Calorimetric study of the solubilization of ethylenediamine,N,N-dimethylaminoethylamine and N,N,N′,N′-tetramethylethylenediamine by reversed AOT micelles

Distribution constants and standard enthalpies of transfer of ethylenediamine (en), N,N-dimethylaminoethylamine (dmen) and N,N,N,N-tetramethylethylenediamine (tmen) partitioned between n-heptane and water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio R (R=[water]/[AOT]) were evaluated by a calorimetric method. The results show that en, dmen and tmen molecules, solubilized in the reversed micelles, are distributed between the micellar aqueous core and the micellar palisade layer. An analysis of the thermodynamic parameters of the partition process demonstrates the peculiar solvent properties of the water containing reversed AOT micelles.     

Determination of pH in reversed micelles

The pH in the reversed micellar system of di(ethylhexyl) sodium sulfosuccinate (Aerosol OT, AOT) / phosphate buffer solutions/octane was determined by a P-NMR technique, and pHs in the reversed micelles containing buffer solutions other than the phosphate buffer solution were measured by the spectrophotometric method with the aid of Phenol Red. pHs in reversed micelles were found to be substantially determined by the buffer capacity of buffer solutions solubilized into the systems. By means of both the methods, pKa of Phenol Red in the systems was found to be 7.7, which is almost consistent with that in water. Analysis of Na-NMR spectra indicates that the mobility of the sodium ion of AOT is independent of the molar ratio of water to AOT when the ratio is above 7 and is restricted strongly by the interaction with the sulfonate group of AOT. The relationship between pH and the mobility of the sodium ion was discussed on the basis of the data of Na-NMR spectra.     

Precipitation of slightly soluble silver salts in reversed AOT micelles: Calorimetric investigation

The enthalpies of precipitation, of AgCl, Agl, Ag₂S and silver tetraphenylborate (AgTPB) in water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio R (R=[water]/[AOT]) at various concentrations of AOT and reagent salts, were measured by a calorimetric technique. The molar enthalpies of precipitation are independent of the surfactant concentration but are dependent on the concentration of the reagent salts and the R value. The molar enthalpies for the same processes in bulk water are not approached even at the highest R value. Effects due to the smallness of the microcrystals and to the interactions between ions and micellar interface are discussed. In part from Doctor of Biology thesis of F. Pinio, University of Palermo, Italy.     

Refractive index of water-AOT-n-heptane microemulsions

Refractive index measurements on water/AOT/n-heptane microemulsions as a function of the volume fraction of the dispersed phase (water plus AOT) and of the water/AOT molar ratio R have been performed at 25°C. The refractive index was found to vary monotonically with without any change in rate during the crossover of the percolation threshold. Such a behavior suggested that, well above the percolation threshold, the water-AOT-n-heptane microemulsions are still formed by water-containing AOT reversed micelles dispersed in the oil phase. The analysis of the experimental data allowed an evaluation the fraction of the water molecules bonded to the AOT head group as a function of R.     

Physicochemical investigation of acrylamide solubilization in sodium bis(2-ethylhexyl)sulfosuccinate and lecithin reversed micelles

The state of acrylamide confined within dry sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and lecithin reversed micelles dispersed in CCl(4) has been investigated by FTIR and (1)H NMR spectroscopy. Measurements have been performed at 25 degrees C as a function of the acrylamide-to-surfactant molar ratio (R) at a fixed surfactant concentration (0.1 mol kg(-1)). The analysis of experimental data, corroborated by the results of SAXS measurements, is consistent with the hypothesis that acrylamide is quite uniformly distributed among reversed micelles mainly located in proximity to the surfactant head-group region and that its presence induces significant unidimensional growth of micellar aggregates. Moreover, the confinement of acrylamide within reversed micelles involves some changes of the typical H-bonded structure of pure solid acrylamide attributable to the establishment of system-specific acrylamide/surfactant head group interactions. Preliminary experiments showed that, by exposure to X-rays, the polymerization of acrylamide can be induced in the confined space of dry AOT and lecithin reversed micelles.     

Structural evolution of a two-component organogel

Dry reverse micelles of AOT in isooctane spontaneously undergo a microstructural transition to an organogel upon the addition of a phenolic dopant, p-chlorophenol. This microstructural evolution has been studied through a combination of light scattering, small-angle neutron scattering (SANS), NMR, and rheology. Several equilibrium stages between the system of dry reverse micelles of AOT and a 1:1 AOT/p-chlorophenol (molar ratio) gel in isooctane have been examined. To achieve this, p-chlorophenol is added progressively to the dilute solutions of AOT in isooctane, and this concentration series is then analyzed. The dry micelles of AOT in isooctane do not undergo any detectable structural change up to a certain p-chlorophenol concentration. Upon a very small increment in the concentration of p-chlorophenol beyond this "threshold" concentration, large strandlike aggregates are observed which then evolve to the three-dimensional gel network.     

Calorimetric study of the solubilization of cholesterol,retinol and retinal by reversed AOT micelles

Distribution constants and standard enthalpies of transfer of cholesterol, retinol and retinal partitioned between n-heptane and water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio (R=[water]/[AOT]) were evaluated by a calorimetric method. The results indicate that, in spite of the bulky hydrocarbon radical, these solubilizates behave like alcohols with a short alkyl chain. Moreover, cholesterol is always solubilized in the palisade layer of the reversed micelles whereas retinol and retinal are preferentially solubilized in the aqueous pseudophase. The influence of the enthalpic and the entropic contributions to the transfer of the solubilizates from n-heptane to reversed AOT micelles are also considered.     

Physicochemical investigation of cobalt–iron cyanide nanoparticles synthesized by a novel solid–solid reaction in confined space

Cobalt–iron cyanide (Co_x[Fe(CN)₆]) nanoparticles have been synthesized by a novel solid–solid reaction in the confined space of dry sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reversed micelles dispersed in n-heptane. The reaction has been carried out by mixing two dry AOT/n-heptane solutions containing CoCl₂ and K₄Fe(CN)₆ or K₃Fe(CN)₆ nanoparticles in the micellar core, respectively. By UV-Vis spectroscopy it was ascertained that, after the mixing process, the formation of stable nanoparticles is fast and complete. Microcalorimetric measurements of the thermal effect due to the Co_x[Fe(CN)₆] nanoparticle formation allowed the determination of the stoichiometric ratio (x) and of the molar enthalpy of reaction in the core of AOT reversed micelles. The observed behavior suggests the occurrence of confinement effects and surfactant adsorption on the nanoparticle surface. Further structural information was achieved by small-angle X-ray scattering (SAXS) measurements. From all liquid samples, interesting salt/AOT composites were prepared by simple evaporation of the apolar solvent. Size, crystal structure, and electronic properties of Co_x[Fe(CN)₆] nanoparticles containing composites were obtained by wide-angle X-ray scattering (WAXS) and X-ray photoelectron spectroscopy (XPS).     

Calorimetric study of the alpha-tocopherol solubility in reversed AOT micelles

The experimental data of heat of mixing (Q) for heterogeneous system alpha-tocopherol/AOT/n-heptane with and without water at 25 degrees C are presented. The Q dependence on AOT (sodium bis (2-ethylhexyl) sulfosuccinate) concentration, and R parameter defined as R=[H2O]/[AOT] with flow calorimetric method were investigated. Using the D'Aprano model (which is formally identical to that used earlier by Magid et al.) the binding constant (K), the distribution constant of alpha-tocopherol (K distr) between hydrocarbon and the micellar phase, and the standard enthalpy of transfer (DeltaH tr 0) of alpha-tocopherol from the hydrocarbon to AOT reversed micelles were calculated. The solubility of alpha-tocopherol in AOT reversed micelles explored with the calorimetric technique was compared to the literature data obtained respectively with UV spectrophotometry for reversed micelles and by other techniques for the phospholipid bilayer.     

Specifics of the formation of J-aggregates of cyanine dyes in solutions of AOT/water/hexane reverse micelles

The behavior of a cyanine dye (3,3′-di-(gamma-sulfopropyl)-4,5,4′,5′-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt) was studied in AOT/water/hexane reverse micelles over a wide range of W at various concentrations of the dye, AOT, and reverse micelles. The processes occurring during the formation of the AOT/water/hexane micellar solution were studied in detail. It has been shown that, before the formation of the stable microemulsion, the dye aggregation processes occur by virtue of the interaction of the dye with the AOT anion. The amount of J-aggregates is proportional to the logarithm of the ratio of the amount of AOT molecules to the amount of dye molecules. The time behavior of J-aggregates after the formation of a micellar structure depends on the concentration of reverse micelles, thereby indicating an important role of intermicellar exchange.     

FT-IR investigation of the acetamide state in AOT reversed micelles

The state of acetamide nanoparticles encapsulated in the hydrophilic core of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reversed micelles and dispersed in CCl ₄ has been investigated by Fourier transform infrared spectroscopy. The analysis of the vibrational spectra reveals even at the higher acetamide to AOT molar ratio some changes of the typical H-bonded structure of solid acetamide ascribable to their small size, confinement effects, and acetamide-AOT head group interactions. The stretching modes of acetamide CO and AOT sulfonate groups indicate unambiguously specific acetamide-AOT head group interactions.     

Conformational studies of the oligomers of L-lysine in reversed micelles

The effect of the chain length on the conformation of oligo-L-lysines (Lys-n, n= 9, 12 and 15) was examined in the reversed micelles of bis(2-ethylhexyl)sodium sulfosuccinate (AOT) in octane by the circular dichroism (CD) measurements. These oligomers seem to take a-structure in these systems. The structure-inducing effect of the reversed micelles is enhanced as the molar ratio of water to AOT (w₀=[H₂O]/[AOT]) becomes smaller. On the other hand, in the aqueous solutions the oligomers having 12 and 15 residues show the conformational transition from random coil to-helical structure by the addition of AOT, but the short oligomer of 9 residues does not show such a conformational transition.     

混合反胶束的电导与微结构研究

反胶束是两亲分子在非极性溶剂中形成的一种有序组合体，在医药、化工、采油、胶束催化及酶催化等领域中有重要应用．与胶束溶液相比，人们对反胶束的形成与结构的了解至今仍不充分．特别是对于由混合表面活性剂形成的反胶束的研究几乎无人涉及．本文采用动态光散射、电导及荧光光谱等手段对阴离子表面活性剂AOT与非离子表面活性剂形成的混合反胶束进行了研究，旨在探讨利用表面活性剂的复配来调节和控制反胶束的结构和性能．亚实验部分二异辛基磺化琉璃酸钠（AOT，Sigma公司）；Brij30为含4个氧乙烯基（EO基）的十二碳醇（AcrosOrgani…     

Effect of solvent quality on aggregate structures of common surfactants

Aggregate structures of two model surfactants, AOT and C12E5 are studied in pure solvents D2O, dioxane-d8 (d-diox) and cyclohexane-d12 (C6D12) as well as in formulated D2O/d-diox and d-diox/C6D12 mixtures. As such these solvents and mixtures span a wide and continuous range of polarities. Small-angle neutron scattering (SANS) has been employed to follow an evolution of the preferred aggregate curvature, from normal micelles in high polarity solvents, through to reversed micelles in low polarity media. SANS has also been used to elucidate the micellar size, shape as well as to highlight intermicellar interactions. The results shed new light on the nature of aggregation structures in intermediate polarity solvents, and point to a region of solvent quality (as characterized by Hildebrand Solubility Parameter, Snyder polarity parameter or dielectric constant) in which aggregation is not favored. Finally these observed trends in aggregation as a function of solvent quality are successfully used to predict the self-assembly behavior of C12E5 in a different solvent, hexane-d14 (C6D14).     

A new reverse wormlike micellar system: mixtures of bile salt and lecithin in organic liquids

We report a new route for forming reverse wormlike micelles (i.e., long, flexible micellar chains) in nonpolar organic liquids such as cyclohexane and n-decane. This route involves the addition of a bile salt (e.g., sodium deoxycholate) in trace amounts to solutions of the phospholipid lecithin. Previous recipes for reverse wormlike micelles have usually required the addition of water to induce reverse micellar growth; here, we show that bile salts, due to their unique "facially amphiphilic" structure, can play a role analogous to that of water and promote the longitudinal aggregation of lecithin molecules into reverse micellar chains. The formation of transient entangled networks of these reverse micelles transforms low-viscosity lecithin organosols into strongly viscoelastic fluids. The zero-shear viscosity increases by more than 5 orders of magnitude, and it is the molar ratio of bile salt to lecithin that controls the viscosity enhancement. The growth of reverse wormlike micelles is also confirmed by small-angle neutron scattering (SANS) experiments on these fluids.     

Complex formation in Aerosol OT reversed micelles between sodium counterion and Kryptofix 221D macrobicyclic ligand

The interaction between 5-decyl-4,7,13,16,21-pentaoxa-1,10-diazabicyclo-[8,8,5]-tricosan (Kryptofix 221D) and reversed micelles of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in n-heptane as a function of AOT and water concentration was investigated by a calorimetric technique. The solubilization of the cryptand in the reversed AOT micelles produces an exothermic effect that increases with R (R=[water]/[AOT]) and is slightly dependent on AOT concentration. Processes due to the formation of a 1:1 complex between the cryptand and the sodium counterion of the AOT and to the transfer of Kryptofix 221D from bulk n-heptane to the micellar palisade layer have been taken into account to rationalize the experimental results. The peculiar solvation state of the sodium counterions near the water-AOT interface has also been considered.In part from the Doctor in Biology thesis of F. Pinio in the University of Palermo.     

Self-assembly of mixed anionic and nonionic surfactants in aqueous solution

We present the phase diagram and the microstructure of the binary surfactant mixture of AOT and C(12)E(4) in D(2)O as characterized by surface tension and small angle neutron scattering. The micellar region is considerably extended in composition and concentration compared to that observed for the pure surfactant systems, and two types of aggregates are formed. Spherical micelles are present for AOT-rich composition, whereas cylindrical micelles with a mean length between 80 and 300 ? are present in the nonionic-rich region. The size of the micelles depends on both concentration and molar ratio of the surfactant mixtures. At higher concentration, a swollen lamellar phase is formed, where electrostatic repulsions dominate over the Helfrich interaction in the mixed bilayers. At intermediate concentrations, a mixed micellar/lamellar phase exists.     

"Snap-shooting" the interface of AOT reverse micelles: use of chemical trapping

The first use of the phenyl cation trapping technique in "snap-shooting" the local molar concentrations of water and sulfosuccinate head-groups in the interfacial region of AOT-2,2,4-trimethylpentane-water reverse micelles has been accomplished. Our results demonstrate that the interfacial concentrations of the sulfosuccinate head-groups in AOT (0.1 M)-2,2,4-trimethylpentane-water reverse micelles are remarkably high (2.75-2.34 M) across the W0 (the molar ratio of water to surfactant) range 12 to 44. However, the interfacial concentrations of water in AOT- 2,2,4-trimethylpentane-water reverse micelles across the same range of solution compositions are significantly lower (27.9-32.0 M) than the molar concentration of bulk water (55.5 M). The present results provide new insight on the microenvironments of interfacially located enzymes such as lipases entrapped in AOT-2,2,4-trimethylpentane-water reverse micelles, the most extensively exploited reverse-micellar system in micellar biotechnology.     

Nanostructure of open water-channel reversed micelles. I. 1H NMR spectroscopy and molecular modeling

A recently proposed model for the rodlike reversed micelles of nickel(II) bis(2-ethylhexyl)phosphate is examined in greater detail using 1H NMR spectroscopy and molecular modeling. 1H NMR spectra show that the solubilized water molecules are situated in a different environment compared with the water molecules in classical (AOT) reversed micelles. Geometry optimization and molecular dynamics simulation clearly indicate that the water molecules are not located in the interior core of the reversed micelles, but instead the water molecules exist in compartments or channels in the surface of these rodlike reversed micelles, thereby confirming the open water-channel model of reversed micelles. Molecular modeling was also employed to examine the effects of surfactant molecular structure, cosurfactant, solvent aromaticity, and temperature on the nanostructure of the reversed micellar aggregates. It is significant that molecular modeling provides an interpretation of the nanostructure of reversed micellar aggregates that is consistent with a variety of known experimental observations reported in the liquid/liquid extraction literature. These findings show that the structure of reversed micelles is much richer at the nanoscale level than previously recognized.     

FT-IR Investigation of the State of Iron(III) Chloride Clusters Confined in AOT Reverse Micelles Dispersed in Carbon Tetrachloride

The state of the water-soluble salt iron(III) chloride in AOT reverse micelles dispersed in carbon tetrachloride has been investigated by FT-IR spectroscopy. Interestingly, while the entrapment of a lot of water-soluble inorganic salts in AOT reverse micelles requires preliminarily the presence of significant amounts of water within the micellar core, solubilization of FeCl₃ occurs without the need to add water in the micellar solution reaching the very high solubility value, expressed as the maximum salt-to-surfactant molar ratio, of 1.30. The analysis of the spectral features of the investigated samples leads to hypothesize that iron(III) chloride is confined within the reverse micellar core as small size melted clusters of ionic species arising from the reactions