Lyotropic properties mesophases

Compared to other biomolecular systems, lipid bilayer membranes and lyotropic lipid mesophases in general have been shown to respond most sensitively to hydrostatic pressure. The methods used in the high pressure studies have mainly included X-ray and neutron diffraction, fluorescence, IR and Raman spectroscopy, light transmission and volumetric measurements. Only a small amount of work has been performed using NMR techniques combined with high-pressure, a field which was pioneered by Jonas and co-workers " although the method is very powerful, non-invasive and allows the study of a series of structural and dynamic properties of the systems in detail and with atomic resolution. 

Noted There are several types of thermotropic and lyotropic cubic mesophases, with different symmetry and miscibility properties when the space groups of these are known, they should be included in parentheses after the term Cub . 

Ferrocene was functionalized at the 1,1 -positions by a sugar moiety (1-amino-l-deoxy-D-sorbitol) and a long alkyl chain 44 in order to obtain lyotropic properties. The substituents, in particular the sugar framework, were selected in view of successful investigations performed with organic-type amphiphilic carbohydrate surfactants. Compound 44 showed both thermotropic and lyotropic mesophases. In the bulk, a SmA phase formed from 98 to 137 °C. When 44 was mixed with an excess of water, a fluid phase was obtained. For the thermotropic SmA phase, a r/-layer spacing... 

Solution properties indicate that the metal-poly(yne)s exist in a rod-like structure. They display lyotropic nematic mesophases [30] and form crystallites with a diameter of up to 50 nm [31]. Absorption and luminescence spectra of the polymers show that 7t-electron conjugation is expanded over the whole polymer chain, and third-order non-linear optical properties are exhibited. For polymer 7 good photocurrents were found in sandwich-diodes. 

The cholesteric structure realized in polypeptide films is a clear example of the fi ozen lyotropic cholesteric mesophase which is relatively stable and retains its properties up to a temperature of =200°C, above which decomposition of the polymer begins. 

Reinitzer discovered liquid crystallinity in 1888 the so-called fourth state of matter.4 Liquid crystalline molecules combine the properties of mobility of liquids and orientational order of crystals. This phenomenon results from the anisotropy in the molecules from which the liquid crystals are built. Different factors may govern this anisotropy, for example, the presence of polar and apolar parts in the molecule, the fact that it contains flexible and rigid parts, or often a combination of both. Liquid crystals may be thermotropic, being a state of matter in between the solid and the liquid phase, or they may be lyotropic, that is, ordering induced by the solvent. In the latter case the solvent usually solvates a certain part of the molecule while the other part of the molecule helps induce aggregation, leading to mesoscopic assemblies. The first thermotropic mesophase discovered was a chiral nematic or cholesteric phase (N )4 named after the fact that it was observed in a cholesterol derivative. In hindsight, one can conclude that this was not the simplest mesophase possible. In fact, this mesophase is chiral, since the molecules are ordered in... 

Finally, much work remains to be done on concentrated micellar solutions, which have been poorly investigated compared to the dilute regime. Interesting properties, such as lyotropic mesophase behavior, are expected to be observed for these concentrated micellar solutions. 

Thermotropic liquid crystalline (LC) phases or mesophases are usually formed by rod-like (calamitic) or disk-like (discotic) molecules. Spheroidal dendrimers are therefore incapable of forming mesophases unless they are flexible, because this would allow them to deform and subsequently line up in a common orientation. However, poly(ethyleneimine) dendrimers were reported to exhibit lyotropic liquid crystalline properties as early as 1988 [123],... 

For therapeutical purposes, a likewise frequently used group of drug compounds are the nonsteroidal anti-inflammatory drugs (NSAID). Among the best known representatives of the aryl acetic acid derivatives is diclofenac as well as ibuprofen, an aryl propionic acid derivative. As both have acidic properties, they dissociate while being dissolved and may form salts with amphiphilic properties. Together with appropriate counterions these amphiphilic organic acids may form lyotropic mesophases with water even at room or body temperature, for example, diclofenac diethylamine... 

Advances in the chemistry of [M(CN)5L]" complexes, for M = Fe, Ru, and Os, have been reviewed.There has been rather little activity in the preparation of novel complexes, but considerable activity in studying the properties, especially solvatochromism and various aspects of kinetics of substitution, of known complexes. However there has been an attempted preparation of [Fe(CN)5(Ci2H25NH2)], in the hope of generating micelles or lyotropic liquid crystals. This preparation appeared to yield [Fe(CN)4(H20)(Ci2H25NH2)], whose alkali metal salts gave a hexagonal mesophase in water, but were also readily hydrolyzed to [Fe(CN)4(H20)2] . Heterobinuclear complexes of the form [(NC)5FeL ML 5] " " have been much studied, especially in relation to intramolecular electron transfer (see Section 5.4.2.2.5). 

Note 3 In lyotropic systems, biaxial nematic mesophases have been identified from the biaxial symmetry of their tensorial properties. 

Aldonamides 5 display smectic thermotropic as well as lyotropic mesophases [70,71] they form helical tubes with diameters between 40 and 500 A and lengths of several pm and have gelation properties [72-76]. 

The development is reviewed of liquid-crystalline polymers whose mesophase formation derives from the nature of the chemical units in the main chain. The emphasis lies primarily on highly aromatic condensation polymers and their applications. The general properties of nematic phases formed by such polymers are surveyed and some chemical structures capable of producing nematic phases are classified in relation to their ability to form lyotropic and thermotropic systems. The synthesis, properties, physical structure and applications of two of the most important lyotropic systems and of a range of potentially important thermotropic polymers are discussed with particular reference to the production and use of fibres, films and anisotropic mouldings. 

It is interesting that work on the internal motions of the molecules that produce lyotropic mesophases is more advanced. This is mainly because of the importance of the microscopic properties of these systems in solubilization and interfacial problems, problems which are encountered in industry as well as in cell membrane biology. The structural and functional roles of lipid molecules in biomembranes are much discussed investigations of the physicochemical properties of lipid media thus might provide orientations for biological studies. Moreover, the findings on the flexibility of the paraffinic chains in lyotropic mesophases might also be relevant to similar problems in thermotropic mesophases. 

Liquid crystalsare an intermediate state in which the molecules in a crystal can undergo a secondary phase transition to a mesophase, which gives them mobility in 1-2 directions. They are birefringent, but possess low properties like a liquid phase. Lyotropic liquid crystals form on uptake of water into a system that increases its mobility, and thermotropic liquid crystals can be disrupted by heating above a transition temperature. Cromolyn sodium (Cox et al., 1971), the HMG-CoA reductase inhibitor SQ33600 (Brittain et al., 1995), and the leukotriefienffagonist L-660,711 (Vadas et al., 1991) are examples of pharmaceuticals that can form liquid crystals. 

Amphiphilic lipopeptides with a hydrophobic paraffinic chain containing from 12 to 18 carbon atoms and a hydrophilic peptidic chain exhibit lyotropic meso-phases and good emulsifying properties. The X-ray diffraction study of the mesophases and of dry lipopeptides showed the existence of three types of mesomorphic structures lamellar, cylindrical hexagonal and body-centred cubic. Two types of polymorphism were also identified one as a function of the length of the peptidic chain and the other as a function of the water content of the mesophases. The emulsifying properties of the lipopeptides in numerous pairs of immiscible liquids such as water/ hydrocarbons and water/base products of the cosmetic industry showed that small amounts of lipopeptides easily give three types of emulsions simple emulsions, miniemulsions and microemulsions. 

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