A soft x-ray probe of a titania photoelectrode sensitized with a triphenylamine dye

We present a thorough soft x-ray photoelectron spectroscopy (XPS) study of a mesoporous titanium dioxide electrode sensitized with the dye 4-(diphenylamino)phenylcyanoacrylic acid, referred to as “L0.” Supported by calculations, the suite of XPS, x-ray absorption spectroscopy, and resonant photoelectron spectroscopy allows us to examine bonding interactions between the dye and the surface and the frontier electronic structure at the molecule-oxide interface. While placing these measurements in the context of existing literature, this paper is intended as a useful reference for further studies of more complex triphenylamine based sensitizers

On the suitability of high vacuum electrospray deposition for the fabrication of molecular electronic devices

We present a series of three studies investigating the potential application of high vacuum electrospray deposition to construct molecular electronic devices. Through the use of time of flight secondary ion mass spectrometry we explore the use of this novel deposition technique to fabricating multilayer structures using materials that are compatible with the same solvents and films containing a mixture of molecules from orthogonal solvents. Using x-ray photoelectron spectroscopy we study the deposition of a polymer blend using electrospray and find evidence of preferential deposition of one of the components

Resonant inelastic X-ray scattering of a Ru photosensitizer: Insights from individual ligands to the electronic structure of the complete molecule

N 1s Resonant Inelastic X-ray Scattering (RIXS) was used to probe the molecular electronic structure of the ruthenium photosensitizer complex cis-bis(isothiocyanato) bis(2,2′-bipyridyl-4,4′-dicarboxylato) ruthenium(II), known as “N3.” In order to interpret these data, crystalline powder samples of the bipyridine-dicarboxylic acid ligand (“bi-isonicotinic acid”) and the single ring analog “isonicotinic acid” were studied separately using the same method. Clear evidence for intermolecular hydrogen bonding is observed for each of these crystalline powders, along with clear vibronic coupling features. For bi-isonicotinic acid, these results are compared to those of a physisorbed multilayer, where no hydrogen bonding is observed. The RIXS of the “N3” dye, again prepared as a bulk powder sample, is interpreted in terms of the orbital contributions of the bi-isonicotinic acid and thiocyanate ligands by considering the two different nitrogen species. This allows direct comparison with the isolated ligand molecules where we highlight the impact of the central Ru atom on the electronic structure of the ligand. Further interpretation is provided through complementary resonant photoemission spectroscopy and density functional theory calculations. This combination of techniques allows us to confirm the localization and relative coupling of the frontier orbitals and associated vibrational losses

Direct synthesis of multiplexed metal nanowire based devices using carbon nanotubes as vector templates

We present the synthesis of metal nanowires in a multiplexed device configuration using single‐walled carbon nanotubes (SWNTs) as nanoscale vector templates. The SWNT templates control the dimensionality of the wires, allowing precise control of their size, shape and orientation; moreover a solution processable approach enables their linear deposition between specific electrode pairs in electronic devices. Electrical characterizations demonstrate the successful fabrication of metal nanowire electronic devices, while multiscale characterization of the different fabrication steps reveals details of the structure and charge transfer between the material encapsulated and the carbon nanotube. Overall the strategy presented allows facile, low‐cost and direct synthesis of multiplexed metal nanowire devices for nanoelectronic applications

Height dependent molecular trapping in stacked cyclic porphyrin nanorings

Stacked layers of cyclic porphyrin nanorings constitute nanoscale receptacles with variable height and diameter which preferentially adsorb sublimed molecules. Using scanning tunnelling microscopy we determine the filling capacity of these nanoring traps, and the dependence of adsorbate capture on stack height and diameter

Electrospray deposition in vacuum as method to create functionally active protein immobilization on polymeric substrates

We demonstrate in this work the deposition of a large biological molecule (fibronectin) on polymeric substrates in a high vacuum environment using an electrospray deposition system. Fibronectin was deposited and its distribution and structure investigated and retention of function (ability to promote cell adhesion) on return to liquid environment is shown. AFM was used to monitor changes in the morphology of the surface before and after fibronectin deposition, whilst the biological activity of the deposited protein is assessed through a quantitative analysis of the biomolecular adhesion and migration of fibroblast cells to the modified surfaces. For the first time we have demonstrated that using high vacuum electrospray deposition it is possible to deposit large protein molecules on polymeric surfaces whilst maintaining the protein activity. The deposition of biological molecules such as proteins with the retention of their activity onto clean well-controlled surfaces under vacuum condition, offers the possibility for future studies utilizing high resolution vacuum based techniques at the atomic and molecular scale providing a greater understanding of protein–surface interface behaviour of relevance to a wide range of applications such as in sensors, diagnostics and tissue engineering

Hypotheses for the Origin of the Hypanis Fan-Shaped Deposit at the Edge of the Chryse Escarpment, Mars: Is it a Delta?

We investigated the origin of the fan-shaped deposit at the end of Hypanis Valles that has previously been proposed as an ExoMars, Mars 2020, and human mission candidate landing site, and found evidence that the landform is an ancient delta. Previous work suggests that the deposit originated from a time of fluvial activity both distinct from and prior to catastrophic outflow, and crater counting placed the deposit’s age at  ≥ 3.6 Ga. We found over 30 thin sedimentary strata in the proposed delta wall, and from our slope analysis conclude that the fluvial sequence is consistent with a lowering/retreating shoreline. We measured nearly horizontal bedding dip angles ranging from 0° to 2° over long stretches of cliff and bench exposures seen in HiRISE images and HiRISE stereo DTMs. From THEMIS night IR images we determined that the fan-shaped deposit has a low thermal inertia (150-240 Jm-2 K-1 s-1/2) and the surrounding darker-toned units correspond to thermal inertia values as high as 270-390 Jm-2 K-1 s-1/2. We interpret these findings to indicate that the fan-shaped deposit consists mostly of silt-sized and possibly finer grains, and that the extremely low grade and large lateral extent of these beds implies that the depositional environment was calm and relatively long-lived. We interpret the geomorphology and composition as incompatible with an alluvial fan or mudflow hypothesis. From our stratigraphic mapping we interpret the order of events which shaped the region. After the Chryse impact, sediment filled the basin, a confined lake or sea formed allowing a large delta to be deposited near its shoreline, the water level receded to the north, darker sedimentary/volcanic units covered the region and capped the light-toned deposit as hydro-volcanic eruptions shaped the interior of Lederberg crater, freeze/thaw cycles and desiccation induced local fracturing, and finally wrinkle ridges associated with rounded cones warped the landscape following trends in degraded crater rims and existing tectonic features. The ancient deltaic deposit we observe today was largely untouched by subsequent catastrophic outflows, and its surface has been only moderately reshaped by over 3 billion years of aeolian erosion