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Since the invention of fluorescent light sources, there is strong interest in Eu3+ activated phosphors as they are able to provide a high color rendering index (CRI) and luminous efficacy, which will also hold for phosphor converted light emitting diodes. Due to an efficient U6+ to Eu3+ energy transfer in Gd3Li3Te2O12:U6+,Eu3+, this inorganic composition shows red photoluminescence peaking at 611 nm. That means Eu3+ photoluminescence can be nicely sensitized via excitation into the U6+ excitation bands. Therefore, photoluminescence properties, such as temperature dependent emission and emission lifetime measurements, are presented. Charge transfer bands were investigated in detail. Additionally, density functional theory calculations reveal the band structure of the pure, i.e., non-doped host material. Obtained theoretical results were evaluated experimentally by the aid of diffuse UV reflectance spectroscopy.

Mixing under high pressure conditions plays a central role in several engineering applications, such as direct-injection engines and liquid rocket engines. Numerical flow simulations have become a complementary tool to study the mixing process under these conditions but require complex thermodynamic modeling as well as validation with accurate experimental data. For this reason, we use experiments of supercritical single-phase jet mixing from the literature, where the mixing is quantified by the mixture speed of sound, as a reference for our work. We here focus on the thermodynamic modeling of multi-component flows under high pressure conditions and the analytical calculation of the mixture speed of sound. Our thermodynamic model is based on cubic equations of state extended for multi-components. Using an extension of OpenFOAM, we perform large-eddy simulations of hexane and pentane injections and compare our results with the experimentally measured mixture speed of sound at specific positions. The simulation results show the same characteristic trends, indicating that the mixing effects are well reproduced in the simulations. Additionally, the effect of the sub-grid scale modeling is assessed by comparing results using different models (Smagorinsky, Vreman, and Wall-Adapting Local Eddy-viscosity). The comprehensive simulation data presented here, in combination with the experimental data, provide a benchmark for numerical simulations of jet mixing in high pressure conditions.

AbstractSome cases of occurrence of matrix effects (mostly ion suppression) in protein‐precipitated plasma samples, and their influence on the validity of plasma concentrations and pharmacokinetic parameters, are discussed. The comparison of matrix effects using either electrospray (TurboIonspray, TISP) or atmospheric pressure chemical ionization (APCI) indicated that APCI is less prone to matrix effects. Nevertheless, TISP is usually the first choice of ionization technique since unknown thermally labile metabolites might be present in the plasma samples causing erroneous results. A high impact of ion suppression on the plasma concentrations after intravenous (i.v.) administration was found, depending on the drug formulation (vehicle). Since ion suppression caused significantly lower plasma concentrations (by a factor of up to 5.5) after i.v. dosing, the area under the curve (AUC) was underestimated and the plasma clearance was consequently erroneously high, with an impact on drug candidate selection. By simple stepwise dilution (e.g. 10‐fold and 50‐fold) of the supernatant of protein‐precipitated plasma samples, including all calibration and quality control samples, the matrix effects were recognized and eliminated. Copyright © 2003 John Wiley & Sons, Ltd.

AbstractClimate change may force organisms to adapt genetically or plastically to new environmental conditions. Invasive species show remarkable potential for rapid adaptation. The ovoviviparous New Zealand mud snail (NZMS),Potamopyrgus antipodarum, has successfully established across Europe with two clonally reproducing mitochondrial lineages since its arrival in the first half of the 19th century. Its remarkable variation in shell morphology was shown to be fitness relevant. We investigated the effects of temperature on shell morphology across 11 populations from Germany and the Iberian Peninsula in a common garden across three temperatures. We analyzed size and shape using geometric morphometrics. For both, we compared reaction norms and estimated heritabilities. For size, the interaction of temperature and haplotype explained about 50% of the total variance. We also observed more genotype by environment interactions indicating a higher degree of population differentiation than in shape. Across the three temperatures, size followed the expectations of the temperature‐size rule, with individuals growing larger in cold environments. Changes in shape may have compensated for changes in size affecting space for brooding embryos. Heritability estimates were relatively high. As indicated by the very low coefficients of variation for clonal repeatability (CVA), they can probably not be compared in absolute terms. However, they showed some sensitivity to temperature, in haplotype t more so than in z, which was only found in Portugal. The lowCVAvalues indicate that genetic variation among European populations is still restricted with a low potential to react to selection. A considerable fraction of the genetic variation was due to differences between the clonal lineages. The NZMS has apparently not been long enough in Europe to accumulate significant genetic variation relevant for morphological adaptation. As temperature is obviously not the sole factor influencing shell morphology, their interaction will probably not be a factor limiting population persistence under a warming climate in Europe.

The importance of fluorinated products in pharmaceutical and medicinal chemistry has necessitated the development of synthetic fluorination methods, of which direct C–H fluorination is among the most powerful. Despite the challenges and limitations associated with the direct fluorination of unactivated C–H bonds, appreciable advancements in manipulating the selectivity and reactivity have been made, especially via transition metal catalysis and photochemistry. Where transition metal catalysis provides one strategy for C–H bond activation, transition-metal-free photochemical C–H fluorination can provide a complementary selectivity via a radical mechanism that proceeds under milder conditions than thermal radical activation methods. One exciting development in C–F bond formation is the use of small-molecule photosensitizers, allowing the reactions i) to proceed under mild conditions, ii) to be user-friendly, iii) to be cost-effective and iv) to be more amenable to scalability than typical photoredox-catalyzed methods. In this review, we highlight photosensitized C–H fluorination as a recent strategy for the direct and remote activation of C–H (especially C(sp3)–H) bonds. To guide the readers, we present the developing mechanistic understandings of these reactions and exemplify concepts to assist the future planning of reactions.

Endocrinological research on wild animals inhabiting remote areas has been hampered by the need to store plasma samples at subzero temperatures. In an attempt to remedy this logistical issue, we here investigate the use of ethanol as an alternative to freezing for the preservation of steroid and indoleamine hormones in avian plasma. Known quantities of the steroids 5alpha-dihydrotestosterone (DHT), testosterone, 17beta-estradiol, corticosterone, and the indoleamine melatonin were added to a stripped pool of chicken plasma. Samples were either immediately frozen at -40 degrees C, or treated with pure ethanol. Ethanol-treated samples were either immediately frozen, or-to simulate storage conditions at various field locations-left sitting at room temperature for one to two months, or incubated at 36 degrees C for one month before all treatment groups were frozen at -40 degrees C. All samples were then analyzed by radioimmunoassay. For DHT and estradiol there were no differences among treatment groups suggesting that ethanol-treatment is as effective as immediate freezing in preserving plasma steroid concentrations. For testosterone, corticosterone and melatonin ethanol-treated samples differed significantly from immediately frozen samples suggesting that caution is needed when comparing absolute concentrations of hormones between samples preserved in different ways. However, differences among ethanol-treated samples in general were small, demonstrating the feasibility of this preservation method in the field at remote locations.

AbstractLightning is the main precursor of natural wildfires and Long-Continuing-Current (LCC) lightning flashes are proposed to be the main igniters of lightning-ignited wildfires (LIW). Previous studies predict a change of the global occurrence rate and spatial pattern of total lightning. Nevertheless, the sensitivity of lightning-ignited wildfire occurrence to climate change is uncertain. Here, we investigate space-based measurements of LCC lightning associated with lightning ignitions and present LCC lightning projections under the Representative Concentration Pathway RCP6.0 for the 2090s by applying a recent LCC lightning parameterization based on the updraft strength in thunderstorms. We find a 41% global increase of the LCC lightning flash rate. Increases are largest in South America, the western coast of North America, Central America, Australia, Southern and Eastern Asia, and Europe, while only regional variations are found in northern polar forests, where fire risk can affect permafrost soil carbon release. These results show that lightning schemes including LCC lightning are needed to project the occurrence of lightning-ignited wildfires under climate change.

Abstract The impact of CO 2 leakage from underground storage formations on shallow water resources is a concerning aspect in CO 2 capture and storage (CCS) risk assessment. In Campo de Calatrava region (Spain), natural CO 2 fluxes from the Earth’s mantle interact with shallow aquifers, resulting in significant changes in their physical and chemical properties. The resultant water is slightly acidic (pH 5.9-6.4), oxidizing, and enriched in iron (up to 6.1×10 -4 mol·L -1 ) and other metals usually found at trace concentrations. Thermodynamic calculations reveal that aqueous Fe(III) carbonate complexes play an important role in the persistence of this high concentration of iron and trace metals in solution.