Di- and Tetrameric Molybdenum Sulfide Clusters Activate and Stabilize Dihydrogen as Hydrides

NaY zeolite-encapsulated dimeric (Mo2S4) and tetrameric (Mo4S4) molybdenum sulfide clusters stabilize hydrogen as hydride binding to Mo atoms. Density functional theory (DFT) calculations and adsorption measurements suggest that stabilization of hydrogen as sulfhydryl (SH) groups, as typical for layered MoS2, is thermodynamically disfavored. Competitive adsorption of H2 and ethene on Mo was probed by quantifying adsorbed CO on partly hydrogen and/or ethene covered samples with IR spectroscopy. During hydrogenation, experiment and theory suggest that Mo is covered predominately with ethene and sparsely with hydride. DFT calculations further predict that, under reaction conditions, each MoxSy cluster can activate only one H2, suggesting that the entire cluster (irrespective of its nuclearity) acts as one active site for hydrogenation. The nearly identical turnover frequencies (24.7 ± 3.3 molethane·h–1·molcluster–1), apparent activation energies (31–32 kJ·mol–1), and reaction orders (∼0.5 in ethene and ∼1.0 in H2) show that the active sites in both clusters are catalytically indistinguishable

Zeolite-Stabilized Di- and Tetranuclear Molybdenum Sulfide Clusters Form Stable Catalytic Hydrogenation Sites

Supercages of faujasite (FAU)‐type zeolites serve as a robust scaffold for stabilizing dinuclear (Mo2S4) and tetranuclear (Mo4S4) molybdenum sulfide clusters. The FAU‐encaged Mo4S4 clusters have a distorted cubane structure similar to the FeMo‐cofactor in nitrogenase. Both clusters possess unpaired electrons on Mo atoms. Additionally, they show identical catalytic activity per sulfide cluster. Their catalytic activity is stable (> 150 h) for ethene hydrogenation, while layered MoS2 structures deactivate significantly under the same reaction conditions

Zeolite-Stabilized Di- and Tetranuclear Molybdenum Sulfide Clusters Form Stable Catalytic Hydrogenation Sites

Supercages of faujasite (FAU)‐type zeolites serve as a robust scaffold for stabilizing dinuclear (Mo2S4) and tetranuclear (Mo4S4) molybdenum sulfide clusters. The FAU‐encaged Mo4S4 clusters have a distorted cubane structure similar to the FeMo‐cofactor in nitrogenase. Both clusters possess unpaired electrons on Mo atoms. Additionally, they show identical catalytic activity per sulfide cluster. Their catalytic activity is stable (> 150 h) for ethene hydrogenation, while layered MoS2 structures deactivate significantly under the same reaction conditions

Glycosylation of Candida albicans cell wall proteins is critical for induction of innate immune responses and apoptosis of epithelial cells.

C. albicans is one of the most common fungal pathogen of humans, causing local and superficial mucosal infections in immunocompromised individuals. Given that the key structure mediating host-C. albicans interactions is the fungal cell wall, we aimed to identify features of the cell wall inducing epithelial responses and be associated with fungal pathogenesis. We demonstrate here the importance of cell wall protein glycosylation in epithelial immune activation with a predominant role for the highly branched N-glycosylation residues. Moreover, these glycan moieties induce growth arrest and apoptosis of epithelial cells. Using an in vitro model of oral candidosis we demonstrate, that apoptosis induction by C. albicans wild-type occurs in early stage of infection and strongly depends on intact cell wall protein glycosylation. These novel findings demonstrate that glycosylation of the C. albicans cell wall proteins appears essential for modulation of epithelial immunity and apoptosis induction, both of which may promote fungal pathogenesis in vivo

Interdigital Resonators in Wideband Ridged-Waveguide Filters

An interdigital resonator approach for wideband filter applications in ridged-waveguide technology is presented. The interdigital arrangement of the ridged-waveguide resonators ensures stronger coupling between the resonators. As the coupling sections are consequently enlarged by the interdigital arrangement of the resonators, more feasible filter structures are possible at increasing frequencies. The approach itself can be easily implemented with conventional filter synthesis formulas, which is demonstrated by two 20 GHz examples with a bandwidth of 2 GHz and 100 MHz, respectively. The designed filters are subsequently compared to the standard implementation of ridged-waveguide filters.</p

The impact of high-end climate change on agricultural welfare

Climate change threatens agricultural productivity worldwide, resulting in higher food prices. Associated economic gains and losses differ not only by region but also between producers and consumers and are affected by market dynamics. On the basis of an impact modeling chain, starting with 19 different climate projections that drive plant biophysical process simulations and ending with agro-economic decisions, this analysis focuses on distributional effects of high-end climate change impacts across geographic regions and across economic agents. By estimating the changes in surpluses of consumers and producers, we find that climate change can have detrimental impacts on global agricultural welfare, especially after 2050, because losses in consumer surplus generally outweigh gains in producer surplus. Damage in agriculture may reach the annual loss of 0.3% of future total gross domestic product at the end of the century globally, assuming further opening of trade in agricultural products, which typically leads to interregional production shifts to higher latitudes. Those estimated global losses could increase substantially if international trade is more restricted. If beneficial effects of atmospheric carbon dioxide fertilization can be realized in agricultural production, much of the damage could be avoided. Although trade policy reforms toward further liberalization help alleviate climate change impacts, additional compensation mechanisms for associated environmental and development concerns have to be considered

Large scale cosmic-ray anisotropy with KASCADE

The results of an analysis of the large scale anisotropy of cosmic rays in the PeV range are presented. The Rayleigh formalism is applied to the right ascension distribution of extensive air showers measured by the KASCADE experiment.The data set contains about 10^8 extensive air showers in the energy range from 0.7 to 6 PeV. No hints for anisotropy are visible in the right ascension distributions in this energy range. This accounts for all showers as well as for subsets containing showers induced by predominantly light respectively heavy primary particles. Upper flux limits for Rayleigh amplitudes are determined to be between 10^-3 at 0.7 PeV and 10^-2 at 6 PeV primary energy.Comment: accepted by The Astrophysical Journa

KASCADE-Grande Limits on the Isotropic Diffuse Gamma-Ray Flux between 100 TeV and 1 EeV

KASCADE and KASCADE-Grande were multi-detector installations to measure individual air showers of cosmic rays at ultra-high energy. Based on data sets measured by KASCADE and KASCADE-Grande, 90% C.L. upper limits to the flux of gamma-rays in the primary cosmic ray flux are determined in an energy range of ${10}^{14} - {10}^{18}$ eV. The analysis is performed by selecting air showers with a low muon content as expected for gamma-ray-induced showers compared to air showers induced by energetic nuclei. The best upper limit of the fraction of gamma-rays to the total cosmic ray flux is obtained at $3.7 \times {10}^{15}$ eV with $1.1 \times {10}^{-5}$. Translated to an absolute gamma-ray flux this sets constraints on some fundamental astrophysical models, such as the distance of sources for at least one of the IceCube neutrino excess models.Comment: Published in The Astrophysical Journal, Volume 848, Number 1. Posted on: October 5, 201

First Experimental Characterization of Microwave Emission from Cosmic Ray Air Showers

We report the first direct measurement of the overall characteristics of microwave radio emission from extensive air showers. Using a trigger provided by the KASCADE-Grande air shower array, the signals of the microwave antennas of the CROME (Cosmic-Ray Observation via Microwave Emission) experiment have been read out and searched for signatures of radio emission by high-energy air showers in the GHz frequency range. Microwave signals have been detected for more than 30 showers with energies above 3*10^16 eV. The observations presented in this Letter are consistent with a mainly forward-directed and polarised emission process in the GHz frequency range. The measurements show that microwave radiation offers a new means of studying air showers at energies above 10^17 eV.Comment: Accepted for publication in PR