Phospholipid crystalline state

From the frequency measurements of the LB-film-deposited QCM plate in water, the behavior of phospholipid LB films can be classified into three types (i) phospholipids having relatively hydrophilic head groups such as DPPC and DPPG are hydrated and then easily flaked from the substrate in the fluid liquid crystalline state above Tc (ii) DPPE and DPPS having the less hydrophilic head groups are hydrated only near their Tc (iii) cholesterol LB films show relatively large hydration behavior even at low temperatures due to the water penetration into the structure defects in the membrane. 

Although the majority of the lipids in M. laidlawii membranes appear to be in a liquid-crystalline state, the system possesses the same physical properties that many other membranes possess. The ORD is that of a red-shifted a-helix high resolution NMR does not show obvious absorption by hydrocarbon protons, and infrared spectroscopy shows no ft structure. Like erythrocyte ghosts, treatment with pronase leaves an enzyme-resistant core containing about 20% of the protein of the intact membrane (56). This residual core retains the membrane lipid and appears membranous in the electron microscope (56). Like many others, M. laidlawii membranes are solubilized by detergents and can be reconstituted by removal of detergent. Apparently all of these properties can be consistent with a structure in which the lipids are predominantly in the bilayer conformation. The spectroscopic data are therefore insufficient to reject the concept of a phospholipid bilayer structure or to... 

Fig. 1.9 Structures adopted by phospholipids in aqueous media. Lpand (gel and liquid crystalline) states exist at low and intermediate temperatures, respectively, and the inverted cylinder (hexagonal) HM state is found at elevated temperatures [93].

In addition to this thermotropic mesomorphism, a lysotropic mesomorphism is observed [98]. The phase transition temperature, Tt, for the transition from the crystalline to the liquid crystalline state decreases as a function of water content. The decrease in Ttis due to destabilization of the crystal lattice in the head group region by water molecules. This, in turn, decreases the interaction between the fatty acid chains. When the water content reaches a certain level, the phospholipids assume a thermodynamically optimal arrangements whereby the fatty acids are directed to the... 

Conformations based on the few available X-ray structures of phospholipids in the crystalline state, generated from energy minimization or from conformational libraries of phospholipid alkyl chains, have been used as starting structures for the simulation. It has been argued that the latter is preferable in order to save time necessary for equilibration when starting from all-trans conformations of the alkyl chains observed in X-ray structures. To build up the configuration of the system, e.g. the lateral positions of the phospholipids, either crystal structure data or programs... 

The third class of lipids found in stratum corneum extracts is represented by cholesterol and cholesteryl esters. The actual role of cholesterol remains enigmatic, and no clear reason for its role in the barrier function has been proposed so far. However, it is possible that contrary to what is the role in cell membranes where cholesterol increases close packing of phospholipids, it can act as kind of a detergent in lipid bilayers of long-chain, saturated lipids.30,31 This would allow some fraction of the barrier to be in a liquid crystalline state, hence water permeable in spite of the fact that not only ceramides, but also fatty acids found in the barrier are saturated, long-chain species.28,32... 

Physically, the membrane may exist in two states the "solid" gel crystalline and the "liquid" fluid crystalline states. For each type of membrane, there is a specific temperature at which one changes into the other. This is the transition temperature (Tc). The Tc is relatively high for membranes containing saturated fatty acids and low for those with unsaturated fatty acids. Thus, bilayers of phosphatidylcholine with two palmitate residues have a Tc = 41°C but that with two oleic acid residues has a Tc = -20°C. The hybrid has a Tc = -5°C. Sphingomyelin bilayer, on the other hand, may have a Tc of close to body temperature. In the gel crystalline state, the hydrophobic tails of phospholipids are ordered, whereas in the fluid crystalline state they are disordered. At body temperature, all eukaryotic membranes appear to be in the liquid crystalline state, and this is caused, in part, by the presence of unsaturated fatty acids and in part by cholesterol. The latter maintains the fatty acid side chains in the disordered state, even below the normal Tc. There is thus no evidence that membranes regulate cellular metabolic activity by changing their physical status from the gel to the fluid state,... 

Hence, the interaction between lipid molecules is very similar in these foam bilayers and it can be supposed that the AF foam bilayers are in the liquid crystalline state within the temperature range studied. This assumption is in agreement with the fact that amniotic fluid contains substantial amount of unsaturated phospholipids, which as known [45], lower considerably the temperature of the chain-melting phase transition. Bearing in mind the similarity of the phase behaviour of a phosphatidylcholine aqueous dispersion and foam bilayers [38-40], it can be supposed that at the temperatures which are important for in vivo systems, the foam bilayers are in the liquid crystalline state. This assumption allows to determine the critical concentration of phosphatidylcholines in amniotic fluid, necessary for formation of a foam bilayer by extrapolation of the Arrhenius dependence of C, for AF foam bilayers to 37°C. Thus, at 37°C C, = 19.9 jxg cm 3 and d, = 1.47. This value of C, at 37°C corresponds to the lower limit (found by other methods [46,47]) of phosphatidylcholine concentration which permits to classify as mature a sample of amniotic fluid. The above value... 

The amphiphilic molecules can occur in lyotropic and thermotropic mesomorph, and the organization of lipid bilayers such as liposomes can exist in a temperature range where all the mesophases from gel stale to liquid crystal state are favored. In the gel state the phospholipid acyl chains are closely packed and the molecular movements are deteriorized, while in the liquid crystalline state, the faity acid moieties are in a more fluid state and are able to move more freely. 

One or more crystalline lamellar (Lc) phases may be formed by all phospholipids at low temperature and/or low levels of hydration. When long and short range order is found in three dimensions then the result is a 3D lamellar crystal, which is a true crystal. The three dimensional crystalline order results from the close packing of two dimensional phospholipid crystalline sheets (Figure 1.90). In all crystalline and ordered states, phospholipid close packing and molecular conhguration is dehned in terms of a number of parameters. These parameters are ct—the mean cross sectional area of a fatty acid alkyl chain perpendicular to the chain axis, 4>—the tilt angle of the chain with respect to bilayer plane, —the thickness of the... 

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