Micelles zwitterionic

SOLVENT EFFECTS ZWiTTERGENTS DETERGENTS MICELLE ZWITTERION ZYMOGEN Zymogen activation,... 

Aqueous cationic micelles speed and anionic micelles inhibit bi-molecular reactions of anionic nucleophiles. Both cationic and anionic micelles speed reactions of nonionic nucleophiles. Second-order rate constants in the micelles can be calculated by estimating the concentration of each reactant in the micelles, which are treated as a distinct reaction medium, that is, as a pseudophase. These second-order rate constants are similar to those in water except for aromatic nucleophilic substitution by azide ion, which is much faster than predicted. Ionic micelles generally inhibit spontaneous hydrolyses. But a charge effect also occurs, and for hydrolyses of anhydrides, diaryl carbonates, chloroformates, and acyl and sulfonyl chlorides and SN hydrolyses, reactions are faster in cationic than in anionic micelles if bond making is dominant. This behavior is also observed in water addition to carbocations. If bond breaking is dominant, the reaction is faster in anionic micelles. Zwitterionic sulfobetaine and cationic micelles behave similarly. 

The solubilization of water in lecithin-reversed micelles has been found to be an exothermic process. This finding confirms that water interacts with the zwitterionic head group of lecithin, promoting the formation of strong intermolecular H bonds [104]. 

Most studies of micellar systems have been carried out on synthetic surfactants where the polar or ionic head group may be cationic, e.g. an ammonium or pyridinium ion, anionic, e.g. a carboxylate, sulfate or sulfonate ion, non-ionic, e.g. hydroxy-compound, or zwitterionic, e.g. an amine oxide or a carboxylate or sulfonate betaine. Surfactants are often given trivial or trade names, and abbreviations based on either trivial or systematic names are freely used (Fendler and Fendler, 1975). Many commercial surfactants are mixtures so that purity can be a major problem. In addition, some surfactants, e.g. monoalkyl sulfates, decompose slowly in aqueous solution. Some examples of surfactants are given in Table 1, together with values of the critical micelle concentration, cmc. This is the surfactant concentration at the onset of micellization (Mukerjee and Mysels, 1970) and can therefore be taken to be the maximum concentration of monomeric surfactant in a solution (Menger and Portnoy, 1967). Its value is related to the change of free energy on micellization (Fendler and Fendler, 1975 Lindman and Wennerstrom, 1980). 

The cmc decreases with increasing chain length of the apolar groups, and is higher for ionic than for non-ionic or zwitterionic micelles. For ionic micelles it is reduced by addition of electrolytes, especially those having low charge density counterions (Mukerjee and Mysels, 1970). Added solutes or cosolvents which disrupt the three-dimensional structure of water break up micelles, unless the solute is sufficiently apolar to be micellar bound (Ionescu et al., 1984). 

The binding constants between the anionic substrates and cationic micelles are large because of the combination of coulombic and hydrophobic effects so rate enhancements may be large even with dilute surfactant. There is binding with non-ionic and zwitterionic micelles despite the absence of coulombic attraction (Bunton et al., 1975). 

Zwitterionic micelles of the sulfobetaine C16H33N+Me2(CH2)3SO 3 have effects very similar to those of cationic micelles (Table 7). This result is understandable if the substrate binds close to the quaternary ammonium center and the anionic sulfate moiety extends into the aqueous region. 

The effect of micelles on these spontaneous hydrolyses is difficult to explain in terms of kinetic solvent effects on these reactions. Mukerjee and his coworkers have refined earlier methods for estimating apparent dielectric constants or effective polarities at micellar surfaces. For cationic and zwitterionic betaine sulfonate micelles Def is lower by ca 15 from the value in anionic dodecyl sulfate micelles (Ramachandran et al., 1982). We do not know whether there is a direct connection between these differences in effective dielectric constant and the relation between reaction rates and micellar charge, but the possibility is intriguing. 

The hydroxyethyl quaternary ammonium ion in (20) is a weak acid the pATa-value of the non-micellizing model compound, choline, is 12.8 (Haber-field and Pessin, 1982). Reactions of the alkoxide zwitterion are therefore followed at relatively high pH, and from the variation of rate constant with... 

These tri-n-octylammonium ions can be functionalized giving the possibility of reactions such as (26). The alkoxide zwitterions are effective nucleophiles and the quantitative treatments described for functional micelles... 

Type B gelatin, 12 440-441 Type II anion exchangers, 14 390 Type I/II zwitterionic SCK micelles, 20 490 Type II metallic superconductors, pinning force in, 23 826... 

The hydrolysis of sulfate monoesters has been studied increasingly in relation to sulfate group transfer in vivo. In general, the rate-enhancing effect on the sulfate cleavage is small even with hydroxamate- or imidazole-functionalized cationic micelles which are extremely effective for the hydrolysis of phenyl esters. Recently, Kunitake and Sakamoto (1979a) found that zwitterionic hydroxamate [47] cleaved 2,4-dinitrophenyl sulfate effectively in cationic and... 

Detergents commonly used to form micelles that are amenable to high-resolution NMR are summarized in Tab. 5.2, and the chemical structures of the most commonly used detergents are presented in Fig. 5.2. Unfortunately, only a few of those needed for use with nonisotopically enriched peptides are commercially available in deuterated form. Most frequently, the zwitterionic DPC or the negatively charged SDS have been used as membrane mimetics. Mixtures of DPC doped with small amounts of SDS may be used to modulate the charge distribution on the micelle surface. It should be emphasized here... 

In the present work, we have synthesized two betaines and three sulfobetaines in very pure form and have determined their surface and thermodynamic properties of micellization and adsorption. From these data on the two classes of zwitterionics, energetics of micellization and adsorption of the hydrophilic head groups have been estimated and compared to those of nonionic surfactants. 

Performance of surfactants is closely related to surface activity and to micelle formation. Both these are due to amphiphilic nature of the surfactant molecule. The molecule contains a nonpolar hydrophobic part, usually, a hydrocarbon chain, and a polar hydrophilic group, which may be nonionic, zwitterionic, or ionic. When the hydrophobic group is a long straight chain of hydrocarbon, the micelle has a small liquid like hydrocarbon core (1,2). The primary driving... 

Equations 4 and 5 are derived by completely ignoring electrostatic contributions to micelle formation, and can be applied only to nonionic and zwitterionic micelle formation. 

Ionic Micelle Formation. Even for ionic micelle formation, the free energy of transfer of one methylene group to a micelle should have a value similar to those for nonionic and zwitterionic micelle formation. The... 

Secondary chemical equilibria, 230,280 see also Secondary equilibria with diprotic acids and zwitterions, equilibrium constants and retention. 241 with micelle ftmtiation, 236... 

Arenediazonium salts and anionic, zwitterionic, and nonionic micelles... 

ARENEDIAZONIUM SALTS AND ANIONIC, ZWITTERIONIC, AND NONIONIC MICELLES... 

Exploiting ATRP as an enabling technology, we have recently synthesised a wide range of new, controlled-structure copolymers. These include (1) branched analogues of Pluronic non-ionic surfactants (2) schizophrenic polymeric surfactants which can form two types of micelles in aqueous solution (3) novel sulfate-based copolymers for use as crystal habit modifiers (4) zwitterionic diblock copolymers, which may prove to be interesting pigment dispersants. Each of these systems is discussed in turn below. 

MEKC is also performed using cationic, nonionic, and zwitterionic surfactants. Widely employed are cationic surfactant consisting of a long chain tetralkylammonium salt, such as cetyltrimeth-ylammonium bromide, which causes the reversal of the direction of the EOE, due to the adsorption of the organic cation on the capillary wall. Other interesting options include the use of mixed micelles resulting from the simultaneous incorporation into the BGE of ionic and nonionic or ionic and zwitterionic surfactants. Chiral surfactants, either natural as bile salts [207] or synthetic [208] are employed for enantiomer separations. 

Types of detergents n, non-ionic a, anionic c, cationic z, zwitterionic N, Aggregation number (average munber of detergent molecules per micelle)... 

Mixed Micelles Showing Negative Deviation -from Ideality. In an aqueous solution containing a mixture o-f Cll an ionic sur-factant and a nonionic sur-factant, or C21 an anionic sur-factant and a cationic sur-factant, or C33 a zwitterionic sur-factant and an anionic sur-factant, the CMC o-f the mixed sur-factant system exhibits a CMC which is substantially less than that predicted by Equation 1 (9.12.18-37). This means that the mixed micelle -formation is enhanced and that the mixing process in the micelle shows negative deviation -from ideality. This is demonstrated -for a cationic/nonionic system in Figure 1. 

Figure 5.2 Top-diagramatic representation of a detergent molecule, (a) Single tailed (b) double tailed (c) zwitterionic (d) bolamphiphilic. Bottom - different types of surfactant aggregates in solution (A) monolayer (B) bilayer (C) liquid-crystallin phase lamellar (D) normal micelles (E) cylindrical micelles (hexagonal) (F) vesicles (liposomes) (G) reversed micelles.

Figure 3 Schematic two-dimensional simplified representation of a proposed spherical zwitterionic micelle containing the Rh/15 catalyst. The hydrocarbon chains of the tenside phosophine (-CH2-CH-(CH2)n-CH3), the hydrophilic head group (-S03 ), the counter ions (Na+ and OH, depicted as X) and the solubilised 1-tetradecene (dotted part, core of the micelle) are schematically indicated to denote their relative locations and not their configuration, number, distribution or relationship to the molecular sizes.

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