2,613 research outputs found

    Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements

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    The 6‐31G* and 6‐31G** basis sets previously introduced for first‐row atoms have been extended through the second‐row of the periodic table. Equilibrium geometries for one‐heavy‐atom hydrides calculated for the two‐basis sets and using Hartree–Fock wave functions are in good agreement both with each other and with the experimental data. HF/6‐31G* structures, obtained for two‐heavy‐atom hydrides and for a variety of hypervalent second‐row molecules, are also in excellent accord with experimental equilibrium geometries. No large deviations between calculated and experimental single bond lengths have been noted, in contrast to previous work on analogous first‐row compounds, where limiting Hartree–Fock distances were in error by up to a tenth of an angstrom. Equilibrium geometries calculated at the HF/6‐31G level are consistently in better agreement with the experimental data than are those previously obtained using the simple split‐valance 3‐21G basis set for both normal‐ and hypervalent compounds. Normal‐mode vibrational frequencies derived from 6‐31G* level calculations are consistently larger than the corresponding experimental values, typically by 10%–15%; they are of much more uniform quality than those obtained from the 3‐21G basis set. Hydrogenation energies calculated for normal‐ and hypervalent compounds are in moderate accord with experimental data, although in some instances large errors appear. Calculated energies relating to the stabilities of single and multiple bonds are in much better accord with the experimental energy differences

    Probing ISM Structure in Trumpler 14 & Carina I Using The Stratospheric Terahertz Observatory 2

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    We present observations of the Trumpler 14/Carina I region carried out using the Stratospheric Terahertz Observatory 2 (STO2). The Trumpler 14/Carina I region is in the west part of the Carina Nebula Complex, which is one of the most extreme star-forming regions in the Milky Way. We observed Trumpler 14/Carina I in the 158 ÎŒ\mum transition of [C\,{\sc ii}] with a spatial resolution of 48â€Čâ€Č'' and a velocity resolution of 0.17 km s−1^{-1}. The observations cover a 0.25∘^\circ by 0.28∘^\circ area with central position {\it l} = 297.34∘^\circ, {\it b} = -0.60∘^\circ. The kinematics show that bright [C\,{\sc ii}] structures are spatially and spectrally correlated with the surfaces of CO clouds, tracing the photodissociation region and ionization front of each molecular cloud. Along 7 lines of sight that traverse Tr 14 into the dark ridge to the southwest, we find that the [C\,{\sc ii}] luminosity from the HII region is 3.7 times that from the PDR. In same los we find in the PDRs an average ratio of 1:4.1:5.6 for the mass in atomic gas:dark-CO gas: molecular gas traced by CO. Comparing multiple gas tracers including HI 21cm, [C\,{\sc ii}], CO, and radio recombination lines, we find that the HII regions of the Carina Nebula Complex are well-described as HII regions with one-side freely expanding towards us, consistent with the champagne model of ionized gas evolution. The dispersal of the GMC in this region is dominated by EUV photoevaporation; the dispersal timescale is 20-30 Myr.Comment: ApJ accepte

    Behavioral Responses to a Repetitive Visual Threat Stimulus Express a Persistent State of Defensive Arousal in Drosophila

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    The neural circuit mechanisms underlying emotion states remain poorly understood. Drosophila offers powerful genetic approaches for dissecting neural circuit function, but whether flies exhibit emotion-like behaviors has not been clear. We recently proposed that model organisms may express internal states displaying “emotion primitives,” which are general characteristics common to different emotions, rather than specific anthropomorphic emotions such as “fear” or “anxiety.” These emotion primitives include scalability, persistence, valence, and generalization to multiple contexts. Here, we have applied this approach to determine whether flies’ defensive responses to moving overhead translational stimuli (“shadows”) are purely reflexive or may express underlying emotion states. We describe a new behavioral assay in which flies confined in an enclosed arena are repeatedly exposed to an overhead translational stimulus. Repetitive stimuli promoted graded (scalable) and persistent increases in locomotor velocity and hopping, and occasional freezing. The stimulus also dispersed feeding flies from a food resource, suggesting both negative valence and context generalization. Strikingly, there was a significant delay before the flies returned to the food following stimulus-induced dispersal, suggestive of a slowly decaying internal defensive state. The length of this delay was increased when more stimuli were delivered for initial dispersal. These responses can be mathematically modeled by assuming an internal state that behaves as a leaky integrator of stimulus exposure. Our results suggest that flies’ responses to repetitive visual threat stimuli express an internal state exhibiting canonical emotion primitives, possibly analogous to fear in mammals. The mechanistic basis of this state can now be investigated in a genetically tractable insect species

    Trait evolution, resource specialization and vulnerability to plant extinctions among Antillean hummingbirds

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    Species traits are thought to predict feeding specialization and the vulnerability of a species to extinctions of interaction partners, but the context in which a species evolved and currently inhabits may also matter. Notably, the predictive power of traits may require that traits evolved to fit interaction partners. Furthermore, local abiotic and biotic conditions may be important. On islands, for instance, specialized and vulnerable species are predicted to be found mainly in mountains, whereas species in lowlands should be generalized and less vulnerable. We evaluated these predictions for hummingbirds and their nectar-food plants on Antillean islands. Our results suggest that the rates of hummingbird trait divergence were higher among ancestral mainland forms before the colonization of the Antilles. In correspondence with the limited trait evolution that occurred within the Antilles, local abiotic and biotic conditions—not species traits—correlate with hummingbird resource specialization and the vulnerability of hummingbirds to extinctions of their floral resources. Specifically, hummingbirds were more specialized and vulnerable in conditions with high topographical complexity, high rainfall, low temperatures and high floral resource richness, which characterize the Antillean Mountains. These findings show that resource specialization and species vulnerability to extinctions of interaction partners are highly context-dependent.B.D., J.D.K., A.C.B., A.M.M.G. and C.R. thank the Danish National Research Foundation for its support of the Center for Macroecology, Evolution and Climate (grant no. DNRF96). P.K.M. thanks the São Paulo Research Foundation (FAPESP) for the postdoctoral grant (grant no. 2015/21457-4). B.I.S. was supported by the Natural Environment Research Council as part of the Cambridge Earth System Science NERC DTP (NE/L002507/1)

    Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements

    Get PDF
    The 6‐31G* and 6‐31G** basis sets previously introduced for first‐row atoms have been extended through the second‐row of the periodic table. Equilibrium geometries for one‐heavy‐atom hydrides calculated for the two‐basis sets and using Hartree–Fock wave functions are in good agreement both with each other and with the experimental data. HF/6‐31G* structures, obtained for two‐heavy‐atom hydrides and for a variety of hypervalent second‐row molecules, are also in excellent accord with experimental equilibrium geometries. No large deviations between calculated and experimental single bond lengths have been noted, in contrast to previous work on analogous first‐row compounds, where limiting Hartree–Fock distances were in error by up to a tenth of an angstrom. Equilibrium geometries calculated at the HF/6‐31G level are consistently in better agreement with the experimental data than are those previously obtained using the simple split‐valance 3‐21G basis set for both normal‐ and hypervalent compounds. Normal‐mode vibrational frequencies derived from 6‐31G* level calculations are consistently larger than the corresponding experimental values, typically by 10%–15%; they are of much more uniform quality than those obtained from the 3‐21G basis set. Hydrogenation energies calculated for normal‐ and hypervalent compounds are in moderate accord with experimental data, although in some instances large errors appear. Calculated energies relating to the stabilities of single and multiple bonds are in much better accord with the experimental energy differences

    NuSTAR and INTEGRAL Observations of a Low/Hard State of 1E1740.7-2942

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    The microquasar 1E1740.7-2942, also known as the "Great Annihilator," was observed by NuSTAR in the summer of 2012. We have analyzed in detail two observations taken ~2 weeks apart, for which we measure hard and smooth spectra typical of the low/hard state. A few weeks later the source flux declined significantly. Nearly simultaneous coverage by INTEGRAL is available from its Galactic Center monitoring campaign lasting ~2.5 months. These data probe the hard state spectrum from 1E1740.7-2942 before the flux decline. We find good agreement between the spectra taken with IBIS/ISGRI and NuSTAR, with the measurements being compatible with a change in flux with no spectral variability. We present a detailed analysis of the NuSTAR spectral and timing data and upper limits for reflection of the high energy emission. We show that the high energy spectrum of this X-ray binary is well described by thermal Comptonization

    Application of super absorbent polymers (SAP) in concrete construction—update of RILEM state-of-the-art report

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    Superabsorbent polymers (SAP) are a new, promising class of chemical admixtures which offer new possibilities in respect of influencing the properties of cement-based materials in the fresh, hardening, and hardened states. Much research work has been done in the last two decades to set the stage for introducing this truly multipurpose agent into the practice of construction. In particular, three RILEM Technical Committees: 196-ICC, 225-SAP and 260-RSC contributed considerably to the related progress by coordinating and combining the efforts of international experts in the field. The major product of the RILEM TC 225-SAP work was the State-of-the-Art Report published in 2012. This comprehensive document covered all topics relevant to the application of SAP as a concrete admixture. Since then further important progress has been made in understanding the working mechanisms of SAP in concrete and the effects of SAP-addition on various concrete properties. The article at hand presents an update on the state-of-the-art and is the concluding document delivered by the RILEM TC 260-RSC

    Azo dye polyelectrolyte multilayer films reversibly re-soluble with visible light

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    Polymeric multilayer films were prepared using a layer-by-layer (LBL) technique on glass surfaces, by repeated and sequential dipping into dilute aqueous solutions of various combinations of water-soluble polyanions (polyacrylic acid (PAA)), polycations (polyallylamine hydrochloride (PAH) or chitosan (CS)), with bi-functional water-soluble cationic azo dyes bismark brown R bismarck brown red or bismark brown Y (BBY), or anionic azo dyes allura red (ALR) or amaranth (AMA), as ionic cross-linkers. The electrostatically-assembled ionically-paired films showed good long-term stability to dissolution, with no re-solubility in water. However, upon exposure to low power visible light under running water, the films photo-disassembled back to their water-soluble constituent components, via structural photo-isomerization of the azo ionic crosslinkers. The relative rate of the disassembly (RRD) of the films was established using UV-Vis spectroscopy, demonstrating that these assemblies can in principle represent fully recyclable, environmentally structurally degradable materials triggered by exposure to sunlight, with full recovery of starting components. A density functional theory treatment of the allura red azo dye rationalizes the geometrical isomerization mechanism of the photo-disassembly and provides insight into the energetics of the optically-induced structural changes that trigger the disassembly and recovery

    Children\u27s Health in Latin America: The Influence of Environmental Exposures

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    Background:Chronic diseases are increasing among children in Latin America. Objective and Methods:To examine environmental risk factors for chronic disease in LatinAmerican children and to develop a strategic initiative for control of these exposures, the WorldHealth Organization (WHO) including the Pan American Health Organization (PAHO), the Collegium Ramazzini, and Latin American scientists reviewed regional and relevant global data. Findings: Industrial development and urbanization are proceeding rapidly in Latin America and environmental pollution has become widespread. Environmental threats to children\u27s health include traditional hazards such as indoor air pollution and drinking water contamination; as well as the newer hazards of urban air pollution; toxic chemicals such as lead, asbestos, mercury,arsenic, and pesticides;hazardous and electronic waste;and climate change. The mix of traditional and modern hazards varies greatly across and within countries reflecting industrialization, urbanization and socioeconomic forces. Conclusions: To control environmental threats to children\u27s health in Latin America, WHO, including PAHO will focus on the most highly prevalent and serious hazards - indoor and outdoor air pollution, water pollution, and toxic chemicals. Strategies for controlling these hazards include developing tracking data on regional trends in children\u27s environmental health(CEH); building a network of Collaborating Centres; promoting biomedical research in CEH;building regional capacity; supporting development of evidence-based prevention policies; studying the economic costs of chronic diseases in children; and developing platforms for dialogue with relevant stakeholders.
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