Micelles aqueous solutions

Micelle-water partition coefficients are extracted by micelle chromatography (high performance liquid chromatography, HPLC) using micelle aqueous solution as mobile phase. For determination of retention times are measured using a usual HPLC system at various concentrations of micelle in the aqueous mobile phase and then estimated from the following equation ... 

The reactions of organic compounds can be catalyzed markedly in micellar solution. Catalysis by both normal micelles in aqueous medium and by reversed micelles in nonpolar solvents is possible (Fendler and Fendler, 1975 Kitahara, 1980). In normal micelles in aqueous medium, enhanced reaction of the solubilized substrate generally, but not always, occurs at the micelle-aqueous solution interface in reversed micelles in nonaqueous medium, this reaction occurs deep in the inner core of the micelle. 

Hoshino and Saji [7] first reported the preparation of azo-dye thin films using FTMA. These films were prepared by controlled-potential electrolysis of the FTMA micelle aqueous solution solubilizing the azo dye at 4-0.3 V versus SCE. The azo-dye molecules exist as sol-ubilizate in the micelles, and are then released from the micelles and deposited... 

Besides their use in detergents and in dispersions as stabilizers, surfactants find many more applications. One interesting application is their solubilization capability inside micelles. Aqueous solutions of... 

The traditional association colloid is of the M R" type where R" is the surfactant ion, studied in aqueous solution. Such salts also form micelles in nonaqueous and nonpolar solvents. These structures, termed inverse micelles, have the polar groups inward if some water is present [198] however, the presence of water may prevent the observation of a well-deflned CMC [198,199]. Very complex structures may be formed in nearly anhydrous media (see Ref. 200). 

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... 

Likewise, Grieco, while working with amphiphile-like reactants, observed an enhanced preference for endo-adduct in aqueous solutions, which he attributed to orientational effects within the micelles that were presumed to be present in the reaction mixture ". Although under the conditions used by Grieco, the presence of aggregates cannot be excluded, other studies have clearly demonstrated that micelle formation is not the reason for the improved selectivities . Micellar a peg tes even tend to diminish the preference for endo adduct. ... 

Critical micelle concentration (Section 19 5) Concentration above which substances such as salts of fatty acids aggre gate to form micelles in aqueous solution Crown ether (Section 16 4) A cyclic polyether that via lon-dipole attractive forces forms stable complexes with metal 10ns Such complexes along with their accompany mg anion are soluble in nonpolar solvents C terminus (Section 27 7) The amino acid at the end of a pep tide or protein chain that has its carboxyl group intact—that IS in which the carboxyl group is not part of a peptide bond Cumulated diene (Section 10 5) Diene of the type C=C=C in which a single carbon atom participates in double bonds with two others... 

Ahphatic amine oxides behave as typical surfactants in aqueous solutions. Below the critical micelle concentration (CMC), dimethyl dodecyl amine oxide exists as single molecules. Above this concentration micellar (spherical) aggregates predorninate in solution. Ahphatic amine oxides are similar to other typical nonionic surfactants in that their CMC decreases with increasing temperature. 

Micellar properties are affected by changes in the environment, eg, temperature, solvents, electrolytes, and solubilized components. These changes include compHcated phase changes, viscosity effects, gel formation, and Hquefication of Hquid crystals. Of the simpler changes, high concentrations of water-soluble alcohols in aqueous solution often dissolve micelles and in nonaqueous solvents addition of water frequendy causes a sharp increase in micellar size. 

Surfactant values are at the critical micelle concentration (CMC) in aqueous solution surfactant/defoamer values are at 0.1% concentration in aqueous solution. 

Product recoveiy from reversed micellar solutions can often be attained by simple back extrac tion, by contacting with an aqueous solution having salt concentration and pH that disfavors protein solu-bihzation, but this is not always a reliable method. Addition of cosolvents such as ethyl acetate or alcohols can lead to a disruption of the micelles and expulsion of the protein species, but this may also lead to protein denaturation. These additives must be removed by distillation, for example, to enable reconstitution of the micellar phase. Temperature increases can similarly lead to product release as a concentrated aqueous solution. Removal of the water from the reversed micelles by molecular sieves or sihca gel has also been found to cause a precipitation of the protein from the organic phase. 

It is well known, that in aqueous solutions the water molecules, which are in the inner coordination sphere of the complex, quench the lanthanide (Ln) luminescence in result of vibrations of the OH-groups (OH-oscillators). The use of D O instead of H O, the freezing of solution as well as the introduction of a second ligand to obtain a mixed-ligand complex leads to either partial or complete elimination of the H O influence. The same effect may be achieved by water molecules replacement from the inner and outer coordination sphere at the addition of organic solvents or when the molecule of Ln complex is introduced into the micelle of the surfactant. 

W. Brown, R. Johnsen, P. Stilbs, B. Lindman. Size and shape of nonionic amphiphile (Ci2Eg) micelles in dilute aqueous solutions as derived from quasielastic and intensity of light scattering, sedimentation and pulsed-field-gradient nuclear magnetic resonance self-diffusion data. J Phys Chem 87 4548-4553, 1983. 

M. Zulauf, K. Weckstrom, J. B. Hayter, V. Degiorgio, M. Corti. Neutron scattering study of micelle structure in isotopic aqueous solutions of poly(oxy-ethylene) amphiphiles. J Phys Chem 29 3411-3417, 1985. 

FIG. 1 Self-assembled structures in amphiphilic systems micellar structures (a) and (b) exist in aqueous solution as well as in ternary oil/water/amphiphile mixtures. In the latter case, they are swollen by the oil on the hydrophobic (tail) side. Monolayers (c) separate water from oil domains in ternary systems. Lipids in water tend to form bilayers (d) rather than micelles, since their hydrophobic block (two chains) is so compact and bulky, compared to the head group, that they cannot easily pack into a sphere [4]. At small concentrations, bilayers often close up to form vesicles (e). Some surfactants also form cyhndrical (wormlike) micelles (not shown). 

Critical micelle concentration (Section 19.5) Concentration above which substances such as salts of fatty acids aggregate to form micelles in aqueous solution. 

The conformation of bovine myelin basic protein (MBP) in AOT/isooctane/water reversed micellar systems was studied by Waks et al. 67). This MBP is an extrinsic water soluble protein which attains an extended conformation in aqueous solution 68 but is more density packed at the membrane surface. The solubilization of MBP in the AOT reversed micelles depends on the water/AOT-ratio w0 68). The maximum of solubilization was observed at a w0-value as low as 5.56. The same value was obtained for another major protein component of myelin, the Folch-Pi proteolipid 69). According to fluorescence emission spectra of MBP, accessibility of the single tryptophane residue seems to be decreased in AOT reversed micelles. From CD-spectra one can conclude that there is a higher conformational rigidity in reversed micelles and a more ordered aqueous environment. 

Lindman, B., Wennerstrdm, H. Micelles. Amphiphile Aggregation in Aqueous Solution, in Topics in Current Chemistry (ed. Boschke, F. L.), p. 3, Berlin—Heidelberg—New York, Springer 1980... 

Micelle (Section 27.2) A spherical cluster of soaplike molecules that aggregate in aqueous solution. The ionic heads of the molecules lie on the outside, where they are solvated by water, and the organic tails bunch together on the inside of the micelle. 

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. 

The pioneering work on amphiphilic polyelectrolytes goes back to 1951, when Strauss et al. [25] first synthesized amphiphilic polycations by quaternization of poly(2-vinylpyridine) with n-dodecyl bromide. They revealed that the long alkyl side chains attached to partially quaternized poly(vinylpyridine)s tended to aggregate in aqueous solution so that the polymers assumed a compact conformation when the mole fraction of the hydrophobic side chains exceeded a certain critical value. Thus, Strauss et al. became the first to show experimentally the intramolecular micellation of amphiphilic polymers and the existence of a critical content of hydrophobic residues which may be compared to the critical micelle concentration of ordinary surfactants. They called such amphiphilic polyelectrolytes polysoaps [25],... 

As has been described in Chapter 4, random copolymers of styrene (St) and 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) form a micelle-like microphase structure in aqueous solution [29]. The intramolecular hydrophobic aggregation of the St residues occurs when the St content in the copolymer is higher than ca. 50 mol%. When a small mole fraction of the phenanthrene (Phen) residues is covalently incorporated into such an amphiphilic polyelectrolyte, the Phen residues are hydrophobically encapsulated in the aggregate of the St residues. This kind of polymer system (poly(A/St/Phen), 29) can be prepared by free radical ter-polymerization of AMPS, St, and a small mole fraction of 9-vinylphenanthrene [119]. 

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... 

In the homologous series of alkane 1-sulfonates, micellization in aqueous solutions begins with the pentanesulfonate at cM = 1 mol/L. The critical micelle concentrations of the technical alkanesulfonates are cM = 0.002 mol/L (sulfo-chlorination route) and cM = 0.44 g/L (sulfoxidation route). 

The conductivity of sodium dodecyl sulfate in aqueous solution and in sodium chloride solutions was studied by Williams et al. [98] to determine the CMC. Goddard and Benson [146] studied the electrical conductivity of aqueous solutions of sodium octyl, decyl, and dodecyl sulfates over concentration ranges about the respective CMC and at temperatures from 10°C to 55°C. Figure 14 shows the results obtained by Goddard and Benson for the specific conductivity of sodium dodecyl sulfate and Table 25 shows the coefficients a and p of the linear equation of the specific conductivity, in mho/cm, vs. the molality of the solution at 25°C. Micellization parameters have been studied in detail from conductivity data in a recent work of Shanks and Franses [147]. 

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]. 

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