The miscibility and film structure of mixed Langmuir monolayer films composed of an anionic gemini N,N,N',N'-dialkyl-N,N'-diacetate ethylenediamine surfactant (Ace(12)-2-Ace(12)) with perfluorotetradecanoic acid (CFCOOH; PF) have been investigated using a variety of thermodynamic and structural characterization methods. The two film components were found to be miscible in monolayers at the air-water interface over a range of compositions and at all but the lowest surface pressures, with attractive interactions occurring between the two components. While pure PF monolayers formed crystalline lattices with hexagonal symmetry and with the surfactant tails oriented normal to the underlying water subphase, the pure gemini surfactant formed amorphous films with little tendency to orient at the subphase. In mixed films with mole ratios of PF:Ace(12)-2-Ace(12) < 2.5, the miscibility of the two components resulted in a nearly complete loss of crystallinity of the PF, though films at higher mole fractions of PF showed some residual crystallinity, albeit with lattice structures that were significantly different from that of pure PF. Miscibility and film structure in this mixed system are discussed in comparison with other mixed gemini surfactant systems in the literature as well as binary mixtures of phospholipids or monomeric fatty acids with PF.

A new member of the N,N,N′,N′-dialkyl-N,N′diacetate ethylenediamine family of anionic gemini surfactants has been synthesized, and its miscibility with the model perfluorocarbon, perfluorotetradecanoic acid (PF), has been investigated in monolayer films at the air−water interface. Thermodynamics of mixing and the accompanying changes in the mixed film structure have been probed using a combination of compression isotherm measurements supported by Brewster angle microscope imaging and X-ray scattering measurements, and results have been compared with those collected for a previously studied, shorter tail chain variant of the surfactant. Thermodynamic measurements showed that the gemini surfactant and perfluorotetradecanoic acid were immiscible, with weak repulsive interactions, manifesting as small positive deviations from ideal mixing, observed between the two film components. Films were highly textured, with micrometer-scale, phase-separated domains readily detectable. Grazing incidence X-ray diffraction measurements showed that the gemini surfactant was disordered in the monolayers, whereas the perfluorocarbon formed discrete crystallites in the disordered matrix. Despite the small deviations from ideal mixing detected in the thermodynamic measurements, the X-ray measurements indicated that the presence of the gemini perturbs the PF crystal lattice from that of pure PF. Finally, X-ray reflectivity measurements showed that the addition of equimolar PF to the gemini monolayer induces a significant increase in the nominal head group thickness of the film, suggesting that interactions between the two surfactants can lead to structural rearrangements of gemini's head group near to the water surface.

Synchrotron-based X-ray scattering measurements of phase-separated surfactant monolayers at the air-water interface provide molecular-level structural information about the packing and ordering of film components. In this work, grazing incidence X-ray diffraction (GIXD) and X-ray reflectivity (XR) measurements were used to collect crystallographic structural information for binary mixed monolayers of arachidic acid (AA, CHCOOH) with perfluorotetradecanoic acid (PA, CFCOOH), a system that has previously been investigated using a variety of thermodynamic and micron-scale structural characterization methods. GIXD measurements at surface pressures of π = 5, 15, and 30 mN/m indicated that AA in pure and mixed films forms a rectangular lattice at π = 5 and 15 mN/m but a hexagonal lattice at π = 30 mN/m. PA formed hexagonal lattices under all conditions, with films being highly ordered and crystalline (as determined by Bragg peak width) at even the lowest surface pressures investigated. Phase separation occurred for all mixed monolayer film compositions and surface pressures, manifesting as diffraction peaks characteristic of the individual components appearing at different in-plane scattering vector q. For both pure and mixed films, the molecular tilt angle of the AA hydrocarbon chain toward the nearest-neighbor was substantial at low pressures but decreased with increasing pressure. The PA fluorocarbon chain showed negligible molecular tilt under all conditions, and was oriented normal to the subphase surface regardless of surface pressure or the presence of AA in the films. In all cases, the two components in the mixed film behaved entirely independently of film composition, which is exactly the expected result for a fully phase-separated, immiscible system. XR measurements of film thickness at the air-water interface supported these results; overall film thickness approached the calculated ideal surfactant tail lengths with increasing surface pressure, indicating nearly normal oriented surfactants. The overall surfactant packing and crystallographic features of the mixed monolayers are discussed in terms of the lipophobic nature of the perfluorinated surfactant as well as in context of thermodynamic miscibility and domain structure formation reported elsewhere in the literature for these mixed monolayer systems.

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The ability of Fe3+ to bind to Langmuir monolayers of an N, N, N′, N′‐dialkyl‐N, N′‐diacetate ethylenediamine gemini surfactant has been explored. Fe3+ in the subphase resulted in the formation of compacted, liquid‐phase monolayers with a mesh‐like morphology at the micron length scale in comparison with expanded, unstructured liquid‐phase monolayers in the absence of iron. The response of the monolayer to subphase Fe3+ was different from that reported for Na+ and Ca2+ for an affiliated, shorter‐tail gemini surfactant. Combined surface potential and X‐ray reflectivity measurements indicated that Fe3+ induced minor conformational changes in the monolayer, suggesting ionic association with the head group. Direct evidence for the binding of iron was provided by total reflection X‐ray fluorescence measurements, which revealed that multiple ions were associated with each head group as opposed to chelating with 1:1 stoichiometry as observed with bulk ethylenediaminetetracetic acid. Cumulative data suggest the adsorption of Fex(OH)y(3x−y)+ complexes with the monolayer surface as has been reported with other charged and uncharged monolayers.