Night-time oxidation of a monolayer model for the air–water interface of marine aerosol - a study by simultaneous neutron reflectometry and in situ infra-red reflection absorption spectroscopy (IRRAS)

This paper describes experiments on the ageing of a monolayer model for the air–water interface of marine aerosols composed of a typical glycolipid, galactocerebroside (GCB). Lipopolysaccharides have been observed in marine aerosols, and GCB is used as a proxy for these more complex lipopolysaccharides. GCB monolayers are investigated as pure films, as mixed films with palmitic acid, which is abundant in marine aerosols and forms a stable attractively mixed film with GCB, particularly with divalent salts present in the subphase, and as mixed films with palmitoleic acid, an unsaturated analogue of palmitic acid. Such mixed films are more realistic models of atmospheric aerosols than simpler single-component systems. Neutron reflectometry (NR) has been combined in situ with Fourier transform infra-red reflection absorption spectroscopy (IRRAS) in a pioneering analysis and reaction setup designed by us specifically to study mixed organic monolayers at the air–water interface. The two techniques in combination allow for more sophisticated observation of multi-component monolayers than has previously been possible. The structure at the air–water interface was also investigated by complementary Brewster angle microscopy (BAM). This study looks specifically at the oxidation of the organic films by nitrate radicals (NO3•), the key atmospheric oxidant present at night. We conclude that NO3• oxidation cannot fully remove a cerebroside monolayer from the surface on atmospherically relevant timescales, leaving its saturated tail at the interface. This is true for pure and salt water subphases, as well as for single- and two-component films. The behaviour of the unsaturated tail section of the molecule is more variable and is affected by interactions with co-deposited species. Most surprisingly, we found that the presence of CaCl2 in the subphase extends the lifetime of the unsaturated tail substantially—a new explanation for longer residence times of materials in the atmosphere compared to lifetimes based on laboratory studies of simplified model systems. It is thus likely that aerosols produced from the sea-surface microlayer at night will remain covered in surfactant molecules on atmospherically relevant timescales with impact on the droplet’s surface tension and on the transport of chemical species across the air–water interface

Translational use of homing peptides: Tumor and placental targeting

HypothesisTissue-specific homing peptides have been shown to improve chemotherapeutic efficacy due to their trophism for tumor cells. Other sequences that selectively home to the placenta are providing new and safer therapeutics to treat complications in pregnancy. Our hypothesis is that the placental homing peptide RSGVAKS (RSG) may have binding affinity to cancer cells, and that insight can be gained into the binding mechanisms of RSG and the tumor homing peptide CGKRK to model membranes that mimic the primary lipid compositions of the respective cells.ExperimentsFollowing cell culture studies on the binding efficacy of the peptides on a breast cancer cell line, a systematic translational characterization is delivered using ellipsometry, Brewster angle microscopy and neutron reflectometry of the extents, structures, and dynamics of the interactions of the peptides with the model membranes on a Langmuir trough.FindingsWe start by revealing that RSG does indeed have binding affinity to breast cancer cells. The peptide is then shown to exhibit stronger interactions and greater penetration than CGKRK into both model membranes, combined with greater disruption to the lipid component. RSG also forms aggregates bound to the model membranes, yet both peptides bind to a greater extent to the placental than cancer model membranes. The results demonstrate the potential for varying local reservoirs of peptide within cell membranes that may influence receptor binding. The innovative nature of our findings motivates the urgent need for more studies involving multifaceted experimental platforms to explore the use of specific peptide sequences to home to different cellular targets

Simultaneous neutron reflectometry and infrared reflection absorption spectroscopy (IRRAS) study of mixed monolayer reactions at the air–water interface

The simultaneous application of neutron reflectometry (NR) and infrared reflection absorption spectroscopy (IRRAS) to the study of the oxidation kinetics of organic monolayers at the air–water interface is described for the first time. This advance was possible thanks to the development of a new sample environment that includes a gas-delivery system and is compatible with in situ application of the two techniques within the constraints of short-term neutron beam-line access. We studied the oxidation of monolayers of the mono-molecular film palmitoleic acid and of a binary mixture of oleic (OA) and stearic (SA) acids by gas-phase ozone. We contrast the two highly complementary techniques and demonstrate that IRRAS provides key additional insight into the alignment of surfactant molecules at the air–water interface. We highlight the potential of the more economical and widely available IRRAS technique to complement NR studies. We also found an apparent increase of the NR signal upon oxidation of a mixed SA/OA monolayer, as well as evidence of slow intensity fluctuations of the SA- generated IRRAS signal. We demonstrate how simultaneous NR-IRRAS substantially enhances future studies of increasingly complex surfactant mixtures and their atmospheric surface reactions

Adsorption of sodium hexanoate on α-alumina.

Neutron reflection and adsorption isotherm measurements have been used to study the adsorption behaviour of hexanoic acid onto α-alumina surfaces. Importantly, the pH dependence of the behaviour has been characterised with a pronounced maximum in adsorption identified at a pH of approximately 5, close to the pKa of the acid. The adsorbed layer is identified as a bilayer, which is reasonable given the hydrophilic nature of both side of the layer, and has a thickness of 13 Å, suggesting significant extent of interdigitation. At pH 5, the layer has much lower extent of hydration relative to the higher pH of 7, consistent with the increased total adsorption at pH 5. A number of different mechanisms for the binding of the hexanoic acid to the surface are considered. The experimental data, combined with calculations using equilibrium/binding constants of the surface and ligands, indicates that a ligand exchange reaction may be the most significant mechanism.This is the author's accepted manuscript. The final version has been published by Elsevier in the Journal of Colloid and Interface Science here: http://www.sciencedirect.com/science/article/pii/S0021979713005560

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.</p

Interactions between flow fields induced by surface dielectric barrier discharge arrays

This study investigates the flow field induced by a surface dielectric barrier discharge (SDBD) system, known for its efficient pollution remediation of volatile organic compounds (VOCs). We aim to understand the flow dynamics that contribute to the high conversion observed in similar systems. Experimental techniques, including schlieren imaging and particle image velocimetry (PIV), applied with high temporal resolution, were used to analyse the flow field. Complementary, fluid simulations are employed to investigate the coupling between streamer and gas dynamics. Results show distinct fluid field behaviours for different electrode configurations, which differ in geometric complexity. The fluid field analysis of the most basic electrode design revealed behaviours commonly observed in actuator studies. The simulation results indicate the local information about the electron density as well as different temporal phases of the fluid flow. The electrode design with mostly parallel grid line structures exhibits confined vortices near the surface. In contrast, an electrode design also used in previous studies, is shown to promote strong gas transport through extended vortex structures, enhancing gas mixing and potentially explaining the high conversion observed.Comment: submitted to Plasma Chemistry and Plasma Processing by Springer Natur