Synthesis, mechanism of formation, and molecular orbital calculations of arylamidoximes

A simple and easy synthesis of ten arylamidoximes from arylnitriles and hydroxylamine is described. The formation of the arylamides has been observed to a much lesser extent in the present work. A new mechanism for the formation of arylamidoximes, as well as arylamides, from arylnitriles and hydroxylamine is suggested. Quantum mechanical calculations have been carried out to support this mechanism. The enthalpy of formation in conjunction with atomic charges of the reactants and intermediates helped to understand more about the generation of the products.

Lead(II)-induced formation and coordination of 3,4-dihydro-3-thioxo-1,2,4-triazin-5(2H)-one

Cyclization of (n)butyl glyoxylate thiosemicarbazone (HBuTSC) under reflux in the presence of Pb(OAc)(2) led to tile formation of the complex [Pb(HTz)(2)] (H(2)Tz = 3,4-dihydro-3-thioxo-1,2,4-triazin-5(2H)-one), which after recrystallization from DMSO afforded the polymer [Pb(Tz)](n), the first example of a Tz(2-) metal complex. (C) 2008 Elsevier B.V. All rights reserved.

Investigating the formation and the properties of monoalkyl carbonates in aqueous medium using capillary electrophoresis with capacitively coupled contactless conductivity detection

Although alkyl carbonic acids (ACAs) and their salts are referred to as instable species in aqueous medium, we demonstrate that a monoalkyl carbonate (MAC) can in fact be easily formed from bicarbonate and an alcohol even in the presence of a high amount of water. A CE system with two capacitively coupled contactless conductivity detectors (C(4)Ds) was used to obtain different parameters about these species and their reactions. Based on the mobilities obtained for a series of alcohols ranging from 1 to 5 carbons, the coefficients of diffusion and the hydrodynamic radii were calculated. When compared with the equivalent carboxylates, MACs have radii systematically smaller. Although the precise pK(a) values of the ACAs could not be obtained, because of the fast decomposition in acid medium, it was possible, for the first time, to show that they are below 4.0. This result suggests that the acidity of an ACA is quite similar to the first hydrogen of H(2)CO(3). Using a new approach to indirectly calibrate the C(4)D, the kinetic constants and the equilibrium constants of formation were also obtained. The results suggest that the increase in the chain length makes the MACs less stable and more inert.

Formation and decomposition of N-alkyinaphthalimides: experimental evidences and ab initio description of the reaction pathways

The kinetics of hydrolysis of 1,8-N-butyl-naphthalimide (1,8-NBN) to 1,8-N-butyl-naphthalamide (1,8-NBAmide) and of 2,3-N-butyl-naphthalimide (2,3-NBN) to 2,3-N-butyl-naphthalamide (2,3-NBAmide), as well as the formation of the respective anhydrides from the amides were investigated in a wide acidity range. 1,8-NBN equilibrates with 1,8-NBAmide in mild alkali. Under the same conditions 2,3-NBN quantitatively yields 2,3-NBAmide. Over a wide range of acidities the reactions of the 1,8- and 2,3-N-butyl-naphthalamides (or imides) yield similar products but with widely different rates and at distinct pH`s. Anhydride formation in acid was demonstrated for 1,8-NBAmide. The reactions mechanisms were rationalized in the manifold pathways of ab initio calculations. The differences in rates and pH ranges in the reactions of the 1,8- and 2,3-N-butyl-naphthalamides were attributed to differences in the stability of the tetrahedral intermediates in alkali as well as the relative stabilities of the five and six-membered ring intermediates. The rate of carboxylic acid assisted 1,8-N-Butyl-naphthalamide hydrolysis is one of the largest described for amide hydrolysis models. Copyright (C) 2010 John Wiley & Sons, Ltd.

Estudo do mecanismo de corrosão por pites em água do mar de aços inoxidáveis supermartensíticos microligados com Nb e Ti

Os aços inoxidáveis supermartensíticos (SMSS) são usados em ambientes agressivos devido à sua boa soldabilidade, boas propriedades mecânicas em temperaturas elevadas e superior resistência à corrosão sob tensão. Aplicações na exploração de petróleo demandam superior combinação de propriedades e os aços inoxidáveis duplex e superduplex têm sido aplicados nessa área, a despeito de seus custos elevados. Os SMSS consistem numa alternativa técnica e econômica ao uso daqueles aços. Nesse trabalho, adições de Nb e Ti foram realizadas com o intuito de minimizar o efeito de sensitização, promover o refino de grãos e foram estudados os aspectos microestruturais e a resistência à corrosão por pites em água do mar. A formação e a evolução dos pites foram acompanhadas por ensaios de corrosão, microscopia óptica e eletrônica, focalizando suas morfologias. O aço com Ti apresentou o melhor desempenho quanto à corrosão, com o maior potencial de corrosão e menor potencial de pite entre os aços em estudo. O aço com Nb, apesar de apresentar potencial de corrosão superior ao do aço sem adição, teve um potencial de pite inferior ao do mesmo.

Chemical evolution of the Galactic bulge as traced by microlensed dwarf and subgiant stars IV. Two bulge populations

Based on high-resolution (R approximate to 42 000 to 48 000) and high signal-to-noise (S/N approximate to 50 to 150) spectra obtained with UVES/VLT, we present detailed elemental abundances (O, Na, Mg, Al, Si, Ca, Ti, Cr, Fe, Ni, Zn, Y, and Ba) and stellar ages for 12 new microlensed dwarf and subgiant stars in the Galactic bulge. Including previous microlensing events, the sample of homogeneously analysed bulge dwarfs has now grown to 26. The analysis is based on equivalent width measurements and standard 1-D LTE MARCS model stellar atmospheres. We also present NLTE Li abundances based on line synthesis of the (7)Li line at 670.8 nm. The results from the 26 microlensed dwarf and subgiant stars show that the bulge metallicity distribution (MDF) is double-peaked; one peak at [Fe/H] approximate to -0.6 and one at [Fe/H] approximate to +0.3, and with a dearth of stars around solar metallicity. This is in contrast to the MDF derived from red giants in Baade's window, which peaks at this exact value. A simple significance test shows that it is extremely unlikely to have such a gap in the microlensed dwarf star MDF if the dwarf stars are drawn from the giant star MDF. To resolve this issue we discuss several possibilities, but we can not settle on a conclusive solution for the observed differences. We further find that the metal-poor bulge dwarf stars are predominantly old with ages greater than 10 Gyr, while the metal-rich bulge dwarf stars show a wide range of ages. The metal-poor bulge sample is very similar to the Galactic thick disk in terms of average metallicity, elemental abundance trends, and stellar ages. Speculatively, the metal-rich bulge population might be the manifestation of the inner thin disk. If so, the two bulge populations could support the recent findings, based on kinematics, that there are no signatures of a classical bulge and that the Milky Way is a pure-disk galaxy. Also, recent claims of a flat IMF in the bulge based on the MDF of giant stars may have to be revised based on the MDF and abundance trends probed by our microlensed dwarf stars.

Chemical evolution of the Galactic bulge as traced by microlensed dwarf and subgiant stars III. Detection of lithium in the metal-poor bulge dwarf MOA-2010-BLG-285S

Context. To study the evolution of Li in the Galaxy it is necessary to observe dwarf or subgiant stars. These are the only long-lived stars whose present-day atmospheric chemical composition reflects their natal Li abundances according to standard models of stellar evolution. Although Li has been extensively studied in the Galactic disk and halo, to date there has only been one uncertain detection of Li in an unevolved bulge star. Aims. Our aim with this study is to provide the first clear detection of Li in the Galactic bulge, based on an analysis of a dwarf star that has largely retained its initial Li abundance. Methods. We performed a detailed elemental abundance analysis of the bulge dwarf star MOA-2010-BLG-285S using a high-resolution and high signal-to-noise spectrum obtained with the UVES spectrograph at the VLT when the object was optically magnified during a gravitational microlensing event (visual magnification A similar to 550 during observation). The Li abundance was determined through synthetic line profile fitting of the (7)Li resonance doublet line at 670.8 nm. The results have been corrected for departures from LTE. Results. MOA-2010-BLG-285S is, at [Fe/H] = -1.23, the most metal-poor dwarf star detected so far in the Galactic bulge. Its old age (12.5 Gyr) and enhanced [alpha/Fe] ratios agree well with stars in the thick disk at similar metallicities. This star represents the first unambiguous detection of Li in a metal-poor dwarf star in the Galactic bulge. We find an NLTE corrected Li abundance of log epsilon(Li) = 2.16, which is consistent with values derived for Galactic disk and halo dwarf stars at similar metallicities and temperatures. Conclusions. Our results show that there are no signs of Li enrichment or production in the Galactic bulge during its earliest phases. Observations of Li in other galaxies (omega Cen) and other components of the Galaxy suggest further that the Spite plateau is universal.

Star formation in the intragroup medium and other diagnostics of the evolutionary stages of compact groups of galaxies

Context. Compact groups of galaxies are entities that have high densities of galaxies and serve as laboratories to study galaxy interactions, intergalactic star formation and galaxy evolution. Aims. The main goal of this study is to search for young objects in the intragroup medium of seven compact groups of galaxies: HCG 2, 7, 22, 23, 92, 100 and NGC 92 as well as to evaluate the stage of interaction of each group. Methods. We used Fabry-Perot velocity fields and rotation curves together with GALEX NUV and FUV images and optical R-band and HI maps. Results. (i) HCG 7 and HCG 23 are in early stages of interaction; (ii) HCG 2 and HCG 22 are mildly interacting; and (iii) HCG 92, HCG 100 and NGC 92 are in late stages of evolution. We find that all three evolved groups contain populations of young blue objects in the intragroup medium, consistent with ages < 100 Myr, of which several are younger than < 10 Myr. We also report the discovery of a tidal dwarf galaxy candidate in the tail of NGC 92. These three groups, besides containing galaxies that have peculiar velocity fields, also show extended HI tails. Conclusions. Our results indicate that the advanced stage of evolution of a group, together with the presence of intragroup HI clouds, may lead to star formation in the intragroup medium. A table containing all intergalactic HII regions and tidal dwarf galaxies confirmed to date is appended.

Abundances in the Galactic bulge: results from planetary nebulae and giant stars

Context. Our understanding of the chemical evolution (CE) of the Galactic bulge requires the determination of abundances in large samples of giant stars and planetary nebulae (PNe). Studies based on high resolution spectroscopy of giant stars in several fields of the Galactic bulge obtained with very large telescopes have allowed important progress. Aims. We discuss PNe abundances in the Galactic bulge and compare these results with those presented in the literature for giant stars. Methods. We present the largest, high-quality data-set available for PNe in the direction of the Galactic bulge (inner-disk/bulge). For comparison purposes, we also consider a sample of PNe in the Large Magellanic Cloud (LMC). We derive the element abundances in a consistent way for all the PNe studied. By comparing the abundances for the bulge, inner-disk, and LMC, we identify elements that have not been modified during the evolution of the PN progenitor and can be used to trace the bulge chemical enrichment history. We then compare the PN abundances with abundances of bulge field giant. Results. At the metallicity of the bulge, we find that the abundances of O and Ne are close to the values for the interstellar medium at the time of the PN progenitor formation, and hence these elements can be used as tracers of the bulge CE, in the same way as S and Ar, which are not expected to be affected by nucleosynthetic processes during the evolution of the PN progenitors. The PN oxygen abundance distribution is shifted to lower values by 0.3 dex with respect to the distribution given by giants. A similar shift appears to occur for Ne and S. We discuss possible reasons for this PNe-giant discrepancy and conclude that this is probably due to systematic errors in the abundance derivations in either giants or PNe (or both). We issue an important warning concerning the use of absolute abundances in CE studies.

The chemical evolution of IC 10

Context. Dwarf irregular galaxies are relatively simple unevolved objects where it is easy to test models of galactic chemical evolution. Aims. We attempt to determine the star formation and gas accretion history of IC 10, a local dwarf irregular for which abundance, gas, and mass determinations are available. Methods. We apply detailed chemical evolution models to predict the evolution of several chemical elements (He, O, N, S) and compared our predictions with the observational data. We consider additional constraints such as the present-time gas fraction, the star formation rate (SFR), and the total estimated mass of IC 10. We assume a dark matter halo for this galaxy and study the development of a galactic wind. We consider different star formation regimes: bursting and continuous. We explore different wind situations: i) normal wind, where all the gas is lost at the same rate and ii) metal-enhanced wind, where metals produced by supernovae are preferentially lost. We study a case without wind. We vary the star formation efficiency (SFE), the wind efficiency, and the time scale of the gas infall, which are the most important parameters in our models. Results. We find that only models with metal-enhanced galactic winds can reproduce the properties of IC 10. The star formation must have proceeded in bursts rather than continuously and the bursts must have been less numerous than similar to 10 over the whole galactic lifetime. Finally, IC 10 must have formed by a slow process of gas accretion with a timescale of the order of 8 Gyr.

TURBULENCE AND THE FORMATION OF FILAMENTS, LOOPS, AND SHOCK FRONTS IN NGC 1275

NGC 1275, the central galaxy in the Perseus cluster, is the host of gigantic hot bipolar bubbles inflated by active galactic nucleus (AGN) jets observed in the radio as Perseus A. It presents a spectacular H alpha-emitting nebulosity surrounding NGC 1275, with loops and filaments of gas extending to over 50 kpc. The origin of the filaments is still unknown, but probably correlates with the mechanism responsible for the giant buoyant bubbles. We present 2.5 and three-dimensional magnetohydrodynamical (MHD) simulations of the central region of the cluster in which turbulent energy, possibly triggered by star formation and supernovae (SNe) explosions, is introduced. The simulations reveal that the turbulence injected by massive stars could be responsible for the nearly isotropic distribution of filaments and loops that drag magnetic fields upward as indicated by recent observations. Weak shell-like shock fronts propagating into the intracluster medium (ICM) with velocities of 100-500 km s(-1) are found, also resembling the observations. The isotropic outflow momentum of the turbulence slows the infall of the ICM, thus limiting further starburst activity in NGC 1275. As the turbulence is subsonic over most of the simulated volume, the turbulent kinetic energy is not efficiently converted into heat and additional heating is required to suppress the cooling flow at the core of the cluster. Simulations combining the MHD turbulence with the AGN outflow can reproduce the temperature radial profile observed around NGC 1275. While the AGN mechanism is the main heating source, the SNe are crucial to isotropize the energy distribution.

Retinoic Acid-Treated Pluripotent Stem Cells Undergoing Neurogenesis Present Increased Aneuploidy and Micronuclei Formation

The existence of loss and gain of chromosomes, known as aneuploidy, has been previously described within the central nervous system. During development, at least one-third of neural progenitor cells (NPCs) are aneuploid. Notably, aneuploid NPCs may survive and functionally integrate into the mature neural circuitry. Given the unanswered significance of this phenomenon, we tested the hypothesis that neural differentiation induced by all-trans retinoic acid (RA) in pluripotent stem cells is accompanied by increased levels of aneuploidy, as previously described for cortical NPCs in vivo. In this work we used embryonal carcinoma (EC) cells, embryonic stem (ES) cells and induced pluripotent stem (iPS) cells undergoing differentiation into NPCs. Ploidy analysis revealed a 2-fold increase in the rate of aneuploidy, with the prevalence of chromosome loss in RA primed stem cells when compared to naive cells. In an attempt to understand the basis of neurogenic aneuploidy, micronuclei formation and survivin expression was assessed in pluripotent stem cells exposed to RA. RA increased micronuclei occurrence by almost 2-fold while decreased survivin expression by 50%, indicating possible mechanisms by which stem cells lose their chromosomes during neural differentiation. DNA fragmentation analysis demonstrated no increase in apoptosis on embryoid bodies treated with RA, indicating that cell death is not the mandatory fate of aneuploid NPCs derived from pluripotent cells. In order to exclude that the increase in aneuploidy was a spurious consequence of RA treatment, not related to neurogenesis, mouse embryonic fibroblasts were treated with RA under the same conditions and no alterations in chromosome gain or loss were observed. These findings indicate a correlation amongst neural differentiation, aneuploidy, micronuclei formation and survivin downregulation in pluripotent stem cells exposed to RA, providing evidence that somatically generated chromosomal variation accompanies neurogenesis in vitro.

Biomass burning in Brazil`s Amazonian ""arc of deforestation"": Burning efficiency and charcoal formation in a fire after mechanized clearing at Feliz Natal, Mato Grosso

Estimates of greenhouse-gas emissions from deforestation are highly uncertain because of high variability in key parameters and because of the limited number of studies providing field measurements of these parameters. One such parameter is burning efficiency, which determines how much of the original forest`s aboveground carbon stock will be released in the burn, as well as how much will later be released by decay and how much will remain as charcoal. In this paper we examined the fate of biomass from a semideciduous tropical forest in the ""arc of deforestation,"" where clearing activity is concentrated along the southern edge of the Amazon forest. We estimated carbon content, charcoal formation and burning efficiency by direct measurements (cutting and weighing) and by line-intersect sampling (LIS) done along the axis of each plot before and after burning of felled vegetation. The total aboveground dry biomass found here (219.3 Mg ha(-1)) is lower than the values found in studies that have been done in other parts of the Amazon region. Values for burning efficiency (65%) and charcoal formation (6.0%, or 5.98 Mg C ha(-1)) were much higher than those found in past studies in tropical areas. The percentage of trunk biomass lost in burning (49%) was substantially higher than has been found in previous studies. This difference may be explained by the concentration of more stems in the smaller diameter classes and the low humidity of the fuel (the dry season was unusually long in 2007, the year of the burn). This study provides the first measurements of forest burning parameters for a group of forest types that is now undergoing rapid deforestation. The burning parameters estimated here indicate substantially higher burning efficiency than has been found in other Amazonian forest types. Quantification of burning efficiency is critical to estimates of trace-gas emissions from deforestation. (C) 2009 Elsevier B.V. All rights reserved.

Chlorophyll Degradation and Formation of Colorless Chlorophyll Derivatives during Soybean (Glycine max L. Merill) Seed Maturation

The natural chlorophyll degradation results in noncolored chlorophyll catabolites (NCCs), but there are controversies if these are the final products. The formation and degradation of NCCs during soybean seed (Glycine max L. Merrill) maturation and two drying temperatures were investigated. Soybean was harvested at six maturation stages. The effect of postharvest drying at 40 and 60 degrees C on the NCC formation was analyzed by high-performance liquid chromatography (HPLC), and results were expressed as areas under the curve. All samples contained fractions with an absorption maximum at 320 nm, typical for NCC. The amounts of NCC increased until 114 days after planting and were significantly lower in advanced maturation stages. These results indicate that the NCC in soybeans might not be the final products of chlorophyll degradation. Their reduction in advanced maturation stages may be due to further metabolization. Heating soybeans at 40 and 60 degrees C promoted unnatural chlorophyll degradation and impaired the formation of NCC.

Hydrodynamical simulations of Galactic fountains - I. Evolution of single fountains

The ejection of the gas out of the disc in late-type galaxies is related to star formation and is due mainly to Type II supernovae. In this paper, we studied in detail the development of the Galactic fountains in order to understand their dynamical evolution and their influence on the redistribution of the freshly delivered metals over the disc. To this aim, we performed a number of 3D hydrodynamical radiative cooling simulations of the gas in the Milky Way where the whole Galaxy structure, the Galactic differential rotation and the supernova explosions generated by a single OB association are considered. A typical fountain powered by 100 Type II supernovae may eject material up to similar to 2 kpc which than collapses back mostly in the form of dense, cold clouds and filaments. The majority of the gas lifted up by the fountains falls back on the disc remaining within a radial distance Delta R = 0.5 kpc from the place where the fountain originated. This localized circulation of disc gas does not influence the radial chemical gradients on large scale, as required by the chemical models of the Milky Way which reproduce the metallicity distribution without invoking large fluxes of metals. Simulations of multiple fountains fuelled by Type II supernovae of different OB associations will be presented in a companion paper.