Urea induces (unexpected) formation of lamellar gel-phase in low concentration of cationic surfactants.

HYPOTHESIS: The unexpected formation of a lamellar structure with concomitant gelation in solutions containing high urea concentration (40 wt%) and relatively low amount of cationic surfactant (3 wt%), indicates that a hierarchically structured complex is formed by both molecules. EXPERIMENTS: Gels formed by combination of aqueous solutions of urea and C12TAB, C14TAB or C16TAB were prepared in different proportions and their structures at microscopic and mesoscopic levels were investigated using XRD and SAXS, respectively. The elastic and viscous moduli and yield stress of the samples were determined and correlated with the composition and structuration of the gels. The lamellar structure is reversibly thermically destroyed and this process was investigated using DSC. FINDINGS: XRD revealed that, at microscopic scale, the gels are formed through crystallization of adducts containing surfactant molecules loaded into the cavities of honeycomb-like urea assemblies. Such crystalline phase arranges itself in lamellae with interplanar distance around ∼20-30 nm, which were observed by SAXS. This hierarchical structure is independent of the chain length of the cationic surfactants. The blocks of lamellae dispersed in the continuous phase form a three-dimensional rigid particulate network structure, giving the characteristic rheological behavior of a hydrogel. DSC revealed a reversible thermal transition at around 20-25 °C, beyond which the adducts and the lamellar phase are destroyed and micelles are formed. The characteristic transition temperature is independent of the chain length of the surfactant, and thus, it is not associated with their Krafft temperatures. The structures of the gels indicate that they resemble alpha-gels formed by fatty-alcohols and surfactants, although they self-assemble by different driving forces.

Safety, Tolerability, and Effects of Sodium Bicarbonate Inhalation in Cystic Fibrosis.

BACKGROUND: Among the many consequences of loss of CFTR protein function, a significant reduction of the secretion of bicarbonate (HCO3-) in cystic fibrosis (CF) is a major pathogenic feature. Loss of HCO3- leads to abnormally low pH and impaired mucus clearance in airways and other exocrine organs, which suggests that NaHCO3 inhalation may be a low-cost, easily accessible therapy for CF. OBJECTIVE: To evaluate the safety, tolerability, and effects of inhaled aerosols of NaHCO3 solutions (4.2% and 8.4%). METHODS: An experimental, prospective, open-label, pilot, clinical study was conducted with 12 CF volunteer participants over 18 years of age with bronchiectasis and pulmonary functions classified as mildly to severely depressed. Sputum rheology, pH, and microbiology were examined as well as spirometry, exercise performance, quality-of-life assessments, dyspnea, blood count, and venous blood gas levels. RESULTS: Sputum pH increased immediately after inhalation of NaHCO3 at each clinical visit and was inversely correlated with rheology when all parameters were evaluated: [G' (elasticity of the mucus) = - 0.241; G″ (viscosity of the mucus) = - 0.287; G* (viscoelasticity of the mucus) = - 0.275]. G* and G' were slightly correlated with peak flow, forced expiratory volume in 1 s (FEV1), and quality of life; G″ was correlated with quality of life; sputum pH was correlated with oxygen consumption (VO2) and vitality score in quality of life. No changes were observed in blood count, venous blood gas, respiratory rate, heart rate, peripheral oxygen saturation of hemoglobin (SpO2), body temperature, or incidence of dyspnea. No adverse events associated with the study were observed. CONCLUSION: Nebulized NaHCO3 inhalation appears to be a safe and well tolerated potential therapeutic agent in the management of CF. Nebulized NaHCO3 inhalation temporarily elevates airway liquid pH and reduces sputum viscosity and viscoelasticity.

A new interpretation of the mechanism of wormlike micelle formation involving a cationic surfactant and salicylate.

HYPOTHESIS: When tetradecyltrimethylammonium bromide, TTAB, is added to aqueous solution of sodium salicylate, NaSal, the threading of the aromatic anion into the micellar palisade leads to the formation of wormlike micelles. Based on the calorimetric titration of NaSal with TTAB, and on the lifetime of fluorescence of salicylate, we propose that the aggregation of the two components directly leads to the formation of wormlike micelles, without any pre-aggregation. EXPERIMENTS: By using an isothermal titration calorimeter, aliquots of TTAB were added to a dilute solution of NaSal. The energy involved in each addition was then integrated and the variation of enthalpy was determined. In the same range of concentrations and molar ratios, the surface tensiometry and time-resolved emission spectroscopy experiments were performed. FINDINGS: A very characteristic calorimetric signal associated with wormlike micelle formation was obtained, being the enthalpy variation of this process, ΔWLMH2980 < 0. When 1.2 mmol L-1 of NaSal is titrated with 11.0 mmol L-1 of TTAB at 298.15 K, ΔfH2980 = -10.31 kJ per mol of injectant. By adding TTAB to NaSal solution, two fluorescence lifetimes of salicylate were observed solely after wormlike micelle being formed. The correspondent lifetime values of 4.0 ns and 7.2 ns are respectively associated with the free and associated species of salicylate. The new results demonstrated that wormlike micelles are the first aggregate formed when TTAB is added to salicylate. This aspect is relevant for understanding the mechanism of wormlike micelles formation.

Rheological and calorimetric study of alkyltrimethylammonium bromide-sodium salicylate wormlike micelles in aqueous binary systems.

HYPOTHESIS: It is known that additives like glycerol and sucrose lead to the swelling of aqueous bilayer Lα phases. The swelling of the Lα phases can be explained by the increase of the refractive index of the mixed solvent, which lowers the van der Waals attraction between the bilayers. Afterwards, the undulation forces between the bilayers can push them apart. This hypothesis was previously extended to wormlike micelles (WLM) of cetyltrimethylammonium bromide (CTAB) and sodium salicylate (NaSal). These types of self-assembly structures have viscoelastic properties, and the zero shear viscosity of these solutions is dependent on the molar ratio NaSal/CTAB, R. At R = 0.6, R = 1.0 and R ≈ 2.6 the viscosity goes, respectively, through a maximum, a minimum and another maximum. These viscosities can be explained by differences in relaxation mechanisms predominant in each region. Similarly to what is observed to bilayer Lα phases, the additives would change the interaction between the WLM, affecting the relaxation processes of each region, altering the profile from two maxima and one minimum to a single maximum in viscosity. In the present manuscript, it is investigated whether it is only the refractive index, other solvent properties, or a combination of several factors that induce these changes in WLM. For this, several additives, forming binary mixtures with water, were studied, through rheology of CTAB/NaSal and calorimetry of tetradecyltrimethylammonium bromide (TTAB)/NaSal. EXPERIMENTS: Herein, we present the zero-shear viscosity diagrams of NaSal and CTAB with glycerol, sucrose, dimethyl sulfoxide, 1,3-butanediol and urea combined with water. Additionally, isothermal titration calorimetry was used to obtain the variations of enthalpy for formation of WLM of TTAB and NaSal in mixtures of water and such additives. FINDINGS: Based on our data, only the refractive index match is not enough to explain the rheological and calorimetric behaviors of the WLM. For instance, sucrose has little effect on the micelles, even at the same refractive index match conditions. Additional characteristics, such as dielectric constant, the cohesivity of the solvent (here symbolized by the Gordon parameter), and the interactions of the additive with the micelles, have to be considered to better describe the results.