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Query: UMLS:C1832588 (PSS)
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The surface pressure of monolayers of an insoluble surfactant, didodecyldimethylammonium bromide (DODAB), has been measured onto subphases with different concentrations of poly(styrenesulfonate) (PSS) and at different temperatures. The presence of PSS in the subphase shifts the surface-pressure (Pi) curves to larger areas per DODAB molecule, A, and shifts the surface phase transition to higher Pi's. The presence of PSS chains decreases the surface electric potential; the decrease is higher than expected from the formation of a double layer between the DODAB molecules and the PSS segments. Increasing the temperature shifts the surface-pressure curves to higher areas and also increases the values of Pi of the surface phase transition. The effect of the PSS chains on the Pi versus A curves is contrary to the one induced by the presence of inert electrolytes in the subphase. The behavior is consistent with the existence of a dense layer of PSS segments beneath the DODAB monolayer at low PSS concentrations, c. Two PSS layers exist at higher concentrations, a dense layer immediately below the DODAB and a less-dense layer, below the first one, that protrudes deep into the subphase. The surface-pressure relaxation curves have been found to be bimodal through the whole range of surface pressures and at all the values of polymer concentration studied. These results point out that the adsorption layers behave mainly as elastic bodies, with zero-frequency elasticity, epsilon(omega = 0), which agrees with the equilibrium compressibility modulus. The increase [epsilon(omega = 1) - epsilon(omega = 0)] has been found to be independent of both polymer concentration and molecular weight. The zero-frequency-dilational viscosity, kappa(omega = 0), strongly increases with Pi in the two-dimensional condensed-liquid region. The surface viscosity strongly decreases with increasing frequency; the decreasing rate is higher than the one found for the monolayers of nonionic insoluble polymers. kappa(omega = 0) has also been found to be independent of both polymer concentration and molecular weight. These results seem to indicate that it is the film formed by the DODAB molecules and the first dense polymer layer that determines the surface viscoelastic moduli of this system.
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PMID:Equilibrium behavior and dilational rheology of polyelectrolyte/insoluble surfactant adsorption films: didodecyldimethylammonium bromide and sodium poly(styrenesulfonate). 1685 57

Nanofiltration (NF) is an attractive technique for reducing F- concentrations to acceptable levels in drinking water, but commercial NF membranes such as NF 270 and NF 90 show minimal Cl-/F- selectivity. In contrast, simple layer-by-layer deposition of 4.5-bilayer poly(styrene sulfonate) (PSS)/poly(diallyldimethylammonium chloride) (PDADMAC) films on porous alumina supports yields NF membranes that exhibit Cl-/F- and Br-/F- selectivities>3 along with solution fluxes that are >3-fold higher than those of the commercial membranes. Fluoride rejection by (PSS/PDADMAC)4PSS membranes, which is >70%, is independent of pressure over a range of 3.6 to 6.0 bar, suggesting that the primary transport mechanism in these films is convection. Moreover, the fact that Br-/F- selectivity is 12% higher than Cl-/F- selectivity suggests that discrimination among the monovalent ions is based on size (Stokes radius). Chloride/fluoride selectivities are essentially constant over Cl-/F- feed ratios from 1 to 60, so these separations will be viable over a range of conditions. Interestingly, PSS/protonated poly(allylamine) films show little Cl-/F- selectivity, and the selectivity of PSS/PDADMAC membranes is a strong function of the number of deposited layers, indicating that NF properties are very sensitive to film structure.
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PMID:Separation of fluoride from other monovalent anions using multilayer polyelectrolyte nanofiltration membranes. 1727 49

The formation of a complex between an anionic spherical polyelectrolyte brush (SPB) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is investigated. The SPB consists of long chains of the strong polyelectrolyte poly(styrene sulfonate) (PSS), which are bound chemically to a solid poly(styrene) core of 56 nm in radius. The SPB are dispersed in water, and the ionic strength is adjusted by addition of NaBr. The resulting complexes are investigated in dilute solution by dynamic light scattering, by electrophoretic light scattering, and by cryogenic transmission electron microscopy (cryo-TEM). The formation of the complex between the SPB and the surfactant can be monitored by a strong shrinking of the surface layer when adding CTAB to dilute suspensions (0.01 wt %) and by a decrease of the effective charge of the complexes. Complex formation starts at CTAB concentrations lower than the critical micelle concentration of this surfactant. If the ratio r of the charges on the SPB to the charge of the added surfactant is exceeding unity, the particles start to flocculate. Cryo-TEM images of the complexes at r = 0.6 measured in salt-free solution show that the surface layer composed of the PSS chains and the adsorbed CTAB molecules is partially collapsed: A part of the chains form a dense surface layer while another part of the chains or aggregates thereof are still sticking out. This can be deduced from the cryo-TEM micrographs as well as from the hydrodynamic radius, which is still of appreciable magnitude. The 1:1 complex (r = 1.0) exhibits a fully collapsed layer formed by the PSS chains and CTAB. If the complex is formed in the presence of 0.05 M NaBr, r = 0.6 leads to globular structures directly attached to the surface of the core particles. All structures seen in the cryo-TEM images can be explained by a collapse transition of the surface layer brought about by the hydrophobic attraction between the polyelectrolyte chains that became partially hydrophobic through adsorption of CTAB.
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PMID:Binding of oppositely charged surfactants to spherical polyelectrolyte brushes: a study by cryogenic transmission electron microscopy. 1731 35

Absolute ion concentration and its profile across polyelectrolyte multilayer films were studied. The films were prepared by alternating adsorption of polyanions and polycations from aqueous solution. Standing-wave X-ray fluorescence was used to map the ion profile. The well-studied multilayer system PSS/PAH was investigated, and bromide ions were used as probe entities. The results show that the sign of the charge of the outermost layer and the washing procedure after finishing the preparation have a decisive effect on the ion concentration and the ion profile. Multilayers with PSS as the outermost layer contain fewer bromide ions than the PAH-terminated multilayers. Exposure to water washes the ions out, but even after 6 h of washing, not all of the bromide ions had been removed.
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PMID:Ion distribution in polyelectrolyte multilayers with standing-wave X-ray fluorescence. 1740 77

Langmuir-Blodgett deposition of a single monolayer of 1,2,4,5-tetrakis[(N-(perfluoroundecanoamidoethyl)-N,N-dimethylammonium)methyl]benzene tetrabromide (1) onto a thin film made from alternating layers of poly(diallydimethylammonium chloride) (PDADMA) and poly(4-styrenesulfonate) (PSS) ions affords a uniform fluorinated surface of low energy. An analogous surface that has been constructed by self-assembly shows the same critical surface tension of 16.5 dyn/cm. A comparison of Zisman plots for these two modified films, in combination with analysis by X-ray photoelectron spectroscopy, indicates that Langmuir-Blodgett deposition produces a higher quality and more densely packed fluorocarbon surface that is very hydrophobic. In sharp contrast, the use of a single-chain analog (i.e., N-(perfluoroundecanoamidoethyl)-N,N,N-trimethylammonium bromide) (2)) affords relatively high energy surfaces by Langmuir-Blodgett deposition and by self-assembly.
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PMID:Fluorocarbon crowning: Langmuir-Blodgett deposition versus self-assembly at molecularly rough surfaces. 1769 74

In this work we build on prior studies of the novel water-soluble cationic conjugated polymer known as "P2" (poly{2,5-bis[3-( N, N, N-triethylammonium bromide)-1-oxapropyl]-1,4-phenylenevinylene}) with a focus on its incorporation into thin films for such applications as photovoltaics or electroluminescent devices. Multilayer assemblies were constructed using P2, the anionic surfactant sodium dodecyl sulfate (SDS), and the polyanion poly(sodium 4-styrene-sulfonate) (PSS) using the technique of layer-by-layer electrostatic self-assembly (LBL-ESA). SDS was observed to affect the layer thicknesses and absorbance characteristics of the films. We show that the optical properties and photo-oxidative resistance can be improved by varying the SDS content in the assemblies. Specifically, the surfactant-complexed poly( p-phenylenevinylene) (PPV) shows an enhanced absorption at longer wavelengths as well as improved photostability. Therefore, our work may have broad implications on the development of stable PPV-based materials in general and their efficient integration into thin films technologies.
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PMID:Controlling layer thickness and photostability of water-soluble cationic poly(p-phenylenevinylene) in multilayer thin films by surfactant complexation. 1894 65

Polystyrene sulfonate (PSS 77 kDa) adsorbed onto oppositely charged dioctadecyldimethylammonium bromide (DODA) monolayers at the air/water interface is investigated with X-ray reflectivity and grazing incidence diffraction. The alkyl tails of DODA in the condensed phase form an oblique lattice with large tilts and intermediate azimuth angle. On PSS adsorption, the alkyl tail structure is maintained; only the tilt angle changes. Bragg peaks caused by flatly adsorbed, aligned PSS chains are observed, when DODA is in the fluid and also when it is in the condensed phase. The two-dimensional lamellar phase is only found at intermediate PSS bulk concentrations (0.001-1 mmol/L). In this phase, the PSS coverage can be varied by a factor of 3, depending on DODA molecular area and polymer bulk concentration. Charge compensation in the lamellar phase is almost achieved at 1 mmol/L. At larger bulk concentrations, PSS adsorbs flatly yet without chain alignment. Presumably, a necessary condition for a two-dimensional lamellar phase is a pronounced electrostatic force which causes a large persistence length as well as repulsion between the aligned chains.
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PMID:Two-dimensional lamellar phase of poly(styrene sulfonate) adsorbed onto an oppositely charged lipid monolayer. 1912 2

The interaction of N-tetradecyl trimethyl ammonium bromide (TTAB) surfactants with poly(sodium styrene sulfonate) (PSS), PSS/poly(allylamine hydrochloride) (PAH), and PSS/poly(diallyl dimethyl ammonium chloride) (PDADMAC) complexes has been studied by means of Raman and IR spectroscopy. The stoichiometry of the polyelectrolyte complexes and of the complexes with TTAB has been established. TTAB molecules bind to single PSS molecules in a coiled liquid-like alkyl configuration up to a molar fraction of 67% in dry state. At higher concentrations, TTAB shows a transition to a crystalline phase. In the case of PSS being complexed with PAH, surfactant binds to PSS with a stoichiometry of 2 molecules of TTAB per sulfonic acid group. Spectroscopic data show that TTAB interacting with PSS/PDADMAC complexes is capable of disassembling this polyelectrolyte complex, but when TTAB interacts with the PSS/PAH complexes this polyelectrolyte pair remains stable. Spectroscopic measurements performed at different humidity showed that dry PSS/PAH complexes display the nu(SO(2)) and nu(s)(SO(3)(-)) bands at positions, which are indicative of the presence of hydrogen bonds between PSS and PAH. Red shifts of these bands when mixing the PSS/PAH complexes with TTAB point to structural rearrangements of the complex when interacting with the surfactant.
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PMID:Spectroscopic studies on the competitive interaction between polystyrene sodium sulfonate with polycations and the N-tetradecyl trimethyl ammonium bromide surfactant. 1993 65

Quantitative in situ attenuated total internal reflection Fourier transform infrared (ATR FTIR) spectroscopy has been used to study the isotherm of poly(sodium 4-styrene sulfonate), PSS, adsorption to a TiO(2) surface in aqueous solution at a pH of 3.5. The effect of adding surfactant cetylpyridinium bromide monohydrate (CPBM) on the adsorption isotherm of PSS was investigated at CPBM concentrations of 3.60 x 10(-7), 1.02 x 10(-5), and 1.04 x 10(-4) M. The use of in situ ATR FTIR allowed for the calculation of the concentration of both PSS and CPBM at the TiO(2)/water interface over the entire course of all experiments. It was found that the addition of a small amount of CPBM, 3.60 x 10(-7) M, to PSS solutions resulted in 23 +/- 3% less PSS accumulating at the TiO(2)/water interface compared to isotherm studies with no CPBM present. The mole ratio of CPBM to PSS varies from 4 +/- 1 to 1 to 20 +/- 4 to 1 in a stepwise manner as the solution concentration of PSS is increased for solutions with a CPBM concentration of 3.60 x 10(-7). The addition of CPBM at concentrations of 1.02 x 10(-5) and 1.04 x 10(-4) M showed distinct differences in the behavior of the PSS isotherm, but at the highest solution PSS concentrations, the amount of PSS at the TiO(2)/water interface compared to that of PSS solutions with no CPBM added is indistinguishable within the experimental uncertainties. For these higher concentrations of CPBM, both PSS and CPBM appear to come to the TiO(2) surface as aggregates and the mole ratio of CPBM to PSS at the TiO(2)/water interface decreases as the concentration of PSS is increased. For a CPBM concentration of 1.02 x 10(-5) M, the mole ratio of CPBM to PSS changes from 139 +/- 29 to 1 to 33 +/- 7 to 1 as the solution PSS concentration is increased. For a CPBM concentration of 1.04 x 10(-4) M, the mole ratio of CPBM to PSS changes from 630 +/- 130 to 1 to 110 +/- 21 to 1 as the solution PSS concentration is increased. Despite the large differences in the CPBM to PSS mole ratios, the amount of PSS that adsorbs to the surface is statistically indistinguishable for CPBM concentrations of 0, 1.02 x 10(-5), and 1.04 x 10(-4) M, indicating that the structure of the PSS molecules in each of the systems does not significantly change in the presence of CPBM.
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PMID:Quantitative in situ attenuated total internal reflection Fourier transform infrared study of the isotherms of poly(sodium 4-styrene sulfonate) adsorption to a TiO2 surface over a range of cetylpyridinium bromide monohydrate concentration. 2006 83

Air-stable magnetic cobalt nanocrystals have been conveniently prepared via a reverse micellar synthesis, followed by a hydrothermal treatment. The synthesis was carried out by first mixing an aqueous solution containing cobalt chloride and poly(sodium 4-styrenesulfonate) (PSS) with an organic mixture containing cetyltrimethylammonium bromide (CTAB) to form reverse micelles, followed by reducing cobalt ions with sodium borohydride. The resultant nanoparticles were then undergone a hydrothermal treatment at 165 degrees C for 8 h to generate well-dispersed CTAB/PSS-encapsulated cobalt nanocrystals with an average diameter of 3.5 +/- 0.5 nm. The nanoparticles were highly crystalline with a hexagonal close-packed crystal phase. The presence of CTAB/PSS complex coatings was identified by FT-IR and UV-vis spectroscopies as well as thermogravimetry analyses. The nanocrystals exhibited superparamagnetic property at room temperature with a saturation magnetization (M(s)) of 95 emu/g. The magnetization could be largely preserved after storage at room temperature for 4 months as the M(s) value only slightly decreased to 88 emu/g (measured at 300 K). Thus, the polymer encapsulation could not only improve thermal stability of the micelles for the growth and nucleation of Co atoms but also protect the resulting cobalt nanocrystals from oxidation through forming an oxygen impermeable sheath.
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PMID:Hydrothermal microemulsion synthesis of oxidatively stable cobalt nanocrystals encapsulated in surfactant/polymer complex shells. 2033 80


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