Surfactant/micelle chemistry

Takahashi, S., Ikkai, Y., Rodriguez-Ahreu, C., Aramaki, K., Ohsuna, T. and Sakamoto, K. (2007) Application of a water soluble alkoxysilane for the formation of mesoporous silica from nonionic surfactant micelles hearing cholesterol. Chemistry Letters, 36, 182— 183. 

The objectives of this work were to (1) study the equilibrium sorption characteristics of an anionic surfactant (SDS) and a nonionic surfactant (Tween 80) to kaolinite, a common soil mineral, as a function of solution chemistry (2) examine the equilibrium partitioning of two HOCs (phenanthrene and naphthalene) to the surfactant micelles and sorbed... 

Another important parameter that has to be deeply considered is the pH. It is well known the role of pH on silica chemistry it affects dissolution and polymerization rate, gel or precipitate formation and the textural properties of the final silica (11). Also for surfactant micelle or cluster templated syntheses of silica-aluminas, the effect of pH on porosity remains relevant and it is strongly influenced by the kind of material and by the synthesis route selected for its preparation. 

It is well recognized in all branches of chemistry that the rate of a chemical reaction can be very sensitive to the nature of the reaction environment. Reactions involving polar or ionic transition states can be especially sensitive to the polarity of the reaction medium. It should not be too surprising, then, that many chemical reactions, especially those in which one reactant may be soluble in water and the other in oil, can exhibit a significant enhancement in rate when carried out in the presence of surfactant micelles. The presence of the micellar species can provide a beneficial effect through two possible mechanisms ... 

Rusanov, A.I. Micellization in Surfactant Solutions, Chemistry Reviews, Part / Harwood Academic Publ. Amsterdam, 1997 Vol. 22. 

The difficulty in direct synthesis of mesoporous transition metal oxides by soft templating (surfactant micelles) arises from their air- and moisture-sensitive sol-gel chemistry [4,10,11]. On the other hand, mesoporous silica materials can be synthesized in nimierous different solvent systems (i.e., water or water-alcohol mixtures), various synthetic conditions (Le., acidic or basic, various concentration and temperature ranges), and in the presence of organic (Le., TMB) and inorganic additives (e.g., CT, SO, and NOs ) [12-15]. The flexibility in synthesis conditions allows one to synthesize mesoporous silica materials with tunable pore sizes (2-50 nm), mesostructures (Le., 2D Hexagonal, FCC, and BCC), bimodal porosity, and morphologies (Le., spheres, rods, ropes, and cubes) [12,14,16-19]. Such a control on the physicochemical parameters of mesoporous TM oxides is desired for enhanced catalytic, electronic, magnetic, and optical properties. Therefore, use... 

Recently, we have introduced a new approach for the synthesis of mono-modal mesoporous transition metal oxides so called University of Connecticut (UCT) mesoporous materials [4]. The developed generic method uses inverse surfactant micelles as nanoreactors where the entire sol-gel chemistry is carried out to form oxide materials. The advantage of using inverse surfactant micelles is to overcome the problems associated by relatively weak S-l hydrogen-bonding interactions. Since the TM sols are confined in the inverse micelles, there is a physical barrier between the neighboring TM... 

Surfactant templating chemistry can be extended to many nonsilicate compositions after modifications to the synthesis route. These materials are less structurally stable than the mesoporous silicates, which is attributed to the thinness of the amorphous pore walls ( 1 to 2 nm). Stucky and coworkers [85,86] showed that this problem could be mitigated by preparing the materials with thicker walls. To prepare mesoporous WO3, they dissolved a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and WCle salt in ethanol, and dried the resulting solution in open air. The tungsten salt reacted with moisture to undergo hydrolysis and condensation reactions. These chemical reactions caused the eventual formation of amorphous WO3 around triblock copolymer micelle-like domains, and after calcination at 400 C, a mesoporous WO3 with thick, nanocrystalline walls ( 5 nm) and surface area of 125 m /g was formed. 

Surfactants have also been of interest for their ability to support reactions in normally inhospitable environments. Reactions such as hydrolysis, aminolysis, solvolysis, and, in inorganic chemistry, of aquation of complex ions, may be retarded, accelerated, or differently sensitive to catalysts relative to the behavior in ordinary solutions (see Refs. 205 and 206 for reviews). The acid-base chemistry in micellar solutions has been investigated by Drummond and co-workers [207]. A useful model has been the pseudophase model [206-209] in which reactants are either in solution or solubilized in micelles and partition between the two as though two distinct phases were involved. In inverse micelles in nonpolar media, water is concentrated in the micellar core and reactions in the micelle may be greatly accelerated [206, 210]. The confining environment of a solubilized reactant may lead to stereochemical consequences as in photodimerization reactions in micelles [211] or vesicles [212] or in the generation of radical pairs [213]. 

The main supramolecular self-assembled species involved in analytical chemistry are micelles (direct and reversed), microemulsions (oil/water and water/oil), liposomes, and vesicles, Langmuir-Blodgett films composed of diphilic surfactant molecules or ions. They can form in aqueous, nonaqueous liquid media and on the surface. The other species involved in supramolecular analytical chemistry are molecules-receptors such as calixarenes, cyclodextrins, cyclophanes, cyclopeptides, crown ethers etc. Furthermore, new supramolecular host-guest systems arise due to analytical reaction or process. 

Eicke, F. H. Surfactants in Nonpolar Solvents. Aggregation and Micellization, in Topics in Current Chemistry (ed. Boschke, F. L.), p. 85, Berlin—Heidelberg—New York, Springer 1980... 

At the present time, "interest in reversed micelles is intense for several reasons. The rates of several types of reactions in apolar solvents are strongly enhanced by certain amphiphiles, and this "micellar catalysis" has been regarded as a model for enzyme activity (. Aside from such "biomimetic" features, rate enhancement by these surfactants may be important for applications in synthetic chemistry. Lastly, the aqueous "pools" solubilized within reversed micelles may be spectrally probed to provide structural information on the otherwise elusive state of water in small clusters. 

It is essential to state that the heavy fractions such as asphaltene and preasphaltene do contain large numbers of polar molecules (23.24). These polar molecules behave exactly as surfactants or amphiphiles (asphaltene usually contains a long-chain substituent (25)). We again have to emphasize that it is almost not possible to create a colloidal micelle from pure hydrocarbon and water without any surfactant. Hence, we conclude to say that asphaltene or asphaltene-like molecules (as-phaltics) will participate in a manner according to membrane-mimetic chemistry. 

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