Monolayers bromide

Fig. IV 23. Penetration of cholesterol monolayers by CTAB (hexadecyl-trimethylam-monium bromide. [From D. M. Alexander, G. T. Barnes, M. A. McGregor, and K. Walker, Phenomena in Mixed Surfactant Systems, in J. F. Scamehom, ed., ACS Symposium Series 311, p. 133, 1986 (Ref. 269). Copyright 1986, American Chemical Society.]...

While the v-a plots for ionized monolayers often show no distinguishing features, it is entirely possible for such to be present and, in fact, for actual phase transitions to be observed. This was the case for films of poly(4-vinylpyri-dinium) bromide at the air-aqueous electrolyte interface [118]. In addition, electrostatic interactions play a large role in the stabilization of solid-supported lipid monolayers [119] as well as in the interactions between bilayers [120]. 

Constmction of multilayers requires that the monolayer surface be modified to a hydroxylated one. Such surfaces can be prepared by a chemical reaction and the conversion of a nonpolar terminal group to a hydroxyl group. Examples of such reactions are the LiAlH reduction of a surface ester group (165), the hydroboration—oxidation of a terminal vinyl group (127,163), and the conversion of a surface bromide using silver chemistry (200). Once a subsequent monolayer is adsorbed on the "activated" monolayer, multilayer films may be built by repetition of this process (Fig. 8). 

In a typical experiment, Israelachvili deposited monolayers of surfactants onto cleaved mica sheets, and evaluated the surface energies using the JKR equation. Fig. 11 contrasts results for mica coated with monolayers of (a) L-a-dipalmitoyl-phosphatidylethanolamine (DMPE) where j/a = = 27 mJ/m and (b) hexa-decyltrimethylammonium bromide (CTAB) where = 20 mJ/m and = 50 mJ/m. ... 

Monolayers of octadecylmercaptan, dioctadecyldithioethylammonium bromide, and dioctadecyldimethylammonium bromide were used as templates for the growth of gold... 

Nanoparticles of the semicondnctor titanium dioxide have also been spread as mono-layers [164]. Nanoparticles of TiOi were formed by the arrested hydrolysis of titanium iso-propoxide. A very small amount of water was mixed with a chloroform/isopropanol solution of titanium isopropoxide with the surfactant hexadecyltrimethylammonium bromide (CTAB) and a catalyst. The particles produced were 1.8-2.2 nm in diameter. The stabilized particles were spread as monolayers. Successive cycles of II-A isotherms exhibited smaller areas for the initial pressnre rise, attributed to dissolution of excess surfactant into the subphase. And BAM observation showed the solid state of the films at 50 mN m was featureless and bright collapse then appeared as a series of stripes across the image. The area per particle determined from the isotherms decreased when sols were subjected to a heat treatment prior to spreading. This effect was believed to arise from a modification to the particle surface that made surfactant adsorption less favorable. 

Tarek et al. [388] studied a system with some similarities to the work of Bocker et al. described earlier—a monolayer of n-tetradecyltrimethylammonium bromide. They also used explicit representations of the water molecules in a slab orientation, with the mono-layer on either side, in a molecular dynamics simulation. Their goal was to model more disordered, liquid states, so they chose two larger molecular areas, 0.45 and 0.67 nm molecule Density profiles normal to the interface were calculated and compared to neutron reflectivity data, with good agreement reported. The hydrocarbon chains were seen as highly disordered, and the diffusion was seen at both areas, with a factor of about 2.5 increase from the smaller molecular area to the larger area. They report no evidence of a tendency for the chains to aggregate into ordered islands, so perhaps this work can be seen as a realistic computer simulation depiction of a monolayer in an LE state. 

The UPD and anodic oxidation of Pb monolayers on tellurium was investigated also in acidic aqueous solutions of Pb(II) cations and various concentrations of halides (iodide, bromide, and chloride) [103]. The Te substrate was a 0.5 xm film electrodeposited in a previous step on polycrystalline Au from an acidic Te02 solution. Particular information on the time-frequency-potential variance of the electrochemical process was obtained by potentiodynamic electrochemical impedance spectroscopy (PDEIS), as it was difficult to apply stationary techniques for accurate characterization, due to a tendency to chemical interaction between the Pb adatoms and the substrate on a time scale of minutes. The impedance... 

Surfactants greatly improve the performance of trans-cinnamaldehyde as a corrosion inhibitor for steel in HCl [741,1590,1591]. They act by enhancing the adsorption at the surface. Increased solubility or dispersibility of the inhibitor is an incidental effect. N-dodecylpyridinium bromide is effective in this aspect far below its critical micelle concentration, probably as a result of electrostatic adsorption of the monomeric form of N-dodecylpyridinium bromide. This leads to the formation of a hydrophobic monolayer, which attracts the inhibitor. On the other hand, an ethoxylated nonylphenol, a nonionic surfactant, acts by incorporating the inhibitor into micelles, which themselves adsorb on the steel surface and facilitate the adsorption of trans-cinnamaldehyde. 

The ITIES with an adsorbed monolayer of surfactant has been studied as a model system of the interface between microphases in a bicontinuous microemulsion [39]. This latter system has important applications in electrochemical synthesis and catalysis [88-92]. Quantitative measurements of the kinetics of electrochemical processes in microemulsions are difficult to perform directly, due to uncertainties in the area over which the organic and aqueous reactants contact. The SECM feedback mode allowed the rate of catalytic reduction of tra 5-l,2-dibromocyclohexane in benzonitrile by the Co(I) form of vitamin B12, generated electrochemically in an aqueous phase to be measured as a function of interfacial potential drop and adsorbed surfactants [39]. It was found that the reaction at the ITIES could not be interpreted as a simple second-order process. In the absence of surfactant at the ITIES the overall rate of the interfacial reaction was virtually independent of the potential drop across the interface and a similar rate constant was obtained when a cationic surfactant (didodecyldimethylammonium bromide) was adsorbed at the ITIES. In contrast a threefold decrease in the rate constant was observed when an anionic surfactant (dihexadecyl phosphate) was used. 

Recently, the newly developed time-resolved quasielastic laser scattering (QELS) has been applied to follow the changes in the surface tension of the nonpolarized water nitrobenzene interface upon the injection of cetyltrimethylammonium bromide [34] and sodium dodecyl sulfate [35] around or beyond their critical micelle concentrations. As a matter of fact, the method is based on the determination of the frequency of the thermally excited capillary waves at liquid-liquid interfaces. Since the capillary wave frequency is a function of the surface tension, and the change in the surface tension reflects the ion surface concentration, the QELS method allows us to observe the dynamic changes of the ITIES, such as the formation of monolayers of various surfactants [34]. 

Figure 3 also contains an example of an ISER-flrel plot for a simple specifically adsorbed species, bromide on silver (solid curve). This plot was extracted from bromide coverage-potential data, obtained from differential capacitance measurements, along with the corresponding potential-dependent intensity of the SERS bromide-surface stretching mode at ca. 160 cm"1 (19.). In this case, the maximum (i.e. unity) value of 0r>1 corresponds to a close-packed bromide monolayer, ca. 1.4 x 10"9 mol cm 2. Again, the ISER-0t 1... 

A confluent monolayer of Madin-Darby canine kidney (MDCK) cells was grown in 96-well plates. Serial tenfold dilutions in minimal essential medium were prepared from the aliquots of allantoic fluid taken from the irradiated specimen. These dilutions were applied to MDCK cells and incubated for 48 h at 36 °C in 5% C02. The cells were then washed two times for 5 min with phosphate buffered saline (PBS) and incubated for 1 h with 100 pi of 0.5 mg/ml solution of 3-(4,5-dimethyl-thiazolyl-2) 2,5-diphenyltetrazolium bromide (MTT, ICN Biochemicals Inc., Aurora, Ohio). After lh, the colored deposit was dissolved in 100 pi DMSO, and optical density in the wells was measured on plate reader Victor 1420 (Perkin Elmer, Finland). Based on the data obtained, the infectious titer of the vims was determined as a decimal logarithm of reciprocal to the dilution of the specimen causing destruction of 50% of cells. The inhibiting action of irradiation was evaluated by decreasing the vims titer. 

A physical model and a theory have been proposed [72], which might be helpful in comparative studies on electrocompres-sive behavior of electrodeposited chloride, bromide, and iodide monolayers on the Au(lll) electrode. The theoretical results were in good agreement with the experimental data, which evidence that the adatom-adatom interactions (especially repulsive ones) and electrosorption valency of halide anions determine the compressibility within halide adlayers. Also, Lipkowski et al. have discussed various aspects of adsorption of halide anions on Au(lll) in a review paper [36]. From this paper, we have taken quantitative data concerning adsorption of halide anions on Au(lll) (cf Fig. 3). 

When a surfactant is injected into the liquid beneath an insoluble monolayer, surfactant molecules may adsorb at the surface, penetrating between the monolayer molecules. However it is difficult to determine the extent of this penetration. In principle, equilibrium penetration is described by the Gibbs equation, but the practical application of this equation is complicated by the need to evaluate the dependence of the activity of monolayer substance on surface pressure. There have been several approaches to this problem. In this paper, previously published surface pressure-area Isotherms for cholesterol monolayers on solutions of hexadecy1-trimethyl-ammonium bromide have been analysed by three different methods and the results compared. For this system there is no significant difference between the adsorption calculated by the equation of Pethica and that from the procedure of Alexander and Barnes, but analysis by the method of Motomura, et al. gives results which differ considerably. These differences indicate that an independent experimental measurement of the adsorption should be capable of discriminating between the Motomura method and the other two. 

For interpreting thesedata, and as a first step towards formulating a model for monolayer penetration, it is clearly desirable to calculate the amount of surfactant that has penetrated the monolayer. This has proved to be a difficult theoretical problem, but in recent years some limited solutions and a general solution have been found. In this paper we examine data for the penetration of cholesterol monolayers by hexadecy1-trimethyl-ammonium bromide (CTAB) (7) and compare the penetration or adsorption values calculated from the different treatments. 

Numerical data are available from our earlier penetration work for a number of monolayer/surfactant systems. The simplest of these systems was selected for this initial analysis the penetration of cholesterol monolayers by hexadecyl-trimethyl-ammonium bromide (CTAB) J). Cholesterol monolayers at 298 K exhibit a single, highly incompressible, condensed phase with the transition to a gaseous phase occurring at a negligibly low surface pressure. CTAB does not appear to undergo surface hydrolysis (10) and the gaseous-to-expanded phase transition occurs at a low concentration (0.043 mmol kg ) and a low surface pressure (1.0 mN m l). 

Investigation of thermodynamic behavior of monolayers formed from mixtures of bis[2-(n-hexadecanoyl)ethyl]methyl(4-vinylbenzyl) ammonium chloride (1) and dioctadecyl-dimethylammonium bromide (5) serves as the second example [116]. The determined surface-pressure/surface-area isotherms of mono-layers prepared from (1) and (5) and from their mixtures are given in Fig. 8. The isotherms showed the expected behavior following the liquid state there was a transition to the solid state in the region of 20-36 mNm 1. This transition was characterized by a pressure, and by a corresponding area, Aj. All isotherms intersected in the vicinity of 30 mNm-1 and, at surface-pressure/surface-area... 

Mixed monolayers of PVPC6 poly-(2-methyl-5-vinyl-hexylpyridinium bromide) and L phosphalidyl inositol monophosphate, were studied as model of complex membranes. 

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