Self-assembly/association types

Ion bridging is a specific type of Coulombic interaction involving the simultaneous binding of polyvalent cations (e.g., Ca, Fe, Cu ) to two different anionic functional groups on biopolymer molecules. This type of ionic interaction is commonly involved in associative self-assembly of biopolymers. As a consequence it is also an important contributory factor in the flocculation (via bridging or depletion) of colloidal particles or emulsion droplets in aqueous media containing adsorbed or non-adsorbed biopolymers (Dickinson and McClements, 1995). 

Molecular recognition directed self-assembling of organized phases has been described recently in the formation 1) of mesophases by association of complementary molecular component, as in 13 (23) 2) of supramolecular liquid crystalline polymers of type 14 (24) and 3) of ordered solid state structures, such as that represented by 15 (25). In all these cases, the incorporation of NLO active groups may be expected to produce materials whose SHG properties would depend on molecular recognition induced self-organization. 

There are two types of objects in supramolecular chemistry supermolecules (i.e., well-defined discrete oligomolecular species that result from the inter-molecular association of a few components), and supramolecular arrays (i.e., polymolecular entities that result from the spontaneous association of a large, undefined number of components) (4, 5). Both are observed in some metal-xanthate structures to be described herein. The most frequent intermolecular forces leading to self-assembly in metal xanthates are so-called secondary bonds . The secondary bond concept has been introduced by Nathaniel W. Alcock to describe interactions between molecules that result in interatomic distances longer than covalent bonds and shorter than the sum of van der Waals radii (6). Secondary bonds [sometimes called soft-soft interactions (7)] are typical for heavier p-block elements and play an important role as bonding motifs in supramolecular organometallic chemistry (8). Other types of intermolecular forces (e.g., Ji- -ji stacking) are also observed in the crystal structures of metal xanthates. 

Artificial membranes are used to study the influence of drug structure and of membrane composition on drug-membrane interactions. Artificial membranes that simulate mammalian membranes can easily be prepared because of the readiness of phospholipids to form lipid bilayers spontaneously. They have a strong tendency to self-associate in water. The macroscopic structure of dispersions of phospholipids depends on the type of lipids and on the water content. The structure and properties of self-assembled phospholipids in excess water have been described [74], and the mechanism of vesicle (synonym for liposome) formation has been reviewed [75]. While the individual components of membranes, proteins and lipids, are made up of atoms and covalent bonds, their association with each other to produce membrane structures is governed largely by hydrophobic effects. The hydrophobic effect is derived from the structure of water and the interaction of other components with the water structure. Because of their enormous hydrogen-bonding capacity, water molecules adopt a structure in both the liquid and solid state. 

All cellular life today incorporates two processes we will refer to as self-assembly and directed assembly (Fig. 1). The latter involves the formation of covalent bonds by energy-dependent synthetic reactions and requires that a coded sequence in one type of polymer in some way direct the sequence of monomer addition in a second polymeric species. On the other hand, spontaneous self-assembly occurs when certain compounds associate through noncovalent hydrogen bonds, electrostatic forces, and nonpolar interactions that stabilize orderly arrangements of small and large molecules. Three well-known examples include the self-assembly of water molecules into ice, DNA... 

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