Structure formation oriented aggregation

Surfactants are amphiphilic molecules which, when dispersed in a solvent, spontaneously self-assemble to form a wide variety of structures, including spherical and asymmetric micelles, hexagonal, lamellar, and a plethora of cubic phases. With the exception of the lamellar phase, each of these phase structures can exist in both normal and reverse orientations with the hydrophobic chains on the exterior of the aggregate, in contact with solvent or vice versa orientation. The range of structures a particular surfactant forms and the concentration range over which they form, depends upon the molecular architecture of the surfactant, its concentration, and the solvent in which it is dispersed. For example, some solvents such as ethanol do not support the formation of aggregates. As most pharmaceutical systems use water as their solvent, this entry will concentrate on aqueous-based systems, although other solvent systems, particularly other non-aqueous polar systems, will be mentioned where appropriate. 

The lowering of the viscosity is associated with the formation of supramole-cular rod-like structures created by aggregation of the solubilized protein chains. Figure 12.9 shows a simple model of isotropic fibroin coils, dissolved in water and arranged into orientationally ordered supramolecular rods. 

The nonhydrolytic M—O—M bond formation via ester elimination between metal alkoxides and carboxylic acids is a well-known approach in sol-gel chemistry. In this direction, titanium -butoxide and acetic acid were used for the nonhydrolytic synthesis of anatase Ti02 nanopartides at 100 °C [92]. Moreover, spindle-shaped nanoporous anatase Ti02 mesocrystals with a single-crystal-like structure and tunable sizes were synthesized in the tetrabutyl titanate and acetic acid system without any additives imder solvothermal conditions [93]. A complex mesoscale assembly process, involving oriented aggregation of tiny anatase nanocrystals and entrapment of in situ produced butyl acetate as a porogen, was proposed for the formation of the mesocrystals. They exhibited a good performance as anode material for lithium ion batteries [93]. 

The formation of ECC is not only an extension of a portion of the macromolecule but also a mutual orientational ordering of these portions belonging to different molecules (intermolecular crystallization), as a result of which the structure of ECC is similar to that of a nematic liquid crystal. After the melt is supercooled below the melting temperature, the processes of mutual orientation related to the displacement of molecules virtually cannot occur because the viscosity of the system drastically increases and the chain mobility decreases. Hence, the state of one-dimensional orientational order should be already attained in the melt. During crystallization this ordering ensures the aggregation of extended portions to crystals of the ECC type fixed by intermolecular interactons on cooling. 

To prevent insolubility resulting from uncontrolled aggregation of extended strands, two adjacent parallel or antiparallel yS-peptide strands can be connected with an appropriate turn segment to form a hairpin. The / -hairpin motif is a functionally important secondary structural element in proteins which has also been used extensively to form stable and soluble a-peptide y9-sheet arrangements in model systems (for reviews, see [1, 4, 5] and references therein). The need for stable turns that can bring the peptide strands into a defined orientation is thus a prerequisite for hairpin formation. For example, type F or II" turns formed by D-Pro-Gly and Asn-Gly dipeptide sequences have been found to promote tight a-pep-tide hairpin folding in aqueous solution. Similarly, various connectors have been... 

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