Synthesis and aqueous solution properties of novel anionic heterogemini surfactants containing a phosphate headgroup.

The physicochemical properties of aqueous solutions of novel anionic heterogemini surfactants (POH-n-ODAm) have been studied on the basis of static/dynamic surface tension, fluorescence, dynamic light scattering (DLS) and cryogenic transmission electron microscope (cryo-TEM) data. The surfactants are synthesized from oleic acid: the hydrocarbon chain (n=6, 8 and 10) is covalently bound to the terminal carbonyl group and a phosphate headgroup is introduced to the cis double bond of an oleic acid derivative. The static surface tension and fluorescence measurements demonstrate that the critical aggregation concentration (cac) is decreased significantly with increasing hydrocarbon chain length, resulting from the increased hydrophobicity and the increased degree of dissymmetry of the surfactants. As is generally seen for gemini surfactants, the measured cac is much lower than that of the monomeric phosphate-type surfactant reported previously. At concentrations well above the cac, the heterogemini surfactants spontaneously form vesicular assemblies in bulk solution, which is confirmed with DLS and cryo-TEM measurements.

Polymerizable anionic gemini surfactants: physicochemical properties in aqueous solution and polymerization behavior.

A novel polymerizable anionic gemini surfactant has been synthesized and the physicochemical properties in aqueous solution have been studied with a combination of various analytical techniques. The surfactant (PA12-2-12) contains two anionic monomeric parts linked with an ethylene spacer and polymerizable methacryloxy groups covalently bound to the terminal of the hydrocarbon chains. The static surface tension data suggest that, when compared with a conventional (non-polymerizable) anionic gemini surfactant (A12-2-12), (i) the interfacial adsorption of PA12-2-12 occurs more effectively from low surfactant concentrations, whereas (ii) a weak interaction of the polymerizable terminal groups with water molecules (and/or the steric hindrance of the polymerizable groups) plays a significant role in the subsequent molecular packing at the air/aqueous solution interface. The latter effect (as well as the electrostatic repulsion between the anionic headgroups) results in a relatively less packed monolayer film, overcoming the strong intermolecular attractive interaction that is frequently seen for gemini surfactant systems. In the region of low added electrolyte concentrations, PA12-2-12 spontaneously forms spherical micelles in aqueous solution, which is confirmed with the Corrin-Harkins analysis (critical micelle concentration (cmc) vs. total counter-ion concentration) and cryogenic transmission electron microscopy (cryo-TEM). The spherical micelles have been polymerized under UV light irradiation in the absence of added electrolytes. Cryo-TEM measurements confirm that no significant change in the original micelle morphology occurs during the polymerization. This offers a possibility that the polymerizable anionic gemini surfactant should be useful as nano-structural organic templates and/or interfacial stabilizers in aqueous solution.

Polymerized assemblies of cationic gemini surfactants in aqueous solution.

A variety of polymerized assemblies of cationic gemini surfactants has been demonstrated as a function of the electrolyte concentration in aqueous solution. The gemini surfactant consists of two cationic monomeric surfactants linked with an ethylene spacer at the level of the quaternary ammonium groups. Polymerizable methacryloxy groups are covalently attached to the terminal of the hydrocarbon chains. In the lower electrolyte concentration region, radical polymerization results in the formation of spherical aggregates [Langmuir 22 (2006) 8293]. However, in the higher electrolyte concentration region, elongated tubular hollow assemblies are observed with transmission electron microscopy, as a result of polymerization of vesicular hollow assemblies spontaneously formed in the aqueous solution. These experimental results suggest that it is possible to prepare different shapes of polymerized assemblies by changing the electrolyte concentration.

Polymerizable cationic gemini surfactant.

A polymerizable cationic gemini surfactant, [CH(2)=C(CH(3))COO(CH(2))(11)N(+)CH(3))(2)CH(2)](2).2Br(-), 1 has been synthesized and its basic interfacial properties were investigated (in water and in the presence of 0.05 M NaBr). For comparison, the properties of monomeric surfactant corresponding to 1, CH(2)=C(CH(3))COO(CH(2))(11)N(+)(CH(3))(3).Br(-), 2, were also investigated. Parameters studied include cmc (critical micelle concentration), C(20) (required to reduce the surface tension of the solvent by 20 mN/m), gamma(cmc) (the surface tension at the cmc), Gamma(cmc) (the maximum surface excess concentration at the air/water interface), A(min) (the minimum area per surfactant molecule at the air/water interface), and cmc/C(20) ratio (a measure of the tendency to form micelles relative to adsorb at the air/water interface). For the polymerizable gemini surfactant, 1, the methacryloxy groups at the terminal of each hydrophobic group in a molecule have no contact with the air/water interface in the monolayer, whereas for the corresponding monomeric surfactant, 2, the methacryloxy group contacts at the interface forming a looped configuration like a bolaamphiphile. Polymerized micelles of the gemini surfactant are fairly small monodisperse and spherical particles with a mean diameter of 3 nm.

The interaction of an anionic gemini surfactant with conventional anionic surfactants.

The interaction in two mixtures of an anionic gemini surfactant having N ,N -dialkylamide and carboxylate groups in a molecule, (CH2)2[N(COC11H23)CH(CO2H)CH2(CO2H)]2. 2NaOH (GA), and conventional anionic surfactants have been investigated in 0.1 M NaCl at pH 5.0. The two mixtures are GA/sodium dodecylsulfate (SDS) and GA/sodium N -dodecanoylglutamate (AGS) at a molar fraction of GA, alphaGA = 0.25 . Mixtures of both GA/SDS and GA/AGS exhibit synergism in surface tension reduction effectiveness. The GA/SDS mixture also exhibits synergism in surface tension reduction efficiency and mixed micelle formation, whereas the GA/AGS mixture does not. The interaction in mixed adsorption film formation is stronger than that in mixed micelle formation for the two mixtures. The interaction in the formation of the mixed adsorption film and the mixed micelle for the GA/SDS mixture is stronger in both formations than that for the GA/AGS mixture. The stronger interaction for the GA/SDS mixture may be caused by the combination of the smaller minimum area per molecule at the air/water interface (Amin) of the head groups in the GA molecule and the larger Amin in the SDS molecule.

Structural effects on surface and micellar properties of alkanediyl-alpha, omega-bis(sodium N-acyl-beta-alaninate) gemini surfactants.

A study of the equilibrium surface properties (in water and in the presence of 0.01 M NaCl) of a novel series of anionic gemini surfactants, alkanediyl-alpha,omega-bis(sodium N-acyl-beta-alaninates), is described. Parameters studied include cmc (critical micelle concentration), C20 (required to reduce the surface tension of the solvent by 20 mN/m), gamma(cmc) (the surface tension at the cmc), Gamma(max) (the maximum surface excess concentration at the air/aqueous solution interface), Amin (the minimum area per surfactant molecule at the air/water interface), and the cmc/C20 ratio (a measure of the tendency to form micelles relative to adsorb at the air/water interface). The geminis with a spacer consisting of two methylene groups show premicellar self-aggregation, both in water and in 0.01 M NaCl, when the N-acyl group contains more than 12 carbon atoms; geminis with a spacer consisting of four methylene groups show no premicellar aggregation even when the N-acyl group contains 16 carbon atoms. For the acyl chain lengths where premicellar aggregation does not occur, the values of the cmc of the geminis with a two-methylene spacer are lower than those for the corresponding analogous geminis with a four-methylene spacer. The premicellar formation for the geminis with a two-methylene spacer is due to the short-chain linkage. The geminis show little or no break in their specific conductance-surfactant molar concentration plots and an increase in the pH at the cmc. This is attributed to protonation of the carboxylate group and strong Na+ release during micellization.