ASU Scholarship Showcase

Multilayer structures of TiO₂/Ag/TiO₂ have been deposited onto flexible substrates by room temperature sputtering to develop indium-free transparent composite electrodes. The effect of Ag thicknesses on optical and electrical properties and the mechanism of conduction have been discussed. The critical thickness (t_c) of Ag mid-layer to form a continuous conducting layer is 9.5 nm and the multilayer has been optimized to obtain a sheet resistance of 5.7 Ω/sq and an average optical transmittance of 90% at 590 nm. The Haacke figure of merit (FOM) for t_c has one of the highest FOMs with 61.4 × 10^-3 Ω^-1/sq.

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH₂, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH₃). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH₂ and LiBeH₃ using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH₂, lithium-beryllium hydride LiBeH₃ exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic that it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH₂ and LiBeH₃ over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH₃ so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.

Cyan fluorescent proteins (CFPs), such as Cerulean, are widely used as donor fluorophores in Förster resonance energy transfer (FRET) experiments. Nonetheless, the most widely used variants suffer from drawbacks that include low quantum yields and unstable flurorescence. To improve the fluorescence properties of Cerulean, we used the X-ray structure to rationally target specific amino acids for optimization by site-directed mutagenesis. Optimization of residues in strands 7 and 8 of the β-barrel improved the quantum yield of Cerulean from 0.48 to 0.60. Further optimization by incorporating the wild-type T65S mutation in the chromophore improved the quantum yield to 0.87. This variant, mCerulean3, is 20% brighter and shows greatly reduced fluorescence photoswitching behavior compared to the recently described mTurquoise fluorescent protein in vitro and in living cells. The fluorescence lifetime of mCerulean3 also fits to a single exponential time constant, making mCerulean3 a suitable choice for fluorescence lifetime microscopy experiments. Furthermore, inclusion of mCerulean3 in a fusion protein with mVenus produced FRET ratios with less variance than mTurquoise-containing fusions in living cells. Thus, mCerulean3 is a bright, photostable cyan fluorescent protein which possesses several characteristics that are highly desirable for FRET experiments.

In proteins, functional divergence involves mutations that modify structure and dynamics. Here we provide experimental evidence for an evolutionary mechanism driven solely by long-range dynamic motions without significant backbone adjustments, catalytic group rearrangements, or changes in subunit assembly. Crystallographic structures were determined for several reconstructed ancestral proteins belonging to a GFP class frequently employed in superresolution microscopy. Their chain flexibility was analyzed using molecular dynamics and perturbation response scanning. The green-to-red photoconvertible phenotype appears to have arisen from a common green ancestor by migration of a knob-like anchoring region away from the active site diagonally across the β barrel fold. The allosterically coupled mutational sites provide active site conformational mobility via epistasis. We propose that light-induced chromophore twisting is enhanced in a reverse-protonated subpopulation, activating internal acid-base chemistry and backbone cleavage to enlarge the chromophore. Dynamics-driven hinge migration may represent a more general platform for the evolution of novel enzyme activities.

A water drop on a superhydrophobic surface that is pinned by wire loops can be reproducibly cut without formation of satellite droplets. Drops placed on low-density polyethylene surfaces and Teflon-coated glass slides were cut with superhydrophobic knives of low-density polyethylene and treated copper or zinc sheets, respectively. Distortion of drop shape by the superhydrophobic knife enables a clean break. The driving force for droplet formation arises from the lower surface free energy for two separate drops, and it is modeled as a 2-D system. An estimate of the free energy change serves to guide when droplets will form based on the variation of drop volume, loop spacing and knife depth. Combining the cutting process with an electrofocusing driving force could enable a reproducible biomolecular separation without troubling satellite drop formation.

Natural selection among tumor cell clones is thought to produce hallmark properties of malignancy. Efforts to understand evolution of one such hallmark—the angiogenic switch—has suggested that selection for angiogenesis can “run away” and generate a hypertumor, a form of evolutionary suicide by extreme vascular hypo- or hyperplasia. This phenomenon is predicted by models of tumor angiogenesis studied with the techniques of adaptive dynamics. These techniques also predict that selection drives tumor proliferative potential towards an evolutionarily stable strategy (ESS) that is also convergence-stable. However, adaptive dynamics are predicated on two key assumptions: (i) no more than two distinct clones or evolutionary strategies can exist in the tumor at any given time; and (ii) mutations cause small phenotypic changes. Here we show, using a stochastic simulation, that relaxation of these assumptions has no effect on the predictions of adaptive dynamics in this case. In particular, selection drives proliferative potential towards, and angiogenic potential away from, their respective ESSs. However, these simulations also show that tumor behavior is highly contingent on mutational history, particularly for angiogenesis. Individual tumors frequently grow to lethal size before the evolutionary endpoint is approached. In fact, most tumor dynamics are predicted to be in the evolutionarily transient regime throughout their natural history, so that clinically, the ESS is often largely irrelevant. In addition, we show that clonal diversity as measured by the Shannon Information Index correlates with the speed of approach to the evolutionary endpoint. This observation dovetails with results showing that clonal diversity in Barrett's esophagus predicts progression to malignancy.

Biophotovoltaic devices employ photosynthetic organisms at the anode of a microbial fuel cell to generate electrical power. Although a range of cyanobacteria and algae have been shown to generate photocurrent in devices of a multitude of architectures, mechanistic understanding of extracellular electron transfer by phototrophs remains minimal. Here we describe a mediatorless bioelectrochemical device to measure the electrogenic output of a planktonically grown cyanobacterium, Synechocystis sp. PCC6803. Light dependent production of current is measured, and its magnitude is shown to scale with microbial cell concentration and light intensity. Bioelectrochemical characterization of a Synechocystis mutant lacking Photosystem II demonstrates conclusively that production of the majority of photocurrent requires a functional water splitting aparatus and electrons are likely ultimately derived from water. This shows the potential of the device to rapidly and quantitatively characterize photocurrent production by genetically modified strains, an approach that can be used in future studies to delineate the mechanisms of cyanobacterial extracellular electron transport.

The Dawn Framing Camera (FC) has imaged the northern hemisphere of the Asteroid (4) Vesta at high spatial resolution and coverage. This study represents the first investigation of the overall geology of the northern hemisphere (22–90°N, quadrangles Av-1, 2, 3, 4 and 5) using these unique Dawn mission observations. We have compiled a morphologic map and performed crater size–frequency distribution (CSFD) measurements to date the geologic units. The hemisphere is characterized by a heavily cratered surface with a few highly subdued basins up to ∼200 km in diameter. The most widespread unit is a plateau (cratered highland unit), similar to, although of lower elevation than the equatorial Vestalia Terra plateau. Large-scale troughs and ridges have regionally affected the surface. Between ∼180°E and ∼270°E, these tectonic features are well developed and related to the south pole Veneneia impact (Saturnalia Fossae trough unit), elsewhere on the hemisphere they are rare and subdued (Saturnalia Fossae cratered unit). In these pre-Rheasilvia units we observed an unexpectedly high frequency of impact craters up to ∼10 km in diameter, whose formation could in part be related to the Rheasilvia basin-forming event. The Rheasilvia impact has potentially affected the northern hemisphere also with S–N small-scale lineations, but without covering it with an ejecta blanket. Post-Rheasilvia impact craters are small (<60 km in diameter) and show a wide range of degradation states due to impact gardening and mass wasting processes. Where fresh, they display an ejecta blanket, bright rays and slope movements on walls. In places, crater rims have dark material ejecta and some crater floors are covered by ponded material interpreted as impact melt.

Oppia Quadrangle Av-10 (288–360°E, ±22°) is a junction of key geologic features that preserve a rough history of Asteroid (4) Vesta and serves as a case study of using geologic mapping to define a relative geologic timescale. Clear filter images, stereo-derived topography, slope maps, and multispectral color-ratio images from the Framing Camera on NASA’s Dawn spacecraft served as basemaps to create a geologic map and investigate the spatial and temporal relationships of the local stratigraphy. Geologic mapping reveals the oldest map unit within Av-10 is the cratered highlands terrain which possibly represents original crustal material on Vesta that was then excavated by one or more impacts to form the basin Feralia Planitia. Saturnalia Fossae and Divalia Fossae ridge and trough terrains intersect the wall of Feralia Planitia indicating that this impact basin is older than both the Veneneia and Rheasilvia impact structures, representing Pre-Veneneian crustal material. Two of the youngest geologic features in Av-10 are Lepida (∼45 km diameter) and Oppia (∼40 km diameter) impact craters that formed on the northern and southern wall of Feralia Planitia and each cross-cuts a trough terrain. The ejecta blanket of Oppia is mapped as ‘dark mantle’ material because it appears dark orange in the Framing Camera ‘Clementine-type’ color-ratio image and has a diffuse, gradational contact distributed to the south across the rim of Rheasilvia. Mapping of surface material that appears light orange in color in the Framing Camera ‘Clementine-type’ color-ratio image as ‘light mantle material’ supports previous interpretations of an impact ejecta origin. Some light mantle deposits are easily traced to nearby source craters, but other deposits may represent distal ejecta deposits (emplaced >5 crater radii away) in a microgravity environment.

The Quadrangles Av-11 and Av-12 on Vesta are located at the northern rim of the giant Rheasilvia south polar impact basin. The primary geologic units in Av-11 and Av-12 include material from the Rheasilvia impact basin formation, smooth material and different types of impact crater structures (such as bimodal craters, dark and bright crater ray material and dark ejecta material). Av-11 and Av-12 exhibit almost the full range of mass wasting features observed on Vesta, such as slump blocks, spur-and-gully morphologies and landslides within craters. Processes of collapse, slope instability and seismically triggered events force material to slump down crater walls or scarps and produce landslides or rotational slump blocks. The spur-and-gully morphology that is known to form on Mars is also observed on Vesta; however, on Vesta this morphology formed under dry conditions.