Ethyl and isopropyl 4-ferrocenylbenzoate.

The title compounds, [Fe(C5H5)(C14H13O2)] and [Fe(C5H5)- (C15H15O2)], respectively, contain the ferrocenyl 5(C5H4) and phenylene ±C6H4± rings in a nearly coplanar arrangement, with interplanar angles of 6.88 (12) and 10.5 (2), respectively. Molecules of the ethyl ester form dimers through 5(C5H5)CÐ H O C hydrogen bonds, with graph set R22 (20), and, together with Csp3ÐH (C5H5) interactions, generate a one-dimensional column (irregular ladder). Molecules of the isopropyl ester aggregate through 5(C5H5)CÐH (C6H4) interactions

BBN and the Primordial Abundances

The relic abundances of the light elements synthesized during the first few minutes of the evolution of the Universe provide unique probes of cosmology and the building blocks for stellar and galactic chemical evolution, while also enabling constraints on the baryon (nucleon) density and on models of particle physics beyond the standard model. Recent WMAP analyses of the CBR temperature fluctuation spectrum, combined with other, relevant, observational data, has yielded very tight constraints on the baryon density, permitting a detailed, quantitative confrontation of the predictions of Big Bang Nucleosynthesis with the post-BBN abundances inferred from observational data. The current status of this comparison is presented, with an emphasis on the challenges to astronomy, astrophysics, particle physics, and cosmology it identifies.Comment: To appear in the Proceedings of the ESO/Arcetri Workshop on "Chemical Abundances and Mixing in Stars in the Milky Way and its Satellites", eds., L. Pasquini and S. Randich (Springer-Verlag Series, "ESO Astrophysics Symposia"

Arctic-Boreal Lake Dynamics Revealed Using CubeSat Imagery

Fine-scale, subseasonal fluctuations in Arctic-Boreal surface water reflect regional water balance and modulate trace gas emissions to the atmosphere but have eluded detection using traditional satellite remote sensing. We use high-resolution (~3–5 m), high-frequency CubeSat sensors to measure near-daily changes in lake surface area through an object-based tracking method that incorporates machine learning to overcome notable limitations of CubeSat imagery. From ~76,000 images we obtain >2.2 million individual observations of changing surface areas for 85,358 lakes in Northern Canada and Alaska between 1 May and 1 October 2017. We find broad-scale lake area declines across diverse climatic, hydrologic, and physiographic terrains. Localized exceptions reveal lowland flooding and aquatic vegetation phenology cycles. Cumulative small shoreline changes of abundant lakes on the Canadian Shield exceed total inundation variations of better-studied lowland environments, revealing a surprisingly dynamic landscape with respect to subseasonal variations in surface water extent and trace gas emissions

Global Characterization of Inland Water Reservoirs Using ICESat-2 Altimetry and Climate Reanalysis

Accurate, transparent knowledge of global reservoir levels is a prerequisite for effective management of water resources. However, no complete database exists because gauge data are not globally available and the current generation of satellite radar altimeters resolves only the world's largest reservoirs. Here, we investigate water level changes in global reservoirs using ICESat-2, National Aeronautics and Space Administration (NASA)'s new satellite laser altimetry mission. In just the first 12 months of the mission, we find that ICESat-2 accurately (±14.1 cm) retrieved water level changes for 3,712 global reservoirs having surface areas ranging from <1 to >10,000 km2. From this new global data set, we identify distinct regional patterns in reservoir level change that can be attributed to both water availability and management strategy. Our findings demonstrate that ICESat-2 will form a crucial component of any global reservoir level inventory and enable new insight into how reservoir management responds to climatic variability and increasing human demand

Methylxanthines Inhibit Primary Amine Oxidase and Monoamine Oxidase Activities of Human Adipose Tissue

Abstract: Background: Methylxanthines including caffeine and theobromine are widely consumed compounds and were recently shown to interact with bovine copper-containing amine oxidase. To the best of our knowledge, no direct demonstration of any interplay between these phytochemicals and human primary amine oxidase (PrAO) has been reported to date. We took advantage of the coexistence of PrAO and monoamine oxidase (MAO) activities in human subcutaneous adipose tissue (hScAT) to test the interaction between several methylxanthines and these enzymes, which are involved in many key pathophysiological processes. Methods: Benzylamine, methylamine, and tyramine were used as substrates for PrAO and MAO in homogenates of subcutaneous adipose depots obtained from overweight women undergoing plastic surgery. Methylxanthines were tested as substrates or inhibitors by fluorimetric determination of hydrogen peroxide, an end-product of amine oxidation. Results: Semicarbazide-sensitive PrAO activity was inhibited by theobromine, caffeine, and isobutylmethylxanthine (IBMX) while theophylline, paraxanthine, and 7-methylxanthine had little effect. Theobromine inhibited PrAO activity by 54% at 2.5 mM. Overall, the relationship between methylxanthine structure and the degree of inhibition was similar to that seen with bovine PrAO, although higher concentrations (mM) were required for inhibition. Theobromine also inhibited oxidation of tyramine by MAO, at the limits of its solubility in a DMSO vehicle. At doses higher than 12 % v/v, DMSO impaired MAO activity. MAO was also inhibited by millimolar doses of IBMX, caffeine and by other methylxanthines to a lesser extent. Conclusions: This preclinical study extrapolates previous findings with bovine PrAO to human tissues. Given that PrAO is a potential target for anti-inflammatory drugs, it indicates that alongside phosphodiesterase inhibition and adenosine receptor antagonism, PrAO and MAO inhibition could contribute to the health benefits of methylxanthines, especially their anti-inflammatory effects

The effects of an experimental programme to support students’ autonomy on the overt behaviours of physical education teachers

Although the benefits of autonomy supportive behaviours are now well established in the literature, very few studies have attempted to train teachers to offer a greater autonomy support to their students. In fact, none of these studies has been carried out in physical education (PE). The purpose of this study is to test the effects of an autonomy-supportive training on overt behaviours of teaching among PE teachers. The experimental group included two PE teachers who were first educated on the benefits of an autonomy supportive style and then followed an individualised guidance programme during the 8 lessons of a teaching cycle. Their behaviours were observed and rated along 3 categories (i.e., autonomy supportive, neutral and controlling) and were subsequently compared to those of three teachers who formed the control condition. The results showed that teachers in the experimental group used more autonomy supportive and neutral behaviours than those in the control group, but no difference emerged in relation to controlling behaviours. We discuss the implications for schools of our findings

Characterisation of insulin analogues therapeutically available to patients

The structure and function of clinical dosage insulin and its analogues were assessed. This included ‘native insulins’ (human recombinant, bovine, porcine), ‘fast-acting analogues’ (aspart, glulisine, lispro) and ‘slow-acting analogues’ (glargine, detemir, degludec). Analytical ultracentrifugation, both sedimentation velocity and equilibrium experiments, were employed to yield distributions of both molar mass and sedimentation coefficient of all nine insulins. Size exclusion chromatography, coupled to multi-angle light scattering, was also used to explore the function of these analogues. On ultracentrifugation analysis, the insulins under investigation were found to be in numerous conformational states, however the majority of insulins were present in a primarily hexameric conformation. This was true for all native insulins and two fast-acting analogues. However, glargine was present as a dimer, detemir was a multi-hexameric system, degludec was a dodecamer (di-hexamer) and glulisine was present as a dimer-hexamer-dihexamer system. However, size-exclusion chromatography showed that the two hexameric fast-acting analogues (aspart and lispro) dissociated into monomers and dimers due to the lack of zinc in the mobile phase. This comprehensive study is the first time all nine insulins have been characterised in this way, the first time that insulin detemir have been studied using analytical ultracentrifugation and the first time that insulins aspart and glulisine have been studied using sedimentation equilibrium. The structure and function of these clinically administered insulins is of critical importance and this research adds novel data to an otherwise complex functional physiological protein

Primordial nucleosynthesis with a varying fine structure constant: An improved estimate

We compute primordial light-element abundances for cases with fine structure constant alpha different from the present value, including many sources of alpha dependence neglected in previous calculations. Specifically, we consider contributions arising from Coulomb barrier penetration, photon coupling to nuclear currents, and the electromagnetic components of nuclear masses. We find the primordial abundances to depend more weakly on alpha than previously estimated, by up to a factor of 2 in the case of ^7Li. We discuss the constraints on variations in alpha from the individual abundance measurements and the uncertainties affecting these constraints. While the present best measurements of primordial D/H, ^4He/H, and ^7Li/H may be reconciled pairwise by adjusting alpha and the universal baryon density, no value of alpha allows all three to be accommodated simultaneously without consideration of systematic error. The combination of measured abundances with observations of acoustic peaks in the cosmic microwave background favors no change in alpha within the uncertainties.Comment: Phys. Rev. D accepted version; minor changes in response to refere

SuperWIMP Dark Matter Signals from the Early Universe

Cold dark matter may be made of superweakly-interacting massive particles, superWIMPs, that naturally inherit the desired relic density from late decays of metastable WIMPs. Well-motivated examples are weak-scale gravitinos in supergravity and Kaluza-Klein gravitons from extra dimensions. These particles are impossible to detect in all dark matter experiments. We find, however, that superWIMP dark matter may be discovered through cosmological signatures from the early universe. In particular, superWIMP dark matter has observable consequences for Big Bang nucleosynthesis and the cosmic microwave background (CMB), and may explain the observed underabundance of 7Li without upsetting the concordance between deuterium and CMB baryometers. We discuss implications for future probes of CMB black body distortions and collider searches for new particles. In the course of this study, we also present a model-independent analysis of entropy production from late-decaying particles in light of WMAP data.Comment: 19 pages, 5 figures, typos correcte

Ward Identities, B-> \rho Form Factors and |V_ub|

The exclusive FCNC beauty semileptonic decay B-> \rho is studied using Ward identities in a general vector meson dominance framework, predicting vector meson couplings involved. The long distance contributions are discussed which results to obtain form factors and |V_ub|. A detailed comparison is given with other approaches.Comment: 30 pages+four postscript figures, an Appendix adde