Intermicellar Interactions Research Articles

Pluronic L64 Micelles near Cloud Point: Investigating the Role of Micellar Growth and Interaction in Critical Concentration Fluctuation and Percolation

The structure and the properties of the (Ethylene Oxide)(13)(Propylene Oxide)(30)(Ethylene Oxide)(13) (Pluronic L64, MW approximately 2900) micelles have been studied in the aqueous medium by small angle neutron scattering (SANS), dynamic light scattering (DLS) and viscometry measurements. The aqueous solutions of this triblock copolymer are unique among the pluronic solutions in showing critical concentration fluctuations and a concomitant enhancement in viscosity on approaching their cloud point. So far these results have been attributed solely to the presence of attractive interaction between the spherical L64 micelles. Recent theoretical studies, on the other hand, suggest that L64 micelles prefer a prolate ellipsoidal structure to sphere (Bedrov et al. Langmuir 2007, 23, 12032) and have a predominantly repulsive intermicellar interaction. A comparative analysis of our SANS data based on the spherical and prolate ellipsoidal structure shows that the L64 micelles can be best described by a prolate ellipsoidal structure, the aspect ratios of which increase progressively with increase in temperature. This, together with our viscosity and DLS studies, suggests that the enhanced viscosity of the copolymer solution near the cloud point arises largely due to the anisotropic growth of the micelles to the worm-like structures. The role of the intermicellar attractive interaction has thus been limited to the observed critical concentration fluctuation, and its effect decreases progressively with increase in copolymer concentration. It has also been shown that the water structure making salts like NaCl reduces the micellar growth temperature and helps in forming worm-like micelles at the room temperature. These studies thus identify the effect of micellar growth and interaction in determining the properties of the copolymer solution near the cloud point, which are the first of its kind in the case of the pluronics.

Persistence of Birefringence in Sheared Solutions of Wormlike Micelles

When aqueous solutions containing wormlike micelles (worms) are sheared, the micellar chains tend to align with the flow, which in turn leads to flow-birefringence. When shear is stopped, the worms rapidly revert to an isotropic state in typical samples, and the birefringence disappears. In this study, we present a system of cationic worms that shows a different behavior: not only do the samples become intensely birefringent when sheared but the birefringence also persists for hours (and even days) after shear is stopped. These results suggest that shear-aligned worms in the sample are trapped in their aligned state for long periods of time, an aspect that is confirmed by cryo-transmission electron microscopy (cryo-TEM). We seek to determine the origin of this unusual behavior. Our results show that the persistent birefringence is observed for cationic worms induced by hydroxy-naphthoate but not salicylate counterions. These observations suggest that the micellar alignment is stabilized by intermicellar attractive interactions (such as pi-pi and cation-pi) that arise when large aromatic counterions are anchored within the micelles.

Structural investigation of viscoelastic micellar water/CTAB/NaNO3 solutions

A highly viscoelastic worm-like micellar solution is formed in hexa- decyltrimethylammonium bromide (CTAB) in the presence of sodium nitrate (NaNO3). A gradual increase in micellar length with increasing NaNO3 was assumed from the rhe- ological measurements where the zero-shear viscosity (·0) versus NaNO3 concentration curve exhibits a maximum. However, upon increase in temperature, the viscosity de- creases. Changes in the structural parameters of the micelles with addition of NaNO3 were inferred from small angle neutron scattering measurements (SANS). The intensity of scattered neutrons in the low q region was found to increase with increasing NaNO3 concentration. This suggests an increase in the size of the micelles and/or decrease of intermicellar interaction with increasing salt concentration. Analysis of the SANS data using prolate ellipsoidal structure and Yukawa form of interaction potential between mi- celles indicate that addition of NaNO3 leads to a decrease in the surface charge of the ellipsoidal micelles which induces micellar growth. Cryo-TEM measurements support the presence of thread-like micelles in CTAB and NaNO3.

Emulsion Texture and Stability: Role of Surfactant Micellar Interactions in the Presence of Proteins

This article presents the results of our recent research on the texture and stability of oil-in-water emulsions containing sucrose ester and proteins. We used both the direct microscopic imaging and nondestructive back-light scattering (Kossel diffraction) techniques to evaluate the emulsion texture and the energy barrier between droplets for two different emulsifier compositions with and without the proteins present. The microinterferometric method employing our capillary force balance was used to study the stability of the confined thin film (containing surfactant micelles and proteins) between two droplets. In addition to the film stability, we also measured the second virial coefficient of the micellar solutions with and without protein and assessed the intermicellar interaction and related it to the stabilities of the emulsions prepared using two different emulsifier compositions. The effect of protein on the oil-in-water emulsion stability was also assessed and was found to lead to the depletion attraction between droplets, resulting in a less stable emulsion. The results offer new insight into the understanding of how the micellar interactions in the presence of proteins affect emulsion texture and stability.

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 small-angle X-ray scattering study of the structure of lysozyme–sodium dodecyl sulfate complexes

The structure of lysozyme–sodium dodecyl sulfate (SDS) complexes in solution is studied using small-angle X-ray scattering (SAXS). The SAXS data cannot be explained by the necklace and bead model for unfolded polypeptide chain interspersed with surfactant micelles. For the protein and surfactant concentrations used in the study, there is only marginal growth of SDS micelles as they complex with the protein. Being a small and rather rigid protein, lysozyme can penetrate the micellar core which is occupied by flexible and disordered paraffin chains and also the shell occupied by the hydrated head groups. A partially embedded swollen micellar model seems appropriate and describes well the scattering data. The SAXS intensity profiles are analyzed by considering the change in the electron scattering length density of the micellar core and shell due to complexation with protein and treating the intermicellar interaction using rescaled mean spherical approximation (RMSA) for charged spheres.

Zeta Potentials and Debye Screening Lengths of Aqueous, Viscoelastic Surfactant Solutions (Cetyltrimethylammonium Bromide/Sodium Salicylate System)

In a series of experiments, we studied the dynamic properties of aqueous surfactant solutions of cetyltrimethylammonium bromide (CTAB) at conditions after adding different amounts of sodium salicylate (NaSal). The aggregates, present in these solutions, are elongated, wormlike micelles, which tend to form entanglement networks. The viscoelastic, gel-like samples were analyzed by means of static, dynamic, and electrophoretic light scattering techniques. We separately investigated the effects of surfactant concentration and added salt on intermicellar interactions. The electrostatic interactions between the anisometric micelles were analyzed by considering the effective dimensions of the aggregates. We calculated the Debye-Huckel lengths from experimental data of the osmotic second virial coefficient and from the diffusion second virial coefficient. It turned out that the results were in good agreement with theoretically estimated values. We also measured the zeta potential and intensity of scattered light in a large range of different salt concentrations keeping the CTAB concentration constant. We observed an isoelectric point and charge reversal of the threadlike micelles at an excess salicylate concentration of about 100 mM. The observed decrease of the zeta potential points to striking processes of counterion condensation. In these solutions, the salicylate ion acts as a cosurfactant, due to its discrepancy between polar and hydrophobic groups. We also detected a simple linear correlation between the zeta potentials and the Debye screening lengths of the surfactant solutions.

Viscoelastic micellar water/CTAB/NaNO 3 solutions: Rheology, SANS and cryo-TEM analysis

Aqueous micellar solutions of the cationic surfactant hexadecyltrimethylammonium bromide (CTAB) and sodium nitrate (NaNO 3) were examined using steady and dynamic rheology, small-angle neutron scattering (SANS) and cryogenic-transmission electron microscopy (cryo-TEM). Upon addition of NaNO 3, the CTAB spherical micelles transform into long, flexible wormlike micelles, conveying viscoelastic properties to the solutions. The zero-shear viscosity ( η 0 ) versus NaNO 3 concentration curve exhibits a well-defined maximum. Likewise, upon increase in temperature, the viscosity decreases. Dynamic rheological data of the entangled micellar solutions can be well described by the Maxwell model. Changes in the structural parameters of the micelles with addition of NaNO 3 were inferred from SANS measurements. The intensity of scattered neutrons at the low q region was found to increase with increasing NaNO 3 concentration. This suggests an increase in size of the micelles and/or decrease of intermicellar interactions with increasing salt concentration. Analysis of the SANS data using prolate ellipsoidal structure and Yukawa form of interaction potential between micelles indicates that addition of NaNO 3 leads to a decrease in the surface charge of the ellipsoidal micelles and consequently an increase in their length. The structural transition from spherical to entangled threadlike micelles, induced by the addition of NaNO 3 to CTAB micelles is further confirmed by cryo-TEM.

Adsorbed Anthranilic Acid Molecules Cause Charge Reversal of Nonionic Micelles

The effect of anthranilic acid, an aromatic amino acid, on the structural characteristics of nonionic micelles of Triton X-100 at different pH values was investigated by light scattering and small-angle neutron scattering (SANS) measurements. The scattered light intensity decreases as pH is increased or decreased on either side of the isoelectric point (IEP = 3.4) of the amino acid. Analysis of the SANS data using a sticky hard-sphere model shows that the micelles are oblate ellipsoids with an axial ratio of approximately 2.3. No significant change could be observed in the size of the micelles with a change in the pH, while the stickiness parameter (tau), which is related to the interaction potential (u(0)) increases on either side of the IEP. As tau increases, u(o) becomes less negative, indicating a decrease in the attractive interaction between nonionic micelles. This can be explained in terms of the changes in the surface charge of the micelles resulting from a shift in the acid-base equilibrium of the adsorbed amino acid. The variation of the intermicellar interaction as calculated from the stickiness parameter is consistent with the picture of reversal of charge of amino acids with pH. This is further supported by the observed variation of the cloud point of the solutions at different pH values. The change in the interparticle interaction is also reflected in the diffusion coefficient of the micelles measured by dynamic light scattering.

Synthesis of a novel star polymer consisting of a dendritic polyamidoamine core and polystyrene arms and its self-assembly to form large multimolecular micelles

This work is focused on the synthesis and self-assembly of novel dendritic star polymers with a dendritic polyamidoamine core and many linear polystyrene arms. The polymers can synchronously form unimolecular micelles (ca. 10 nm) and large multimolecular micelles (ca. 100 nm) in selected solvents (tetrahydrofuran/methanol) at room temperature. Atomic force microscopy, scanning electron microscopy, and dynamic light scattering measurements have provided direct evidence that the large micelles are a kind of multimicelle aggregate with the basic building units of unimolecular micelles. Accordingly, a possible self-assembly process is put forward, and a new aggregate model, termed multimicelle aggregate, is suggested to explain the formation of the large micelles. In the multimicelle aggregate model, the large micelles are the aggregates of small micelles associated by intermicellar interactions such as hydrogen bonds and p–p stacking interactions. It is the first demonstration of the self-assembly mechanism for the large multimolecular micelles generated from the solution self-assembly of dendritic star polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Structure and Interactions in Micellar Solutions: Molecular Simulations of Pluronic L64 Aqueous Solutions

Coarse-grained, implicit solvent molecular simulations have been conducted to investigate the structure and interactions of L64 Pluronic micelles in aqueous solutions. Simulations of an L64 solution beginning with monodisperse micelles (aggregation number Nagg = 40 chains) resulted in a narrow Gaussian distribution of Nagg centered around 40. While not fully equilibrated, this distribution supports the supposition that L64 micelles with Nagg = 40 are representative of the conditions considered and model employed. Detailed analysis of intramicellar monomers distribution and micelle shapes revealed that L64 micelles have a scalene ellipsoidal shape. Additional simulations of solutions containing 125 micelles constrained to have Nagg = 40 at polymer volume fractions of 0.024 and 0.110 were performed to study micelle-micelle structure factor, single micelle form factor, and total scattering intensity. The ability of various models utilized in analysis of scattering profiles in micellar solutions to describe the structure of the model L64 solutions was investigated. Investigation of the potential of mean force between two micelles reveals that the interactions between micelles are repulsive but on a length scale smaller than the mean micelle diameter, indicating that the micellar shape fluctuations are important in determining intermicellar interactions.

Structural Characterization of Frozen n-Heptane Solutions of Metal-Containing Reverse Micelles

The microstructure of temperature-quenched solutions of reverse micelles formed by sodium, cobalt, ytterbium, and cobalt/ytterbium bis(2-ethylhexyl)sulfosuccinate in n-heptane has been investigated by SAXS and EXAFS. Some changes in the X-ray absorption spectra with respect to the same systems at room temperature have been observed. The analysis of the SAXS spectra leads to the hypothesis that at 77 K the closed spherical structure of reverse micelles is retained and that during the temperature quench they undergo a clustering process involving the transition from a quite random dispersion to the formation of more or less large clusters of strongly packed reverse micelles. This behavior is attributed to competitive effects caused by the temperature decrease. The prevalence of intermicellar attractive interactions with respect to Brownian motions leading to a collapse to more compact structure is in competition with the rapid decrease of reverse micelle diffusion rate involving a freezing of the local structures. In the case of cobalt, ytterbium, and cobalt/ytterbium bis(2-ethylhexyl)sulfosuccinate reverse micelles, further information from EXAFS measurements indicates that within the reverse micelle core exists a quite ordered nanosized domain composed of water, surfactant counterions, and oxygen atoms of the SO3- head groups. The conservation of local order and inverse structure during the clustering phenomenon that results from the fast freezing with liquid nitrogen of solutions of reverse micelles could have biological implications, i.e., the preservation of tissue samples at cryogenic temperatures.

Coexistence and Growth of Micellar Species in a Sugar-Based Surfactant/Phenol Mixture Studied by Analytical Ultracentrifugation

Knowledge of the shape and size of surfactant micelles in the presence of small organic molecules is important for understanding the solubilization properties of micellar phases. In this work, structural information on micelles of mixed n-dodecyl-beta-d-maltoside (DM) and phenol, including the aggregation number, diffusion coefficient, and effective radius, was obtained using an analytical ultracentrifugation technique. The micelles were found to increase in size and undergo shape transition from quasispherical to cylindrical with an increase in the surfactant and phenol concentrations in the micellar phase. Importantly, the coexistence of different micellar species was observed in certain cases with the larger species double the size of the smaller one. Based on the results obtained, a two-step micellar growth model is proposed to describe the micelles shape transition in the system. In the first step, the micelles expand continuously, whereas in the second step, it undergoes a sudden shift from the existing micellar species to a larger species causing the coexistence of two micellar species. This micellar growth is attributed to molecular packing and intermicellar interaction energy parameters. The mechanism proposed can be applied to other mixed systems and utilized for devising chemicals for the efficient removal of pollutants.

Influence of organic additives on the clouding phenomena of promethazine hydrochloride solutions

This paper reports the influence of organic additives (alcohols, amino acids, sugars) on the micellization and cloud point (CP) of a phenothiazine drug, promethazine hydrochloride (PMT). The critical micelle concentration (CMC) of the drug, determined by surface tension measurements in the presence of a representative of each additive class (i.e., butanol, leucine, arabinose), are used to evaluate the maximum surface excess concentration (Γ max) and the minimum area per surfactant molecule (A min) at the air/water interface. Γ max increases and CMC/A min decreases with increasing concentration of the additives, which indicate mixed micelle formation. The intermicellar interaction coefficients in the mixed micelles (β m and β σ are also calculated, and their negative values imply attractive interactions. Effect of pH revealed CP decrease with increasing pH due to deprotonation of PMT molecules. Effect of amino acids depended upon their nature and polarity, whereas sugars caused a CP decreasing effect. Aliphatic alcohols as well as cycloalkanols and diols decreased the CP. In the presence of arabinose, increase in drug concentration resulted in the CP increase, while increase in pH showed an opposite trend. Results are interpreted on the basis of mixed micelle formation, hydrophobic interactions, and change in solvent structure.

The effect of pharmaceuticals on the nanoscale structure of PEO–PPO–PEO micelles

We present results on the effects of various hydrophobic drugs and additives on the micellar structure of Pluronic F127 solutions. Small-angle neutron scattering experiments on 5 wt% F127 solutions were used to measure micelle core size ( R 1), micelle corona size ( R 2), intermicellar interaction distance ( R int), polydispersity ( σ), and aggregation number ( N agg); dynamic light scattering was used to measure critical micelle concentration (CMC); and ultraviolet spectroscopy was used to measure drug solubility and apparent micelle–water partition coefficient ( K mw). The core and corona size were found to generally increase in the presence of the drugs, as did R int. Both σ and N agg were found to decrease in the presence of most of the drugs, and the CMC was found to vary considerably with no clear correlation. A design of experiments (DOE) approach was used to analyze the results and build empirical correlations. All of the parameters from the SANS experiments were found to depend strongly on drug solubility, with a weak dependence on K mw in most cases. The aggregation number, however, was found to depend strongly on both K mw and solubility. The correlations can be used to roughly predict the structural parameters of F127 micelles for other hydrophobic drugs.

Contrast Variation SANS Investigation of Composition Distributions in Mixed Surfactant Micelles

Small angle neutron scattering measurements have been performed on three systems (HFDeP-d5-C (N-1(1,1,2,2-tetrahydroperfluorodecanoyl)pyridinium-d5 chloride)/C16PC in 63 mM NaCl; HFDeP-d5-C/C12PC in 200 mM NaCl, and as an example of an ideally mixed system, SDS/SDS-d25 in 200 mM NaCl) containing micelles formed in a binary mixture of surfactants, in order to investigate the composition distribution of the mixed micelles. The experimental data were collected varying the contrast between the average scattering length density of micelles and aqueous solvent by changing the H2O/D2O ratio. Analysis of data includes a model-independent approach--the indirect Fourier transformation method and direct modeling-simultaneous fit at all contrasts by the scattering from micelles of equal size and shape with composition distribution and an effective interaction. It has earlier been shown (Almgren, M.; Garamus, V. M. J. Phys. Chem. B 2005, 109, 11348) that for micelles of equal size, independent of the composition, and with negligible intermicellar interactions, the scattered intensity at zero angle varies quadratically with the contrast, with the minimum intensity at the nominal match point proportional to sigma2, the variance of the micelle composition distribution. Within the regular solution framework, the composition distribution and its variance are uniquely defined by the value of the interaction parameter and the micelle aggregation number. At 25 degrees C, the first system gave sigma = 0.37, corresponding to a broad, bimodal composition distribution, the second sigma = 0.22, a broad distribution with a shallow minimum at the midpoint. For SDS/SDS-d25, we found sigma = 0.006 +/- 0.030, which is a smaller value than that of the binominal composition distribution expected for an ideally mixed system.

Microemulsion Droplets Decorated by Brij700 Block Copolymer: Phase Behavior and Structural Investigation by SAXS and SANS

The phase behavior and structure of a four-component microemulsion system forming droplets with an oil core surrounded by the non-ionic C12E5 surfactant in water and "decorated" by long PEO chains using the block copolymer/surfactant Brij 700 has been studied. The surfactant-to-oil volume ratio, the coverage density of the droplets with decorating molecules, and the temperature were varied. For a surfactant-to-oil volume ratio of 2, the solutions form isotropic and clear solutions at room temperature, and the addition of Brij molecules stabilize the micelles: the transition to an opaque phase is shifted to higher temperatures as the surface coverage increases. At a surfactant-to-oil ratio of 1, the isotropic microemulsion phase is confined to a very narrow range of temperature, which location is shifted to increasing temperature, as the amount of Brij at the surface of the droplet is increased. For large surface coverages, the lower emulsification boundary varies roughly linearly with the surface coverage. The structure of the droplet phase was investigated by small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). For a surfactant-to-oil ratio of 2, the SANS data revealed a transition from rodlike to spherical particles when Brij molecules are added to the system, which induces a larger curvature of the surfactant film. For a surfactant-to-oil ratio of 1, the droplets are nearly spherical at all surface coverages. The intermicellar interactions effects become increasingly more pronounced as Brij is added, due to the introduction of the highly swollen corona. A quantitative analysis of some of the SAXS data was done using an advanced model based on Monte Carlo simulations. It demonstrates the strong chain-chain interactions within the corona and confirms the increased interparticle interactions, as the coverage density is increased.

Molecular Dynamics Simulations of Mixed Cationic/Anionic Wormlike Micelles

Simulations of mixed cationic/anionic wormlike micellar systems have been carried out for a wide range of compositions, including pure anionic and cationic systems. It was found that the wormlike micelle formed by only cationic surfactant molecules is unstable and transforms to a set of small spherical micelles. Adding anionic surfactants with a short hydrophobic chain (only eight carbon atoms) results in stable wormlike micelles. The 34/66 cationic/anionic worm is stable and symmetrical, while the 50/50 mixture yields a flattened worm, indicating a phase transition to the lamellar phase. All these observations are in excellent agreement with the experimental results of Raghavan et al. (Langmuir 2002, 18, 3797), and they provide a molecular mechanism for their observations. The addition of octyltrimethylammonium chloride increases the radius of the worm due to the bigger hydrophobic part. Meanwhile, the length of the worms decreases with the concentration of cationic surfactant and reaches a minimum for the 50/50 mixture. The latter system is of special interest due to a zero surface charge density. The worm with the electrostatically neutral surface was used to investigate intermicellar interactions. The molecular dynamics (MD) simulations show that the merging process requires a substantial activation energy even in the case of reduced electrostatic repulsion.

Self-Assembly of Medium-Chain Alkyl Monoglucosides in Ammonium Sulfate Solutions with Poly(ethylene glycol)

We study the phase behavior and microstructure of alkyl-beta-monoglucosides with intermediate chain lengths (octyl- and nonyl-beta-glucoside) in aqueous solutions containing ammonium sulfate and poly(ethylene glycol) (PEG). When the glucoside surfactants are mixed with PEG of molecular weight 3350 or larger, two different phase transitions are observed in the temperature range 0-100 degrees C, with lower and upper miscibility gaps separated by a one-phase isotropic region. Isothermal titration calorimetry is used to quantify the effect of PEG on the micellization properties of the alkyl monoglucosides, whereas small-angle neutron scattering gives insight into the microstructure of the surfactant/polymer mixtures near the liquid-liquid phase boundary. Results show that the range and the strength of the interactions in these solutions are highly affected by the presence of PEG. Solutions with nonyl-beta-glucoside contain larger micelles than those with octyl-beta-glucoside, and the intermicellar interactions are much stronger and longer ranged. The relevance of these findings for membrane protein crystallization is discussed.

Controlled Stacking of Charged Block Copolymer Micelles

Using poly(acrylic acid)-b-poly(methyl acrylate)-b-polystyrene (PAA-b-PMA-b-PS) triblock copolymers or a mixture of different molecular weight PAA-b-PS diblock copolymers, stacks of polymeric micellar assemblies, such as disks and Y-shaped cylinders, were formed through intermicellar interactions. Whereas micelles hierarchically stacked together, micellar interactions within the stack defined a uniform micelle geometry and size for up to micrometers in length. The kinetic pathway dependence and stability of the stacked assemblies were studied, and possible intermicellar interactions between micelles within the stacks are proposed.