Structural investigation of sulfobetaines and phospholipid monolayers at the air-water interface.

Mixtures of sulfobetaine based lipids with phosphocholine phospholipids are of interest in order to study the interactions between zwitterionic surfactants and the phospholipids present in cell membranes. In this study we have investigated the structure of mixed monolayers of sulfobetaines and phosphocholine phospholipids. The sulfobetaine used has a single 18-carbon tail, and is referred to as SB3-18, and the phospholipid used is DMPC. Surface pressure-area isotherms of the samples were used to determine whether any phase transitions were present during the compression of the monolayers. Neutron and X-ray reflectometry were then used to investigate the structure of these monolayers perpendicular to the interface. We found that the average headgroup and tail layer thickness was reasonably consistent across all mixtures, with a variation of less than 3 Å reported in the total thickness of the monolayers at each surface pressure. However, by selective deuteration of the two components of the monolayers, it was found that the two components have different tail layer thicknesses. For the mixture with equal compositions of DMPC and SB3-18 or with a higher composition of DMPC the tail tilts were found to be constant, resulting in a greater tail layer thickness for SB3-18 due to its longer tail. For the mixture higher in SB3-18 this was not the case, the tail tilt angle for the two components was found to be different and DMPC was found to have a greater tail layer thickness than SB3-18 as a result.

Self-assembled nanostructures in ionic liquids facilitate charge storage at electrified interfaces.

Driven by the potential applications of ionic liquids (ILs) in many emerging electrochemical technologies, recent research efforts have been directed at understanding the complex ion ordering in these systems, to uncover novel energy storage mechanisms at IL-electrode interfaces. Here, we discover that surface-active ILs (SAILs), which contain amphiphilic structures inducing self-assembly, exhibit enhanced charge storage performance at electrified surfaces. Unlike conventional non-amphiphilic ILs, for which ion distribution is dominated by Coulombic interactions, SAILs exhibit significant and competing van der Waals interactions owing to the non-polar surfactant tails, leading to unusual interfacial ion distributions. We reveal that, at an intermediate degree of electrode polarization, SAILs display optimum performance, because the low-charge-density alkyl tails are effectively excluded from the electrode surfaces, whereas the formation of non-polar domains along the surface suppresses undesired overscreening effects. This work represents a crucial step towards understanding the unique interfacial behaviour and electrochemical properties of amphiphilic liquid systems showing long-range ordering, and offers insights into the design principles for high-energy-density electrolytes based on spontaneous self-assembly behaviour.

Tuning Micellar Structures in Supercritical CO2 Using Surfactant and Amphiphile Mixtures.

For equivalent micellar volume fraction (ϕ), systems containing anisotropic micelles are generally more viscous than those comprising spherical micelles. Many surfactants used in water-in-CO2 (w/c) microemulsions are fluorinated analogues of sodium bis(2-ethylhexyl) sulfosuccinate (AOT): here it is proposed that mixtures of CO2-philic surfactants with hydrotropes and cosurfactants may generate elongated micelles in w/c systems at high-pressures (e.g., 100-400 bar). A range of novel w/c microemulsions, stabilized by new custom-synthesized CO2-phillic, partially fluorinated surfactants, were formulated with hydrotropes and cosurfactant. The effects of water content (w = [water]/[surfactant]), surfactant structure, and hydrotrope tail length were all investigated. Dispersed water domains were probed using high pressure small-angle neutron scattering (HP-SANS), which provided evidence for elongated reversed micelles in supercritical CO2. These new micelles have significantly lower fluorination levels than previously reported (6-29 wt % cf. 14-52 wt %), and furthermore, they support higher water dispersion levels than other related systems (w = 15 cf. w = 5). The intrinsic viscosities of these w/c microemulsions were estimated based on micelle aspect ratio; from this value a relative viscosity value can be estimated through combination with the micellar volume fraction (ϕ). Combining these new results with those for all other reported systems, it has been possible to "map" predicted viscosity increases in CO2 arising from elongated reversed micelles, as a function of surfactant fluorination and micellar aspect ratio.

Shape Modification of Water-in-CO2 Microemulsion Droplets through Mixing of Hydrocarbon and Fluorocarbon Amphiphiles.

An oxygen-rich hydrocarbon (HC) amphiphile has been developed as an additive for supercritical CO2 (scCO2). The effects of this custom-designed amphiphile have been studied in water-in-CO2 (w/c) microemulsions stabilized by analogous fluorocarbon (FC) surfactants, nFG(EO)2, which are known to form spherical w/c microemulsion droplets. By applying contrast-variation small-angle neutron scattering (CV-SANS), evidence has been obtained for anisotropic structures in the mixed systems. The shape transition is attributed to the hydrocarbon additive, which modifies the curvature of the mixed surfactant films. This can be considered as a potential method to enhance physicochemical properties of scCO2 through elongation of w/c microemulsion droplets. More importantly, by studying self-assembly in these mixed systems, fundamental understanding can be developed on the packing of HC and FC amphiphiles at water/CO2 interfaces. This provides guidelines for the design of fluorine-free CO2 active surfactants, and therefore, practical industrial scale applications of scCO2 could be achieved.

Evidence of Lipid Exchange in Styrene Maleic Acid Lipid Particle (SMALP) Nanodisc Systems.

Styrene-alt-maleic acid lipid particles (SMALPs) are self-assembled discoidal structures composed of a polymer belt and a segment of lipid bilayer, which are capable of encapsulating membrane proteins directly from the cell membrane. Here we present evidence of the exchange of lipids between such "nanodiscs" and lipid monolayers adsorbed at either solid-liquid or air-liquid interfaces. This behavior has important implications for the potential uses of nanodiscs.

Surfactants at the Design Limit.

This article analyzes how the individual structural elements of surfactant molecules affect surface properties, in particular, the point of reference defined by the limiting surface tension at the aqueous cmc, γcmc. Particular emphasis is given to how the chemical nature and structure of the hydrophobic tails influence γcmc. By comparing the three different classes of surfactants, fluorocarbon, silicone, and hydrocarbon, a generalized surface packing index is introduced which is independent of the chemical nature of the surfactants. This parameter ϕcmc represents the volume fraction of surfactant chain fragments in a surface film at the aqueous cmc. It is shown that ϕcmc is a useful index for understanding the limiting surface tension of surfactants and can be useful for designing new superefficient surfactants.

Bioinspired bactericidal surfaces with polymer nanocone arrays.

Infections resulting from bacterial biofilm formation on the surface of medical devices are challenging to treat and can cause significant patient morbidity. Recently, it has become apparent that regulation of surface nanotopography can render surfaces bactericidal. In this study, poly(ethylene terephthalate) nanocone arrays are generated through a polystyrene nanosphere-mask colloidal lithographic process. It is shown that modification of the mask diameter leads to a direct modification of centre-to-centre spacing between nanocones. By altering the oxygen plasma etching time it is possible to modify the height, tip width and base diameter of the individual nanocone features. The bactericidal activity of the nanocone arrays was investigated against Escherichia coli and Klebsiella pneumoniae. It is shown that surfaces with the most densely populated nanocone arrays (center-to-center spacing of 200 nm), higher aspect ratios (>3) and tip widths <20 nm kill the highest percentage of bacteria (∼30%).

Surface and bulk properties of surfactants used in fire-fighting.

HYPOTHESIS: Reports on the colloidal and interfacial properties of fluorocarbon (FC) surfactants used in fire-fighting foam formulations are rare. This is primarily because these formulations are complex mixtures of different hydrocarbon (HC) and fluorocarbon (FC) surfactants. By developing a greater understanding of the individual properties of these commercial FC surfactants, links can be made between structure and respective surface/ bulk behaviour. Improved understanding of structure property relationships of FC surfactants will therefore facilitate the design of more environmentally responsible surfactant replacements. EXPERIMENTS: Surface properties of three partially fluorinated technical grade surfactants were determined using tensiometry and neutron reflection (NR), and compared with a research-grade reference surfactant (sodium perfluorooctanoate (NaPFO)). To investigate the bulk behaviour and self-assembly in solution, small-angle neutron (SANS) scattering was used. FINDINGS: All FC surfactants in this study generate very low surface tensions (< 20 mN m-1) which are comparable, and in some cases, lower than fully-fluorinated surfactant analogues. The complementary techniques (tensiometry and NR) allowed direct comparison to be made with NaPFO in terms of adsorption parameters such as surface excess and area per molecule. Surface tension data for these technical grade FC surfactants were not amenable to reliable interpretation using the Gibbs adsorption equation, however NR provided reliable results. SANS has highlighted how changes in surfactant head group structure can affect bulk properties. This work therefore provides fresh insight into the structure property relationships of some industrially relevant FC surfactants, highlighting properties which are essential for development of more environmentally friendly replacements.

Solubilisation of oils in aqueous solutions of a random cationic copolymer.

HYPOTHESIS: Reports of random copolymers capable of solubilising hydrophobic oils are rare. This is primarily because random copolymers are unlikely to self-assemble into suitable aggregates (or micelles) in water. A random copolymer with a "blocky" (or lumpy) microstructure may have potential to solubilise hydrophobic oils in water. This type of polymer would have advantages over block copolymers which are more laborious and costly to synthesise. EXPERIMENTS: The solubilising capacity of a blocky random copolymer, namely poly(methyl methacrylate-co-2-dimethylaminoethyl methacrylate) (PMMA-co-PDMAEMA) is assessed by UV-visible spectroscopy and compared with common reference surfactants. The relative solubilising performance of random copolymers (across a narrow range of DMAEMA mol % fraction) for aromatic and aliphatic oils was also studied. The morphology of the aggregates was monitored as a function of the solubilisation capacity by small-angle neutron scattering (SANS) and dynamic-light scattering (DLS). FINDINGS: Similarly to well-defined block copolymers, these random copolymers have a specific preference for solubilising aromatic over aliphatic oils. Increasing hydrophobicity of the copolymer enhances the solubilisation capacity. SANS has highlighted that aggregates become swollen and more uniform/spherical with increasing concentration of aromatic solubilisate, and that the aromatic solubilisate partitions throughout the random copolymer aggregates.

Langmuir monolayers composed of single and double tail sulfobetaine lipids.

HYPOTHESIS: Owing to structural similarities between sulfobetaine lipids and phospholipids it should be possible to form stable Langmuir monolayers from long tail sulfobetaines. By modification of the density of lipid tail group (number of carbon chains) it should also be possible to modulate the two-dimensional phase behaviour of these lipids and thereby compare with that of equivalent phospholipids. Potentially this could enable the use of such lipids for the wide array of applications that currently use phospholipids. The benefit of using sulfobetaine lipids is that they can be synthesised by a one-step reaction from cheap and readily available starting materials and will degrade via different pathways than natural lipids. The molecular architecture of the lipid can be easily modified allowing the design of lipids for specific purposes. In addition the reversal of the charge within the sulfobetaine head group relative to the charge orientation in phospholipids may modify behaviour and thereby allow for novel uses of these surfactants. EXPERIMENTS: Stable Langmuir monolayers were formed composed of single and double tailed sulfobetaine lipids. Surface pressure-area isotherm, Brewster Angle Microscopy and X-ray and neutron reflectometry measurements were conducted to measure the two-dimensional phase behaviour and out-of-plane structure of the monolayers as a function of molecular area. FINDINGS: Sulfobetaine lipids are able to form stable Langmuir monolayers with two dimensional phase behaviour analogous to that seen for the well-studied phospholipids. Changing the number of carbon tail groups on the lipid from one to two promotes the existence of a liquid condensed phase due to increased Van der Waals interactions between the tail groups. Thus the structure of the monolayers appears to be defined by the relative sizes of the head and tail groups in a predictable way. However, the presence of sub-phase ions has little effect on the monolayer structure, behaviour that is surprisingly different to that seen for phospholipids.

Responsive materials based on magnetic polyelectrolytes and graphene oxide for water clean-up.

HYPOTHESIS: Owing to attractive interactions between negatively charged graphene oxide (GO) and a paramagnetic cationic polyelectrolyte (polyallydimethylammonium chloride with a FeCl4(-) counterion (Fe-polyDADMAC) it should be possible to generate magnetic materials. The benefit of using charge-based adsorption is that the need to form covalently linked magnetic materials is offset, which is expected to significantly reduce the time, energy and cost to make such responsive materials. These systems could have a wide use and application in water treatment. EXPERIMENTS: Non-covalent magnetic materials were formed through the mixing of Fe-pDADMAC and GO. A systematic study was conducted by varying polymer concentration at a fixed GO concentration. UV-Vis was used to confirm and quantify polymer adsorption onto GO sheets. The potential uses of the systems for water purification were demonstrated. FINDINGS: Fe-polyDADMAC adsorbs to the surface of GO and induces flocculation. Low concentrations of the polymer (<9mmol/L) favour flocculation, whereas higher concentrations (>20mmol/L) induce restabilization. Difficult-to-recover gold nanoparticles can be separated from suspensions as well as the pollutant antibiotic tetracycline. Both harmful materials can be magnetically recovered from the dispersions. This system therefore has economical and practical applications in decontamination and water treatment.