The [4+2]‐Cycloaddition of α‐Nitrosoalkenes with Thiochalcones as a Prototype of Periselective Hetero‐Diels–Alder Reactions—Experimental and Computational Studies

The [4+2]‐cycloadditions of α‐nitrosoalkenes with thiochalcones occur with high selectivity at the thioketone moiety of the dienophile providing styryl‐substituted 4H‐1,5,2‐oxathiazines in moderate to good yields. Of the eight conceivable hetero‐Diels–Alder 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 α‐nitrosoalkene also adds competitively to the thioketone moiety of the thiochalcone dimer affording bis‐heterocyclic [4+2]‐cycloadducts. The experiments are supported by high‐level DFT calculations that were also extended to related hetero‐Diels–Alder 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 1,2‐dithiin and 2H‐thiopyran 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: Mórakert 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 farmers’ 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 members’ 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, $Re$, 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 $Re$, 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 ∼55 µg 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 un­explored 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 $\lambda$ 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