High-pressure/high-temperature synthesis of transition metal oxide perovskites

Perovskite and related Ruddlesden-Popper type transition metal oxides synthesised at high pressures and temperatures during the last decade are reviewed. More than 60 such new materials have been reported since 1995. Important developments have included perovskites with complex cation orderings on A and B sites, multiferroic bismuth-based perovskites, and new manganites showing colossal magnetoresistance (CMR) and charge ordering properties

Top-down estimate of a large source of atmospheric carbon monoxide associated with fuel combustion in Asia

We simulate the oceanic and atmospheric distribution of methyl iodide (CH3I) with a global 3-D model driven by assimilated meteorological observations from the Goddard Earth Observing System of the NASA Data Assimilation Office and coupled to an oceanic mixed layer model. A global compilation of atmospheric and oceanic observations is used to constrain and evaluate the simulation. Seawater CH3I(aq) in the model is produced photochemically from dissolved organic carbon, and is removed by reaction with Cl− and emission to the atmosphere. The net oceanic emission to the atmosphere is 214 Gg yr−1. Small terrestrial emissions from rice paddies, wetlands, and biomass burning are also included in the model. The model captures 40% of the variance in the observed seawater CH3I(aq) concentrations. Simulated concentrations at midlatitudes in summer are too high, perhaps because of a missing biological sink of CH3I(aq). We define a marine convection index (MCI) as the ratio of upper tropospheric (8–12 km) to lower tropospheric (0–2.5 km) CH3I concentrations averaged over coherent oceanic regions. The MCI in the observations ranges from 0.11 over strongly subsiding regions (southeastern subtropical Pacific) to 0.40 over strongly upwelling regions (western equatorial Pacific). The model reproduces the observed MCI with no significant global bias (offset of only +11%) but accounts for only 15% of its spatial and seasonal variance. The MCI can be used to test marine convection in global models, complementing the use of radon-222 as a test of continental convection.Engineering and Applied Science

Investigation of Superconducting Gap Structure in TbFeAsO0.9_{0.9}F0.1_{0.1} using Point Contact Andreev Reflection

Bulk samples of TbFeAsO$_{0.9}$F$_{0.1}$ (T$_{c}$(on) = 50K) were measured by point contact Andreev reflection spectroscopy. The spectra show unambiguous evidence for multiple gap-like features plus the presence of high bias shoulders. By measuring the spectra as a function of temperature with both gold and superconducting niobium tips, we establish that the gap-like features are associated with superconducting order parameter in this material. We discuss whether the well defined zero bias conductance peak that we observe infrequently is associated with a nodal superconducting order parameter.Comment: 11 pages, 5 figures, published versio

Simulated observation of tropospheric ozone and CO with the Tropospheric Emission Spectrometer (TES) satellite instrument

The Tropospheric Emission Spectrometer (TES) on board NASA's Aura satellite (to be launched in 2004) will provide measurements of global distributions of ozone, CO, and other key chemical species in the troposphere. In order for TES to meet a design lifetime of 5 years, it has been determined that a global survey strategy with ∼50% duty cycle must be identified. In this study, simulated concentrations of ozone and CO from the GEOS-CHEM global three-dimensional (3-D) model of troposphere chemistry are used as a time-varying synthetic atmosphere for demonstrating and assessing the capabilities of TES nadir observations. Autocorrelation analyses of the model species fields for different time lags identify a significant 1-day correlation and support a 1-day-on/1-day-off observation strategy. Three major steps are then taken to demonstrate and evaluate TES products: (1) species profiles along the TES orbit track are sampled from the model 3-D time-varying fields with cloudy scenes (50-60% of total scenes) removed; (2) nadir-retrieved profiles (“level 2 products”) are obtained from these “true” synthetic profiles using TES retrieval characteristic functions; (3) interpolated daily global maps (“level 3 products”) are generated to compare with the original model fields. The latter comparison indicates that the error in the level 3 products relative to the true fields for ozone and CO is <10% in ∼70% of cases and <20% in 80–90% of cases. The three major sources of error lie in the asynoptic orbital sampling, the retrieval, and the level 3 global mapping.Engineering and Applied Science

Tunable Visible and Near-IR Photoactivation of Light-Responsive Compounds by Using Fluorophores as Light-Capturing Antennas

Although the corrin ring of vitamin B12 is unable to efficiently absorb light beyond 550 nm, it is shown that commercially available fluorophores can be used as antennas to capture long-wavelength light to promote scission of the Co-C bond at wavelengths up to 800 nm. The ability to control the molecular properties of bioactive species with long visible and near-IR light has implications for drug delivery, nanotechnology, and the spatiotemporal control of cellular behavior

In Situ Template Generation for Zincophosphate Synthesis Leading to C2H7N4O-ZnPO4 Containing Template-to-Template N--H...O Hydrogen Bonds

The synthesis, structure and some properties of C{sub 2}H{sub 7}N{sub 4}O {center_dot} ZnPO{sub 4} (guanylurea zinc phosphate) are reported. The cationic template was prepared in situ by partial hydrolysis of the neutral 2-cyanoguanidine starting material. The resulting structure contains a new, unprotonated, zincophosphate layer topology as well as unusual N-H-O template-to-template hydrogen bonds which help to stabilize a ''double sandwich'' of templating cations between the inorganic sheets. Crystal data: C{sub 2}H{sub 7}N{sub 4}O {center_dot} ZnPO{sub 4}, M{sub r} = 229.44, monoclinic, P2{sub 1}/c, a = 13.6453 (9) {angstrom}, b = 5.0716 (3) {angstrom}, c = 10.6005 (7) {angstrom}, {beta} = 95.918 (2){sup 0}, V = 729.7 (1) {angstrom}{sup 3}, R(F) = 0.034, wR(F) = 0.034

Incommensurate spin order in the metallic perovskite MnVO3

Incommensurate Mn spin order has been discovered in the perovskite MnVO3 containing localized 3d5 Mn2+ and itinerant 3d1 V4+ states. This phase has a distorted Pnma crystal structure (a = 5.2741(6) Å, b = 7.4100(11) Å, and c = 5.1184(8) Å at 300 K) and is metallic at temperatures of 2-300 K and at pressures of up to 67 kbar. Neutron scattering reveals a (0.29 0 0) magnetic vector below the 46 K spin ordering transition, and both helical and spin density wave orderings are consistent with the diffraction intensities. Electronic structure calculations show large exchange splittings of the Mn and V 3d bands, and (kx 0 0) crossings of the Fermi energy by spin up and down V 3d bands may give rise to Ruderman-Kittel-Kasuya-Yosida coupling of Mn moments, in addition to their superexchange interactions. © 2011 American Physical Society

Plasticity to ocean warming is influenced by transgenerational, reproductive, and developmental exposure in a coral reef fish

Global warming is expected to drive some ectothermic species beyond their thermal tolerance in upcoming decades. Phenotypic plasticity, via developmental or transgenerational acclimation, is a critical mechanism for compensation in the face of environmental change. Yet, it remains to be determined if the activation of beneficial phenotypes requires direct exposure throughout development, or if compensation can be obtained just through the experience of previous generations. In this study, we exposed three generations of a tropical damselfish to combinations of current-day (Control) and projected future (+1.5°C) water temperatures. Acclimation was evaluated with phenotypic (oxygen consumption, hepatosomatic index, physical condition) and molecular (liver gene expression) measurements of third-generation juveniles. Exposure of grandparents/parents to warm conditions improved the aerobic capacity of fish regardless of thermal conditions experienced afterwards, representing a true transgenerational effect. This coincided with patterns of gene expression related to inflammation and immunity seen in the third generation. Parental effects due to reproductive temperature significantly affected the physical condition and routine metabolic rate (oxygen consumption) of offspring, but had little impact on gene expression of the F3. Developmental temperature of juveniles, and whether they matched conditions during parental reproduction, had the largest influence on the liver transcriptional program. Using a combination of both phenotypic and molecular approaches, this study highlights how the conditions experienced by both previous and current generations can influence plasticity to global warming in upcoming decades