Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH2), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition–Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving CuIII intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity

Herschel/HIFI observations of molecular emission in protoplanetary nebulae and young planetary nebulae

We performed Herschel/HIFI observations of intermediate-excitation molecular lines in the far-infrared/submillimeter range in a sample of ten protoplanetary nebulae and young planetary nebulae. The high spectral resolution provided by HIFI yields accurate measurements of the line profiles. The observation of these high-energy transitions allows an accurate study of the excitation conditions, particularly in the warm gas, which cannot be properly studied from the low-energy lines. We have detected FIR/sub-mm lines of several molecules, in particular of 12CO, 13CO, and H2O. Emission from other species, like NH3, OH, H2^{18}O, HCN, SiO, etc, has been also detected. Wide profiles showing sometimes spectacular line wings have been found. We have mainly studied the excitation properties of the high-velocity emission, which is known to come from fast bipolar outflows. From comparison with general theoretical predictions, we find that CRL 618 shows a particularly warm fast wind, with characteristic kinetic temperature Tk >~ 200 K. In contrast, the fast winds in OH 231.8+4.2 and NGC 6302 are cold, Tk ~ 30 K. Other nebulae, like CRL 2688, show intermediate temperatures, with characteristic values around 100 K. We also discuss how the complex structure of the nebulae can affect our estimates, considering two-component models. We argue that the differences in temperature in the different nebulae can be due to cooling after the gas acceleration (that is probably due to shocks); for instance, CRL 618 is a case of very recent acceleration, less than ~ 100 yr ago, while the fast gas in OH 231.8+4.2 was accelerated ~ 1000 yr ago. We also find indications that the densest gas tends to be cooler, which may be explained by the expected increase of the radiative cooling efficiency with the density.Comment: 24 pages, 31 figure

The Physical Parameters of the Micro-quasar S26 in the Sculptor Group Galaxy NGC 7793

NGC 7793 - S26 is an extended source (350 pc $\times$ 185 pc) previously studied in the radio, optical and x-ray domains. It has been identified as a micro-quasar which has inflated a super bubble. We used Integral Field Spectra from the Wide Field Spectrograph on the ANU 2.3 m telescope to analyse spectra between 3600--7000 \AA. This allowed us to derive fluxes and line ratios for selected nebular lines. Applying radiative shock model diagnostics, we estimate shock velocities, densities, radiative ages and pressures across the object. We show that S26 is just entering its radiative phase, and that the northern and western regions are dominated by partially-radiative shocks due to a lower density ISM in these directions. We determine a velocity of expansion along the jet of 330 km s$^{-1}$, and a velocity of expansion of the bubble in the minor axis direction of 132 km s$^{-1}$. We determine the age of the structure to be $4.1\times10^5$ yr, and the jet energy flux to be $(4-10)\times10^{40}$ erg s$^{-1}$ The jet appears to be collimated within $\sim0.25$ deg, and to undergo very little precession. If the relativistic $\beta \sim 1/3$, then some 4 M$_{\odot}$ of relativistic matter has already been processed through the jet. We conclude that the central object in S26 is probably a Black Hole with a mass typical of the ultra-luminous X-ray source population which is currently consuming a fairly massive companion through Roche Lobe accretion.Comment: Accepted for publication in MNRAS; 12 pages, 7 figures and 3 table

Valproic acid restricts mast cell activation by Listeria monocytogenes.

Mast cells (MC) play a central role in the early containment of bacterial infections, such as that caused by Listeria monocytogenes (L.m). The mechanisms of MC activation induced by L.m infection are well known, so it is possible to evaluate whether they are susceptible to targeting and modulation by different drugs. Recent evidence indicates that valproic acid (VPA) inhibits the immune response which favors L.m pathogenesis in vivo. Herein, we examined the immunomodulatory effect of VPA on L.m-mediated MC activation. To this end, bone marrow-derived mast cells (BMMC) were pre-incubated with VPA and then stimulated with L.m. We found that VPA reduced MC degranulation and cytokine release induced by L.m. MC activation during L.m infection relies on Toll-Like Receptor 2 (TLR2) engagement, however VPA treatment did not affect MC TLR2 cell surface expression. Moreover, VPA was able to decrease MC activation by the classic TLR2 ligands, peptidoglycan and lipopeptide Pam3CSK4. VPA also reduced cytokine production in response to Listeriolysin O (LLO), which activates MC by a TLR2-independent mechanism. In addition, VPA decreased the activation of critical events on MC signaling cascades, such as the increase on intracellular Ca2+ and phosphorylation of p38, ERK1/2 and -p65 subunit of NF-κB. Altogether, our data demonstrate that VPA affects key cell signaling events that regulate MC activation following L.m infection. These results indicate that VPA can modulate the functional activity of different immune cells that participate in the control of L.m infection

Simultaneous and optical follow-up GRB observations by BOOTES

Since 1998 BOOTES has provided follow-up observations for more than 70 GRBs; the most important results obtained so far are the detection of an OT in the GRB 000313 error box and the non-detection of optical emission simultaneous to the high-energy emission for several GRBs (both long/soft and short/hard events)

Trasformaciones eclesiales. Propuestas del papa Francisco para una iglesia en pastoral

Jorge Mario Bergoglio llegó al Vaticano con un sentido de autocrítica y con el propósito de hacer cambios sustanciales. Lo que propone el papa es que la Iglesia católica deje de ser autorreferencial, salga de sí misma y vaya hacia las periferias, no solo geográficas sino también las existenciales. Sin embargo, todo cambio enfrenta inercias, más cuando se busca una trasformación desde dentro de una institución milenaria. En este libro, académicos de cinco universidades mexicanas analizan la figura, el discurso y las acciones de Francisco en sus primeros años en la sede papal, así como las críticas internas y externas a su labor, lo que permite dimensionar el alcance de la tarea que se ha impuesto el sumo pontífice

Elevated levels of plasma homocysteine, deficiencies in dietary folic acid and uracil–DNA glycosylase impair learning in a mouse model of vascular cognitive impairment

Dietary deficiencies in folic acid result in elevated levels of plasma homocysteine, which has been associated with the development of dementia and other neurodegenerative disorders. Previously, we have shown that elevated levels of plasma homocysteine in mice deficient for a DNA repair enzyme, uracil–DNA glycosylase (UNG), result in neurodegeneration. The goal of this study was to evaluate how deficiencies in folic acid and UNG along with elevated levels of homocysteine affect vascular cognitive impairment, via chronic hypoperfusion in an animal model. Ung+/+ and Ung−/− mice were placed on either control (CD) or folic acid deficient (FADD) diets. Six weeks later, the mice either underwent implantation of microcoils around both common carotid arteries. Post-operatively, behavioral tests began at 3-weeks, angiography was measured after 5-weeks using MRI to assess vasculature and at completion of study plasma and brain tissue was collected for analysis. Learning impairments in the Morris water maze (MWM) were observed only in hypoperfused Ung−/− FADD mice and these mice had significantly higher plasma homocysteine concentrations. Interestingly, Ung+/+ FADD produced significant remodeling of the basilar artery and arterial vasculature. Increased expression of GFAP was observed in the dentate gyrus of Ung−/− hypoperfused and FADD sham mice. Chronic hypoperfusion resulted in increased cortical MMP-9 protein levels of FADD hypoperfused mice regardless of genotypes. These results suggest that elevated levels of homocysteine only, as a result of dietary folic acid deficiency, don’t lead to memory impairments and neurobiochemical changes. Rather a combination of either chronic hypoperfusion or UNG deficiency is required

Identidad, territorio y promocion de la salud

El presente trabajo se enmarca dentro de un proyecto de extensión que se desarrolla durante el 2012, acreditado y financiado por la UNLP, denominado “Identidad, territorio y salud. Construcción de identidades colectivas y transferencia institucional en torno al primer nivel de atención en el Barrio Federal de Ensenada”. Este barrio cuenta con una población aproximada de 480 habitantes y está ubicado en la zona de Gran La Plata, Pcia. de Buenos Aires. El objetivo del trabajo consiste en fortalecer la apropiación y promoción de la salud colectiva, entendida ésta como un proceso construido históricamente por cada sociedad, que se crea y recrea en todos los aspectos de la vida cotidiana de los sujetos. La propuesta metodológica se sustenta en un proceso dialógico entre los sujetos involucrados: vecinos de barrio Federal y los integrantes del equipo del trabajo extensionista. Desde este marco (pedagógico horizontal) desarrollamos actividades grupales de carácter lúdico-recreativo, que a primera vista no aparentan tener una relación con el proceso salud-enfermedad, propio del imaginario social, pero implícitamente, estarían abarcando y generando cambios en el significado asignado del mismo. Partimos de la idea de fortalecer el sentirse bien, no en el estricto sentido biológico, sino como aquella capacidad para crear momentos y actividades con pares en un mismo territorio y generando lazos entre vecinos y entre éstos y la institución de salud del barrio. De este modo, las actividades se desarrollan principalmente en la sala de espera de la unidad sanitaria y en la plaza circundante. Hemos definido tres líneas de trabajo: artístico, narrativo-plástico y de producción audiovisual y medioambiente. En los encuentros se trabaja con diferentes recursos, propios de disciplinas como música, plástica, teatro, danza, escultura, circo, artes audiovisuales, literatura, entre otros. El carácter interdisciplinario de este proyecto, conformado por estudiantes de las carreras de Trabajo Social y Antropología, un artista escultor y dirigido y coordinado por docentes y graduados de las Facultades de Ciencias Medicas, Humanidades y Ciencias de la Educación y Trabajo Social, enriquece las perspectivas de abordaje y fortalece la visión social, integral y colectiva de la salud. Consolidar acciones identitarias del barrio, generadas a partir de la promoción de la salud, es el principal desafío a alcanzar

The First Molecular Phylogeny of Strepsiptera (Insecta) Reveals an Early Burst of Molecular Evolution Correlated with the Transition to Endoparasitism

A comprehensive model of evolution requires an understanding of the relationship between selection at the molecular and phenotypic level. We investigate this in Strepsiptera, an order of endoparasitic insects whose evolutionary biology is poorly studied. We present the first molecular phylogeny of Strepsiptera, and use this as a framework to investigate the association between parasitism and molecular evolution. We find evidence of a significant burst in the rate of molecular evolution in the early history of Strepsiptera. The evolution of morphological traits linked to parasitism is significantly correlated with the pattern in molecular rate. The correlated burst in genotypic-phenotypic evolution precedes the main phase of strepsipteran diversification, which is characterised by the return to a low and even molecular rate, and a period of relative morphological stability. These findings suggest that the transition to endoparasitism led to relaxation of selective constraint in the strepsipteran genome. Our results indicate that a parasitic lifestyle can affect the rate of molecular evolution, although other causal life-history traits correlated with parasitism may also play an important role