Swelling of poly(ethylene oxide) gel in aqueous solutions of sodium dodecyl sulfate with added sodium chloride

The swelling behavior of poly(ethylene oxide) (PEO) gels in aqueous solutions of sodium dodecyl sulfate (SDS) with and without NaCl was investigated. In the absence of NaCl, PEO gels with different degrees of cross-linking began to swell from a concentration lower than the critical micelle concentration (cmc) of SDS, then showed sigmoidal enhancements of swelling in a higher SDS concentration region until the degrees of swelling reached maximum values. The SDS concentration at which the swelling began to appear was in reasonable agreement with the critical aggregation concentration (cac) value reported for the aqueous PEO system. For the cases where NaCl was present, the swelling behavior of PEO gel was different from that when NaCl was absent in the following way. The concentrations where the swelling begins to appear, and hence those where the degree of swelling rises steeply, decreased with an increase in NaCl concentration. The ultimate degrees of swelling at higher concentration regions also decreased with an increase in the NaCl concentration. The lowering of the SDS concentrations at which the PEO gel began to swell is in line with the decreases in the cmc of SDS solutions containing NaCl and also with the decreases in the cac of PEO solution. Electronic Publication     

Modulating properties of aqueous sodium dodecyl sulfate by adding hydrophobic ionic liquid

Altering and modifying important physicochemical properties of aqueous surfactant solutions is highly desirable as far as potential applications of such systems are concerned. Changes in the properties of aqueous solutions of a common anionic surfactant sodium dodecyl sulfate (SDS) are assessed in the presence of a common and popular 'hydrophobic' ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6)). Upon addition of up to approximately 0.10 wt% bmimPF(6), a dramatic decrease in critical micelle concentration (cmc) is accompanied by an increase in the degree of counterion dissociation (alpha) and micellar aggregation number (N(agg)) indicating micellar growth. However, in the range 0.10 wt% < or = bmimPF(6) 2.00 wt%, relatively gradual decrease in alpha and N(agg) is observed along with no change in cmc. Significantly decreased microfluidity of the aqueous SDS solutions on addition of bmimPF(6) is indicated by a fluorescence microviscosity probe 1,3-bis-(1-pyrenyl)propane which suggests partitioning of bmimPF(6) into the SDS micellar phase. Behavior of solvatochromic fluorescence probes, pyrene, pyrene-1-carboxaldehyde, and 2-(p-toluidino)naphthalene-6-sulfonate, confirms interaction, and possible complexation, between IL bmimPF(6) and anionic micellar surface. Increased solubility of bmimPF(6) with increasing SDS concentration further confirms SDS-bmimPF(6) interactions. Presence of strong electrostatic attraction between bmim(+) and anionic micellar surface is proposed to be the most dominant reason for these observations. All-in-all, unique role of a hydrophobic ionic liquid bmimPF(6) in modifying the properties of aqueous anionic sodium dodecyl sulfate is demonstrated.     

Aggregation and adsorption of sodium dioctylsulfosuccinate in aqueous ammonium chloride solution: role of mixed counterions

The critical micelle concentration (cmc) of sodium dioctylsulfosuccinate (AOT) was determined at 25 °C from surface tension and fluorescence methods in aqueous NH(4)Cl solution for assessing the influence of mixed counterions on the special counterion binding behavior (SCB) of AOT. The SCB of AOT refers to a sudden twofold increase in the value of the counterion binding constant (β) in aqueous medium when the concentration (c(*)) of the added 1:1 sodium salt is about 0.015 mol kg(-1), and it has been tested so far for sodium ion only. In the presence of sodium and ammonium mixed counterions also the SCB of AOT exist, but with lower c(*) (0.009 mol kg(-1) NH(4)Cl). Synergism in the cmc occurs due to mixed counterions. In the case of inorganic counterions, unlike the case with organic counterions, the cmc is dependent on the total counterion concentration in solution and negligibly on the specific type of counterion. Na(+) and NH(4)(+) bind almost equally to the micelle in the region of low β (below c(*)), but in the region of high β (above c(*)) NH(4)(+) binds predominantly. It has been shown that the theoretical expression for the surface excess of ionic surfactant+electrolyte system containing a single counterion can also be used to evaluate the surface excess in the presence of mixed counterions if the two counterions are considered to undergo Henry-type adsorption at the air-solution interface.     

Conductometric study of antidepressant drug-cationic surfactant mixed micelles in aqueous solution

Conductivity measurements have been carried out on aqueous solutions of two antidepressant drugs (nortriptyline hydrochloride and clomipramine hydrochloride) with four cationic surfactants (monomeric: cetyltrimethylammonium bromide, tetradecylammonium bromide; dimeric: 1,5-pentanediyl-alpha-omega-bis(hexadecyldimethylammonium bromide), 1,4-butanediyl-alpha,omega-bis(hexadecyldimethylammonium bromide) as well as with sodium chloride. Counterions from NaCl adsorb to the charged headgroup of the drug molecules and reduce the repulsion, hence cmc decreases. cmc values decreased with the addition of surfactants indicating mixed micelle formation. Experimental mole fraction of surfactants in micelle (X1) and their ideal values (X1 id) also support this explanation. Interaction parameter, beta, and excess free energy of micellization are negative suggesting synergism in mixed state. Activity coefficients are less than unity which means non-ideal mixing.     

Transport coefficients of aqueous dodecyltrimethylammonium bromide solutions: comparison between experiments, analytical calculations and numerical simulations

We study dynamical properties of ionic species in aqueous solutions of dodecyltrimethylammonium bromide, for several concentrations below and above the critical micellar concentration (cmc). New experimental determinations of the electrical conductivity are given which are compared to results obtained from an analytical transport theory; transport coefficients of ions in these solutions above the cmc are also computed from Brownian dynamics simulations. Analytical calculations as well as the simulation treat the solution within the framework of the continuous solvent model. Above the cmc, three ionic species are considered: the monomer surfactant, the micelle and the counterion. The analytical transport theory describes the structural properties of the electrolyte solution within the mean spherical approximation and assumes that the dominant forces which determine the deviations of transport processes from the ideal behavior (i.e., without any interactions between ions) are hydrodynamic interactions and electrostatic relaxation forces. In the simulations, both direct interactions and hydrodynamic interactions between solutes are taken into account. The interaction potential is modeled by pairwise repulsive 1/r(12) interactions and Coulomb interactions. The input parameters of the simulation (radii and self-diffusion coefficients of ions at infinite dilution) are partially obtained from the analytical transport theory which fits the experimental determinations of the electrical conductivity. Both the electrical conductivity of the solution and the self-diffusion coefficients of each species computed from Brownian dynamics are compared to available experimental data. In every case, the influence of hydrodynamic interactions (HIs) on the transport coefficients is investigated. It is shown that HIs are crucial to obtain agreement with experiments. In particular, the self-diffusion coefficient of the micelle, which is the largest and most charged species in the present system, is enhanced when HIs are included whereas the diffusion coefficients of the monomer and the counterion are roughly not influenced by HIs.     

Properties of polyethylene glycol (23) lauryl ether with cetyltrimethylammonium bromide in mixed aqueous solutions studied by self-diffusion coefficient NMR

NMR self-diffusion coefficient measurements have been used to study the properties of polyethylene glycol (23) lauryl ether (Brij-35) with cetyltrimethylammonium bromide (CTAB) in the mixed aqueous solutions with different mole fractions of CTAB. By fitting the self-diffusion coefficients to the two-state exchange model, the critical micelle concentrations of the two solutes in the mixed solutions (cmc*1 and cmc*2) were obtained. The critical mixed micelle concentrations (cmc*) were then evaluated by the sum of cmc*1 and cmc*2, which are in good agreement with the results measured by the surface tension method. The cmc* values are lower than those of the ideal case of mixing, which indicates that the behavior of the CTAB/Brij-35 system is nonideal. Moderate interactions between CTAB and Brij-35 in their mixtures can be deduced from the interaction parameters (betaM) based on the cmc* obtained by the NMR self-diffusion method. The compositions (x1) of the mixed micelles at different total surfactant concentrations were also evaluated. By using these results, a possible mechanism of mixed micellar formation and a picture of the formation of nonsimultaneous CTAB/Brij-35 binary mixed micelle were proposed. In contrast to the case of CTAB/TX-100 system, Brij-35 molecules have a tendency to form micelles first at any mole fraction of CTAB. The mixed micellar self-diffusion coefficients (Dm) increase slightly at lower CTAB molar ratios, and then speed up with increasing CTAB mole fraction.     

Electrical conductivity study on micelle formation of long-chain imidazolium ionic liquids in aqueous solution

Electrical conductivity was measured for aqueous solutions of long-chain imidazolium ionic liquids (IL), 1-alkyl-3-methylimidazolium bromides with C(12)-C(16) alkyl chains. The break points appeared in specific conductivity (kappa) vs concentration (c) plot indicates that the molecular aggregates, i.e., micelles, are formed in aqueous solutions of these IL species. The critical micelle concentration (cmc) determined from the kappa vs c plot is somewhat lower than those for typical cationic surfactants, alkyltrimethylammonium bromides with the same hydrocarbon chain length. The electrical conductivity data were analyzed according to the mixed electrolyte model of micellar solution, and the aggregation number, n, and the degree of counter ion binding, beta, were estimated. The n values of the present ILs are somewhat smaller than those reported for alkyltrimethylammonium bromides, which may be attributed to bulkiness of the cationic head group of the IL species. The thermodynamic parameters for micelle formation of the present ILs were estimated using the values of cmc and beta as a function of temperature. The contribution of entropy term to the micelle formation is superior to that of enthalpy term below about 30 degrees C, and it becomes opposite at higher temperature. This coincides with the picture drawn for the micelle formation of conventional ionic surfactants.     

Concentration-dependent aggregation patterns of conjugated bile salts in aqueous sodium chloride solutions

Based on light scattering intensity measurements, a critical concentration for micelle formation can be assigned to sodium taurodeoxycholate in aqueous electrolyte solutions. For sodium taurocholate a progressive aggregation even at very low concentrations of bile salt is indicated. Surface tension and diffusion coefficients are also reported.     

Salting-out effects in aqueous ionic liquid solutions: cloud-point temperature shifts

The effects of the addition of three inorganic salts, namely, NaCl, Na(2)SO(4), and Na(3)PO(4), on the liquid-liquid (L-L) phase diagram of aqueous solutions containing the model ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF(4)], were investigated. All three inorganic salts trigger salting-out effects, leading to significant upward shifts of the L-L demixing temperatures of the systems. The magnitude of the shifts depends on both the water-structuring nature of the salt and its concentration; that is, the effects are correlated with the ionic strength of the solution and the Gibbs free energy of hydration of the inorganic salt. The pH effect and the occurrence of salt precipitation in concentrated solutions are also discussed.     

Probing the micellization of diblock and triblock copolymers of poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) and poly(ethylene glycol) in aqueous and NaCl salt solutions

The micelle formation of a series of amphiphilic block copolymers in aqueous and NaCl solutions was studied by a fluorescent probe technique using pyrene as a "model drug". These copolymers were synthesized from poly (ethylene glycol) (PEG) and l-lactide by a new calcium ammoniate catalyst. They had fixed PEG block lengths (44, 104 or 113 ethylene oxide units) and various poly(l-lactide) (PLLA) block lengths (15–280 lactide units). The critical micelle concentration (cmc) was found to decrease with increasing PLLA content. The distinct dissimilarity of the cmc values of diblock and triblock copolymers based on the same block length of PEG provided evidence for the different configurations of their micelles. It was also observed that the introduction of NaCl salt significantly contributed to a decrease in the cmcs of the copolymers with short PEG and PLLA blocks, while it had less influence on the cmcs of copolymers with long PEG or PLLA blocks. The dependence of partition coefficients ranging from 0.2×10⁵ to 1.9×10⁵ on the PLLA content in the copolymer and on the micelle configuration was also discussed. The contribution of NaCl salt to increasing the partition of pyrene into a micellar phase was observed.     

Static and dynamic light-scattering studies on micellar solutions of alkyldimethylbenzylammonium chlorides

Static (SLS) and dynamic (DLS) light-scattering techniques were applied to the study of the aggregation of dodecyl- (C12DBACl), tetradecyl- (C14DBACl), and hexadecyldimethylbenzylammonium (C16DBACl) chlorides in water and in 0.01 and 0.05 m NaCl aqueous solutions at 25 degrees C. Results of SLS measurements yielded critical micelle concentration (cmc) values for aqueous and NaCl solutions. The aggregation numbers of the micelles for the homologous surfactants are low but increase with chain length and ionic strength of the solution. Various patterns of changes of the diffusion coefficient, D, as a function of chain length, molality, and with ionic strength were found for the studied surfactants. Transformations in the structure of micelles of C14DBACl in 0.01 m NaCl occur at a concentration of surfactant of about 0.01 m. Such transformations, presumably due to rodlike structure, are the more extensive the higher the concentration of NaCl. The concentration of C16DBACl in 0.05 m NaCl covers the range where already repulsive interactions between micelles occur, as judged by the strongly negative slope of the D versus molality plot. To provide additional information on the suggested transformations, complementary viscosity measurements for C14DBACl in 0.01 m of NaCl have been performed.     

Thermodynamic properties of surfactant sodium n-heptyl sulfonate in water and in aqueous solutions of poly(ethylene glycol) at different temperatures

The volumetric, compressibility and electrical conductivity properties of sodium n-heptyl sulfonate (C₇SO₃Na) in pure water and in aqueous poly(ethylene glycol) (PEG) solutions were determined at different temperatures below and above the micellar composition range. At each temperature, the infinite dilution apparent molar volumes of the monomer and micellar state of C₇SO₃Na in aqueous PEG solutions respectively are smaller and larger than those in pure water. However, the values of the infinite dilution apparent molar isentropic compressibility of both monomer and micellar states of C₇SO₃Na in aqueous PEG solutions are larger than those in pure water. Thermodynamic parameters of micellization of investigated surfactant in water and in aqueous solutions of PEG at different temperatures were estimated and it was found that the micelle formation process is endothermic and therefore, this process must be driven by entropy increase. The calculated Gibbs free energies of micellization for aqueous PEG solutions are more negative than those for pure water and become more negative by increasing temperature. The variation of the critical micelle concentration (CMC) of C₇SO₃Na in water and in aqueous PEG solutions with temperature was obtained and a comparison between the CMC of C₇SO₃Na obtained from different thermodynamic properties was also made.     

Micelle formation of nonionic surfactants in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate: surfactant chain length dependence of the critical micelle concentration

Micellization behavior was investigated for polyoxyethylene-type nonionic surfactants with varying chain length (C(n)E(m)) in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)). Critical micelle concentration (cmc) was determined from the variation of (1)H NMR chemical shift with the surfactant concentration. The logarithmic value of cmc decreased linearly with the number of carbon atoms in the surfactant hydrocarbon chain, similarly to the case observed in aqueous surfactant solutions. However, the slope of the straight line is much smaller in bmimBF(4) than in aqueous solution. Thermodynamic parameters for micelle formation estimated from the temperature dependence of cmc showed that the micellization in bmimBF(4) is an entropy-driven process around room temperature. This behavior is also similar to the case in aqueous solution. However, the magnitude of the entropic contribution to the overall micellization free energy in bmimBF(4) is much smaller compared with that in aqueous solution. These results suggest that the micellization in bmimBF(4) proceeds through a mechanism similar to the hydrophobic interaction in aqueous surfactant solutions, although the solvophobic effect in bmimBF(4) is much weaker than the hydrophobic effect.     

Effect of sodium salicylate, sodium oxalate, and sodium chloride on the micellization and adsorption of sodium deoxycholate in aqueous solutions

The salicylate ion increases the rate of bile flow (choleretic effect) and bile salts are known to affect the colonic absorption of oxalate. Owing to this physiological relevance of salicylate and oxalate ions, critical micelle concentration (cmc) values of sodium deoxycholate (NaDC) were determined in aqueous sodium oxalate, sodium salicylate, and sodium chloride solutions by using surface tension, fluorescence, and EMF methods. The results indicate, besides a counterion effect, the influence of coanions on the cmc. In the range from 25 to 40 °C, cmc increases almost linearly with temperature. In the temperature range from 30 to 40 °C, the counterion binding constant β of NaDC micelles has the same value (0.17±0.01) in the presence of sodium chloride and sodium salicylate. On the other hand, in sodium oxalate solution β=0.05±0.02 when oxalate concentration is less than or equal to c* and β=0.48±0.04 above c*, where c*≈0.038 mol kg(-1). EMF measurements also supported this type of counterion binding to NaDC micelles in sodium oxalate solutions. In sodium oxalate solution, at c* a change in the shape of deoxycholate micelles is expected to take place. Salicylate, oxalate, and chloride coanions have a similar effect on the adsorption of NaDC. This study reveals that the choleretic effect of salicylate is not due to the influence of salicylate ions on the micellization of NaDC.     

Study of the aggregation of nonylammonium chloride in aqueous solutions of sodium chloride by vapor pressure osmometry

We determined osmotic coefficients from vapor pressure osmometry (VPO) measurements on aqueous solutions of nonylammonium chloride in the presence of NaCl at 30°C. VPO data were subsequently used to determine the critical micelle concentration (CMC) of the solutions of this surfactant. The values of this parameter obtained from VPO are well correlated with those obtained from light scattering. No premicellar aggregation was observed at surfactant concentrations below the CMC. The osmotic coefficients below the CMC may be evaluated from the extended form of the Debye–Hückel equation. Above the CMC, the dependence of the osmotic coefficient on the surfactant concentration was indicative of the occurrence of aggregation rather than the interactions in the system. Some comments are made on the uncertainty in the value of some parameters in micellar solutions and possible source of error using the VPO technique in these solutions.     

Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.     

Surface adsorption and micelle formation of surface active ionic liquids in aqueous solution

Aqueous solutions of three kinds of surface active ionic liquids composed of the 1-alkyl-3-methylimidazolium cation have been investigated by means of surface tension and electrical conductivity measurements at room temperature (298 K). The surface tension measurements provided a series of parameters, including critical micelle concentration (cmc), surface tension at the cmc (gammacmc), adsorption efficiency (pC20), and effectiveness of surface tension reduction (Picmc). In addition, with application of the Gibbs adsorption isotherm, maximum surface excess concentration (Gammamax) and minimum surface area/molecule (Amin) at the air-water interface were estimated. The effect of sodium halides, NaCl, NaBr, and NaI, on the surface activity was also investigated. It was found that both the pC20 and the Picmc were rather larger than those reported for traditional ionic surfactants and the cmc values were somewhat lower than those for typical cationic surfactants, alkyltrimethylammonium bromides, and comparable to typical anionic surfactants, sodium alkyl sulfates. These results demonstrate that the surface activity of long-chained imidazolium IL is somewhat superior to that of conventional ionic surfactants.     

Micelle formation by N-alkyl-N-methylpyrrolidinium bromide in aqueous solution

The micellization of the ionic liquid N-alkyl-N-methylpyrrolidinium bromide (C(n)MPB, n = 12, 14 and 16) in aqueous solutions was investigated by surface tension measurements, electrical conductivity and static luminescence quenching. The effectiveness of the surface tension reduction (Π(cmc)), maximum surface excess concentration (Γ(max)) and the minimum area (A(min)) occupied per surfactant molecule at the air/water interface can be obtained from the surface tension measurements at 25 °C. The critical micelle concentration (cmc) at different temperatures and a series of thermodynamic parameters (ΔG, ΔH and ΔS) of micellization were evaluated from electrical conductivity measurements in the temperature range of 25-45 °C. The thermodynamic parameters show that the micelle formation is entropy-driven at low temperature and enthalpy-driven at high temperature. Furthermore, the micelle aggregation number (N(agg)) of C(n)MPB was calculated according to the Turro-Yekta method through static luminescence quenching and found that N(agg) (49, 55, and 59) increased with the hydrophobic chain length of C(n)MPB.     

Interaction between a partially fluorinated alkyl sulfate and gelatin in aqueous solution

The interaction of a partially fluorinated alkyl sulfate, sodium 1H,1H,2H,2H-perfluorooctyl sulfate (C6F13CH2CH2OSO3Na), with the polyampholyte gelatin has been examined in aqueous solution using surface tension and small-angle neutron scattering (SANS). The 19F chemical shift of each fluorine environment in the surfactant is unaltered by the addition of gelatin, indicating that there is no contact between the gelatin and the fluorocarbon core of the micelle. The chemical shift of the two methylene groups closest to the headgroup is altered when gelatin is present, disclosing the location of the polymer. The critical micelle concentration (cmc) of the surfactant, cmc = 17+/-1 mM, corresponds to an effective alkyl chain (CnH2n+1) length of n = 11. In the presence of gelatin, the cmc is substantially reduced as expected, cmc(1) = 4+/-1 mM, which is also consistent with an effective alkyl chain length of n = 11. In the presence of the fluorosurfactant, the monotonic decay of the SANS from the gelatin-only system is replaced by a substantial peak at an intermediate Q value mirroring the micellar interaction. At low ionic strengths, the gelatin/micelle complex can be described by an ellipsoid. At higher ionic strengths, the electrostatic interaction between the micelles is screened and the peak in the gelatin scattering disappears. The correlation length describing the network structure decreases with increasing SDS concentration as the bound micelles promote a collapse of the network.     

Diffusion Coefficients of Three Organic Solutes in Aqueous Sodium Dodecyl Sulfate Solutions

Tracer diffusion coefficients of phenol, toluene, and benzoic acid in aqueous solutions of sodium dodecyl sulfate (SDS) were measured by the Taylor dispersion technique. In addition, the viscosities and densities of the SDS solutions were measured. For phenol and toluene, the effect of micelle formation on the diffusion coefficient is pronounced. When the SDS concentration is below the critical micelle concentration (cmc), the diffusion coefficients are almost independent of the SDS concentration. However, above the cmc there is a rapid decrease in the diffusion coefficients, and the apparent diffusion coefficients of the two solutes are the weighted average of free solute diffusion and the micelle diffusion. A model is presented to describe the diffusion behavior of the two solutes in aqueous micellar solutions of SDS. The interaction between the two solutes and the micelles has been investigated and the fraction of each solute that is solubilized by the micelles is estimated from the measured apparent diffusion coefficient. For benzoic acid, the diffusion coefficient is dependent on the joint contribution of the benzoic acid molecules that are solubilized by the micelles as well as the corresponding benzoate ions. The effect of micelle formation on the diffusion coefficient of benzoic acid is not as pronounced as for phenol and toluene. Copyright 2000 Academic Press.