Lyotropic liquid crystal
Historically the term was used to describe materials composed of amphiphilic molecules upon the addition of a solvent. Such molecules comprise a water-loving 'hydrophilic' head-group (which may be ionic or non-ionic) attached to a water-hating, 'hydrophobic' group.
When in solution those groups of molecules aggregate together and the resulting different type of solvent-induced extended anisotropic arrangement generates the long-range order of the phases. As the concentration of amphiphilic molecules is increased, several different type of lyotropic liquid crystal structures occur in solution. Each of these different types has a different extent of molecular ordering within the solvent matrix, from spherical micelles to larger cylinders, aligned cylinders and even bilayered and multiwalled aggregates.
Types of lyotropic systems
A typical amphiphilic flexible surfactant can form aggregates through a self-assembly process that results of specific interactions between the molecules of the amphiphilic mesogen and those of the non-mesogenic solvent.
In aqueous media, the driving force of the aggregation is the "hydrophobic effect". The aggregates formed by amphiphilic molecules are characterised by structures in which the hydrophilic head-groups shield the hydrophobic chains from contact with water.
For most lyotropic systems aggregation occurs only when the concentration of the amphiphile exceeds a critical concentration (known variously as the 'critical micelle concentration' (CMC) or the 'critical aggregation concentration (CAC)'). Micellar solutions are often denoted by the symbol L1.
Above the CMC the self-assembled amphiphile aggregates exist as independent entities, in equilibrium with monomeric amphiphiles in solution, and with no long ranged orientational or positional (translational) order. These dispersions are generally referred to as 'micellar solutions', the constituent aggregates being known as 'micelles', and are 'isotropic' phases (i.e. not liquid crystalline).
True lyotropic liquid crystalline phases are formed as the concentration of amphiphile in water is increased beyond the point where the micellar aggregates are forced to be disposed regularly in space. For amphiphiles that consist of a single hydrocarbon chain the concentration at which the first liquid crystalline phases are formed is typically in the range 25-30 wt%.
Liquid Crystalline Phases and Composition/Temperature
The simplest liquid crystalline phase that is formed by spherical micelles is the 'micellar cubic', denoted by the symbol I1. This is a highly viscous, optically isotropic phase in which the micelles are arranged on a cubic lattice. At higher amphiphile concentrations the micelles fuse to form cylindrical aggregates of indefinite length, and these cylinders are arranged on a long-ranged hexagonal lattice. This lyotropic liquid crystalline phase is known as the 'hexagonal phase', or more specifically the 'normal topology' hexagonal phase and is generally denoted by the symbol HI.
At higher concentrations of amphiphile the 'lamellar phase' is formed. This phase is denoted by the symbol Lα and can be considered the lyotropic equivalent of a smectic A mesophase. This phase consists of amphiphilic molecules arranged in bilayer sheers separated by layers of water. Each bilayer is a prototype of the arrangement of lipids in cell membranes.
For most amphiphiles that consist of a single hydrocarbon chain, one or more phases having complex architectures are formed at concentrations that are intermediate between those required to form a hexagonal phase and those that lead to the formation of a lamellar phase. Often this intermediate phase is a bicontinuous cubic phase.
|Schematic showing the aggregation of amphiphiles into micelles and then into lyotropic liquid crystalline phases as a function of amphiphile concentration and of temperature.|
In principle, increasing the amphiphile concentration beyond the point where lamellar phases are formed would lead to the formation of the inverse topology lyotropic phases, namely the inverse cubic phases, the inverse hexagonal phase (HII) and the inverse micellar cubic phase. In practice inverse topology phases are more readily formed by amphiphiles that have at least two hyrocarbon chains attached to a headgroup. The most abundant phospholipids that are found in cell membranes of mammalian cells are examples of amphiphiles that readily form inverse topology lyotropic phases.
It is possible that specific molecules are dissolved in lyotropic mesophases, where they can be located mainly inside, outside, or at the surface of the aggregates.
Some of such molecules act as dopants, inducing specific properties to the whole phase, other ones can be considered simple guests with limited effect on the surrounding environment but possibly strong consequences on their physico-chemical properties, and some of them are used as probe to detect molecular-level properties of the whole mesophase in specific analytical techniques.
The term lyotropic has also been applied to the liquid crystalline phases that are formed by certain polymeric materials, particularly those consisting of rigid rod-like macromolecules, when they are mixed with appropriate solvents. Examples are suspensions of rod-like viruses such as the Tobacco Mosaic Virus as well as man-made colloidal suspensions of non-spherical colloidal particles. Other examples include DNA and Kevlar, which dissolve in sulfuric acid to give a lyotropic phase. It is noted that in these cases the solvent acts to lower the melting point of the materials thereby enabling the liquid crystalline phases to be accessible. These liquid crystalline phases are closer in architecture to thermotropic liquid crystalline phases than to the conventional lyotropic phases. In contrast to the behaviour of amphiphilic molecules, the lyotropic behaviour of the rod-like molecules does not involve self-assembly.
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