2,036 research outputs found
The [4+2]âCycloaddition of αâNitrosoalkenes with Thiochalcones as a Prototype of Periselective HeteroâDielsâAlder ReactionsâExperimental and Computational Studies
The [4+2]âcycloadditions of αânitrosoalkenes with thiochalcones occur with high selectivity at the thioketone moiety of the dienophile providing styrylâsubstituted 4Hâ1,5,2âoxathiazines in moderate to good yields. Of the eight conceivable heteroâDielsâAlder adducts only this isomer was observed, thus a prototype of a highly periselective and regioselective cycloaddition has been identified. Analysis of crude product mixtures revealed that the αânitrosoalkene also adds competitively to the thioketone moiety of the thiochalcone dimer affording bisâheterocyclic [4+2]âcycloadducts. The experiments are supported by highâlevel DFT calculations that were also extended to related heteroâDielsâAlder reactions of other nitroso compounds and thioketones. These calculations reveal that the title cycloadditions are kinetically controlled processes confirming the role of thioketones as superdienophiles. The computational study was also applied to the experimentally studied thiochalcone dimerization, and showed that the 1,2âdithiin and 2Hâthiopyran isomers are in equilibrium with the monomer. Again, the DFT calculations indicate kinetic control of this process
Benefits of a marketing cooperative in transition agriculture: MĂłrakert purchasing and service co-operative
The paper analyses the potential benefits of marketing cooperatives in Hungary, employing a transaction cost economics framework. We found that the purchased quantity, the existence of contracts, flexibility and trust are the most important factors farmers consider when selling their products via a cooperative. The most striking result is that diversification has positive influences on the share of cooperatives in farmersâ sale. Furthermore, farmers with larger bargaining power have less willingness to sell their product to the cooperative. Surprisingly, asset specificity has rather negative effects on the share of cooperatives in membersâ sales
CN and HCN in Dense Interstellar Clouds
We present a theoretical investigation of CN and HCN molecule formation in
dense interstellar clouds. We study the gas-phase CN and HCN production
efficiencies from the outer photon-dominated regions (PDRs) into the opaque
cosmic-ray dominated cores. We calculate the equilibrium densities of CN and
HCN, and of the associated species C+, C, and CO, as functions of the
far-ultraviolet (FUV) optical depth. We consider isothermal gas at 50 K, with
hydrogen particle densities from 10^2 to 10^6 cm^-3. We study clouds that are
exposed to FUV fields with intensities 20 to 2*10^5 times the mean interstellar
FUV intensity. We assume cosmic-ray H2 ionization rates ranging from 5*10^-17
s^-1, to an enhanced value of 5*10^-16 s^-1. We also examine the sensitivity of
the density profiles to the gas-phase sulfur abundance.Comment: Accepted for publication in ApJ, 33 pages, 8 figure
Chaotic flow and efficient mixing in a micro-channel with a polymer solution
Microscopic flows are almost universally linear, laminar and stationary
because Reynolds number, , is usually very small. That impedes mixing in
micro-fluidic devices, which sometimes limits their performance. Here we show
that truly chaotic flow can be generated in a smooth micro-channel of a uniform
width at arbitrarily low , if a small amount of flexible polymers is added
to the working liquid. The chaotic flow regime is characterized by randomly
fluctuating three-dimensional velocity field and significant growth of the flow
resistance. Although the size of the polymer molecules extended in the flow may
become comparable with the micro-channel width, the flow behavior is fully
compatible with that in a table-top channel in the regime of elastic
turbulence. The chaotic flow leads to quite efficient mixing, which is almost
diffusion independent. For macromolecules, mixing time in this microscopic flow
can be three to four orders of magnitude shorter than due to molecular
diffusion.Comment: 8 pages,7 figure
Artificial Neural Networks Modeling to Reduce Industrial Air Pollution
Abstract. Nitric acid production plants emit small amounts of nitrogen oxides (NOx) to the environment. As the regulatory authorities demand the reduction of the resulting air pollution, existing plants are looking for economical ways to comply with this demand. Several Artificial Neural Networks (ANN) models were trained from several months of operating plant data to predict the NOx concentration in the tail gas, and their total amount emitted the environment. The training of the ANN model was done by the Guterman-Boger algorithm set that generates a non-random initial connection weights, suggests a small number of hidden neurons, avoids, and escapes from, local minima encountered during the training. The ANN models gave small errors, 0.6 % relative error on the NOx concentration prediction and 0.006 kg/hour on daily emission in the 20-45 kg NOx/hour range. Knowledge extraction from the trained ANN models revealed the underlying relationships between the plant operating variables and the NOx emission rate, especially the beneficial effect of cooling the absorbed gas and reticulating liquids in the absorption towers. Clustering the data by the patterns of the hidden neurons outputs of auto-associative ANN models of the same data revealed interesting insights
A simple vapor-diffusion method enables protein crystallization inside the HARE serial crystallography chip
Fixed-target serial crystallography has become an important method for the study of protein structure and dynamics at synchrotrons and X-ray free-electron lasers. However, sample homogeneity, consumption and the physical stress on samples remain major challenges for these high-throughput experiments, which depend on high-quality protein microcrystals. The batch crystallization procedures that are typically applied require time- and sample-intensive screening and optimization. Here, a simple protein crystallization method inside the features of the HARE serial crystallography chips is reported that circumvents batch crystallization and allows the direct transfer of canonical vapor-diffusion conditions to in-chip crystallization. Based on conventional hanging-drop vapor-diffusion experiments, the crystallization solution is distributed into the wells of the HARE chip and equilibrated against a reservoir with mother liquor. Using this simple method, high-quality microcrystals were generated with sufficient density for the structure determination of four different proteins. A new protein variant was crystallized using the protein concentrations encountered during canonical crystallization experiments, enabling structure determination from âŒ55â
”g of protein. Additionally, structure determination from intracellular crystals grown in insect cells cultured directly in the features of the HARE chips is demonstrated. In cellulo crystallization represents a comparatively unÂexplored space in crystallization, especially for proteins that are resistant to crystallization using conventional techniques, and eliminates any need for laborious protein purification. This in-chip technique avoids harvesting the sensitive crystals or any further physical handling of the crystal-containing cells. These proof-of-principle experiments indicate the potential of this method to become a simple alternative to batch crystallization approaches and also as a convenient extension to canonical crystallization screens
Gamow-Teller Strengths of the Inverse-Beta Transition 176Yb --> 176Lu for Spectroscopy of Proton-Proton and other sub-MeV Solar Neutrinos
Discrete Gamow-Teller (GT) transitions, 176Yb-->176Lu at low excitation
energies have been measured via the (3He,t) reaction at 450 MeV and at 0
degrees. For 176Yb, two low-lying states are observed, setting low thresholds
Q(neutrino)=301 and 445 keV for neutrino capture. Capture rates estimated from
the measured GT strengths, the simple two-state excitation structure, and the
low Q(neutrino) in Yb--Lu indicate that Yb-based neutrino-detectors are well
suited for a direct measurement of the complete sub-MeV solar electron-neutrino
spectrum (including pp neutrinos) where definitive effects of flavor conversion
are expected
Effects of Neutrino Oscillation on the Supernova Neutrino Spectrum
The effects of three-flavor neutrino oscillation on the supernova neutrino
spectrum are studied. We calculate the expected event rate and energy spectra,
and their time evolution at the Superkamiokande (SK) and the Sudbury Neutrino
Observatory (SNO), by using a realistic neutrino burst model based on numerical
simulations of supernova explosions. We also employ a realistic density profile
based on a presupernova model for the calculation of neutrino conversion
probability in supernova envelopes. These realistic models and numerical
calculations allow us to quantitatively estimate the effects of neutrino
oscillation in a more realistic way than previous studies. We then found that
the degeneracy of the solutions of the solar neutrino problem can be broken by
the combination of the SK and SNO detections of a future Galactic supernova.Comment: 10 pages, 14 figures, corrected versio
Tracing star formation in galaxies with molecular line and continuum observations
We report our recent progress on extragalactic spectroscopic and continuum
observations, including HCN(J=1-0), HCO(J=1-0), and CN(N=1-0) imaging
surveys of local Seyfert and starburst galaxies using the Nobeyama Millimeter
Array, high-J CO observations (J=3-2 observations using the Atacama
Submillimeter Telescope Experiment (ASTE) and J=2-1 observations with the
Submillimeter Array) of galaxies, and 1.1 mm continuum observations
of high-z violent starburst galaxies using the bolometer camera AzTEC mounted
on ASTE.Comment: 6 pages, 5 figures, To appear in proceedings of "Far-Infrared and
Submillimeter Emission of the Interstellar Medium", EAS Publication Series,
Bad Honnef, November 2007, Eds. C. Kramer, S. Aalto, R. Simon. See
http://www.nro.nao.ac.jp/~f0212kk/FIR07/kk-ver20.pdf for a version with high
resolution figure
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