Natural systems, supramolecular

All of these interactions involve a host and a guest as well as their surroundings like solvation, crystal lattice, and gas phase. Electrostatic interactions are the driving force behind the ion pairing (ion-ion, ion-dipole, dipole-dipole, etc.) interactions, which are undeniably important in natural and supramolecular systems. The electrostatic interaction energy E is given by... 

These problems have been addressed in a wide variety of imaginative and novel ways and progress in anion complexation has been rapid in recent years " to the extent that it has now been described by Lehn as a full member of the field of supramolecular chemistry. It is important to note that the search for anion-selective receptors has not been limited to the mimicry of Mother Nature s approach. Indeed, a great number of the hosts developed are far from being biocompatible as the tools of the chemist are not limited to the building blocks of natural systems. This aspect of anion recognition chemistry lies at the heart of supramolecular chemistry, the interface between chemistry and biology. ... 

Biological systems have provided much of the inspiration for the development of supramolecular chemistry (see Chapters 1 and 6). One ofthe main challenges in this area is to mimic the enzymatic systems and to understand the assembly processes involved. These natural systems have an extremely high selectivity and catalytic efficiency. Although there are many successful results in this area [26], a complete understanding of these systems is still lacking. 

As one example, the observation of hydrogen bonding [7] in natural systems such as peptide helices and DNA base pairs led to a theoretical understanding of this phenomenon. This understanding has permitted the use of hydrogen bonding in synthesis, leading to the preparation of such diverse structures as Rebek s capsules [8], Lehn s supramolecular polymers [9], and Whitesides rosettes [10]. 

Because of their efficiency in natural systems in giving supramolecular aggregates, aminoacids have been implemented extensively in calix[4]arene scaffolds. Di- and tetrasubstitution with aminoacid derivatives have been investigated observing different behaviors depending on the orientation of the chiral residues attached to the calix[4]arene scaffold. Derivatives compris-... 

Supramolecular chirogenesis is widely observed and plays a vital role in a large number of natural systems such as the DNA double helix, the sec-... 

An excellent example where a capsid virus has been given a new supramolecular application can be found in the work of Nolte who took an icosahedral capsid virus, cowpea chloritic mottle virus (CCMV) and used it as a nanoreactor for polymer synthesis [30], Natural CCMV spontaneously assembles in acidic aqueous solution and disassembles in basic solution. The capsid contains pores open at pH 5 to release RNA into the host. Once the RNA leaves, the empty capsule is left. The Nolte group was able to assemble the subunits around polystyrene sulfonate with a mass of 9.9 kDa but the resulting structure had a different morphology to the natural system. Indeed, capsules formed around polymers with masses between 2 and 85 kDa but not around those with masses above 100 kDa. This raised the question of the potential for polymers to form within a capsid but to test the possibility a mixture of botanical, biological and chemical approaches was needed. 

Of course, the above suggestion ignores the problem of possible supramolecular functionality. Whereas the natural systems are invariably characterised by high functionality in terms of their biochemical roles, in contrast, the functionality of the majority of synthetic assemblies so far investigated has very often been either minimal or, indeed, absent altogether. The incorporation of designed functionality into supramolecular systems will thus undoubtedly continue to attract increased attention in future studies. 

A distinctive feature of using weak, non-covalent forces, or for that matter metal-donor bonds, in molecular assemblies is that such interactions are normally readily reversible so that the final product is in thermodynamic equilibrium with its components (usually via its corresponding partially assembled intermediates). This leads to an additional property of most supramolecular systems they have an in-built capacity for error correction not normally available to fully covalent systems. Such a property is clearly of major importance for natural systems with their multitude of intermolecular contacts. It is a factor that will assume increasing importance for the construction of the new (larger) synthetic systems mentioned previously - as both the number of intermolecular contacts present and overall structural complexity are increased. 

Discotic molecules are of interest for their solution properties and their intriguing supramolecular architectures, in which a level of control in two-dimensional structures can be reached, that shows them to be of particular interest as models for natural systems. Their relatively poor mechanical properties,... 

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