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The structural and dynamic characteristics of dioctadecyldimethylammonium bromide (DODAB) monolayers on a pure water subphase were investigated by surface film balance, Brewster angle microscopy, and relaxation in area and surface pressure at constant surface pressure and area, respectively. The first compression-expansion cycle of the monolayer is not reversible and the second pi-A compression isotherm deviates to larger molecular areas relative to the first one. At a microscopic level this hysteresis may be assigned to an irreversible hydration of the ammonium groups of DODAB. The morphology and reflectivity of DODAB monolayers during compression and expansion on the monolayer depend on the monolayer history. Bright domains randomly dispersed were observed during compression before collapse. Surprisingly, this random distribution of domains changes into a fractal-like structure during the monolayer expansion in a narrow range of surface pressures. This morphology does not form when the monolayer is previously compressed above the collapse surface pressure. 2D foam-like structure is often observed when the film is expanded at maximum area. Relaxation phenomena in DODAB monolayers are attributed to monolayer reorganization and nucleation of liquid-condensed domains from the liquid-expanded phase. These time-dependent processes are irreversible.
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PMID:Memory effects on the interfacial characteristics of dioctadecyldimethylammonium bromide monolayers at the air-water interface. 1469 9

We have investigated the electrolyte-induced collapse of a polyelectrolyte brush covalently attached to a planar solid surface. Positively charged poly-4-vinyl [N-methyl-pyridinium] (MePVP) brushes were prepared in situ at the surface by free radical chain polymerization using a surface-immobilized initiator monolayer ("grafting from" technique) and 4-vinylpyridine as the monomer, followed by a polymer-analogous quaternization reaction. The height of the brushes was measured as a function of the external salt concentration via multiple-angle null ellipsometry. As predicted by mean-field theory, the height of the MePVP brushes remains unaffected by the addition of low amounts of external salt. At higher salt concentrations the brush height decreases. The extent to which the brush shrinks strongly depends on the nature of the salt present in the environment. MePVP brushes collapse to almost the dry layer thickness upon the addition of potassium iodide to a contacting aqueous medium. In contrast, the collapse of MePVP brushes having bromide or chloride counterions is much less pronounced. These brushes remain in a highly swollen state even after large amounts of salt have been added to the solution.
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PMID:Electrolyte-induced collapse of a polyelectrolyte brush. 1526 12

A series of mesostructured Cu-SiO2 composites have been synthesized with sodium metasilicate (Na2SiO3) and cuprammonia nitrate (Cu(NH3)4(NO3)2) respectively used as Si and Cu sources. The synthetic procedures were conducted at room temperature, and cetyltrimethylammonia bromide was used as a template. Under our experimental conditions, ordered mesoporous Cu-SiO2 composites could be obtained with a copper content up to 16.8 wt %. Average pore diameters (2.80-3.15 nm), wall thickness (1.30-2.20 nm), and specific surface area (1020-690 m2/g) are found to vary linearly with copper content (0-16.8 wt %). Results of thermal gravimetry-differential thermal analysis reveal the collapse temperature of the order structure starts at approximately 1250 K for mesoporous Cu-SiO2 with 16.8 wt % copper content. As indicated by the outcomes of inductively coupled plasma and X-ray photoelectron spectroscopy studies, copper is mainly incorporated inside the pore wall rather than embedded on the wall surface. Copper species strongly interact with silica, and calcination at high temperatures cannot cause phase separation between silica and copper oxide. Cu status in mesoporous Cu-SiO2 composites is similar to that in copper silicate in neighboring structures. Based on the results, a S+ I- I+ I- mechanism is proposed in which copper entities are surrounded by silicon species during synthesis of the mesostructured composite.
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PMID:Novel coassembly route to Cu-SiO2 MCM-41-like mesoporous materials. 1583 67

Multiply charged electrospray ions from concentrated solutions of Heptyl4N+Br- (designated A+B- hereafter) in formamide are analyzed mass spectrometrically (MS) following mobility selection in ambient air in a differential mobility analyzer (DMA). Most of the sharp mobility peaks seen are identified as (AB)(n)A+ clusters, with 0 < or = n < ot = 5. One anomalously abundant and mobile ion is identified as NH4+(AB)4. Six ions in the (AB)n(A+)2 series are also identified, completing and correcting earlier mobility data for singly and doubly charged ions up to masses of almost 9000 Da. The more mobile of two broad humps seen in the mobility spectrum includes m/z values approximately from 2500 up to 12,000 Da. It is formed primarily by multiply charged (AB)n(A+)z clusters with multiple ammonium bromide adducts. Because of overlapping of many peaks of different m/z and charge state z, only a few individual species can be identified by MS alone in this highly congested region. However, the spectral simplification brought about by mobility selection upstream of the MS reveals a series of broad modulations in m/z space, with all ions resolved in the second, third, ...sixth modulation being in charge states z = 2, 3, ...6, respectively. Extrapolation of this trend beyond the sixth wave fixes the ion charge state (in some cases up to z = 15) and mass (beyond m = 175,000 u). This wavy structure had been previously observed and explained in terms of ion evaporation kinetics from volatile drops, though without mass identification. All observations indicate that the clusters are formed as charged residues, but their charge state is fixed by the Iribarne-Thomson ion evaporation mechanism. Consequently, the measured curve of cluster diameter versus z yields the two parameters governing ion evaporation kinetics. Clusters with z > 1 and electrical mobility Z > 0.495 cm2/V/s are metastable and evaporate a singly charged cluster, probably (AB)2A+, between the DMA and the MS. Plotting the electrical mobilities Z of the clusters in the form (z/Z)1/2 versus m(1/3) (both proportional to cluster diameter) collapse the data for all cluster sizes and charge states into one single straight line for Z below 0.495 cm2/V/s. This linear relation reveals a uniform apparent cluster density of 0.935 g/cm3 and an effective hard-sphere diameter of the air molecules of 0.44 nm. An anomalous mobility increase is observed at diameters below 3 nm.
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PMID:Tandem mobility mass spectrometry study of electrosprayed tetraheptyl ammonium bromide clusters. 1586 73

Liquid phase deposition (LPD) of silica from soluble silicates has been performed in the presence of dodecyltrimethylammonium bromide (DTAB), sodium dodecyl sulfate (SDS) and sodium dodecylbenzyl sulfate (SDBS). The morphology of the silica varies between semi-ordered uniform spheres to low porosity agglomerates, with the choice and concentration of the surfactants. The agglomerate structures depend on the charge of the surfactant (and hence the retention of micelles under acidic LPD conditions and/or the ionic character of the surfactant solution), the critical micelle concentration (as compared to the concentration of the silica precursor), and the ionic strength of the solution. The application of surfactant micelles as templates for LPD silica is counter to a previous proposal that suggested the ionic strength of the silicate solution would cause the collapse of the ionic vesicles. The size of spherical silica particles is controlled by the relative concentration of the surfactant and the LPD precursor.
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PMID:Effect of surfactant on particle morphology for liquid phase deposition of submicron silica. 1591 80

The adsorption and complexation of polystyrene sulfonate (a highly charged anionic polyelectrolyte) and a series of cationic surfactants, alkyltrimethylammonium bromide, CnTAB, n = 8-16, at the air-water interface has been studied by combining surface tension and ellipsometry measurements. We find that increasing the chain length of the surfactant from 8 to 10 carbons leads to a sharp increase in adsorption of PSS/CnTAB complexes. When the surfactant tail length is further increased to 12 and 14 carbons, surface adsorption becomes less favored than macroscopic phase separation, resulting in a partial surface depletion. Furthermore, we find that when surface tensions are plotted against surfactant/monomer molar concentration ratio, all data collapse to a single curve. This result shows that the surfactant-polymer molar ratio, s/p, is a key parameter for tuning the surface activity of the complexes formed.
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PMID:Interfacial microgels formed by oppositely charged polyelectrolytes and surfactants. Part 2. Influence of surfactant chain length and surfactant/polymer ratio. 1598 75

The formation of complexes between the cationic surfactant dodecyl trimethylammonium bromide (DTAB) and the comb-type anionic polyelectrolytes poly(sodium acrylate-co-sodium 2-acrylamido-2-methylpropane sulfonate)-g-poly(N,N-dimethylacrylamide) (P(NaA-co-NaAMPS)-g-PDMAMx) was investigated in dilute aqueous solutions by means of turbidimetry, pyrene fluorescence probing, viscometry, z-potential measurements, and dynamic light scattering. The comb-type copolymers consist of an anionic copolymer backbone, P(NaA-co-NaAMPS), containing 84 mol % NaAMPS units, while the weight percentage, x, of the PDMAM side chains varies from x = 12% (w:w) up to x = 58% (w:w). It was found that, contrary to the water-insoluble complexes formed between the linear polyelectrolyte P(NaA-co-NaAMPS) and DTAB, the solubility in water of the complexes formed between the comb-type copolymers and DTAB is significantly improved with increasing x. The complexation process starts at the same critical aggregation concentration (about 2 orders of magnitude lower than the critical micelle concentration of DTAB), regardless of x, and it is accompanied by charge neutralization and appearance of hydrophobic microdomains. Both effects lead to the substantial collapse of the polyelectrolyte chain upon addition of DTAB. However, the complexes of the comb-type copolymers with DTAB are stabilized in water as nanoparticles, and probably consisted of a water-insoluble core (the polyelectrolyte/surfactant complex), protected by a hydrophilic nonionic PDMAM corona. The size of the nanoparticles varies from approximately 35 nm up to approximately 120 nm, depending on x.
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PMID:Water-soluble complexes between cationic surfactants and comb-type copolymers consisting of an anionic backbone and hydrophilic nonionic poly(N,N-dimethylacrylamide) side chains. 1617 30

Silica particles are hydrophobized either by chemical graft of alkyl chains or by physical adsorption of cationic surfactants, alkyltrimethylammonium bromide. The effects of the two modification methods on the monolayer behavior of silica particles at the air/water interface are studied, as well as the packing structure of the particulate films. The results show that the hydrophobicity of particles chemically modified by octanol (SiO2-C8) and dodecanol (SiO2-C12) are similar and higher than that modified by butanol (SiO2-C4). The monolayer composed of particles with higher hydrophobicity shows a large lift-off area, higher compressibility, and significant hysteresis due to the higher particle-particle interaction. As a result, the particulate films exhibit 2-dimensional (2D) aggregative domains of closely-packed structure, but with particle free regions presenting among the domains. The monolayer prepared by SiO2-C4 shows a contrary behavior resulted from the higher particle-water interaction. The particles modified by adsorption of cationic surfactants have an amphiphilic property at the air/water interface. Such monolayer exhibits lower compressibility and hysteresis, higher re-spreading characteristic, and a lower collapse pressure compared with those of the chemically modified particles. A particulate film with high uniformity and closely-packed structure can be obtained by using the octyltrimethylammonium bromide (OTAB) modified particles. When the alkyl chain of surfactant increases, the packing of the particles becomes looser. Such phenomenon is probably caused from the higher probability for the long-chain surfactants to stay at the air/water interface which obstructs the intimate contact of particles.
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PMID:Monolayer behavior of silica particles at air/water interface: a comparison between chemical and physical modifications of surface. 1618 71

We have examined the polymer-surfactant interaction in mixed solutions of the cationic surfactants, i.e., dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, tetradecyltriphenylphosphonium bromide, and tetradecylpyridinium bromide and a semiflexible anionic polyelectrolyte carboxymethylcellulose in water and aqueous salt solutions by various techniques: tensiometry, viscosimetry or ion-selective electrode method, and dynamic light scattering. We have investigated the effect of varying surfactant chain length, head group size, counterion, and ionic strength on the critical aggregation concentration (CAC) of mixed polymer surfactant systems and the collapse of the polymer molecule under different solution conditions. The CAC decreases with increasing alkyl chain length. Above a certain surfactant concentration, mixed aggregates start growing until their macroscopic phase separation. The growth is more rapid with greater surfactant tail length and with increasing head group size. This is attributed in both cases to the increasing hydrophobic interaction between polymer and surfactant. Among surfactants with monovalent halide counterions, iodide induces the strongest binding, reflected by the onset of growth of the mixed aggregates at low surfactant concentration. This is perhaps related to the decreasing hydration of the counterion from chloride to iodide. The surfactant concentration at which the viscosity of the solution starts to decrease sharply is smaller than the CAC, and probably reflects polymer chain shrinkage due to noncooperative binding.
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PMID:Interaction of cationic surfactants with carboxymethylcellulose in aqueous media. 1637 17

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


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