Lyotropic
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A liquid crystalline mesophase is called lyotropic (a
portmanteau A portmanteau word, or portmanteau (, ) is a blend of wordslyo- "dissolve" and -tropic "change" ) if formed by dissolving an
amphiphilic An amphiphile (from the Greek αμφις amphis, both, and φιλíα philia, love, friendship), or amphipath, is a chemical compound possessing both hydrophilic (''water-loving'', polar) and lipophilic (''fat-loving'') properties. Such a compo ...
mesogen A mesogen is a compound that displays liquid crystal properties. Mesogens can be described as disordered solids or ordered liquids because they arise from a unique state of matter that exhibits both solid- and liquid-like properties called the li ...
in a suitable solvent, under appropriate conditions of concentration, temperature and pressure. A mixture of soap and water is an everyday example of a lyotropic liquid crystal. Historically, the term was used to describe the common behavior of materials composed of amphiphilic molecules upon the addition of a
solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
. Such molecules comprise a water-loving
hydrophilic A hydrophile is a molecule or other molecular entity that is attracted to water molecules and tends to be dissolved by water.Liddell, H.G. & Scott, R. (1940). ''A Greek-English Lexicon'' Oxford: Clarendon Press. In contrast, hydrophobes are ...
head-group (which may be ionic or non-ionic) attached to a water-hating,
hydrophobic In chemistry, hydrophobicity is the physical property of a molecule that is seemingly repelled from a mass of water (known as a hydrophobe). In contrast, hydrophiles are attracted to water. Hydrophobic molecules tend to be nonpolar and, t ...
group. The micro-phase segregation of two incompatible components on a nanometer scale results in different type of solvent-induced extended anisotropic arrangement, depending on the volume balances between the hydrophilic part and hydrophobic part. In turn, they generate the long-range order of the phases, with the
solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
molecules filling the space around the compounds to provide fluidity to the system. In contrast to thermotropic liquid crystals, lyotropic liquid crystals have therefore an additional degree of freedom, that is the concentration that enables them to induce a variety of different 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

Examples of amphiphilic compounds are the salts of fatty acids,
phospholipids Phospholipids, are a class of lipids whose molecule has a hydrophilic "head" containing a phosphate group and two hydrophobic "tails" derived from fatty acids, joined by an alcohol residue (usually a glycerol molecule). Marine phospholipids t ...
. Many simple amphiphiles are used as detergents. A mixture of soap and water is an everyday example of a lyotropic liquid crystal. Biological structures such as fibrous proteins showings relatively long and well-defined hydrophobic and hydrophilic ‘‘blocks’’ of aminoacids can also show lyotropic liquid crystalline behaviour.


Amphiphile self-assembly

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 hydrophobic effect is the observed tendency of nonpolar substances to aggregate in an aqueous solution and exclude water molecules. The word hydrophobic literally means "water-fearing", and it describes the segregation of water and nonpolar ...
". The aggregates formed by amphiphilic molecules are characterised by structures in which the hydrophilic head-groups expose their surface to aqueous solution, shielding 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 In colloidal and surface chemistry, the critical micelle concentration (CMC) is defined as the concentration of surfactants above which micelles form and all additional surfactants added to the system will form micelles. The CMC is an important c ...
(CMC) or the critical aggregation concentration (CAC)). At very low amphiphile concentration, the molecules will be dispersed randomly without any ordering. At slightly higher (but still low) concentration, above the CMC, self-assembled amphiphile aggregates exist as independent entities in equilibrium with monomeric amphiphiles in solution, but with no long ranged orientational or positional (translational) order. As a result, phases are isotropic (i.e. not liquid crystalline). These dispersions are generally referred to as ' micellar solutions', often denoted by the symbol L1, while the constituent spherical aggregates are known as '
micelles A micelle () or micella () (plural micelles or micellae, respectively) is an aggregate (or supramolecular assembly) of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension (also known as associated coll ...
'. At higher concentration, the assemblies will become ordered. 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 {{unreferenced, date=April 2017 A micellar cubic phase is a lyotropic liquid crystal phase formed when the concentration of micelles dispersed in a solvent (usually water) is sufficiently high that they are forced to pack into a structure having lon ...
', denoted by the symbol I1. This is a highly viscous, optically isotropic phase in which the micelles are arranged on a cubic lattice. Prior to becoming
macroscopic The macroscopic scale is the length scale on which objects or phenomena are large enough to be visible with the naked eye, without magnifying optical instruments. It is the opposite of microscopic. Overview When applied to physical phenomena a ...
liquid crystals, tactoids are formed, which are liquid crystal microdomains in an isotrophic phase. 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 A hexagonal phase of lyotropic liquid crystal is formed by some amphiphilic molecules when they are mixed with water or another polar solvent. In this phase, the amphiphile molecules are aggregated into cylindrical structures of indefinite lengt ...
', or more specifically the '
normal topology Normal(s) or The Normal(s) may refer to: Film and television * ''Normal'' (2003 film), starring Jessica Lange and Tom Wilkinson * ''Normal'' (2007 film), starring Carrie-Anne Moss, Kevin Zegers, Callum Keith Rennie, and Andrew Airlie * ''Norma ...
' hexagonal phase and is generally denoted by the symbol HI. At higher concentrations of amphiphile the '
lamellar phase Lamellar phase refers generally to packing of polar-headed long chain nonpolar-tail molecules in an environment of bulk polar liquid, as sheets of bilayers separated by bulk liquid. In biophysics, polar lipids (mostly, phospholipids, and rarely, gl ...
' 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 sheets separated by layers of water. Each bilayer is a prototype of the arrangement of
lipids Lipids are a broad group of naturally-occurring molecules which includes fats, waxes, sterols, fat-soluble vitamins (such as vitamins A, D, E and K), monoglycerides, diglycerides, phospholipids, and others. The functions of lipids include ...
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 In the mathematical field of topology, a homeomorphism, topological isomorphism, or bicontinuous function is a bijective and continuous function between topological spaces that has a continuous inverse function. Homeomorphisms are the isomorph ...
. Increasing the amphiphile concentration beyond the point where lamellar phases are formed would lead to the formation of the
inverse topology Inverse or invert may refer to: Science and mathematics * Inverse (logic), a type of conditional sentence which is an immediate inference made from another conditional sentence * Additive inverse (negation), the inverse of a number that, when a ...
lyotropic phases, namely the inverse cubic phases, the inverse hexagonal columnar phase (columns of water encapsulated by amphiphiles, (HII) and the inverse micellar cubic phase (a bulk liquid crystal sample with spherical water cavities). In practice inverse topology phases are more readily formed by amphiphiles that have at least two hydrocarbon 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. Even within the same phases, 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. The objects created by the 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 thermotropic liquid crystals do, forming large-scale versions of all the thermotropic phases (such as a nematic phase of rod-shaped micelles).


Host molecules

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.


Rod-like macromolecules

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
virus A virus is a submicroscopic infectious agent that replicates only inside the living cells of an organism. Viruses infect all life forms, from animals and plants to microorganisms, including bacteria and archaea. Since Dmitri Ivanovsk ...
es such as the
tobacco mosaic virus ''Tobacco mosaic virus'' (TMV) is a positive-sense single-stranded RNA virus species in the genus ''Tobamovirus'' that infects a wide range of plants, especially tobacco and other members of the family Solanaceae. The infection causes characteri ...
as well as synthetic macromolecules, such as Li2Mo6Se6 nanowire or colloidal suspensions of non-spherical colloidal particles.
Cellulose Cellulose is an organic compound with the formula , a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose is an important structural component of the primary cell w ...
and cellulose derivatives form lyotropic liquid crystal phases as do nanocrystalline ( nanocellulose) suspensions. Other examples include DNA and
Kevlar Kevlar (para-aramid) is a strong, heat-resistant synthetic fiber, related to other aramids such as Nomex and Technora. Developed by Stephanie Kwolek at DuPont in 1965, the high-strength material was first used commercially in the early 1970s a ...
, 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 Self-assembly is a process in which a disordered system of pre-existing components forms an organized structure or pattern as a consequence of specific, local interactions among the components themselves, without external direction. When the ...
.


Disk-like macromolecules / Nanosheets

Examples of lyotropic liquid crystals can also be generated using 2D nanosheets. The most striking example of a true nematic phase has been demonstrated for many smectite
clays Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4). Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...
. The issue of the existence of such a lyotropic phase was raised by Langmuir in 1938, but remained an open question for a very long time and was only confirmed recently. With the rapid development of nanosciences, and the synthesis of many new anisotropic 2D nanoparticles, the number of such Nematic mesophase based on 2D nanosheet has increased quickly, with, for example graphene oxide colloidal suspensions. Noteworhty, a lamellar phase was even discovered, H3Sb3P2O14, which exhibits hyperswelling up to ~250 nm for the interlamellar distance.


References


Further reading

* * {{cite book , author=Fennell Evans D. and Wennerström H. , title= The Colloidal Domain , location = New York , publisher=
Wiley VCH Wiley-VCH is a German publisher owned by John Wiley & Sons. It was founded in 1921 as Verlag Chemie (meaning "Chemistry Press": VCH stands for ''Verlag Chemie'') by two German learned societies. Later, it was merged into the German Chemical Socie ...
, date=1999 , isbn=0-471-24247-0 Chemical properties Phases of matter Liquid crystals