Micelles media

Kortan AR, Hull R, Opila RL, Bawendi MG, Steigerwald ML, Carroll PJ, Brus LE (1990) Nucleation and Growth of Cdse on Zns Quantum Crystallite Seeds, and Vice Versa, in Inverse Micelle Media. J Am Chem Soc 112 1327-1332... 

Kortan A R, Hull R and Opila R L 1990 Nucleation and growth of CdSe on ZnS quantum crystallite seeds and vice versa in inverse micelle media J. Am. Chem. Soc. 112 1327... 

Table I. Acid/Base Characteristics of Sensors 2a-f in Micelle Media ...

Raquel F. Correia, Suzana M. Andrade. (2012). Aggregation and Disaggregation of Anionic Aluminium Phthalocyanines in Cationic Pre-MiceUe and Micelle Media a Fluorescence Study. J. Photochemistry and Photobiology A Chemistry. 1-27. 

TABLE 4 Third-Order Nonlinear Optical Properties of Polymers Synthesized by Enzyme-Catalyzed Reactions in Reverse Micelle Media... 

From Table III, the triplet lifetime is seen to increase strongly upon increasing the concentration of Q, especially above the CMC value. The higher viscosity of the micelle medium impedes the quenching of triplets by impurities an ions the triplet lifetime is then governed by the slow exit of Q from the micelle and is seen in their primarily first-order decay. 

As shown by the data in Fig. 12.4 these micelle stabilized catalysts were considerably more active for alkene hydrogenation than the P-2 nickel borides. The hydrogenation run using a preformed P-2 catalyst in a reversed micelle medium proceeded at a faster rate than the reaction run over P-2 nickel boride in... 

A) P-2 nickel boride catalyst B) preformed P-2 nickel boride added to a micelle suspension C) nickel boride formed in the presence of a reversed phase micelle medium. (Redrawn using data from Ref 46.)... 

Let us assume that each polar group is capable of screening hydrocarbon core from contact with water over some area spg. This area is dependent not only on the size of a polar group, but also on its interactions with the solvent, i.e. on hydration. The value of a at micelle - medium interface is determined by the degree to which hydrocarbon core is shielded the lower the degree of screening, the higher a. 

A study of the photochemical behaviour of phenyladamantyl ketone (7) in benzene has shown that the reactions are dominated by fission processes (a Norrish Type I reaction) to yield the products shown in Scheme 2 When the irradiation is carried out in hexadecyltrimethylammonium chloride (HDTCl) solution, adamantane (AdH) is the main product. There is a poor mass balance in this experiment which is thought to be due to interaction of the PhCO radical with the miceller medium. When Cu is used as a radical trap a different distribution of products is observed (Scheme 2, third entry). 

Figure C2.3.7. Snapshot of micelle of sodium octanoate obtained during molecular dynamics simulation. The darkest shading is for sodium counter-ions, the lightest shading is for oxygens and the medium shading is for carbon atoms. Reproduced by pennission from figure 2 of [36].

A micelle-bound substrate will experience a reaction environment different from bulk water, leading to a kinetic medium effect. Hence, micelles are able to catalyse or inhibit organic reactions. Research on micellar catalysis has focused on the kinetics of the organic reactions involved. An overview of the multitude of transformations that have been studied in micellar media is beyond the scope of this chapter. Instead, the reader is referred to an extensive set of review articles and monographs" ... 

The catalytic effect on unimolecular reactions can be attributed exclusively to the local medium effect. For more complicated bimolecular or higher-order reactions, the rate of the reaction is affected by an additional parameter the local concentration of the reacting species in or at the micelle. Also for higher-order reactions the pseudophase model is usually adopted (Figure 5.2). However, in these systems the dependence of the rate on the concentration of surfactant does not allow direct estimation of all of the rate constants and partition coefficients involved. Generally independent assessment of at least one of the partition coefficients is required before the other relevant parameters can be accessed. 

We have demonstrated that due to inhomogeneous distribution of both reaction partners in the micelles, the pseudophase model leads to erroneous estimates of the second-order rate Constantin the micellar pseudophase, so that conclusions regarding the medium of the reaction cannot be derived through this model. However, analysis of substituent effects and endo-exo ratios of the Diels-Alder adducts indicate that the reaction experiences a water-like medium. 

Colloidal State. The principal outcome of many of the composition studies has been the delineation of the asphalt system as a colloidal system at ambient or normal service conditions. This particular concept was proposed in 1924 and described the system as an oil medium in which the asphaltene fraction was dispersed. The transition from a coUoid to a Newtonian Hquid is dependent on temperature, hardness, shear rate, chemical nature, etc. At normal service temperatures asphalt is viscoelastic, and viscous at higher temperatures. The disperse phase is a micelle composed of the molecular species that make up the asphaltenes and the higher molecular weight aromatic components of the petrolenes or the maltenes (ie, the nonasphaltene components). Complete peptization of the micelle seems probable if the system contains sufficient aromatic constituents, in relation to the concentration of asphaltenes, to allow the asphaltenes to remain in the dispersed phase. 

The progression of an ideal emulsion polymerization is considered in three different intervals after forming primary radicals and low-molecular weight oligomers within the water phase. In the first stage (Interval I), the polymerization progresses within the micelle structure. The oligomeric radicals react with the individual monomer molecules within the micelles to form short polymer chains with an ion radical on one end. This leads to the formation of a new phase (i.e., polymer latex particles swollen with the monomer) in the polymerization medium. 

Based on the Smith-Ewart theory, the number of latex particles formed and the rate of polymerization in Interval II is proportional with the 0,6 power of the emulsifier concentration. This relation was also observed experimentally for the emulsion polymerization of styrene by Bartholomeet al. [51], Dunn and Al-Shahib [52] demonstrated that when the concentrations of the different emulsifiers were selected so that the micellar concentrations were equal, the same number of particles having the same size could be obtained by the same polymerization rates in Interval II in the existence of different emulsifiers [52], The number of micelles formed initially in the polymerization medium increases with the increasing emulsifier concentration. This leads to an increase in the total amount of monomer solubilized by micelles. However, the number of emulsifier molecules in one micelle is constant for a certain type of emulsifier and does not change with the emulsifier concentration. The monomer is distributed into more micelles and thus, the... 

Very large solvent effects arc also observed for systems where the monomers can aggregate either with themselves or another species. For example, the apparent kp for polymerizable surfactants, such as certain vinyl pyridinium salts and alkyl salts of dimethylaminoalkyl methacrylates, in aqueous solution above the critical micelle concentration (cmc) are dramatically higher than they are below the cmc in water or in non-aqueous media.77 This docs not mean that the value for the kp is higher. The heterogeneity of the medium needs to be considered. In the micellar system, the effective concentration of double bonds in the vicinity of the... 

Sodium dodecyl sulfate and hydrogen dodecyl sulfate have been used as catalysts in the denitrosation iV-nitroso-iV-methyl-p-toluenesulfonamide [138]. The kinetics of condensation of benzidine and p-anisidine with p-dimethylamino-benzaldehyde was studied by spectrophotometry in the presence of micelles of sodium dodecyl sulfate, with the result that the surfactant increases the rate of reaction [188]. The kinetics of reversible complexation of Ni(II) and Fe(III) with oxalatopentaaminecobalt(III) has been investigated in aqueous micellar medium of sodium dodecyl sulfate. The reaction occurs exclusively on the micellar surface [189]. Vitamin E reacts rapidly with the peroxidized linoleic acid present in linoleic acid in micellar sodium dodecyl sulfate solutions, whereas no significant reaction occurs in ethanol solution [190]. 

Micellar medium has received great attention because it solubilizes, concentrates and orientates the reactants within the micelle core and in this way accelerates the reaction and favors the regio- and stereoselectivity of the process [68], In addition the micellar medium is cheap, can be reused, is more versatile than cyclodextrins and more robust than enzymes. With regard to Diels Alder reactions, we may distinguish between (i) those in which one or both reagents are surfactants which make up the micellar medium, and (ii) those that are carried out in a micellar medium prepared by a suitable surfactant. 

Even entrapment of entire cells within reversed micelles without loss of their functionality has been achieved. For example, mitochondria and bacteria (Actinobacter cal-coaceticus, Escherichia coli, Corynebacterium equi) have been successfully solubilized in a microemulsion consisting of isopropyl pahnitate, polyoxyethylene sorbitan trioleate [162], Enhanced hydrogen photoproduction by the bacterium Rhodopseudomonas sphaeroides or by the coupled system Halobacterium halobium and chloroplasts organelles entrapped inside the aqueous core of reversed micelles with respect to the same cells suspended in normal aqueous medium has been reported [183,184],... 

Moreover, stable liquid systems made up of nanoparticles coated with a surfactant monolayer and dispersed in an apolar medium could be employed to catalyze reactions involving both apolar substrates (solubilized in the bulk solvent) and polar and amphiphilic substrates (preferentially encapsulated within the reversed micelles or located at the surfactant palisade layer) or could be used as antiwear additives for lubricants. For example, monodisperse nickel boride catalysts were prepared in water/CTAB/hexanol microemulsions and used directly as the catalysts of styrene hydrogenation [215]. 

Solutions of surfactant-stabilized nanogels share both the advantage of gels (drastic reduction of molecular diffusion and of internal dynamics of solubilizates entrapped in the micellar aggregates) and of nonviscous liquids (nanogel-containing reversed micelles diffuse and are dispersed in a macroscopicaUy nonviscous medium). Effects on the lifetime of excited species and on the catalytic activity and stability of immobilized enzymes can be expected. 

It follows that in spite of the apolar coat surrounding water-containing AOT-reversed micelles and their dispersion in an apolar medium, some microscopic processes are able to establish intermicellar attractive interactions. These intermicellar interactions between AOT-reversed micelles increase with increasing temperature or the chain length of the hydrocarbon solvent molecule, thus leading to the enhancement of the clustering process [244-246], whereas they are reduced in the presence of inorganic salts [131]. 

The structure of these gel-like systems of micelles is very different from that of conventional electrophoresis media made from chemically and physically cross-linked polymers of polyacrylamide and agarose [75], The absence of chemical or physical cross-links in the Pluronic gel-like phases may allow a larger degree of freedom for macromolecular transport around the obstacles that make up the medium than occurs in conventional electrophoresis media. 

To check if PemB is surface exposed, E. chrysanthemi cells were subjected to proteolysis. Treatment of the cell suspension with trypsin, proteinase K or chimotrypsin at a concentration of 0.1 to 1 mg/ml for 1 h did not cause PemB proteolysis or its liberation into the medium. Cell pre-treatment with EDTA-lysozyme, which renders the periplasmic proteins accessible to proteases, gave no effect. PemB was also resistant to proteolytic digestion in extract of cells disrupted by sonication or in a French press. Only addition of Triton X-100 (up to 0.1%) causing formation of the micelles with PemB lead to a quick proteolyis of this protein (data not shown). In another approach to analyse the PemB exposition, bacterial cells were labelled with sulfo-NHS-biotin. This compound is unable to cross membranes and biotinylation... 

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