Molecule amphiphilic

As one might expect from the discussion of the liquid crystals in Sects. 5.2.1 and 5.2.2, condis crystals may result whenever a paraffin chain is attached to a part of 

One of the first observations of such stepwise, separate phase transitions of the paraffinic part of an amphiphilic molecule was made on tetra-n-amyl ammonium thiocyanate At 315 K the crystals undergo a major first-order transition [AS = 71 J/(K mol) with a 4.8 % volume change]. The final transition to the isotropic, molten salt at 323 K is entropically smaller [AS. = 59 J/(K mol) with a n gible volume change]. Since typical alkali thiocyanate entropies of fusion are 30-40 J/(K mol) it is reasonable to assume that the high-temperature crystal state is that of a condis crystals with considerable conformational freedom. 

A series of n-alkyltrimethylammonium halides that shows a well-resolved condis state has been described recently The results of thermal analyses on these com- 

Data of Ref. DSC curves were only registered from 270 to 600 K and lower temperature transitions may have been omitted for example for n = 15 in Ref one can find additional solid-solid transitions at 326 and 346 K with entropy changes of 9.8 and 17.1 J/(K mol) 

A detailed thermal and X-ray analysis exists for a series of anhydrous Na soaps From these measurements it can be derived that the soaps with alkyl-chains of 8, 16 and 18 carbon atoms undergo a crystal to condis crystal transition at about 390 K 

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Harris J and Rice S A 1988 A lattice model of a supported monolayer of amphiphile molecules—Monte Carlo simulations J. Ohem. Phys. 88 1298-306... 

Another important class of materials which can be successfiilly described by mesoscopic and contimiiim models are amphiphilic systems. Amphiphilic molecules consist of two distinct entities that like different enviromnents. Lipid molecules, for instance, comprise a polar head that likes an aqueous enviromnent and one or two hydrocarbon tails that are strongly hydrophobic. Since the two entities are chemically joined together they cannot separate into macroscopically large phases. If these amphiphiles are added to a binary mixture (say, water and oil) they greatly promote the dispersion of one component into the other. At low amphiphile... 

The relation between the architecture of the molecules and the spatial morphology into which they assemble has attracted longstanding interest because of their importance in daily life. Lipid molecules are important constituents of the cell membrane. Amphiphilic molecules are of major importance for teclmological applications (e.g., in detergents and the food industry). 

As early as 1969, Wlieeler and Widom [73] fomuilated a simple lattice model to describe ternary mixtures. The bonds between lattice sites are conceived as particles. A bond between two positive spins corresponds to water, a bond between two negative spins corresponds to oil and a bond coimecting opposite spins is identified with an amphiphile. The contact between hydrophilic and hydrophobic units is made infinitely repulsive hence each lattice site is occupied by eitlier hydrophilic or hydrophobic units. These two states of a site are described by a spin variable s., which can take the values +1 and -1. Obviously, oil/water interfaces are always completely covered by amphiphilic molecules. The Hamiltonian of this Widom model takes the form... 

This Blume-Eiiiery-GrifSths (BEG) model [74] has been studied both by mean field calculations as well as by simulations. There is no pronounced difference between the amphiphile molecules S= 0, the oil or the water. Indeed, the model was first suggested in a quite different context. An extension of the model by Schick and Shih [75] includes an additional interaction of tlie fomi... 

Amphiphilic Molecules. In just about all cases of lyotropic Hquid crystals, the important component of the system is a molecule with two very different parts, one that is hydrophobic and one that is hydrophilic. These molecules are called amphiphilic because when possible they migrate to the iaterface between a polar and nonpolar Hquid. Soaps such as sodium laurate and phosphoHpids such as a-cephalin [5681-36-7] (phosphatidylethanolamine) (2) are important examples of amphiphilic molecules which form Hquid crystal phases (see Lecithin Soap). 

The monolayer resulting when amphiphilic molecules are introduced to the water—air interface was traditionally called a two-dimensional gas owing to what were the expected large distances between the molecules. However, it has become quite clear that amphiphiles self-organize at the air—water interface even at relatively low surface pressures (7—10). For example, x-ray diffraction data from a monolayer of heneicosanoic acid spread on a 0.5-mM CaCl2 solution at zero pressure (11) showed that once the barrier starts moving and compresses the molecules, the surface pressure, 7T, increases and the area per molecule, M, decreases. The surface pressure, ie, the force per unit length of the barrier (in N/m) is the difference between CJq, the surface tension of pure water, and O, that of the water covered with a monolayer. Where the total number of molecules and the total area that the monolayer occupies is known, the area per molecules can be calculated and a 7T-M isotherm constmcted. This isotherm (Fig. 2), which describes surface pressure as a function of the area per molecule (3,4), is rich in information on stabiUty of the monolayer at the water—air interface, the reorientation of molecules in the two-dimensional system, phase transitions, and conformational transformations. 

A (macro)emulsion is formed when two immiscible Hquids, usually water and a hydrophobic organic solvent, an oil, are mechanically agitated (5) so that one Hquid forms droplets in the other one. A microemulsion, on the other hand, forms spontaneously because of the self-association of added amphiphilic molecules. During the emulsification agitation both Hquids form droplets, and with no stabilization, two emulsion layers are formed, one with oil droplets in water (o /w) and one of water in oil (w/o). However, if not stabilized the droplets separate into two phases when the agitation ceases. If an emulsifier (a stabilizing compound) is added to the two immiscible Hquids, one of them becomes continuous and the other one remains in droplet form. 

The most complex and powerful coarse-grained models are those which retain the chain character of the amphiphile molecules. 

Amphiphilic molecules (surfactants) are composed of two different parts hydrophobic tail and hydrophilic head [1 ]. Due to their chemical structure they self-assemble into internal surfaces in water solutions or in mixtures of oil and water, where the tails are separated from the water solvent. These surfaces can form closed spherical or cylindrical micelles or bicontinuous phases [3,5]. In the latter case a single surface extends over the volume of the system and divides it into separated and mutually interwoven subvolumes. 

FIGURE 2.6 An amphiphilic molecule sodium palmltate. Amphiphilic molecules are frequently symbolized by a ball aud zig-zag Hue structure,, where the ball represents the... 

As schematically shown in Fig. 1C, a carrier is an amphiphilic molecule capable of residing at the membrane aqueous interface with its lipophilic side interacting with the lipid of the membrane, with polar moieties directed outward into the aqueous phase, and with the polar moieties of a chemical nature to induce an ion into interaction. In the process of a carrier interacting and complexing with the ion, it... 

This kind of ester acts as a nonionic surfactant if the alkanol groups contain hydrophilic moieties. If only two molecules of alkanoles are added to the phosphoric acid molecule an acid or secondary dialkyl phosphoric acid ester is formed that are an amphiphilic molecule by itself see Eq. (5). 

Phosphorus-containing surfactants are amphiphilic molecules, exhibiting the same surface-active properties as other surfactants. That means that they reduce the surface tension of water and aqueous solutions, are adsorbed at interfaces, form foam, and are able to build micelles in the bulk phase. On account of the many possibilities for alteration of molecular structure, the surface-active properties of phosphorus-containing surfactants cover a wide field of effects. Of main interest are those properties which can only be realized with difficulty or in some cases not at all by other surfactants. Often even quantitative differences are highly useful. 

The terminology of L-B films originates from the names of two scientists who invented the technique of film preparation, which transfers the monolayer or multilayers from the water-air interface onto a solid substrate. The key of the L-B technique is to use the amphiphih molecule insoluble in water, with one end hydrophilic and the other hydrophobic. When a drop of a dilute solution containing the amphiphilic molecules is spread on the water-air interface, the hydrophilic end of the amphiphile is preferentially immersed in the water and the hydrophobic end remains in the air. After the evaporation of solvent, the solution leaves a monolayer of amphiphilic molecules in the form of two-dimensional gas due to relatively large spacing between the molecules (see Fig. 15 (a)). At this stage, a barrier moves and compresses the molecules on the water-air interface, and as a result the intermolecular distance decreases and the surface pressure increases. As the compression from the barrier proceeds, two successive phase transitions of the monolayer can be observed. First a transition from the gas" to the liquid state. 

Fig. 15—Sketch of preparation of L-B films (a) spread amphiphilic molecules on water surface, (b) compress the molecules using the barrier to get close packed and ordered molecular film, (c) transfer the film onto a substrate through the vertical immerse/retreat process, (d) transfer the film by horizontal lifting.

The most commonly used amphiphiles to build L-B hlms for tribological applications are the straight chain hydrocarbon compounds with simple functional groups such as the fatty acids, including stearic acids, arachidic acids, and behenic acids [32], but other amphiphilic molecules, e.g., 2,4-heneicosanedione and 2-docosylamina-5-nitropyridine, are also applied in some cases. There are two major systems of self-assembled monolayers, namely the alkylsilance derivatives (e.g., OTS, octadecyltrichlorosilane) on hydroxylated surfaces and the alkanethiols on metal substrates, which have been investigated extensively to examine their properties as solid lubricants and protective surface films [31 ]. 

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