionalized Nanoscopic Gridlike Coordination Arrays... 

The examples represented here have demonstrated our increasing ability to design and to manipulate ever larger supramolecular systems and merge concepts from supramolecular and polymer chemistry. Yet we are still far Irom approaching the perfection and versatility and, most important, the functionality of biomolecules and their superstructures. Like in biology, macromolecules and the competition between macromolecular order and disorder will play a dominant role in the preparation of functional molecular devices and nanoscopic objects. 

Another remarkable feature of responsive polymeric systems is that interactions on the molecular scale (the stimulus of some sort) lead to macroscopically detectable changes that are finally employed for the function (e.g., directed delivery of drugs). As the molecular-scale interactions and macroscopic function are so intimately linked it is noteworthy that rather few studies have dealt with the nanoscopic level of these materials. This may be due to the fact that many conventional methods of physical polymer characterization may simply not be able to resolve the many different, often counteracting interactions [18, 49, 50]. In processes like a response of any kind, solvent-polymer, solvent-solvent, and polymer-polymer interactions all play a cmcial role. Better understanding of the structure and interactions on the nanoscale is not only of value in itself but it may also shed light on similar processes in biomacromolecules and may aid the design and control of responsive polymers with respect to their applications [8, 48, 49]. These applications can be counted to the above-mentioned societal need of health, as responsive polymers are hot candidates for, e.g., drug or nucleic acid delivery purposes. 

Molecular self-assembly has been recognized as a powerful approach to designer soft materials with a nanoscopic structural precision [llj. However, self-assembled nanostructures are inherently subject to disruption with heating and exposure to solvents. The HBC nanotubes are not exceptional. Thus, for practical applications of the nanotubes, one has to consider postmodification of their nanostructures for covalent connection of the assembled HBC units. Because the inner and outer surfaces of the nanotubes are covered with TEG chains, incorporation of a polymerizable functionality into the TEG termini allows for the formation of surface polymerized nanotubes with an enhanced morphological stability. 

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