Small-angle X-ray scattering in sodium dodecyl sulfate solutions and micelle clustering

The small-angle X-ray scattering (SAXS) in micellar sodium dodecyl sulfate solutions has been studied in the range of overall concentrations c from 8 mM (CMC₁) to 300 mM and the absolute values of scattering vector q from 0.07 to 3.0 nm^–1. The total intensity of isotropic scattering has been revealed to increase with solution concentration. At c > 27 mM, the SAXS spectra have been found to exhibit an interference peak, which testifies a correlation in the arrangement of micelles in the bulk solution. This peak corresponds to the magnitude of q close to 1.55 nm^–1. Using the position of this maximum, average distance r₀ between the centers of micelles has been determined, which is equal to 4.1 nm and remains almost unchanged upon an increase in the overall concentration of sodium dodecyl sulfate. The observed regularities have been explained in terms of the DLVO theory taking into account the electrostatic and molecular intermicellar interaction.     

Miscibility of sodium dodecyl sulfate and sodium decyl sulfate in the adsorbed film and micelle

The interfacial tension of the aqueous solution of sodium dodecyl sulfate (SDS) and sodium decyl sulfate (SDeS) mixture against hexane was measured as a function of the total molality and composition of the surfactant mixture at 298.15 K under atmospheric pressure. The compositions of adsorbed film and micelle were evaluated numerically by applying the thermodynamic relations to the experimental results. These results were shown in the form of the phase diagrams of adsorption and micelle formation and compared with those of the aqueous solution of sodium perfluorooctanoate (SPFO) and SDeS mixture. It was found that the diagrams of SDS and SDeS system have swollen cigar shapes and are quite different from those of SPFO and SDeS system which show non-ideal mixing both in the adsorbed film and micelle. This finding was attributed to the fact that the interaction between fluorocarbon and hydrocarbon chains is weaker than that between hydrocarbon chains.     

Study of mixed micellar aqueous solutions of sodium dodecyl sulfate and amino acids

Thermodynamic properties of sodium dodecyl sulfate (SDS) in micellar aqueous solutions of L-serine and L-threonine were determined by fluorescence spectroscopy and dynamic light scattering techniques. The values of Gibbs free energy, enthalpy and entropy of the process of micelle formation were calculated using the critical micelle concentration and degree of dissociation. Changes in critical micelle concentration of SDS with the addition of amino acids were examined by both conductivity and pyrene I ₁/I ₃ ratio methods at different temperatures. The pyrene fluorescence spectra were used to study the change of micropolarity produced by the interaction of SDS with amino acids. The aggregation behavior of SDS was explained in terms of structural changes in mixed solutions. The data on dynamic light scattering suggest that size of SDS micelles was influenced by the presence of amino acids.     

Aggregation of sodium dodecyl sulfate in aqueous sodium chloride solutions

Summary Aqueous solutions of sodium dodecyl sulfate with added sodium chloride (0–0.3 mol kg^–1) were studied at 298.2 K in order to calculate the molar standard free energy of micelle formationG _m . The following properties were measured: (i) aggregation number by membrane osmometry, (ii) counter-ion binding and sodium ion activities by electromotive force, (iii) critical micelle concentration by electromotive force and fluorescence spectrophotometry. The results indicate thatG _m . is independent of the NaCl concentration.     

Molecular dynamics simulation of pyrene solubilized in a sodium dodecyl sulfate micelle

In the present work, the structural and dynamical aspects of the solubilization process of pyrene within a sodium dodecyl sulfate micelle were studied using molecular dynamics simulations. Our results showed that free pyrene as the fluorescence probe can be spontaneously solubilized into the micelle and prefers to be located in the hydrophobic core region. As the local concentration of pyrene increased, two molecular probes could enter into the core hydrophobic region and the excited dimer of pyrene molecules was formed, showing a stacking mode of π-π conjugation. Since the π-π stacking interaction between the two pyrene molecules was very weak, formation of the excimer was a dynamic process with the two pyrene molecules alternately separating and associating with each other. In this case, the two pyrene molecules were found to be mainly distributed in the palisade layer of the micelle due to the balance between the weak π-π stacking interaction and the hydrophobic interaction of probe molecules with the surfactant tails.     

The structure and rheology of mixed micellar solutions of sodium dodecyl sulfate and dodecyldimethylamine oxide

The paper presents the results of viscosity measurements by capillary and rotational viscometry for aqueous solutions of sodium dodecyl sulfate and dodecyldimethylamine oxide and data on the hydrodynamic radii of aggregates obtained from dynamic light scattering measurements. A wide range of solution compositions predominantly containing dodecyldimethylamine oxide was studied at 308.15 K; the total content of surfactants was from 1 to 15 wt %, pH ～ 8. Solution viscosities were found to change by several orders of magnitude when the composition of the system was varied; the dependence of viscosity on the ratio of surfactants passes through maximum and inflections. The dependences of viscosity and hydrodynamic radii on the ratio between two surfactants were similar in character. The conclusion was drawn that various nanostructural rearrangements occurred in the solutions studied and synergistic effects were observed.     

The influence of high-frequency electromagnetic fields on the critical micelle concentration in aqueous solutions of sodium dodecyl sulfate

It was established that the critical micelle concentration in solutions of sodium dodecyl sulfate changed under the action of high-frequency electromagnetic fields (60, 120, and 160 MHz). The thermodynamic functions of micelle formation were calculated. Original Russian Text ? I.E. Stas’, O.P. Mikhailova, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 2, pp. 397–399.     

Photooxidative decomposition of sodium dodecyl sulfate in aqueous solutions

Kinetic features and the mechanism of photooxidative decomposition of sodium dodecyl sulfate in an aqueous solution under the action of pulsed short-wavelength UV light with a continuous spectrum upon introduction of hydrogen peroxide was studied.     

Interaction of cellulase with sodium dodecyl sulfate at critical micelle concentration level

The interactions between Trichoderma reesei cellulase and an anionic surfactant, sodium dodecyl sulfate (SDS), at critical micelle concentration level have been investigated using isothermal titration calorimetry, fluorescence spectroscopy, and circular dichroism. SDS micelles have dual interactions with cellulase: electrostatic at first and then hydrophobic interactions. When the concentration of SDS is smaller than 45.0 mM, SDS micelles cause a partial loss in the hydrolytic activity together with a steep decrease in the -helical content of cellulase. With further increasing the concentration of SDS, however, a re-formation of the -helical structure and a partial recovery of the hydrolytic activity of cellulase induced by SDS micelles are observed. Taken together, these results indicate that SDS micelles exert dual effects on cellulase through binding as both a denaturant and a recovery reagent.     

Ionic liquids as modulators of the critical micelle concentration of sodium dodecyl sulfate

Critical micelle concentration (CMC) of sodium dodecyl sulfate (SDS), an anionic surfactant, has been investigated in aqueous solutions of a variety of room temperature ionic liquids (RTILs): 1,3-dimethylimidazolium iodide (Me2IM-I, 2), 1-butyl-3-methylimidazolium chloride (BMIM-Cl, 3), 1-hexyl-3-methylimidazolium chloride (HxMIM-Cl, 4), 1-methyl-3-octylimidazolium chloride (MOIM-Cl), 5, and 1-methyl-3-octylimidazolium tetrafluoroborate (MOIM-BF4, 6). The CMC of SDS is shown to correlate with the nature of the alkyl groups in the RTILs; SDS showed appreciably higher CMCs in presence of ionic liquids 2 and 3, whereas in the presence of ionic liquids 4, 5, and 6 much smaller CMCs were observed. The nature of the gigenions, Cl- or BF4-, has no noticeable effect on the observed CMC values.     

Structure and dynamics of concentrated micellar solutions of sodium dodecyl sulfate

In micellar solutions of sodium dodecyl sulfate, as the concentration of surfactants increases, the spheroid shape of the micelles changes from almost spherical to ellipsoidal with increasing ratio of half-axes ratio, and further the transition to cylindrical micelles occurs. The micelles in an aqueous solution can directly contact (compact aggregates) or be separated from one another by layers of intermicellar medium (periodical colloid structures). In the latter case, the thickness of the layer can significantly exceed the micelle size, and then no mutual correlation in micelle arrangement is observed. According to the data of small-angle X-ray scattering, the relationship between the surfactant concentration and formation of “quasi-crystalline” micellar structure is nonlinear, which can be due to both micelle aggregation processes and nonuniformity of their structure. The possible influence of ordered micellar structures on the diffusion mobility of micelles is shown.     

Effective self-diffusion coefficients of ions in sodium dodecyl sulfate micellar solutions

The effective self-diffusion coefficients of ions in premicellar and micellar solutions of sodium dodecyl sulfate are measured by the NMR self-diffusion method at 40°C. The obtained regularities are explained using a proposed model that takes into account the possible surface diffusion of counterions bound with micelles. This effect is shown to markedly influence the charge transfer in micellar solutions. Based on the results obtained, the self-diffusion coefficients of bound Na⁺ counterions are estimated and the causes and ranges of their variations are indicated.     

无探针荧光光谱法测定十二烷基硫酸钠的临界胶束浓度

建立了无探针荧光光谱法测定表面活性剂临界胶束浓度(CMC)的新方法,测定了典型阴离子表面活性剂十二烷基硫酸钠(SDS)在水溶液中的CMC,并与表面张力法和电导率法的测定结果进行了对比。结果表明,荧光光谱法样品用量少,测定的SDS的CMC与传统方法一致,说明采用无探针荧光光谱法能够测定一些物质的临界浓度。     

Electrokinetic properties of mixed solutions of dodecyldimethylamine oxide and sodium dodecyl sulfate: specific adsorption effects of small ions

Electrophoretic light-scattering measurements and potentiometric titrations were carried out on aqueous mixtures of dodecyldimethylamine oxide and sodium dodecyl sulfate. The electrophoretic mobility and the surface charge density of the micelles were always negative, ranging from –2.5 to –3.1×10^–4 cm²V^–1s^–1, and –0.033 to –0.045 cm^–2, respectively, for all surfactant mixing ratios, indicating the specific adsorption of Cl^–, in addition to Na⁺, on micelles. The solution pH, as well as the aggregation number previously reported, displayed maxima at intermediate surfactant mole fractions, that is, the non-ideal behavior. The fractional adsorption of Na⁺ per surfactant molecule in the micelles increased gradually with mixing fraction up to 0.82 atX=[SDS]/([SDS]+[C₁₂DAO])=1, while that of Cl^– decreased from 0.25 atX=0 to zero atX>0.4.     

Electrical percolation in micellar sodium dodecyl sulfate solutions. a phenomenological consideration

Effects of electrical percolation accompanying variations in overall surfactant concentration с have been studied by the example of micellar sodium dodecyl sulfate solutions. It has been found that, in the studied concentration range of 0.001–1.2 M, dependences of electrical conductivity K on c may exhibit at least three break points, with the dK/dc derivatives changing in the vicinities of these points. At two of these points, which are reliably identified and correspond to critical micelle concentrations (CMC₁ and CMC₂), they decrease. At the third concentration, lying between CMC₁ and CMC₂, the dK/dc derivative increases. A substantiated assumption has been put forward that this break point, at which the dK/dc derivative increases, results from the clustering of micelles and the appearance of channels with a higher specific conductivity, which is provided by the contribution from the electrical conductivity of the diffuse and dense parts of micelle electrical double layers, upon the formation of clusters. The ionic surfactant concentration that corresponds to the break point at which the dK/dc value increases has been denoted as the critical percolation concentration.     

Osmotic pressure of micellar sodium dodecyl sulfate solutions in the presence of NaCl

The concentration dependence of osmotic pressure π_s of micellar solutions of an ionic surfactant in the presence of a background electrolyte is theoretically considered in terms of the Debye-Hückel theory with due regard for the premicellar association and interaction of micelles. On the basis of the quasi-chemical theory of micellization, the system composition is determined and the thickness of the electrical double layer of micelles is calculated. Within the framework of a cell model and the ideas of the molecular and ion-electrostatic interaction of micelles, which varies in relation to the degree of micellization, osmotic pressure in a sodium dodecyl sulfate-0.01 M NaCl system is calculated during variations in the overall surfactant concentrations. The results obtained are in good qualitative and quantitative agreement with available experimental data. At the same time, the results of calculating π_s values in terms of the Debye-Hückel theory without consideration for the interaction of micelles do not allow explanation of the experimental regularities.     

Investigation of the state of 8-hydroxyquinoline in aqueous sodium dodecyl sulfate solutions

The influence of sodium dodecyl sulfate on the dissociation of protonated 8-hydroxyquinoline in aqueous solutions is investigated by potentiometric titration at 293 K. The constants of direct binding of 8-hydroxyquinoline with the monomers and micelles of sodium dodecyl sulfate are determined by the computer simulation of the most probable processes. The role of electrostatic and hydrophobic interactions in the studied system is discussed.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 231–234.Original Russian Text Copyright © 2005 by Ramenskaya, Vladimirova.