Long, straight chain saturated fatty acids form homogeneous, featureless monolayers on a supramolecular length scale at the water–air interface. In contrast, a naturally occurring saturated branched fatty acid, 18-methyl eicosanoic acid (18-MEA) has been observed to form three-dimensional domains of size 20–80 nm, using a combination of Langmuir trough, Atomic Force Microscopy (AFM) images of the deposited monolayers, and Neutron reflectometry (NR) and X-Ray reflectometry (XRR). It is hypothesized that these domains result from the curvature of the water surface induced by the steric constraints of the methyl branch. Accordingly, in this work, we investigate in situ the structure of such films using Grazing Incidence Small Angle X-ray Scattering and Diffraction (GISAXS and GIXD). The branched fatty acids indeed form curved nanodomains as revealed by their two-dimensional scattering pattern whereas straight chain fatty acids form the expected featureless film, with no GISAXS scattering peaks. Mixed monolayers consisting of 18-MEA and eicosanoic acid (EA) display a phase transition in the structure from hexagonally packed at high 18-MEA ratio to structures with one-dimensional translational ordering (aligned stripes) for 50:50 mol% and lower ratios. Moreover, the GIXD patterns of monolayers containing 18-MEA display a peak with curved distribution of intensity, indicating a continuous distribution of collective molecular orientations, consistent with the local curvature of the water surface. Finally, we report on an unusual double peak phenomenon in the GISAXS data that is interpreted as being due to a hexagonal packing of elliptical domains – i.e. with two characteristic dimensions. Synchrotron X-Ray scattering experiments have thus unambiguously confirmed the self-assembly, out of plane, “cobbling” of the water interface by these branched structures.

Branched fatty acids, such as those found on the surface of hair and wool, have recently been shown to form novel 3D self-assembly curvature structures at the air–water interface—nanocaps. On the hair surface, the branched fatty acid 18-methyleicosanoic acid (18-MEA) is expressed together with shorter, unbranched, straight chain fatty acids to form a protective palisade layer. The biological function of the chain length differences was hitherto unknown. Using a combination of atomic force microscopy and Langmuir isotherms, a safe, versatile route for tuneable nanopatterning of solid surfaces is demonstrated, via fatty acid interfacial nanocap deposition from biomimetic mixtures. Further, it is shown that chain length dependence of the interaction with the branched chain is exquisitely sensitive, leading to profoundly different morphologies in the self-assembly structures. The vastly enhanced properties of the mixed films compared to the individual components alone reveals the biological origin of the hair surface composition.

3D texturing by self-assembly at the air-water interface has recently been proposed. The hypothesis of this work is that, if this is true, such domain formation should be inferable directly from pressure-area isotherms and be thermodynamically stable. Monolayers of branched fatty acid mixtures with straight chain analogues and their stability are thus studied using a combination of pressure-area isotherms, thermodynamic analysis, in situ Brewster angle microscopy, and atomic force microscopy of both LB-deposited and drop-cast films on silicon wafers. Isotherms reflecting the behavior of monodisperse 3D domains are shown to be independent of compression rate and display long-term stability. Gibbs analysis further confirms the thermodynamic rather than kinetic origin of such novel species by revealing that deviations from ideal mixing can be explained only a priori by differences in the topography of the water surface, thus also indirectly confirming the self-assembly deformation of the water interface. The intrinsic self-assembly curvature and miscibility of the two fatty acids is confirmed by drop-casting, which also provides a rapid, tunable thin-film preparation approach. Finally, the longevity of the nanostructured films is extraordinary, the long-range order of the deposited films increases with equilibration time at the water interface, and the integrity of the nanopatterns remains intact on the scale of years.

It is shown that the air-liquid interface can be made to display the same rich curvature phenomena as common lyotropic liquid crystal systems. Through mixing an insoluble, naturally occurring, branched fatty acid, with an unbranched fatty acid of the same length, systematic variation in the packing constraints at the air-water interface could be obtained. The combination of atomic force microscopy and neutron reflectometry is used to demonstrate that the water surface exhibits significant tuneable topography. By systematic variation of the two fatty acid proportions, ordered arrays of monodisperse spherical caps, cylindrical sections, and a mesh phase are all observed, as well as the expected lamellar structure. The tuneable deformability of the air-water interface permits this hitherto unexplored topological diversity, which is analogous to the phase elaboration displayed by amphiphiles in solution. It offers a wealth of novel possibilities for the tailoring of nanostructure.

A simple, insoluble monolayer of fatty acid is shown to induce 3D nanotexturing of the air–water interface. This advance has been achieved through the study of monolayers of a methyl-branched long chain fatty acid, analogous to those found on the surface of hair and wool, directly at the air–water interface. Specular neutron reflectometry combined with AFM probing of deposited monolayers shows pronounced 3D surface domains, which are absent for unbranched analogues and are attributed to hydrocarbon packing constraints. The resulting surface topographies of the water far exceed the height perturbation that can be explained by the presence of capillary waves of a free liquid surface. These have hitherto been considered the only source of perturbation of the flatness of a planar water interface under gravity in the absence of topographical features from the presence of extended, globular or particulate matter. This amounts to a paradigm shift in the study of interfacial films and opens the possibility of 3D texturing of the air–water interface.

For more than a hundred years of interfacial science, long chain fatty acids have been the primary system for the study of floating monolayers at the air–water interface due to their amphiphilic nature and system simplicity: an insoluble hydrocarbon chain and a soluble carboxyl group at a flat air–water interface. Despite―or perhaps rather due to―the assumed simplicity of such systems and the maturity of the research field, the seemingly fundamentally rooted notion of a two-dimensional water surface has yet to be challenged.

The naturally occurring methyl-branched long chain fatty acid 18-methyleicosanoic acid and one of its isomers form monolayers consisting of monodisperse domains of tens of nanometres, varying in size with the placement of the methyl branch. The ability of domain-forming monolayers to three-dimensionally texture the air–water interface is investigated as a result of hydrocarbon packing constraints owing to the methyl branch.

In this work, neutron reflectometry has been used to study monolayers of branched long chain fatty acids directly at the air–water interface, which allowed precise probing of how a deformable water surface is affected by monolayer structure. Such films were also transferred by Langmuir–Blodgett deposition to the air–solid interface, and subsequently imaged by atomic force microscopy. Combined, the results unanimously―and all but unambiguously―show that the self-assembly of branched long chain fatty acids texture the air–water interface, inducing domain formation by a local curvature of the water surface, and thus controverting the preconceived notion of a planar air–water interface. The size and shape of the observed domains are shown to be tuneable using three different parameters: in mixed systems of branched and unbranched fatty acids, with varying hydrocarbon length of the straight chain, and altering subphase electrolyte properties. Each of these factors effectively allows changing the local curvature of the monolayer, much like analogous three-dimensional systems in bulk lyotropic crystals. This precise tuneability opens up for sustainable nanopatterning. Finally, the results lead to a plausible hypothesis of self-healing properties as to why the surface of hair and wool have a significant proportion of branched fatty acid.

Under mer än hundra år av ytkemisk forskning har långa fettsyror utgjort ett standardsystem vid studier av monomolekylära skikt på fasgränsytan mellan luft och vatten. Här utnyttjas systemets enkelhet och fettsyrors amfifila egenskaper: de består av en hydrofil karboxylgrupp och en hydrofob kolkedja, vilket leder till att de adsorberas på en plan vatten–luftgränsyta. Systemets antagna enkelhet och fältets mognad till trots – eller snarare till följd av detta – har lett till att den förutfattade uppfattningen om en tvådimensionell vattenyta ännu ej ifrågasatts.

Den naturligt förekommande förgrenade fettsyran 18-metyleikosansyra och en av dess isomerer bildar monoskikt bestående av tiotals nanometer stora monodispersa domäner vars storlek varierar beroende på metylförgreningens placering på kolkedjan. Här undersöks hur dessa domäntäckta monoskikt strukturerar den underliggande vattenytan ut ur det tvådimensionella planet till följd av hur metylförgreningen begränsar intilliggande kolkedjors tätpackningsförmåga.

I avhandlingen har neutronspridning använts för att studera monoskikt av förgrenade fettsyror direkt på vatten–luftgränsytan. Metoden har möjliggjort att noggrant undersöka hur en formbar vattenyta påverkas av monoskiktets tredimensionella struktur. Sådana monoskikt har även överförts till fasta ytor med hjälp av Langmuir–Blodgettdeponering för att därefter karakteriseras med atomkraftsmikroskopi. Sammantaget har resultaten från dessa mättekniker enhälligt – om än allt utom strikt – bevisat att självassociering av grenade fettsyror kröker den underliggande vatten–luftgränsytan, vilket medför de uppvisade egenskaperna till domänformation. Detta bestrider föreställningen om en plan vattenyta. Form och storlek hos de observerade domänerna kan regleras genom att ändra kompositionen i blandsystem med förgrenade och raka fettsyror, variera längden på den raka fettsyran och genom att ändra subfasens elektrolytsammansättning. Vardera av dessa parametrar möjliggör lokal förändring av monoskiktets och därmed vattenytans krökning, vilket kan likställas med motsvarande självassocierande tredimensionella strukturer som miceller och flytande kristallina faser. Denna precisa styrning av domänformationen gör det möjligt att med hållbar kemi skapa varaktiga nanostrukturerade ytor. Slutligen har resultaten från den här avhandlingen lett fram till en hypotes relaterad till självläkande egenskaper, som beskriver varför den grenade fettsyran 18-metyleikosansyra står för en betydande del av fettsyrakompositionen på hårets yttersta gränsskikt.

The quartz crystal microbalance (QCM) has been used to study how the interfacial layer of an ionic liquid dissolved in a polar oil at low weight percentages responds to changes in applied potential. The changes in surface composition at the QCM gold surface depend on both the magnitude and sign of the applied potential. The time-resolved response indicates that the relaxation kinetics are limited by the diffusion of ions in the interfacial region and not in the bulk, since there is no concentration dependence. The measured mass changes cannot be explained only in terms of simple ion exchange; the relative molecular volumes of the ions and the density changes in response to ion exclusion must be considered. The relaxation behavior of the potential between the electrodes upon disconnecting the applied potential is more complex than that observed for pure ionic liquids, but a measure of the surface charge can be extracted from the exponential decay when the rapid initial potential drop is accounted for. The adsorbed film at the gold surface consists predominantly of ionic liquid despite the low concentration, which is unsurprising given the surtactant-like structures of (some of) the ionic liquid ions. Changes in response to potential correspond to changes in the relative numbers of cations and anions, rather than a change in the oil composition. No evidence for an electric field induced change in viscosity is observed. This work shows conclusively that electric potentials can be used to control the surface composition, even in an oil-based system, and paves the way for other ion solvent studies.

Using neutron reflectivity, the electro-responsive structuring of the non-halogenated ionic liquid (IL) trihexyl(tetradecyl)phosphonium-bis(mandelato)borate, [P6,6,6,14][BMB], has been studied at a gold electrode surface in a polar solvent. For a 20% w/w IL mixture, contrast matched to the gold surface, distinct Kiessig fringes were observed for all potentials studied, indicative of a boundary layer of different composition to that of the bulk IL-solvent mixture. With applied potential, the amplitudes of the fringes from the gold-boundary layer interface varied systematically. These changes are attributable to the differing ratios of cations and anions in the boundary layer, leading to a greater or diminished contrast with the gold electrode, depending on the individual ion scattering length densities. Such electro-responsive changes were also evident in the reflectivities measured for the pure IL and a less concentrated (5% w/w) IL-solvent mixture at the same applied potentials, but gave rise to less pronounced changes. These measurements, therefore, demonstrate the enhanced sensitivity achieved by contrast matching the bulk solution and that the structure of the IL boundary layers formed in mixtures is strongly influenced by the bulk concentration. Together these results represent an important step in characterising IL boundary layers in IL-solvent mixtures and provide clear evidence of electro-responsive structuring of IL ions in their solutions with applied potential.

Vibrational sum frequency spectroscopy (VSFS) complemented by surface pressure isotherm and neutron reflectometry (NR) experiments were employed to investigate the interactions between propofol, a small amphiphilic molecule that currently is the most common general anaesthetic drug, and phospholipid monolayers. A series of biologically relevant saturated phospholipids of varying chain length from C18 to C14 were spread on either pure water or propofol (2,6-bis(1-methylethyl)phenol) solution in a Langmuir trough, and the change in the molecular structure of the film, induced by the interaction with propofol, was studied with respect to the surface pressure. The results from the surface pressure isotherm experiments revealed that propofol, as long as it remains at the interface, enhances the fluidity of the phospholipid monolayer. The VSF spectra demonstrate that for each phospholipid the amount of propofol in the monolayer region decreases with increasing surface pressure. Such squeeze out is in contrast to the enhanced interactions that can be exhibited by more complex amphiphilic molecules such as peptides. At surface pressures of 22–25 mN m−1, which are relevant for biological cell membranes, most of the propofol has been expelled from the monolayer, especially in the case of the C16 and C18 phospholipids that adopt a liquid condensed phase packing of its alkyl tails. At lower surface pressures of 5 mN m−1, the effect of propofol on the structure of the alkyl tails is enhanced when the phospholipids are present in a liquid expanded phase. Specifically, for the C16 phospholipid, NR data reveal that propofol is located exclusively in the head group region, which is rationalized in the context of previous studies. The results imply a non-homogeneous distribution of propofol in the plane of real cell membranes, which is an inference that requires urgent testing and may help to explain why such low concentration of the drug are required to induce general anaesthesia.