High sensitivity of 17O NMR to p-d hybridization in transition metal perovskites: first principles calculations of large anisotropic chemical shielding

A first principles embedded cluster approach is used to calculate O chemical shielding tensors, sigma, in prototypical transition metal oxide ABO_3 perovskite crystals. Our principal findings are 1) a large anisotropy of sigma between deshielded sigma_x ~ sigma_y and shielded sigma_z components (z along the Ti-O bond); 2) a nearly linear variation, across all the systems studied, of the isotropic sigma_iso and uniaxial sigma_ax components, as a function of the B-O-B bond asymmetry. We show that the anisotropy and linear variation arise from large paramagnetic contributions to sigma_x and sigma_y due to virtual transitions between O(2p) and unoccupied B(nd) states. The calculated isotropic delta_iso and uniaxial delta_ax chemical shifts are in good agreement with recent BaTiO_3 and SrTiO_3 single crystal 17O NMR measurements. In PbTiO_3 and PbZrO_3, calculated delta_iso are also in good agreement with NMR powder spectrum measurements. In PbZrO_3, delta_iso calculations of the five chemically distinct sites indicate a correction of the experimental assignments. The strong dependence of sigma on covalent O(2p)-B(nd) interactions seen in our calculations indicates that 17O NMR spectroscopy, coupled with first principles calculations, can be an especially useful tool to study the local structure in complex perovskite alloys.Comment: 12 pages, 3 figures, and 3 Table

Montezuma Quail Management in Arizona: Addressing Needs of a Consistent, Dedicated Public With a Variable, Inconsistent Resource

Montezuma quail (Cyrtonyx montezumae) are unique among species of quail in habitat, diet, and behavior; these distinctions combined with an exotic appearance, and distribution in warmer climates in the United States have made them a popular game bird among a dedicated cadre of upland bird hunters. Montezuma quail are not, however, unique in population fluctuations which are largely affected by climatic factors. The history of harvest management for Montezuma quail in Arizona has generally been one of increasing season lengths and bag limits since the first 2-day hunt in 1960. There have, however, been several instances when season dates and bag limits have been changed, largely in response to public demand from individuals and groups that believed efforts to reduce harvest would protect populations and reduce fluctuation of bird numbers. Research directed specifically at the influence of harvest on Montezuma quail populations has found quail numbers fluctuate independent of potential harvest levels. Density-dependent survival, compensatory mortality, and self-regulating hunter numbers are often invoked to explain fluctuation of quail numbers independent of harvest regulations. We reviewed current literature relative to these issues and investigated Montezuma quail harvest characteristics to inform management options. Hunter numbers, based on hunter questionnaire data collected between 1987 and 2009, had greater influence (r2 1⁄4 0.616) on Montezuma quail harvest than either birds/day (r2 1⁄4 0.474), or days/hunter (r2 1⁄4 0.229) suggesting restricting hunter numbers would affect harvest more than reducing bag limits or season length. The average Montezuma quail hunters in Arizona harvested , 2 birds/day, , 6 birds/season, and hunted , 4 days/season. Dedicated hunters typical of those seeking harvest restrictions are not ‘average’ hunters and often have inflated views of the impact of hunting on annual fluctuations in bird numbers. Efforts to control harvest commensurate with perceived bird populations would be ineffective at maintaining reliable bird numbers and would be inconsistent with the current state of knowledge relative to effects of hunting on Montezuma quail numbers. Alternative management options including increasing public information and education efforts may be more effective at satisfying the needs of the dedicated community of Montezuma quail enthusiasts

Temperature-dependent Raman scattering of DyScO3 and GdScO3 single crystals

We report a temperature-dependent Raman scattering investigation of DyScO3 and GdScO3 single crystals from room temperature up to 1200 {\deg}C. With increasing temperature, all modes decrease monotonously in wavenumber without anomaly, which attests the absence of a structural phase transition. The high temperature spectral signature and extrapolation of band positions to higher temperatures suggest a decreasing orthorhombic distortion towards the ideal cubic structure. Our study indicates that this orthorhombic-to-cubic phase transition is close to or higher than the melting point of both rare-earth scandates (\approx 2100 {\deg}C), which might exclude the possibility of the experimental observation of such a phase transition before melting. The temperature-dependent shift of Raman phonons is also discussed in the context of thermal expansion

Nanoscale Smoothing and the Analysis of Interfacial Charge and Dipolar Densities

The interface properties of interest in multilayers include interfacial charge densities, dipole densities, band offsets, and screening-lengths, among others. Most such properties are inaccesible to direct measurements, but are key to understanding the physics of the multilayers. They are contained within first-principles electronic structure computations but are buried within the vast amount of quantitative information those computations generate. Thus far, they have been extracted from the numerical data by heuristic nanosmoothing procedures which do not necessarily provide results independent of the smoothing process. In the present paper we develop the theory of nanosmoothing, establishing procedures for both unpolarized and polarized systems which yield interfacial charge and dipole densities and band offsets invariant to the details of the smoothing procedures when the criteria we have established are met. We show also that dipolar charge densities, i. e. the densities of charge transferred across the interface, and screening lengths are not invariant. We illustrate our procedure with a toy model in which real, transversely averaged charge densities are replaced by sums of Gaussians.Comment: 30 pages, 15 figures, 4 table

Mechanistische Untersuchungen der elektrochemischen Sauerstoffentwicklung auf Modellelektroden; Stabilität der Elektroden, Natur der Oxide und Intermediate

Diagramme Sonstige Körperschaft, die mit dem Werk in Verbindung steht dem Förderkatalog entnommen Förderkennzeichen BMBF 03SF0507 Unterschiede zwischen dem gedruckten Dokument und der elektronischen Ressource können nicht ausgeschlossen werden Langzeitarchivierung durch Technische Informationsbibliothek (TIB) / Leibniz-Informationszentrum Technik und Naturwissenschaften und Universitätsbibliothe

Increased expression of heme-binding protein 1 early in Alzheimer's disease is linked to neurotoxicity.

Alzheimer's disease is the most prevalent neurodegenerative disorder leading to progressive cognitive decline. Despite decades of research, understanding AD progression at the molecular level, especially at its early stages, remains elusive. Here, we identified several presymptomatic AD markers by investigating brain proteome changes over the course of neurodegeneration in a transgenic mouse model of AD (3×Tg-AD). We show that one of these markers, heme-binding protein 1 (Hebp1), is elevated in the brains of both 3×Tg-AD mice and patients affected by rapidly-progressing forms of AD. Hebp1, predominantly expressed in neurons, interacts with the mitochondrial contact site complex (MICOS) and exhibits a perimitochondrial localization. Strikingly, wildtype, but not Hebp1-deficient, neurons showed elevated cytotoxicity in response to heme-induced apoptosis. Increased survivability in Hebp1-deficient neurons is conferred by blocking the activation of the mitochondrial-associated caspase signaling pathway. Taken together, our data highlight a role of Hebp1 in progressive neuronal loss during AD progression

Predicting the distribution of canine leishmaniasis in western Europe based on environmental variables.

The domestic dog is the reservoir host of Leishmania infantum, the causative agent of zoonotic visceral leishmaniasis endemic in Mediterranean Europe. Targeted control requires predictive risk maps of canine leishmaniasis (CanL), which are now explored. We databased 2187 published and unpublished surveys of CanL in southern Europe. A total of 947 western surveys met inclusion criteria for analysis, including serological identification of infection (504, 369 dogs tested 1971-2006). Seroprevalence was 23 2% overall (median 10%). Logistic regression models within a GIS framework identified the main environmental predictors of CanL seroprevalence in Portugal, Spain, France and Italy, or in France alone. A 10-fold cross-validation approach determined model capacity to predict point-values of seroprevalence and the correct seroprevalence class (20%). Both the four-country and France-only models performed reasonably well for predicting correctly the 20% seroprevalence classes (AUC >0 70). However, the France-only model performed much better for France than the four-country model. The four-country model adequately predicted regions of CanL emergence in northern Italy (<5% seroprevalence). Both models poorly predicted intermediate point seroprevalences (5-20%) within regional foci, because surveys were biased towards known rural foci and Mediterranean bioclimates. Our recommendations for standardizing surveys would permit higher-resolution risk mapping

Placental transfusion: a review

Recently there have been a number of studies and presentations on the importance of providing a placental transfusion to the newborn. Early cord clamping is an avoidable, unphysiologic intervention that prevents the natural process of placental transfusion. However, placental transfusion, although simple in concept, is affected by multiple factors, is not always straightforward to implement, and can be performed using different methods, making this basic procedure important to discuss. Here, we review three placental transfusion techniques: delayed cord clamping, intact umbilical cord milking and cut-umbilical cord milking, and the evidence in term and preterm newborns supporting this practice. We will also review several factors that influence placental transfusion, and discuss perceived risks versus benefits of this procedure. Finally, we will provide key straightforward concepts and implementation strategies to ensure that placental-to-newborn transfusion can become routine practice at any institution

An electronic nose in the discrimination of patients with asthma and controls.

BACKGROUND: Exhaled breath contains thousands of volatile organic compounds (VOCs) that could serve as biomarkers of lung disease. Electronic noses can distinguish VOC mixtures by pattern recognition. OBJECTIVE: We hypothesized that an electronic nose can discriminate exhaled air of patients with asthma from healthy controls, and between patients with different disease severities. METHODS: Ten young patients with mild asthma (25.1 +/- 5.9 years; FEV(1), 99.9 +/- 7.7% predicted), 10 young controls (26.8 +/- 6.4 years; FEV(1), 101.9 +/- 10.3), 10 older patients with severe asthma (49.5 +/- 12.0 years; FEV(1), 62.3 +/- 23.6), and 10 older controls (57.3 +/- 7.1 years; FEV(1), 108.3 +/- 14.7) joined a cross-sectional study with duplicate sampling of exhaled breath with an interval of 2 to 5 minutes. Subjects inspired VOC-filtered air by tidal breathing for 5 minutes, and a single expiratory vital capacity was collected into a Tedlar bag that was sampled by electronic nose (Cyranose 320) within 10 minutes. Smellprints were analyzed by linear discriminant analysis on principal component reduction. Cross-validation values (CVVs) were calculated. RESULTS: Smellprints of patients with mild asthma were fully separated from young controls (CVV, 100%; Mahalanobis distance [M-distance], 5.32), and patients with severe asthma could be distinguished from old controls (CVV, 90%; M-distance, 2.77). Patients with mild and severe asthma could be less well discriminated (CVV, 65%; M-distance, 1.23), whereas the 2 control groups were indistinguishable (CVV, 50%; M-distance, 1.56). The duplicate samples replicated these results. CONCLUSION: An electronic nose can discriminate exhaled breath of patients with asthma from controls but is less accurate in distinguishing asthma severities. CLINICAL IMPLICATION: These findings warrant validation of electronic noses in diagnosing newly presented patients with asthma

Structure and properties of a novel fulleride Sm6C60

A novel fulleride Sm6C60 has been synthesized using high temperature solid state reaction. The Rietveld refinement on high resolution synchrotron X-ray powder diffraction data shows that Sm6C60 is isostructural with body-centered cubic A6C60 (A=K, Ba). Raman spectrum of Sm6C60 is similar to that of Ba6C60, and the frequencies of two Ag modes in Sm6C60 are nearly the same as that of Ba6C60, suggesting that Sm is divalent and hybridization between C60 molecules and the Sm atom could exist in Sm6C60. Resistivity measurement shows a weak T-linear behavior above 180 K, the transport at low temperature is mainly dominated by granular-metal theory.Comment: 9 pages, 3 figures, submitted to Phys. Rev. B (March 12, 1999