Liquid crystal
Liquid crystals are substances that exhibit a phase of matter
that has properties between those of a conventional liquid, and
those of a solid crystal. For instance, a liquid crystal (LC)
may flow like a liquid, but have the molecules in the liquid
arranged and oriented in a crystal-like way. There are many
different types of LC phases, which can be distinguished based
on their different optical properties (such as birefringence).
When viewed under a microscope using a polarized light source, a
liquid crystal material will appear to have a distinct texture.
Each 'patch' in the texture corresponds to a domain where the LC
molecules are oriented in a different direction. Within a
domain, however, the molecules are well ordered. Liquid crystal
materials may not always be in an LC phase (just as water is not
always in the liquid phase: it may also be found in the solid or
gas phase). Liquid crystals can be divided into thermotropic and
lyotropic LCs. Thermotropic LCs exhibit a phase transition into
the LC phase as temperature is changed, whereas lyotropic LCs
exhibit phase transitions as a function of concentration.
Molecules that exhibit liquid crystal phases are called mesogens.
For a molecule to display an LC phase, it must generally be
rigid and anisotropic (i.e. longer in one direction than
another). Most mesogens fall into the 'rigid-rod' class (calamitic
mesogens), which orient based on their long axis. Disk-like (discotic)
mesogens are also known, and these orient in the direction of
their short axis. In addition to molecules, polymers and
colloidal suspensions can also form LC phases. For instance,
micrometre-sized objects (such as anisotropic colloids, latex
particles, clay platelets, and even some viruses, such as the
tobacco mosaic virus) can organize themselves in liquid crystal
phases.
The various LC phases (called mesophases) can be characterized
by the type of ordering that is present. One can distinguish
positional order (whether or not molecules are arranged in any
sort of ordered lattice) and orientational order (whether or not
molecules are pointing in the same direction), and moreover
order can be either short-range (only between molecules close to
each other) or long-range (extending to larger, sometimes
macroscopic, dimensions). Most thermotropic LCs will have an
isotropic phase at high temperature. That is, heating will
eventually drive them into a conventional liquid phase
characterized by random and isotropic molecular ordering (little
to no long-range order), and fluid-like flow behavior. Under
other conditions (for instance, lower temperature), an LC might
inhabit one or more phases with significant anisotropic
orientational structure and long-range orientational order while
still having an ability to flow. The orientational order may be
quasicrystalline.
The ordering of liquid crystalline phases is extensive on the
molecular scale. This order extends up to the entire domain
size, which may be on the order of micrometres, but usually does
not extend to the macroscopic scale as often occurs in classical
crystalline solids. However, some techniques (such as the use of
boundaries or an applied electric field) can be used to enforce
a single ordered domain in a macroscopic liquid crystal sample.
The ordering in a liquid crystal might extend along only one
dimension, with the material being essentially disordered in the
other two directions.
Thermotropic phases are those that occur in a certain
temperature range. If the temperature is raised too high,
thermal motion will destroy the delicate cooperative ordering of
the LC phase, pushing the material into a conventional isotropic
liquid phase. At too low a temperature, most LC materials will
form a conventional (though anisotropic) crystal. Many
thermotropic LCs exhibit a variety of phases as temperature is
changed. For instance, a particular mesogen may exhibit various
smectic and nematic (and finally isotropic) as temperature is
increased.
One of the most common LC phases is the nematic, where the
molecules have no positional order, but they do have long-range
orientational order. Thus, the molecules flow and are randomly
distributed as in a liquid, but they all point in the same
direction (within each domain). Most nematics are uniaxial: they
have one axis that is longer and preferred, with the other two
being equivalent (can be approximated as cylinders). Some liquid
crystals are biaxial nematics, meaning that in addition to
orienting their long axis, they also orient along a secondary
axis.
The smectic phase is one where in addition to orientation order,
the mesogens are grouped into layers, enforcing long-range
positional order in one direction. In the smectic A phase, the
molecules point perpendicular to the layer planes, whereas in
the smectic C phase, the molecules are tilted with respect to
the layer planes. In hexatic phases, the mesogens in a
particular layer take on a roughly hexagonal close-packed
ordering, with typically no registry between adjacent smectic
layers. It is also possible to find examples of liquid crystals
where the registry between layers is fairly strong, hence there
is three dimensional positional (and possibly even orientational)
order. These phases are called crystal mesophases, and are in
fact nearly as ordered as solid crystals (although they still
exhibit fluid-like flow).
The chiral nematic phase exhibits chirality (handedness). This
phase is often called the cholesteric phase because it was first
observed for cholesterol derivatives. Only chiral molecules
(i.e.: those that lack inversion symmetry) can give rise to such
a phase. This phase exhibits a twisting of the molecules along
the director, with the molecular axis perpendicular to the
director. The finite twist angle between adjacent molecules is
due to their asymmetric packing, which results in longer-range
chiral order. In the smectic C* phase, the molecules orient
roughly along the director, with a finite tilt angle, and a
twist relative to other mesogens. This results in, again, a
spiral twisting of molecular axis along the director.
The chiral pitch refers to the distance (along the director)
over which the mesogens undergo a full 360º twist (but note that
the structure repeats itself every half-pitch, since the
positive and negative directions along the director are
equivalent). The pitch may be varied by adjusting temperature or
adding other molecules to the LC fluid. For many types of liquid
crystals, the pitch is on the same order as the wavelength of
visible light. This causes these systems to exhibit unique
optical properties, such as selective reflection. These
properties are exploited in a number of optical applications.
Disk-shaped mesogens can orient themselves in a layer-like
fashion known as the discotic nematic phase. If the disks pack
into stacks, the phase is called a discotic columnar. The
columns themselves may be organized into rectangular or
hexagonal arrays. Chiral discotic phases, similar to the chiral
nematic phase, are also known.
Biological liquid crystals
Lyotropic liquid-crystalline nanostructures are abundant in
living systems. Accordingly, lyotropic liquid crystals attract
particular attention in the field of biomimetic chemistry. In
particular, biological membranes and cell membranes are a form
of liquid crystal. Their constituent rod-like molecules (e.g.,
phospholipids) or lecithins are organized perpendicularly to the
membrane surface, yet the membrane is fluid and elastic. The
constituent molecules can flow in-plane quite easily, but tend
not to leave the membrane, and can flip from one side of the
membrane to the other with some difficulty. These liquid crystal
membrane phases can also host important proteins such as
receptors freely "floating" inside, or partly outside, the
membrane.
Many other biological structures exhibit LC behavior. For
instance, the concentrated protein solution that is extruded by
a spider to generate silk is, in fact, a liquid crystal phase.
The precise ordering of molecules in silk is critical to its
renowned strength. DNA and many polypeptides can also form LC
phases. Since biological mesogens are usually chiral, chirality
often plays a role in these phases.
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