Studies of Lyotropics

Lyotropic polymeric LC, formed by dissolving two aromatic polyamides in concentrated sulphuric acid, have been studied using variable-director 13C NMR experiments.324 The experimental line shapes at different angles w.r.t the external field were used to extract macromolecular order and dynamic in these ordered fluids. An interesting application of lyotropic LC is for the chiral discrimination of R- and S-enantiomers, and has recently been demonstrated by Courtieu and co-workers.325 The idea was to include a chiral compound 1-deutero-l-phenylethanol in a chiral cage (e.g., /1-cyclodextrin) which was dissolved and oriented by the nematic mean field in a cromolyn-water system. Proton-decoupled 2H NMR spectrum clearly showed the quad-rupolar splittings of the R- and S-enantiomers. The technique is applicable to water-soluble solutes. 

MAS has been applied to a highly viscous cubic phase of a lyotropic LC formed by 1-monooleolyl-rac-glycerol and water in order to obtain liquid-like and 13C spectra.330 Deuterium, sodium, and fluorine NMR spectroscopy have been applied to study the phase behaviour of several dilute lamellar systems formed by low concentrations of an ra-hexadecylpyridinium salt, a sodium salt (e.g., NaBr, NaCl, or sodium trifluoroacetate), 1-hexanol, and D20.331 The 2H, 19F, and 23Na splittings were used to monitor the phase equilibria. The last two studies are motivated by the search of new lyotropic LC for the alignment of biomolecules. 

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Lockwood, F. E. Benchaita, M. T. Friberg, S. E. "Study of Lyotropic Liquid Crystals in Viscometric Flow and Elastohydrodynamic Contact," ASLE Trans., 1987, Vol. 30, pp. 539-548. 

The present review is dedicated to the memory of Professor Kunieda Hironobu and his fundamental scientific contribution in the study of lyotropic liquid crystals. 

Converse flexoelectric studies of lyotropic liquid crystals, such as vesicles, is still an active subject. Notably, the sensory mechanism of outer hair cell composite membranes " can be understood by the flexoelectric properties of the lipid bilayer. The converse of this effect, i.e., a voltage-generated curvature, has also been observed and was discussed by Todorov et Another related phenomenon is the ferroelectricity which results from the tilted layered structures of chiral molecules, which has been discussed extensively since the 1980s.Ferroelectric phases are called... 

A. C. Tracey, P. Diehl Lyotropic Liquid Crystals 18 figures, 3 tables. IV, 85 pages. 1975 Contents Nuclear Magnetic Resonance Studies in Lyotropic Liquid Crystals Introduction.— Studies of Lyotropic Liquid Crystals. — Studies of Molecular and Ionic Species Dissolved in the Nematic Phase of Lyotropic Liquid Crystals. 

Radler M J, Landes B G, Nolan S J, Broomall C F, Chritz T C, Rudolf P R, Mills M E and Bubeck R A (1994) In situ X-ray scattering studies of lyotropic liquid crystalline PBO and PBZT monolament drawing, J Polym, Sci Part B Polym Phys 32 2567-2573. 

Halle, B. and Furo, I., NMR studies of lyotropic liquid crystals, in Phase Transitions in Complex Fluids, Toledano, P. and Figueiredo Neto, A. M. (Eds), World Scientific, Singapore, 1998, pp. 81-109. 

Measurement of ligand-binding by proteins or peptides Study of lyotropic salt effects in hydro-phobic chromatography... 

In the field of natural products, there is growing interest in the increasing range of carbohydrates that are being found to be liquid crystalline [78-80], swinging interest back to the role of liquid crystals in biological systems, where recent studies of lyotropic mesomorphism in deoxyguanosine... 

Soviet specialists have made a basic contribution to the creation and evolution of Ais field, particularly in the study of lyotropic systems as the basis for high-strength fibers and the first thermotropic liquid-crystal polymers which were created from comb-shaped macromolecules. 

Recent solid state NMR studies of liquid crystalline materials are surveyed. The review deals first with some background information in order to facilitate discussions on various NMR (13C, ll, 21 , I9F etc.) works to be followed. This includes the following spin Hamiltonians, spin relaxation theory, and a survey of recent solid state NMR methods (mainly 13C) for liquid crystals on the one hand, while on the other hand molecular ordering of mesogens and motional models for liquid crystals. NMR studies done since 1997 on both solutes and solvent molecules are discussed. For the latter, thermotropic and lyotropic liquid crystals are included with an emphasis on newly discovered liquid crystalline materials. For the solute studies, both small molecules and weakly ordered biomolecules are briefly surveyed. 

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. 

In Vivo Proton NMR Studies in Skeletal Musculature is covered by J. Machann, G. Steidle, C. Thamer, I. Mader and F. Schick this is followed by an account on Quality Assessment of Horticultural Products by NMR from B. P. Hills and C. J. Clark Applications of NMR to Thermostable Proteins is reviewed by E. Alberti, R. Consonni and L. Zetta High Pressure NMR Studies on Lyotropic Lipid Mesophases and Model Biomembrances are reviewed by R. Winter W. S. Veeman discusses Diffusion in a Closed Sphere finally L. Griffiths covers Automatic Analysis of NMR Spectra. It is a pleasure for me to record my gratitude to all of the authors and to the production team for this volume. 

The study of thermotropic, as well as of lyotropic LC polymers is directly linked to a series of practical tasks, regarding the construction of polymeric materials with set properties. For instance, making use of anisotropy of the LC state in processing (particularly in moulding) of polymeric materials discloses impressive prospects for the production of so called high modulus fibers and films 18 25). 

The brief data presented in this chapter concerning the initial steps of structure formation in LC polymer solutions, are significant from two viewpoints. On the one hand, the study of these processes provides quantitative information about the molecular parameters and IMM of LC polymers, which is the basis for the understanding and prediction of physico-chemical behaviour of polymeric liquid crystals in bulk. On the other hand, understanding of the features of intramolecular structure formation in dilute solution, reveals broad prospects for the investigation of the formation of lyotropic LC systems of polymers with mesogenic side groups, which is in its infancy 195). 

The chemical potentials measured so far do not allow the formulation of thermodynamic criteria for the formation of lyotropic mesophases. Some qualitative remarks, however, can be made. Of particular interest are Ekwall s studies of the relations between the water binding of the mesophases, their ionization, x-ray parameters, and vapor pressures (4). For common soaps at room temperature mesophases can be observed only in the presence of amounts of water that hydrate the ionic and polar groups. Hydration is therefore characteristic of aqueous lyotropic mesophases as well as micellar systems (1, 2, 3). The binding of counterions to the micelles and to the mesoaggregates seems to be of a similar electrostatic nature. The addition of NaCl greatly affects the lamellar phase D and, to a lesser extent, phase E in these phases the counterions are more strongly bound than by micelles in the solution... 

The widespread interest in transport across membranes of living cells has led to studies of diffusion in lyotropic liquid crystals. Biological membranes are generally thought to contain single bimolecular leaflets of phospholipid material, leaflets which are like the large, flat micelles of lamellar liquid crystals. No effort is made here to review the literature on transport either across actual cell membranes or across single bimolecular leaflets (black lipid films) which have often been used recently as model systems for membrane studies. Instead, experiments where lamellar liquid crystals have been used as model systems are discussed. 

Interest in thermotropic liquid crystals has focussed mainly on macroscopic properties studies relating these properties to the microscopic molecular order are new. Lyotropic liquid crystals, e.g. lipid-water systems, however, are better known from a microscopic point of view. We detail the descriptions of chain flexibility that were obtained from recent DMR experiments on deuterated soap molecules. Models were developed, and most chain deformations appear to result from intramolecular isomeric rotations that are compatible with intermodular steric hindrance. The characteristic times of chain motions can be estimated from earlier proton resonance experiments. There is a possibility of collective motions in the bilayer. The biological relevance of these findings is considered briefly. Recent similar DMR studies of thermotropic liquid crystals also suggest some molecular flexibility. 

Roux, D. and Safinya, C.R. (1988) A synchrotron X-ray study of competing undulation and electrostatic interlayer interactions in fluid multimembrane lyotropic phases. J. Physique France, 49, 307-318. 

There have been a lot of studies of cholesteric films and gels in order to exploit their potential as specific optical media and as other functional materials. Most of the preparations were achieved by modification or improvement of previous attempts to immobilize the cholesteric structure of cellulose derivatives into the bulky networks either by crosslinking of cellulosic molecules with functional side-chains in the liquid-crystalline state [203], or by polymerization of monomers as lyotropic solvents for cellulose derivatives [204-206],... 

The study of liquid crystals rapidly becomes complex because both the thermotropic and lyotropic types are polymorphic. The lyotropic type exists in at least six phases according to Brown Johnson. Materials of this type generally exhibit a molecular weight in the range of 250-500. Many of these materials are described as lipids, and frequently as phospholipids. On addition of water to a crystal composed of these materials, the molecular structure initially collapses to form a lamellar structure. Further dilution may result in additional structural changes before an isotropic solution is reached. 

Solutions of the aromatic polyamides (PpBA, PpPTA and PmPTA), the polybenzazoles (PBT and PBO), poly(benzyl glutamate) (PBG) and hydroxypropylcellulose (HPC) are the most studied main chain lyotropic systems and our understanding of the behaviour of lyotropics is based on investigations of this relatively small number of materials (Moldenaers, 1996). They form main chain liquid crystals because of their rigid molecular structure in the appropriate solvents. Two kinds of solvents are used (Collyer, 1996) ... 

The surfactant association structures have a long history of research ranging from the McBaln introduction of the aqueous micellar concept(1.) over the interpretation of mlcelllzatlon as a critical phenomenon — — to the analysis of the structure of lyotropic liquid crystals(A) and the comprehensive picture of the phase relations in water/surfactant/amphlphile systems.These studies have emphasized the relation between the association structures in isotropic liquid solutions and the liquid crystalline phases. Parallel extensive investigations in crystalline/ liquid crystalline lipid structureshave provided important insight in the mechanisms of the associations. 

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