Interstitial Hydrogen in Fe/V Superstructures: Lattice Site Location and Thermal Vibration.

We report real space location of hydrogen in single crystalline Fe/V superstructures. Anisotropic strain is quantified versus hydrogen concentration by using the yield of backscattered primary 2 MeV ^{4}He ions for incidence in different crystallographic directions. From a comparison of ion channeling in combination with ^{1}H(^{15}N,αγ)^{12}C nuclear reaction analysis and Monte Carlo simulations we show that hydrogen is located in octahedral z sites and quantify its vibrational amplitude of 0.2 Å.

On the interaction of softwood hemicellulose with cellulose surfaces in relation to molecular structure and physicochemical properties of hemicellulose.

The substantial part of the water-soluble hemicellulose fraction, obtained when processing cellulose to produce paper and other products, has so far been discarded. The aim of this work is to reveal the interfacial properties of softwood hemicellulose (galactoglucomannan, GGM) in relation to their molecular and solution structure. In this study the sugar composition of GGM was characterised by chemical analysis as well as 1D and 2D NMR spectroscopy. Previously it has been demonstrated that hemicellulose has high affinity towards cellulose and has the ability to alter the properties of cellulose based products. This study is focused on the interactions between hemicellulose and the cellulose surface. Therefore, adsorption to hydrophobized silica and cellulose surfaces of two softwood hemicellulose samples and structurally similar seed hemicelluloses (galactomannans, GMs) was studied with ellipsometry, QCM-D and neutron reflectometry. Aqueous solutions of all samples were characterized with light scattering to determine how the degree of side-group substitution and molecular weight affect the conformation and aggregation of these polymers in the bulk. In addition, hemicellulose samples were studied with SAXS to investigate backbone flexibility. Light scattering results indicated that GM polymers form globular particles while GGMs were found to form rod-like aggregates in the solution. The polysaccharides exhibit higher adsorption to cellulose than on hydrophobic surfaces. A clear correlation between the increase in molecular weight of polysaccharides and increasing adsorbed amount on cellulose was observed, while the adsorbed amount on the hydrophobic surface was fairly independent of the molecular weight. The obtained layer thickness was compared with bulk scattering data and the results indicated flat conformation of the polysaccharides on the surface.

Nuclear Spin Incoherent Neutron Scattering from Quantum Well Resonators.

We report the detection and quantification of nuclear spin incoherent scattering from hydrogen occupying interstitial sites in a thin film of vanadium. The neutron wave field is enhanced in a quantum resonator with magnetically switchable boundaries. Our results provide a pathway for the study of dynamics at surfaces and in ultrathin films using inelastic and/or quasielastic neutron scattering methods.

Interfacial properties of lipid sponge-like nanoparticles and the role of stabilizer on particle structure and surface interactions.

The advantage of using nonlamellar lipid liquid crystalline phases has been demonstrated in many applications, such as drug delivery, protein encapsulation and crystallisation. We have recently reported that a mixture of mono- and diglycerides is able to form sponge-like nanoparticles (L3-NPs) with large enough aqueous pores to encapsulate macromolecules such as proteins. Here we use small angle neutron scattering (SANS) to reveal morphology, structural and chemical composition of these polysorbate 80 (P80) stabilized sponge phase nanoparticles, not previously known. Our results suggest that L3-NPs have a core-shell sphere structure, with a shell rich in P80. It was also found that even if P80 is mostly located on the surface, it also contributes to the formation of the inner sponge phase structure. An important aspect for the application and colloidal stability of these particles is their interfacial properties. Therefore, the interfacial behaviour of the nanoparticles on hydrophilic silica was revealed by Quartz crystal microbalance with dissipation (QCM-D) and neutron reflectivity (NR). Adsorption experiments reveal the formation of a thin lipid layer, with the dimension corresponding to a lipid bilayer after L3-NPs are in contact with hydrophilic silica. This suggests that the diglycerol monoleate/Capmul GMO-50/P80 particles reorganize themselves on this surface, probably due to interactions between P80 head group and SiO2.

Electro-responsivity of ionic liquid boundary layers in a polar solvent revealed by neutron reflectance.

Using neutron reflectivity, the electro-responsive structuring of the non-halogenated ionic liquid (IL) trihexyl(tetradecyl)phosphonium-bis(mandelato)borate, [P6,6,6,14][BMB], has been studied at a gold electrode surface in a polar solvent. For a 20% w/w IL mixture, contrast matched to the gold surface, distinct Kiessig fringes were observed for all potentials studied, indicative of a boundary layer of different composition to that of the bulk IL-solvent mixture. With applied potential, the amplitudes of the fringes from the gold-boundary layer interface varied systematically. These changes are attributable to the differing ratios of cations and anions in the boundary layer, leading to a greater or diminished contrast with the gold electrode, depending on the individual ion scattering length densities. Such electro-responsive changes were also evident in the reflectivities measured for the pure IL and a less concentrated (5% w/w) IL-solvent mixture at the same applied potentials, but gave rise to less pronounced changes. These measurements, therefore, demonstrate the enhanced sensitivity achieved by contrast matching the bulk solution and that the structure of the IL boundary layers formed in mixtures is strongly influenced by the bulk concentration. Together these results represent an important step in characterising IL boundary layers in IL-solvent mixtures and provide clear evidence of electro-responsive structuring of IL ions in their solutions with applied potential.

Depth resolved grazing incidence neutron scattering experiments from semi-infinite interfaces: a statistical analysis of the scattering contributions.

Grazing incidence neutron scattering experiments offer surface sensitivity by reflecting from an interface at momentum transfers close to total external reflection. Under these conditions the penetration depth is strongly non-linear and may change by many orders of magnitude. This fact imposes severe challenges for depth resolved experiments, since the brilliance of neutron beams is relatively low in comparison to e.g. synchrotron radiation. In this article we use probability density functions to calculate the contribution of scattering at different distances from an interface to the intensities registered on the detector. Our method has the particular advantage that the depth sensitivity is directly extracted from the scattering pattern itself. Hence for perfectly known samples exact resolution functions can be calculated and visa versa. We show that any tails in the resolution function, e.g. Gaussian shaped, hinders depth resolved experiments. More importantly we provide means for a descriptive statistical analysis of detector images with respect to the scattering contributions and show that even for perfect resolution near surface scattering is hardly accessible.

Interactions of perfluoroalkyl substances with a phospholipid bilayer studied by neutron reflectometry.

The interactions between perfluoroalkyl substances (PFASs) and a phospholipid bilayer (1,2-dimyristoyl-sn-glycero-3-phosphocholine) were investigated at the molecular level using neutron reflectometry. Representative PFASs with different chain length and functional groups were selected in this study including: perfluorobutane sulfonate (PFBS), perfluorohexanoate (PFHxA), perfluorohexane sulfonate (PFHxS), perfluorononanoate (PFNA), perfluorooctane sulfonate (PFOS), and perfluorooctane sulfonamide (FOSA). All PFASs were found to interact with the bilayer by incorporation, indicating PFAS ability to accumulate once ingested or taken up by organisms. The interactions were observed to increase with chain length and vary with the functional group as SO2NH2(FOSA)>SO2O-(PFOS)>COO-(PFNA). The PFAS hydrophobicity, which is strongly correlated with perfluorocarbon chain length, was found to strongly influence the interactions. Longer chain PFASs showed higher tendency to penetrate into the bilayer compared to the short-chain compounds. The incorporated PFASs could for all substances but one (PFNA) be removed from the lipid membrane by gentle rinsing with water (2mLmin-1). Although short-chain PFASs have been suggested to be the potentially less bioaccumulative alternative, we found that in high enough concentrations they can also disturb the bilayer. The roughness and disorder of the bilayer was observed to increase as the concentration of PFASs increased (in particular for the high concentrations of short-chain substances i.e. PFHxA and PFBS), which can be an indication of aggregation of PFASs in the bilayer.

Non-lamellar lipid assembly at interfaces: controlling layer structure by responsive nanogel particles.

Biological membranes do not only occur as planar bilayer structures, but depending on the lipid composition, can also curve into intriguing three-dimensional structures. In order to fully understand the biological implications as well as to reveal the full potential for applications, e.g. for drug delivery and other biomedical devices, of such structures, well-defined model systems are required. Here, we discuss the formation of lipid non-lamellar liquid crystalline (LC) surface layers spin-coated from the constituting lipids followed by hydration of the lipid layer. We demonstrate that hybrid lipid polymer films can be formed with different properties compared with the neat lipid LC layers. The nanostructure and morphologies of the lipid films formed reflect those in the bulk. Most notably, mixed lipid layers, which are composed of glycerol monooleate and diglycerol monooleate with poly(N-isopropylacrylamide) nanogels, can form films of reverse cubic phases that are capable of responding to temperature stimulus. Owing to the presence of the nanogel particles, changing the temperature not only regulates the hydration of the cubic phase lipid films, but also the lateral organization of the lipid domains within the lipid self-assembled film. This opens up the possibility for new nanostructured materials based on lipid-polymer responsive layers.

Concentration dependence of hydrogen diffusion in clamped vanadium (0 0 1) films.

The chemical diffusion coefficient of hydrogen in a 50 nm thin film of vanadium (0 0 1) is measured as a function of concentration and temperature, well above the known phase boundaries. Arrhenius analysis of the tracer diffusion constants reveal large changes in the activation energy with concentration: from 0.10 at 0.05 in H V-1 to 0.5 eV at 0.2 in H V-1. The results are consistent with a change from tetrahedral to octahedral site occupancy, in that concentration range. The change in site occupancy is argued to be caused by the uniaxial expansion of the film originating from the combined hydrogen induced expansion and the clamping of the film to the substrate.

Neutron Reflectometry reveals the interaction between functionalized SPIONs and the surface of lipid bilayers.

The safe application of nanotechnology devices in biomedicine requires fundamental understanding on how they interact with and affect the different components of biological systems. In this respect, the cellular membrane, the cell envelope, certainly represents an important target or barrier for nanosystems. Here we report on the interaction between functionalized SuperParamagnetic Iron Oxide Nanoparticles (SPIONs), promising contrast agents for Magnetic Resonance Imaging (MRI), and lipid bilayers that mimic the plasma membrane. Neutron Reflectometry, supported by Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) experiments, was used to characterize this interaction by varying both SPION coating and lipid bilayer composition. In particular, the interaction of two different SPIONs, functionalized with a cationic surfactant and a zwitterionic phospholipid, and lipid bilayers, containing different amount of cholesterol, were compared. The obtained results were further validated by Dynamic Light Scattering (DLS) measurements and Cryogenic Transmission Electron Microscopy (Cryo-TEM) images. None of the investigated functionalized SPIONs were found to disrupt the lipid membrane. However, in all case we observed the attachment of the functionalized SPIONs onto the surface of the bilayers, which was affected by the bilayer rigidity, i.e. the cholesterol concentration.

Depth profiling charge accumulation from a ferroelectric into a doped Mott insulator.

The electric field control of functional properties is a crucial goal in oxide-based electronics. Nonvolatile switching between different resistivity or magnetic states in an oxide channel can be achieved through charge accumulation or depletion from an adjacent ferroelectric. However, the way in which charge distributes near the interface between the ferroelectric and the oxide remains poorly known, which limits our understanding of such switching effects. Here, we use a first-of-a-kind combination of scanning transmission electron microscopy with electron energy loss spectroscopy, near-total-reflection hard X-ray photoemission spectroscopy, and ab initio theory to address this issue. We achieve a direct, quantitative, atomic-scale characterization of the polarization-induced charge density changes at the interface between the ferroelectric BiFeO3 and the doped Mott insulator Ca(1-x)Ce(x)MnO3, thus providing insight on how interface-engineering can enhance these switching effects.

Finite-size effects: hydrogen in Fe/V(001) superlattices.

We investigate the effect of finite size on phase boundaries of hydride formation in ultrathin metallic films, using Fe/V(001) superlattices as a model system. The critical temperature is determined to scale linearly with the inverse thickness of the V layers. The decrease of the ordering temperature with decreasing layer thickness arises from the missing H neighbors at the interfaces, analogous to observed finite-size effects in magnetic layers and nanosized ice crystals.

Strong interlayer coupling in van der Waals heterostructures built from single-layer chalcogenides.

Semiconductor heterostructures are the fundamental platform for many important device applications such as lasers, light-emitting diodes, solar cells, and high-electron-mobility transistors. Analogous to traditional heterostructures, layered transition metal dichalcogenide heterostructures can be designed and built by assembling individual single layers into functional multilayer structures, but in principle with atomically sharp interfaces, no interdiffusion of atoms, digitally controlled layered components, and no lattice parameter constraints. Nonetheless, the optoelectronic behavior of this new type of van der Waals (vdW) semiconductor heterostructure is unknown at the single-layer limit. Specifically, it is experimentally unknown whether the optical transitions will be spatially direct or indirect in such hetero-bilayers. Here, we investigate artificial semiconductor heterostructures built from single-layer WSe2 and MoS2. We observe a large Stokes-like shift of ∼ 100 meV between the photoluminescence peak and the lowest absorption peak that is consistent with a type II band alignment having spatially direct absorption but spatially indirect emission. Notably, the photoluminescence intensity of this spatially indirect transition is strong, suggesting strong interlayer coupling of charge carriers. This coupling at the hetero-interface can be readily tuned by inserting dielectric layers into the vdW gap, consisting of hexagonal BN. Consequently, the generic nature of this interlayer coupling provides a new degree of freedom in band engineering and is expected to yield a new family of semiconductor heterostructures having tunable optoelectronic properties with customized composite layers.

Using light transmission to watch hydrogen diffuse.

Because of its light weight and small size, hydrogen exhibits one of the fastest diffusion rates in solid materials, comparable to the diffusion rate of liquid water molecules at room temperature. The diffusion rate is determined by an intricate combination of quantum effects and dynamic interplay with the displacement of host atoms that is still only partially understood. Here we present direct observations of the spatial and temporal changes in the diffusion-induced concentration profiles in a vanadium single crystal and we show that the results represent the experimental counterpart of the full time and spatial solution of Fick's diffusion equation. We validate the approach by determining the diffusion rate of hydrogen in a single crystal vanadium (001) film, with net diffusion in the [110] direction.

Hydrogen distribution in Nb/Ta superlattices.

The distribution of hydrogen in Nb/Ta superlattices has been investigated by combined neutron reflectivity and x-ray scattering. We provide evidence to support that strain modulations determined with x-ray diffraction can be interpreted as modulations in hydrogen content. We show that the hydrogen concentration is modulated and favors Nb, in agreement with previous studies. We measure the concentration directly using neutron reflectivity and demonstrate no detectable change in the distribution of hydrogen with temperature, in stark contrast to previous studies.

Significance of self-trapping on hydrogen diffusion.

The diffusion rate of hydrogen in Nb was calculated using ab initio molecular dynamics simulations. At low temperatures the hydrogen is strongly trapped in a local strain field which is caused by the elastic response of the lattice. At elevated temperatures, the residence time (τ) of hydrogen in an interstitial site is not sufficient for fully developing the local strain field. This unbinding of the interstitial hydrogen and the strain field increases the hopping rate (1/τ) at elevated temperatures (>400 K). These results call for a revision of the conceptual framework of diffusion of hydrogen in transition metals at elevated temperatures.