Supramolecular electrostatic assembly

Fluorescence lifetime measurements on the aggregate have shown that the rate constant of the intermolecular energy transfer from the zinc porphyrin unit to the free-base porphyrin unit has been evaluated to be 3.0 x 109 s-1. This value is reasonable from a model in which dendritic donor 6b and acceptor 5a contact each other directly at their exterior surfaces (Scheme 2). Therefore, electrostatic assembly of positively and negatively charged dendrimers provides a promising supramolecular approach to construct photofunctional materials with nanometric precision. 

The general chemistry used in this approach involves the combination of a limited amount of an amine-terminated dendrimer core reagent with an excess of carboxylic acid terminated dendrimer shell reagent [31]. These two charge differentiated species are allowed to self-assemble into the electrostatically driven supramolecular core-shell tecto(dendrimer) architecture. After equilibration, covalent bond formation at these charge neutralized dendrimer contact sites is induced with carbodiimide reagents (Scheme 1). 

Combined physical/supramolecular methods have also been applied for the organization of porphyrins. The layer-by-layer method,based on alternating electrostatic assembly of materials, has been used to assemble porphyrins (Figure 7), and their potential as sensing elements was assessed. Also, porphyrinoids such as N-confused porphyrins have been incorporated in LB films and used as a selective sensor for iodide anions based on the incorporation of these anions in the LB films upon their transfer to a substrate. In that work, only iodide anions formed a stable... 

The most used approaches for the construction of multiporphyrin systems are the self-assembly methods. For example, electrostatic assembly is an easy and widely used method based on the interaction of oppositely charged porphyrins for preparation of more complex systems [1-12]. Self-assembly of porphyrins are also possible by coordination of nucleophihc groups to the central metal ion or using compounds having two nucleophihc sites to coordinate two metalloporphyrins [13-22]. These methods have been used not only for the preparation of porphyrin dimers and trimers, but also for the formation of larger supramolecular networks. Despite the apparent simphcity of the preparation methods of multiporphyrin materials by self-assembly, they generally are less stable as compared to covalently bond... 

Xu and co-workers reported the use of enz5miatic dephosphorylation to induce a sol-gel transition [86]. The small-molecule fluorenylmethyloxycarbonyl (FM0C]-t3n osine phosphate was exposed to a phosphatase, and the resulting removal of phosphate groups led to a reduction in electrostatic repulsions, supramolecular assembly by stacking of the fluorenyl groups, and eventual gelation. 

The following sections contain a review of many of the varied synthetic systems that have been developed to date utilising noncovalent interactions to form assembhes of molecules. These sections are loosely demarcated according to the most important type of noncovalent interactions utilized in conferring supramolecular order (ie, van der Waal s interactions, electrostatic interactions, and hydrogen bonds). For extensive reviews, see References 1,2,4—6,22,46,49,110—112. Finally, the development of self-assembling, self-replicating synthetic systems is noted. 

DNA is ideally suited as a structural material in supramolecular chemistry. It has sticky ends and simple rules of assembly, arbitrary sequences can be obtained, and there is a profusion of enzymes for modification. The molecule is stiff and stable and encodes information. Chapter 10 surveys its varied applications in nanobiotechnology. The emphasis of Chapter 11 is on DNA nanoensembles, condensed by polymer interactions and electrostatic forces for gene transfer. Chapter 12 focuses on proteins as building blocks for nanostructures. 

Fabrication of organic thin films based on sponfaneous molecular assembly has been considered as one of fhe powerful approaches to create novel supramolecular systems. In this context, multilayer films were fabricated by layer-by-layer electrostatic deposition techniques based on the electrostatic interaction between dsDNA and the positively charged polymer poly(diallyldimethylammonium chloride) (PDDA) on GC surfaces. A uniform assembly of PDDA/DNA multilayer films was achieved, based on the adsorption of the negatively charged DNA molecules on the positively charged substrate [55]. 

Studies on molecular recognition by artificial receptors are thus one of the most important approaches to such characterization in relation to supramolecular chemistry [4]. Functional simulation of intracellular receptors in aqueous media has been actively carried out with attention to various noncovalent host-guest interactions, such as hydrophobic, electrostatic, hydrogen-bonding, charge-transfer, and van der Waals modes [5-10]. On the other hand, molecular recognition by artificial cell-surface receptors embedded in supramolecular assemblies has been scarcely studied up to the present time, except for channel-linked receptors [11-13]. 

---