Gavin Hazell

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.

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.

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.

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.

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.