Polymer-surfactant interactions: binding mechanism of sodium dodecyl sulfate to poly(diallyldimethylammonium chloride)

The binding mechanism of poly(diallyldimethylammonium chloride), PDAC, and sodium dodecyl sulfate, SDS, has been comprehensively studied by combining binding isotherms data with microcalorimetry, zeta potential, and conductivity measurements, as well as ab initio quantum mechanical calculations. The obtained results demonstrate that surfactant-polymer interaction is governed by both electrostatic and hydrophobic interactions, and is cooperative in the presence of salt. This binding results in the formation of nanoparticles, which are positively or negatively charged depending on the molar ratio of surfactant to PDAC monomeric units. From microcalorimetry data it was concluded that the exothermic character of the interaction diminishes with the increase in the surfactant/polymer ratio as well as with an increase in electrolyte concentration.     

Molecular dynamics simulation of interactions between a sodium dodecyl sulfate micelle and a poly(ethylene oxide) polymer

We have performed atomistic molecular dynamics simulations of an anionic sodium dodecyl sulfate (SDS) micelle and a nonionic poly(ethylene oxide) (PEO) polymer in aqueous solution. The micelle consisted of 60 surfactant molecules, and the polymer chain lengths varied from 20 to 40 monomers. The force field parameters for PEO were adjusted by using 1,2-dimethoxymethane (DME) as a model compound and matching its hydration enthalpy and conformational behavior to experiment. Excellent agreement with previous experimental and simulation work was obtained through these modifications. The simulated scaling behavior of the PEO radius of gyration was also in close agreement with experimental results. The SDS-PEO simulations show that the polymer resides on the micelle surface and at the hydrocarbon-water interface, leading to a selective reduction in the hydrophobic contribution to the solvent-accessible surface area of the micelle. The association is mainly driven by hydrophobic interactions between the polymer and surfactant tails, while the interaction between the polymer and sulfate headgroups on the micelle surface is weak. The 40-monomer chain is mostly wrapped around the micelle, and nearly 90% of the monomers are adsorbed at low PEO concentration. Simulations were also performed with multiple 20-monomer chains, and gradual addition of polymer indicates that about 120 monomers are required to saturate the micelle surface. The stoichiometry of the resulting complex is in close agreement with experimental results, and the commonly accepted "beaded necklace" structure of the SDS-PEO complex is recovered by our simulations.     

Molecular dynamics simulations of mixed cationic/anionic wormlike micelles

Simulations of mixed cationic/anionic wormlike micellar systems have been carried out for a wide range of compositions, including pure anionic and cationic systems. It was found that the wormlike micelle formed by only cationic surfactant molecules is unstable and transforms to a set of small spherical micelles. Adding anionic surfactants with a short hydrophobic chain (only eight carbon atoms) results in stable wormlike micelles. The 34/66 cationic/anionic worm is stable and symmetrical, while the 50/50 mixture yields a flattened worm, indicating a phase transition to the lamellar phase. All these observations are in excellent agreement with the experimental results of Raghavan et al. (Langmuir 2002, 18, 3797), and they provide a molecular mechanism for their observations. The addition of octyltrimethylammonium chloride increases the radius of the worm due to the bigger hydrophobic part. Meanwhile, the length of the worms decreases with the concentration of cationic surfactant and reaches a minimum for the 50/50 mixture. The latter system is of special interest due to a zero surface charge density. The worm with the electrostatically neutral surface was used to investigate intermicellar interactions. The molecular dynamics (MD) simulations show that the merging process requires a substantial activation energy even in the case of reduced electrostatic repulsion.     

Colloid stability of sodium dihexadecyl phosphate/poly(diallyldimethylammonium chloride) decorated latex

The colloid stability of supramolecular assemblies composed of the synthetic anionic lipid sodium dihexadecyl phosphate (DHP) on cationic poly(diallyldimethylammonium chloride) (PDDA) supported on polystyrene sulfate (PSS) microspheres was evaluated via turbidimetry kinetics, dynamic light scattering for particle sizing, zeta-potential analysis, and determination of DHP adsorption on PDDA-covered particles. At 0.05 g/L PDDA and 5 x 10(9) PSS particles/mL, PDDA did not induce significant particle flocculation and a vast majority of PDDA covered single particles were present in the dispersion so that this was the condition chosen for determining DHP concentration (C) effects on particle size and zeta-potentials. At 0.8 mM DHP, charge neutralization, maximal size, and visible precipitation indicated extensive flocculation and minimal colloid stability for the DHP/PDDA/PSS assembly. At 0.05 g L(-1) PDDA, isotherms of high affinity for DHP adsorption on PDDA-covered particles presented a plateau at a limiting adsorption of 135 x 10(19) DHP molecules adsorbed per square meter PSS which was well above bilayer deposition on a smooth particle surface. The polyelectrolyte layer on hydrophobic particles was swelled and fluffy yielding ca. 6 +/- 1.5 nm hydrodynamic thickness. Maximal and massive adsorption of DHP lipid onto this layer produced polydisperse DHP/PDDA/PSS colloidal particles with low colloid stability and which, at best, remained aggregated as doublets over a range of large lipid concentrations so that it was not possible to evaluate the mean total thickness for the deposited film. The assembly anionic lipid/cationic PDDA layer/polymeric particle was relatively stable as particle doublets only well above charge neutralization of the polyelectrolyte by the anionic lipid, at relatively large lipid concentrations (above 1 mM DHP) with charge neutralization leading to extensive particle aggregation.     

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.     

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     

Study of sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles

Sodium dodecyl sulfate (SDS)-poly(propylene oxide) methacrylate (PPOMA) (of molecular weight M(w) = 434 g x mol(-1)) mixtures have been studied using conductimetry, static light scattering, fluorescence spectroscopy, and 1H NMR. It has been shown that SDS and PPOMA form mixed micelles, and SDS and PPOMA aggregation numbers, N(ag SDS) and N(ag PPOMA), have been determined. Total aggregation numbers of the micelles (N(ag SDS) + N(ag PPOMA)) and those of SDS decrease upon increasing the weight ratio R = PPOMA/SDS. Localization of PPOMA inside the mixed micelles is considered (i) using 1H NMR to localize the methacrylate function at the hydrophobic core-water interface and (ii) by studying the SDS-PPO micellar system (whose M(w) = 400 g x mol(-1)). Both methods have indicated that the PPO chain of the macromonomer is localized at the SDS micelle surface. Models based on the theorical prediction of the critical micellar concentration of mixed micelles and structural model of swollen micelles are used to confirm the particular structure proposed for the SDS-PPOMA system, i.e., the micelle hydrophobic core is primarily composed of the C12 chains of the sodium dodecyl sulfate, the hydrophobic core-water interface is made up of the SDS polar heads as well as methacrylate functions of the PPOMA, the PPO chains of the macromonomer are adsorbed preferentially on the surface, i.e., on the polar heads of the SDS.     

Association between branched poly(ethyleneimine) and sodium dodecyl sulfate in the presence of neutral polymers

In the present paper, the effect of different neutral polymers on the self-assemblies of hyperbranched poly(ethyleneimine) (PEI) and sodium dodecyl sulfate (SDS) has been investigated at different ionization degrees of the polyelectrolyte molecules. The investigated uncharged polymers were poly(ethyleneoxide), poly(vinylpyrrolidone) and dextran samples of different molecular mass. Dynamic light scattering and electrophoretic mobility measurements demonstrate that the high molecular mass PEO or PVP molecules adsorb considerably onto the surface of the PEI/SDS nanoparticles. At appropriate concentrations of PVP or PEO, sterically stabilized colloidal dispersions of the polyelectrolyte/surfactant nanoparticles with hydrophobic core and hydrophilic corona can be prepared. These dispersions have considerable kinetic stability at high ionic strengths where the accelerated coagulation of the PEI/SDS nanoparticles results in precipitation in the absence of the neutral polymers. In contrast, the addition of dextran does not affect considerably the kinetic stability of PEI/SDS mixtures because of its low adsorption affinity towards the surface of the polyelectrolyte/surfactant nanoparticles.     

Physicochemistry of interaction between the cationic polymer poly(diallyldimethylammonium chloride) and the anionic surfactants sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium N-dodecanoylsarcosinate in water and isopropyl alcohol-water media

The physicochemistry of interaction of the cationic polymer poly(diallyldimethylammonium chloride) (PDADMAC) with the anionic surfactants sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium N-dodecanoylsarcosinate was studied in detail using tensiometry, turbidimetry, calorimetry, viscometry, dynamic light scattering (DLS), and scanning electron microscopy (SEM). Fair interaction initially formed induced small micelles of the surfactants and later on produced free normal micelles in solution. The interaction process yielded coacervates that initially grew by aggregation in the aqueous medium and disintegrated into smaller species at higher surfactant concentration. The phenomena observed were affected by the presence of isopropyl alcohol (IP) in the medium. The hydrodynamic sizes of the dispersed polymer and its surfactant-interacted species were determined by DLS measurements. The surface morphologies of the solvent-removed PDADMAC and its surfactant-interacted complexes from water and IP-water media were examined by the SEM technique. The morphologies witnessed different patterns depending on the composition and the solvent environment. The head groups of the dodecyl chain containing surfactants made differences in the interaction process.     

Interaction of slightly cross-linked gels of poly(diallyldimethylammonium bromide) with sodium dodecyl sulfate. Diffusion of surfactant ions in gel

The dynamics of the changing microenvironment of the fluorescent probe pyrene in slightly cross-linked networks of poly(diallyldimethylmmonium bromide) during diffusion of sodium dodecyl sulfate (SDS) in the gel phase has been investigated by fluorescence spectroscopy. Values of the spectral ratio I₃/I₁ for pyrene monomer included in SDS micelles in the swollen networks fall between the corresponding values for pyrene in water and for pyrene dissolved in SDS micelles in aqueous solution. In the narrow interval of the surfactant concentrations in the gel phase, the formation of pyrene excimers is observed. The values of the critical micelle concentration in the gel phase (ca. 5 × 10^?4 to 8 × 10^?4 mol/L) are tenfold lower than in aqueous solutions of the surfactant. The effective micellar diffusion coeffecient D in the gel phase increases with increasing swelling of the network. © 1993 John Wiley & Sons, Inc.     

Separation and selectivity of benzophenones in micellar electrokinetic chromatography using sodium dodecyl sulfate micelles or sodium cholate modified mixed micelles

The separation and selectivity of nine benzophenones in micellar electrokinetic chromatography (MEKC) using sodium dodecyl sulfate (SDS) micelles or sodium cholate (SC) modified mixed micelles were investigated in the pH range 6.5-8.0. The results indicate that the combined effects of buffer pH and SC concentration can greatly affect the separation and selectivity of benzophenones, particularly for benzophenones possessing a hydroxyl substituent at the 4-position of the aromatic ring with respect to the carbonyl moiety when using SDS-SC mixed micelles. Better separability can be obtained with SDS-SC mixed micelles than with SDS micelles. Complete separation of nine benzophenones in MEKC can be achieved with an appropriate choice of buffer pH and the concentration of SDS micelles or SC modified mixed micelles. The dependence of the migration order of those benzophenones based on their structures and solute-micelle interactions is discussed.     

Influence of aquo-organic solvent media on the self-aggregation of sodium dodecyl sulfate (SDS) and its interaction with polyvinylpyrrolidone (PVP)

Influence of mixed aquo-organic solvents viz. water-dimethyl sulfoxide (DMSO), water-formamide (FA), water-dioxane (DX), and water-ethylene glycol (EG) on the micellization of sodium dodecylsulfate (SDS) alone and in presence of neutral polymer polyvinyl pyrrolidone (PVP) was studied. Interaction with PVP initially witnessed formation of critical aggregation concentration (CAC) in the favor of formation of induced small micelles of SDS at a concentration lower than the normal critical micelle concentration (CMC), and later found the formation of normal micelles with extended critical micelle concentrations (CMC_e) in solution. The SDS-PVP interaction depended on the nature and composition of the mixed solvents. Besides CAC and CMC_e, the maximum Gibbs surface excess at the interface (Γ _max), the minimum area (A _min) of the dissociated amphiphile anion, and enthalpy of micellization (ΔH _m ⁰ ) were also determined. Configurational state of PVP in aquo-organic media was investigated by the methods of viscometry, dynamic light scattering (DLS), and scanning electron microscope (SEM) methods. The [η] and Huggins constant (k _H) were considered to ascertain the overall configuration of PVP in solution. The complexes were formed and aggregated at different stages of their molecular composition. The aggregate sizes were determined by DLS, and the surface morphologies in the solvent removed states were examined by SEM. With reference to bulk and interfacial phenomena, polymer-surfactant interaction is thus considered to be important, and the detailed study herein under taken for SDS-PVP combination and PVP alone in mixed aquo-organic solvent media is a new sort of attempt. Figure

DX and DMSO influenced [η] of PVP, SDS interacted PVP enthalpogram and the SEM image of the PVP in 10 wt% DX     

Molecular dynamics simulations of aggregation behavior of sodium dodecyl sulfate on SiO2 and CaCO3 surfaces

Molecular dynamics simulations were carried out to investigate the aggregation behavior of anionic surfactant sodium dodecyl sulfate (SDS) on the surfaces of SiO₂ and CaCO₃. The results indicate that SDS molecules formed a spherical micelle structure near the SiO₂ surface; moreover, there were more head groups near the SiO₂ surface. However, they could form a self‐assemble film on the CaCO₃ surface. The self‐assemble film of SDS on the CaCO₃ surface was more stable than that on the SiO₂ surface. Our simulation results have a certain significance to understand the aggregation behavior of SDS on different surfaces on molecular level.     

Molecular dynamics simulations of a poly(p-phenylene) oligomer

We have studied the conformation and coefficient of thermal expansion in the poly(p-phenylene) oligomer p-sexiphenyl (C₃₆H₂₆) by molecular dynamics simulations. Studies of the backbone phenyl–phenyl torsion angle in a simulated p-sexiphenyl crystal at room temperature indicate the presence of torsional librations of approximately ±20°. Further analysis of the phenyl–phenyl backbone torsion angle in less closely packed regions of the simulated crystal (crystal ends) indicate the presence of 180° phenyl ring flips, in agreement with solid-state deuterium NMR data on poly(p-phenylene oligomers). The linear coefficient of thermal expansion was also calculated and found to be negative, in qualitative agreement with experimental data on rigid-rod compounds. © 1993 John Wiley & Sons, Inc.     

Time effects on the rheological behavior of hydrophobically modified polyacrylamide aqueous solutions mixed with sodium dodecyl sulfate (SDS)

The transient response of hydrophobically modified polyacrylamides (HMPAM) aqueous solutions with sodium dodecyl sulfate (SDS) during step shear rate experiments was evaluated. The experimental protocol involved employing first a low shear rate for a specific time, followed by an abrupt increase in shear rate (applied for the same time) and then finally reducing the shear rate to the initial value and recording the sample relaxation with time. While the second step was characterized by a general anti-thixotropic behavior, a large viscosity peak was observed at the third step at very short times followed by a thixotropic relaxation of the viscosity value. This peak was interpreted as a consequence of the formation of a transient network during the relaxation process. A kinetic model was used to better understand and to describe the thixotropy of HMPAM solutions in the presence of SDS. The kinetic constants obtained from the model decrease in value when the shear rate applied during the second step increases, reflecting the increase in recovery time needed for the system to relax back to a lower strain rate. As expected, as the degree of hydrophobic association increases or the degree of fluid structuring increases, the kinetic constant values strongly decrease.     

Molecular dynamics study of solubilization of cyclohexane,benzene, and phenol into mixed micelles composed of sodium dodecyl sulfate and octaethylene glycol monododecyl ether

Molecular dynamics calculations of a mixed micelle composed of sodium dodecyl sulfate (SDS) and octaethylene glycol monododecyl ether (C₁₂E₈) were performed for six compositions (SDS/C₁₂E₈ = 100/0, 80/20, 60/40, 40/60, 20/80, and 0/100) to investigate the composition dependence of the mixed micelle structure and solubilization of cyclohexane, benzene, and phenol molecules by the micelle. The radial density distribution of the hydrophilic polyoxyethylene (POE) group of C₁₂E₈ as a function of distance from the micelle center is very sharp for micelles with high SDS content because the POE group captures a Na⁺ ion in solution and wraps around it to form a compact crown-ether-like complex. The hydrophobic dodecyl groups of SDS and C₁₂E₈ were separately distributed in the mixed micelle core. ΔG(r) evaluated for each solute showed that despite the structural changes of the micelle the binding strength of the solute molecules to the micelle did not change significantly. © 2019 Wiley Periodicals, Inc.     

Crystallization and aggregation behaviors of calcium carbonate in the presence of poly(vinylpyrrolidone) and sodium dodecyl sulfate

An anionic surfactant interacts strongly with a polymer molecule to form a self-assembled structure, due to the attractive force of the hydrophobic association and electrostatic repulsion. In this crystallization medium, the surfactant-stabilized inorganic particles adsorbed on the polymer chains, as well as the bridging effect of polymer molecules, controlled the aggregation behavior of colloidal particles. In this presentation, the spontaneous precipitation of calcium carbonate (CaCO3) was conducted from the aqueous systems containing a water-soluble polymer (poly(vinylpyrrolidone), PVP) and an anionic surfactant (sodium dodecyl sulfate, SDS). When the SDS concentrations were lower than the onset of interaction between PVP and SDS, the precipitated CaCO3 crystals were typically hexahedron-shaped calcite; the increasing SDS concentration caused the morphologies of CaCO3 aggregates to change from the flower-shaped calcite to hollow spherical calcite, then to solid spherical vaterite. These results indicate that the self-organized configurations of the polymer/surfactant supramolecules dominate the morphologies of CaCO3 aggregates, implying that this simple and versatile method expands the morphological investigation of the mineralization process.     

Molecular dynamics simulations of a poly(ethylene oxide) surface

Potentials developed earlier for crystalline and amorphous bulk PEO systems have been used for the MD simulation of a PEO surface model. The surface comprises the outer region of a 122 Å-thick sheet of PEO in which the PEO, -(CH₂-CH₂-O)_n- chains run obliquely across the cell, and are terminated by C₂H₅ ethyl groups. The atoms on one side of the sheet are tethered to facilitate a satisfactory Ewald summation. The sheet expands from its ‘crystalline’ width of 122 Å to 128 Å in the simulated model. Simulations were performed at three temperatures: 300 K, 400 K and 500 K. Different behaviour in the surface layer was found compared to that in the bulk. The structural and dynamical properties of the surface were analyzed at each temperature.