Guest molecule molecular recognition

This chapter presents a selective glimpse of this dynamic family of spherical macromolecnles for newcomers to the topic in order to help them better appreciate the field that has been extensively reviewed elsewhere. This chapter is divided into several parts to emphasize the structmal diversity and their potential applications. First, a study of the internal structure of the dendritic architecture, emphasizing the different types, followed by a study of their interactions with other molecules or atoms, such as in the case of host-guest chemistry, molecular recognition, or encapsulation inside the dendrimer. Finally, there is a small section that will address the intermolecular interactions of dendrimers and dendrons to either themselves or other nano-objects. In this past quarter century, tens of thousands of papers have been published producing a wide variety of different dendritic architectures with varied structural components capable of novel supramolecular interactions. Therefore, only an overview describing their structure with representative examples and practical purposes will be discussed, when appropriate. 

Dendrimers ([3] dendrimers and other dendritic polymers [4]) are repeatedly branched molecules that can contain selected functional groups in predetermined sites of their multiarmed structure. In spite of their large structures, that usually make dendrimers attractive as host molecules, suitably designed dendrimers can be involved as guests in molecular recognition phenomena (for some recent examples, see [5-12]). In such cases, the host species does not interact with the whole... 

The possibility to resolve the two enantiomers of 27a (or 26) by crystalline complexa-tion with optically active 26 (or 27a) is mainly due to differences in topological complementarity between the H-bonded chains of host and guest molecules. In this respect, the spatial relationships which affect optical resolution in the above described coordination-assisted clathrates are similar to those characterizing some optically resolved molecular complexes S4). This should encourage additional applications of the lattice inclusion phenomena to problems of chiral recognition. 

Supramolecular chemistry takes into consideration the weak and reversible non-covalent interactions between molecules, which include H-bond-ing, metal coordination, hydrophobic forces, van der Waals forces, n—n interactions, and covers different research fields, for example, molecular recognition, host-guest chemistry, mechanically interlocked and nanochemistry. 

Carbohydrates not only act as ligands, but they can also provide scaffolds for molecular recognition processes. It is well known that cyclodextrins (CDs) are able to form an inclusion complex with specific guest molecules. In the last years, NMR experiments combined with other techniques have been used to highlight different recognition events. 

The exploitation of the reactivity of molecular crystals lies close to the origins of crystal engineering and is at the heart of the pioneering work of Schmidt [47a]. The idea is that of organizing molecules in the solid state using the principles of molecular recognition and self-assembly. Successful results have been obtained with bimolecular reactions, particularly [2+2] photoreactivity and cyclisation [47b,c]. Another important area is that of host-guest chemistry. 

A molecule that contains one or more binding sites that can accommodate inorganic or organic ions referred to as guests. The binding site could even be a cavity within a crystal structure. Although enzymes clearly qualify as examples of host molecules, the term is usually restricted to structures such as crown ethers, macrocycles, and cyclodextrins. Nevertheless, these hosts do serve as models for molecular recognition. See also Crown Ethers Macrocycles Inclusion Complexes... 

Native enzymes show remarkably sharp substrate specificities. Actually, an enzyme can sometimes distinguish a slight difference of shapes between its specific and nonspecific guests, even if the electronic states of both are almost the same. The term molecular recognition is used to describe such ability of the molecule (enzyme). Inclusion compounds are supersimplified, but very appropriate systems for elucidation of the nature of the molecular recognition, since interactions between the inclusion host and a substrate are not more complicated than can be measured or even calculated. In this section, we will survey the recent results on the crystal structures of the inclusion compounds, and based on the information, the probable driving force for the inclusion is discussed in detail. 

Figure 7.1.4. The scheme of formation of [2.2.2]cryptand. marked the start of molecular recognition studies. As described in Chapters 2 and 3, the Pedersen analysis was later extended by Lehn s studies of the complementarity of sizes and shapes ofthe cryptand cavities and their guests, and by Cram s preorganization studies. In general, crown ethers and cryptands exhibit analogous complexation behaviour. Thus, similarly to the former host molecules, cryptands in the free, uncomplexed state elongate the vacant cavity by rotating a methylene group inward. Thus, the N...N distance in [2.2.2]-cryptand 54 across the cavity is extended to almost 70 pm [18] whilst, in the complexed...

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