Effect of compressed CO2 on the critical micelle concentration and aggregation number of AOT reverse micelles in isooctane

The effect of compressed CO2 on the critical micelle concentration (cmc) and aggregation number of sodium bis-2-ethylhexylsulfosuccinate (AOT) reverse micelles in isooctane solution was studied by UV/Vis and fluorescence spectroscopy methods in the temperature range of 303.2-318.2 K and at different pressures or mole fractions of CO2 (X(CO2)). The capacity of the reverse micelles to solubilize water was also determined by direct observation. The standard Gibbs free energy (DeltaGo(m)), standard enthalpy (DeltaHo(m)), and standard entropy (DeltaSo(m)) for the formation of the reverse micelles were calculated by using the cmc data determined. It was discovered that the cmc versus X(CO2) curve and the DeltaGo(m) versus X(CO2) curve for a fixed temperature have a minimum, and the aggregation number and water-solubilization capacity of the reverse micelles reach a maximum at the X(CO2) value corresponding to that minimum. These results indicate that CO2 at a suitable concentration favors the formation of and can stabilize AOT reverse micelles. A detailed thermodynamic study showed that the driving force for the formation of the reverse micelles is entropy.     

Enhanced stabilization of reverse micelles by compressed CO2

The effect of compressed CO2 on the solubilization capacity of water in reverse micelles of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in longer chain n-alkanes was studied at different temperatures and pressures. It was found that the amount of solubilized water is increased considerably by CO2 in a suitable pressure range. The suitable CO2 pressure range in which the solubilization capacity of water could be enhanced decreased with increasing W0 (water-to-AOT molar ratio). The microenvironments in the CO2-stabilized reverse micelles were investigated by UV/Vis adsorption spectroscopy with methyl orange (MO) as probe. The mechanism by which the reverse micelles are stabilized by CO2 is discussed in detail. The main reason is likely to be that CO2 has a much smaller molecular volume than the n-alkane solvents studied in this work. Therefore, it can penetrate the interfacial film of the reverse micelles and stabilize them by increasing the rigidity of the micellar interface and thus reducing the attractive interaction between the droplets. However, if the CO2 pressure is too high, the solvent strength of the solvents is reduced markedly, and this induces phase separation in the micellar solution.     

Effect of compressed CO2 on the properties of lecithin reverse micelles

Lecithin is a very useful biosurfactant. In this work, the effects of compressed CO 2 on the critical micelle concentration (cmc) of lecithin in cyclohexane and solubilization of water, lysozyme, and PdCl 2 in the lecithin reverse micelles were studied. The micropolarity and pH value of the polar cores of the reverse micelles with and without CO 2 were also investigated. It was found that CO 2 could reduce the cmc of the micellar solution and enhance the capacity of the reverse micelles to solubilize water, the biomolecule, and the inorganic salt significantly. Moreover, the water pools could not be formed in the reverse micelles in the absence of CO 2 because of the limited amount of water solubilized. However, the water pools could be formed in the presence of CO 2 because large amounts of water could be solubilized. All of these provide more opportunity for effective utilization of this green surfactant. The possible mechanism for tuning the properties of the reverse micelles by CO 2 is discussed.     

Electrochemical extraction of proteins by reverse micelle formation

The transfer of proteins by the anionic surfactant bis(2-ethylhexyl) sulfosuccinate (AOT) at a polarized 1,2-dichloroethane/water (DCE/W) interface was investigated by means of ion-transfer voltammetry. When the tetrapentylammonium salt of AOT was added to the DCE phase, the facilitated transfer of certain proteins, including cytochrome c (Cyt c), ribonuclease A, and protamine, could be controlled electrochemically, and a well-defined anodic wave for the transfer was obtained. At low pH values (e.g., pH 3.4), the anodic wave was usually well-separated from the wave for the formation of protein-free (i.e., unfilled) reverse micelles. The anodic wave for the protein transfer was analyzed by applying the theory for facilitated transfer of ions by charged ligands and then supplying information regarding the number of AOT anions reacting with one protein molecule and the total charge carried by the protein transfer. However, controlled-potential electrolyses performed for the transfer of Cyt c, which is red, revealed that the protein-AOT complexes were unstable in DCE and liable to aggregate at the interface when the pH of the W phase was 3.4. At pH 7.0, when formation of unfilled reverse micelles occurred simultaneously, the protein-AOT complexes appeared to be stabilized, probably via fusion with unfilled reverse micelles.     

Effect of pharmaceuticals on thermoreversible gelation of PEO-PPO-PEO copolymers

Pluronic F127, a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), has generated considerable interest as a drug delivery vehicle due to its ability to gel at physiological temperatures. This work examines the gelation behavior of Pluronic F127 in the presence of a series of hydrophobic pharmaceuticals, to determine whether there is any correlation between gelation and physicochemical parameters of drug solutes. The study includes the local anesthetics dibucaine, lidocaine, and tetracaine; the pharmaceutical additives methyl paraben, ethyl paraben, and propyl paraben; the anti-cancer agents paclitaxel and baccatin III; and the anti-inflammatory agent sulindac. The results indicate that the presence of local anesthetics and pharmaceutical additives allows F127 solutions to form gels at lower copolymer concentrations; local anesthetics and pharmaceutical additives also shift gelation down to a lower gelation temperature. This behavior is strongly dependent on drug solubility; poorly soluble drugs (paclitaxel, baccatin III, sulindac) do not change the lower gelation temperature or minimum F127 concentration for gelation. An equation relating the decrease in gelation temperature to drug solubility is presented, and the equation fits the data well. The results have significant positive implications on the toxicity and economic issues related to use of Pluronic F127 in drug delivery.     

Effect of compressed CO2 on the chloroperoxidase catalyzed halogenation of 1,3-dihydroxybenzene in reverse micelles

The effect of compressed CO2 on the specific activity of chloroperoxidase (CPO) to catalyze the chlorination of 1,3-dihydroxybenzene in cetyltrimethylammonium chloride (CTAC)/H2O/octane/pentanol reverse micellar solution was studied. The results show that the specific activity of the enzyme can be enhanced significantly by compressed CO2, and the specific activity can be tuned continuously by changing pressure. The mechanism for the specific activity enhancement of the enzyme by CO2 was also studied. We believe that compressed CO2 can be utilized to tune some other enzyme catalytic reactions in different reverse micellar systems with potential advantages.     

Enhanced solubilization of bovine serum albumin in reverse micelles by compressed CO2

The effect of compressed CO2 on the solubilization of bovine serum albumin (BSA) in water/sodium bis-(2-ethylhexyl) sulfosuccinate (AOT)/isooctane reverse micelles was studied by observing phase behavior and recording UV-visible spectra under different conditions. The pH values within the water cores of reverse micelles at different CO2 pressures were also determined. The solubilization capacity of the reverse micelles for the protein increased considerably as CO2 pressure increased within the low-pressure range, but decreased at higher CO2 pressures, so that the micelles eventually lost their ability to solubilize the protein. The effect of CO2 on the stability of the reverse micelles played an important role in the relationship between pressure and protein solubility. A "multicomplex" model was proposed to explain these effects. The different solublization capacities within different pressure ranges demonstrates the unique advantage of using compressed CO2 in the extraction of proteins with reverse micelles.     

Three-dimensionally ordered porous membranes prepared via self-assembly and reverse micelle formation from well-defined amphiphilic block copolymers

Block copolymers of poly(pentafluorostyrene) (PFS) and poly(tert-butyl acrylate) (PtBA), or PFS-b-PtBA copolymers, were synthesized via consecutive atom transfer radical polymerizations (ATRPs). Amphiphilic block copolymers of PFS and poly(acrylic acid) (PFS-b-PAAC copolymers) were prepared via hydrolysis of the corresponding PFS-b-PtBA copolymers. The chemical structure and composition of the PFS-b-PtBA and PFS-b-PAAC block copolymers were studied by nuclear magnetic resonance (NMR) spectroscopy, themogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The amphiphilic PFS-b-PAAC copolymers were cast into porous membranes by phase inversion in aqueous media. The surface and cross-sectional morphology of the PFS-b-PAAC membranes were studied by scanning electron microscopy (SEM). Membranes with well-defined pores of sizes in the micrometer range were obtained as a result of inverse micelle formation. The pH of the aqueous media for phase inversion and the PAAC content in the PFS-b-PAAC copolymers could be used to adjust the pore size of the membranes.     

Molecular dynamics simulation of a reverse micelle self assembly in supercritical CO2

In this communication we report on molecular dynamics computer simulations of self-assembly of reverse micelles in supercritical carbon dioxide. The reverse micelles contain perfluoropolyether ammonium carboxylate surfactants and an aqueous core. We observed a quick self-assembly of these micelles over time periods of approximately 5 ns, irrespective of initial conditions. In most cases, the self-assembled perfluorinated reverse micelles have a nice spherical shape and properties consistent with experiments. When the fluorinated surfactant is replaced by its hydrogenated analogue, the assembled aggregate contains a region of direct contact between water and carbon dioxide, indicating that hydrogenated surfactant is not a good agent for creation of microemulsions in water/carbon dioxide mixtures.     

Salt induced micellization of very hydrophilic PEO-PPO-PEO block copolymers in aqueous solutions

Symmetrical poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), PEO-PPO-PEO, triblock copolymers with 80% polyethylene oxide (PEO, the hydrophilic end blocks) and polypropylene oxide (PPO, the hydrophobic middle block) usually remain as molecularly dissolved at ambient temperature even at fairly high-concentrations (2 wt.% or more). However, the micellization is induced at lower concentration/temperature in the presence of salts. The results on salt induced micellization from four such hydrophilic copolymers Pluronic^® F38, F68, F88 and F108 obtained from several independent techniques are described. FTIR and fluorescence results provide essentially identical critical micelle temperatures (CMTs) showing marked decrease with increase in PPO molecular weight and in the presence of salt. These copolymers were weakly surface active and did not show a clear break point in surface tension concentration plot typical of surfactants. While addition of salt decreases the cloud point, no significant micelle growth was observed even at temperature close to cloud point (CP). Marked increased in solubilization of an oil dye was observed in presence of KCl. Different methods showed good agreement in temperature/salt-induced micellization of these hydrophilic copolymers.     

Hydrothermal synthesis of ZnO nanobundles controlled by PEO-PPO-PEO block copolymers

Homocentric ZnO nanobundles with pyramidlike and hexagonal prism shapes were synthesized in colloidal systems formed by PEO-PPO-PEO amphiphilic block copolymers. The prism- and pyramidlike ZnO crystals were produced by L64 and F68, respectively, which may be attributed to the different growth rates of various crystal facets. It was proposed that the two processes for crystallization, including nucleation and crystal growth, happened in the macromolecular micelles under hydrothermal conditions. The room-temperature photoluminescence spectra of the ZnO products showed sharp ultraviolet emission located around 390 nm originating from the radiative recombination of free excitons. The sharp emission, with a half-maximum of about 8 nm, gave a powerful attestation that the sample was of high crystal quality, which was consistent with the SEM and TEM observations. The single ultraviolet emission is important for the application of ZnO-based materials in the electronic and photonic realms.     

Adsolubilization of 2-naphthol into adsorbed layer of PEO-PPO-PEO triblock copolymers on hydrophilic silica

Adsolubilization of 2-naphthol into an adsorbed layer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers (Pluronics) on hydrophilic silica has been investigated. Four kinds of Pluronics (P103, P105, P123, and F108) were used in order to understand the effect of the hydrophobicity of surfactant on the adsolubilization. The order of the adsorption in the saturation level was found to be P123 approximately P103 > P105 > F108, meaning that Pluronics with higher hydrophobicity can adsorb preferentially to the silica surface. Indeed, this order was parallel to the order of the adsolubilization amount of 2-naphthol. In the case of co-addition of the Pluronics and 2-naphthol, the adsolubilization amount increased gradually at lower surfactant concentration regions, reached a maximum, and then decreased with increasing concentration of the Pluronics. The maximum amount appeared at critical polymolecular micelle concentration of each Pluronics. On the other hand, the final decrement was not observed when 2-naphthol was added after replacement of the Pluronics supernatant by the Pluronics free solution. These results suggest that adsolubilization behavior is influenced by the existence of the polymolecular micellar aggregates in the solution phase.     

Effect of ionic liquids on the aggregation behavior of PEO-PPO-PEO block copolymers in aqueous solution

Effect of 1-butyl-3-methyl-imidazolium bromide (BmimBr) on the aggregation behavior of PEO-PPO-PEO Pluronic P104 aqueous solution was studied by Fourier transform infrared (FTIR) spectroscopy, freeze fracture transmission electron microscopy (FF-TEM), dynamic light scattering (DLS), and NMR spectroscopy. When the BmimBr concentration was below 1.232 mol/L, the critical micelle temperature (CMT) of Pluronic P104 remained constant, while the size of micelles increased with increasing the BmimBr concentration; above this concentration, the CMT of Pluronic P104 decreased abruptly, and bigger clusters of BmimBr were formed. The selective nuclear Overhauser effect (NOE) spectrum indicates that the PO block of the P104 interacts with the butyl group of the Bmim+ cation by hydrophobic interaction. It suggests that when the concentration of BmimBr is below 1.232 mol/L, there are P104 micelles in the aqueous solution with BmimBr embedding to the micellar core, while above this concentration, P104 micelles and BmimBr clusters coexist in the system.     

Adsolubilization of 2-naphthol into adsorbed layers of triblock PEO-PPO-PEO copolymers on hydrophobic silica particles

Adsolubilization of 2-naphthol into an adsorbed layer of triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, Pluronics) copolymers on hydrophobically modified silica particles has been investigated. Four kinds of Pluronics (P103, P105, P123, and F108) were employed in order to understand the effect of the hydrophobicity of the surfactants on the adsolubilization. The amount of the Pluronics adsorbed of the maximum/saturation adsorption level was increased with a decrease in the HLB value, suggesting that the more hydrophobic Pluronics (P103 and P123) adsorb preferentially onto the hydrophobic silica surface over the more hydrophilic Pluronics (P105 and F108). The greater adsorbed amount of the more hydrophobic surfactants resulted in a greater amount of 2-naphthol adsolubilized into the adsorbed Pluronics layers. In the case of simultaneous addition of the Pluronics and 2-naphthol, the amount adsolubilized into the adsorbed P123 and P103 layers increased in their low-surfactant-concentration regime, reached a maximum, and then decreased with a further increase in the Pluronics concentration. On the other hand, for both the P105 and F108 copolymers, a decrease in the adsolubilized amount was not observed over the whole range of copolymer concentration investigated. This difference is attributed to a difference in the hydrophobicity of the micellar aggregates in solution and of the adsorbed layers on the hydrophobic surface. When 2-naphthol was added after replacement of the Pluronics supernatant by a surfactant-free solution, the final decrease in the adsolubilization was insignificant for all the Pluronics. Indeed, the maximum amount of adsolubilization was comparable to the corresponding amount obtained in the case of simultaneous addition.     

Effect of compressed CO2 on crystallization and melting behavior of isotactic polypropylene

Compressed gases such as CO₂ above their critical temperatures provide a highly tunable technique that has been shown to induce changes in phase behavior, crystallization kinetics and morphology of the polymers. Gas induced plasticization of the polymer matrix has been studied in a large number of polymers such as polystyrene, and poly(ethylene terephathalate). The knowledge of polymer–gas interactions is fundamental to the study of phenomena such as solubility and diffusivity of gases in polymers, dilation of polymers and in the development of applications such as foams and barrier materials.In this paper, we describe the interactions of compressed CO₂ with isotactic polypropylene (PP). Crystallization of various PPs in presence of compressed CO₂ was evaluated using a high pressure differential scanning calorimeter (HPDSC). CO₂ plasticized the polymer matrix and decreased the crystallization temperature, T_c by ∼8 °C for PP at a pressure of 650 psi CO₂. The decrease as a function of pressure was −0.173 °C/bar and did not change with the molecular architecture of PP. Both crystallization kinetics and melting behavior are evaluated.Since solubility and diffusivity are important thermodynamic parameters that establish the intrinsic gas transport characteristics in a polymer, solubility of CO₂ in PP was measured using a high-pressure electrobalance and compared with cross-linked polyethylene. At 50 °C, solubility followed Henry’s law and at a pressure of 200 psi about 1% CO₂ dissolved in PP. Similar solubility was achieved in PE at a pressure of 160 psi. Higher solubility of CO₂ in PE is attributed to its lower crystallinity and lower T_g, than PP. Diffusion coefficients were calculated from the sorption kinetics using a Fickian transport model. Diffusivity was independent of pressure and PE showed higher diffusivity than PP. Preliminary foaming studies carried out using a batch process indicate that both PP and PE can be foamed from the solid state to form microcellular foams. Cell size and cell density were ∼10 μm and 10⁸ cells/cm³, respectively in PE. Differences in morphology between the foams for these polymers are attributed to the differences in diffusivity.     

Molecular simulation of an aerosol OT reverse micelle: 1. The shape and structure of a micelle

The simulation of an Aerosol OT micelle in the apolar environment is performed via the molecular dynamics method in the approximation of a coarse-grain model. The mean size and shape of a micelle, as well as its molecular structure, are determined as functions of the water-surfactant ratio and aggregation number. Geometric parameters of aggregates are estimated through calculation of the inertia tensors of its internal portion under the assumption of an ellipsoidal shape of a micelle. Radial profiles of the partial density and pair correlation functions are obtained, which are used to calculate coordination numbers for water molecules, counterions, and surface-active ions. The most probable arrangement of water molecules and surfactant anions are found on the basis of orientation distribution functions.     

Influence of surfactant structure on reverse micelle size and charge for nonpolar electrophoretic inks

Electrophoretic inks, which are suspensions of colorant particles that are controllably concentrated and dispersed by applied electric fields, are the leading commercial technology for high-quality reflective displays. Extending the state of the art for high-fidelity color in these displays requires improved understanding and control of the colloidal systems. In these inks, reverse micelles in nonpolar media play key roles in media and particle charging. Here we investigate the effect of surfactant structure on reverse micelle size and charging properties by synthesizing different surfactants with variations in polyamine polar head groups. Small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS) were used to determine the micelle core plus shell size and micelle hydrodynamic radius, respectively. The results from SAXS agreed with DLS and showed that increasing polyamines in the surfactant head increased the micelle size. The hydrodynamic radius was also calculated on the basis of transient current measurements and agreed well with the DLS results. The transient current technique further determined that increasing polyamines increased the charge stabilization capability of the micelles and that an analogous commercial surfactant OLOA 11000 made for a lower concentration of charge-generating ions in solution. Formulating magenta inks with the various surfactants showed that the absence of amine in the surfactant head was detrimental to particle stabilization and device performance.     

Dendrimer-influenced supramolecular structure formation of block copolymers

The water content-dependent supramolecular structure formation of polystyrene-block-poly(acrylic acid) (PS-b-PAA) copolymer in the presence of a fourth-generation amine-terminated poly(amido amine) dendrimer (PAMAM) is investigated by dynamic light scattering, turbidity measurements, and transmission electron microscopy. The solvent system for this study is a mixture of dioxane/THF and water. A very complex turbidity profile is observed with increasing water content in the system and is explained by the presence of various aggregated structures based on strong interactions between the amine-containing dendrimers and the poly(acrylic acid) blocks of the polymer. The onset of the self-assembly of single chains of PS-b-PAA (primary structure) into single and multiple dendrimer core inverse micelles (secondary structure) is detected as very low water contents of cw < 2% wt (cwc). These micelles consist of dendrimers coated with PAA blocks, which are connected to the corresponding PS chains that form the corona. Further addition of water leads to an association of these micelles into compound multiple dendrimer core inverse micelles (tertiary structure) in the range of cw = approximately 6 to approximately 10% wt. At still higher water content, some of the acrylic acid chains of the block copolymer move from the vicinity of the dendrimer to the outside of the aggregates, resulting in a decrease in the size of the formed structures and the acquisition of progressively increasing hydrophilic character of the aggregates. Multiple dendrimer core inverse onion micelles are formed, which agglomerate into compound multiple dendrimer core inverse onion micelles at cw = approximately 12 to approximately 18% wt. Above this water content, vesicular structures are formed. The complexity is unusual for block copolymer systems and illustrates the importance of strong interactions in structure formation.     

Superhydrophobic surfaces fabricated by spray-coating micelle solutions of comb copolymers

A series of comb copolymers (poly(arylene alkylene ether) (FPAE)-polystyrene (PS)) with a highly fluorinated FPAE main chain and narrow dispersed PS-grafted chains have been prepared. They are used to prepare micelle solutions in methanol/acetone (M/A) mixed solvents which are good for the FPAE main chains and poor for the PS-grafted chains. In these solutions, the PS-grafted chains form the cores and the FPAE main chains form the corona layers of micelle particles. Uniform micelle particles are achieved because of the narrow molecular weight dispersion of the PS chain length. The micelle solutions are spray-coated onto glass substrates to fabricate hydrophobic surfaces. It is found that the stability of the micelle particles increases with the length of the PS-grafted chains, which further influences the morphology and hydrophobicity of the spray-coated films. The effects of the M/A ratio and the copolymer concentration on the morphology and hydrophobicity of the coating surfaces are also studied. The results prove that a binary nano/microsurface structure is important to achieve a superhydrophobic surface with a low contact angle hysteresis. This binary structure is formed from conglomeration of micelle particles by spray coating the micelle solutions. The best sample reported in this paper has a static contact angle of 163° and a sliding angle of 5.9°. This fabrication procedure is facile, less time consuming, and easily applicable for large-scale surface treatment.     

Control of self-aldol condensation by pressure manipulation under compressed CO2

Under supercritical CO2 conditions, simple adjustment of the pressure was found to successfully control the ratio of aldol to enal product in the self-aldol condensation of aldehyde, in which the enal product was obtained in a maximum selectivity of 94% at the critical pressure of 12MPa, whereas 85% selectivity to the aldol product was achieved at the subcritical region.