Liquids fluidity

Liquid crystals combine properties of both liquids (fluidity) and crystals (long range order in one, two, or three dimensions). Examples of liquid crystalline templates formed by amphiphiles are lyotropic mesophases, block copolymer mesophases, and polyelectrolyte-suxfactant complexes. Their morphological complexity enables the template synthesis of particles as well as of bulk materials with isotropic or anisotropic morphologies, depending on whether the polymerization is performed in a continuous or a discontinuous phase. As the templating of thermotropic liquid crystals is already described in other reviews [47] the focus here is the template synthesis of organic materials in lyotropic mesophases. 

A liquid has a definite volume but not a definite shape, with particles that stick firmly but not rigidly. Although the particles are held together by strong attractive forces and are in close contact with one another, they are able to move freely. Particle mobility gives a liquid fluidity and causes it to take the shape of the container in which it is stored. Note how water looks as a liquid in Figure 1.5b. 

The existence of structural elements (clusters) in liquid causes supplementary resistance during the movement through a tube (canal, capallaiy) this resistance increases with a diminution of the tube cross-section. In very thin tubes (nanocapillaries), if their diameters are compared with the sizes of structural elements, ordinary liquid apparently could not flow. Meanwhile, the second liquid fluidity, with a diminution of the tube cross-section, even increases owing to the reduction of turbulence. 

The state of an adsorbate is often described as mobile or localized, usually in connection with adsorption models and analyses of adsorption entropies (see Section XVII-3C). A more direct criterion is, in analogy to that of the fluidity of a bulk phase, the degree of mobility as reflected by the surface diffusion coefficient. This may be estimated from the dielectric relaxation time Resing [115] gives values of the diffusion coefficient for adsorbed water ranging from near bulk liquids values (lO cm /sec) to as low as 10 cm /sec. 

In summary, pure liquid water consists of HgO molecules held in a random, three-dimensional network that has a local preference for tetrahedral geometry but contains a large number of strained or broken hydrogen bonds. The presence of strain creates a kinetic situation in which HgO molecules can switch H-bond allegiances fluidity ensues. 

Figure 7.5 The Enhanced Fluidity Liquid Chromatography range. This occupies the volume in the phase diagram below the locus of critical temperatures, above and below the locus of critical pressures, and is composed mostly of the less volatile mobile-phase component. Reproduced by permission of the American Chemical Society.

Y. Cui and S. V. Olesik, High-performance liquid cliromatography using mobile phases with enhanced fluidity . Anal. Chem. 63 1812-1819 (1991). 

S. V. Olesik, Applications of enhanced-fluidity liquid chromatography in separation science an update , in Unified Chromatography, J. E. Parcher and T. L. Chester (Eds), ACS. Symposium Series 748, American Chemical Society, Wasliington, DC, pp 168-178 (2000). 

Flussigkeits-. liquid, fluid, hydraulic, hydrostatic. -bad, n. liquid bath, -dichtemesser, m. hydrometer, -druck, m. pressure of a liquid, hydrostatic pressure, -ffirderung, /. conveyance of liquids, -gemisch, n. mixture of liquids, liquid mixture, -grad, m. degree of fluidity viscosity. -gradmesser, m. viscosimeter. -Unse, /. (Micros.) immersion objective, -mass, n. liquid measure, -menge. 

If fluidity, the physical property of a substance that enables it to flow and incompressibility were the only properties required, any liquid that is not too thick might be used in a hydraulic system. However, a satisfactory liquid for a particular system must possess a number of other properties. The most important properties and some characteristics are discussed in the following paragraphs. 

One type of material that has transformed electronic displays is neither a solid nor a liquid, but something intermediate between the two. Liquid crystals are substances that flow like viscous liquids, but their molecules lie in a moderately orderly array, like those in a crystal. They are examples of a mesophase, an intermediate state of matter with the fluidity of a liquid and some of the molecular order of a solid. Liquid crystalline materials are finding many applications in the electronics industry because they are responsive to changes in temperature and electric fields. 

Liquid crystals form a state of matter intermediate between the ordered solid and the disordered liquid. These intermediate phases are called mesophases. In the crystalline state the constituent molecules or ions are ordered in position and orientation, whereas in the liquid state the molecules possess no positional and orientational ordering. Liquid crystals combine to some extent the properties of both the crystalline state (optical and electrical anisotropy) and the liquid state (fluidity). 

In addition to chemical reactions, the isokinetic relationship can be applied to various physical processes accompanied by enthalpy change. Correlations of this kind were found between enthalpies and entropies of solution (20, 83-92), vaporization (86, 91), sublimation (93, 94), desorption (95), and diffusion (96, 97) and between the two parameters characterizing the temperature dependence of thermochromic transitions (98). A kind of isokinetic relationship was claimed even for enthalpy and entropy of pure substances when relative values referred to those at 298° K are used (99). Enthalpies and entropies of intermolecular interaction were correlated for solutions, pure liquids, and crystals (6). Quite generally, for any temperature-dependent physical quantity, the activation parameters can be computed in a formal way, and correlations between them have been observed for dielectric absorption (100) and resistance of semiconductors (101-105) or fluidity (40, 106). On the other hand, the isokinetic relationship seems to hold in reactions of widely different kinds, starting from elementary processes in the gas phase (107) and including recombination reactions in the solid phase (108), polymerization reactions (109), and inorganic complex formation (110-112), up to such biochemical reactions as denaturation of proteins (113) and even such biological processes as hemolysis of erythrocytes (114). 

The fluidity of the cellular membrane presents a limiting factor at low temperatures. After a decrease in temperature, membranes are too rigid and must therefore be desaturated. Normally, membranes are in a liquid crystalline form... 

Liquid crystal sounds like a contradiction. Liquids are fluid, their molecules continually changing places in a manner that is not particularly well organized. Crystals are immobile, their molecules locked into fixed positions that form regular patterns. Yet, not only does this unusual combination of fluidity and regular patterns exist, it plays important roles in biological organisms. 

Rheological determinations are destructive of the structures they measure for this reason they do not portray the actual structure of the dispersion at rest. Accordingly, various methods have been devised for extrapolating to zero the results of measurements at various shear rates. The most useful one has been the conversion of viscosities to fluidities at various shear rates and the extrapolation of the resulting nearly linear relationship to zero shear, as shown in Figure 7. Sometimes a power of the shear rate, D, provides a better distinction between a sol (essentially a liquid) and a gel (essentially a solid), as shown in the figure, but the difference between a finite intercept (sol) and zero fluidity (gel) is largely fictitious because of the dependence of the intercept on the exponent n. 

Major determinants of membrane fluidity may be grouped within two categories [53] (1) intrinsic determinants, i.e., those quantifying the membrane composition and phase behavior, and (2) extrinsic determinants, i.e., environmental factors (Table 1). In general, any manipulation that induces an increase in the molal volume of the lipids, e.g., increase in temperature or increase in the fraction of unsaturated acyl chains, will lead to an increase in membrane fluidity. In addition, several intrinsic and extrinsic factors presented in Table 1 determine the temperature at which the lipid molecules undergo a transition from the gel state to liquid crystalline state, a transition associated with a large increase in bilayer fluidity. 

Lee, S. T. and Olesik, S. V., Normal-phase high-performance liquid chromatography using enhanced fluidity liquid mobile phases, /. Chromatogr. A, 707, 217, 1995. 

In liquid-solid extraction (LSE) the analyte is extracted from the solid by a liquid, which is separated by filtration. Numerous extraction processes, representing various types and levels of energy, have been described steam distillation, simultaneous steam distillation-solvent extraction (SDE), passive hot solvent extraction, forced-flow leaching, (automated) Soxh-let extraction, shake-flask method, mechanically agitated reflux extraction, ultrasound-assisted extraction, y -ray-assisted extraction, microwave-assisted extraction (MAE), microwave-enhanced extraction (Soxwave ), microwave-assisted process (MAP ), gas-phase MAE, enhanced fluidity extraction, hot (subcritical) water extraction, supercritical fluid extraction (SFE), supercritical assisted liquid extraction, pressurised hot water extraction, enhanced solvent extraction (ESE ), solu-tion/precipitation, etc. The most successful systems are described in Sections 3.3.3-3.4.6. Other, less frequently... 

Being bordered by the solid and liquid states, the liquid crystal state has some of the order of a solid, combined with the fluidity of a liquid. As such, it is an anisotropic fluid and it is this anisotropy that has led to the widespread application of liquid crystals. 

Recently, due to increased interest in membrane raft domains, extensive attention has been paid to the cholesterol-dependent liquid-ordered phase in the membrane (Subczynski and Kusumi 2003). The pulse EPR spin-labeling DOT method detected two coexisting phases in the DMPC/cholesterol membranes the liquid-ordered and the liquid-disordered domains above the phase-transition temperature (Subczynski et al. 2007b). However, using the same method for DMPC/lutein (zeaxanthin) membranes, only the liquid-ordered-like phase was detected above the phase-transition temperature (Widomska, Wisniewska, and Subczynski, unpublished data). No significant differences were found in the effects of lutein and zeaxanthin on the lateral organization of lipid bilayer membranes. We can conclude that lutein and zeaxanthin—macular xanthophylls that parallel cholesterol in its function as a regulator of both membrane fluidity and hydrophobicity—cannot parallel the ability of cholesterol to induce liquid-ordered-disordered phase separation. 

Cholesterol s presence in liposome membranes has the effect of decreasing or even abolishing (at high cholesterol concentrations) the phase transition from the gel state to the fluid or liquid crystal state that occurs with increasing temperature. It also can modulate the permeability and fluidity of the associated membrane—increasing both parameters at temperatures below the phase transition point and decreasing both above the phase transition temperature. Most liposomal recipes include cholesterol as an integral component in membrane construction. 

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