Electrostatic self-assembly of neutral and polyelectrolyte block copolymers and oppositely charged surfactant

We investigated the phase behavior and the microscopic structure of the colloidal complexes constituted from neutral/polyelectrolyte diblock copolymers and oppositely charged surfactant by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The neutral block is poly(N-isopropylacrylamide) (PNIPAM), and the polyelectrolyte block is negatively charged poly(acrylic acid) (PAA). In aqueous solution with neutral pH, PAA behaves as a weak polyelectrolyte, whereas PNIPAM is neutral and in good-solvent condition at ambient temperature, but in poor-solvent condition above approximately 32 degrees C. This block copolymer, PNIPAM-b-PAA with a narrow polydispersity, is studied in aqueous solution with an anionic surfactant, dodecyltrimethylammonium bromide (DTAB). For a low surfactant-to-polymer charge ratio Z lower than the critical value ZC, the colloidal complexes are single DTAB micelles dressed by a few PNIPAM-b-PAA. Above ZC, the colloidal complexes form a core-shell microstructure. The core of the complex consists of densely packed DTA+ micelles, most likely connected between them by PAA blocks. The intermicellar distance of the DTA+ micelles is approximately 39 A, which is independent of the charge ratio Z as well as the temperature. The corona of the complex is constituted from the thermosensitive PNIPAM. At lower temperature the macroscopic phase separation is hindered by the swollen PNIPAM chains. Above the critical temperature TC, the PNIPAM corona collapses leading to hydrophobic aggregates of the colloidal complexes.     

Salt effect on the complex formation between polyelectrolyte and oppositely charged surfactant in aqueous solution

The complex formation between sodium carboxymethylcellulose (NaCMC) and dodecyltrimethylammonium bromide (DTAB) at various sodium bromide concentrations (C(NaBr)) has been studied by microcalorimetry, turbidimetric titration, steady-state fluorescence measurements, and the fluorescence polarization technique. The addition of salt is found to influence the formation of NaCMC/DTAB complexes markedly. At C(NaBr) = 0.00, 0.01, 0.02, 0.10, and 0.20 M, DTAB monomers form micelle-like aggregates on NaCMC chains to form NaCMC/DTAB complexes above the critical surfactant concentration (C1). At C(NaBr) = 0.23 M, DTAB molecules first form micelles above a 2.46 mM DTAB concentration prompted by the added salt, and then, above C1 = 4.40 mM, these micelles can aggregate with NaCMC chains to form NaCMC/DTAB complexes. However, at C(NaBr) = 0.25 M, there is no NaCMC/DTAB complex formation because of the complete salt screening of the electrostatic attraction between DTAB micelles and NaCMC chains. It is also surprisingly found that the addition of NaBr can bring out a decrease in C1 at C(NaBr) < 0.20 M. Moreover, the addition of NaBr to a mixture of 0.01 g/L NaCMC and 3.6 mM DTAB can directly induce the formation of NaCMC/DTAB complexes. This salt-enhancing effect on the complex formation is explained as the result of competition between the screening of interaction of polyelectrolyte with surfactant and the increasing of polyelectrolyte/surfactant interaction owing to the growth of micelles by added salt. When the increasing of polyelectrolyte/surfactant interaction exceeds the screening of interaction, the complex formation can be enhanced.     

Co-adsorption of carboxymethyl-cellulose and cationic surfactants at the air-water interface

We investigated the interaction between an anionic polyelectrolyte (carboxymethylcellulose) and cationic surfactants (DTAB, TTAB, and CTAB) at the air/water interface, using surface tension, ellipsometry, and Brewster angle microscopy techniques. At low surfactant concentration, a synergistic phenomenon is observed due to the co-adsorption of polyelectrolyte/surfactant complexes at the interface, which decreases the surface tension. When the surfactant critical aggregation concentration (cac) is reached, the adsorption saturates and the thickness of the adsorbed monolayer remains constant until another characteristic surfactant concentration, C0, is reached, at which all the polymer charges are bound to surfactant in bulk. Above C0, the absorbed monolayer becomes much thicker, suggesting adsorption of bulk aggregates, which have become more hydrophobic due to charge neutralization.     

Role of the preparation procedure in the formation of spherical and monodisperse surfactant/polyelectrolyte complexes

Complexes formed by a double-tail cationic surfactant, didodecyldimethyl ammonium bromide, and an anionic polyelectrolyte, an alternating copolymer of poly(styrene-alt-maleic acid) in its sodium salt form, were investigated with respect to variation in the charge ratio (x) between the polyelectrolyte negative charges and the surfactant positive charges. The morphology and microstructure of the complexes were studied by light microscopy and small-angle X-ray scattering for different preparation conditions. Independent of the sample preparation procedure and the charge ratio x, the X-ray results show that the microscopic structure of the complexes is a condensed lamellar phase. By contrast, the morphology of the complexes changes dramatically with the preparation procedure. The complexes formed by mixing a surfactant solution and a polyelectrolyte solution strongly depend on x and are always extremely heterogeneous in size and shape. Surprisingly, we show that, when the two solutions interdiffuse slowly, spherical complexes of micrometric and rather uniform size are systematically obtained, independently on the initial relative amount of surfactant and polyelectrolyte. The mechanism for the formation of these peculiar complexes is discussed.     

Stoichiometric complexes of polyelectrolyte and azo-functionalized surfactant

The Stoichiometric (1:1) complexes, comprising of a quaternary ammonium surfactant derived from azobenzene and the anionic polyelectrolyte poly(styrene sulfonate), were studied in solution. The studies were based on UV/Visible spectroscopy. Furthermore, aqueous solutions were prepared by the addition of excess surfactant. The kinetic data (t _1/2 and % cis) for the complexes in water with added dodecyltrimethylammonium bromide (DTAB) were collected, which suggests that the 1:1 complexes are resolubilized in water by the additional DTAB.     

Polymer-Surfactant Interactions and the Effect of Tail Size Variation on Micellization Process of Cationic ATAB Surfactants in Aqueous Medium

The interactions between oppositely charged surfactant-polymer systems have been studied using surface tension and conductivity measurements and the dependence of aggregation phenomenon over the polyelectrolyte concentration and chain length of cationic ATAB surfactants, cetyltrimethyl ammonium bromide (CTAB), tetradecyltrimethyl ammonium bromide (TTAB), and dodecyltrimethyl ammonium bromide (DTAB) have been investigated. It was observed that cationic surfactants induce cooperative binding with anionic polyelectrolyte at critical aggregation concentration (cac). The cac values of ATAB surfactants in the presence of anionic polyelectrolyte, sodium carboxy methyl cellulose (NaCMC), are considerably lower than their critical micelle concentration (cmc). After the complete complexation, free micelles are formed at the apparent critical micelle concentration (acmc), which is slightly higher in polyelectrolyte aqueous solution than in pure water. Among the cationic surfactants (i.e., CTAB, TTAB, and DTAB), DTAB was found to have least interaction with NaCMC. Surfactants with longer tail size strongly favor the interaction, indicating the dependence of aggregation phenomenon on the structure, morphology, and tail length of the surfactant.      

Surfactant polymer interactions between strongly interacting cationic surfactants and anionic polyelectrolytes from conductivity and turbidity measurements

The interactions between oppositely charged surfactant/polymer mixtures have been studied using conductivity and turbidity measurements. The dependence of aggregation phenomenon on the chain length and head group modifications of conventional cationic surfactants, i.e., hexadecyl- (HTAB), tetradecyl- (TTAB), and dodecyltrimethylammonium bromides (DTAB) and dimeric cationic surfactants, i.e., decyl- (DeDGB) and dodecyldimethylgemini bromides (DDGB), is investigated. It was observed that cationic surfactants induce cooperative binding with anionic polyelectrolytes at critical aggregation concentration (cac). The cac values are considerably lower than the critical micelle concentration (cmc) values for the same surfactant. After the complete complexation, free micelles are formed at the apparent critical micelle concentration (acmc), which is slightly higher in aqueous polyelectrolyte than in pure water. Among the conventional and dimeric cationic surfactants, DTAB and DeDGB, respectively, have been found to have least interactions with oppositely charged polyelectrolytes.     

Characterization of the core-shell nanoparticles formed as soluble hydrogen-bonding interpolymer complexes at low pH

The formation of soluble hydrogen-bonding interpolymer complexes between poly(acrylic acid) (PAA) and poly(acrylic acid-co-2-acrylamido-2-methyl-1-propane sulfonic acid)-graft-poly(N,N-dimethylacrylamide) (P(AA-co-AMPSA)-g-PDMAM) at pH=2.0 was studied. A viscometric study showed that in semidilute solution a physical gel is formed due to the interconnection of the anionic P(AA-co-AMPSA) backbone of the graft copolymer, in a transient network, by means of the complexes formed between the PDMAM side chains of the graft copolymer and PAA. Dynamic and static light scattering measurements, in conjunction with small-angle neutron scattering measurements, suggest the formation of core-shell colloidal nanoparticles in dilute solution, comprised by an insoluble PAA/PDMAM core surrounded by an anionic P(AA-co-AMPSA) corona. Even if larger clusters are formed in semidilute solution, the size of the insoluble core remains practically stable. Atomic force microscopy performed under ambient conditions reveal that the particles collapse and flatten upon deposition on a substrate, with dimensions close to the ones of the dry hydrophobic core.     

Formation of hybrid wormlike micelles upon mixing cetyl trimethylammonium bromide with poly(methyl methacrylate-co-sodium styrene sulfonate) copolymers in aqueous solution

The association of cetyltrimethylammonium bromide, CTAB, with a series of P(MMAx-co-SSNa) random copolymers of sodium styrene sulfonate (SSNa) with methyl methacrylate (MMA) was explored in aqueous solution as a function of the MMA molar content, x, of the copolymers. The polyelectrolyte/surfactant complexation in aqueous solution was verified through pyrene fluorescence probing. In addition, turbidimetry studies in dilute or more concentrated aqueous solutions elucidated the phase separation behavior of the P(MMAx-co-SSNa)/CTAB systems as a function of the copolymer composition x and the surfactant to polyelectrolyte mixing charge ratio. It is found that practically phase separation is completely suppressed within the studied mixing range when the MMA content of the copolymers is ～30-40 mol%. For lower MMA contents the polyelectrolyte/surfactant complex separates out from water, while for higher x values the solubility limits of the copolymers in water are attained. For the intermediate MMA contents, viscoelastic systems are obtained in more concentrated polymer/surfactant solutions provided that the polyelectrolyte is fully complexed with the cationic surfactant ((1)H NMR results). Moreover, the (1)H NMR studies indicate that hybrid P(MMAx-co-SSNa)/CTAB wormlike micelles are formed in water under these conditions. Finally, it is shown that addition of salt prevents syneresis problems and facilitates the rheological investigation.     

Effect of surfactant type on surfactant-maltodextrin interactions: isothermal titration calorimetry, surface tensiometry, and ultrasonic velocimetry study

Isothermal titration calorimetry (ITC), surface tensiometry, and ultrasonic velocimetry were used to characterize surfactant-maltodextrin interactions in buffer solutions (pH 7.0, 10 mM NaCl, 20 mM Trizma base, 30.0 degrees C). Experiments were carried out using three surfactants with similar nonpolar tail groups (C12) but different charged headgroups: anionic (sodium dodecyl sulfate, SDS), cationic (dodecyl trimethylammonium bromide, DTAB), and nonionic (polyoxyethylene 23 lauryl ether, Brij35). All three surfactants bound to maltodextrin, with the binding characteristics depending on whether the surfactant headgroup was ionic or nonionic. The amounts of surfactant bound to 0.5% w/v maltodextrin (DE 5) at saturation were < 0.3 mM Brij35, approximately 1-1.6 mM SDS, and approximately 1.5 mM DTAB. ITC measurements indicated that surfactant binding to maltodextrin was exothermic. Surface tension measurements indicated that the DTAB-maltodextrin complex was more surface active than DTAB alone but that SDS- and Brij35- maltodextrin complexes were less surface active than the surfactants alone.     

Complexes of polyelectrolyte-neutral double hydrophilic block copolymers with oppositely charged surfactant and polyelectrolyte

Complexes between sodium (sulfamate-carboxylate)isoprene/ethylene oxide double hydrophilic diblock copolymers (SCIEO) and dodecyltrimethylammonium bromide (DTMAB), as well as quaternized poly(2-vinylpyridine) (QP2VP), were studied in aqueous solutions, at pH 7. The complexes are formed due to electrostatic interactions between the anionic groups of the polyelectrolyte block of the copolymers and the cationic groups of the surfactant or the homopolyelectrolyte. The structure of the complexes was investigated as a function of the mixing ratio of the two components in solution and ionic strength by static, dynamic, and electrophoretic light scattering, atomic force microscopy, and fluorescence spectroscopy. The mass and size of the complexes depend on the mixing ratio between the components. A transition from intrachain to an interchain association was observed for block copolymer/ surfactant complexes. SCIEO/QP2VP complexes were found to respond to increasing concentrations of added salt. Spherical and ellipsoid shaped complexes with a core-shell micellar like structure were formed in the systems studied.     

Electroless deposition of Ni-P-nano-ZrO2 composite coatings in the presence of various types of surfactants

Ni-P-nano-ZrO(2) coatings were produced using the electroless deposition technique. To prevent agglomeration of zirconia nanoparticles in the plating bath, various surfactant additives (anionic, cationic, and nonionic) were used. The most stable bath was obtained with the addition of dodecyltrimethylammonium bromide (DTAB). The impact of this surfactant on the deposition rate, coating composition, and topography, as well as ζ potential of particles, was examined. Surface morphology and composition of the Ni-P-nano-ZrO(2) composite coatings was analyzed by various techniques including scanning electron microscopy (SEM) equipped with in situ energy-dispersive X-ray (EDX) spectroscopy. Coatings with a clearly greater amount of zirconia (21.88-22.10 wt.%) were obtained from baths containing DTAB in concentrations equal to or above its critical micelle concentration (cmc). For these surfactant concentrations, the reduction of Ni and P content was observed.     

Thermosensitive poly(N-isopropylacrylamide-co-acrylamide) hydrogels: Synthesis, swelling and interaction with ionic surfactants

Thermosensitive hydrogels were prepared by free-radical polymerization in aqueous solution from N-isopropylacrylamide (NIPA) and acrylamide (AAm) monomers. N,N-Methylenebis(acrylamide) (MBAAm) was used as a crosslinker. A kinetic study of the absorption determined the transport mechanism. The diffusion coefficients of these hydrogels were calculated for the Fickian mechanism. It was shown that the swelling behavior of the P(NIPA-co-AAm) hydrogels can be controlled by changing the amount of MBAAm. The swelling equilibrium of the P(NIPA-co-AAm) hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In SDS and DTAB solutions, the equilibrium swelling ratio of the hydrogels increased, this is ascribed to the conversion of non-ionic P(NIPA-co-AAm) hydrogel into polyelectrolyte hydrogels due to binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method, it was found that the electric conductivity of the P(NIPA-co-AAm)—surfactant systems depended strongly on both the type and concentration of surfactant solutions.     

X-ray diffraction study of the structure of carboxymethylcellulose-cationic surfactant complexes.

We have investigated dilute aqueous solutions of an anionic polymer (carboxymethylcellulose) mixed with cationic surfactants of different chain lengths (dodecyl to octadecyl trimethylammonium bromides: DTAB, TTAB, CTAB and OTAB). The structures of the concentrated phases formed above the precipitation threshold were studied by X-ray diffraction. Different body-centred cubic structures with space groups Pm3n were observed in the presence of surfactant with a short aliphatic chain (DTAB), despite the fact that the polymer persistence length is comparable to the repeat distance of the structure (5 nm). For larger surfactant chain lengths (TTAB and CTAB), the structure of the precipitates can be either cubic (Pm3n) or 2D hexagonal depending on the initial surfactant and polymer concentrations. For still larger chain length (OTAB), the structure becomes lamellar. This structural evolution from micellar cubic towards 2D hexagonal and lamellar is attributed to the decrease of the local curvature of the surfactant aggregates, as observed for flexible synthetic polymers and short DNA fragments under similar conditions. Furthermore, the structure of the bulk complexes formed just below the precipitation threshold anticipates the structure seen in the precipitated phases.     

Interactions of a hydrophobically modified polymer with oppositely charged surfactants

The interaction of a hydrophobically modified anionic polymer (PMAOVE) with a cationic surfactant (DTAB) was studied using a multi-technique approach: turbidity, surface tension, and viscosity measurements, as well as EPR (5-doxyl stearic acid) and fluorescence (pyrene) probe techniques were used. In the investigated pH range (4-10), the cationic surfactant headgroups interact with the anionic carboxylic groups of the polymer backbone. In addition, nonpolar interactions of the surfactant chains with the n-octyl chains of PMAOVE stabilize the PMAOVE-DTAB complexes. Charge neutralization of the anionic polymer by the cationic surfactant leads to precipitation of the PMAOVE-DTAB complex at a certain DTAB concentration range. Further addition of DTAB causes a charge reversal of the complex and, subsequently, resolubilization of the precipitate. At an acidic pH (pH = 4), a second precipitation was observed, which is probably caused by conformational changes in the PMAOVE-DTAB complex. This second precipitate can be resolubilized by further addition of surfactant. At a neutral and basic pH, this second precipitation is absent. EPR analysis indicates that the surfactants form an ordered structure at the extended polymer chain at a neutral and basic pH, whereas at an acidic pH, a less ordered surfactant layer is formed on the coiled polymer with more hydrophobic microdomains.     

Interactions Between Polymers and Nanoparticles: Formation of “Supermicellar” Hybrid Aggregates

Abstract

When polyelectrolyte‐neutral block copolymers are mixed in solutions to oppositely charged species (e.g., surfactant micelles, macromolecules, proteins, etc.), there is the formation of stable “supermicellar” aggregates combining both components. The resulting colloidal complexes exhibit a core‐shell structure, and the mechanism yielding to their formation is electrostatic self‐assembly. In this contribution, we report on the structural properties of “supermicellar” aggregates made from yttrium‐based inorganic nanoparticles (radius 2 nm) and polyelectrolyte‐neutral block copolymers in aqueous solutions. The yttrium hydroxyacetate particles were chosen as a model system for inorganic colloids, and also for their use in industrial applications as precursors for ceramic and opto‐electronic materials. The copolymers placed under scrutiny are the water‐soluble and asymmetric poly(sodium acrylate)‐b‐poly(acrylamide) diblocks. Using static and dynamical light‐scattering experiments, we demonstrate the analogy between surfactant micelles and nanoparticles in the complexation phenomenon with oppositely charged polymers. We also determine the sizes and the aggregation numbers of the hybrid organic–inorganic complexes. Several additional properties are discussed, such as the remarkable stability of the hybrid aggregates and the dependence of their sizes on the mixing conditions.     

Nanoparticles based on polyelectrolyte complexes: effect of structure and net charge on the sorption capability for solved organic molecules

 The sorption of solved organic molecules such as p-nitrophenol or dyes on previously formed nanoparticles based on polyelectrolyte/micelle complexes or polycation/polyanion complexes was studied. It could be shown that the sorption capability strongly depends on the structure and properties of the complex particles. Investigations have been made with complex particles that differ in their hydrophobic/hydrophilic structure, size and net charge. Such complex aggregates could be prepared by mixing the cationic surfactant dodecylamido-ethyldimethylbenzylammonium chloride, the polycations poly(diallyldimethylammonium chloride) or poly(methacryloyloxyethyldimethylbenzylammonium chloride) and the copolymers of maleic acid with propene or methylstyrene as anionic components. It is found that the sorption capability increases with increasing molar mass and hydrophobic properties of the components used. In addition, the concentration ratio c _polym/c _org.poll that was required to reach optimal sorption conditions could be decreased by the use of macromolecules with high molar masses. The best results were obtained by using cationic stabilized complex particles formed with high-molar-mass polycations as sorbents for anionic dye molecules. Received: 10 November 1999 Accepted: 24 February 2000     

Polyelectrolyte complexes. I. Synthesis and characterization of some insoluble polyanion-polycation complexes

The synthesis of some water-insoluble synthetic polyelectrolyte complexes formed between a weak polyanion and a strong polycation was followed. Sodium salts of poly(acrylic acid) and of some copolymers of acrylic acid with itaconic acid or maleic acid were used as anionic polymers. Cationic polyelectrolytes with quaternary ammonium salt groups in the main chain were used as strong polycations. The cationic polymers were different as concerns both the content of quaternary nitrogen atoms and the degree of branching. The complex formation was followed by the variation of the conductivity and of the specific viscosity of the reaction medium as well as by the turbidimetric titration versus the unit molar ratio polyanion/polycation. The deviation of the endpoint from stoichiometry was influenced mainly by the structure of the complementary polymers and by their molecular weights. The greater the structural differences, the higher the endpoint deviation from stoichiometry. Only insoluble polyelectrolyte complexes (PEC) were obtained in all the polyanion/polycation systems taken into account. The PECs were separated and characterized by elemental and spectral analyses as compared with the complementary polymers. © 1996 John Wiley & Sons, Inc.     

Anionic hybrid threadlike micelle formation in an aqueous solution

Novel anionic hybrid threadlike micelle formation was found in an aqueous solution of an anionic surfactant, sodium tetradecylsulfate (NaC(14)S), and partially quarternized polyelectrolyte at ca. 0.55, poly(N,N-diallyl-N-methylamine-ran-N,N-diallyl-N-ethyl-N-methylammonium bromide) (P(DAM/DAEMBr)). The system precipitated insoluble complexes at a composition of iso-electric points, forming long and stable hybrid threadlike micelles at a composition close to an iso-molar point between NaC(14)S and P(DAM/DAEMBr) in monomer units. Then, the system turned into transparent liquids and showed remarkable viscoelasticity due to entanglements between the formed anionic hybrid threadlike micelles.     

Size-dependent interaction of silica nanoparticles with different surfactants in aqueous solution

The size-dependent interaction of anionic silica nanoparticles with ionic (anionic and cationic) and nonionic surfactants has been studied using small-angle neutron scattering (SANS). The surfactants used are anionic sodium dodecyl sulfate (SDS), cationic dodecyltrimethyl ammonium bromide (DTAB), and nonionic decaoxyethylene n-dodecylether (C(12)E(10)). The measurements have been carried out for three different sizes of silica nanoparticles (8, 16, and 26 nm) at fixed concentrations (1 wt % each) of nanoparticles and surfactants. It is found that irrespective of the size of the nanoparticles there is no significant interaction evolved between like-charged nanoparticles and the SDS micelles leading to any structural changes. However, the strong attraction of oppositely charged DTAB micelles with silica nanoparticles results in the aggregation of nanoparticles. The number of micelles mediating the nanoparticle aggregation increases with the size of the nanoparticle. The aggregates are characterized by fractal structure where the fractal dimension is found to be constant (D ≈ 2.3) independent of the size of the nanoparticles and consistent with diffusion-limited-aggregation-type fractal morphology in these systems. In the case of nonionic surfactant C(12)E(10), micelles interact with the individual silica nanoparticles. The number of adsorbed micelles per nanoparticle increases drastically whereas the percentage of adsorbed micelles on nanoparticles decreases with the increase in the size of the nanoparticles.