Hydrogen bonding host-guest interaction

Some practical applications of non-covalent interactions are also very interesting. The basis of the separation of enantiomers by the chromatographic method21 is the preferential interaction of one enantiomer of a substance with one enantiomer of another substance, which is usually part of the chiral stationary phase. Non-covalent interactions are more frequent hydrogen bonding, host-guest and donor-acceptor interactions. 

One class is polymers capable of forming inter- or intra-polymer associations via secondary interactions (electrostatic, hydrogen bonding, host-guest, or hydrophobic interactions). In Fig. 39a, two linear chains form a star-shaped macromolecule by the association of supramolecular motifs. This star-shaped chain obviously behaves differently in the flow field compared with individual linear constituents (Fig. 26). 

Calorimetric analysis reqnires some prior knowledge of the nature of the interaction. The formation of hydrogen-bonded host-guest complexes with dicarboxy-lates in DMSO was fonnd to be exothermic (19). Endothermic association would require a reversal in the treatment of binding effectiveness. 

The network structures to be discussed will all involved hydrogen bonding as the supramolecular synthon. It should be noted however that other interactions such as coordinate bonds and host-guest interactions may also organise host molecules into network structures. Coordination polymers constructed from molecular hosts may involve functionalised calixarenes [8-11], cyclotriveratrylene [12], or cucurbituril [13]. Calixarenes have also been used to build up network structures via host-guest interactions [14,15]. It is also notable that volatile species may be trapped within the solid state lattice of calix[4] arene with a structure entirely composed of van der Waals interactions [16]. 

Very recently a new method was developed that opens the possibility to polymerize even hydrophobic monomers in aqueous solution. This method is based on the finding that hydrophobic monomers can be made water-soluble by incorporation in the cavities of cyclodextrins. It has to be mentioned that no covalent bonds are formed by the interaction of the cyclodextrin host and the water-insoluble guest molecule. Obviously only hydrogen bonds or hydrophobic interactions are responsible for the spontaneous formation and the stability of these host-guest complexes. X-ray diffraction pattern support this hypothesis. Radical polymerization then occurs via these host-guest complexes using water-soluble initiators. Only after a few percent conversion the homogeneous solution becomes turbid and the polymer precipitates. 

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]. 

Figures 53 and 54 show the structure of the 3/98d complex as it exists in the unit cell [154, 303], Unlike the complexes with 98a-c, the 98d complex has both hydroxyl groups of one 3 hydrogen bonded to both carbonyl groups of one molecule of 98d. As a result, the diyne backbone is curved (Figure 53) [154, 303], There is no reason to believe that the walls of the reaction cavity experienced by 98d or by transients, lOld and 102d derived from it, in optically active 3 complexes are any more rigid or contain less free volume than do the other complexes. The enantiomeric purity of the product must result from specific attractive host-guest interactions retained along the...

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