Interaction of octaethylene glycol n-dodecyl monoether with dioctadecyldimethylammonium bromide and chloride vesicles

Several different methods were used to investigate the vesicle-to-micelle transition induced by the addition of the nonionic surfactant octaethylene glycol n-dodecyl monoether (C12E8) to spontaneously formed vesicle dispersions of dioctadecyldimethylammonium bromide and chloride (DODAX, X = Cl- and Br-). Dynamic light scattering reveals that fast mode micelles are formed upon addition of C12E6. The micellar mode becomes progressively dominant as the C12E8/DODAX molar ratio (R) is increased until the vesicle-to-micelle transition is complete. Turbidity, calorimetry, fluorescence quantum yield, and anisotropy measurements indicate two critical compositions: the first, R-sat, when the vesicle bilayer is saturated with C12E8 and the second, R-sol, which corresponds to the complete vesicle-to-micelle transition. Below R-sat the vesicles swell due to incorporation of the surfactant into the vesicle bilayer, and above R-sat mixed micelles and bilayer structures coexist, the determined R-sat and R-sol range from 0 to 1 and 4 to 6, respectively, depending on the surfactant counterion and the experimental method used. Cryo-transmission electron microscopy micrographs show that when R approximate to 4, micelles coexist with extended bilayer fragments. In pure DODAX (1.0 mM) dispersions, unilamellar vesicles are observed. According to the DSC results, C12E8 lowers the gel-to-liquid crystalline transition temperature, T-m, of DODAX and broadens the main transition peak which disappears around R approximate to 5 and 6 for DODAC and DODAB, respectively.

Vesicle-to-micelle transition in dioctadecyldimethylammonium bromide and dioctadecyldimethylammonium chloride dispersions induced by octaethylene glycol n-dodecyl monoether. An isothermal titration calorimetry study

We have used isothermal titration calorimetry to investigate the vesicle-to-micelle transition in dioctadecyldimethylammonium bromide (DODAB) and chloride (DODAC) vesicle dispersions induced by the nonionic surfactant octaethylene glycol n-dodecyl monoether (C12E8) at room temperature. Small and giant unilamellar vesicles were prepared by sonication and without sonication, respectively, of the pure cationic surfactants at low concentrations in water. The titration of 1.0 mM DODAX (X = Cl- and Br-) by a concentrated micellar solution of C12E8 shows that the enthalpy of interaction (DeltaH(obs)) of C12E8 in micellar form with DODAX is always endothermic. The titration curves are understood on the basis of superposition of the enthalpies of partitioning of C12E8 into the bilayer, of micelle formation and of vesicle-to-micelle transformation. The enthalpy, DeltaH(obs), initially increases owing to the incorporation of C12E8 into the vesicle bilayer until the C12E8/DODAX saturation ratio (R-sat) is reached, then DeltaH(obs) decreases, in different ways for DODAB and DODAC, owing to degradation of vesicles and formation of mixed micelles and intermediary structures up to the C12E8/DODAX solubilization ratio, R-sol. Above R-sol only mixed micelles exist. The surfactant solubilization takes place in three stages. All the critical ratios are lower for DODAB than for DODAC, meaning that C12E8 solubilizes more strongly in DODAB for example, R-sat is 0.8 for DODAB and 1.2 for DODAC. Sonication has no significant effect on the transition.

Structural and thermal characterization of dioctadecyldimethylammonium bromide dispersions by spin labels

Dioctadecyldimethylammonium bromide (DODAB) dispersions obtained by simply mixing the amphiphile in water, and by bath-sonication, were investigated by electron spin resonance (ESR) of stearic acids and their methyl ester derivatives, labeled at the 5th and 16th carbons of the acyl chain. The ESR spectra indicate that the non-sonicated dispersions are formed mainly by one population of DODAB vesicles, either in the gel (T < T-m) or in the liquid-crystalline (T > T-m) state. Around T-m there is a co-existence of the two phases, with a thermal hysteresis of about 3.2 degreesC. In sonicated DODAB dispersions, spin labels indicate two different environments even for temperatures far below T-m: one similar to that obtained with non-sonicated samples, a gel phase, and another one in the liquid-crystalline state. The fluid phase domain present below T-m could correspond to either the periphery of bilayer fragments, reported to be present in sonicated DODAB dispersions, or to high curvature vesicles. (C) 2001 Elsevier B.V. Ireland Ltd. All rights reserved.

Phase transition in dioctadecyldimethylammonium bromide and chloride vesicles prepared by different methods

The gel to liquid crystalline phase transition of the double-chained cationic dioctadecyldimethylammonium chloride and bromide (DODAX, X = Cl- or Br-) in aqueous vesicle dispersions prepared by non-sonication, sonication and extrusion has been investigated using high-sensitivity differential scanning calorimetry (DSC). The transition temperature (T-m) is a function of the preparation method, amphiphile concentration, vesicle curvature and nature of the counterion. DSC thermograms for DODAB and DODAC non-sonicated vesicle dispersions exhibit a single endothermic peak at T-m roughly independent of concentration up to 10 mM. Extrusion broadens the transition peak and shifts T-m downwards. Sonication, however, broadens slightly the transition peak and tends to shift T-m upwards suggesting that extrusion and sonication form vesicles with different characteristics. DODAC always exhibits higher T-m than DODAB irrespective of the preparation method. T-m changes as follows: T-m (sonicated) greater than or equal to T-m (non-sonicated) > T-m (extruded). Hysteresis of about 7 degrees C was observed for DODAB vesicle dispersions. (C) 2000 Elsevier B.V. Ireland Ltd. All rights reserved.

The effect of ionic strength on the structural organization of dioctadecyldimethylammonium bromide in aqueous solution

High-curvature and stabilized vesicles of dioctadecyldimethylammonium bromide (DODABr) can be formed spontaneously in aqueous electrolytic solution. It is shown by cryo-transmission electron microscopy that 5.0 mM DODABr molecules associate in water at a temperature above its gel-to-liquid-crystalline phase transition temperature (T(m)approximate to45 degreesC) in a variety of complex bilayer structures. However, in the presence of NaCl the preferred structures formed are unilamellar and bilamellar vesicles with high curvature and the dispersion is polydisperse in size and geometry, but the main vesicle population contains spherical, flattened and smoothed structures. It is, however, less polydisperse than the corresponding salt-free dispersion, and the size polydispersity and the vesicle curvature radius tend to decrease with NaCl concentration. Long cylindrical bilamellar vesicles, with a very thin water layer separating the bilayers are also formed in the presence of 10 mM NaCl. The effect of the ionic strength on T-m, obtained by differential scanning calorimetry, is shown to depend on the nature of the counterion: Br- decreases, whereas Cl- increases Tm of DODABr, indicating different affinity of these counterions for the vesicle surfaces.

Extruded vesicles of dioctadecyldimethylammonium bromide and chloride investigated by light scattering and cryogenic transmission electron microscopy

Combined dynamic and static light scattering (DLS, SLS) and cryogenic transmission electron microscopy (cryo-TEM) were used to investigate extruded cationic vesicles of dioctadecyldimethylammonium chloride and bromide (DODAX, X being Cl- or Br-). In salt-free dispersions the mean hydrodynamic diameter, D-h, and the weight average molecular weight, M-w, are larger for DODAB than for DODAC vesicles, and both D-h and M-w increase with the diameter (phi) of the extrusion filter. NaCl (NaBr) decreases (increases) the DODAB (DODAC) vesicle size, reflecting the general trend of DODAB to assemble as larger vesicles than DODAC. The polydispersity index is lower than 0.25, indicating the dispersions are rather polydisperse. Cryo-TEM micrographs show that the smaller vesicles are spherical while the larger ones are oblong or faceted, and the vesicle samples are fairly polydisperse in size and morphology. They also indicate that the vesicle size increases with phi and DODAB assembles as larger vesicles than DODAC. Lens-shaped vesicles were observed in the extruded preparations. Both light scattering and cryo-TEM indicate that the vesicle size is larger or smaller than phi when phi is smaller or larger than the optimal phi* approximate to 200 nm. (C) 2008 Elsevier B.V. All rights reserved.

Interaction between Pluronic F127 and Dioctadecyldimethylammonium Bromide (DODAB) Vesicles Studied by Differential Scanning Calorimetry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermotropic phase behavior in aqueous mixtures of dioctadecyldimethylammonium bromide and alkyltrimethylammonium bromide surfactant series studied by differential scanning calorimetry

The effect of the micelle-forming surfactant series alkyltrimethylammonium bromide (C(n)TAB, n = 12, 14, 16 and 18) on the thermotropic phase behavior of dioctadecyldimethylammonium bromide (DODAB) vesicles in water was investigated by differential scanning calorimetry at constant 5.0 mM total surfactant concentration and varying individual surfactant concentrations. The pre-, post- and main transition temperatures (T-s, T-p and T-m), melting enthalpy (Delta H) and peak width of the main transition (Delta T-1/2) are reported as a function of the surfactant molar fraction. No clear dependence of these parameters on the C(n)TAB chain length was found. At 5 mM, neat DODAB in water exhibits two transition temperatures, T-s = 32.1 and T-m = 42.7 degrees C, as obtained from the DSC upscans, but not a clear T-p. For every n, except n = 12, T-s vanishes as CnTAB concentration increases and approaches CMC. T-m behaves differently for different n, the longer C(14)TAB and C(16)TAB decrease, while C(18)TAB increases T-m with increasing concentration. The data indicate that changes in T-m, T-s, T-p and Delta H of the transition are related not only to the extent of C(n)TAB affinity to DODAB but also to the surfactant chain length. Accordingly, C18TAB yields a more compact bilayer, thus increasing T-m, while C(14)TAB and C(1G)TAB yield a less organized bilayer and reduce T-m. C(12)TAB does not much affect T-s and T-m, although it yields T-p approximate to 51.6 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

Aggregation behavior of aqueous dioctadecyldimethylammonium bromide/monoolein mixtures: A multitechnique investigation on the composition and temperature

A recently described non-viral gene delivery system [dioctadecyldimethylammonium bromide (DODAB)/monoolein (MO)] has been studied in detail to improve knowledge on the interactions between lamellar (DODAB) and non-lamellar-forming (MO) lipids, as a means to enhance their final cell transfection efficiency. Indeed, the morphology, fluidity, and size of these cationic surfactant/neutral lipid mixtures play an important role in the ability of these systems to complex nucleic acids. The different techniques used in this work, namely dynamic light scattering (DLS), fluorescence spectroscopy, differential scanning calorimetry (DSC), cryogenic transmission electron microscopy (cryo-TEM), light microscopy (LM), and surface pressure-area isotherms, allowed fully characterization of the phase behavior and aggregate morphology of DODAB/MO mixtures at different molar ratios. Overall, the results indicate that the final morphology of DODAB/MO aggregates depends on the balance between the tendency of DODAB to form zero-curvature bilayer structures and the propensity of MO to form non-bilayer structures with negative curvature. These results also show that in the MO-rich region, an increase in temperature has a similar effect on aggregate morphology as an increase in MO concentration. (C) 2012 Elsevier B.V. All rights reserved.

Thermal and Structural Behavior of Dioctadecyldimethylammonium Bromide Dispersions Studied by Differential Scanning Calorimetry and X-Ray Scattering

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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.

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.

Dioctadecyldimethylammonium:Monoolein Nanocarriers for Efficient in Vitro Gene Silencing

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