Ozonolysis of fatty acid monolayers was studied to understand the fate of organic-coated aerosols under realistic atmospheric conditions. Specifically, we investigated the effects of temperature and salinity on the degradation of oleic acid at the air–water interface and the persistence of the aged surfactant film at the surface. The presence of a residual film is of atmospheric importance, as surface monolayers affect the physical properties of the droplets and because of the role they play in cloud formation. This occurs via several effects, most notably via surface tension reduction. The interplay between atmospheric aerosol loading and the formation, nature, and persistence of clouds is a key uncertainty in climate modelling. Our data show that a residual surface film, which we suspect to be formed of nonanoic acid and a mixture of azelaic and 9-oxononanoic acids, is retained at the interface after ozonolysis at near-zero temperatures but not at room temperature. Given the low-temperature conditions used here are atmospherically realistic, the persistence of a product film must be considered when assessing the impact of unsaturated fatty acid partitioned to the air–water interface. The presence of stable (non-oxidisable) reaction products also opens the possibility of build-up of inert monolayers during the aerosol life cycle with potential implications for cloud formation. Furthermore, we measured the kinetic behaviour of these films and found that the reactions are not significantly affected by the shift to a lower temperature with rate coefficients determined to be (2.2 ± 0.4) × 10⁻¹⁰ cm² s⁻¹ at 21 ± 1 ^∘C and (2.2 ± 0.2) × 10⁻¹⁰ cm² s⁻¹ at 2 ± 1 ^∘C.

Neutron and x-ray reflectometry (NR and XRR) are powerful techniques to investigate the structural, morphological and even magnetic properties of solid and liquid thin films. While neutrons and x-rays behave similarly in many ways and can be described by the same general theory, they fundamentally differ in certain specific aspects. These aspects can be exploited to investigate different properties of a system, depending on which particular questions need to be answered. Having demonstrated the general applicability of neural networks to analyze XRR and NR data before (Greco et al 2019 J. Appl. Cryst. 52 1342), this study discusses challenges arising from certain pathological cases as well as performance issues and perspectives. These cases include a low signal-to-noise ratio, a high background signal (e.g. from incoherent scattering), as well as a potential lack of a total reflection edge (TRE). By dynamically modifying the training data after every mini batch, a fully-connected neural network was trained to determine thin film parameters from reflectivity curves. We show that noise and background intensity pose no significant problem as long as they do not affect the TRE. However, for curves without strong features the prediction accuracy is diminished. Furthermore, we compare the prediction accuracy for different scattering length density combinations. The results are demonstrated using simulated data of a single-layer system while also discussing challenges for multi-component systems.

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.

Pre-adsorbed branched brush layers were formed on silica surfaces by adsorption of a diblock copolymer consisting of a linear cationic block and an uncharged bottle-brush block. The charge of the silica surface was found to affect the adsorption, with lower amounts of the cationic polyelectrolyte depositing on less charged silica. Cleaning under basic conditions rendered surfaces more negatively charged (more negative zeta-potential) than acid cleaning and was therefore used to increase polyelectrolyte adsorption. The structure of adsorbed layers of the diblock copolymer was as determined by neutron reflectometry found to be about 70 nm thick and very water rich (97%). Interactions between the anionic surfactant sodium dodecylsulfate (SDS) and such pre-adsorbed diblock polymer layers were studied by neutron reflectometry and by optical reflectometry. Optical reflectometry was also used for deducing interactions between the individual blocks of the diblock copolymer and SDS at the silica/aqueous interface. We find that SDS is readily incorporated in the diblock copolymer layer at low SDS concentrations, and preferentially co-localized with the cationic block of the polymer next to the silica surface. At higher SDS concentrations some desorption of polyelectrolyte/surfactant complexes takes place.

Lipoproteins play a central role in the development of atherosclerosis. High and low-density lipoproteins (HDL and LDL), known as 'good' and 'bad' cholesterol, respectively, remove and/or deposit lipids into the artery wall. Hence, insight into lipid exchange processes between lipoproteins and cell membranes is of particular importance in understanding the onset and development of cardiovascular disease. In order to elucidate the impact of phospholipid tail saturation and the presence of cholesterol in cell membranes on these processes, neutron reflection was employed in the present investigation to follow lipid exchange with both HDL and LDL against model membranes. Mirroring clinical risk factors for the development of atherosclerosis, lower exchange was observed in the presence of cholesterol, as well as for an unsaturated phospholipid, compared to faster exchange when using a fully saturated phospholipid. These results highlight the importance of membrane composition on the interaction with lipoproteins, chiefly the saturation level of the lipids and presence of cholesterol, and provide novel insight into factors of importance for build-up and reversibility of atherosclerotic plaque. In addition, the correlation between the results and well-established clinical risk factors suggests that the approach taken can be employed also for understanding a broader set of risk factors including, e.g., effects of triglycerides and oxidative stress, as well as local effects of drugs on atherosclerotic plaque formation.