Micellar mechanisms

As previously stated, the use of templates such as DBSA, HDTMAB, and PEOPE allows the formation of well-defined micellar structures in aqueous solution when the template concentration is above its CMC. In a recent publication [38], the polymerization with a bifunctional sodium dodecyl diphenyloxide disulfonate (DODD) as template was proposed to proceed by a micellar mechanism in the same way (Scheme 2). In an aqueous acid solution of DODD and aniline, anilium ions locate at the micellar interface, with benzene parts penetrating into the hydrophobic core of the DODD micelle to form the complex (as illustrated in Scheme 3b). At the concentration of 0.055 mol a slight turbidity was observed in solution, indicating micellar aggregation. Once the micellar structure is formed and the enzyme is added to the aqueous medium, addition of H2O2 triggers the polymerization of anilinium ions around micelles (Scheme 3). 

The rate of polymerization was found to be independent of emulsifier concentration around CMC (1.8x10 4mol dm 3) and up to ca. 10 3 mol dm 3 and then strongly increased with increasing emulsifier concentration (Fig. 5). It can be seen that, for this system, the break in the dependence of the rate on surfactant concentration does not coincide with the CMC of either the surfactant or the surfactant/PEO-MA macromonomer. In fact, these two values are identical at room temperature at 50 °C the CMC of the surfactant is lower than at 20 °C. The kinetics of particle nucleation for the present nonionic polymerization of BA may not follow a micellar mechanism. 

In the emulsifier free-emulsion polymerization the reaction loci are formed by nucleation of amphiphilic macromomer micelles (micellar mechanism) or by... 

Recent physical-chemical observations on native mammalian systems reveal that the proposed mixed micellar mechanism of lipid solubilization and transport in both bile and in upper small intestinal contents is incomplete [1,260-263]. Bile is predominantly a mixed micellar solution but, particularly when supersaturated with Ch, also contains small liquid-crystalline vesicles which, as suggested from model systems [239], are another vehicle for Ch and L transport. In dog bile which is markedly unsaturated with Ch [258], these vesicles exist in dilute concentrations and may be markers of the detergent properties of BS on the cells lining the biliary tree and/or related to the mode of bile formation at the level of the canaliculus. In human hepatic bile, which is generally dilute and markedly supersaturated with Ch, these vesicles may be the predominant form of Ch and L solubilization and transport [261]. If hepatic bile is extremely dilute, it is theoretically possible that no BS-L-Ch micelles may be present [268] all of the lipid content may be aggregated... 

Analysis precluded exchange of quencher by micellar mechanisms. 

At the beginning of an emulsion polymerization performed above the CMC, the free radicals generated in the aqueous phase promote the nucleation of particles by the homogeneous and micellar mechanisms explained previously. The fact that the surface area of all monomer droplets is by far much smaller than that of all the other colloidal species makes it unlikely that the radicals existing in the aqueous phase enter and polymerize into monomer droplets. Thus, the droplets play the role of monomer reservoirs. The diffusion of this component through the aqueous phase provides the monomer needed to replace that consumed by reaction and to swell the polymer produced in the particles. 

When a water-soluble initiator is added to a microemul-sion, polymer particles are nucleated mainly by the micellar mechanism. The role of the monomer-swollen micelles in microemulsion polymerization is not only to act as nucle-ation loci and surfactant reservoir but also as monomer reservoir. The fast nucleation rate leads to the initial increment of Rp. As the monomer is polymerized, its concentration in micelles diminishes and eventually monomer concentration within polymer particles decreases as well [205]. As a consequence, the nucleation and polymerization rates tend to decrease, explaining in this way the maximum in the Rp evolution curve experimentally observed. The final latex consists of surfactant-stabilized polymer particles that typically contain only polymer and empty micelles formed by excess surfactant. 

The decrease of the exponent of [N] with increasing VC concentration was ascribed to decreasing sensitivity of Rp to emulsifier type and stability of polymer particles. The rate of polymerization of BA favors the micellar mechanism, whereas that of VC favors the homogeneous nucleation and particle coagulation. 

Reversibly fonned micelles have long been of interest as models for enzymes, since tliey provide an amphipatliic environment attractive to many substrates. Substrate binding (non-covalent), saturation kinetics and competitive inliibition are kinetic factors common to botli enzyme reaction mechanism analysis and micellar binding kinetics. 

An expression for the number of particles formed during Stage I was developed, assuming micellar entry as the formation mechanism (13), where k is a constant varying from 0.37 to 0.53 depending on the relative rates of radical adsorption in micelles and polymer particles, r is the rate of radical generation, m is the rate of particle growth, is the surface area covered by one surfactant molecule, and S is the total concentration of soap molecules. 

The debate as to which mechanism controls particle nucleation continues. There is strong evidence the HUFT and coagulation theories hold tme for the more water-soluble monomers. What remains at issue are the relative rates of micellar entry, homogeneous particle nucleation, and coagulative nucleation when surfactant is present at concentrations above its CMC. It is reasonable to assume each mechanism plays a role, depending on the nature and conditions of the polymerization (26). 

The study of the mechanism of cloud point micellar extractions by phases of non-ionic surfactant (NS) is an aspect often disregarded in most literature reports and, thus, is of general interest. The effective application of the micellar extraction in the analysis is connected with the principled and the least studied problem about the influence of hydrophobicity, stmcture and substrate charge on the distribution between the water and non-ionic surfactant-rich phase. 

The kinetic mechanism of emulsion polymerization was developed by Smith and Ewart [10]. The quantitative treatment of this mechanism was made by using Har-kin s Micellar Theory [18,19]. By means of quantitative treatment, the researchers obtained an expression in which the particle number was expressed as a function of emulsifier concentration, initiation, and polymerization rates. This expression was derived for the systems including the monomers with low water solubility and partly solubilized within the micelles formed by emulsifiers having low critical micelle concentration (CMC) values [10]. 

Various kinetic models on particle formation were proposed by different researchers. These may be classified as follows (1) radical absorption mechanisms by Gardon [28-34] and Fisch and Tsai [13], (2) micellar nucleation newer models by Nomura et al. [35,36] and by Hansen and Ugelstad [37], (3) homogeneous nucleation by Fistch and coworkers [13,38,39]. 

Figure 5a indicates the effect of the CTAB concentration on the rate constants of the complexes of 38b and 38c. In the case of the water soluble 38b ligand, the rate increases with increasing CTAB concentration up to a saturation level. This type of saturation kinetics is usually interpreted to show the incorporation of a ligand-metal ion complex into a micellar phase from a bulk aqueous phase, and the catalytic activity of the complex is higher in the micellar phase than in the aqueous phase. In the case of lipophilic 38c, a very similar curve as in Fig. 4 is obtained. At a first glance, there appears to be a big difference between these two curves. However, they are rather common in micellar reactions and obey the same reaction mechanism 27). 

Our micellar models show unusually high catalytic activities as compared with other related model systems. Foregoing results and discussions may be summarized by referring to a generalized mechanism of catalysis shown in Scheme 5. 

Scheme 5. Summarized mechanism of the catalysis of the micellar model of a metalloenzyme...

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]. 

In another study of the physical behavior of soap-LSDA blends, Weil and Linfield [35] showed that the mechanism of action of such mixtures is based on a close association between the two components. In deionized water this association is mixed micellar. Surface tension curves confirm the presence of mixed micelles in deionized water and show a combination of optimum surface active properties, such as low CMC, high surface concentration, and low surface concentration above the CMC. Solubilization of high Krafft point soap by an LSDA and of a difficulty soluble LSDA by soap are related results of this association. Analysis of dispersions of soap-LSDA mixtures in hard water shows that the dispersed particles are mixtures of soap and LSDA in the same proportion as they were originally added. These findings are inconsistent with the view that soap reacts separately with hard water ions and that the resulting lime soap is suspended by surface adsorption of LSDA. The suspended particles are responsible for surface-active properties and detergency and do not permit deposits on washed fabric unlike those found after washing with soap alone. 

We begin the discussion of EPM by elaborating on this physical picture. Figure 1 shows a typical emulsion CSTR reactor and polymerization recipe. The magnified portion of the latex shows the various phases and the major species involved. The latex consists of monomers, water, surfactant, initiator, chain transfer agent, and added electrolyte. We used the mechanism for particle formation as described in Feeney et al. (8-9) and Hansen and Ugelstad (2). We have not found it necessary to invoke the micellar entry theory 2, 2/ 6./ 11/ 12/ 14. 

Prindle and Ray (ZB.) have recently analyzed the same styrene data using a hybrid model consisting of the micellar nucleation mechanism above the CMC and of the homogeneous nucleation and coagulation mechanism below the CMC. Their simulations show a much steeper rise in the particle number concentration precisely at the CMC than predicted by EPM. Their hybrid model does not appear to predict that the particle concentration levels off at high surfactant concentrations. 

No version of micellar entry theory has been proposed, which is able to explain the experimentally observed leveling off of the particle number at high and low surfactant concentrations where micelles do not even exist. There is a number of additional experimental data that refute micellar entry such as the positively skewed early time particle size distribution (22.), and the formation of Liesegang rings (30). Therefore it is inappropriate to include micellar entry as a particle formation mechanism in EPM until there is sufficient evidence to do so. 

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