From Surfaces to Interfaces: Ambient Pressure XPS and Beyond

The rapidly increasing field of surfaces under ambient conditions of temperature, and pressure in gas and liquid environments, reflects the importance of understanding surface properties in conditions closer to practical situations. This has been enabled by the emergence in the last two decades of a number of new techniques, both spectroscopy and microscopy, that can deliver atomic scale information with the required surface/interface sensitivity. Here we present a short review of recent advances to illustrate the novel understanding derived from the use of new techniques focusing on the gas–solid interface, where two barriers have been bridged: the pressure gap, and the temperature gap. The later gap is very important when dealing with weakly bound molecules, where only by the presence of gas at a suitable pressure can a measurable coverage of adsorbed molecules be achieved. The temperature gap manifests also in the removal of kinetic barriers. Future developments to continue extending the range of pressures are also mentioned. Finally, new challenges that appear, both from X-ray and electron-induced damage to the sample, and from contamination under high pressure of desired gases, while maintaining very low pressures of undesirable ones

Predicting Surface Clustering at Ambient Conditions from Thermodynamic Data

Scanning tunneling microscopy (STM) has proved to be a prime tool to characterize the atomic structure of crystal surfaces under UHV conditions. With the development of high-pressure scanning tunneling microscopy (HP-STM), the scope of this technique has been largely extended, as new structures were found to occur under gas phase chemical potentials achieved under ambient conditions. Particularly interesting is the substantial restructuring of initially flat and stable surfaces into new orientations by formation of nanoclusters. Here we discuss the possible generality of this phenomenon by analyzing cases where atomically flat surfaces of certain transition metals undergo such changes in the presence of CO at room temperature (RT) while some remain unchanged. From our analysis we argue that such changes can be predicted from thermodynamic data published in the literature, particularly from the difference in adsorption energy on low-and high-coordination sites, like terrace and step sites, which can be obtained from thermal desorption spectroscopy (TDS) measurements, and possibly also from theoretical calculations. For the vicinal surfaces with high Miller indices, changes in the repulsive elastic interactions between the ordered steps due to adsorbates may also play an important role

Angular momentum transport in protostellar discs

Angular momentum transport in protostellar discs can take place either radially, through turbulence induced by the magnetorotational instability (MRI), or vertically, through the torque exerted by a large-scale magnetic field that threads the disc. Using semi-analytic and numerical results, we construct a model of steady-state discs that includes vertical transport by a centrifugally driven wind as well as MRI-induced turbulence. We present approximate criteria for the occurrence of either one of these mechanisms in an ambipolar diffusion-dominated disc. We derive ``strong field'' solutions in which the angular momentum transport is purely vertical and ``weak field'' solutions that are the stratified-disc analogues of the previously studied MRI channel modes; the latter are transformed into accretion solutions with predominantly radial angular-momentum transport when we implement a turbulent-stress prescription based on published results of numerical simulations. We also analyze ``intermediate field strength'' solutions in which both modes of transport operate at the same radial location; we conclude, however, that significant spatial overlap of these two mechanisms is unlikely to occur in practice. To further advance this study, we have developed a general scheme that incorporates also the Hall and Ohm conductivity regimes in discs with a realistic ionization structure.Comment: 8 pages, 4 figures, 1 table; accepted for publication in MNRA

Cell migration on material-driven fibronectin microenvironments

Cell migration is a fundamental process involved in a wide range of biological phenomena. However, how the underlying mechanisms that control migration are orchestrated is not fully understood. In this work, we explore the migratory characteristics of human fibroblasts using different organisations of fibronectin (FN) triggered by two chemically similar surfaces, poly(ethyl acrylate) (PEA) and poly(methyl acrylate) (PMA); cell migration is mediated via an intermediate layer of fibronectin (FN). FN is organised into nanonetworks upon simple adsorption on PEA whereas a globular conformation is observed on PMA. We studied cell speed over the course of 24 h and the morphology of focal adhesions in terms of area and length. Additionally, we analysed the amount of cell-secreted FN as well as FN remodelling. Velocity of human fibroblasts was found to exhibit a biphasic behaviour on PEA, whereas it remained fairly constant on PMA. FA analysis revealed more mature focal adhesions on PEA over time contrary to smaller FAs found on PMA. Finally, human fibroblasts seemed to remodel adsorbed FN more on PMA than on PEA. Overall, these results indicate that the cell–protein–material interface affects cell migratory behaviour. Analysis of FAs together with FN secretion and remodelling were associated with differences in cell velocity providing insights into the factors that can modulate cell motility

Electrospun fibrinogen-PLA nanofibres for vascular tissue engineering

Here we report on the development of a new type of hybrid fibrinogen–polylactic acid (FBG–PLA) nanofibres (NFs) with improved stiffness, combining the good mechanical properties of PLA with the excellent cell recognition properties of native FBG. We were particularly interested in the dorsal and ventral cell response to the nanofibres' organization (random or aligned), using human umbilical endothelial cells (HUVECs) as a model system. Upon ventral contact with random NFs, the cells developed a stellate-like morphology with multiple projections. The well-developed focal adhesion complexes suggested a successful cellular interaction. However, time-lapse analysis shows significantly lowered cell movements, resulting in the cells traversing a relatively short distance in multiple directions. Conversely, an elongated cell shape and significantly increased cell mobility were observed in aligned NFs. To follow the dorsal cell response, artificial wounds were created on confluent cell layers previously grown on glass slides and covered with either random or aligned NFs. Time-lapse analysis showed significantly faster wound coverage (within 12 h) of HUVECs on aligned samples vs. almost absent directional migration on random ones. However, nitric oxide (NO) release shows that endothelial cells possess lowered functionality on aligned NFs compared to random ones, where significantly higher NO production was found. Collectively, our studies show that randomly organized NFs could support the endothelization of implants while aligned NFs would rather direct cell locomotion for guided neovascularization

Radial and vertical angular momentum transport in protostellar discs

Angular momentum in protostellar discs can be transported either radially, through turbulence induced by the magnetorotational instability (MRI), or vertically, through the torque exerted by a large-scale magnetic field. We present a model of steady-state discs where these two mechanisms operate at the same radius and derive approximate criteria for their occurrence in an ambipolar diffusion dominated disc. We obtain "weak field'' solutions - which we associate with the MRI channel modes in a stratified disc - and transform them into accretion solutions with predominantly radial angular-momentum transport by implementing a turbulent-stress prescription based on published results of numerical simulations. We also analyze "intermediate field strength'' solutions in which both radial and vertical transport operate at the same radial location. Our results suggest, however, that this overlap is unlikely to occur in real discs.Comment: 5 pages, 2 figures, 1 table, aastex.cls. Accepted for publication in Astrophysics & Space Scienc

Operando STM study of the interaction of imidazolium-based ionic liquid with graphite

Understanding interactions at the interfaces of carbon with ionic liquids (ILs) is crucially beneficial for the diagnostics and performance improvement of electrochemical devices containing carbon as active materials or conductive additives in electrodes and ILs as solvents or additives in electrolytes. The interfacial interactions of three typical imidazolium-based ILs, 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (AMImTFSI) ILs having ethyl (C2), butyl (C4) and octyl (C8) chains in their cations, with highly oriented pyrolytic graphite (HOPG) were studied in-situ by electrochemical scanning tunneling microscopy (EC-STM). The etching of HOPG surface and the exfoliation of graphite/graphene flakes as well as cation intercalation were observed at the HOPG/C2MImTFSI interface. The etching also takes place in C4MImTFSI at −1.5 V vs Pt but only at step edges with a much slower rate, whereas C8MIm+ cations adsorbs strongly on the HOPG surface under similar conditions with no observable etching or intercalation. The EC-STM observations can be explained by the increase in van der Waals interaction between the cations and the graphite surface with increasing length of alkyl chains

Nanoimaging of Organic Charge Retention Effects: Implications for Nonvolatile Memory, Neuromorphic Computing, and High Dielectric Breakdown Devices

While a large variety of organic and molecular materials have been found to exhibit charge memory effects, the underlying mechanism is not well-understood, which hinders rational device design. Here, we study the charge retention mechanism of a nanoscale memory system, an organic monolayer on a silicon substrate, with Au nanoparticles on top serving as the electrical contact. Combining scanning probe imaging/manipulation and density functional simulations, we observe stable charge retention effects in the system and attributed it to polaron effects at the amine functional groups. Our findings can pave the way for applications in nonvolatile memory, neuromorphic computing, and high dielectric breakdown devices

When Langmuir is too simple: H-2 dissociation on Pd(111) at high coverage

Recent experiments of H2 adsorption on Pd(111) [T. Mitsui et al., Nature (London) 422, 705 (2003)] have questioned the classical Langmuir picture of second order adsorption kinetics at high surface coverage requiring pairs of empty sites for the dissociative chemisorption. Experiments find that at least three empty sites are needed. Through density functional theory, we find that H2 dissociation is favored on ensembles of sites that involve a Pd atom with no direct interaction with adsorbed hydrogen. Such active sites are formed by aggregation of at least 3 H-free sites revealing the complex structure of the "active sites.