Surfactants amphipathic structure

Effects of Surfactants on Solutions. A surfactant changes the properties of a solvent in which it is dissolved to a much greater extent than is expected from its concentration effects. This marked effect is the result of adsorption at the solution s interfaces, orientation of the adsorbed surfactant ions or molecules, micelle formation in the bulk of the solution, and orientation of the surfactant ions or molecules in the micelles, which are caused by the amphipathic structure of a surfactant molecule. The magnitude of these effects depends to a large extent on the solubility balance of the molecule. An efficient surfactant is usually relatively insoluble as individual ions or molecules in the bulk of a solution, eg, 10-2 to 10-4 mol/L. 

A surface-active agent (or surfactant) is a substance that lowers the surface or interfacial tension of the medium in which it is dissolved. Surfactants have a characteristic molecular structure consisting of hydrophobic and hydrophilic groups. This is known as an amphipathic structure, and causes not only concentration of the surfactant at the surface and reduction of the surface tension of the solvent, but also orientation of the molecule at the surface with its hydrophilic group in the aqueous phase and its hydrophobic group oriented away... 

The classification of surfactants into denaturing and nondenaturing poses the question as to the origin of the distinction between the two types of behavior. Since all surfactants have an amphipathic structure, why do synthetic ionic surfactants denature proteins while natural ionics and synthetic nonionics do not The answer must clearly... 

Proteins are biopolymers that are encountered in many applications, such as food emulsions, hair conditioners, photographic emulsions, and various medical diagnostic products. Many of these applications are frequently based on the unique surface activity of the proteins, which is reflected in functional properties such as foaming, emulsification, and gelling. The proteins are composed of polymeric chains containing many hydrophobic and hydrophilic domains, often giving the molecules an amphipathic structure somewhat similar to that of polymeric surfactants. 

Surfactants are the ultimate example of an amphipathic structure. They combine a long-chain alkyl group, which is hydrophobic, with an ionic group (sometimes polar group). 

The amphipathic structure of surfactant molecules not only results in their concentration at a liquid surface and consequent alteration of the surface tension but also causes orientation of the adsorbed molecules such that the lyophobic groups are directed away from the bulk solvent phase (Figure 3.3). The resulting controlled molecular orientation produces some of the most important macroscopic effects observed for surface-active materials, as will be discussed in subsequent chapters. For now, it is more important to understand the qualitative relationships between the nature of interfaces and the general chemical structures required for a molecule to exhibit significant surface activity. 

Meso- and (+ )-azobis[6-(6-cyanododecanoic acid)] were synthesized by Porter et al. (1983) as an amphipathic free radical initiator that could deliver the radical center to a bilayer structure controllably for the study of free radical processes in membranes. The decomposition pathways of the diazenes are illustrated in Fig. 36. When the initiator was decomposed in a DPPC multilamellar vesicle matrix, the diazenes showed stereo-retention yielding unprecedented diastereomeric excesses, as high as 70%, in the recombination of the radicals to form meso- and (+ )-succinodinitriles (Brittain et al., 1984). When the methyl esters of the diazene surfactants were decomposed in a chlorobenzene solution, poor diastereoselectivity was observed, diastereomeric excesses of 2.6% and 7.4% for meso- and ( )-isomers respectively, which is typical of free radical processes in isotropic media (Greene et al, 1970). 

In considering the structure of micelles, we continue to base our discussion on aqueous, anionic surfactant solutions as prototypes of amphipathic systems. Cationic micelles are structured no differently from anionics, and nonionics are described parenthetically at appropriate places in the discussion. We summarize present thinking about the structure of micelles at surfactant concentrations equal to or only slightly above the CMC. We see that in nonaqueous systems (Section 8.8) and in concentrated aqueous systems (Section 8.6), the surfactant molecules are organized quite differently from the structure we describe here. 

At relatively low concentrations of surfactant, the micelles are essentially the spherical structures we discussed above in this chapter. As the amount of surfactant and the extent of solubilization increase, these spheres become distorted into prolate or oblate ellipsoids and, eventually, into cylindrical rods or lamellar disks. Figure 8.8 schematically shows (a) spherical, (b) cylindrical, and (c) lamellar micelle structures. The structures shown in the three parts of the figure are called (a) the viscous isotropic phase, (b) the middle phase, and (c) the neat phase. Again, we emphasize that the orientation of the amphipathic molecules in these structures depends on the nature of the continuous and the solubilized components. 

Flexible macromolecules, such as proteins, and small molecules, such as surfactants, are amphipathic and may form a layer at the oil-water interface. These molecules may also partly stabilize emulsions by forming a physical barrier to close contact, thereby reducing the attractive van der Waals forces to ineffective levels (Dalgleish, 1989). Repulsion can arise in either of two ways and physico-chemical calculations are available for both mechanisms in oil-in-water systems. Either the approaching protein-coated particles will tend to compress or alternatively interpenetrate the adsorbed protein layer on adjacent particles. The optimum structure of the stabilizing protein will be dealt with in the section on protein as an ingredient. 

Surface-active agents (surfactants) are substances which, at low concentrations, adsorb onto the surfaces or interfaces of a system and alter the surface or interfacial free energy and the surface or interfacial tension. Surface-active agents have a characteristic structure, possessing both polar (hydrophilic) and non-polar (hydrophobic) regions in the same molecule. Thus surfactants are said to be amphipathic in nature. The wide range of uses for surfactants in pharmaceutical products and systems is the subject of this article. 

Photochemical processes in heterogeneous systems, and across micelle boundaries in particular, clearly has great potential. The photolysis of amphipathic alkylcobaloximes in mixed micelles shows a co-operative effect owing to structure.The photoreduction of anthraquinone in aqueous micellar solution has been compared with that in non-aqueous solution.The dimerization of 3-(n-butyl)cyclopentenone is solvent-dependent and the ratio of isomeric products depends on surfactant concentration. It is suggested that this can be used as a means of critical micellar concentration determination. 

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