Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs)

Direct measurements of ionic liquid layering at a single mica-liquid interface and in nano-films between two mica-liquid interfaces.

The layering of ionic liquids close to flat, charged interfaces has been identified previously through theoretical and some experimental measurements. Here we present evidence for oscillations in ion density ('layering') in a long chain ionic liquid (1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide) near the interface with mica using two complementary approaches. Neutron reflection at the ionic liquid-mica interface is used to detect structure at a single interface, and surface force balance (SFB) measurements carried out with the same ionic liquid reveal oscillatory density in the liquid confined between two mica sheets. Our findings imply the interfacial structure is not induced by confinement alone. Structural forces between two mica surfaces extend to approximately twice the distance of the density oscillations measured at a single interface and have similar period in both cases.We thank BP for funding (KLB and LRG), the EPSRC for a Doctoral Prize (AMS), and the John Fell Fund (Oxford University) for financial support. SP and AMS are grateful for support from the ERC under grant 676861: LIQUISWITCH

Lipoprotein ability to exchange and remove lipids from model membranes as a function of fatty acid saturation and presence of cholesterol

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

Morphology of bile salts micelles and mixed micelles with lipolysis products, from scattering techniques and atomistic simulations

Hypotheses Bile salts (BS) are biosurfactants released into the small intestine, which play key and contrasting roles in lipid digestion: they adsorb at interfaces and promote the adsorption of digestive enzymes onto fat droplets, while they also remove lipolysis products from that interface, solubilising them into mixed micelles. Small architectural variations on their chemical structure, specifically their bile acid moiety, are hypothesised to underlie these conflicting functionalities, which should be reflected in different aggregation and solubilisation behaviour. Experiments The micellisation of two BS, sodium taurocholate (NaTC) and sodium taurodeoxycholate (NaTDC), which differ by one hydroxyl group on the bile acid moiety, was assessed by pyrene fluorescence spectroscopy, and the morphology of aggregates formed in the absence and presence of fatty acids (FA) and monoacylglycerols (MAG) – typical lipolysis products – was resolved by small-angle X-ray/neutron scattering (SAXS, SANS) and molecular dynamics simulations. The solubilisation by BS of triacylglycerol-incorporating liposomes – mimicking ingested lipids – was studied by neutron reflectometry and SANS. Findings Our results demonstrate that BS micelles exhibit an ellipsoidal shape. NaTDC displays a lower critical micellar concentration and forms larger and more spherical aggregates than NaTC. Similar observations were made for BS micelles mixed with FA and MAG. Structural studies with liposomes show that the addition of BS induces their solubilisation into mixed micelles, with NaTDC displaying a higher solubilising capacity

On the Stability of Oligo(ethylene glycol) (C(11)EG(6)OMe) SAMs on Gold: Behavior at Elevated Temperature in Contact with Water

In this study the temperature dependent confor-mation of hexa(ethylene glycol) self-assembling monolayers (SAMs) under aqueous conditions (in situ) is investigated. To this end characteristic absorption modes in the fingerprint region (1050-1500 cm(-1)) were monitored with real-time polarization modulation infrared spectroscopy. We found a temperature induced conformational change from predominantly helical to helical/all-trans. The process may be divided into two temperature regimes. Up to 40 °C the process is reversible after drying the monolayers in air and successive reimmersion in water, indicating a strong binding of the water molecules to the SAM. At higher temperatures, the conformational change is irreversible. Additionally, a rapid change to a larger mode width and a shift of the mode position to higher wavenumbers (blue-shift) at about 50 °C indicates structural changes caused by decreasing crystallinity of the SAM. While the conformational changes up to 40 °C are supposed to originate from an increased conformational freedom in combination with a stronger interaction with water molecules, the irreversibility and rapid change of mode characteristics at higher temperatures indicate chemical degradation. Complementary measurements in air show a fast and virtually complete reversibility up to 40 °C underlining the effect of the interaction of the ethylene glycol moiety with water. At temperatures above 50 °C modes indicating ester and formate groups appear, supporting the idea of chemical degeneration. Moreover, the temperature behavior is coverage dependent. At incomplete coverage the structural order of the SAM starts decreasing at lower temperatures. This study shows, that the conformational and structural change of hexa(ethylene glycol) SAMs at elevated temperature is an interplay of conformational changes of the SAM, its interaction with water and at higher temperatures its chemical degradation. Our experiments also underline the importance of the in situ analysis on the film structure