Catalysis micelles

The catalytic activity of surfactant micelles and the effect of the concentration of reagents in micelle catalysis are tested on hydrolysis of esters of phosphorus acids [25],... 

It has become Increasingly evident that the surfactants are accomplishing more than the solubilization of the organic compounds. Certainly phase transfer catalysis would be expected to occur In the emulsion system and this has been proposed In several organic synthesis studies (21-26). The term micelle catalysis, has not been used to any extent In electrochemistry. Instead terms such as Ion pairing and Ion bridging have been used to explain the acceleration of electrode reactions by the presence of a variety of Ions In the Interface between the solution and the electrode (40-A2). Obviously these processes are the same king of processes one postulates In micelle catalysis. 

The three effects. Increased solubility, micelle catalysis, and the Increased range of available oxidation potentials allows one to see normally unobserved oxidation waves for a number of compounds, a few of which are listed In Table I. 

Micelle catalysis of such reactions as the hydrolysis of ethyl benzoate have been extensively studied (53,54). Although platinum does not normally catalyze the hydrolysis. If one Inserts a piece of platinum Into a solution In which the micelle catalyzed reaction Is occurring the rate Is accelerated (50). 

The inhibition of micelle catalysis has been treated similarly by making the additional assumptions that the interaction of the substrate, S, with the micelles does not affect their formation or their interaction with the inhibitor, I, and that inhibition is competitive, i.e. that incorporation... 

IV. Micelle Catalysis of Hydrolysis and Solvolysis A. Carboxylic Esters... 

The electrostatic model for the micellar effect on the hydrolysis of phosphate monoesters is also consistent with the results of inhibition studies (Bunton et al., 1968, 1970). The CTAB catalyzed hydrolysis of the dinitrophenyl phosphate dianions was found to be inhibited by low concentrations of a number of salts (Fig. 9). Simple electrolytes such as sodium chloride, sodium phosphate, and disodium tetraborate had little effect on the micellar catalysis, but salts with bulky organic anions such as sodium p-toluenesulfonate and sodium salts of aryl carboxylic and phosphoric acids dramatically inhibited the micelle catalysis by CTAB. From equation 14 and Fig. 10, the inhibitor constants, K, were calculated (Bunton et al., 1968) and are given in Table 9. The linearity of the plots in Fig. 10 justifies the assumption that the inhibition is competitive and that incorporation of an inhibitor molecule in a micelle prevents incorporation of the substrate (see Section III). Comparison of the value of for phenyl phosphate and the values of K for 2,4-and 2,6-dinitrophenyl phosphates suggests that nitro groups assist the... 

The issue of water in reverse micellar cores is important because water swollen reverse micelles (reverse microemulsions) provide means for carrying almost any water-soluble component into a predominantly oil-continuous solution (see discussions of microemulsions and micellar catalysis below). In tire absence of water it appears tliat premicellar aggregates (pairs, trimers etc.) are commonly found in surfactant-in-oil solutions [47]. Critical micelle concentrations do exist (witli some exceptions). 

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... 

This localization phenomenon has also been shown to be important in a case of catalysis by premicellar aggregates. In such a case [ ] premicellar aggregates of cetylpyridinium chloride (CPC) were shown to enhance tire rate of tire Fe(III) catalysed oxidation of sulphanilic acid by potassium periodate in tire presence of 1,10-phenantliroline as activator. This chemistry provides a lowering of tire detection limit for Fe(III) by seven orders of magnitude. It must also be appreciated, however, tliat such premicellar aggregates of CPC actually constitute mixed micelles of CPC and 1,10-phenantliroline tliat are smaller tlian conventional CPC micelles. 

A particularly interesting type of micellar catalysis is the autocatalytic self-replication of micelles [58]. Various examples have been described, but a particularly interesting case is the biphasic self-reproduction of aqueous caprylate micelles [59]. In this system ethyl caprylate undergoes hydroxyl catalysed hydrolysis to produce the free carboxylate anion, caprylate. Caprylate micelles then fonn. As these micelles fonn, they solubilize ethylcaprylate and catalyse further production of caprylate anion and caprylate micelles. 

What is the effect of micelles on the aqueous Diels-Alder reaction Can micellar catalysis be combined with Lewis-acid catalysis In Chapter 5 these aspects will discussed. 

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 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". ... 

Studies of micellar catalysis of himolecular reactions of uncharged substrates have not been frequent" ". Dougherty and Berg performed a detailed analysis of the kinetics of the reaction of 1-fluoro-2,4-dinitrobenzene with aniline in the presence of anionic and nonionic surfactants. Micelles induce increases in the apparent rate constant of this reaction. In contrast, the second-order rate constant for reaction in the micellar pseudophase was observed to be roughly equal to, or even lower than the rate constant in water. 

This chapter describes the effects of micelles on the Diels-Alder reaction of compounds 5,1 a-g (see Scheme 5.1) with cyclopentadiene (5.2). As far as we know, our study is the first detailed kinetic analysis of micellar catalysis of a Diels-Alder reaction. 

The use of dienophile 5.1 also allows study of the effect of micelles on the Lewis-acid catalysed reaction. These studies are described in Section 5.2.2. and represent the first in-depth study of Lewis-acid catalysis in conjunction with micellar catalysis , a combination that has very recently also found application in synthetic organic chemistry . ... 

In this section the influence of micelles of cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) and dodecyl heptaoxyethylene ether (C12E7) on the Diels-Alder reaction of 5.1a-g with 5.2 in the absence of Lewis-add catalysts is described (see Scheme 5.1). Note that the dienophiles can be divided into nonionic (5.1a-e), anionic (5.If) and cationic (5.1g) species. A comparison of the effect of nonionic (C12E7), anionic (SDS) and cationic (CTAB) micelles on the rates of their reaction with 5.2 will assess of the importance of electrostatic interactions in micellar catalysis or inhibition. 

Inspired by the many hydrolytically-active metallo enzymes encountered in nature, extensive studies have been performed on so-called metallo micelles. These investigations usually focus on mixed micelles of a common surfactant together with a special chelating surfactant that exhibits a high affinity for transition-metal ions. These aggregates can have remarkable catalytic effects on the hydrolysis of activated carboxylic acid esters, phosphate esters and amides. In these reactions the exact role of the metal ion is not clear and may vary from one system to another. However, there are strong indications that the major function of the metal ion is the coordination of hydroxide anion in the Stem region of the micelle where it is in the proximity of the micelle-bound substrate. The first report of catalysis of a hydrolysis reaction by me tall omi cell es stems from 1978. In the years that... 

With the aim of catalysis of the Diels-Alder reaction of 5.1 with 5.2 by metallo micelles, preliminary studies have been performed using the surfactants 5.5a-c and 5.6 (Scheme 5.2). Unfortunately, the limited solubility of these surfactants in the pH region that allows Lewis-acid catalysis of the Diels-... 

In all surfactant solutions 5.2 can be expected to prefer the nonpolar micellar environment over the aqueous phase. Consequently, those surfactant/dienophile combinations where the dienophile resides primarily in the aqueous phase show inhibition. This is the case for 5.If and S.lg in C12E7 solution and for S.lg in CTAB solution. On the other hand, when diene, dienophile and copper ion simultaneously bind to the micelle, as is the case for Cu(DS)2 solutions with all three dienophiles, efficient micellar catalysis is observed. An intermediate situation exists for 5.1c in CTAB or C12E7 solutions and particularly for 5.If in CTAB solution. Now the dienophile binds to the micelle and is slid elded from the copper ions that apparently prefer the aqueous phase. Tliis results in an overall retardation, despite the possible locally increased concentration of 5.2 in the micelle. 

Interestingly, at very low concentrations of micellised Qi(DS)2, the rate of the reaction of 5.1a with 5.2 was observed to be zero-order in 5.1 a and only depending on the concentration of Cu(DS)2 and 5.2. This is akin to the turn-over and saturation kinetics exhibited by enzymes. The acceleration relative to the reaction in organic media in the absence of catalyst, also approaches enzyme-like magnitudes compared to the process in acetonitrile (Chapter 2), Cu(DS)2 micelles accelerate the Diels-Alder reaction between 5.1a and 5.2 by a factor of 1.8710 . This extremely high catalytic efficiency shows how a combination of a beneficial aqueous solvent effect, Lewis-acid catalysis and micellar catalysis can lead to tremendous accelerations. 

In retrospect, this study has demonstrated the limitations of two commonly accepted methods of analysing solubilisation and micellar catalysis, respectively. It has become clear that solubilisate ririg-current induced shifts need to be interpreted with due caution. These data indicate a proximity of solubilisate and parts of the surfactant and, strictly, do not specify the location within the micelle where the encounter takes place. Also the use of the pseudophase model for bimolecular reactions requires precaution. When distribution of the reactants over the micelle is not comparable, erroneous results are likely to be obtained... 

Chapter 5 also demonstrates that a combination of Lewis-acid catalysis and micellar catalysis can lead to accelerations of enzyme-like magnitudes. Most likely, these accelerations are a consequence of an efficient interaction between the Lewis-acid catalyst and the dienophile, both of which have a high affinity for the Stem region of the micelle. Hence, hydrophobic interactions and Lewis-acid catalysis act cooperatively. Unfortunately, the strength of the hydrophobic interaction, as offered by the Cu(DS)2 micellar system, was not sufficient for extension of Lewis-acid catalysis to monodentate dienophiles. 

Chapter 5 describes a study of the effect of micelles on the Diels-Alder reaction of 1 with 2. Literature studies on micellar catalysis of Diels-Alder reactions invariably failed to reveal significant accelerations. These results are unexpected, since most Diels-Alder reactants have a high affinity for... 

Micellar catalysis of azo coupling reactions was first studied by Poindexter and McKay (1972). They investigated the reaction of a 4-nitrobenzenediazonium salt with 2-naphthol-6-sulfonic and 2-naphthol-3,6-disulfonic acid in the presence of sodium dodecylsulfate or hexadecyltrimethylammonium bromide. With both the anionic and cationic additives an inhibition (up to 15-fold) was observed. This result was to be expected on the basis of the principles of micellar catalysis, since the charges of the two reacting species are opposite. This is due to the fact that either of the reagents will, for electrostatic reasons, be excluded from the micelle. 

Monomers of die type Aa B. are used in step-growth polymerization to produce a variety of polymer architectures, including stars, dendrimers, and hyperbranched polymers.26 28 The unique architecture imparts properties distinctly different from linear polymers of similar compositions. These materials are finding applications in areas such as resin modification, micelles and encapsulation, liquid crystals, pharmaceuticals, catalysis, electroluminescent devices, and analytical chemistry. 

Micellar catalysis to enhance or diminish the rate of chemical reactions is well known [97]. Of somewhat greater interest is the influence of micelles on competing reactions, e.g., proton-catalyzed reactions. An example related to the effect of alkanesulfonates is the epoxidation of simple aliphatic olefins. The reaction of olefins and hydrogen peroxide catalyzed by strongly acidic Mo(VI)... 

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