Phospholipid liquid crystalline form

The above-mentioned physicochemical properties of phospholipids lead to spontaneous formation of bilayers. Depending on the water-lipid ratio, on the type of phospholipids, and the temperature, the bilayer exists in different, defined mesomorphic physical organizations. These are the La high-temperature liquid crystalline form, the Lp gel form with restricted movement of the hydrocarbon chains, and an inverted hexagonal phase, Hn (see Sections 1.3.1 and 1.3.2). 

Cholesterol and phospholipid are present in many tissues, and it is possible, though unproved, that they exist outside the systems mentioned in liquid crystalline form. One interesting possibility is the eye. Pirie (80) has shown that cholesterol and its esters are present in the tapetum lucidum, backing the retina, of the opossum. Some years ago, Pirie kindly showed me her preparations of this tissue, and there was no doubt that cholesterol was present in liquid crystalline form, but since the tissue had been excised, one could not exclude an artifact. Since then, Fergason (14) has demonstrated iridescence in mixtures of cholesterol esters, and it is known that unpolarized light is split by thin layers of these substances into a transmitted beam (clockwise) and a reflected beam (anticlockwise). The need for a mirror backing to the retina has already been stated by Pirie, and... 

Phospholipids are important components of biological membranes. Various classes of phospholipid occur, and within each class, a distribution of fatty acid residues is found. A variety of physical techniques have shown that a number of pure phospholipids undergo a transition from a crystalline to a liquid crystalline form at a temperature dependent upon the presence and type of unsaturation in the fatty acid residues. The implications of these results to the dispersibility of phospholipids in water, the formation of myelin tubes, the production of model membranes, and to the natural biological systems, are discussed. 

The chloroform solution of lipids (Solution A) is placed in a 50-mL round-bottomed spherical Quick-fit flask. Following evaporation of the solvent in a rotary evaporator at about 37°C, a thin lipid film is formed on the walls of the flask. The film is flushed for about 60 seconds with oxygen-free nitrogen (N2) to ensure complete solvent removal and to replace air. Two milliliters of distilled water and a few glass beads are added into the flask, the stopper is replaced, and the flask shaken vigorously by hand or mechanically until the lipid film has been transformed into a milky suspension. This process is carried out above the liquid-crystalline transition temperature (7/) of the phospholipid component of liposomes (> 7/) by prewarming the water... 

Lyotropic liquid-crystalline nanostructures are abundant in living systems. Accordingly, lyotropic LC have been of much interest in such fields as biomimetic chemistry. In fact, biological membranes and cell membranes are a form of LC. Their constituent rod-like molecules (e.g., phospholipids) are organized perpendicularly to the membrane surface yet, the membrane is fluid and elastic. The constituent molecules can flow in plane quite easily but tend not to leave the membrane, and can flip from one side of the membrane to the other with some difficulty. These LC membrane phases can also host important proteins such as receptors freely floating inside, or partly outside, the membrane. 

Monolayers are best formed from water-insoluble molecules. This is expressed well by the title of Gaines s classic book Insoluble Monolayers at Liquid-Gas Interfaces [104]. Carboxylic acids (7-13 in Table 1, for example), sulfates, quaternary ammonium salts, alcohols, amides, and nitriles with carbon chains of 12 or longer meet this requirement well. Similarly, well-behaved monolayers have been formed from naturally occurring phospholipids (14-17 in Table 1, for example), as well as from their synthetic analogs (18,19 in Table 1, for example). More recently, polymerizable surfactants (1-4, 20, 21 in Table 1, for example) [55, 68, 72, 121], preformed polymers [68, 70, 72,122-127], liquid crystalline polymers [128], buckyballs [129, 130], gramicidin [131], and even silica beads [132] have been demonstrated to undergo monolayer formation on aqueous solutions. 

The appearance of tubular myelin-like structures in swollen lecithin was observed by light microscopy well before the systematic investigation of liposomes [351-352]. Similarly, it was also demonstrated some time ago that the addition of calcium ions converted phospholipid liposomes to cochleate cylinders [353]. Subsequent studies have, however, revealed that the system is extremely complex. For example, examination of the phase-transition behavior of synthetic sodium di-n-dodecyl phosphate [(C12H2sO)2PO2Na+ or NaDDP] and calcium di-n-dodecyl phosphate [Ca(DDP)2] showed the presence of many diverse structures [354]. In particular, hydrated NaDDP crystals were shown to form lyotropic liquid-crystalline phases which transformed, upon heating to 50 °C, to myelin-like tubes. Structures of the tubes formed were found... 

Liquid crystals, liposomes, and artificial membranes. Phospholipids dissolve in water to form true solutions only at very low concentrations ( 10-10 M for distearoyl phosphatidylcholine). At higher concentrations they exist in liquid crystalline phases in which the molecules are partially oriented. Phosphatidylcholines (lecithins) exist almost exclusively in a lamellar (smectic) phase in which the molecules form bilayers. In a warm phosphatidylcholine-water mixture containing at least 30% water by weight the phospholipid forms multilamellar vesicles, one lipid bilayer surrounding another in an "onion skin" structure. When such vesicles are subjected to ultrasonic vibration they break up, forming some very small vesicles of diameter down to 25 nm which are surrounded by a single bilayer. These unilamellar vesicles are often used for study of the properties of bilayers. Vesicles of both types are often called liposomes.75-77... 

Hydrophobically modified polybetaines combine the behavior of zwitterions and amphiphilic polymers. Due to the superposition of repulsive hydrophobic and attractive ionic interactions, they favor the formation of self-organized and (micro)phase-separated systems in solution, at interfaces as well as in the bulk phase. Thus, glasses with liquid-crystalline order, lyotropic mesophases, vesicles, monolayers, and micelles are formed. Particular efforts have been dedicated to hydrophobically modified polyphosphobetaines, as they can be considered as polymeric lipids [5,101,225-228]. One can emphasize that much of the research on polymeric phospholipids was not particularly focused on the betaine behavior, but rather on the understanding of the Upid membrane, and on biomimicking. So, often much was learnt about biology and the life sciences, but little on polybetaines as such. 

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