AOT Micelles Research Articles

Urea effect on aggregation and adsorption of sodium dioctylsulfosuccinate in water

Understanding the mechanism that controls the folding/unfolding of proteins in the presence of urea continues to be a subject of research, and since micelles mimic biological aggregates, equal importance has been given to the study of surfactants in the presence of urea. Despite several studies on the effect of urea on the behavior of reverse micelles and microemulsions based on sodium dioctylsulfosuccinate (AOT), the urea effect on AOT regular micelles has not been investigated and hence it is studied herein by using surface tension, steady-state fluorescence, and dynamic light scattering methods. The effect of urea on the behavior of AOT is found to be different below and above 1.0molkg−1 urea (cu). The critical micelle concentration (cmc) is almost independent of urea concentration below cu, whereas it increases with increasing urea amount above cu. In AOT+urea aqueous solution below cu, added NaCl at a particular critical concentration (c*) induces sudden increase in the values of (i) counterion binding constant, (ii) aggregation number, (iii) fluorescence intensity ratio of pyrene excimer to monomer, and (iv) hydrodynamic diameter of AOT aggregate, whereas such changes are suppressed by urea above cu. NaCl-induced shape change in AOT micelle takes place if urea concentration is below cu, but hindered above cu. The adsorption behavior of AOT at the air–solution interface as a function of NaCl is also found to be different below and above cu. The urea effect is explained in terms of increase in the polarity of the medium, better solvation of head groups and counterions, and weakening of head group–head group and head group–counterion interactions.

Curcumin in Reverse Micelle: An Example to Control Excited-State Intramolecular Proton Transfer (ESIPT) in Confined Media

In this Article, we focused on the modulation of the photophysical properties of curcumin, an anti-cancer drug, in aqueous and nonaqueous reverse micelles of AOT in n-heptane using steady-state and time-resolved fluorescence spectroscopy. The instability of curcumin is a common problem which restricts its numerous applications like Alzheimer disease, HIV infections, cystic fibrosis, etc. Our study reveals that curcumin shows comparatively higher stability after encapsulation into the interfacial region of the reverse micelle. To get a vivid description of the microenvironment, we added hydrogen-bond-donor (HBD) as well as non-hydrogen-bond-donor (NBD) core solvents. For experimental purposes, we used water, ethylene glycol (EG), glycerol (GY) as HBD solvents and N,N-dimethyl formamide (DMF) as a NBD solvent. With increasing amount of core solvents, irrespective of HBD or NBD, the fluorescence intensity and lifetime of curcumin increase with remarkable red-shift inside the reverse micelle. This is attributed to the modulation of the nonradiative rates associated with the excited-state intermolecular hydrogen bonding between the pigment and the polar solvents. We obtained a high partition constant at W0 = 0 (W0 = [core solvent]/[AOT]) which is certainly due to the hydrogen bonding between the negatively charged sulfonate group of AOT and hydroxyl groups of curcumin. Steady-state anisotropy and time-resolved results give an idea about the microenvironment sensed by the curcumin molecules. The red-shift of emission spectra, increase in the value of ET(30), as well as the increase in the fluorescence lifetime were interpreted as being caused by the partition of the probe between the micellar interface and the polar core solvent. Indeed, we show here that it is possible to control the excited state intramolecular proton transfer (ESIPT) process of curcumin by simply changing the properties of the AOT reverse micelle interfaces by choosing the appropriate polar solvents to make the reverse micelle media.

Study of influence of ionic additives to AOT reverse microemulsions by liquid chromatography, IR and UV–visible spectroscopy

Reverse micellar mobile phases based on sodium bis(2-ethylhexyl) sulfosuccinate (AOT) were used as mobile phases in HPLC. The chromatographic behavior of the model compounds was studied on the basis of reverse micellar mobile phases modified by salt additives. Structural changes of water pools of reverse micelles depending from AOT concentration in the presence or absence of structure-making and structure-breaking ions was investigated by IR-Spectroscopy. The OH stretching vibrational absorption spectra in the region of 3000–3800cm−1 were fitted into three subpeaks with a Monte Carlo method. The binding of o-nitroaniline (o-NA) to the micelles of AOT was determined by UV–visible spectroscopy. The different influence of kosmotropic and chaotropic anions on the binding constant Kb was revealed.

Evidence for a Critical Micelle Concentration of Surfactants in Hydrocarbon Solvents

The concentration-dependent aggregation of two surfactants, anionic sodium dioctylsulfosuccinate (Aerosol OT or AOT) and nonionic pentaethylene glycol monododecyl ether (C12E5), has been studied in cyclohexane-D12 using small-angle neutron scattering (SANS). A clear monomer-to-aggregate transition has been observed for both surfactants, spherical inverse micelles for AOT and hank-like micelles for C12E5. This suggests that a critical micelle concentration exists for surfactants of these kinds in nonpolar solvents. The nature of the transition is different for the two surfactants. AOT aggregates are the same size and shape with decreasing concentration until a sharp critical micelle concentration, after which they cannot be detected. However, C12E5 aggregates gradually decrease in size. These differences demonstrate that the strength of the solvophobic effect can influence the formation of surfactant aggregates in nonaqueous solvents.

Quenching of the triplet state of safranine-O by aliphatic amines in AOT reverse micelles studied by transient absorption spectroscopy

The photophysics of Safranine-O (3,6-diamino-2,7-dimethyl-5 phenyl phenazinium chloride) (SfH(+)Cl(-)) was investigated in reverse micelles (RMs) of AOT (sodium bis(2-ethylhexyl)sulfosuccinate) with special emphasis on the triplet state processes. The triplet is formed in its monoprotonated form, independently of the pH of the water used to prepare the RMs. While the intersystem crossing quantum yields in RMs are similar to those in organic solvents, the triplet lifetime is much longer. Since the pH in the water pool of AOT RMs is close to 5 and the triplet state of the dye is subjected to proton quenching, the long lifetime indicates that the dye resides in a region where it cannot be reached by protons during its lifetime. All the measurements indicate that the dye is localized in the interface, sensing a medium of micropolarity similar to EtOH : water (3:1) mixtures. The quenching by aliphatic amines was also investigated. While the quenching by the hydrophobic tributylamine is similar to that in methanol, the hydro-soluble triethanolamine is one order of magnitude more effective in RMs than in homogeneous solution. In the latter case the quenching process is interpreted by a very fast intramicellar quenching, the overall kinetics being controlled by the exchange of amine molecules between RMs. Semireduced dye is formed in the quenching process in RMs in the di-protonated state with a comparable quantum yield to the monoprotonated state formed in homogeneous solvents. The results point to the advantage of the reverse micellar system for the generation of active radicals for the initiation of vinyl polymerization, since a much lower concentration of amine can be employed with similar quantum yields.

Determining the hydrodynamic radii of AOT micelles with silver nanoparticles by means of photon correlation spectroscopy

The possibility of determining the sizes of micelles of sodium di(2-ethylhexyl)sulfosuccinate (AOT) with silver nanoparticles in decane against the background of a large excess of empty micelles by means of photon correlation spectroscopy with unimodal analysis of the autocorrelation function is demonstrated. Contributions from all components to the light scattering are estimated by measuring the static (Rayleigh) light scattering and allowing for partial absorption of the laser radiation by silver nanoparticles. Areas of the correct determination of the hydrodynamic radius of the micelles with nanoparticles are determined via unimodal analysis of the autocorrelation function in dependence on the nanoparticle size (10–2 nm) and silver concentration (1–30 mM) at a constant AOT concentration (0.25 mol/L) and aqueous pseudophase content (1 vol %).

EPD of Reverse Micelle Pd and Pt Nanoparticles onto InP and GaN for High-Response Hydrogen Sensors

We investigated properties of nanolayers electrophoretically deposited (EPD) onto semiconductor indium phosphide (InP) or gallium nitride (GaN) single crystals from colloid solutions of metal palladium (Pd), platinum (Pt) or bimetallic Pd/Pt nanoparticles (NPs) in isooctane. Colloids with metal NPs were prepared by reaction of metal compounds with the reducing agent hydrazine in water confined to reverse micelles of surfactant AOT.. Chopped DC electric voltage was applied for the time period to deposit metal NPs, only partly covering surface of the wafer. The deposits were image-observed by scanning electron microscopy (SEM)..Diodes with porous Schottky contacts were made by printing colloidal graphite on the NPs deposited surface and making ohmic contact on the blank side of the wafer. The diodes showed current-voltage characteristics of excellent rectification ratio and barrier height values close to Schottky-Mott limit, which was an evidence of negligible Fermi level pinning. Large increase of current was observed after switching on a flow of gas blend hydrogen in nitrogen (H2/N2). The diodes were measured with various H2/N2in the range from 1000 ppm to 1 ppm of H2. Current change ratios about 106and about 10 were achieved with 1000 ppm and 1 ppm H2/N2.

Abnormal polymorph conversion of calcium carbonate from calcite to vaterite

Inspired by mineralization in biological organisms, the production of higher ordered CaCO3 crystals modified by surfactants has received much attention. Normal micelles formed by anionic surfactant, sodium bis-2-ethylhexyl-sulfosuccinate (aerosol OT, AOT), was used as a template to direct the growth of CaCO3 crystals in the present work. When the concentration of the AOT increased from 0.5 to 5.0mM, the polymorph of CaCO3 crystals changed from almost pure aragonite to almost pure vaterite at 150°C. In the meantime, various morphologies of vaterite were obtained, such as astral and hexagonal structures. Based on the time-resolved experiments, we suggested that AOT micelles induced the formation of these structures. And the micelles were wrapped in the hexagonal structures, and dissolved in the aqueous solution with increase of the experimental time. Thus, hollow shells were produced. Abnormal polymorph transformation of CaCO3 crystals from the calcite to the vaterite was found. These effects of AOT on polymorph and morphology of CaCO3 crystals have not been reported as far as we know.

Multiresonant Coherent Multidimensional Spectroscopy of the Vibrationally Induced Decarboxylation of AOT: Deuterium Oxide Reverse Micelles

The multiresonant coherent multidimensional spectroscopy study of D(2)O in AOT micelles reveals two unexpected features in addition to those expected for D(2)O. These features appear when the excitation pulse time ordering defines either fully coherent Liouville pathways or partially coherent pathways where there are intermediate populations. The features shift as the excitation pulse ordering changes between the two sets of pathways. They are attributed to the asymmetric stretch mode of CO(2) that is formed by the infrared excited decarboxylation of AOT. The cross-peaks' intensity is enhanced when the excitation pulse is resonant with the CO(2) P and R branches for the fully coherent pathways, but they are depressed at the P and R branch resonances for the partially coherent pathways. The enhancement is attributed to the simultaneous production of CO(2) during the first excitation pulse when it is resonant with both the CO(2) and the D(2)O. The depression is attributed to the absorption of the last excitation pulse by the CO(2) produced by the previous two excitation pulses. We believe that the decarboxylation occurs because of energy transfer from multiply excited D(2)O molecules. It may cause a Norrish type I α-cleavage in the AOT that is followed by a Hunsdiecker reaction β-scission of the radical to form the CO(2). This experiment demonstrates the marriage of infrared induced chemistry and multiresonant coherent multidimensional spectroscopy into a single nonlinear process.

Dynamics of water confined to reverse AOT micelles

We use quasi-elastic neutron scattering (QENS) to study the dynamics of water confined inside reverse micelles. As a model system we use a water-in-oil droplet microemulsion based on the anionic surfactant AOT (sodium bis[2-ethylhexyl] sulfosuccinate), that forms spherical water droplets coated by a monolayer of AOT dispersed in the continuous oil matrix. Combining neutron time-of-flight (TOF) and backscattering (BS) spectroscopy, we access the dynamical behaviour of water over three decades in time from pico- to nanoseconds. We investigate the influence of reverse micelle size on the water dynamics by comparing two sample systems with bigger and smaller water core radii of about Rc ≈ 12 A and 7 A. The temperature is varied over a range where both microemulsion systems are stable, from room temperature down to the region where the confined water is supercooled: 260 K ≤ T ≤ 300 K. Taking explicitly into account the previously measured diffusion of entire reverse micelles in the oil matrix we find the average mobility of the confined water to be considerably slowed with respect to bulk water. The translational diffusion decreases with decreasing reverse micelle size. Dependent on the reverse micelle size we can interpret our data by assuming two dynamically separated water fractions. We identify the faster one with bulk-like water in the middle of the core while the slower one seems to be surfactant bound water. We find that 4 molecules of water per AOT molecule are immobilized on the timescale of QENS, i.e. shorter than nanoseconds.

Granulomes hépatiques pseudo-sarcoidosiques et carcinome hépato-cellulaire : à propos d’un cas et revue de la littérature

Fusarium solani pisi cutinase microencapsulated in reversed micelles of AOT (bis(2-ethylhexyl) sodium sulfosuccinate) was used to catalyse the alcoholysis of butyl acetate (acyl donor) with hexanol. In the present study the stability of cutinase is evaluated comparatively with the initial activity in order to obtain a set of conditions to fully optimise the system. The start conditions were selected based on a synergy of the results assigned in previous work, where relevant parameters for the cutinase activity, such as temperature, buffer molarity, pH, amount of water, surfactant, hexanol and butyl acetate concentrations were studied. Using a 2(5−1) factorial design expanded further to a central composite design (CCD), the effects of each factor mentioned above (with exception of temperature and acetate concentration) on the stability were calculated and the interactions were determined. The surface methodology applied to the results showed that cutinase, incubated at 40°C retained a high activity level (90%) after 3 days when microencapsulated at W0 (molar ratio of water to surfactant) 2.7. The W0 values in the range 5–8 led to optimal-specific activities with lower stability. A hexanol concentration of 500–600 mm was essential to prevent deactivation and at the same time allowed relatively high initial rates. A pH value of 8.0–8.55 and a buffer molarity of 200 mm were suitable for both activity and stability. Cutinase in AOT reversed micelles has been usually reported to be very sensitive to temperature, however, in this work, at an incubation temperature of 40°C, cutinase displayed half-lives significantly greater than previously stated. The main reasons for this are the presence of hexanol and the reduced water content that promote a stabilisation of cutinase structure inside the micelles. The thermostability experiments performed with the selected conditions led to a half-life of 53 days, confirming the model predictions.

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.

The Effect of Surface Modification on the Magnetic Properties of CoFe2O4 Nano-Particles Synthesized by the Hydrothermal Method

Cobalt ferrite (CoFe2O4) nano-particles were synthesized by the hydrothermal method with the addition of a surfactant sodium bis(2-ethylhexyl) sulphosuccinate (AOT). Characterization measurements including X-ray diffraction, transmission electron microscopy and Fourier transform infrared spectroscopy showed that all the final products were single-phase CoFe2O4 nano-crystals with AOT molecules bonding to the surfaces, the average crystallite sizes were all near 25 nm, and the lattice constant increased with the increasing mass of AOT. The magnetic hysteresis loops measured at room temperature indicated that the bonding of the AOT to the surfaces led to an increase of the saturation magnetization (Ms), the coercivity (Hc) and the remanence ratio (Mr/Ms). Furthermore, as the concentration of AOT reached the critical micelle concentration (CMC), turning points were observed in the the curves of Hc, Mr/Ms and K(eff) (effective magnetic anisotropy constants) versus. the mass of AOT due to the formation of the AOT micelles.

Micellar Shape Driven Counterion Binding. Small-Angle Neutron Scattering Study of AOT Micelle

Sodium dioctylsulfosuccinate (AOT) micelle has a special counterion binding behavior in aqueous electrolyte medium, viz., the counterion binding constant (β) abruptly increases by 2-fold at about 0.015 mol dm(-3) NaCl concentration (c*), but not in sodium salicylate (NaSa) solution. Since counterions affect the structure and performance of ionic surfactants, ascertaining the cause for the sudden shift in the β value of AOT micelle is of fundamental importance. In this study the special counterion binding behavior of AOT micelle has been ascertained at 40 °C by carrying out surface tension, zeta potential, and fluorescence emission (pyrene probe) measurements. The results of the small-angle neutron scattering experiment carried out at 40 °C showed that at c* the shape of AOT micelle changes from prolate spheroid to rodlike in NaCl solution, but not in NaSa solution, thus establishing micellar shape change as responsible for the abrupt change in β value. The absence of sudden shift in β of AOT micelle in NaSa solution is attributed to the binding of salicylate coanion to AOT micelle through hydrophobic interaction.

Thermochemical study of silver halide nanoparticles formation conditions in AOT inverted micelles

AgCl and AgBr nanoparticles formation conditions were studied by a thermochemical method in AOT (sodium bis(2-ethylhexyl)sulfosuccinate) inverted micellar systems, in AOT—dioctyl sulfide (DOS) mixed micelles, and (for comparison) in aqueous solutions. The heats of formation of AgCl and AgBr nanoparticles in AOT micelles in exchange reactions with potassium halides are, respectively, −55.5 × (1 ± 0.07) and −68.6 × (1 ± 0.07) kJ/mol, that is, smaller in magnitude than the values obtained for aqueous solutions (−68 × (1 ± 0.07) and −88 × (1 ± 0.07) kJ/mol). This difference arises from the existence of particle interactions causing the formation of coagulation contacts between halide particles followed by precipitation in an aqueous phase and the absence of such interactions in a micellar medium. DOS interacts with AOT (to form mixed micelles) and with silver ions (in long-term contact), thus reducing the heats of reactions.

Investigation of the activity and stability of papain in different micellar systems

Hydrolysis of PyrPheAlaPNa, catalyzed by papain in reverse micelles of ionogenic surfactant of Aerosol OT, and in octane, was studied in the presence and in the absence of nonionogenic surfactants of a different nature. As found, the dependence of the catalytic activity of papain on the hydration degree of the surfactant in reverse micelles of AOT has two maxima, corresponding to the activity of monomeric and oligomeric forms of the enzyme. It was established that the addition of nonionogenic surfactant of a different nature to the Aerosol OT in octane leads to changes of the catalytic properties of the enzyme, in particular, to its activation in the presence of Pluronic L61. Nanoemulsions of nontoxic nonionogenic surfactant and organic solvents, lecithin and Tween 20 in eucalyptus oil were created and characterized; with the use of the photon-correlation spectroscopy technique it was shown that the size of such particles lie in the range from 34 to 266 nm, depending on the water content, nature, and the concentration of system components, and factors regarding its shape lie in the interval 20–30, suggesting the presence of particles with a rod-like shape. It is important to note that in such systems, suitable for use in medicine and cosmetology, the activity of papain was revealed.

Electrokinetic Potential of Nanoparticles in Reverse AOT Micelles: Photometric Determination and Role in the Processes of Heterocoagulation, Separation, and Concentration

A simple photometric method for determining the electrophoretic mobility of nano- and microparticles in reverse micelles and in solvents with a low dielectric permittivity (2-5) has been developed. The method is based on the use of a thermostatically controlled diaphragm-based optical cell (length 2 cm) with three vertical plane-parallel electrodes (2 x 3 cm; interelectrode gap, 0.3 cm) placed into a standard photocolorimeter. When an electrostatic field (100-600 V) is applied, the particles begin to move away from the electrode of the same polarity. The path traveled by the particles for a given time (2-30 s) is calculated from the change in the optical density of the solution in the near-electrode zone. The electrophoretic potential of nanoparticles in the model systems, calculated from the values of electrophoretic mobility by Huckel-Onsager theory, varied from 70 (Ag nanoparticles in AOT micelles in decane) to -73 mV (aggregated SiO(2) nanoparticles in a decane-chloroform mixture). Calculations by the classical Deryaguin-Landau-Verwey-Overbeek (DLVO) theory determined the contribution of the electrostatic interaction to the stability of the studied systems. We have shown that the surface charge of nanoparticles permits: (1) an electrophoretic concentration of the charged nanoparticles (Ag) with an enrichment factor of up to 10(4), (2) the separation of nanoparticles with zero (C(60)) and a high (Ag) electrokinetic potentials, and (3) the formation of electrostatically bound aggregates (Ag-SiO(2)) through the heterocoagulation of oppositely charged particles.

Interactions and Aggregations in Aqueous and Brine Solutions of Poly(diallydimethylammonium chloride)/Sodium Bis(2-ethylhexyl) Sulfosuccinate

The interactions between the anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and the polycation poly(diallydimethylammonium chloride) (PDDAC), the aggregations of AOT and PDDAC-bound AOT in PDDAC/AOT aqueous solutions, and the influence of salt on the interactions and aggregations have been studied by isothermal titration calorimetry (ITC), dynamic light scattering (DLS), and negative staining transmission electron microscopy (TEM). The adsorptions of AOT onto PDDAC and the formations of PDDAC-bound AOT micelles, free AOT micelles, and AOT vesicles were examined, and the corresponding critical concentrations were determined. Combining calculations of thermodynamic parameters with the above three experimental techniques, it was shown that the micellization of free AOT is driven by entropy gain, while the adsorption of AOT onto PDDAC and the micellization of PDDAC-bound AOT are driven by both enthalpy and entropy. It was also found that addition of salt enhances the binding of AOT onto PDDAC through the ion exchange and favors the formations of PDDAC/AOT micelles, free AOT micelles, and free AOT vesicles but prevents the transition of PDDAC/AOT micelles to the vesicles. Thermodynamic analysis suggested that the adsorption of AOT onto PDDAC and the micellization of PDDAC/AOT in PDDAC/AOT brine solutions are different in mechanism compared with that in corresponding aqueous solutions.

An Alpha-Helical Peptide in AOT Micelles Prefers to be Localized at the Water/Headgroup Interface

A model alpha-helical peptide encapsulated in a reverse micelle is used to study the structure and dynamics of proteins under constrained environments that mimic the membrane-water environment in cells. Molecular dynamics simulations of the self assembly of systems composed of a peptide, sodium bis(2-ethylhexyl) sulfosuccinate (AOT), water, and isooctane show that the peptide prefers to be located at the water/AOT headgroups interface. We explore the effect of the AOT headgroup charge and the peptide charge and find that the peptides migrate to the interface in all cases. These results show that the peptides prefer the constrained hydration environment of the AOT headgroups. The driving force for this configuration is the gain in entropy by released water molecules that otherwise would solvate the protein and surfactant headgroups

Study of the factors affecting the extraction of soybean protein by reverse micelles

In this work, the forward and back extraction of soybean protein by reverse micelles was studied. The reverse micellar systems were formed by anionic surfactant sodium bis(2-ethyl hexyl) sulfosuccinate (AOT), isooctane and KCl solution. The effects of AOT concentration, aqueous pH, KCl concentration and phase volume ratio on the extraction efficiency of soybean protein were tested. Suitability of reverse micelles of AOT and Triton-X-100/AOT mixture in organic solvent toluene for soybean protein extraction was also investigated. The experimental results lead to complete forward extraction at the AOT concentration 120 mmol l(-1), aqueous pH 5.5 and KCl concentration 0.8 mol l(-1). The backward extraction with aqueous phase (pH 5.5) resulted in 100% extraction of soybean protein from the organic phase.