Cholesteryl liquid crystals

Liquid crystals were discovered by an Austrian biologist, Frederich Reinitzer, in 1888. Reinitzer found that cholesteryl benzoate, a biological chemical, melts to form a hazy liquid. At a higher temperature, the haziness disappears. This clear state is what we know now as a liquid crystal. 

Several mixtures of hexanethiol capped gold nanopartides and triphenylene based discotic LCs have been studied. These mixtures display liquid crystal behavior (columnar mesophases) and an enhancement in the DC conductivity, due to the inclusion of gold nanoparticies into the matrix of the organic LC [70]. Other studies of mixtures of gold nanoparticies with mesogens indude a series of cholesteryl phenoxy alkanoates. The inclusion of the nanopartides does not change the inherent liquid crystal properties of the cholesteryl derivative but the mesophases are thermally stabilized [71]. 

Thermotropic cholesterics were officially discovered2 in 1888 by the Austrian botanist Friederich Reinitzer, while studying the melting of cholesterol esters cholesteryl benzoate first melted to give a cloudy liquid that, at higher temperature, turned into an ordinary clear liquid. The cloudy liquid (the mesophase) was a thermotropic cholesteric liquid crystal. These phases... 

The phase transitions of cholesteryl nonanoate have been studied with a new apparatus for thermal analytical microscopy. The enantiomer ratio of some chiral sulphoxides can be changed from racemic to a modest preference for one enantiomeric form by dissolution in a cholesteryl ester in its liquid-crystalline ( cholesteric ) state. 5,6-Epoxycholestan-3-yl p-nitrobenzoates exhibit liquid-crystal properties, but 5,6-diols and dibromides are inactive. ... 

The history of liquid crystals started with the pioneer works of Reinitzer and Lehmann (the latter constructed a heating stage for his microscope) at the end of the nineteenth century. Reinitzer was studying cholesteryl benzoate and found that this compound has two different melting points and undergoes some unexpected color changes when it passes from one phase to another [1]. In fact, he was observing a chiral nematic liquid crystal. 

Liquid Crystals Liquid-crystal phases may occur between the solid and the liquid phase. Cholesteryl myristate, for example, exists in a liquid-crystal phase between 71 and 85°C [6]. The appearance of liquid-crystal phases depends on the molecular structure. Compounds with elongated structures that are fairly rigid in the central part of the molecule are likely candidates for liquid crystals. The homologous series of p-alkoxybenzylidene-p-n-butylanilines is just one example for compounds with liquid-crystal phases. An excellent introduction to liquid crystals and their properties has been written by Collings [6]. 

Mesophase materials are possible for all three classes of molecules. Biological mesophases were already discovered in the middle of the 19th Century. Reinitzer later described the special two-stage melting of cholesteryl benzoate. These materials were then named liquid crystals by Lehmann in 1904 5). Small molecule mesophase materials will be referred to from time to time in this review as reference materials. 

Price and Wendorff31 > and Jabarin and Stein 32) analyzed the solidification of cholesteryl myristate. Under equilibrium conditions it changes at 357.2 K from the isotropic to the cholesteric mesophase and at 352.9 K to the smectic mesophase (see Sect. 5.1.1). At 346.8 K the smectic liquid crystal crystallized to the fully ordered crystal. Dilatometry resulted in Avrami exponents of 2, 2, and 4 for the respective transitions. The cholesteric liquid crystal has a second transition right after the relatively quick formation of a turbid homeotropic state from the isotropic melt. It aggregates without volume change to a spherulitic texture. This process was studied by microscopy32) between 343 and 355.2 K and revealed another nucleation controlled process with an Avrami exponent of 3. 

Adamski and Klimczyk analyzed cholesteryl pelargonate36) and caproate 37) liquid crystal to fully-ordered-crystal transitions over a temperature range of about 25 K. Again, the appearance of the fully ordered crystals was that of a spherulitic superstructure. The nucleation was time dependent, and the linear growth rate of the spherulites decreased with decreasing temperature by a factor 1/2 to 1/3, in contrast to the nonanoate and acetate. The Avrami exponent was close to 4 as judged from the measurement of the crystallized volume in the field of view under the microscope. 

Tsuji, K., Sorai, M. and Seki, S. New finding of glassy liquid crystal — a non-equilibrium state of cholesteryl hydrogen phthalate. Bull. Chem. Soc., Japan 44, 1452 (1971)... 

Name 2-Ethylhexyl carbonate coated or bonded on cholesteryl silica (room temperature liquid crystal) Structure ... 

Cytochrome c Capillary etched with liquid crystals (cholesteryl or cyanopentoxy modified) 60 mM Citric acid and 50 mM P-alanine, pH 3.00 700 or 500 mm x 50 pm i.d 450 or 250 mm effective length, open tubular CEC... 

Figure 4. Effect on the separation of isomers on a liquid crystal column (20 m cholesteryl cinnamate) when increasing column temperature to mesophase transition temperature and beyond (left), and then gradually cooling (right) below mesophase transition. Peaks represent, in increasing retention time, hexadecane, heptadecane, (Z)-, and (E)-9-tetradecen-l-ol acetate.

Cholesteryl esters, as cholesteric liquid crystals, seem to offer no particular advantages as media for asymmetric synthesis. Several reactions conducted in... 

Since the description of liquid crystallinity for cholesteryl benzoate and cholesteryl acetate at the end of the 19th century by Reinitzer [1], an intense activity has been devoted to thermotropic liquid crystals, especially since the early 1970s, owing to the fabrication and application of liquid crystal displays in electronic technology. 

The term liquid crystal was first applied to compounds that, unlike most compounds that melt in a single step at a definite temperature, show one or more well-defined phases between the solid and the true liquid. Otto Lehmann in 1888 was contacted by Friedrich Reinitzer who had observed that crystalline cholesteryl benzoate, on heating, seemed to have two melting points.At 145.5° C a cloudy liquid forms that, on further heating, changes sharply to a clear liquid at 178.5° C. On cooling the reverse order of phases was found. The turbid liquid is doubly refracting, like the anisotropic crystals described in Chapter 5, hence the... 

Craven, B. M., and DeTitta, G. T. Cholesteryl myristate structure of the crystalline solid and mesophases. J. Chem. Soc., Perkin Trans. 77,814-822 (1976). Templer, R., and Attard, G. The world of liquid crystals. The fourth state of matter. New Scientist 1767 25-29 (1991). 

A second category of liquid crystals is the type produced when certain substances, notably the esters of cholesterol, are heated. These systems are referred to as thermotropic liquid crystals and, although not formed by surfactants, their properties will be described here for purposes of comparison. The formation of a cloudy liquid when cholesteryl benzoate is heated to temperatures between 145 and 179°C was first noted in 1888 by the Austrian botanist Reinitzer. The name liquid crystal was applied to this cloudy intermediate phase because of the presence of areas with crystal-like molecular stmcture within this solution. 

Although the technical applications of low molar mass liquid crystals (LC) and liquid crystalline polymers (LCP) are relatively recent developments, liquid crystalline behavior has been known since 1888 when Reinitzer (1) observed that cholesteryl benzoate melted to form a turbid melt that eventually cleared at a higher temperature. The term liquid crystal was coined by Lehmann (2) to describe these materials. The first reference to a polymeric mesophase was in 1937 when Bawden and Pirie (2) observed that above a critical concentration, a solution of tobacco mosaic virus formed two phases, one of which was bireffingent. A liquid crystalline phase for a solution of a synthetic polymer, poly(7-benzyl-L-glutamate), was reported by Elliot and Ambrose (4) in 1950. 

Variable-temperatxure H NMR studies on human bile show that considerable dynamic structural information is available, particularly at very high fields, e.g. 600 MHz. Hie micellar cholesteryl esters that are abundant in bile appear to show liquid crystal behaviour, and it is possible to use NMR measurements to map the phase diagram for the complex biliary matrix. 

Several cholestrlc liquid crystals have been evaluated as stationary phases In HPLC W. Cholesteric esters, for the most part, are liquid crystals In the range 20 to 100°C. Cholesteryl-... 

Van Deun et al. were the first to observe near-infrared luminescence from lanthanide-doped liquid crystal mixtures They studied the spectroscopic properties of the lanthanide(III) / -diketonate complexes [L (dbm)3(phen)], where Ln = neodymium, erbium, ytterbium, and dbm is dibenzoylmethane, in the liquid crystal MBBA. By incorporation of an erbium(III)-doped nematic liquid crystal (ErCls dissolved in E7) in the pores of microporous silicon, narrowing of the erbium(III) emission band in the near-infrared was observedJ Luminescent optically active liquid crystals were obtained by doping [Eu(tta)3-3H20] into a mixture of cho-lesteryl nonanoate, cholesteryl tetradecanoate and the ternary liquid crystal mixture ZLI1083 from MerckJ ... 

The discovery of the liquid crystal state should be traced back to a story taking place one hundred years ago. Austria botanist F. Reinitzer observed a peculiar phenomenon in 1888 — under a microscope (Reinitzer, 1888), cholesteryl nonanoate melted into a cloudy liquid at 145.5 °C as the temperature rose to 178.5 °C, it suddenly became clear. When cooling down, the substance briefly appeared violet-blue just before becoming an... 

In 1888 the Austrian botanist and chemist Friedrich Reinitzer, interested in the chemical function of cholesterol in plants, noticed that the cholesterol derivative cholesteryl benzoate had two distinct melting points. At 145.5°C (293.9°F) the solid compound melted to form a turbid fluid, and this fluid stayed turbid until 178.5°C (353.3°F), at which temperature the turbidity disappeared and the liquid became clear. On cooling the liquid, he found that this sequence was reversed. He concluded that he had discovered a new state of matter occupying a niche between the crystalline solid and liquid states the liquid crystalline state. More than a century after Reinitzer s discovery, liquid crystals are an important class of advanced materials, being used for applications ranging from clock and calculator displays to temperature sensors. 

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