Supramolecular forms

Some methylzinc thiolates with bulky groups on the sulfur form self-assembled aggregates with cage structures and four-coordinate zinc. Thus, the /crt-butyl derivative is a pentamer, [MeZnSBu js, 16, (in benzene solution) [33] and the isopropyl derivative is an octamer, [MeZnSPr jg, 17 [34]. According to cryoscopic measurements [4] the latter is hexameric in benzene solution, indicating facile interconversion between variously aggregated (supramolecular) forms. 

Q[n] and drug delivery are emerging as an exciting area in the supramolecular context. Q[n] have the potential to contribute to the resolution of some drug delivery difficulties that include bioavailability, bio and chemical stability, improvements in efficacy and efficiency, limiting toxicity, and side effects. In relative terms, only a few examples of this potential have so far been realized. As we increase our understanding of the physical and chemical capabilities of Q[n] and develop new derivatives and supramolecular forms, Q[n] will be one of the drug delivery tools used in the clinic in future. 

Day AI, Blanch RJ, Arnold AP, Lorenzo S, Lewis GR, Dance 1. A cucurbituril-based gyroscane a new supramolecular form. Angew Chem Int Ed 2002 2 275-7. 

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. 

A second class of monolayers based on van der Waal s interactions within the monolayer and chemisorption (in contrast with physisorption in the case of LB films) on a soHd substrate are self-assembled monolayers (SAMs). SAMs are well-ordered layers, one molecule thick, that form spontaneously by the reaction of molecules, typically substituted-alkyl chains, with the surface of soHd materials (193—195). A wide variety of SAM-based supramolecular stmctures have been generated and used as functional components of materials systems in a wide range of technological appHcations ranging from nanoHthography (196,197) to chemical sensing (198—201). 

Liquid Crystalline Structures. In certain ceUular organeUes, deoxyribonucleic acid (DNA) occurs in a concentrated form. Striking similarities between the optical properties derived from the underlying supramolecular organization of the concentrated DNA phases and those observed in chiral nematic textures have been described (36). Concentrated aqueous solutions of nucleic acids exhibit a chiral nematic texture in vitro (29,37). 

The main supramolecular self-assembled species involved in analytical chemistry are micelles (direct and reversed), microemulsions (oil/water and water/oil), liposomes, and vesicles, Langmuir-Blodgett films composed of diphilic surfactant molecules or ions. They can form in aqueous, nonaqueous liquid media and on the surface. The other species involved in supramolecular analytical chemistry are molecules-receptors such as calixarenes, cyclodextrins, cyclophanes, cyclopeptides, crown ethers etc. Furthermore, new supramolecular host-guest systems arise due to analytical reaction or process. 

The mechanism of recognition of most supramolecular entities (such as abiotic receptors) is the formation of several hydrogen bonds. Since heterocyclic tautomers possess both strong HBA and HBD properties (see Sections III,G, V,D,2, and VI,G), they are often used for this purpose. For instance, the hydrogen bond network formed by 5,5 -linked bis(2-pyridones) has been used by Dickert to obtain sensors (96BBG1312). 

On the other hand, it has also become clear that a materials-oriented synthesis of conjugated poly(phenylene)s cannot narrow its attention to properties of molecules only in solution, but has to include aspects of processing and supramolecu-lar ordering as well. The rigid-rod character of PPPs therefore suggests the use of chain stiffness as a structure-forming principle in the design of supramolecular motifs. 

The results presented up to here concern only one-dimensional oligomers and polymers of the PPP-lype. This section is mainly focussed on the electronic properties of extended re-chains and on the morphology of solid PPPs using chain-stiffness as a structure-forming principle for supramolecular architectures. 

Supramolecular structures formed during the crystallization of the melt under a tensile stress have already been described by Keller and Machin25. These authors have proposed a model for the formation of structures of the shish-kebab type according to which crystallization occurs in two stages in the first stage, the application of tensile stress leads to the extension of the molecules and the formation of a nucleus from ECC and the second stage involves epitaxial growth of folded-chain lamellae. 

Cyclophanes or 7r-spherands have played a central role in the development of supramolecular chemistry forming an important class of organic host molecules for the inclusion of metal ions or organic molecules via n-n interactions. Particular examples are provided by their applications in synthesis [80], in the development of molecular sensors [81], and the development of cavities adequate for molecular reactions with possible applications in catalysis [82]. The classical organic synthesis of cyclophanes can be quite complex [83], so that the preparation of structurally related molecules via coordination or organometallic chemistry might be an interesting alternative. 

Some related examples with BR2 monocapped ligands are also known [181] and one of these molecules, 129, assembles to an interesting supramolecular structure, in which the cobalt(III) ions in a methylcobaloxime unit are coordinated to the pyridine residues of the bridging B(py)(OMe) group (Fig. 34). The dinuclear complex forms a large rectangular cage that is limited by the two pyridine residues and the cobaloxime moieties. The two pyridine... 

It is well known the tendency of polysaccharides to associate in aqueous solution. These molecular associations can deeply affect their function in a particular application due to their influence on molecular weight, shape and size, which determines how molecules interact with other molecules and water. There are several factors such as hydrogen bonding, hydrophobic association, an association mediated by ions, electrostatic interactions, which depend on the concentration and the presence of protein components that affect the ability to form supramolecular complexes. 

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