Fredric M. Menger

Re-evaluating the Gibbs analysis of surface tension at the air/water interface.

Molecular areas of soluble films at the air/water interface have traditionally been calculated by applying the Gibbs equation to the steep linear decline in surface tension as the bulk concentration increases. This approach presupposes that the interface is saturated in the Gibbs region, thereby allowing a single unique area to be calculated. We show that the areas derived by the Gibbs equation (typically 50-60 A(2)/molecule) are much too large to account for the abrupt surface tension decline. Moreover, a surface tension/concentration plot was observed for a system where micelle formation does not interfere with the Gibbs region. Nonetheless, the surface tension plot leveled off, ostensibly owing to saturation, when the Gibbs approach predicted a continued linear decline, proving that the interface in the Gibbs region is not saturated as generally assumed. This conclusion means that the hundreds of published molecular areas obtained by the Gibbs approach should be reconsidered.

Additional Support for a Revised Gibbs Analysis

Gibbs-determined areas of >60 A(2)/molecule for many common surfactants cause rather small surface tension reductions when measured on a Langmuir film balance. This is inconsistent with an air/water interface being saturated throughout the steep linear decline in plots of surface tension versus ln [surfactant]. In support for a gradually populating interface in the linear region, we have found that sodium docosanyl sulfate lowers the surface tension by only 7 mN/m when compressed to 50 A(2)/molecule. When docosanyltrimethylmmonium bromide is compressed to 65 A(2)/molecule, the surface tension is lowered about 15 mN/m as compared to a 30-40 mN/m drop occurring within the range of typical Gibbs analysis. Saturation of the interface is often obscured by competitive micelle formation that levels the surface tension versus ln [surfactant] plot before saturation has a chance to do so.

Electrostatic Binding among Equilibrating 2-D and 3-D Self-Assemblies

Six organic additives, each bearing a different number of anionic charges, were added to a large excess of cationic surfactant (dodecyltrimethylammonium bromide, DTAB). The surface-tension vs log [DTAB] plot for solutions containing DTAB/trianion = 15:1 showed an abrupt break (routinely taken as the critical micelle concentration, CMC) at 2.9 mM. This constitutes a 5-fold decrease compared with a CMC of 15 mM for pure aqueous DTAB. There is a 10-fold decrease in the break-point concentration caused by a mere 3 mol % of hexanion. Corresponding CMC values from DTAB/trianion mixtures, measured by both conductivity and diffusion NMR, gave normal values of 14 mM. The unusual discrepancy between the CMC based on surface tension and on the two bulk methods was attributed to saturation of the air/water interface by a DTAB/trianion complex far below the concentration at which the micelles form. Thus, the sharp break seen in surface-tension CMC plots need not in fact attest to actual micelle formation as is almost universally assumed in colloid chemistry.

Biomembrane sensitivity to structural changes in bound polymers.

Anionic liposomes containing a 4:1 molar ratio of neutral to anionic phospholipids were treated with an excess of five zwitterionic polymers differing only in the spacer length separating their cationic and anionic moieties. Although the polymers do not disrupt the structural integrity of the liposomes, they can induce spacer-dependent molecular rearrangements within the liposomes. Thus, the following were observed: spacer length = 1, no binding to the liposomes; spacer length = 2, adsorption to the liposomes, but no molecular rearrangement; spacer length = 3, lateral lipid segregation but little or no flip-flop; spacer length = 4 or 5, lateral lipid segregation and flip-flop. These diverse behaviors are relevant to the use of biomedical formulations where polyelectrolytes play a role.

Self-assembling systems: mining a rich vein.

This paper summarizes a few of the self-assembling systems investigated in the authors laboratory over the years. These include systems that mimic an enzyme, solubilize drugs, release encapsulated guests, assemble via hydrophobic surfaces, exhibit hysteresis in films, link cancer cells to vesicles, and destroy toxic compounds. Although the amphiphilic molecules are all rather different, one overriding theme predominates: just as the properties of molecules are not simple extrapolations from atoms, properties of self-assemblies are not simple extrapolations from molecules. Groups of molecules, properly assembled, can accomplish much more than an equal number of molecules functioning separately.

Self-assembly of cationic surfactants that contain thioether groups in the hydrophobic tails.

Self-assembly in aqueous solutions of cationic surfactants that carry thioether groups in their hydrophobic tails has been investigated. Of particular interest was the identification of possible changes in the aggregate structure due to the presence of sulfur atoms. Solutions of four different compounds [CH(3)CH(2)S(CH(2))(10)N(CH(3))(3)(+)Br(-) (2-10), CH(3)(CH(2))(5)S(CH(2))(6)N(CH(3))(3)(+)Br(-) (6-6), CH(3)(CH(2))(7)S(CH(2))(6)N(CH(3))(3)(+)Br(-) (8-6), and CH(3)(CH(2))(7)S(CH(2))(8)N(CH(3))(3)(+)Br(-) (8-8)] were characterized by (1)H NMR, (13)C NMR, NMR diffusometry, and conductivity measurements. In addition to investigating aqueous solutions containing each of the thioethers present as the sole solute, mixtures of 2-10 or 6-6 with dodecyltrimethylammonium bromide (DTAB) were studied. The addition of a sulfide group to the hydrophobic tail causes an increase in the critical micelle concentration but has a limited effect on the aggregate structure. Micelles are formed at a well-defined concentration for all of the investigated surfactants and surfactant mixtures. However, a comparison of the behavior of concentrated solutions of 8-8 to that of solutions of hexadecyltrimethylammonium bromide (CTAB) of similar concentrations suggests that the presence of a sulfur atom decreases the tendency for micellar growth. This may be a consequence of a slightly higher preference for the micellar surface of a sulfur atom as compared to that of a methylene group in a similar position, an idea that is also supported by results for the surfactant mixtures.

Unusual Aqueous-Phase Behavior of Cationic Amphiphiles with Hydrogen-Bonding Headgroups

Two cationic surfactants with hydroxyl and carbamate hydrogen-bonding sites at their headgroups were synthesized. Both surfactants are ionic liquids (one of them at room temperature). Samples are isotropic solutions over the entire 0-100% concentration range, which is highly unusual for ionic surfactants. Surface tension, NMR, and conductivity measurements indicate classical micelle formation in aqueous solutions with CMCs below 10 mM. Pulse-gradient spin-echo (PGSE) NMR confirms micelle formation and provides micellar hydrodynamic radii of about 3.8 nm. Because this value is larger than the length of the extended surfactant molecules, about 2.7 nm, it appears that hydrogen-bonded water of hydration contributes substantially to the effective micelle size. At higher concentrations (above 25 wt %), surfactant solutions become viscous, but line broadening in the NMR is small relative to that found with a conventional cationic surfactant (CTAB). Thus, long rod formation, the source of line broadening in the latter, is absent with the new surfactants. Finally, PGSE NMR data show a 5-fold decrease in the diffusion coefficient between 5 and 20 wt %, above which the diffusion coefficients remain constant. The results are best explained by micelle clustering that is likely aided by intermicellar hydrogen bonding. The possibility of an isotropic liquid crystal (LC) phase with cubic symmetry is discussed and dismissed, demonstrating that LC formation of ionic surfactants at high concentrations, the usual behavior in past work, need not occur. Nor is there a definite connection between ionic liquid behavior and isotropic morphology.