Hydrophobic surfactant molecules

One of the most important characteristics of micelles is their ability to take up all kinds of substances. Binding of these compounds to micelles is generally driven by hydrophobic and electrostatic interactions. The dynamics of solubilisation into micelles are similar to those observed for entrance and exit of individual surfactant molecules. Their uptake into micelles is close to diffusion controlled, whereas the residence time depends on the sttucture of the molecule and the solubilisate, and is usually in the order of 10 to 10" seconds . Hence, these processes are fast on the NMR time scale. 

Soap is one example of a broader class of materials known as surface-active agents, or surfactants (qv). Surfactant molecules contain both a hydrophilic or water-liking portion and a separate hydrophobic or water-repelling portion. The hydrophilic portion of a soap molecule is the carboxylate head group and the hydrophobic portion is the aUphatic chain. This class of materials is simultaneously soluble in both aqueous and organic phases or preferential aggregate at air—water interfaces. It is this special chemical stmcture that leads to the abiUty of surfactants to clean dirt and oil from surfaces and produce lather. 

Carboxjiates with a fiuorinated alkyl chain ate marketed by the 3M/Industrial Chemical Products Company under the trade name Fluotad surfactants. They also include other functional derivatives of fiuorinated and perfluorinated alkyl chains. Replacement of hydrogens on the hydrophobe by fluorine atoms leads to surfactant molecules of unusually low surface tension. This property imparts excellent leveling effectiveness. 

In highly diluted solutions the surfactants are monodispersed and are enriched by hydrophil-hydrophobe-oriented adsorption at the surface. If a certain concentration which is characteristic for each surfactant is exceeded, the surfactant molecules congregate to micelles. The inside of a micelle consists of hydrophobic groups whereas its surface consists of hydrophilic groups. Micelles are dynamic entities that are in equilibrium with their surrounded concentration. If the solution is diluted and remains under the characteristic concentration, micelles dissociate to single molecules. The concentration at which micelle formation starts is called critical micelle concentration (cmc). Its value is characteristic for each surfactant and depends on several parameters [189-191] ... 

The interfacial activity is determined by the sterical properties of the molecule. At the interface the spatial demand A0 of the hydrophobic part of the molecule is higher because of the second chain of the internal sulfonate compared with the terminal sulfonate. Thus, the surface concentration of the surfactant molecules is lower. That means that the hydrocarbon chains are laterally oriented and therefore cover the interface between the solution surface and air more completely. Because the ratio of the spatial demand of the head group to the volume of the alkyl chain governs the radius of the micellar surface, it... 

Soaps and detergents contain surfactant molecules that have both hydrophobic... 

The structure of these globular aggregates is characterized by a micellar core formed by the hydrophilic heads of the surfactant molecules and a surrounding hydrophobic layer constituted by their opportunely arranged alkyl chains whereas their dynamics are characterized by conformational motions of heads and alkyl chains, frequent exchange of surfactant monomers between bulk solvent and micelle, and structural collapse of the aggregate leading to its dissolution, and vice versa [2-7]. 

Sodium stearate is a typical surfactant molecule. It has an ionic, hydrophilic head and a nonpolar, hydrophobic tail. 

One of the most attractive roles of liquid liquid interfaces that we found in solvent extraction kinetics of metal ions is a catalytic effect. Shaking or stirring of the solvent extraction system generates a wide interfacial area or a large specific interfacial area defined as the interfacial area divided by a bulk phase volume. Metal extractants have a molecular structure which has both hydrophilic and hydrophobic groups. Therefore, they have a property of interfacial adsorptivity much like surfactant molecules. Adsorption of extractant at the liquid liquid interface can dramatically facilitate the interfacial com-plexation which has been exploited from our research. 

A protein-surfactant-water complex forms in the solid phase. Upon adsorption of a certain number of surfactant molecules, the complex s hydrophobicity increases, driving its transport into the liquid phase. 

In emulsion polymerization, a solution of monomer in one solvent forms droplets, suspended in a second, immiscible solvent. We often employ surfactants to stabilize the droplets through the formation of micelles containing pure monomer or a monomer in solution. Micelles assemble when amphiphilic surfactant molecules (containing both a hydrophobic and hydrophilic end) organize at a phase boundary so that their hydrophilic portion interacts with the hydrophilic component of the emulsion, while their hydrophobic part interacts with the hydrophobic portion of the emulsion. Figure 2.14 illustrates a micellized emulsion structure. To start the polymerization reaction, a phase-specific initiator or catalyst diffuses into the core of the droplets, starting the polymerization. 

When surfactant molecules contain more than one distribution, for example, a distribution of chain lengths in the hydrophobic and hydrophilic portions, two-dimensional liquid chromatography (2DLC) is a very powerful method for complete analysis. One can get the full quantitation of the distribution of molecular size by using the 2DLC technique. For example, take a surfactant molecule like alcohol ethoxylates (AE s) having a general structure of... 

A surfactant was defined in Chapter 8 as an agent, soluble or dispersible in a liquid, which reduces the surface tension of the liquid [1]. It is helpful to visualise surfactant molecules as being composed of opposing solubility tendencies. Thus, those effective in aqueous media typically contain an oil-soluble hydrocarbon-based chain (the hydrophobe) and a smaller water-solubilising moiety which may or may not confer ionic character (the hydrophile). The limitations of space do not permit a comprehensive detailed treatment of the chemistry of surfactants. The emphasis is therefore on a broad-brush discussion of the principal types of surfactant encountered in textile preparation and coloration processes. Comprehensive accounts of the chemistry and properties of surfactants are available [2-13]. A useful and lucid account of the chemistry and technology of surfactant manufacturing processes is given by Davidsohn and Milwidsky [ 14] ... 

In water the surfactant molecules orient themselves with their hydrophobes at the centre of the cluster. The CMC is typically quite low, perhaps 0.5-0.2 g/l. At concentrations lower than this the molecules orient themselves only at the interfaces of the solution, and it is this effect which brings about the lowering of surface tension. Once the CMC is reached the... 

Although the notion of monomolecular surface layers is of fundamental importance to all phases of surface science, surfactant monolayers at the aqueous surface are so unique as virtually to constitute a special state of matter. For the many types of amphipathic molecules that meet the simple requirements for monolayer formation it is possible, using quite simple but elegant techniques over a century old, to obtain quantitative information on intermolecular forces and, furthermore, to manipulate them at will. The special driving force for self-assembly of surfactant molecules as monolayers, micelles, vesicles, or cell membranes (Fendler, 1982) when brought into contact with water is the hydrophobic effect. 

Fig. 10 Cross sections of (a) spherical and cylindrical micelles, and (b) cylindrical and lamellar vesicles in aqueous solution. Each surfactant molecule making up the structures has a polar head-group, depicted as a circle, and a nonpolar, hydrophobic chain, depicted as a zigzag.

Based on the above qualitative discussion of the characteristics of the Jt-A curves, we now provide a useful kinetic model for the molecular aggregation. Let [S] and [D] be the concentration of PhDA2-8 molecules in the "regular" and "aggregated states, respectively. The "regular" state corresponds to the usual conformation of a surfactant molecule at the interface, i.e., the hydrophilic head faces the hydrophilic environment and the hydrophobic tail is expelled from the interface towards the hydrophobic environment. Then the aggregation can be described as... 

Upon reaction, the heterogenized catalyst can be easily separated from the reaction mixture by filtration and then recycled. The hydro-phobic substrate is microemulsified in water and subjected to an orga-nometallic catalyst, which is entrapped within a partially hydrophobized sol-gel matrix. The surfactant molecules, which carry the hydrophobic substrate, adsorb/desorb reversibly on the surface of the sol-gel matrix breaking the micellar structure, spilling their substrate load into the porous medium that contains the catalyst. A catalytic reaction then takes place within the ceramic material to form the desired products that are extracted by the desorbing surfactant, carrying the emulsified product back into the solution. 

In order to separate neutral compounds, Terabe et al. [13] added surfactants to the buffer electrolyte. Above their critical micellar concentration (cmc), these surfactants form micelles in the aqueous solution of the buffer electrolyte. The technique is then called Micellar electrokinetic capillary chromatography, abbreviated as MECC or MEKC. Micelles are dynamic structures consisting of aggregates of surfactant molecules. They are highly hydrophobic in their inner structure and hydrophilic at the outer part. The micelles are usually... 

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