Hydrocarbon tail

This form is obeyed fairly well above x values of 5-10 dyn/cm in Fig. Ill-15c. Limiting areas or a values of about 22 per molecule result, nearly independent of chain length, as would be expected if the molecules assume a final orientation that is perpendicular to the surface. Larger A values are found for longer-chain surfactants, such as sodium dodecyl sulfate, and this has been attributed to the hydrocarbon tails having a variety of conformations [127]. 

The preceding evidence for orientation at the interface plus the considerations given in Section III-3 make it clear that the polar end is directed toward the water and the hydrocarbon tails toward the air. On the other hand, the evidence from the study of the Gibbs monolayers (Section III-7) was that the smaller molecules tended to lie flat on the surface. It will be seen that the orientation... 

An essential component of cell membranes are the lipids, lecithins, or phosphatidylcholines (PC). The typical ir-a behavior shown in Fig. XV-6 is similar to that for the simple fatty-acid monolayers (see Fig. IV-16) and has been modeled theoretically [36]. Branched hydrocarbons tails tend to expand the mono-layer [38], but generally the phase behavior is described by a fluid-gel transition at the plateau [39] and a semicrystalline phase at low a. As illustrated in Fig. XV-7, the areas of the dense phase may initially be highly branched, but they anneal to a circular shape on recompression [40]. The theoretical evaluation of these shape transitions is discussed in Section IV-4F. 

The behavior of insoluble monolayers at the hydrocarbon-water interface has been studied to some extent. In general, a values for straight-chain acids and alcohols are greater at a given film pressure than if spread at the water-air interface. This is perhaps to be expected since the nonpolar phase should tend to reduce the cohesion between the hydrocarbon tails. See Ref. 91 for early reviews. Takenaka [92] has reported polarized resonance Raman spectra for an azo dye monolayer at the CCl4-water interface some conclusions as to orientation were possible. A mean-held theory based on Lennard-Jones potentials has been used to model an amphiphile at an oil-water interface one conclusion was that the depth of the interfacial region can be relatively large [93]. 

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... 

Chain models capture the basic elements of the amphiphilic behaviour by retaining details of the molecular architecture. Ben-Shaul et aJ [ ] and others [ ] explored the organization of tlie hydrophobic portion in lipid micelles and bilayers by retaining the confonuational statistics of the hydrocarbon tail withm the RIS (rotational isomeric state) model [4, 5] while representing the hydrophilic/liydrophobic mterface merely by an... 

With all-atom simulations the locations of the hydrogen atoms are known and so the order parameters can be calculated directly. Another structural property of interest is the ratio of trans conformations to gauche conformations for the CH2—CH2 bonds in the hydrocarbon tail. The trans gauche ratio can be estimated using a variety of experimental techniques such as Raman, infrared and NMR spectroscopy. 

Lipid bilayer (Section 26 4) Arrangement of two layers of phospholipids that constitutes cell membranes The polar termini are located at the inner and outer membrane-water interfaces and the lipophilic hydrocarbon tails cluster on the inside... 

Figure 12.13 Photosynthetic pigments are used hy plants and photosynthetic bacteria to capture photons of light and for electron flow from one side of a membrane to the other side. The diagram shows two such pigments that are present in bacterial reaction centers, bacteriochlorophyll (a) and ubiquinone (b). The light-absorbing parts of the molecules are shown in yellow, attached to hydrocarbon "tails" shown in green.

Nuclear dipole-dipole interaction is a veiy important relaxation mechanism, and this is reflected in the relationship between 7, and the number of protons bonded to a carbon. The motional effect is nicely shown by tbe 7 values for n-decanol, which suggest that the polar end of the molecule is less mobile than the hydrocarbon tail. Comparison of iso-octane with n-decanol shows that the entire iso-octane molecule is subject to more rapid molecular motion than is n-decanol—compare the methyl group T values in these molecules. 

When soaps are dispersed in water, the long hydrocarbon tails cluster together on the inside of a tangled, hydrophobic ball, while the ionic heads on the surface of the cluster stick out into the water layer. These spherical dusters, called micelles, are shown schematically in Figure 27.1. Grease and oil droplets... 

Phospholipids are found widely in both plant and animal tissues and make up approximately 50% to 60% of cell membranes. Because they are like soaps in having a long, nonpolar hydrocarbon tail bound to a polar ionic head, phospholipids in the cell membrane organize into a lipid bilayer about 5.0 nm (50 A) thick. As shown in Figure 27.2, the nonpolar tails aggregate in the center of the bilayer in much the same way that soap tails aggregate in the center of a micelle. This bilayer serves as an effective barrier to the passage of water, ions, and other components into and out of cells. 

The adsorption of aliphatic alcohols, which adsorb on metals with the hydrocarbon tail facing the electrode surface, shows different patterns on real Ag crystal faces440,441 with respect to quasi-perfect single-crystal face electrodes.442-444 This specific point will be discussed in detail in Section III. 

Fig. 2a-f. Mesogenic molecules with differing degrees of polar and sterical asymmetry a symmetric molecule with rigid core and two hydrocarbon tails b terminally polar molecule (arrow indicates the permanent dipole) c swallow-tailed (hiforked) molecule d hanana shaped molecule e terminally fluorinated molecule f polyphilic molecule (hatched areas correspond to the fluorinated fragment)... 

It has been proposed that the overlapping of the surfactant hydrocarbon tails is mainly responsible for the micelle-micelle interactions [247]. However, since tail-tail interactions are of the same order of magnitude as tail-apolar solvent interactions, it seems more reasonable to consider the overlapping of the surfactant hydrocarbon tails as an effect rather than the origin of the micelle-micelle interactions. 

Figure 41-3. Diagrammatic representation of a phospholipid or other membrane lipid. The polar head group is hydrophilic, and the hydrocarbon tails are hydrophobic or lipophilic. The fatty acids in the tails are saturated (S) or unsaturated (U) the former are usually attached to carbon 1 of glycerol and the latter to carbon 2. Note the kink in the tail of the unsaturated fatty acid (U), which is important in conferring increased membrane fluidity.

Figure 41-4. Diagrammatic cross-section of a micelle. The polar head groups are bathed in water, whereas the hydrophobic hydrocarbon tails are surrounded by other hydrocarbons and thereby protected from water. Micelles are relatively small (compared with lipid bilayers) spherical structures.

Cholesterol modifies the fluidity of membranes. At temperatures below the T, it interferes with the interaction of the hydrocarbon tails of fatty acids and thus increases fluidity. At temperatures above the T, , it limits disorder because it is more rigid than the hydrocarbon tails of the fatty acids and cannot move in the membrane to the same extent, thus timiting fluidity. At... 

Step 3 - The pipet is reinserted into the liquid, resulting in apposition of the hydrocarbon tails of the attached monolayer to those of the original monolayer, forming a bilayer (27) ... 

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