Micellization and intermicellar interactions in aqueous sodium dodecyl benzene sulfonate solutions

Quasielastic light scattering was used to investigate the size and shape of sodium dodecyl benzene sulfonate (SDBS) micelles in aqueous solutions. Measurements were made as a function of temperature and NaCl and SDBS concentrations. Light scattering data indicate that the micelles are spherocylinders with a semiminor axis of 22 Å. The length of the micelles increases strongly with salt concentration and decreases with temperature. The minimum micelle has an aggregation number of n⁰ = 28 and a hydrodynamic radius of R = 22 Å. Diffusion coefficient and intensity data were analyzed using a thermodynamic theory of micellar aggregation and a model based on DLVO theory of interactions.     

Molecular dynamics study of the structure and mechanism of formation of molecular associates in aqueous solutions of surfactants

The process of micelle formation in an aqueous solution of the surfactant was simulated by the computer experiment. It was established by the molecular dynamics method that micelles are formed through the formation of premicellar associates of the surfactant. The practical absence of an attraction between single molecules of sodium pentadecyl sulfonate (SPDS) and premicellar associates dissolved in water was shown for a SPDS—water system. The function of the radial distribution of Na⁺ counterions towards polar groups of SPDS molecules in water and on the surfaces of micelles and premicellar associates was studied by the molecular dynamics method. The presence of dissociated and non-dissociated polar groups of the SPDS molecular on the micelle surface was found. The data obtained are consistent with the existence concepts on micelle formation processes.     

丙烯酰胺型阴离子表面活性单体的化学结构与其胶束化行为

对两种丙烯酰胺型阴离子表面活性单体(2-丙烯酰胺基十四烷磺酸钠, NaAMC₁₄S; 2-丙烯酰胺基十二烷磺酸钠, NaAMC₁₂S)的化学结构与胶束化行为的关系进行了较深入的研究. 使用紫外分光光度法测定了NaAMC₁₄S, NaAMC₁₂S及十二烷基磺酸钠(SDS)在水中的溶解度, 同时采用表面张力法(环法)测定了它们在不同温度下的临界胶束浓度CMC; 采用稳态荧光探针法测定了不同浓度的胶束聚集数与本征胶束聚集数. 实验结果表明, 与普通表面活性剂相比, 由于丙烯酰胺型阴离子表面活性单体分子中具有两个亲水头基, 在水中的溶解性能较强, 故具有较低的Krafft温度; 在溶液表面的饱和吸附量低, 故降低水表面张力的能力较差, 即表面活性差; 疏水缔合的胶团较为疏松, 故聚集数很小; 胶束内分子间的疏水相互作用较弱, 故临界胶束浓度CMC较高.     

Effect of concentration on surfactant micelle shapes —A molecular dynamics study

Many aspects of the behavior of surfactants have not been well understood due to the coupling of many different mechanisms. Computer simulation is, therefore, attractive in the sense that it can explore the effect of different mechanisms separately. In this paper, the shapes, structures and sizes of sodium dodecylbenzenesulfonate (SDBS) micelles under different concentrations in an oil/water mixture were studied via molecular dynamics (MD) simulations using a simplified atomistic model which basically maintains the hydrophile and lipophile properties of the surfactant molecules. Above the critical micellar concentration (cmc), surfactant molecules aggregate spontaneously to form a wide variety of assemblies, from spherical to rodlike, wormlike and bilayer micelles. Changes in their ratios of the principle moments of inertia (g₁/g₃, g₂/g₃) indicated the transition of micelle shapes at different concentrations. The aggregation number of micelle is found to have a power-law dependence on surfactant concentration.     

Unlike surfactant–polymer interactions of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate with water-soluble polymers

Single and mixed micelle formation by sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS) and their mixtures in pure water and in the presence of water-soluble polymers such as Synperonic 85 (triblock polymer, TBP), hydroxypropylcellulose (HPC), and carboxymethylcellulose sodium salt (CMC) were studied with the help of conductivity, pyrene fluorescence, cyclic voltammetry, and viscosity measurements. Conductivity measurements showed a single aggregation process for pure surfactants and their mixtures both in pure water as well as in the presence of water-soluble polymers. Triple breaks corresponding to two aggregation processes for SDS, SDBS, and their mixture in the presence of TBP were observed from fluorescence measurements. The first one demonstrated the critical aggregation process due to the adsorption of surfactant monomers on TBP macromolecule. The second one was attributed to the participation of surfactant–polymer aggregates formed at the first one, in the micelle formation process. The aggregation number ( N _agg) of single and mixed micelles and diffusion coefficient ( D) of electroactive probe were computed from the fluorescence and cyclic voltammetry measurements, respectively. Both parameters, along with the viscosity results, indicated stronger SDS–polymer interactions in comparison to SDBS–polymer interactions. Mixed surfactant–polymer interactions showed compensating effects of both pure surfactants. The nature of mixed micelles was found to be ideal in all cases, as evaluated by applying the regular solution and Motomura's approximations.     

Structural,electrostatic and thermodynamic properties of the surface of spherical micelles in solutions of sodium <Emphasis Type="Italic">n</Emphasis>-alkyl sulfate homologues. I. Structural characteristics

Using the aggregation numbers of micelles and the effective sizes of hydrated surfactant ions and counterions of the first coordination sphere, we calculated the average geometric characteristics of the surface layer of ionic spherical micelles in solutions of the sodium n-alkyl sulfate homologues with n _C = 8, 10, 12, and 14 carbon atoms in the molecule; in particular, we established 1) the size of the micelle core; 2) the thickness of the electrical double layer on the surface; 3) the mutual arrangement parameters of hydrophilic and hydrophobic ions; 4) the number of “free” water molecules and showed their dependence on the homologue number and the degree of binding of counterions.     

Intermicellar material exchange in reverse micelles formed by ionic AOT and nonionic Igepal surfactants studied by means of pulse radiolysis. Influence of the temperature

The recombination of thiocyanate anion radicals, (SCN) ₂ ⁻ , formed pulse radiolytically within the water pools of reverse micelles stabilized with anionic AOT and nonionic Igepal surfactants, was proved as an indicator reaction to study intermicellar exchange. It was found that the exchange process is slower inIgepal than in AOT reverse micelles with the same water to surfactant ratio. The apparent activation enthalpy and entropy of the exchange process were determined in different alkanes. For the AOT and Igepal reverse micelles the activation parameters increase with the droplet size, but for the AOT systems they do not significantly change with the increase of droplet concentration. For non-percolated systems the activation parameters for Igepal reverse micelles approach those for AOT reverse micelles. This result supports existing suggestions that the mechanism of intermicellar exchange does not differ in principle between reverse micelles stabilized with ionic and nonionic surfactants.     

A small-angle neutron scattering study of the ethyl (n-octyl) phosphate micelles in water

Summary Mixed-double chain anionic surfactants, barium- and lithium-salts of ethyl(n-octyl) phosphate (EOP), which are asymmetric in the molecular shape, and a series of identical chain di-n-alkyl phosphate lithium salts have been synthezized. The limiting partial molar volume of a PO ₄ ^– group (23.43±0.41 cm³ mol^–1) for use in small-angle neutron scattering analysis was determined by density measurements of a series of identical chain di-n-alkyl phosphate lithium salts. For lithium EOP-D₂O system, a critical micellar concentration (2.3 wt%) was determined by³¹P NMR spectra. The micellar shape and size in the EOP-water binary system has been investigated by using small-angle neutron scattering (SANS) spectra. It has been found that the micelles of barium EOP in water have the shape of a prolate spheroid and aggregation numbers (n) equal to 48 at 23°C and 52 at 50°C. For the lithium EOP-micellar system, it has been found that the minimum micelle with an aggregation numbern=21 is spherical and micellar growth and variation from the spherical to the prolate shape might occur with an increase in concen tration above the CMC.     

SANS from Pluronic P85 in d-water

Small-angle neutron scattering (SANS) has been used to investigate Pluronic P85 (EO₂₆PO₄₀EO₂₆) copolymer in deuterated water. A range of P85 fractions were measured for a wide sample temperature window. A rich phase behavior is reported. Unimers were observed below the critical micelle formation condition. At fixed P85 fraction, a number of micellar phases were observed upon increasing temperature; first spherical micelles, then cylindrical micelles, then lamellar micelles. At the highest temperature, a demixed lamellae phase was observed. Analysis of the SANS data consisted in fits to an empirical Guinier-Porod model that was appropriate for data fitting in the various phases at low P85 fractions. When the P85 fraction increased, an inter-particle structure factor was included to analyze SANS data from concentrated spherical micelles. At high P85 fractions, paracrystalline structures were observed as evidenced by an enhanced inter-particle interaction peak. A phase diagram for P85/d-water was obtained showing the various phases. Focusing on the spherical micelles phase for one sample composition, a core-shell model was used to fit SANS data and obtain sizes and scattering length densities. Using material balance equations, information such as the aggregation number (i.e., number of Pluronic macromolecules per micelle) and the number of hydration water molecules in the shell region are determined.     

<Superscript>13</Superscript>C NMR investigation of the structure of alkylammonium chloride micells in aqueous solutions

¹³C NMR chemical shifts are obtained for aqueous solutions of alkylammonium chlorides (C₆–C₉) in the region of the critical micelle concentration (CMC). A new method of processing ¹³C NMR experimental data for aqueous solutions of alkylammonium chlorides is developed to calculate the aggregation numbers N of micelles and the equilibrium constants K of the micelle formation within the law of mass action. With the use of these N and K values the standard Gibbs energy of the micelle formation and its increment of −1.8 kJ/mol are found for the methylene group. A small increment confirms the hypothesis about the structure of micelles consisting of both contact and hydrated associates. The structural model of the association of alkylammonium chlorides in water, the effect of alkyl chain length on the CMC, the hydrophobic interaction, the formation of hydrate associates, and also a possible classification of surfactants based on this are discussed.     

Distribution of the methyl radical adduct of N‐benzylidene‐1‐diethoxyphosphoryl‐1‐methylethylamine N‐oxide‐type nitrones in water–sodium dodecyl sulfate micelles: an electron paramagnetic resonance spin trapping study

The behavior of the methyl radical adduct of six β‐phosphorylated nitrones in the N‐benzylidene‐1‐diethoxyphosphoryl‐1‐methylethylamine N‐oxide series in the presence of sodium dodecyl sulfate (SDS) micelles was followed by electron paramagnetic resonance spectroscopy. Except when the highly hydrophilic trap 4‐PyOPN (2) was used, all the adducts were found to partition significantly between micelles and the bulk aqueous phase. The average correlation time τ of the exchange of spin adducts between SDS micelles and water was found to be in the range 5 × 10^?8—4 × 10^?7 s, which is in the region of the life time of an SDS monomer in the micelle structure. In each case, the adduct affinity for the micelles has been quantified by evaluating its micelle–water distribution coefficient K_d. Copyright © 2002 John Wiley & Sons, Ltd.     

Physicochemical characterization of phospholipid solubilized mixed micelles and a hydrodynamic model of interfacial fluorescence quenching

Mixed micelles of solubilized dimyristoyl phosphatidylcholine (DMPC) and the zwitterionic detergent dodecyldimethylammoniopropane sulfonate are characterized employing time-resolved fluorescence quenching (TRFQ), electron spin resonance (ESR), and surface tensiometry toward the goal of investigating interfacial reactions using these micelles as host reaction media. The properties measured are the micelle aggregation numbers, interfacial hydration index, microviscosity, and the critical micelle concentrations for various molar fractions, XDMPC, of DMPC, 0相似文献   

Solute exchange between surfactant micelles by micelle fragmentation and fusion

Stopped-flow time-scan experiments on both Triton X-100 (TX100) micelle and sodium dodecylsulfate (SDS) micelles, with the pyrene-containing triglyceride 1 as a probe, establish that there are two distinct solute exchange mechanisms with rates on the time scale of milliseconds to minutes. One process exhibits second order kinetics with a rate proportional to the concentration of empty micelles. For TX100 micelles, this process is rapid (k₂≈10⁶ M⁻¹ s⁻¹ at 24.6°C) and is characterized by an activation energy of 160 kJ mol⁻¹. From the fact that this rate is nearly independent of the structure of the probe we infer that the exchange involves micelle fusion to form a short-lived super-micelle, followed by fragmentation to form two normal (or ‘proper’) micelles. The rate of the first-order process decreases as the size of the probe increases (1-octylpyrene>1-dodecylpyrene>1). For SDS, both rates are very sensitive to the salt (NaCl) concentration. All indications point to this exchange process involving rate-limiting fragmentation of the micelle into two sub-micelles, these in turn grow back to normal micelles by addition of surfactant monomers or by collision with other sub-micelles. We explain the dependence of this rate on the nature of the probe by suggesting that only sub-micelles of a certain size are capable of carrying the probe with them as they separate from the original micelle.     

Aggregation of sodium 1-(n-alkyl)naphthalene-4-sulfonates in aqueous solution: micellization and microenvironment characteristics

In aqueous solution, the micellization and microenvironment characteristics of the micelle assemblies of three anionic surfactants, sodium 1-(n-alkyl)naphthalene-4-sulfonates (SANS), have been investigated by steady-state fluorescence and time-resolved fluorescence decay techniques using pyrene, Ru(bpy)3(2+), and 1,6-diphenyl-1,3,5-hexatriene as fluorescence probes. The critical micelle concentrations (cmc's), effective carbon atom numbers (neff's), hydrophilic-lipophilic balances (HLBs), mean micelle aggregation numbers, micropolarities, and microviscosities of these surfactant micelles have been determined. The logarithmic cmc of the alkylnaphthalene sulfonates decreases linearly with an increase in the neff. The logarithmic aggregation number of the alkylnaphthalene sulfonates increases linearly with an increase in the neff. However, in contrast to the alkylsufonates and the alkylbenzene sulfonates, the aggregation for these alkylnaphthalene sulfonate molecules is less sensitive to the increase in the neff. The micropolarity of these alkylnaphthalene sulfonate micelles is less sensitive to the increase in the alkyl chain length and is lower than that of sodium dodecyl sulfate (SDS). The microviscosity of these alkylnaphthalene sulfonate micelles increases with an increase in the alkyl chain length and is lower than those of nonionic surfactants and zwitterionic surfactants. These results suggest that naphthyl rings have a notable effect on the micellization of SANS.     

Specific Features of the Preparation of AgI Nanocrystals in Reverse Micelles of Aerosol OT

It was shown that the interrelation between the mean size of AgI nanocrystals prepared in the water pools of reverse micelles as a result of reaction between KI and AgNO₃ and the pool diameter has a complex pattern and is determined mainly by the stability of micellar system. Microemulsions with small micelles (the pool diameter is up to 2 nm) are stable due to the presence of micelle oligomeric phase, regardless of the effect of water structurization in pools. In microemulsions with pool diameters from 2 to 6 nm, such an oligomeric phase is absent that leads to the avalanche-like growth of nanocrystals due to their aggregation in organic phase. As the diameter of micelle pools increases above 6 nm, the microemulsions are stabilized because of the limited dimensions of structured water layer and the deceleration of intermicellar exchange. When the excess amount of KI is added to microemulsion, the screening shell of ions is formed around nanocrystals, thus complicating the formation of icelike structure of water in micelle pools.     

Micelle and Solvent Relaxation in Aqueous Sodium Dodecylsulfate Solutions

Dielectric spectra have been measured for aqueous sodium dodecylsulfate (SDS) solutions up to 0.1 mol L^?1 at 25 °C over the frequency range 0.005≤ν GHz^?1≤89. The spectra exhibit two relaxation processes at approximately 0.03 GHz and 0.2 GHz associated with the presence of micelles in addition to the dominant solvent relaxation process at approximately 18 GHz and a small contribution at approximately 1.8 GHz due to H₂O molecules hydrating the micelles. Detailed analysis reveals that the micelles bind 20 water molecules per SDS unit, but not as strongly as trimethylalkylammonium halide surfactants do. The relaxation times and amplitudes of both micelle relaxation processes can be simultaneously analysed with the theory of Grosse, yielding the effective volume of a SDS unit in the micelle and the lateral diffusion coefficient of the bound counterions. The findings of this investigation fully corroborate recent molecular dynamics simulations on structure and dynamics of SDS micelles.     

Synthesis of poly(dipeptide)s on the surface of functional micelle and reversed micelle

Amphiphilic active 4-dodecanoyl-2-nitrophenyl esters of dipeptide containing β-alanine ( 1 – 5 ) were prepared and their polycondensation was studied in detail. The critical micelle concentrations of the active esters 1 – 5 were determined in water by the dye method and the apparent mean aggregation number of reversed micelles formed by model compound 6 was determined by the osmotic method. The results of polycondensation can be explained by assuming that aggregations such as micelle and reversed micelle play an important role in polycondensation. The obtained new poly(dipeptide)s were examined by IR, ¹H NMR, x-ray diffraction, and circular dichroism spectra.     

The size of sodium dodecyl sulfate micelles in the presence ofn-alcohols as determined by fluorescence quenching measurements

The steady-state fluorescence quenching technique was used to investigate the effect of the presence of a series of alcohol homologues of mid-sized straight chain on the size of mixed micelles of sodium dodecyl sulfate (SDS). We used pyrene at concentration of ca. 10^–6M, where only its monomer exhibits any fluorescence, as fluorescent probe, and cetylpiridinium chloride at concentrations in the range (1–9)×10^–5 M as quencher. This technique allows one to determine the micellar aggregation number. The number of alcohol molecules per micelle was calculated from reported values for the micelle-water partition coefficient. On the assumption of spherical micelles, their hydrophobic radii was then calculated. The hypothesis that micelle size is determined by the available surface area per charged headgroup is discussed in the light of the results obtained.     

Interactional and aggregation behavior of twin tail cationic surfactants with pluronic L64 in aqueous solution

The aqueous mixed systems of twin tail cationic surfactants didodecyldimethylammonium bromide, ditetradecyldimethylammonium bromide, and dihexadecyldimethylammonium bromide with pluronic L64 have been studied to determine the bulk aggregation and interactional behavior. Various experimental techniques, namely small-angle neutron scattering (SANS), fluorescence, conductivity, and surface tension, have been employed to investigate the mixed micellization. The SANS data analysis has been employed to determine the shapes of different aggregates formed. Pure twin tail cationic surfactants form vesicles whereas the micelles of pure pluronic L64 are spherical. The mixed systems (surfactant + L64) also form spherical micelles, and the spherical shape of mixed micelles is predominantly controlled by pluronic L64. Various interfacial parameters such as surface excess (Γ _max), minimum area per molecule (A _min), and thermodynamic parameters such as the standard Gibbs free energy of micellization (DG_mic⁰ \Delta G_{{mic}}^{{0}} ), Gibbs free energy of adsorption (DG_ads⁰ \Delta G_{{ads}}^{{0}} ), and effective Gibbs free energy (DG_eff⁰ \Delta G_{{eff}}^{{0}} ) have been determined from the surface tension measurements. The results were interpreted on the basis of pseudophase separation model and regular solution theory. The interactions of each surfactant with pluronic L64 are found to be nonideal and antagonistic. The repulsive nature of the interaction is explained on the basis of the changes in the microenvironment of micelles of pluronic L64. Micelles of pluronic L64 are less hydrophobic and contains significant amount of water, and inclusion of hydrophobic alkyl chains of twin tail cationic surfactants disturbs this microenvironment of pluronic L64 micelle.