Liquid crystal materials other lyotropic phases

There are some materials that exhibit more than one transition in changing from the solid to the liquid state. The molecular ordering in these mesophases lies between that of a solid and that of an isotropic liquid. This kind of material is known as a liquid crystal. Liquid crystals show physical properties in both the solid and liquid states. There are two types of liquid crystal one is lyotropic, whose phase transition is caused by changing the concentration or pH value of the solution, and the other is thermotropic, whose phase transition occurs on changing the temperature. 

This chapter focuses on the fixation of lyotropic liquid crystalline phases by the polymerization of one (or more) component(s) following equilibration of the phase. The primary emphasis will be on the polymerization of bicontinuous cubic phases, a particular class of liquid crystals which exhibit simultaneous continuity of hydrophilic — usually aqueous — and hydrophobic — typically hydrocarbon — components, a property known as bicontinuity (1), together with cubic crystallographic symmetry (2). The potential technological impact of such a process lies in the fact that after polymerization of one component to form a continuous polymeric matrix, removal of the other component creates a microporous material with a highly-branched, monodisperse, triply-periodic porespace (3). 

As their name implies, liquid crystals are materials whose structures and properties are intermediate between those of isotropic liquids and crystalline solids (2). They can be of two primary types. Thermotropic liquid crystalline phases are formed at temperatures intermediate between those at which the crystalline and isotropic liquid phases of a mesogenic compound exist. Substances which exhibit thermotropic phases are generally rod- or disc-like in shape, and contain flexible substituents attached to a relatively rigid molecular core. Lyotropic liquid crystalline phases are formed by amphiphilic molecules (e.g. surfactants) in the presence of small amounts of water or other polar solvent. In general, the constituent molecules in a liquid crystal possess orientational order reminiscent of that found in the crystalline phase, yet retain some degree of the fluidity associated with the isotropic liquid phase. 

Liquid crystals combine properties of both liquids (fluidity) and crystals (long range order in one, two, or three dimensions). Examples of liquid crystalline templates formed by amphiphiles are lyotropic mesophases, block copolymer mesophases, and polyelectrolyte-suxfactant complexes. Their morphological complexity enables the template synthesis of particles as well as of bulk materials with isotropic or anisotropic morphologies, depending on whether the polymerization is performed in a continuous or a discontinuous phase. As the templating of thermotropic liquid crystals is already described in other reviews [47] the focus here is the template synthesis of organic materials in lyotropic mesophases. 

Lyotropic liquid crystals are principally systems that are made up of amphiphiles and suitable solvents or liquids. In essence an amphiphilic molecule has a dichotomous structure which has two halves that have vastly different physical properties, in particular their ability to mix with various liquids. For example, a dichotomous material may be made up of a fluorinated part and a hydrocarbon part. In a fluorinated solvent environment the fluorinated part of the material will mix with the solvent whereas the hydrocarbon part will be rejected. This leads to microphase separation of the two systems, i.e., the hydrocarbon parts of the amphiphile stick together and the fluorinated parts and the fluorinated liquid stick together. The reverse is the case when mixing with a hydrocarbon solvent. When such systems have no bend or splay curvature, i.e., they have zero curvature, lamellar sheets can be formed. In the case of hydrocarbon/fluorocarbon systems, a mesophase is formed where there are sheets of fluorocarbon species separated from other such sheets by sheets of hydrocarbon. This phase is called the La phase. In the La phase the molecules are orientationally ordered but positionally disordered, and as a consequence the amphiphiles are arranged perpendicular to the lamellae. The La phase of lyotropics is therefore equivalent to the smectic A phase of thermotropic liquid crystals. 

There are two principal categories of mesophases, thermotropic and lyotropic. Thermotropic liquid crystals are formed within a particular range of temperature in a molten material, with no solvent present, whereas lyotropic liquid crystals are formed by some substances when they are dissolved in a solvent. Within each of these categories there are three distinct classes of mesophases, which were first identified by Friedel in 1922. The simplest of these to describe are the nematic and smectic classes, illustrated schematically in fig. 12.16. These phases are formed by long thin rigid molecules which tend to line up parallel to each other. 

It is now certain that metal carboxylates were the first metal-containing liquid crystals, reported in 1855 with Heinz s work on magnesium tetradecanoate. Then, many other mesomorphic mono-, di-, and tri-valent carboxylate complexes, with the general formula [M(02CC H2 +i)J (x=l, 2, 3) or [M2(02CC H2 +i)4] were prepared. Some of them were described in 1910 by Vorlander." These materials may show thermotropic nematic, smectic, cubic, and columnar mesophases, but also, when dissolved in water or alkanes, lyotropic mesophases. While not all of the compounds described in this section show columnar phases, it was decided to keep these materials together. 

In the phrase liquid-crystalline, the crystalline adjective refers to the faa that these materials are sufSdentiy ordered to diffract an X-ray beam in a way analogous to that of normal crystalline materials. On the other hand, the liquid part specifies that there is frequently sufSdent disorder for the material to flow like a liquid. liquid crystals can be divided into thermotropic, that exhibit a phase transition with change of temperature, and lyotropic, that exhibit phase transition as a function of both temperature and concentration of the LC molecules in a solvent. Both low molecular wdght materials and polymers " 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. LC networks of flexible chains have the following three properties (1) they can be extensively deformed (as described for elastomers throughout this book), (2) the deformation produces alignment of the chains, and (3) alignment of the chains is central to the formation of LC phases. Elastomers of this type have been the subject of numerous studies, as described in several detailed reviews. ... 

Most mesogenic salts derived from aliphatic acids, (R-COO) M (R = alkyl (normal and branched) or alkenyl M=Li, Na, K, Rb, Cs, NH4, Tl, Pb or other metal) form layered structures (lamellar phases, neat phases) that are similar to smectic A phases. However, mesogenic salts form double layers and are not miscible with smectic A phases [276]. Some of the materials show very complicated polymorphism with a large number of mesophases [276-279]. In general, the transition temperatures of the salts are quite high compared with those of nonpolar liquid crystals. Most of the salts can also form lyotropic liquid crystals. 

Simplistically stated, the hydrophobic effect may be defined as the tendency of water to reject any contact with substances of a nonpolar or hydrocarbon nature. The existence of this effect was first recognized in the study of the extremely low solubility of hydrocarbons in water. The principles involved were later successfully applied to the elucidation of the native conformation of protein molecules by Kauz-mann The application of these ideas to the study of membrane structures has been advanced by Singer. Recently, Tanford published an entire book on the hydrophobic effect, including the influence of this interaction on the formation of micelles, lipid bilayers, membranes and other ordered structures. Aside from Singer s and Tanford s" statements on the decisive role of the hydrophobic effect on lyotropics, the lyotropic liquid-crystal literature seems peculiarly unaware of this phenomenon. Winsor s extensive review with its systematic analysis (R-theory) of the many lyotropic phases does not take the hydrophobic effect into account. More recent reviews of lyotropic liquid crystals do not mention the phenomenon. We hope that the present discussion will help to advance the realization of the importance of the hydrophobic effect to lyotropics. The material of the following sections is taken chiefly from Ref. [3] with some assistance from Refs. [2] and [4]. 

Lyotropic liquid crystals are obtained when an appropriate concentration of a material is dissolved in a solvent (Collings and Hird 1997 Neto et al. 2005). The most common systems are those formed by water and amphiphilic molecules (molecules that possess a hydrophilic part that interacts strongly with water and a hydrophobic part that is water insoluble), such as soaps, detergents and lipids. There are a number of phases observed in such water-amphiphiUc systems, as the composition and temperature are varied some appear as spherical micelles, and others possess ordered stmctures with one-, two-, or three-dimensional positional order. Examples of these kinds of molecules are soaps and various phospholipids, like those present in cell membranes (Lukask and Harden 1985). 

In 1997, Wang et al. were the first to show that ordered porous materials can be synthesized through electrodeposition using a lyotropic liquid crystal phase to electrodeposit porous plati-num.i i Since then, many other scientists have used this approach to make porous materials through... 

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