Solutions micellar

Micelles are the simplest organised form of the self-assembly produced by amphiphilic molecules due to the so-called hydrophobic effect , firstly recognized by Tanford.NMR parameters experience dramatic effects as a result of the strong intermolecular interactions among the amphiphiles. In the case of isotropic liquid systems, NMR experiments can be easily performed and modelled, since many advances have been produced in the last two decades.Hence, information on critical micelle concentration (c.m.c.), molecular conformations and interactions, counterion binding, hydration can be obtained from chemical shifts, relaxation, and self-diffusion NMR measurements, also in mixed systems. 

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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]. 

S. A. Safran, Theory of Structure and Phase Transitions in Globular Microemulsions, in Micellar Solutions and Microemulsions, S. H. Chen and R. Rajagopalan, eds.. Springer-Verlag, New York, 1990, Chapter 9. 

Utilizing FT-EPR teclmiques, van Willigen and co-workers have studied the photoinduced electron transfer from zinc tetrakis(4-sulfonatophenyl)porphyrin (ZnTPPS) to duroquinone (DQ) to fonn ZnTPPS and DQ in different micellar solutions [34, 63]. Spin-correlated radical pairs [ZnTPPS. . . DQ ] are fomied initially, and the SCRP lifetime depends upon the solution enviromnent. The ZnTPPS is not observed due to its short T2 relaxation time, but the spectra of DQ allow for the detemiination of the location and stability of reactant and product species in the various micellar solutions. While DQ is always located within the micelle, tire... 

Micellization is a second-order or continuous type phase transition. Therefore, one observes continuous changes over the course of micelle fonnation. Many experimental teclmiques are particularly well suited for examining properties of micelles and micellar solutions. Important micellar properties include micelle size and aggregation number, self-diffusion coefficient, molecular packing of surfactant in the micelle, extent of surfactant ionization and counterion binding affinity, micelle collision rates, and many others. 

Other solubilization and partitioning phenomena are important, both within the context of microemulsions and in the absence of added immiscible solvent. In regular micellar solutions, micelles promote the solubility of many compounds otherwise insoluble in water. The amount of chemical component solubilized in a micellar solution will, typically, be much smaller than can be accommodated in microemulsion fonnation, such as when only a few molecules per micelle are solubilized. Such limited solubilization is nevertheless quite useful. The incoriDoration of minor quantities of pyrene and related optical probes into micelles are a key to the use of fluorescence depolarization in quantifying micellar aggregation numbers and micellar microviscosities [48]. Micellar solubilization makes it possible to measure acid-base or electrochemical properties of compounds otherwise insoluble in aqueous solution. Micellar solubilization facilitates micellar catalysis (see section C2.3.10) and emulsion polymerization (see section C2.3.12). On the other hand, there are untoward effects of micellar solubilization in practical applications of surfactants. Wlren one has a multiphase... 

It is of particular interest to be able to correlate solubility and partitioning with the molecular stmcture of the surfactant and solute. Likes dissolve like is a well-wom plirase that appears applicable, as we see in microemulsion fonnation where reverse micelles solubilize water and nonnal micelles solubilize hydrocarbons. Surfactant interactions, geometrical factors and solute loading produce limitations, however. There appear to be no universal models for solubilization that are readily available and that rest on molecular stmcture. Correlations of homologous solutes in various micellar solutions have been reviewed by Nagarajan [52]. Some examples of solubilization, such as for polycyclic aromatics in dodecyl sulphonate micelles, are driven by hydrophobic... 

Figure C2.3.12. Two-dimensional neutron scattering by EOggPO gEOgg (Pluronic F88) micellar solution under shear witli (a) tlie sample shear axis parallel to tlie beam, and (b) tlie sample rotated 35° around tlie vertical axis. Reflections for several of tlie Miller indices expected for a bee lattice are annotated. Reproduced by pennission from figure 4 of [84]-...

The kinetic data are essentially always treated using the pseudophase model, regarding the micellar solution as consisting of two separate phases. The simplest case of micellar catalysis applies to unimolecTilar reactions where the catalytic effect depends on the efficiency of bindirg of the reactant to the micelle (quantified by the partition coefficient, P) and the rate constant of the reaction in the micellar pseudophase (k ) and in the aqueous phase (k ). Menger and Portnoy have developed a model, treating micelles as enzyme-like particles, that allows the evaluation of all three parameters from the dependence of the observed rate constant on the concentration of surfactant". ... 

Analogously, the effect of micelles on the rate of the unimolecular retro Diels-Alder reaction has been studied. Also here only a modest retardation" or acceleration" is observed. Likewise, the presence of micelles has been reported to have a modest influence on an intramolecular Diels-Alder reaction . Studies on the endo-exo selectivity of a number of different Diels-Alder reactions in micellar media lead to comparable conclusions. Endo-exo selectivities tend to be somewhat smaller in micellar solutions than in pure water, but still are appreciably larger than those in organic media In contrast, in microemulsions the endo-exo selectivity is reduced significantly" ... 

Table 5.4. Apparent second-order rate constants (ycjfp) for the reaction of 5.1c with 5.2 in micellar solutions of Co(DS)2, Ni(DS)2, Cu(DS)2 and Zn(DS)2 compared to the second-order...

In order to obtain more insight into the local environment for the catalysed reaction, we investigated the influence of substituents on the rate of this process in micellar solution and compared this influence to the correspondirg effect in different aqueous and organic solvents. Plots of the logarithms of the rate constants versus the Hammett -value show good linear dependences for all... 

S. H. Chen and R. Rajagoplan, Micellar Solutions and Microemulsions, Springer-Vedag, New York, 1990. 

Product recoveiy from reversed micellar solutions can often be attained by simple back extrac tion, by contacting with an aqueous solution having salt concentration and pH that disfavors protein solu-bihzation, but this is not always a reliable method. Addition of cosolvents such as ethyl acetate or alcohols can lead to a disruption of the micelles and expulsion of the protein species, but this may also lead to protein denaturation. These additives must be removed by distillation, for example, to enable reconstitution of the micellar phase. Temperature increases can similarly lead to product release as a concentrated aqueous solution. Removal of the water from the reversed micelles by molecular sieves or sihca gel has also been found to cause a precipitation of the protein from the organic phase. 

These effects appearance is explained by the nature of hydrophobic interactions and the stixrctural organization of micellar solutions. The host-guest phenomena determine the increase of the selectivity of analytical reactions in the surf actant-based organized systems. 

POLYCYCLIC AROMATIC HYDROCARBONS LUMINESCENCE DETERMINATION USING MICELLAR SOLUTIONS... 

The aim of this work is the development of pyrene determination in gasoline and contaminated soils. For this purpose we used room temperature phosphorescence (RTP) in micellar solutions of sodium dodecylsulphate (SDS). For pyrene extraction from contaminated soils hexane was used. Then exttacts earned in glass and dried. After that remains was dissolved in SDS solution in the presence of sodium sulphite as deoxygenation agent and thallium (I) nitrate as heavy atom . For pyrene RTP excitation 337 nm wavelength was used. To check the accuracy of the procedures proposed for pyrene determining by RTP, the pyrene concentrations in the same gasoline samples were also measured by GC-MS. 

Distribution of benzodiazepines in system micellar pseudophase - water was investigated in micellar solutions of sodium dodecylsulfate. The protonization constants of benzodiazepines were determined by the UV-spectophotometry. Values of protonization constants increase with increasing of sodium dodecylsulfate concentration. The binding constants of two protolytic forms of benzodiazepines with a micellar pseudo-phase and P, values were evaluated from obtained dependence. 

According to the conception of the development of the system of spectra of additive properties stated by I.G. Per kov the use of spectra of second order, represented by AS arrays, measured concerning two axes the length of a wave and water phase pH in monophase, pseudomonophase (micellar solutions) and twophase systems is of great interest. 

In the case of micellar solutions, studied in this work, the monomers interact via two-body potentials. The non-bonded particles interact via the repulsive part of a Lennard-Jones potential... 

D. Blankschtein, G. Thurston, G. Benedek. Phenomenological theory of equilibrium thermodynamic properties and phase separation of micellar solutions. J Chem Phys 25 7268-7288, 1986. 

Ultrafiltration of micellar solutions combines the high permeate flows commonly found in ultrafiltration systems with the possibility of removing molecules independent of their size, since micelles can specifically solubilize or bind low molecular weight components. Characteristics of this separation technique, known as micellar-enhanced ultrafiltration (MEUF), are that micelles bind specific compounds and subsequent ultrafiltration separates the surrounding aqueous phase from the micelles [70]. The pore size of the UF membrane must be chosen such, that the micelles are retained but the unbound components can pass the membrane freely. Alternatively, proteins such as BSA have been used in stead of micelles to obtain similar enan-tioselective aggregates [71]. 

Catalysis and Inhibition in Solutions of Synthetic Polymers and in Micellar Solutions H. Morawetz... 

In recent years micellar solutions of sodium dodecyl sulfate are being used increasingly in analytical determinations, chemical reactions, and catalysis. 

Mechanisms of micellar reactions have been studied by a kinetic study of the state of the proton at the surface of dodecyl sulfate micelles [191]. Surface diffusion constants of Ni(II) on a sodium dodecyl sulfate micelle were studied by electron spin resonance (ESR). The lateral diffusion constant of Ni(II) was found to be three orders of magnitude less than that in ordinary aqueous solutions [192]. Migration and self-diffusion coefficients of divalent counterions in micellar solutions containing monovalent counterions were studied for solutions of Be2+ in lithium dodecyl sulfate and for solutions of Ca2+ in sodium dodecyl sulfate [193]. The structural disposition of the porphyrin complex and the conformation of the surfactant molecules inside the micellar cavity was studied by NMR on aqueous sodium dodecyl sulfate micelles [194]. 

Preparation of monodisperse vesicles with variable size by dilution of mixed micellar solutions of bile salt and phosphatidylcholine, Biochim. Biophys. Acta, 775. 111-114. 

The entrapment of a-chymotrypsin, lysozyme, and myehn in AOT-reversed micelles is accompanied by an increase in the micellar water content and in the size of the micelle. As a consequence of the redistribution of water among reversed micelles, the micellar solution results in being constituted by large protein-containing micelles and small unfilled ones [169],... 

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