1,216 research outputs found

    Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic

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    An efficient ligand combination: A new bis(diphosphine) nickel(II) complex (see picture) is described. A ΔG° value of 0.84 kcal mol^(−1) for hydrogen addition for this complex was calculated from the experimentally determined equilibrium constant. This complex displayed reversible electrocatalytic activity for hydrogen production and oxidation at low overpotentials, which are characteristic for hydrogenase enzymes

    Splitting of multiple hydrogen molecules by bioinspired diniobium metal complexes: a DFT study

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    Splitting of molecular hydrogen (H2) into bridging and terminal hydrides is a common step in transition metal chemistry. Herein, we propose a novel organometallic platform for cleavage of multiple H2 molecules, which combines metal centers capable of stabilizing multiple oxidation states, and ligands bearing positioned pendant basic groups. Using quantum chemical modeling, we show that low-valent, early transition metal diniobium(II) complexes with diphosphine ligands featuring pendant amines can favorably uptake up to 8 hydrogen atoms, and that the energetics are favored by the formation of intramolecular dihydrogen bonds. This result suggests new possible strategies for the development of hydrogen scavenger molecules that are able to perform reversible splitting of multiple H2 molecules

    Sequestration of Martian CO2 by mineral carbonation

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    Carbonation is the water-mediated replacement of silicate minerals, such as olivine, by carbonate, and is commonplace in the Earth’s crust. This reaction can remove significant quantities of CO2 from the atmosphere and store it over geological timescales. Here we present the first direct evidence for CO2 sequestration and storage on Mars by mineral carbonation. Electron beam imaging and analysis show that olivine and a plagioclase feldspar-rich mesostasis in the Lafayette meteorite have been replaced by carbonate. The susceptibility of olivine to replacement was enhanced by the presence of smectite veins along which CO2-rich fluids gained access to grain interiors. Lafayette was partially carbonated during the Amazonian, when liquid water was available intermittently and atmospheric CO2 concentrations were close to their present-day values. Earlier in Mars’ history, when the planet had a much thicker atmosphere and an active hydrosphere, carbonation is likely to have been an effective mechanism for sequestration of CO2

    The Consolidation of the White Southern Congressional Vote

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    This article explores the initial desertion and continued realignment of about one-sixth of the white voters in the South who, until 1994, stood by Democratic congressional candidates even as they voted for Republican presidential nominees. Prior to 1994, a sizable share of the white electorate distinguished between Democratic congressional and presidential candidates; since 1994 that distinction has been swept away. In 1992, a majority of white southern voters was casting their ballot for the Democratic House nominee; by 1994, the situation was reversed and 64 percent cast their ballot for the Republican. Virtually all categories of voters increased their support of Republican congressional candidates in 1994 and the following elections further cement GOP congressional support in the South. Subsequent elections are largely exercises in partisanship, as the congressional votes mirror party preferences. Republicans pull nearly all GOP identifiers, most independents, and a sizeable minority of Democratic identifiers. Democrats running for Congress no longer convince voters that they are different from their party’s presidential standard bearers—a group that has consistently been judged unacceptable to overwhelming proportions of the southern white electorate.Yeshttps://us.sagepub.com/en-us/nam/manuscript-submission-guideline

    Beyond fossil fuel–driven nitrogen transformations

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    How much carbon does it take to make nitric acid? The counterintuitive answer nowadays is quite a lot. Nitric acid is manufactured by ammonia oxidation, and all the hydrogen to make ammonia via the Haber-Bosch process comes from methane. That's without even accounting for the fossil fuels burned to power the process. Chen et al. review research prospects for more sustainable routes to nitrogen commodity chemicals, considering developments in enzymatic, homogeneous, and heterogeneous catalysis, as well as electrochemical, photochemical, and plasma-based approaches

    Heterosexual interactions of pairs of laboratory-housed stumptail macaques (Macaca arctoides) under continuous observation with closed-circuit video recording

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    Female-male interaction of heterosexual pairs of stumptail macaques, housed together continuously, was studied 24 hr per day using closed-circuit video recording. Two pairs were studied for approximately 2 months each. Although no generalizations can be made from such a small sample, no aspect of behavioral interaction varied significantly with the stage of the menstrual cycle of the female partner. Copulation occurred regularly but only during the daylight hours. Both pairs showed several peak ejaculation days (5-21 ejaculations/day), which were distributed throughout the entire menstrual cycle. In general, the highest number of ejaculations was observed to occur when the animals were put together either for the first time or following a separation of a few days. In one pair the female became pregnant, and from the fifth week of pregnancy onward there was a gradual increase in male aggression, coinciding with a decrease in male sexual and grooming behavior. In a second study eight different pairs were observed during the first day together and male copulatory behavior was studied. Two patterns of copulatory behavior could be discerned: pairs displaying a high number of ejaculations (19-38) and pairs displaying a low number of ejaculations (4-8). With regard to the interejaculatory interval (IEI), the male stumptail appeared to be unique. In contrast to what has been reported for other mammals, i.e., a steady increase in IEI with subsequent ejaculations, the stumptail showed increasing IEIs only during the first three to four, as well as between the last, ejaculations; in between, the IEI remained relatively constant. The maximum number of consecutive ejaculations observed was 38, displayed during a 10-hr time period (mean (± SEM)IEI, 12.9 ± 3.5 min)

    Virtual Special Issue on Catalysis at the U.S. Department of Energy’s National Laboratories

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    Catalysis research at the U.S. Department of Energy’s (DOE’s) National Laboratories covers a wide range of research topics in heterogeneous catalysis, homogeneous/molecular catalysis, biocatalysis, electrocatalysis, and surface science. Since much of the work at National Laboratories is funded by DOE, the research is largely focused on addressing DOE’s mission to ensure America’s security and prosperity by addressing its energy, environmental, and nuclear challenges through transformative science and technology solutions. The catalysis research carried out at the DOE National Laboratories ranges from very fundamental catalysis science, funded by DOE’s Office of Basic Energy Sciences (BES), to applied research and development (R&D) in areas such as biomass conversion to fuels and chemicals, fuel cells, and vehicle emission control with primary funding from DOE’s Office of Energy Efficiency and Renewable Energy. National Laboratories are home to many DOE Office of Science national scientific user facilities that provide researchers with the most advanced tools of modern science, including accelerators, colliders, supercomputers, light sources, and neutron sources, as well as facilities for studying the nanoworld and the terrestrial environment. National Laboratory research programs typically feature teams of researchers working closely together, often joining scientists from different disciplines to tackle scientific and technical problems using a variety of tools and techniques available at the DOE national scientific user facilities. Along with collaboration between National Laboratory scientists, interactions with university colleagues are common in National Laboratory catalysis R&D. In some cases, scientists have joint appointments at a university and a National Laboratory. This ACS Catalysis Virtual Special Issue {http://pubs.acs.org/page/accacs/vi/doe-national-labs} was motivated by Christopher Jones and Rhea Williams, who sent out the invitations to all of DOE’s National Laboratories where catalysis research is conducted. All manuscripts submitted went through the standard rigorous peer review required for publication in ACS Catalysis. A total of 29 papers are published in this virtual special issue, which features some of the recent catalysis research at 11 of DOE’s National Laboratories: Ames Laboratory (Ames), Argonne National Laboratory (ANL), Brookhaven National Laboratory (BNL), Lawrence Berkeley National Laboratory (LBNL), Lawrence Livermore National Laboratory (LLNL), National Energy Technology Laboratory (NETL), National Renewable Energy Laboratory (NREL), Oak Ridge National Laboratory (ORNL), Pacific Northwest National Laboratory (PNNL), Sandia National Laboratory (SNL), and SLAC National Accelerator Laboratory (SLAC). In this preface, we briefly discuss the history and impact of catalysis research at these particular DOE National Laboratories, where the majority of catalysis research continues to be conducted

    Accessible High-Throughput Virtual Screening Molecular Docking Software for Students and Educators

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    We survey low cost high-throughput virtual screening (HTVS) computer programs for instructors who wish to demonstrate molecular docking in their courses. Since HTVS programs are a useful adjunct to the time consuming and expensive wet bench experiments necessary to discover new drug therapies, the topic of molecular docking is core to the instruction of biochemistry and molecular biology. The availability of HTVS programs coupled with decreasing costs and advances in computer hardware have made computational approaches to drug discovery possible at institutional and non-profit budgets. This paper focuses on HTVS programs with graphical user interfaces (GUIs) that use either DOCK or AutoDock for the prediction of DockoMatic, PyRx, DockingServer, and MOLA since their utility has been proven by the research community, they are free or affordable, and the programs operate on a range of computer platforms

    Agronomic and Economic Performance Characteristics of Conventional and Low-External-Input Cropping Systems in the Central Corn Belt

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    We conducted a 9-ha field experiment near Boone, IA, to test the hypothesis that yield, weed suppression, and profit characteristics of low-external-input (LEI) cropping systems can match or exceed those of conventional systems. Over a 4-yr period, we compared a conventionally managed 2-yr rotation system {corn (Zea mays L.)/soybean [Glycine max (L.) Merr.]} with two LEI systems: a 3-yr corn/soybean/small grain + red clover (Trifolium pratense L.) rotation, and a 4-yr corn/soybean/small grain + alfalfa (Medicago sativa L.)/alfalfa rotation. Synthetic N fertilizer use was 59 and 74% lower in the 3- and 4-yr systems, respectively, than in the 2-yr system; similarly, herbicide use was reduced 76 and 82% in the 3- and 4-yr systems. Corn and soybean yields were as high or higher in the LEI systems as in the conventional system, and weed biomass in corn and soybean was low (≤4.2 g m−2) in all systems. Experimentally supplemented giant foxtail (Setaria faberi Herrm.) seed densities in the surface 20 cm of soil declined in all systems; supplemented velvetleaf (Abutilon theophrasti Medik.) seed densities declined in the 2- and 4-yr systems and remained unchanged in the 3-yr system. Without subsidy payments, net returns were highest for the 4-yr system (540ha−1yr−1),lowestforthe3−yrsystem(540 ha−1 yr−1), lowest for the 3-yr system (475 ha−1 yr−1), and intermediate for the 2-yr system ($504 ha−1 yr−1). With subsidies, differences among systems in net returns were smaller, as subsidies favored the 2-yr system, but rank order of the systems was maintained
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