pH sensitive adsorption of polypeptide/sodium dodecyl sulfate mixtures

Neutron reflectivity and surface tension have been used to investigate the pH sensitivity of the adsorption of poly-L-lysine hydrobromide and sodium dodecyl sulfate mixtures at the air-solution interface. The surface tension variation with surfactant concentration is complex, and between the critical aggregation concentration and critical micellar concentration there is a marked increase in the surface tension. The neutron reflectivity results show that this is associated with a depletion of the surface of polypeptide/surfactant complexes. The variations in the adsorption and surface tension with pH are attributed to changes in the polypeptide conformation at the interface and in solution.     

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.     

Thermodynamic and aggregation properties of sodium dodecyl sulfate in aqueous binary mixtures of isomeric butanediols

The effect of aqueous binary mixtures of isomeric butanediols on the micellization of sodium dodecyl sulfate has been investigated. Conductivity and fluorescence techniques were employed to determine the critical micellar concentration, the degree of dissociation of the counterions and the aggregation numbers of the surfactants in these binary blends. Differential conductivity plots were employed to distinguish between the cooperative and the stepwise aggregation process of the surfactant in each solvent system. The mass-action model was employed to calculate the hydrophobic and the electrostatic contributions to the Gibbs energy of micellization as well as the monomer and the counterion concentrations in the postmicellar region. The thermodynamic parameters calculated for each system indicate that the micellization process occurs more readily in the presence of cosolvent owing to the formation of mixed micelles. Received: 5 July 2000 Accepted: 25 July 2000     

Micelles in mixtures of sodium dodecyl sulfate and a bolaform surfactant

Mixtures composed of water, sodium dodecyl sulfate (SDS), and a bolaform surfactant with two aza-crown ethers as polar headgroups (termed Bola C-16) were investigated by modulating the mole ratios between the components. The two surfactants have ionic and nonionic, but ionizable, headgroups, respectively. The ionization is due to the complexation of alkali ions by the aza-crown ether unit(s). Structural, thermodynamic, and transport properties of the above mixtures were investigated. Results from surface tension, translational self-diffusion, and small angle neutron scattering (SANS) are reported and discussed. Interactions between the two surfactants to form mixed micelles result in a combination of electrostatic and hydrophobic contributions. These effects are reflected in the size and shape of the aggregates as well as in transport properties. The translational diffusion of the components in mixed micelles, in particular, depends on the Bola C-16/SDS mole ratio. Nonideality of mixing of the two components was inferred from the dependence of the critical micelle concentration, cmc, on the mole fraction of Bola C-16. This behavior is also reflected in surface adsorption and in the area per polar headgroup at the air-water interface. SANS data analysis for the pure components gives results in good agreement with previous findings. An analysis of data relative to mixed systems allows us to compute some structural parameters of the mixed aggregates. The dependence of aggregation numbers, nu(T), on the Bola C-16/SDS mole ratio displays a maximum that depends on the overall surfactant content and is rationalized in terms of the nonideality of mixing. Aggregates grow perpendicularly to the major rotation axis, as formerly observed in the Bola C-16 system, and become progressively ellipsoidal in shape.     

New thermodynamic/electrostatic models of adsorption and tension equilibria of aqueous ionic surfactant mixtures: application to sodium dodecyl sulfate/sodium dodecyl sulfonate systems

The nonideal adsorbed solution (NAS) theory has been formally extended to adsorption at the air/water interface from aqueous mixtures of ionic surfactants, explicitly accounting for the surface potential of the adsorbed monolayer with the Gouy-Chapman theory. This new ionic NAS (iNAS) theory is thermodynamically consistent and, when coupled to a micellization model, is valid for concentrations below and above the mixed cmc. Counterion binding is incorporated into the model using two fractional binding parameters, beta(sigma) for the adsorbed monolayer and beta(m) for the micelles. The regular solution theory is used to model the nonideal interactions within the adsorbed monolayer and within the mixed micelles. New tension data for an equimolar mixture of sodium dodecyl sulfate (SDS) and sodium dodecyl sulfonate (SDSn) at two salinities fit this model well when mixing is ideal. The total surface densities, the surface compositions, and the surface potentials for the mixed monolayers are calculated. When there is no added salt, at total surfactant concentrations below the mixed cmc, the adsorbed monolayer is enriched in SDSn, but at total concentrations at and above the mixed cmc, the adsorbed monolayer is nearly an equimolar mixture. In the presence of 100 mM NaCl, the adsorbed monolayer is nearly an equimolar mixture, independent of the total surfactant concentration.     

Adsorption, association and precipitation in hexadecyltrimethylammonium bromide/sodium dodecyl sulfate mixtures

The phase equilibria of surfactant aqueous mixtures, hexadecyltrimethylammonium bromide and sodium dodecyl sulfate, have been studied by polarizing microscopy, quasielastic light scattering, conductivity, potentiometric, electrophoretic, and surface tension measurements. Adsorption at the air/solution interface, association and precipitation in bulk solution strongly depended on the molar ratio and the concentration of surfactants. Catanionic vesicles coexisted with crystalline catanionic salts in a broad concentration range. The relative proportions of crystallites and vesicles varied according to the concentration and the molar ratio of the surfactants. The solid crystalline phase was progressively converted to catanionic vesicles with increasing surfactant molar ratio. At the highest excess of one of the surfactants transition from catanionic vesicles to mixed micelles occurred. The formation and stability of different phases are discussed in terms of surfactant molecular packing constraints and electrostatic interactions in the headgroup region. Surfactant tail-length asymmetry and the change of electrostatic interactions in the headgroup region from attractive to repulsive are governing factors for the transition from planar to curved bilayers. Received: 9 June 1998 Accepted: 18 August 1998     

Adsorption pattern of mixtures of trimethylammonium-modified hydroxyethylcellulose and sodium dodecyl sulfate at solid-liquid interfaces

We studied mixtures of aqueous solutions of cationic hydroxyethylcellulose JR400 polymer and anionic sodium dodecyl sulfate using dynamic light scattering and atomic force microscopy (AFM). A ternary phase diagram was established showing three interesting realms of the polymer-surfactant-water mixture: a preprecipitation area of lowered viscosity (polymer excess) compared to the pure polymer solution, a postprecipitation area (resolubilization at surfactant excess), and highly diluted samples with a stoichiometrical surfactant-polymer ratio close to that of maximum precipitation. Samples with various compositions representing these areas were imaged by atomic force microscopy on mica and on hydrophobically modified silica in contact mode. A correlation between light scattering data concerning particle size and, more important, structuring in the bulk on one hand and AFM images on the other hand was observed. It was revealed that the influence of surface properties is of less importance for adsorption, compared to the influence of the mixture in the bulk, provided that the mixture is prepared prior to adsorption.     

The wettability of polytetrafluoroethylene by aqueous solutions of sodium dodecyl sulfate and propanol mixtures

Advancing contact-angle (theta) measurements were carried out with aqueous solutions of propanol and four series of aqueous solutions of dodecyl sulfate (SDDS) and propanol mixtures at constant dodecyl sulfate concentrations equal to 1 x 10(-5), 6 x 10(-4), 1 x 10(-3), and 1 x 10(-2)M, respectively. The obtained results indicate that in the range of propanol concentrations studied there were considerable contact-angle changes, with exception of the solution series at a constant concentration value of SDDS higher than its critical micelle concentration. From the results of contact-angle measurements and application of the Gibbs and Young equations the ratio of the excess concentration of surfactant and propanol at the solid-aqueous solution interface to the excess of their concentration at the aqueous solution-air interface was calculated. From the calculations it appears that there is a straight linear dependence between the adhesion tension and surface tension of aqueous solutions of SDDS and propanol mixtures, and the slope of the line is equal to -1, which suggests that the surface excess of the SDDS and propanol mixture at the polytetrafluoroethylene-solution interface is the same as the at the solution-air interface. The extrapolation of the straight line to the point corresponding to the surface tension of the aqueous solution, which completely spreads over the polytetrafluoroethylene surface, gives a critical surface tension of wetting equal to 23.7 mN/m. On the basis of the critical surface tension and the Young and modified Szyszkowski equations it was found that in a polytetrafluoroethylene-aqueous solution of the SDDS and propanol mixture, the interface tension can be predicted by the modified Szyszkowski equation.     

Micellization of sodium dodecyl sulfate and polyoxyethylene dodecyl ethers in solution

The effect of polyoxyethylene type nonionic surfactants (C₁₂E _n n = 3, 4, 5, 6, 7 and 8) on the aqueous solution of sodium dodecyl sulfate (SDS) in absence and presence of NaCl was examined using small-angle neutron scattering (SANS), dynamic light scattering (DLS), and viscosity measurements. Upon addition of C₁₂E _n , micellar size of SDS was found to increase significantly, and such micellar elongation was further enhanced in the presence of NaCl. Micellar growth is most significant in presence of shorter moieties of C₁₂E _n (e.g., n = 3, 4) as compared to higher ethereal oxygen content. The results of structural investigations with SANS and DLS to confirm this assumption are reported. The cloud point of C₁₂E _n has increased upon addition of SDS and decrease with NaCl, and a typical behavior is observed when both SDS and NaCl were present.     

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.     

Temperature-induced intermicellization and contraction in aqueous mixtures of sodium dodecyl sulfate and an amphiphilic diblock copolymer

Aqueous solutions of a thermoresponsive amphiphilic diblock copolymer, containing poly(N-isopropylacrylamide), in the presence of the anionic sodium dodecyl sulfate (SDS) surfactant can undergo a temperature-induced transition from loose intermicellar clusters to collapsed core–shell nanostructures. The polymer–surfactant mixtures have been characterized with the aid of turbidity, small-angle neutron scattering (SANS), intensity light scattering (ILS), dynamic light scattering (DLS), shear viscosity, and rheo-small angle light scattering (rheo-SALS). In the absence of SDS, compressed intermicellar structures are formed at intermediate temperatures, and at higher temperatures further aggregation is detected. The SANS results disclose a structure peak in the scattered intensity profile at the highest measured temperature. This peak is ascribed to the formation of ordered structures (crystallites). In the presence of a low amount of SDS, a strong collapse of the intermicellar clusters is observed at moderate temperatures, and only a slight renewed interpolymer association is found at higher temperatures because of repulsive electrostatic interactions. Finally, at moderate surfactant concentrations, temperature-induced loose intermicellar clusters are detected but no shrinking was registered in the considered temperature range. At a high level of SDS addition, large polymer–surfactant complexes appear at low temperatures, and these species are compressed at elevated temperatures. The rheo-SALS results show that the transition structures are rather fragile under the influence of shear flow.     

Self aggregation of binary mixtures of sodium dodecyl sulfate and polyoxyethylene alkyl ethers in aqueous solution

The mixed micelles of sodium dodecyl sulphate (SDS) with Brij35 and Brij 97 were studied separately by fluorescence measurement using pyrene as fluorescent probe. In the range of 0–1.0 mole fraction (X) of added SDS to Brij solutions, the cmc value of the mixed micelles varies from 0.085 to 8 mmol with Brij 35 and 0.04 to 8 mmol with Brij 97. The aggregation number also changes. A measure of the stability of mixed micelles is also presented. The interaction parameter ₁₂ and the chain–chain contribution parameter (B₁) are extracted from the analysis of the results. This parameter B₁ is related to the standard free energy change associated with the introduction of one ionic species into a nonionic micelle coupled with the release of one nonionic species from the micelle. The clouding behaviour of Brij 97 in the presence of SDS was investigated and the associated thermodynamic parameters of clouding were generated and discussed.     

Thermotropic phase behavior of cationic gemini surfactants and their equicharge mixtures with sodium dodecyl sulfate

The lyotropic phase behavior for the neat cationic gemini surfactants alkanediyl-alpha,omega-bis(alkyldimethylammonium bromide), designated here as m-s-m, has been investigated previously in several works, but the thermotropic behavior has not been well characterized. Only for 15-s-15 and 14-s-12 have thermotropic liquid crystals (Lc) been reported. In this work, for the first time and in contrast to previous reports, we observe thermotropic Lc formation for m-2-m geminis with m = 12, 14, 16, and 18, by means of polarizing microscopy and differential scanning calorimetry (DSC). Furthermore, we investigate mixtures of m-2-m and SDS, m-2-m Br2.2SDS, which exhibit crystal-to-crystal phase transitions at lower temperature and, at high temperature, smectic Lc phases. The transition temperatures and enthalpies for Lc phases, obtained by DSC, present clear trends upon increase of the chain lengths. Combining Langmuir film experiments, possible lamellar arrangements for the different phases are tentatively discussed.     

Interaction between polyacrylamide and sodium dodecyl sulfate

Summary Some preliminar results about the interaction between -SDS and polyacrylamide reveal that without added salts, the two compounds mixt by keeping their own properties while, in salt presence, there is probably complex formation.

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Resumé Quelques résultats préliminaires de l'étude des interactions entre SDS et polyacrylamide montrent un comportement diffèrent en presence et en absence de sels; dans ce dernier cas seulement on peut s'attendre à la formation de complexes.

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With 3 figures     

Interaction between casein and sodium dodecyl sulfate

The interaction of the anionic surfactant sodium dodecyl sulfate (SDS) with 2.0 mg/ml casein was first investigated using isothermal titration calorimetry (ITC), dynamic light scattering (DLS), and fluorescence spectra. ITC results show that individual SDS molecules first bind to casein micelles by the hydrophobic interaction. The micelle-like SDS aggregate is formed on the casein chains when SDS concentration reaches the critical aggregation concentration (c1), which is far below the critical micellar concentration (cmc) of SDS in the absence of casein. With the further increase of SDS concentration to the saturate binding concentration c2, SDS molecules no longer bind to the casein chains, and free SDS micelles coexist with casein micelles bound with SDS aggregates in the system. DLS results show that the addition of SDS leads to an increase in the hydrodynamic radius of casein micelles with bound surfactant at SDS concentration higher than 4 mM, and also an increase in the casein monomer molecule (or submicelles) at SDS concentration higher than 10 mM. Fluorometric results suggest the addition of SDS leads to some changes in the binding process of hydrophobic probes to casein micelles.     

Physicochemical properties of quaternized poly(amidoamine) dendrimers with alkyl groups and of their mixtures with sodium dodecyl sulfate

The physicochemical properties of quaternized poly(amidoamine) dendrimers (generation 4) with methyl or octyl groups and of their mixtures with sodium dodecyl sulfate (SDS) in aqueous solutions have been investigated using several techniques including surface tension, fluorescence of pyrene, and dynamic light scattering. In the single systems of the dendrimers, the dendrimer with octyl groups shows lower surface tension and lower micropolarity than the dendrimer with methyl groups. The hydrodynamic radii of two quaternized poly(amidoamine) dendrimers are considerably large, indicating the formation of aggregates. In the mixed systems of quaternized poly(amidoamine) dendrimers and SDS, the dendrimer with octyl groups-SDS mixed system shows very low surface tension and low micropolarity even in the presence of extremely low SDS concentration compared to those of the dendrimer with methyl groups-SDS mixed system. Maximum turbidity for both systems is observed at around the mixed molar ratio of dendrimer:SDS=1:1.5 where distinct changes have also been confirmed by surface tension, fluorescence of pyrene, and electrical conductivity measurements.     

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.     

Competitive adsorption of sodium dodecyl sulfate and polyethylene oxide at the air/water interface

Geoinspired synthetic chrysotile, which represents an ideal asbestos reference standard, has been utilized to investigate homomolecular exchange of bovine serum albumin (BSA), the major plasma protein, between the adsorbed and dissolved state at the interface between asbestos fibers and biological medium. FTIR spectroscopy has been used to quantify BSA structural modifications due to surface adhesion on chrysotile fibers as a function of the surface coating extent. Circular dichroism spectroscopy has been used to investigate the adsorption/desorption equilibrium through analysis of the BSA structural perturbations after protein desorption from chrysotile surface. Data results show clearly that in the solid state BSA modifications are driven by surface interaction with the substrate, following a bimodal adsorption evidenced by two different binding constants. On the other hand, BSA desorbed in solution is able to rearrange, in the lack of substrate, although keeping irreversible modifications with respect to the native species. The lack of regaining its native structure certainly affects albumin interaction with biological environment. The present investigation on the stoichiometric synthetic geoinspired chrysotile nanocrystals is the first approach toward a deeper attempt to use standard synthetic chrysotile reference samples in mimicking the behavior of asbestos fibers and allows to better understand their interaction with a biological environment.     

Adsorption at the air/water interface in dodecylammonium chloride/sodium dodecyl sulfate mixtures

The composition and properties of the adsorption films of dodecylammonium chloride/sodium dodecyl sulfate at the air/water interface depend on interactions between the film molecules and equilibria in the bulk phase (monomer-micelle and/or monomerprecipitate equilibria).The negative value of surface molecular interaction parameter ^mon calculated using the regular solution theory indicates strong attractive interactions between adsorbed molecules. Electrostatic interactions between oppositely charged ionic head groups enhance the adsorption of surfactants and decrease the minimum molar area of surfactant molecules at the air/water interface. The addition of an oppositely charged surfactant enhances packing at the air/water interface and transition from a liquid expanded to a liquid condensed state. Surface potential measurements reveal positive values for the mixtures investigated, implying the cationic surfactant ions are closer to the surface than the anionic ones.