Schottky-type grain boundaries in CCTO ceramics

In this work we studied electrical barriers existing at CaCu₃Ti₄O₁₂ (CCTO) ceramics using dc electrical measurements. CCTO pellets were produced by solid state reaction method and X-ray diffractograms showed which single phase polycrystalline samples were obtained. The samples were electrically characterized by dc and ac measurements as a function of temperature, and semiconductor theory was applied to analyze the barrier at grain boundaries. The ac results showed the sample’s permittivity is almost constant (10⁴) as function of temperature at low frequencies and it changes from 100 to 10⁴ as the temperature increases at high frequencies. Using dc measurements as a function of temperature, the behavior of barriers was studied in detail. Comparison between Schottky and Poole-Frenkel models was performed, and results prove that CCTO barriers are more influenced by temperature than by electric field (Schottky barriers). Besides, the behavior of barrier width as function of temperature was also studied and experimental results confirm the theoretical assumptions.     

The origin for tubular growth of TiO2 nanotubes: A fluoride rich layer between tube-walls

High resolution Scanning Auger Electron Spectroscopy (AES) is used to demonstrate the compositional variation across self-organized TiO₂ nanotube layers grown in fluoride containing ethylene glycol electrolytes. The analysis results show a distinct fluoride rich layer in between the TiO₂ nanotubes and particularly in the triple points of the hexagonally ordered nanotubular arrays. AES analysis further revealed that extended e-beam exposure leads to a decrease in the fluoride signal (electron beam induced decomposition of fluoride species). The proof of the existence of a fluoride rich layer located between the tube walls strongly supports fluoride dissolution as the reason for a transition from a porous to a tubular morphology.     

Dealloying of platinum-aluminum thin films: dynamics of pattern formation

The application of focused ion beam (FIB) nanotomography and Rutherford backscattering spectroscopy (RBS) to dealloyed platinum-aluminum thin films allows for an in-depth analysis of the dominating physical mechanisms of nanoporosity formation during the dealloying process. The porosity formation due to the dissolution of the less noble aluminum in the alloy is treated as result of a reaction-diffusion system. The RBS and FIB analysis yields that the porosity evolution has to be regarded as superposition of two independent processes, a linearly propagating diffusion front with a uniform speed and a slower dissolution process in regions which have already been passed by the diffusion front. The experimentally observed front evolution is captured by the Fisher-Kolmogorov-Petrovskii-Piskounov (FKPP). The slower dissolution is represented by a zero-order rate law which causes a gradual porosity in the thin film.     

Fermi bubbles: giant, multibillion-year-old reservoirs of Galactic center cosmic rays

Recently evidence has emerged for enormous features in the γ-ray sky observed by the Fermi-LAT instrument: bilateral "bubbles" of emission centered on the core of the Galaxy and extending to around ± 10 kpc from the Galactic plane. These structures are coincident with a nonthermal microwave "haze" and an extended region of x-ray emission. The bubbles' γ-ray emission is characterized by a hard and relatively uniform spectrum, relatively uniform intensity, and an overall luminosity 4×10(37) erg/s, around 1 order of magnitude larger than their microwave luminosity while more than order of magnitude less than their x-ray luminosity. Here we show that the bubbles are naturally explained as due to a population of relic cosmic ray protons and heavier ions injected by processes associated with extremely long time scale (? 8 Gyr) and high areal density star formation in the Galactic center.     

Lateral shearing interferometry of high-harmonic wavefronts

We present a technique for frequency-resolved wavefront characterization of high harmonics based on lateral shearing interferometry. Tilted replicas of the driving laser pulse are produced by a Mach-Zehnder interferometer, producing separate focii in the target. The interference of the resulting harmonics on a flat-field extreme ultraviolet spectrometer yields the spatial phase derivative. A comprehensive set of spatial profiles, resolved by harmonic order, validate the technique and reveal the interplay of single-atom and macroscopic effects.     

Zipping up: cooperativity drives the synthesis of graphene nanoribbons

We investigate the cooperative effects controlling the synthesis of a graphene nanoribbon on the Au(111) surface starting from an anthracene polymer using density functional calculations including van der Waals interactions. We focus on the high-temperature cyclodehydrogenation step of the reaction and find that the reaction proceeds by simultaneously transferring two H-atoms from the anthracene units to the Au surface, leaving behind a C-C bond in the process. This step is significantly more favorable than the three other potential reaction paths. Moreover, we find that successive dehydrogenations proceed from one end of the polyanthracene and propagate step-by-step through the polymer in a domino-like fashion.     

Spatial correlations of density and structural fluctuations in liquid water: a comparative simulation study

We use large-scale classical simulations employing different force fields to study spatial correlations between local density and structural order for water in the liquid temperature range. All force fields investigated reproduce the main features of the experimental SAXS structure factor S(q), including the minimum at small q, and the recent TIP4P/2005 parametrization yields almost quantitative agreement. As local structural order parameters we consider the tetrahedrality and the number of hydrogen bonds and calculate all pure and mixed spatial two-point correlation functions. Except for the density-density correlation function, there are only weak features present in all other correlation functions, showing that the tendency to form structural clusters is much weaker than the well-known tendency of water to form density clusters (i.e., spatially correlated regions where the density deviates from the mean). In particular, there are only small spatial correlations between local density and structural fluctuations, suggesting that features in density-density correlations (such as measured by the structure factor) are not straightforwardly related to spatial correlations of structure in liquid water.     

Millisecond dynamics in glutaredoxin during catalytic turnover is dependent on substrate binding and absent in the resting states

Conformational dynamics is important for enzyme function. Which motions of enzymes determine catalytic efficiency and whether the same motions are important for all enzymes, however, are not well understood. Here we address conformational dynamics in glutaredoxin during catalytic turnover with a combination of NMR magnetization transfer, R(2) relaxation dispersion, and ligand titration experiments. Glutaredoxins catalyze a glutathione exchange reaction, forming a stable glutathinoylated enzyme intermediate. The equilibrium between the reduced state and the glutathionylated state was biochemically tuned to exchange on the millisecond time scale. The conformational changes of the protein backbone during catalysis were followed by (15)N nuclear spin relaxation dispersion experiments. A conformational transition that is well described by a two-state process with an exchange rate corresponding to the glutathione exchange rate was observed for 23 residues. Binding of reduced glutathione resulted in competitive inhibition of the reduced enzyme having kinetics similar to that of the reaction. This observation couples the motions observed during catalysis directly to substrate binding. Backbone motions on the time scale of catalytic turnover were not observed for the enzyme in the resting states, implying that alternative conformers do not accumulate to significant concentrations. These results infer that the turnover rate in glutaredoxin is governed by formation of a productive enzyme-substrate encounter complex, and that catalysis proceeds by an induced fit mechanism rather than by conformer selection driven by intrinsic conformational dynamics.     

Pulsed laser deposition of polymer-metal nanocomposites

Different polymer-metal nanocomposites, metal clusters on a polymer surface and for the first time also polymer/metal multilayers, were pulsed laser deposited at a wavelength of 248 nm. Poly(methyl methacrylate) (PMMA) and Bisphenol A dimeth-acrylate (BisDMA), which strongly differ in their hardness of 3 and 180 N/mm², respectively, were taken as polymer components. Metals Ag and Cu were chosen because of their different reactivity to polymers. When depositing Ag on PMMA, spherical clusters are formed due to high diffusion and total coalescence. For Cu, much smaller grains with partially elongated shapes occur because of lower diffusivity and incomplete coalescence. Compared to the results on the soft PMMA, the clusters formed on the harder BisDMA are much larger due to higher diffusivity on this underlayer. In PMMA/Cu multilayers, wavy layered structures and buckling is observed due to relaxation of compressive stress in the Cu layers. Smooth Cu layers with higher thicknesses can only be obtained, when the hardness of the polymer is sufficiently high, as in the case of BisDMA/Cu multilayers.     

Cyst Reduction by Melatonin in a Novel Drosophila Model of Polycystic Kidney Disease

Autosomal dominant polycystic kidney disease (ADPKD) causes progressive cystic degeneration of the renal tubules, the nephrons, eventually severely compromising kidney function. ADPKD is incurable, with half of the patients eventually needing renal replacement. Treatments for ADPKD patients are limited and new effective therapeutics are needed. Melatonin, a central metabolic regulator conserved across all life kingdoms, exhibits oncostatic and oncoprotective activity and no detected toxicity. Here, we used the Bicaudal C (BicC) Drosophila model of polycystic kidney disease to test the cyst-reducing potential of melatonin. Significant cyst reduction was found in the renal (Malpighian) tubules upon melatonin administration and suggest mechanistic sophistication. Similar to vertebrate PKD, the BicC fly PKD model responds to the antiproliferative drugs rapamycin and mimics of the second mitochondria-derived activator of caspases (Smac). Melatonin appears to be a new cyst-reducing molecule with attractive properties as a potential candidate for PKD treatment.