Sizes of ionic surfactant micelles and their clustering according to data on viscosity of micellar solutions

Data available on the viscosity of micellar solutions of surfactants belonging to the homologous series of alkyltrimethylammonium bromides containing 10, 12, 14, and 16 carbon atoms in their alkyl chains, as well as sodium dodecyl sulfate solutions, have been analyzed. It has been shown that the systems under consideration may be adequately described by the Einstein equation. The results obtained have made it possible to identify the concentration ranges in which the intermicellar interaction does not affect significantly the flow of the micellar solutions. Data on the relative viscosity of the studied micellar solutions have been employed to calculate the hydrodynamic radii of micelles formed by the surfactants with different lengths of hydrocarbon radicals in their molecules.     

Solubilisation of camptothecin by nonionic surfactants and alkyldimethylamine oxides

The solubilisation of poorly soluble antineoplastic drug camptothecin by nonionic surfactants (polysorbates and octylphenol ethoxylates) and alkyldimethylamine oxide surfactants with the alkyl chain length 8 to 16 carbon atoms was investigated. The hydrophobicity of the solubilising agent turned out to be the primary structural parameter controlling the solubility efficiency of camptothecin in an aqueous solution. The quantitative parameter of solubilisation (drug loading coefficient) provided values in the range of 0.1–1.2% and 0.1–1.0% for alkyldimethylamine oxides and nonionic surfactants, respectively. The decreasing number of oxyethylene units and the extension of the hydrophobic part of nonionic surfactant molecule resulted in the increase of camptothecin solubility. From the dynamic light scattering measurements, the hydrodynamic diameter values of camptothecin-loaded alkyldimethylamine oxide and nonionic micelles were found in the range of 4–42 nm and 5–120 nm, respectively. The experimental values confirmed the increase in micellar size with the increasing alkyl chain length. The values of the packing parameter of camptothecin-loaded dodecyldimethylamine oxide micelles indicate their spherical shape at all the investigated surfactant concentrations. A simple computer model of camptothecin-loaded dodecyldimethylamine oxide micelle provided the diameter of the structure cross section which is consistent with the experimental values.      

The effect of acidity on micellization in dodecyldimethylamine oxide-sodium dodecyl sulfate aqueous mixtures

The effect of acidity on micellization in aqueous solutions of dodecyldimethylamine oxide-sodium dodecyl sulfate mixtures is studied. The CMC values are determined for acidic and nonacidified solutions at 50 °C and different ratios of two surfactants. The measurements are taken using potentiometry, conductometry, and tensiometry techniques. The CMC values are calculated within the framework of a quasi-chemical model of micellization modified with regard to the specific features of the system under consideration. Nonacidified solutions are modeled as a mixture of anionic and nonionic surfactants, whereas acidic solutions are treated as a mixture of anionic and cationic surfactants. The results of model calculations are in satisfactory agreement with the experimental data.     

Effect of hydrogen-bonding interactions on the self-assembly formation of sodium N-(11-acrylamidoundecanoyl)-L-serinate, L-asparaginate, and L-glutaminate in aqueous solution

Aggregation behavior of three N-acyl amino acid surfactants, sodium N-(11-acrylamidoundecanoyl)-l-serinate (SAUS), sodium N-(11-acrylamidoundecanoyl)-l-asparaginate (SAUAS), and sodium N-(11-acrylamidoundecanoyl)-l-glutaminate (SAUGL), was studied in aqueous solution by use of surface tension, fluorescence, dynamic light scattering, and transmission electron microscopic techniques. The amphiphiles have been shown to initially form flexible bilayer structures, which upon increase of surfactant concentration transform into closed spherical vesicles. The transmission electron micrographs of the aqueous solutions of the surfactants confirmed the existence of spherical vesicles. Dynamic light scattering measurements were performed to obtain hydrodynamic radii of the vesicles. Circular dichroism spectra of the amphiphiles indicated formation of chiral helical aggregates in the case of SAUS. The self-assembly formation of the amphiphiles has been discussed in light of the intermolecular hydrogen bonding interaction of the amide groups.     

Mixed Micellization of Dodecyldimethylamine Oxide with Bile Salts in Aqueous Solutions

Micellar behavior of dodecyldimethylamine oxide (DMDAO) with bile salts [sodium deoxycholate (NaDC) and sodium cholate (NaC)] with and without NaCl was studied by surface tension. Interaction parameters of the mixed micelles were estimated using Rubingh's theory. Strong synergism observed for each mixed system, which is a common feature shown by anionic-cationic mixtures. The mixed solutions remained clear even at equimolar ratio. Different behavior of the two bile salts is explained on the basis of their orientation in cationic micelles.     

A new model to study the phase transition from microstructures to nanostructures in ionic/ionic surfactants mixture

The phase behavior and aggregate structures of mixtures of the oppositely charged surfactants cetyltrimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) are explored at high dilution by pulsed field gradient stimulated echo (PFG-STE) NMR. The aggregation numbers and hydrodynamic radii of vesicles and mixed micelles were determined by a combination of viscosity and self-diffusion coefficient measurements. The average size of the mixed micelles was larger than that of micelles containing uniformly charged head groups. Analysis of the variations of the self-diffusion coefficient and viscosity with changing concentration of CTAB or SDS in the cationic-rich and anionic-rich regions revealed a phase transition from vesicles to mixed micelles. Differences in the lengths of the CTAB and SDS hydrophobic chains stabilize vesicles relative to other microstructures (e.g., liquid crystalline and precipitate phase), and vesicles form spontaneously over a wide range of compositions in both cationic-rich and anionic-rich solutions. The results obtained from conductometry measurements confirmed this transition. Finally, according to the capacitor model, a new model was developed for estimating the surface potentials and electrostatic free energy (g(elec)). Then we investigated the variations of electrostatic and transfer free energy in phase transition between mixed micelle and vesicle.     

Mass action model for solute distribution between water and micelles. Partial molar volumes of butanol and pentanol in dodecyl surfactant solutions

The densities of 1-butanol and 1-pentanol were measured in aqueous solutions of dodecyltrimethylammonium bromide and dodecyldimethylamine oxide and the partial molar volumes at infinite dilution of the alcohols in aqueous surfactants solutions were obtained. The observed trends of this quantity as a function of the surfactant concentration were rationalized using a mass-action model for the alcohol distribution between the aqueous and the micellar phase. At the same time, the model was revised to account for the alcohol effect on the surfactant micellization equilibrium. The partial molar volume of alcohols in the aqueous and in the micellar phases and the ratios between the binding constant and the aggregation number were calculated. These thermodynamic quantities are nearly the same in the two surfactants analyzed in this paper but differ appreciably from those in sodium dodecylsulfate. The apparent molar volume of surfactants in some hydroalcoholic solutions at fixed alcohol concentration were also calculated. In the micellization region the trend of this quantity as a function of the surfactant concentration shows a hump, which depends on the alcohol concentration and on the alcohol alkyl chain length. The alcohol extraction from the aqueous to the micellar phase due to the addition of the surfactant can account for the observed trends.     

Surface Tension,Activity of Counterion,and Conductivity of the Quaternary System Dodecyldimethylamine Oxide,TX‐100, HCl,and Water

We have investigated the mixing behavior of the mixtures of dodecyldimethylamine oxide (DDAO) and Triton X‐100 (TX‐100) at different ratios of the two surfactants and at different values of pH. From the equilibrium surface tension measurements, the critical micelle concentration (CMC) and surface tensions at CMC data were obtained as functions of the composition. For the binary mixtures of dodecyldimethylamine oxide and TX‐100 at different ratios in the natural values of pH, the behaviors of the mixtures deviate positively from ideal during micellization. The minimum of CMC of the mixtures of dodecyldimethylamine oxide and Triton X‐100 was observed in the range 4.0?) increased with the decrease of pH. At pH=4.99, the activities of the counterion decreased with the increase of the concentration of TX‐100 at a constant concentration of DDAO. At pH=1.96, the activities of the counterion increased with the increase of the concentration of TX‐100. However, the conductivities of the solution decreased with the increase of the concentration of TX‐100 at both pH=4.99 and pH=1.96. The experimental results show that the effect of TX‐100 on the activities of the counterion at pH=4.99 is different from that at pH=1.96.     

Isothermal titration calorimetry and dynamic light scattering studies of interactions between gemini surfactants of different structure and Pluronic block copolymers

The interactions between triblock copolymers of poly(ethylene oxide) and poly(propylene oxide), P103 and F108, EO(n)PO(m)EO(n), m=56 and n=17 and 132, respectively, and m-s-m type gemini surfactants, m=8, 10, 12, and 18, and s = 3, 6, 12, and 16, have been studied in aqueous solution using isothermal titration calorimetry and dynamic light scattering techniques. The enthalpograms of F108 as a function of surfactant concentration show one broad peak at polymer concentrations C(p) < or = 0.50 wt%, below the cmc of the copolymer at 25 degrees C. It is attributed to interactions between the surfactant and the triblock copolymer monomer. DLS results show hydrodynamic radii (R(h)) initially consistent with copolymer monomers that change to values consistent with gemini surfactant micelles as the surfactant concentration is increased. In P103 solutions at C(p) > or = 0.05 wt%, two peaks appear in the enthalpograms, and they are attributed to the interactions between the gemini surfactant and the micelle or monomer forms of the copolymer. An origin-based nonlinear fitting program was employed to deconvolute the two peaks and to obtain estimates of peak properties. An estimate of the fraction of copolymer in aggregated form was also obtained. The enthalpy change due to interactions between the surfactants and P103 aggregates is very large compared to values obtained for traditional surfactants. This suggests that extensive reorganization of copolymer aggregates and surrounding solvent occurs during the interaction. DLS results for the P103 systems containing C(p) > or = 0.05% show evidence of very large aggregates in solution, likely P103 micelle clusters. The transitions observed in the hydrodynamic radii are consistent with a breakdown of micelle clusters with addition of gemini surfactant, followed by mixed micelle formation and/or deaggregation into monomer P103. This is followed by interactions similar to those typically observed in surfactant-nonionic polymer systems. Mechanisms for the interaction and the observed structural changes are discussed.     

Effect of Surfactants on the Film Drainage

Drainage of a partially mobile thin liquid film between two deformed and nondeformed gas bubbles with different radii is studied. The lubrication approximation is used to obtain the influence of soluble and insoluble surfactants on the velocity of film thinning in the case of quasi-steady state approach. The material properties of the interfaces (surface viscosity, Gibbs elasticity, surface diffusivity, and/or bulk diffusivity) are taken into account. In the case of deformed bubbles the influence of the meniscus is illustrated assuming simple approximated shape for the local film thickness. Simple analytical solutions for large and small values of the interfacial viscosity, and for deformed and nondeformed bubbles, are derived. The correctness of the boundary conditions used in the literature is discussed. The numerical analysis of the governing equation shows the region of transition from partially mobile to immobile interfaces. Quantitative explanation of the following effects is proposed: (i) increase of the mobility due to increasing bulk and surface diffusivities; (ii) role of the surface viscosity, comparable to that of the Gibbs elasticity; and (iii) significant influence of the meniscus on the film drainage due to the increased hydrodynamic resistance. Copyright 1999 Academic Press.     

Properties of Surface and Micelle in a pH‐Mediated Ternary Surfactant Mixture in Salt Solution

We have investigated the mixing behavoir of a pH‐mediated ternary surfactant mixture at constant ratio of dodecyldimethylamine oxide (DDAO) and Triton X‐100 (9:1). From the equilibrium surface tension measurements at different pHs, the critical micelle concentration (cmc) data were obtained as functions of the pH. Values of the cmc and composition of the micelles were predicted using the regular solution approximation. To some extent, the experimental cmc values agree with the predicted cmc. The average degree of ionization of dodecyldimethylamine oxide in the mixed surfactant systems was estimated using potentiometric titrations. The surface electric potential of the micelles (Ψ_o) was determined using two methods, one by hydrogen ion titration and the other by the dissociation constants of an acid‐base indicator. In a high degree of ionization of DDAO in the micelles phase (a_m), Ψ_o estimated from acid‐base indicator is much higher than that from hydrogen ion titration. In the protonated dodecyldimethylamine oxide/TX‐100 binary surfactant system, Ψ_o estimated from hydrogen ion titration was as high as 89 mV. The micellar aggregation numbers evaluated by the steady‐state fluorescence probe method increase with pH except at pH=5.03. At pH=5.03, the maximum micelle aggregation number was observed.     

Self-assembly formation of amphiphilic molecules mixed with photoreactive,aromatic unsaturated-acids: examination by light scattering

Light scattering measurement was carried out for aqueous solutions of amphiphilic molecules mixed with aromatic unsaturated carboxylic acids. Their structures are discussed according to sizes of molecular assemblies evaluated. In aqueous solutions of hexadecyltrimethylammonium hydroxide with 2-indenecarboxylic acid, short rodlike micelles were formed on mixing at a ratio of 11. Particles in aqueous solutions of dodecyldimethylamine oxide and cinnamic acid varied from micelles to vesicles with increasing cinnamic acid concentration. The structures were related to the effective photocyclodimerization of olefins and the stereochemical selectivity of cyclodimers.     

Configuration and hydrodynamic properties of fully acetylated salep glucomannan

The polysaccharide of salep orchid tuber was shown to be a glucomannan with a glucose/mannose ratio of 2.6 and an acetyl content of 2.1%. After extraction from the powdered root with water, the triacetate derivative was prepared and its configurational and hydrodynamic properties examined. The polymer yielded a series of fractions from 615 to 4170 in weight-average degree of polymerization. Light-scattering, viscosity, and osmometry experiments were conducted. Intrinsic viscosity results were interpreted according to the hydrodynamic theory of Eizner and Ptitsyn resulting in a value of ζ/η₀ = 20 ± 6 A. for the ratio of monomeric friction coefficient to solvent viscosity and a corresponding value of a = 55 ± 4 A. for the persistence length, closely similar to those reported for other β-1,4-linked polysaccharides. The theoretical Flory coefficient increased with increasing molecular weight but was less than the limiting value of Φ₀ = 2.86 × 10²³ mole^?1. The dependence of the light-scattering radius of gyration of the glucomannan polymer on the contour length showed that the configuration of the heteropolymer was similar to that of other β-1,4-linked polysaccharides which have only glucose or mannose in the main chain. Calculated radii of gyration based on the Porod-Kratky persistence length were found to be smaller than radii found by light scattering on the fractions.     

Thermosensitive noncovalently bonded block copolymerlike micelles from interpolymer complexes

Interpolymer complexes between polystyrene‐b‐poly(2‐vinylpyridine), (PS‐P2VP), and poly(methacrylic acid) (PMAA), have been studied in dioxane. Dioxane is a good solvent for PS‐P2VP copolymers but it is a nonsolvent for PMAA at room temperature. In this way noncovalent bonded micelles are formed after mixing the solutions of the polymers at 60 °C and then allowing them to cool at room temperature. Static and dynamic light scattering as well as viscosity measurements have been used to study the dependence of aggregate mass and size as a function of the molar ratio of functional groups in PS‐P2VP/PMAA mixtures, as well as temperature. Plots of apparent average molecular weight and hydrodynamic radius of the aggregates versus amine to carboxyl group ratio show a maximum at a ratio close to one. The size of the aggregates decreases at higher ratios because of the formation of more stable micelles with smaller cores. In all cases rather compact structures were formed, as evidenced by viscometry. The mass of the aggregates was found to decrease by an increase in temperature while hydrodynamic radii were increased. This was attributed to the increase of the thermodynamic quality of the solvent toward PMAA as temperature increases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6230–6237, 2004     

Solution behavior of linear-dendritic rod diblock copolymers in methanol

The solution behavior of spherical dendrimers as well as hybrid-linear dendritic diblock copolymers has been extensively studied, and the size, shape, and ability of these polymers to encapsulate small molecules have led to their comparison with traditional micelles. We have recently reported the synthesis of a new dendritic copolymer architecture, the linear-dendritic rod diblock copolymer, and in this work, we examine the solution behavior of these unique polymers in methanol at 25 degrees C, using dynamic light scattering and intrinsic viscosity measurements. The diblock copolymers consist of a linear poly(ethylene oxide)-poly(ethylene imine) diblock copolymer backbone around which poly(amido amine) branches have been divergently synthesized from the poly(ethylene imine) block. The hydrodynamic radii and the viscometric radii of the polymers were found to increase slowly with increasing generation up to generation 3.5; however, after generation 3.5, the radii were found to increase very rapidly. This increase can be explained by an elongation of the dendritic block into a more rodlike configuration and a corresponding breakdown of the spherical approximation used to calculate the radii. The intrinsic viscosity of the amine and ester terminated polymers was found to follow two very different trends at low generation; however, at higher generations, they followed similar, yet slightly different, curves with the values for the amine terminated polymers only a little larger than those of the ester terminated polymers. At low generations, the chemistry of the end groups and its interaction with the solvent were found to be more important, whereas at higher generations, the highly branched nature of the dendritic block was the more important factor. For the ester terminated polymers, a maximum in the intrinsic viscosity occurred at generation 1.5. Since this maximum occurred at a much lower generation number than is traditionally seen for spherical dendrimers, new scaling relations for the intrinsic viscosity of dendritic rod polymers were developed and were found to support this observation. A minimum in the intrinsic viscosity was also observed at generation 3.5 for the ester terminated polymers and a minimum or leveling off in the intrinsic viscosity at generation 4.0 was found for the amine terminated polymers, which can be attributed to the transitioning of the polymers to a more elongated, rodlike shape and the increased influence of the shape factor on the intrinsic viscosity.     

The Viscous Properties of Anionic/Cationic and Cationic/Nonionic Mixed Surfactant Systems

The behavior of mixed cationic/anionic and cationic/nonionic surfactants solutions have been studied by viscosimetry. The systems studied were sodium dodecyl sulfate (SDS)/cetyltrimethylammonium bromide (CTAB) and CTAB/Brij (polyoxyethylene lauryl ether, n = 10 and 23) in aqueous and sodium chloride solutions. The relative viscosity of single nonionic surfactant solutions is larger than that of SDS or CTAB solutions. It increases with the number of ethylene oxide groups. In the mixed systems, viscosity deviates from ideal behavior. The deviation results from electrostatic interactions. The surfactant mixture composition affects the self-assembled microstructure and rheology. A new mixed system that forms clear micellar solution above CMC was detected. In CTAB/Brij systems, the experimental data also deviate from ideal behavior due to mixed micelle formation and electroviscous effect. This effect is less pronounced than that of SDS/CTAB system and could be suppressed by adding an electrolyte (NaCl).     

Structure and dynamic properties of colloidal asphaltene aggregates

The abundant literature involving asphaltene often contrasts dynamic measurements of asphaltene solutions, highlighting the presence of small particle sizes between 1 and 3 nm, with static scattering measurements, revealing larger aggregates with a radius of gyration around 7 nm. This work demonstrates the complementary use of the two techniques: a homemade dynamic light scattering setup adapted to dark and fluorescent solutions, and small-angle X-ray and neutron scattering. Asphaltene solutions in toluene are prepared by a centrifugation separation to investigate asphaltene polydispersity. These experiments demonstrate that asphaltene solutions are made of Brownian colloidal aggregates. The hydrodynamic radii of asphaltene aggregates are between 5 and 10 nm, while their radii of gyration are roughly comparable, between 3.7 and 7.7 nm. A small fraction of asphaltenes with hydrodynamic and gyration radii around 40 nm is found in the pellet of the centrifugation tube. The fractal character of the largest clusters is observed from small angle scattering nearly on a decade length scale. Previous results on aggregation mechanisms are confirmed ( Eyssautier, J., et al. J. Phys. Chem. B 2011 , 115 , 6827 ): nanoaggregates of 3 nm radius, and with hydrodynamic properties also frequently illustrated in the literature, aggregate to form fractal clusters with a dispersity of aggregation number.     

Dilute solution properties,chain stiffness,and liquid crystalline properties of cellulose propionate

The solution properties of cellulose derivatives are of interest from both technological and purely scientific aspects. At high concentrations these solutions form liquid crystalline structures. In dilute solution cellulosic chains can be described as semiflexible or wormlike with properties intermediate between random coils and rigid rods. A series of fractions of cellulose propionate have been examined by dilute solution viscometry, static and dynamic light scattering, and polarizing microscopy. Power law exponents are considerably larger than those observed for flexible chains and analysis of the intrinsic viscosity and hydrodynamic radii has yielded chain diameters and Kuhn statistical segment lengths. Corresponding aspect ratios from the hydrodynamic measurements are in good agreement with those obtained from polarizing microscopy, as analyzed in light of Flory's theory. Some aggregation and specific solvent effects have been observed, however separation of these effects has proven to be difficult. Results of these studies are compared to previous work for other cellulose derivatives. ©1995 John Wiley & Sons, Inc.     

Fluorocarbon-containing Hydrophobically Associating Polymers: II Synthesis and Characterization of Terpolymer of Acrylamide,Acryloyloxyethyl Trimethyl Ammonium Chloride and (N-ethyl perfluorooctane sulfoamido) Ethyl Acrylate

Flurocarbon-modified hydrophobically associating terpolymers have been prepared via copolymerization of acrylamide (AM), acryloyloxyethyl trimethyl ammonium chloride (DMAEA-Q) and a small amount of flurocarbon-containing acrylate (RFA) as a hydrophobic third monomer. Three series of terpolymers (AM/DMAEA/Q molar ratio 70/30, 50/50 and 30/70 with various amounts of RFA) were synthesized and the rheological properties of terpolymer solutions were studied. A pronounced hydrophobic association between the fluorocarbon groups in the terpolymer's solutions was observed. The solutions showed pseudoplastic behavior. Evidence for hydrophobic aggregation between the fluorocarbon groups was observed from the viscosity versus concentration profile, effects of shear rate and the addition of NaCl and surfactants on the viscosity of terpolymer solutions. © 1997 John Wiley & Sons, Ltd.