RESUMEN
We have developed oleic acid-based partially fluorinated gemini surfactants with carboxylic acid headgroups. The fluorocarbon chain is covalently bound to the terminal carbonyl group of oleic acid via a -CH(2)CH(2)OCO- unit, and the carboxylic acid headgroups are introduced to the cis double bond of oleic acid via -OCOCH(2)CH(2)- units. The aqueous solution properties of these surfactants were studied at pH 9 in the presence of 10 mmol dm3 NaCl by means of static surface tension, pyrene fluorescence, and dynamic light scattering measurements. The resulting surface tension data demonstrate that the partially fluorinated gemini surfactants exhibit excellent surface activity in their dilute aqueous solutions. In addition, the surfactants are suggested to form micellar aggregates 24 nm in diameter. We also studied the aqueous temperature-concentration phase diagrams of the partially fluorinated gemini surfactants (disodium salts) on the basis of visual observations (through a crossed polarizer), polarized optical microscopy, and small angle X-ray scattering measurements. Several phase states including micellar solution phase, hexagonal phase, bicontinuous cubic phase, and lamellar phase were observed along with the coexistence of these phases in certain regions. Assemblies with lesser positive curvature tend to be formed with increasing surfactant concentration, increasing temperature, and increasing fluorocarbon chain length. A comparison of the phase diagrams of the partially fluorinated and hydrogenated surfactant systems suggests that close molecular packing is inhibited within the assemblies of the partially fluorinated surfactants because of the limited miscibility between the fluorocarbon and hydrocarbon units. To the best of our knowledge, this is the first systematic report focusing on the temperature-concentration phase diagrams of (partially) fluorinated gemini surfactants over a wide range of compositions and temperatures.
Asunto(s)
Calcitriol/análogos & derivados , Fenómenos Químicos , Halogenación , Ácido Oléico/química , Transición de Fase , Tensoactivos/química , Calcitriol/química , Ácidos Carboxílicos/química , Fluorocarburos/química , Concentración de Iones de Hidrógeno , Cristales Líquidos , Micelas , Soluciones , Tensión Superficial , Temperatura , AguaRESUMEN
Anionic gemini surfactants with carboxylic acid headgroups have been synthesized from oleic acid. The hydrocarbon chain is covalently bound to the terminal carbonyl group of oleic acid via an ester bond, and the carboxylic acid headgroups are introduced to the cis double bond of oleic acid via disuccinyl units. The surfactants exhibit pH-dependent protonation-deprotonation behavior in aqueous solutions. In alkaline solutions (pH 9 in the presence of 10 mmol dm(-3) NaCl as the background electrolyte), the surfactants can lower the surface tension as well as form molecular assemblies, even in the region of low surfactant concentrations. Under acidic (pH 3) or neutral (pH 6-7) conditions, the surfactants are intrinsically insoluble in aqueous media and form a monolayer at the air/water interface. In this study, we have investigated physicochemical properties such as the function of the hydrocarbon chain length by means of static surface tension, pyrene fluorescence, dynamic light scattering, surface pressure-area isotherms, and infrared external reflection measurements.