Lyotropic liquid crystals

A lyotropic liquid crystal consists of two or more components that exhibit liquid-crystalline properties in certain concentration ranges. In the lyotropic phases, solvent molecules fill the space around the compounds to provide fluidity to the system. In contrast to thermotropic liquid crystals, these lyotropics have another degree of freedom of concentration that enables them to induce a variety of different phases.

A compound which has two immiscible hydrophilic and hydrophobic parts within the same molecule is called an amphiphilic molecule. Many amphiphilic molecules show lyotropic liquid-crystalline phase sequences depending on the volume balances between the hydrophilic part and hydrophobic part. These structures are formed through the micro-phase segregation of two incompatible components on a nanometer scale. Soap is an everyday example of a lyotropic liquid crystal.

The content of water or other solvent molecules changes the self-assembled structures. At very low amphiphile concentration, the molecules will be dispersed randomly without any ordering. At slightly higher (but still low) concentration, amphiphilic molecules will spontaneously assemble into micelles or vesicles. This is done so as to 'hide' the hydrophobic tail of the amphiphile inside the micelle core, exposing a hydrophilic (water-soluble) surface to aqueous solution. These spherical objects do not order themselves in solution, however. At higher concentration, the assemblies will become ordered. A typical phase is a hexagonal columnar phase, where the amphiphiles form long cylinders (again with a hydrophilic surface) that arrange themselves into a roughly hexagonal lattice. This is called the middle soap phase. At still higher concentration, a lamellar phase (neat soap phase) may form, wherein extended sheets of amphiphiles are separated by thin layers of water. For some systems, a cubic (also called viscous isotropic) phase may exist between the hexagonal and lamellar phases, wherein spheres are formed that create a dense cubic lattice. These spheres may also be connected to one another, forming a bicontinuous cubic phase.

The objects created by amphiphiles are usually spherical (as in the case of micelles), but may also be disc-like (bicelles), rod-like, or biaxial (all three micelle axes are distinct). These anisotropic self-assembled nano-structures can then order themselves in much the same way as liquid crystals do, forming large-scale versions of all the thermotropic phases (such as a nematic phase of rod-shaped micelles).

For some systems, at high concentration, inverse phases are observed. That is, one may generate an inverse hexagonal columnar phase (columns of water encapsulated by amphiphiles) or an inverse micellar phase (a bulk liquid crystal sample with spherical water cavities).

A generic progression of phases, going from low to high amphiphile concentration, is:

• Discontinuous cubic phase (micellar cubic phase)
• Hexagonal phase (hexagonal columnar phase) (middle phase)
• Bicontinuous cubic phase
• Lamellar phase
• Bicontinuous cubic phase
• Reverse hexagonal columnar phase
• Inverse cubic phase (Inverse micellar phase)

Even within the same phases, their self-assembled structures are tunable by the concentration: for example, in lamellar phases, the layer distances increase with the solvent volume. Since lyotropic liquid crystals rely on a subtle balance of intermolecular interactions, it is more difficult to analyze their structures and properties than those of thermotropic liquid crystals.

Similar phases and characteristics can be observed in immiscible diblock copolymers.