Liquid crystalline phases typical structures

Both low molecular weight materials [145] and polymers [146,147] can show liquid crystallinity. In the case of polymers, it frequently occurs in very stiff chains such as the Kevlars and other aromatic polyamides. It can also occur with flexible chains, however, and it is these flexible chains in the elastomeric state that are the focus of the present discussion. One reason such liquid-crystalline elastomers are of particular interest is the fact that (i) they can be extensively deformed (as described for elastomers throughout this chapter), (ii) the deformation produces alignment of the chains, and (iii) alignment of the chains is central to the formation of liquid-crystalline phases. Because of fascinating properties related to their novel structures, liquid-crystalline elastomers have been the subject of numerous studies, as described in several detailed reviews [148-150]. The purpose here will be to mention some typical elastomers exhibiting liquid crystallinity, to describe some of their properties, and to provide interpretations of some of these properties in molecular terms. 

Surfactants are used in a variety of applications, frequently in the form of dilute aqueous solutions. However, it is not cost effective to transport, store, and display in retail outlets surfactant products such as household detergents in this form. Accordingly, it is important to have products that dissolve quickly and to understand what aspects of surfactant composition and structure promote rapid dissolution. The dissolution process is more complex for surfactants than for most other materials because it typically involves formation of one or more concentrated and highly viscous liquid crystalline phases, which are not present initially and which could potentially hinder dissolution. In this article the rates and mechanisms of surfactant dissolution are reviewed and discussed. 

In aqueous solutions of Cm-(EO)n amphiphilic molecules, two interesting features are observed. First, isotropic micellar solutions undergo phase separation on heating. Such behavior is typical of hydrophobic interaction and is also observed for several water-soluble polymers. Hydrophobic interaction results from a change of order in the water structure [54]. Second, at high concentration, liquid crystalline phase behavior is observed with several structures [55]. 

Figure 3.17 Patterns of liquid crystalline phases of surfactants under the polarisation microscope (a) hexagonal phase the typical fan-like structure can be seen, (b) lamellar droplets with typical Maltese crosses and (c) lamellar phase.

Liquid-crystalline phases are characterized to some degree by the shape of the molecules and by their packing arrangements and ordering in the mesomorphic state. Typically, molecules can have cither disc- or rod-like shapes and can form discotic or calamitic mesophases, respectively. Ferrocene liquid crystal systems that have so far been synthesized tend to have molecular structures that are lath- or rod-like in shape, and consequently the phases observed are calamitic. However, this does not preclude the possibility that a polysubstituted ferrocene could be prepared where the molecular shape is disc-like, thereby holding out the prospect of possibly producing discotic/columnar phases. 

A liquid crystal is a general term used to describe a variety of anisotropic structures formed by amphiphilic molecules, typically but not exclusively at high concentrations. Hexagonal, lamellar, and cubic phases are all examples of liquid crystalline phases. These phases have been examined as drug delivery systems because of their stability, broad solubilization potential, ability to delay the release of encapsulated drug, and, in the case of lamellar phases, their ability to form closed, spherical bilayer structures known as vesicles, which can entrap both hydrophobic and hydrophilic drug. This section will review SANS studies performed on all liquid crystalline phases, except vesicles, which will be considered separately. Vesicles will be considered separately because, with a few exceptions, generally mixed systems, vesicles (unlike the other liquid crystalline phases mentioned) do not form spontaneously upon dispersal of the surfactant in water and because there have been many more SANS studies performed on these systems. 

In contrast to typical chiral thermotropic constituent molecules, protein molecules have a huge number of chiral centres, and the twist between assembled proteins is typically much larger (-1/10 of a revolution). We can expect to find a range of similar liquid crystalline phases in protein aggregates, although with significantly smaller lattice parameters (compared with typical protein dimensions). Indeed, the aggregation processes of (e.g. structural) proteins may be driven by their chirality as much as by their molecular shape (and amphiphilicity). This is discussed in more detail in Chapter 6. 

When surface active agents are considered, a further complication may be encountered. Because of their surface active nature, the surfactants not only emich at the surfaces, but also form extended structures themselves. At low concentrations, the surfactants remain as dissolved monomers or asssociate to oligomers. However, when the critical micellization concentration (cmc) is surpassed, a cooperative association is activated to micelles (1 to 10 nm) consisting typically of some 50 to 100 monomers. At stiU higher concentrations, or in the presence of cosurfactants (alcohols, amines, fatty acids, etc.), liquid crystalline phases may separate. These phases have an infinite order on the x-ray scale, but may remain as powders on the NMR (nuclear magnetic resonance) scale. When the lamellar liquid crystalline phase is in equilibrium with the liquid micellar phase the conditions are optimal for emulsions to form. The interface of the emulsion droplets (1 to 100 pm) are stabilized by the lamellar liquid crystal. Both the micelles and the emulsions may be of the oil in water (o/w) or water in oil (w/o) type. Obviously, substances that otherwise are insoluble in the dispersion medium may be solubilized in the micelles or emulsified in the emulsions. For a more thorough analysis, the reader is directed to pertinent references in the literature. ... 

More lipophilic surfactants form larger, nonspherical micelles, vesicles, or lyotropic liquid crystalline phases at rather low concentrations in water. For example, at temperatures above those where the chains form crystalline structures, phospholipids and other surfactants with two relatively long hydrocarbon chains typically form the lamellar liquid crystalline phase consisting of many parallel surfactant bilayers separated by water layers. The hydrocarbon interiors of the bilayers are rather fluid as in micelles. Of course, in this case a true phase separation occurs beginning at a definite surfactant concentration. 

Since the chain length of tallow components is essentially between C14 and Cis, the total number of different structures in the softener active exceeds 15 [26], The raw material also contains mono- and usually tri-tallow derivatives. Most of those molecules are not water soluble and do not associate into micelles, but form stable colloidal dispersions in water. Maltese crosses can be observed using an optical microscope under polarized light (Figure 12.7), revealing the presence of strongly birefringent particles, typical of liquid crystalline phases [88,89],... 

The presence of liquid-crystalline material at the emulsion interface has been shown by electron microscopy using the freeze-etching technique 18). Typical liquid-crystalline structures are shown in Figure 16. These liquid-crystalline compositions are viscous, and the lamellar phase displays pseudoplastic rheology. The lamellar phase is the most important of all liquid-crystalline phases for emulsion stability. The presence of a liquid-crystalline phase causes a reduction of the available London-van der Waals forces for coalescence 16). As a consequence of the reduction of the influence of these dispersion forces and the high viscosity of the liquid-crystal layer, the time for coalescence is increased dramatically. 

The formation of liquid-crystal structures also reduces the need for dispersant, because much of the liquid crystal consists of water and oil phases. A typical emulsifier concentration of about 7% is sufficient to give 40% liquid-crystalline phase in one-to-one emulsion 16). 

In most of the emulsions, surfactants alone are not able to sufficiently reduce the interfacial tension between oil and water. Cosurfactants further reduce the interfacial tension and increase the fluidity of the interfacial film. The use of cosurfactants imparts sufficient flexibility to the interfacial film to take up different curvatures, which may be required to form microemulsion over a wide range of proportions of the components. The main role of cosurfactant is to destroy liquid crystalline or gel structures that form in place of a microemulsion phase. Typically used cosurfactants are short chain alcohols (C3-C8), glycols such as propylene glycol, medium chain alcohols, amines, or acids. - Cosurfactants are mainly used in microemulsion formulation for the following reasons ... 

---