Membrane with liquid crystals

The close relationship between cell membranes and liquid crystals has already been cited as a stimulus for research on transport of ions and various uncharged molcules in liquid crystals. However, dynamic behavior of membranes is not limited to transport processes. Ambrose (50) has provided a fascinating description of cell surfaces in constant motion with pseudopodia continually forming, growing, and disappearing. He also noted that such behavior is quite different for normal and cancer cells, at least for the cell types he studied. 

Wide-line spectra are observed for solids, or for systems In solution with very long (with respect to the Inverse of the quadrupole splitting) correlation times for re-orlentatlon. Examples of the latter are collagen fibres, membranes, and liquid crystals. As many examples of this type of study were given In our earlier review (2), we shall confine ourselves to collagen and membranes. 

Lyotropic liquid crystals are obtained when an appropriate concentration of a material is dissolved in some solvent. The most common systems are those formed by water and amphiphilic molecules (molecules that possess a hydrophilic part that interacts strongly with water and a hydrophobic part that is water insoluble) such as soaps, detergents, and lipids. Here the most important variable controlling the existence of the liquid crystalline phase is the amount of solvent (or concentration). There are quite a number of phases observed in such water-amphiphilic systems, as the composition and temperature are varied some appear as spherical micelles, and others possess ordered structures with one-, two-, or three-dimensional positional order. Examples of these kinds of molecules are soaps (Fig. 1.8) and various phospholipids like those present in cell membranes. Lyotropic liquid crystals are of interest in biological studies. ... 

The thickness of the membrane phase can be either macroscopic ( thick )—membranes with a thickness greater than micrometres—or microscopic ( thin ), i.e. with thicknesses comparable to molecular dimensions (biological membranes and their models, bilayer lipid films). Thick membranes are crystalline, glassy or liquid, while thin membranes possess the properties of liquid crystals (fluid) or gels (crystalline). 

All ion-exchanger membranes with fixed ion-exchanger sites are porous to a certain degree (in contrast to liquid membranes and to membranes of ion-selective electrodes based on solid or glassy electrolytes, such as a single crystal of lanthanum fluoride). 

Phospholipids, which are one of the main structural components of the membrane, are present primarily as bilayers, as shown by molecular spectroscopy, electron microscopy and membrane transport studies (see Section 6.4.4). Phospholipid mobility in the membrane is limited. Rotational and vibrational motion is very rapid (the amplitude of the vibration of the alkyl chains increases with increasing distance from the polar head). Lateral diffusion is also fast (in the direction parallel to the membrane surface). In contrast, transport of the phospholipid from one side of the membrane to the other (flip-flop) is very slow. These properties are typical for the liquid-crystal type of membranes, characterized chiefly by ordering along a single coordinate. When decreasing the temperature (passing the transition or Kraft point, characteristic for various phospholipids), the liquid-crystalline bilayer is converted into the crystalline (gel) structure, where movement in the plane is impossible. 

Guizard, C., Bac, A., Barboiu, M. and Hovnanaian, N. (2000) Organic-inorganic hybrid materials with specific solute and gas transport properties for membrane and sensors applications. Molecular Crystals and Liquid Crystals, 354, 91-106. 

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. 

The mixing of nematogenic compounds with chiral solutes has been shown to lead to cholesteric phases without any chemical interactions.147 Milhaud and Michels describe the interactions of multilamellar vesicles formed from dilauryl-phosphotidylcholine (DLPC) with chiral polyene antibiotics amphotericin B (amB) and nystatin (Ny).148 Even at low concentrations of antibiotic (molar ratio of DLPC to antibiotic >130) twisted ribbons are seen to form just as the CD signals start to strengthen. The results support the concept that chiral solutes can induce chiral order in these lyotropic liquid crystalline systems and are consistent with the observations for thermotropic liquid crystal systems. Clearly the lipid membrane can be chirally influenced by the addition of appropriate solutes. 

The earliest approach to explain tubule formation was developed by de Gen-nes.168 He pointed out that, in a bilayer membrane of chiral molecules in the Lp/ phase, symmetry allows the material to have a net electric dipole moment in the bilayer plane, like a chiral smectic-C liquid crystal.169 In other words, the material is ferroelectric, with a spontaneous electrostatic polarization P per unit area in the bilayer plane, perpendicular to the axis of molecular tilt. (Note that this argument depends on the chirality of the molecules, but it does not depend on the chiral elastic properties of the membrane. For that reason, we discuss it in this section, rather than with the chiral elastic models in the following sections.)... 

The Helfrich-Prost model was extended in a pair of papers by Ou-Yang and Liu.181182 These authors draw an explicit analogy between tilted chiral lipid bilayers and cholesteric liquid crystals. The main significance of this analogy is that the two-dimensional membrane elastic constants of Eq. (5) can be interpreted in terms of the three-dimensional Frank constants of a liquid crystal. In particular, the kHp term that favors membrane twist in Eq. (5) corresponds to the term in the Frank free energy that favors a helical pitch in a cholesteric liquid crystal. Consistent with this analogy, the authors point out that the typical radius of lipid tubules and helical ribbons is similar to the typical pitch of cholesteric liquid crystals. In addition, they use the three-dimensional liquid crystal approach to derive the structure of helical ribbons in mathematical detail. Their results are consistent with the three conclusions from the Helfrich-Prost model outlined above. 

The second issue concerns the anisotropy of the membrane. The models presented in this section all assume that the membrane has the symmetry of a chiral smectic-C liquid crystal, so that the only anisotropy in the membrane plane comes from the direction of the molecular tilt. With this assumption, the membrane has a twofold rotational symmetry about an axis in the membrane plane, perpendicular to the tilt direction. It is possible that a membrane... 

It is also possible that a membrane might have an even lower symmetry than a chiral smectic-C liquid crystal in particular, it might lose the twofold rotational symmetry. This would occur if the molecular tilt defines one orientation in the membrane plane and the direction of one-dimensional chains defines another orientation. In that case, the free energy would take a form similar to Eq. (5) but with additional elastic constants favoring curvature. The argument for tubule formation presented above would still apply, but it would become more mathematically complex because of the extra elastic constants. As an approximation, we can suppose that there is one principal direction of elastic anisotropy, with some slight perturbations about the ideal twofold symmetry. In that approximation, we can use the results presented above, with 4) representing the orientation of the principal elastic anisotropy. 

To discuss the models in this section, we should mention two issues. First, the models assume the membrane is sufficiently soft that the tilt direction can vary with an energy cost that scales as (Vc(j)2. This is appropriate if the membrane is in a fluid phase like a smectic-C liquid crystal, with order in the tilt direction but not in the positions of the molecules. It is also appropriate if the membrane is in a tilted hexatic phase, with order in the orientations of the intermolecular bonds as well as the tilt. However, this assumption is not appropriate if the membrane is in a crystalline phase, because the tilt direction would be locked to the crystalline axes, and varying it would cost more energy than (V(f>)2. 

Alkyl chain(s) with carbohydrates at both termini (bolaamphiphiles) have also been reported since they are potential building blocks for the construction of membrane mimetics with a single monolayer [78]. Bisgluconamide and lactobionamides 6b (sug=Glc-A or Lac-A, X=NH) were studied for their crystalline properties and their arrangements in water [39, 40]. Alkyl-a,cc)-dimannitol 6b (sug=Man-ol, n=16-22) [66] or bolaamphiphiles with identical or different carbohydrates at both ends of the alkyl chain 6a (sug=D-Glc/, D-Galp, DL-Xyl-oI) were found to form micelles and lyotropic liquid crystals as well [41]. 

New glycolipids have to be synthesized to get further insights into liquid crystal properties (mainly lyotropic liquid crystals), surfactant properties (useful in the extraction of membrane proteins), and factors that govern vesicle formation, stability and tightness. New techniques have to be perfected in order to allow to make precise measurements of thermodynamic and kinetic parameters of binding in 3D-systems and to refine those already avalaible with 2D-arrays. Furthermore, molecular mechanics calculations should also be improved to afford a better modeling of the conformations of carbohydrates at interfaces, in relation with physical measurements such as NMR. 

Michl, J. and Thulstrup, E. W. (1986) Spectroscopy with Polarized Light-Solute Alignment by Photoselection, in Liquid Crystals, Polymers, and Membranes, VCH Publishers, New York. 

Lyotropic liquid crystals they display liquid crystalline behavior when mixed with another material in the right concentration (typically a solvent). They can also be a mixture of more than two components (e.g., cell membranes). 

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