Richard K. Heenan

SANS at pulsed neutron sources : Present and future prospects

Small-angle diffraction with a pulsed neutron source, using time-of-flight analysis to separate neutrons of different wavelengths, offers a very wide simultaneous Q range coupled to good Q resolution. Data reduction to allow for wavelength-dependent effects may be achieved as a matter of routine. The cold neutron flux available from accelerator-based neutron sources does not yet fully match that of the most intense reactor sources. Simulations show that the performance of proposed future instrumentation would be largely complementary to that of the best fixed-wavelength instruments.

Magnetic Control over Liquid Surface Properties with Responsive Surfactants

are well known. Here we report for the first time ionicliquid surfactants that are magneto-responsive, thus offeringthe potential to perturb liquid emulsions simply by theapplication of an external magnetic field. Although ionicliquids(ILs)containingtransitionmetalcomplexeshavebeenknown for some time,

Anionic Surfactants and Surfactant Ionic Liquids with Quaternary Ammonium Counterions

Small-angle neutron scattering and surface tension have been used to characterize a class of surfactants (SURFs), including surfactant ionic liquids (SAILs). These SURFs and SAILs are based on organic surfactant anions (single-tail dodecyl sulfate, DS, double-chain aerosol-OT, AOT, and the trichain, TC) with substituted quaternary ammonium cations. This class of surfactants can be obtained by straightforward chemistry, being cheaper and more environmentally benign than standard cationic SAILs. A surprising aspect of the results is that, broadly speaking, the physicochemical properties of these SURFs and SAILs are dominated by the nature of the surfactant anion and that the chemical structure of the added cation plays only a secondary role.

Variation of surfactant counterion and its effect on the structure and properties of Aerosol-OT-based water-in-oil microemulsions

The sodium salt of the di-chained anionic surfactant bis-2-ethylhexylsulfosuccinate [Aerosol-OT or Na(AOT)] stabilises essentially monodisperse, spherical water-in-oil microemulsion (w/o) droplets in alkanes over a wide range of pressure, temperature and composition. In order to investigate the effect of change in counterion charge and size on the microemulsion properties, we have replaced the Na+ counterion by doubly charged ions. The surfactant is then M2+(AOT)2·nH2O: M is from the series Mg2+, Ca2+, Co2+, Ni2+, Cu2+ and Zn2+, and n is the number of water ligands associated with the surfactant molecule. The value of n was determined by FTIR and depends on M2+, but can be between 2 and 8 per molecule of M2+(AOT)2 depending on the nature of M. The ion replacement, assessed by UV–VIS spectrophotometry, is ca. 100% efficient. The effect of temperature on the phase stability of the single-phase M2+(AOT)2 water-in-oil (w/o) microemulsion systems is negligible, in contrast to that observed for the corresponding Na(AOT) system. The structure and properties of the microemulsion are found to be dependent on the counterion identity. Small-angle neutron scattering (SANS) and viscosity measurements provide evidence for the existence of rod-shaped aggregates for Co2+, Ni2+, Cu2+ and Zn2+ at low water constants given by w=[H2O]/[AOT]≈ 5, whilst for Mg2+ and Ca2+ spherical aggregates are present as for Na+. On further addition of water at constant surfactant concentration (w > 10) with Co2+, Ni2+, Cu2+ and Zn2+ the aggregates undergo a shape change, and a more spherical structure is favoured. The results may be explained in terms of the interaction of the different counterions with the SO–3 head group of the surfactant.

Nanoemulsions Prepared by a Two-Step Low-Energy Process

A simple low-energy two-step dilution process has been applied in oil/surfactant/water systems with pentaoxyethylene lauryl ether (C12E5), dodecyldimethylammonium bromide, sodium bis(2-ethylhexyl)sulfosuccinate, sodium n-dodecyl sulfate-pentanol, and hexadecyltrimethylammonium bromide-pentanol. Appropriate formulations were chosen for the concentrate to be diluted with water to generate oil-in-water (O/W) emulsions or nanoemulsions. For the system of decane/C12E5/water, bluish, transparent nanoemulsions having droplet radii of the order of 15 nm were formed, only when the initial concentrate was a bicontinuous microemulsion, whereas opaque emulsions were generated if the concentrate began in an emulsion-phase region. Nanoemulsions generated in the system decane/C12E5/water have been investigated both by dynamic light scattering (DLS) and contrast-variation small-angle neutron scattering (SANS). The SANS profiles show that nanodroplets exist as spherical core-shell (decane-C12E5) particles, which suffer essentially no structural change on dilution with water, at least for volume fractions phi down to 0.060. These results suggest that the nanoemulsion droplet structure is mainly controlled by the phase behavior of the initial concentrate and is largely independent of dilution. A discrepancy between apparent nanoemulsion droplet sizes was observed by comparing DLS and SANS data, which is consistent with long-range droplet interactions occurring outside of the SANS sensitivity range. These combined phase behavior, SANS, and DLS results suggest a different reason for the stability/instability of nanoemulsions compared with earlier studies, and here it is proposed that a general mechanism for nanoemulsion formation is homogeneous nucleation of oil droplets during the emulsification.

Eumelanin buildup on the nanoscale: aggregate growth/assembly and visible absorption development in biomimetic 5,6-dihydroxyindole polymerization.

Establishing structure-property relationships in the black insoluble eumelanins, the key determinants of human pigmentation and skin photoprotective system, is a considerable conceptual and experimental challenge in the current drive for elucidation of the biological roles of these biopolymers and their application as advanced materials for organoelectronics. Herein, we report a new breakthrough toward this goal by the first detailed investigation on the nanoscale level of the oxidative polymerization of 5,6-dihydroxyindole (DHI), a model process of eumelanin synthesis. On the basis of a combined use of spectrophotometry, dynamic light scattering (DLS), and small-angle neutron scattering (SANS) investigations, it was possible to unveil the dynamics of the aggregation process before precipitation, the key relationships with visible light absorption and the shape of fundamental aggregates. The results indicated a polymerization mechanism of the type: Polymer(n) + DHI(x) = Polymer(n+x), where DHI(x) indicates monomer, dimer, or low oligomers (x ≤ 5). During polymerization, visible absorption increases rapidly, reaching a plateau. Particle growth proceeds slowly, with formation of 2-D structures ~55 nm thick, until precipitation occurs, that is, when large aggregates with a maximum hydrodynamic radius (R(h)) of ~1200 nm are formed. Notably, markedly smaller R(h) values, up to ~110 nm, were determined in the presence of poly(vinyl alcohol) (PVA) that was shown to be an efficient aggregation-preventing agent for polymerizing DHI ensuring water solubilization. Finally, it is shown that DHI monomer can be efficiently and partially irreversibly depleted from aqueous solutions by the addition of eumelanin suspensions. This behavior is suggested to reflect oxidant-independent competing pathways of polymer synthesis and buildup via monomer conversion on the active aggregate surface contributing to particle growth. Besides filling crucial gaps in DHI polymerization, these results support the attractive hypothesis that eumelanins may behave as a peculiar example of living biopolymers. The potential of PVA as a powerful tool for solution chemistry-based investigations of eumelanin supramolecular organization and for technological manipulation purposes is underscored.

Scalable Method for the Reductive Dissolution, Purification, and Separation of Single-Walled Carbon Nanotubes

As synthesized, bulk single-walled carbon nanotube (SWNT) samples are typically highly agglomerated and heterogeneous. However, their most promising applications require the isolation of individualized, purified nanotubes, often with specific optoelectronic characteristics. A wide range of dispersion and separation techniques have been developed, but the use of sonication or ultracentrifugation imposes severe limits on scalability and may introduce damage. Here, we demonstrate a new, intrinsically scalable method for SWNT dispersion and separation, using reductive treatment in sodium metal-ammonia solutions, optionally followed by selective dissolution in a polar aprotic organic solvent. In situ small-angle neutron scattering demonstrates the presence of dissolved, unbundled SWNTs in solution, at concentrations reaching at least 2 mg/mL; the ability to isolate individual nanotubes is confirmed by atomic force microscopy. Spectroscopy data suggest that the soluble fraction contains predominately large metallic nanotubes; a potential new mechanism for nanotube separation is proposed. In addition, the G/D ratios observed during the dissolution sequence, as a function of metal:carbon ratio, demonstrate a new purification method for removing carbonaceous impurities from pristine SWNTs, which avoids traditional, damaging, competitive oxidation reactions.

Small Angle Neutron Scattering Using Sans2d

The Loq small angle neutron scattering (SANS) instrument at ISIS target station one (TS1) has proved an extremely popular and immensely productive SANS facility over the last 20 years. Loq is routinely operated with a 25 Hz disc chopper removing alternate neutron pulses from the 50 Hz source to provide a usable wavelength range of 2.2 to 10 Å. Scattered neutrons are recorded on a 0.64 m square 3He multiwire proportional counter (Ordela 2661N) fixed at ∼ 4 m from the sample, with a total flight path of 15 m from the decoupled liquid hydrogen moderator [1].

Universal Surfactant for Water, Oils, and CO2

A trichain anionic surfactant sodium 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulfonate (TC14) is shown to aggregate in three different types of solvent: water, heptane, and liquid CO(2). Small-angle neutron scattering (SANS) has been used to characterize the surfactant aggregates in water, heptane, and dense CO(2). Surface tension measurements, and analyses, show that the addition of a third branched chain to the surfactant structural template is critical for sufficiently lowering the surface energy, tipping the balance between a CO(2)-incompatible surfactant (AOT) and CO(2)-philic compounds that will aggregate to form micelles in dense CO(2) (TC14). These results highlight TC14 as one of the most adaptable and useful surfactants discovered to date, being compatible with a wide range of solvent types from high dielectric polar solvent water to alkanes with low dielectrics and even being active in the uncooperative and challenging solvent environment of liquid CO(2).

Tuneable mechanical properties in low molecular weight gels

The mechanical properties of gels are critical to the final targeted applications. Depending on the application, different properties may be required. Here, we show that the mechanical strength and ability to recover of gels formed using a low molecular weight gelator can be controlled by two independent factors (i) the volume fraction of co-solvent (in this case DMSO) in the system and (ii) the temperature cycle used. These differences correlate with the large scale structure of the network that is formed from the self-assembled fibres. This opens up the potential to prepare gels with very different properties at the same final conditions, allowing the effect of microstructure to be probed.