ABSTRACT
The complexation between hexadecyl- and dodecyltrimethylammonium bromides (CTAB and DTAB) with sodium poly[(vinyl alcohol)-co-(vinyl sulfate)] (PVAS) copolymer of low charge density has been investigated using pyrene fluorescence spectroscopy, electrophoretic mobility, turbidity, and dynamic light scattering measurements. The results indicate that the binding of the cationic surfactant occurs in three steps. At low surfactant concentrations, the cationic amphiphile binds to the vinyl sulfate groups. Above charge neutralization, surfactant binding may occur on the surface of the hydrophobic vinyl sulfate/CnTAB nanoassemblies. At even higher concentrations, the surfactant binds on the nonionic vinyl alcohol units of the polyion which reswells the PVAS/CnTAB complexes and makes them highly soluble in water. In earlier studies on oppositely charged ionic surfactants and homopolyelectrolytes the impact of mixing protocols was found remarkable, especially at surfactant excess, where these systems can be trapped in the charge stabilized colloidal dispersion state. In contrast, in the case of PVAS/CnTAB mixtures the effect of mixing is less pronounced and diminishes with increasing ionic strength or decreasing alkyl chain length of the surfactant. These findings are rationalized by taking into account the different binding mechanism of surfactants on oppositely charged homopolyelectrolytes and double hydrophilic copolymers.
ABSTRACT
The soluble complexes of oppositely charged macromolecules and amphiphiles, formed in the one-phase concentration range, are usually described on the basis of the beads on a string model assuming spherelike bound surfactant micelles. However, around and above the charge neutralization ionic surfactant to polyion ratio, a variety of ordered structures of the precipitates and large polyion/surfactant aggregates have been reported for the different systems which are difficult to connect to globular-like surfactant self-assembly units. In this article we have demonstrated through SAXS measurements that the structure of precipitates and those of the soluble polyion/mixed surfactant complexes of poly(diallyldimethylammonium chloride) (PDADMAC), sodium dodecyl sulfate (SDS), and dodecyl-maltoside (DDM) are strongly correlated. Specifically, SDS binds to the PDADMAC molecules in the form of small cylindrical surfactant micelles even at very low SDS-to-PDADMAC ratios. In this way, these anisometric surfactant self-assemblies formed in excess polyelectrolyte mimic the basic building units of the hexagonal structure of the PDADMAC/SDS precipitate and/or suspensions formed at charge equivalence or at higher SDS-to-PDADMAC ratios. The presence of DDM reduces the cmc and cac for the system but does not alter significantly the structure of the complexes in either the one-phase or two-phase region. The only exception is for samples at SDS-to-PDADMAC ratios close to charge neutralization and a high concentration of DDM where the precipitate forms a multiphasic or distorted hexagonal structure.
ABSTRACT
In the present paper, the impact of dodecyl maltoside (C12G2) on the association of sodium poly(styrenesulfonate) (PSS) with dodecyl- and hexadecyltrimethylammonium bromides (DTAB and CTAB) was studied. A low amount of nonionic surfactant enhances the binding of the investigated cationic amphiphiles on PSS, reducing the cationic surfactant-to-polyanion ratio needed for charge neutralization and precipitation. This effect is more pronounced for DTAB than for CTAB due to the considerably higher free surfactant concentration of the former cationic amphiphile. The synergistic surfactant binding also affects the nonequilibrium features of PSS/CTAB association via enhancing the kinetically stable concentration range of overcharged polyion/surfactant nanoparticle dispersions. With increasing C12G2 concentration, however, an opposite effect of the uncharged additive dominates. Namely, the CTAB molecules are solubilized excessively into mixed surfactant micelles, which reduces the surface charge of the PSS/CTAB/C12G2 nanoparticles and thus destabilizes their dispersion. At appropriately large nonionic surfactant concentrations, the binding of CTAB is largely reduced, resulting in the redissolution of the precipitate. In contrast, neither the destabilization nor the resolubilization effects of the added dodecyl maltoside were observed for the PSS/DTAB system due to the much lower driving force of DTAB binding compared to CTAB. Our results clearly demonstrate that the alkyl chain length of the ionic amphiphile has a pronounced effect on both the equilibrium and nonequilibrium aspects of polyion/mixed surfactant complexation which might be further exploited in various next generation applications.
Subject(s)
Bromides/chemistry , Glucosides/chemistry , Polystyrenes/chemistry , Surface-Active Agents/chemistry , Trimethyl Ammonium Compounds/chemistryABSTRACT
The various commercial applications of oppositely charged polyelectrolytes (P) and ionic surfactants (S) with added nonionic amphiphiles initiated intensive research on the polyion/mixed surfactant interaction. A large group of earlier studies revealed that one of the major effects of the nonionic cosurfactants is the suppression of the associative phase separation of P/S systems. In contrast, recent studies indicated that in the dilute surfactant concentration range the added uncharged amphiphile enhances the precipitation concentration range. In order to rationalize these observations, the mixtures of poly(diallyldimethylammonium chloride) (PDADMAC), sodium dodecyl sulfate (SDS), and dodecyl maltoside (C12G2) are investigated using a variety of experimental methods. It is shown that the nonionic cosurfactant has two distinct and competing impacts on the mixed surfactant binding onto the polyions. The composition dependent variation of the chemical potentials of the amphiphiles determines which of these effects is the dominant one, explaining the seemingly diverse earlier observations and their interpretations. We also demonstrate that the nonionic amphiphile affects considerably the nonequilibrium features of polyion/ionic surfactant complexation. Namely, the presence of the uncharged surfactant can destabilize the colloidal dispersion of P/S nanoparticles formed in the two-phase composition range. However, at the same concentration range highly stable dispersions of polyion/mixed surfactant nanoparticles can be produced through the application of a new two-step solution preparation technique. This method is based on the order of addition effect of the two surfactants which can be utilized in future scientific and industrial applications.
ABSTRACT
The effect of uncharged surfactant additives on the oppositely charged polyion/ionic surfactant complexation is usually described as a direct equilibrium association between the polyelectrolyte molecules and free mixed micelles analogous to the polyion/colloidal particle interactions. This approach predicts that the binding of the ionic surfactant to the polyelectrolyte molecules can be completely suppressed by increasing the nonionic-to-ionic surfactant ratio. In the present work, it is shown that the addition of nonionic surfactants to poly(diallyldimethylammonium chloride)/sodium dodecyl sulfate mixtures considerably enhances the binding of the anionic surfactant to the polycation in the dilute surfactant concentration regime. The dynamic light scattering, turbidity, electrophoretic mobility and fluorescence spectroscopic measurements are consistent with the synergic binding of the ionic and nonionic surfactants to the polyelectrolyte molecules. The enhanced surfactant binding could be utilized for the preparation of stable colloidal dispersions of novel polyion/mixed surfactant nanoparticles over a wide composition range provided that adequate mixing protocols are used. These results clearly indicate that the nonionic surfactant additives can be successfully used to tune the nonequilibrium association of oppositely charged macromolecules and amphiphiles.
ABSTRACT
In this article, the impact of different neutral polymers on the kinetic stability of charge-stabilized poly(diallyldimethylammonium chloride) (PDADMAC)/sodium dodecylsulfate (SDS) colloidal dispersions is analyzed using dynamic light scattering, electrophoretic mobility, turbidity, and coagulation kinetics measurements. Poly(ethyleneoxide) (PEO), poly(vinylpyrrolidone) (PVP), and dextran of comparable molecular masses as well as a higher-molecular-weight dextran sample were tested as nonionic additives. The light scattering and mobility data indicate that the PEO and PVP molecules may adsorb on the surface of the PDADMAC/SDS nanoparticles formed in the presence of excess surfactant. The primary effect of these additives is manifested in enhanced coagulation of the PDADMAC/SDS nanoparticles due to bridging at lower polymer concentrations and depletion flocculation at higher polymer concentrations. These findings are in sharp contrast to the earlier published effect of the same nonionic polymers on the poly(ethyleneimine) (PEI)/SDS colloidal dispersions, which can be sterically stabilized at appropriate PEO or PVP concentrations. However, the adsorption of the investigated dextran samples is negligible on the PDADMAC/SDS nanoparticles. Therefore, dextran molecules may cause only depletion flocculation in the PDADMAC/SDS system in the vicinity of the critical overlap concentration.
