Interfacial concentrations of chloride and bromide and selectivity for ion exchange in vesicles prepared with dioctadecyldimethylammonium halides, lipids, and their mixtures

The local concentrations of chloride, Cl b, and bromide, Br b, in the interface of vesicles prepared with dioctadecyldimethylammonium chloride, DODAC, or bromide, DODAB, dipalmitoylphosphatidylcholine, DPPC, dimyristoylphosphatidylcholine, DMPC, and mixtures of DMPC, DPPC, and DODAC were determined by chemical trapping by analyzing product yields from spontaneous dediazoniation of vesicle-bound 2,6-dimethyl-4-hexadecylbenzenediazonium ion. The values of Cl b and Br b in DODAC and DODAB vesicles increase with vesicle size, in agreement with previous data showing that counterion dissociation decreases with vesicle size. Addition of tetramethylammonium chloride displaces bromide from the DODAB vesicular interface. The value for the selectivity constant for Br/Cl exchange at the DODAB vesicular interface obtained by chemical trapping was ∼2.0, well within values obtained for comparable amphiphiles. In vesicles of DPPC the values of Cl b were very sensitive to the nature of the cation and decreased in the order Ca 2+ > Mg 2+ > Li + > Na + > K + = Cs + = Rb + ≥ +. The effect of the cation becomes more important as temperature increases above the phase transition temperature, T m, of the lipid. The values of Cl b increased sigmoidally with the mol % of DODAC in vesicles prepared with DODAC/lipid mixtures. In sonicated vesicles prepared with DODAC and DMPC (or DPPC), the values of Cl b reach local concentrations measured for the pure amphiphile at 80 mol % DODAC. These results represent the first extensive study of local concentration of ions determined directly by chemical trapping in vesicles prepared with lipids, synthetic ampliiphiles, and their mixtures.

Behavior of bromide in the photoelectrocatalytic process and bromine generation using nanoporous titanium dioxide thin-film electrodes

In this study, the photoelectrocatalytic behavior of bromide and generation of bromine using TiO2 was investigated in the separate anode and cathode reaction chambers. Our results show that the generation of bromine begins around a flatband potential of -0.34 V vs. standard calomel electrode (SCE) at pH 3.0 under UV illumination and increases with an increase in positive potential, finally reaching a steady-state concentration at 1.0 V vs. SCE. Maximum bromine formation occurs over the range of pH 4-6, decreasing sharply at conditions where the pH > 7. © 2003 Elsevier Ltd. All rights reserved.

Reversibility of Thermal Transitions in Dilute Dioctadecyl-Dimethyl-Ammonium Bromide Vesicles

Dioctadecyl-dimethyl-ammonium bromide (DODAB) vesicles can be characterized by their differential scanning calorimetry (DSC) thermograms comprised of two endotherms at T (s) a parts per thousand 36 A degrees C and T (m) a parts per thousand 45 A degrees C in the heating, ascribed respectively to the subgel-to-gel and gel-to-liquid crystalline transitions, and two exotherms at T'(m) a parts per thousand 40 A degrees C and T'(s) a parts per thousand 16 A degrees C in the cooling, ascribed respectively to the liquid crystalline-to-gel and gel-to-subgel transitions. It has been reported but not proved that the T (m)-transitions, the T'(m)-transitions, the T (s)-transitions, and the T'(s)-transitions are reverse to each other, displaying hystheresis Delta T (m) a parts per thousand 5 A degrees C and Delta T (s) a parts per thousand 20-25 A degrees C, respectively. By investigating the effects of the initial scanning temperature (T (i)) on the transition enthalpies (Delta H (m), Delta H (s), Delta H'(m) and Delta H'(s)), we have seen that these transitions are the reverse to each other and display different kinetics.

Preliminary X-ray crystallographic studies of a Lys49-phospholipase A(2) homologue from Bothrops pirajai venom complexed with p-bromophenacyl bromide and alpha-tocopherol inhibitors

PrTX-I, a non-catalytic and myotoxic Lys49-PLA(2) from Bothrops pirajai venom has been crystallized alone and in complex with bromophenacyl bromide (BPB), alpha-tocopherol and alpha-tocopherol acetate inhibitors. These crystals have shown to diffract X-rays between 2.34 and 1.65 angstrom resolution. All complexes crystals are isomorphous and belong to the space group P2(1) whereas native PrTX-I crystals belong to the P3(1)21.

Effect of hexadecyltrimethylammonium bromide-based microemulsions on the rate of decomposition of the beta-lactam antibiotic cephaclor

Microemulsions of hexadecyltrimethylammonium bromide (HTAB)/n-butanol/hexadecane/water catalyze the intramolecular degradation of cephaclor. The rate increase is a sensitive function of the microemulsion volume fraction and salt concentration. The effects of microemulsions, analyzed quantitatively using a pseudophase ion-exchange model, assumed that the extent of ion dissociation from the microemulsions varies with volume fraction. Comparison of micellar and microemulsion effects on the same reaction shows that microemulsions are less effective catalysts. Acceleration decreased significantly by increasing the relative proportion of n-butanol ratio in microemulsions and by addition of n-butanol in HTAB micelles. Comparison of the activation parameters of the reaction in aqueous solution, microemulsions, and micelles suggests that catalysis by both aggregates is driven mainly by entropic contributions.

Thallium Bromide Deposited Using Spray Coating

Spray coating was used to produce thallium bromide samples on glass substrates. The influence of several fabrication parameters on the final structural properties of the samples was investigated. Substrate position, substrate temperature, solution concentration, carrying gas, and solution flow were varied systematically, the physical deposition mechanism involved in each case being discussed. Total deposition time of about 3.5 h can lead to 62-mu m-thick films, comprising completely packed micrometer-sized crystalline grains. X-ray diffraction and scanning electron microscopy were used to characterize the samples. On the basis of the experimental data, the optimum fabrication conditions were identified. The technique offers an alternative method for fast, cheap fabrication of large-area devices for the detection of high-energy radiation, i.e., X-rays and gamma-rays, in medical imaging.

Interfacial concentrations of chloride and bromide in zwitterionic micelles with opposite dipoles: Experimental determination by chemical trapping and a theoretical description

Interfacial concentrations of chloride and bromide ions, with Li+, Na+, K+, Rb+, Cs+, trimethylammonium (TMA(+)), Ca2+, and Mg2+ as counterions, were determined by chemical trapping in micelles formed by two zwitterionic surfactants, namely N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and hexadecylphosphorylcholine (HDPC) micelles. Appropriate standard curves for the chemical trapping method were obtained by measuring the product yields of chloride and bromide salts with 2,4,6-trimethyl-benzenediazonium (BF4) in the presence of low molecular analogs (N,N,N-trimethyl-propane sulfonate and methyl-phosphorylcholine) of the employed surfactants. The experimentally determined values for the local Br- (Cl-) concentrations were modeled by fully integrated non-linear Poisson Boltzmann equations. The best fits to all experimental data were obtained by considering that ions at the interface are not fixed at an adsorption site but are free to move in the interfacial plane. In addition, the calculation of ion distribution allowed the estimation of the degree of ion coverage by using standard chemical potential differences accounting for ion specificity. (C) 2012 Elsevier Inc. All rights reserved.

Self-Assembly of Poly(4-vynil-N-alkylpyridinium) Bromide onto Silica: Effect of Side-Chain Length on Structural Aspects at a Molecular Level

Self-assembly of poly(4-vynil-N-alkyl)pyridinium bromide with alkyl side chains of 2, 5, 7, 10, or 16 carbons from ethanolic solutions onto flat silica surfaces was studied by means of ellipsometry, atomic force microscopy (AFM), contact angle measurements, and sum-frequency generation (SFG) vibrational spectroscopy in the CH3 and CH2 stretch region. Ab initio quantum-chemical calculations on the N-alkylpyridinium side-group with restricted Hartree-Fock (RHF) method and 6-311G (d,p) basis set were C one to estimate the charge distribution along the pyridinium ring and the alkyl side-chain. SFG results showed that longer side chains promote the disorientation of the alkyl groups at the surface, corroborating with the contact angle values. AFM images revealed film homogeneity, regardless the alkyl side group. However, after 24 h contact with water, ringlike structures appeared on the film surfaces, when the polycation alkyl side chain had 7 or less carbons, and as the alkyl chain increased to 10 or 16 carbons, the films dewetted because the hydrophobic interactions prevailed over the electrostatic interactions between the pyridinium charged groups and the negatively charged SiO2 surface. Under acid conditions (HCl 0.1 mol.L-1), the film mean thickness values decreased up to 50% of original values when the alkyl side chains were ethyl or pentyl groups due to ion-pair disruption, but for longer groups they remained unchanged. Quantum-chemical optimization and Mulliken electron population showed that (i) from C2 to C15 the positive charge at the headgroup (HG) decreased 0.025, while the charge at combined HG + alpha-CH2 increased 0.037; and (ii) for C6 or longer, the alkyl side group presents a tilt in the geometry, moving away from the plane. Such effects summed up over the whole polymer chain give support to suggest that when the side chains are longer than 7 carbons, the hydrophobic interaction decreases film stability and increases acid resistance.

Cloride and bromide concentrations and Br-/Cl- molar ratios in pore fluids at ODP Site 134-833

Other than halite diagenesis and organic matter degradation, Cl- and Br- are considered to be conservative in marine pore fluids. Consequently, Br-/Cl- ratios should remain constant during most diagenetic reactions. Nonetheless, Br-/Cl- molar ratios decrease to 0.00127 (~18% less than seawater value) in pore fluids from Site 833 in the Aoba Basin of the New Hebrides convergent margin despite the lack of halite diagenesis and little organic matter. Sediment at this site is largely volcanic ash, which becomes hydrated with depth as it converts to clay and zeolite minerals. These hydration reactions remove sufficient water to increase the concentrations of most solutes including Cl- and Br-. The resulting concentration gradients drive diffusion, but calculations indicate that diffusion does not decrease the Br-/Cl- ratio. Some Cl- may be leached from the ash, but insufficient amounts are available to cause the observed decrease in Br-/Cl- ratio. The limited source of Cl- suggests that proportionately more Br- than Cl- is lost from the fluids to the diagenetic solids. Similar nonconservative behavior of Cl- and Br- may occur during fluid circulation at ridge crests and flanks, thereby influencing the halide distribution in the crust.