Unilamellar vesicles obtained by simply mixing dioctadecyldimethylammonium chloride and bromide with water

Optically clear dispersions of dioctadecyldimethylammonium bromide and chloride (DODAX, X = Br-, Cl-) in water can be obtained by simply mixing the amphiphiles at low concentrations (I mM) and at a temperature safely above the gel to liquid crystalline phase transition temperature (T-m approximate to 45-48 degrees C) of DODAX in water. Under these conditions, dynamic light scattering shows that, at room temperature, the dispersions contain two well-defined populations of large vesicles with average hydrodynamic radii (RH) of 80 and 337 nm for DODAB and of 69 and 247 nm for DODAC. Cryo-transmission electron microscopy (cryo-TEM) micrographs show that DODAX vesicles are unilamellar and polydisperse with apparent radius up to 800 nm. The vesicles are stable for at least I month according to the ageing time-dependence of the turbidity and molar absorption coefficient. (c) 2006 Elsevier B.V.. All rights reserved.

Salt-induced sphere-to-disk transition of octadecyltrimethylammonium bromide micelles

We have used surface tension measurements, differential scanning calorimetry (DSC), dynamic light scattering (DLS), and cryo-transmission electron microscopy (cryo-TEM) to investigate the dynamic and structural behavior of octadecyltrimethylammonium bromide (C(18)TAB) micelles in water and NaBr solution. The surface tension data for fixed C(18)TAB concentrations of 25 mM and varied NaBr additions (0-50 mM) shows that the critical micelle concentration (cmc) increases after an initial decrease at 0.5 mM NaBr. This unusual effect has been explained using results from DSC and DLS. At low salt concentrations (below ca. 25 mM) the relaxation time distribution is bimodal with a dominant fast mode due to spherical micelles. Above ca. 35 mM NaBr disklike structures are favored and the relaxation time distribution is more closely unimodal. The postulated sphere-to-disk transition is supported by cryo-TEM micrographs. A pronounced increase in the micellar effective hydrodynamic radius (R-H) is observed as the NaBr concentration is increased above about 35 mM; below 35 mM the R-H of the spherical micelles changes Little with ionic strength.

Cationic liposomes in mixed didodecyldimethylammonium bromide and dioctadecyldimethylammonium bromide aqueous dispersions studied by differential scanning calorimetry, nile red fluorescence, and turbidity

The thermotropic phase behavior of cationic liposomes in mixtures of two of the most investigated liposome-forming double-chain lipids, dioctadecyldimethylammonium bromide (DODAB) and didodecyldimethylammonium bromide (DDAB), was investigated by differential scanning calorimetry (DSC), turbidity, and Nile Red fluorescence. The dispersions were investigated at 1.0 mM total surfactant concentration and varying DODAB and DDAB concentrations. The gel to liquid-crystalline phase transition temperatures (T-m) of neat DDAB and DODAB in aqueous dispersions are around 16 and 43 degrees C, respectively, and we aim to investigate the T-m behavior for mixtures of these cationic lipids. Overall, DDAB reduces the T-m of DODAB, the transition temperature depending on the DDAB content, but the T-m of DDAB is roughly independent of the DODAB concentration. Both DSC and fluorescence measurements show that, within the mixture, at room temperature (ca. 22 degrees C), the DDAB-rich liposomes are in the liquid-crystalline state, whereas the DODAB-rich liposomes are in the gel state. DSC results point to a higher affinity of DDAB for DODAB liposomes than the reverse, resulting in two populations of mixed DDAB/DODAB liposomes with distinctive phase behavior. Fluorescence measurements also show that the presence of a small amount of DODAB in DDAB-rich liposomes causes a pronounced effect in Nile Red emission, due to the increase in liposome size, as inferred from turbidity results.

Dioctadecyldimethylammonium bromide vesicles prepared by the surfactant removal method

Dioctadecyldimethylammonium bromide (DODAB) is a double chain vesicle-forming cationic surfactant, whereas octa-ethyleneglycol mono-n-dodecyl ether (C12E8) is a single chain micelle-forming nonionic surfactant. At room temperature (ca. 22 degrees C) C12E8 molecules self-assemble in water as micelles while DODAB is insoluble. A mixture of DODAB and C12E8, however, can be soluble in water at room temperature depending on the relative amount of the compounds. We report the formation of small unilamellar vesicles (SUVs) by dialyzing at room temperature a mixture of 1.0 mM DODAB with 10 mM C12E8 in water. Extended bilayers are formed as well in equilibrium with vesicles. Such structures are viewed by a cryogenic transmission electron microscopy (cryo-TEM) image. (c) 2006 Elsevier B.V. All rights reserved.

Fragment and vesicle structures in sonicated dispersions of dioctadecyldimethylammonium bromide

Dynamic light scattering has been used to investigate sonicated aqueous dispersions of dioctadecyldimethylammonium bromide (DODAB). The hydrodynamic radius (R-H) of the scattering particles and the mean scattering intensity (I) have been monitored as functions of the DODAB concentration and temperature (T). In the dilute regime, the relaxation time distribution of the sonicated dispersion of DODAB is bimodal with the slow mode dominating the distribution. The slow and fast modes are respectively characteristic of vesicles and bilayer fragments with R-H values of 22 and 8.5 nm (25 degrees C) and 20 and 6 nm (50 degrees C), respectively. The total scattered intensity initially decreased with temperature up to 45 degrees C (T-c), above which it was constant; identical behavior was observed for the slow mode intensity, but the fast mode intensity was constant with temperature change, showing that T-c is a property of the vesicles and not of the bilayer fragments. At T-c the slow vesicle mode becomes narrower whereas the fast fragment mode shows no change. on aging, the dispersion showed a slow transition from bimodal to a rather broad single-modal relaxation time distribution. The corresponding R-H was 33.8 nm when measured 10 months after preparation. These results suggest that aqueous sonicated dispersions of DODAB are metastable.

Analysis of the ethidium bromide bound to DNA by photoacoustic and FTIR spectroscopy

Under physiological conditions B-form DNA is an exceedingly stable structure. However, experimental evidences obtained through nuclear magnetic resonance and fluorescence anisotropy suggest that the structure of the double helix fluctuates substantially. We describe photoacoustic phase modulation frequency measurements of ethidium bromide (Eb) with calf thymus, DNA. As in fluorescence phase modulation measurements, we used an intercalating dye as a probe; however, we monitored the triplet excited state lifetime at different ionic strengths. The triplet lifetime of Eb varied from about 0.30 ms, with no DNA present, to 20 ms, (at a DNA:Eb molar ratio of 5). With salt titration, this value falls, to about 2.0 ms. This result suggests, a strong coupling between the phenantridinium ring of the ethidium and the base pairs because of the stacking movement of the DNA molecule under salt effect. This, effect may be understood considering DNA as a polyelectrolyte. The counterions, in the solution shield the phosphate groups, reducing the electrostatic repulsion force between them, hence compacting the DNA molecule. The results from Fourier transform infrared demonstrated two important bands: 3187 cm(-1) corresponding to the symmetric stretching of the NH group of the bases, and 1225 cm(-1) corresponding to the asymmetric stretching of phosphate groups shifted toward higher wavenumbers, suggesting a proximity between the intercalant and base pairs and a modification of the DNA backbone state, both induced by salt accretion.

A new biophysics approach using photoacoustic spectroscopy to study the DNA-ethidium bromide interaction

We have examined the binding processes of ethidium bromide interacting with calf thymus DNA using photoacoustic spectroscopy. These binding processes are generally investigated by a combination of absorption or fluorescence spectroscopies with hydrodynamic techniques. The employment of photoacoustic spectroscopy for the DNA-ethidium bromide system identified two binding manners for the dye. The presence of two isosbestic points (522 and 498 nm) during DNA titration was evidence of these binding modes. Analysis of the photoacoustic amplitude signal data was performed using the McGhee-von Hippel excluded site model. The binding constant obtained was 3.4 x 10(8) M(bp)(-1), and the number of base pairs excluded to another dye molecule by each bound dye molecule (n) was 2. A DNA drug dissociation process was applied using sodium dodecyl sulfate to elucidate the existence of a second and weaker binding mode. The dissociation constant determined was 0.43 mM, whose inverse value was less than the previously obtained binding constant, demonstrating the existence of the weaker binding mode. The calculated binding constant was adjusted by considering the dissociation constant and its new value was 1.2 x 10(9) M(bp)(-1) and the number of excluded sites was 2.6. Using the photoacoustic technique it is also possible to obtain results regarding the dependence of the quantum yield of the dye on its binding mode. While intercalated between two adjacent base pairs the quantum yield found was 0.87 and when associated with an external site it was 0.04. These results reinforce the presence of these two binding processes and show that photoacoustic spectroscopy is more extensive than commonly applied spectroscopies.

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.