Functional micelles

Nanocrystals are fabricated by using reverse micelles. Functionalized surfactants are employed. 

O Reilly RK, Hawker CJ, Wooley KL. Cross-linked block copolymer micelles functional nanostructures of great potential and versatility. Chem Soc Rev 2006 35 1068-1083. 

MECC separations are conducted in open capillaries, hence eddy diffusion is not problematic. However, the columns behave in many ways like packed columns, with the micelles functioning as uniformly sized and evenly dispersed packing particles. In packed columns, resistance to mass transfer in the mobile phase is reduced (i.e., efficiency improved) when smaller particles are used because the "diffusion distance" between particles is decreased. Average inter-micellar" distance is the analogous parameter in MECC. This distance can be decreased by increasing surfactant concentration. 

Figure 17.1 Solution-state self-assembly of amphiphilic diblock copolymers into spherical micelles. (Reproduced from R.K. O Reilly, C.J. Hawker and K.L. Wooley, Cross-linked block copolymer micelles Functional nanostructures of great potential and versatility, Chemical Society Reviews, 35, 1068-1083, 2006, by permission of the Royal Society of Chemistry.)...

The computational efficiency of this approach allows at the same time models with a resolution close to atomistic and simulations on very large length and timescales.""" For example, these models have been applied to study the interaction and the dynamical exchange of block copolymer chains between a spherical micelle (functioning as drug nanocarrier) and a lipid bilayer (as model of cell surface) also in the presence of drug molecules (iboprufen) in the micelle core. Simulations of 12 nm large micelles with membrane bilayers over several microseconds of simulations could be achieved on home-cluster facilities."" ... 

VI. UNIMER MICELLES FUNCTIONALIZED WITH PHOTOACTIVE CHROMOPHORES... 

The concentration of free surfactant, counterions, and micelles as a function of overall surfactant concentration is shown in Fig. XIII-13. Above the CMC, the concentration of free surfactant is essentially constant while the counterion concentration increases and... 

Figrue BE 16.20 shows spectra of DQ m a solution of TXlOO, a neutral surfactant, as a function of delay time. The spectra are qualitatively similar to those obtained in ethanol solution. At early delay times, the polarization is largely TM while RPM increases at later delay times. The early TM indicates that the reaction involves ZnTPPS triplets while the A/E RPM at later delay times is produced by triplet excited-state electron transfer. Calculation of relaxation times from spectral data indicates that in this case the ZnTPPS porphyrin molecules are in the micelle, although some may also be in the hydrophobic mantle of the micelle. Furtlier,... 

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... 

Bde salts, cholesterol, phosphoHpids, and other minor components are secreted by the Hver. Bile salts serve three significant physiological functions. The hydrophilic carboxylate group, which is attached via an alkyl chain to the hydrophobic steroid skeleton, allows the bile salts to form water-soluble micelles with cholesterol and phosphoHpids in the bile. These micelles assist in the solvation of cholesterol. By solvating cholesterol, bile salts contribute to the homeostatic regulation of the amount of cholesterol in the whole body. Bile salts are also necessary for the intestinal absorption of dietary fats and fat-soluble vitamins (24—26). 

MeutralSoluble Salts. So dium sulfate [7757-82-6] and, to a considerably lesser extent, sodium chloride [7647-14-5] are the principal neutral soluble salts used in laundering compositions. They are often considered to be fillers although they perform an important standardizing function enabling the formulator to manufacture powders of a desired, controlled density. Sodium sulfate, in addition, lowers the critical micelle concentration of organic surfactants and thus the concentration at which effective washing can be achieved. 

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]. 

The function of emulsifier in the emulsion polymerization process may be summarized as follows [45] (1) the insolubilized part of the monomer is dispersed and stabilized within the water phase in the form of fine droplets, (2) a part of monomer is taken into the micel structure by solubilization, (3) the forming latex particles are protected from the coagulation by the adsorption of monomer onto the surface of the particles, (4) the emulsifier makes it easier the solubilize the oligomeric chains within the micelles, (5) the emulsifier catalyzes the initiation reaction, and (6) it may act as a transfer agent or retarder leading to chemical binding of emulsifier molecules to the polymer. 

Micelles in water are described as spherical aggregates of a surfactant monomer27 30). They somewhat resemble to enzyme proteins in structures and functions, although the details are yet the subjects of recent controversies 29,30). There are numerous studies of micellar models of enzymes 28), but the examples of those of metalloenzymes are very few 31 37). In particular, there are no examples of micellar models of carboxypeptidase or carbonic anhydrase except ours 36,37). 

The above enantioselectivities are obviously complex functions of many factors, perhaps even more complex than in natural enzymes. Complexity is partly due to the present co-micellar system in which it is difficult to analyze separately the interaction of the substrate with the achiral micelle, and that of the substrate with the catalyst complex. 

In the latter function, the reagent behaves as a surfactant and forms a cationic micelle at a concentration above the critical micelle concentration (1 x 10 4M for CTMB). The complexation reactions occurring on the surface of the micelles differ from those in simple aqueous solution and result in the formation of a complex of higher ligand to metal ratio than in the simple aqueous system this effect is usually accompanied by a substantial increase in molar absorptivity of the metal complex. 

Generally speaking we consider that most micro-organisms live and grow in aqueous environments, and that the cytoplasm within cells in which enzymes function is also aqueous. On die other hand, most lipids are only sparingly soluble in aqueous media. Cholesterol, for example, has a solubility of less than 2 mg l 1 (equivalent to a concentration of less than 5 pmol l 1). Even at much lower concentrations (25-40 nmol l 1) it tends to aggregate into micelles. There is, therefore, a general problem of how to supply lipid substrates at sufficient concentration to produce reaction kinetics that are appropriate for industrial purposes. 

Functionalized polyelectrolytes are promising candidates for photoinduced ET reaction systems. In recent years, much attention has been focused on modifying the photophysical and photochemical processes by use of polyelectrolyte systems, because dramatic effects are often brought about by the interfacial electrostatic potential and/or the existence of microphase structures in such systems [10, 11], A characteristic feature of polymers as reaction media, in general, lies in the potential that they make a wider variety of molecular designs possible than the conventional organized molecular assemblies such as surfactant micelles and vesicles. From a practical point of view, polymer systems have a potential advantage in that polymers per se can form film and may be assembled into a variety of devices and systems with ease. 

Van Paassen [57] describes the CMC of some polyether carboxylates with different fatty chains and EO degrees (Fig. 2). In an extensive study, Binana-Limbele et al. [59] investigated the micellar properties of the alkylpolyether carboxylates of the general formula CnH + OCF CH OCI COONa with n = 8, x = 5, and n = 12 and x = 5,1, and 9, by means of electrical conductivity (CMC, apparent micellar ionization degree) and time-resolved fluorescence probing (micelle aggregation number A7) as a function of temperature and surfactant concentration (Table 1). 

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