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At least 703 records · Page 39

Igneous history of the aubrite parent asteroid - Evidence from the Norton County enstatite achondrite

Numerous specimens of the Norton County enstatite achondrite (aubrite) were studied by optical microscopy, electron microprobe, and neutron-activation analysis. Norton County is found to be a fragmental impact breccia, consisting of a clastic matrix made mostly of crushed enstatite, into which are embedded a variety of mineral and lithic clasts of both igneous and impact melt origin. The Norton County precursor materials were igneous rocks, mostly plutonic orthopyroxenites, not grains formed by condensation from the solar nebula. The Mg-silicate-rich aubrite parent body experienced extensive melting and igneous differentiation, causing formation of diverse lithologies including dunites, plutonic orthopyroxenites, plutonic pyroxenites, and plagioclase-silica rocks. The presence of impact melt breccias (the microporphyritic clasts and the diopside-plagioclase-silica clast) of still different compositions further attests to the lithologic diversity of the aubrite parent body.

Okada, Akihiko↗

NASA's Lunar Robotic Architecture Study

This report documents the findings and analysis of a 60-day agency-wide Lunar Robotic Architecture Study (LRAS) conducted by the National Aeronautics and Space Administration (NASA). Work on this study began in January 2006. Its purpose was to: Define a lunar robotics architecture by addressing the following issues: 1) Do we need robotic missions at all? If so, why and under what conditions? 2) How would they be accomplished and at what cost? Are they within budget? 3) What are the minimum requirements? What is the minimum mission set? 4) Integrate these elements together to show a viable robotic architecture. 5) Establish a strategic framework for a lunar robotics program. The LRAS Final Report presents analysis and recommendations concerning potential approaches related to NASA s implementation of the President's Vision for Space Exploration. Project and contract requirements will likely be derived in part from the LRAS analysis and recommendations contained herein, but these do not represent a set of project or contract requirements and are not binding on the U.S. Government unless and until they are formally and expressly adopted as such. Details of any recommendations offered by the LRAS Final Report will be translated into implementation requirements. Moreover, the report represents the assessments and projects of the report s authors at the time it was prepared; it is anticipated that the concepts in this report will be analyzed further and refined. By the time some of the activities addressed in this report are implemented, certain assumptions on which the report s conclusions are based will likely evolve as a result of this analysis. Accordingly, NASA, and any entity under contract with NASA, should not use the information in this report for final project direction. Since the conclusion of this study, there have been various changes to the Agency's current portfolio of lunar robotic precursor activities. First, the Robotic Lunar Exploration Program (RLEP) has been renamed the Lunar Precursor and Robotic Program (LPRP). On May 17, 2006, the Lunar Reconnaissance Orbiter (LRO) was confirmed to enter its implementation phase. Last, a new low-cost secondary payload known as the Lunar Crater Observation and Sensing Satellite (LCROSS) was co-manifested to launch with LRO in 2008. These changes are consistent with the conclusions and recommendations of this study, but came too late to be specifically reflected in this report.

Mulville, Daniel R.↗

30 WS North Base Wind Study

The 30 Weather Squadron (30 WS) is concerned about strong winds observed at their northern towers without advance warning. They state that terrain influences along the extreme northern fringes of Vandenberg Air Force Base (VAFB) make it difficult for forecasters to issue timely and accurate high wind warnings for northeasterly wind events. These events tend to occur during the winter or early spring when they are under the influence of the Great Basin high pressure weather regime. The Launch Weather Officers (LWOs) have seen these rapid wind increases in the current northern Towers 60, 70 and 71 in excess of their 35 kt operational warning threshold. For this task, the 30 WS requested the Applied Meteorology Unit (AMU) analyze data from days when these towers reported winds in excess of 35 kt and determine if there were any precursors in the observations that would allow the LWOs to better forecast and warn their operational customers for these wind events. The 30 WS provided wind tower data for the cool season (October - March) from the period January 2004-March 20 IO. The AMU decoded and evaluated the wind tower data for 66 days identified by the 30 WS as having high-wind events. Out of the 66 event days, only 30 had wind speed observations of > or =35 kt from at least one of the three northern towers. The AMU analyzed surface and upper air charts to determine the synoptic conditions for each event day along with tower peak wind speed and direction time series and wind rose charts for all 30 event days. The analysis revealed a trend on all event days in which the tower winds shifted to the northeast for a period of time before the first recorded > or =35 kt wind speed. The time periods for the 30 event days ranged from 20 minutes to several hours, with a median value of 110 minutes. This trend, if monitored, could give the 30 WS forecasters a precursor to assist in issuing an operational warning before a high wind event occurs. The AMU recommends developing a high-wind alert capability for VAFB using a local mesoscale model to forecast these wind events. The model should incorporate all of the VAFB local data sets and have a forecast capability of between 2 to 24 hours. Such a model would allow the meteorologists at VAFB to alert the operational customers of high wind events in a timely manner so protective action could be taken.

Wheeler, Mark↗

Quantitative Analysis of the Reduction Kinetics Responsible for the One-Pot Synthesis of Pd–Pt Bimetallic Nanocrystals with Different Structures

We report a quantitative understanding of the reduction kinetics responsible for the formation of Pd–Pt bimetallic nanocrystals with two distinctive structures. The syntheses involve the use of KBr to manipulate the reaction kinetics by influencing the redox potentials of metal precursor ions via ligand exchange. In the absence of KBr, the ratio between the initial reduction rates of PdCl 4 2– and PtCl 4 2– was about 10.0, leading to the formation of Pd@Pt octahedra with a core–shell structure. In the presence of 63 mM KBr, the products became Pd–Pt alloy nanocrystals. In this case, the ratio between the initial reduction rates of the two precursors dropped to 2.4 because of ligand exchange and, thus, the formation of PdBr 4 2– and PtBr 4 2– . The alloy nanocrystals took a cubic shape owing to the selective capping effect of Br – ions toward the {100} facets. Relative to the alloy nanocubes, the Pd@Pt core–shell octahedra showed substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). Specifically, the specific (1.51 mA cm –2 ) and mass (1.05 A mg –1 Pt) activities of the core–shell octahedra were enhanced by about four- and three-fold relative to the alloy nanocubes (0.39 mA cm –2 and 0.34 A mg –1 Pt, respectively). Even after 20000 cycles of accelerated durability test, the core–shell octahedra still exhibited a mass activity of 0.68 A mg –1 Pt, twice that of a pristine commercial Pt/C catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Systematic Analysis of Metabolic Bottlenecks in the Methylerythritol 4-Phosphate (MEP) Pathway of Zymomonas mobilis

Engineered microorganisms have the potential to convert renewable substrates into biofuels and valuable bioproducts, which offers an environmentally sustainable alternative to fossil-fuel-derived products. Isoprenoids are a diverse class of biologically derived compounds that have commercial applications as various commodity chemicals, including biofuels and biofuel precursor molecules.

isoprene↗

Transient convective delayed neutron precursor of {sup 235}U for the molten salt reactor experiment

This work investigates the delayed neutron precursors from the fission of {sup 235}U in molten salt reactors. The six delayed neutron groups predict the spatial distribution of the advective transport for radioactive mass transfer in the molten-salt reactor experiment (MSRE). The Mole code, using the framework of the Multiphysics Object-Oriented Simulation Environment (MOOSE), was used to compute the delayed neutron concentration of the whole system. This approach can be used for analysis of reactivity in circulating conditions. The effect of delayed neutron concentrations on the static or dynamic behavior of the system in MSRE was analyzed. Using this approach, the pattern and validation of delayed neutron for a range of parameters of interest are reported and discussed herein. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Structural Constraints of Vaccine-Induced Tier-2 Autologous HIV Neutralizing Antibodies Targeting the Receptor-Binding Site

Antibodies that neutralize autologous transmitted/founder (TF) HIV occur in most HIV-infected individuals and can evolve to neutralization breadth. Autologous neutralizing antibodies (nAbs) against neutralization-resistant (Tier-2) viruses are rarely induced by vaccination. Whereas broadly neutralizing antibody (bnAb)-HIV-Envelope structures have been defined, the structures of autologous nAbs have not. Here, we show that immunization with TF mutant Envs gp140 oligomers induced high-titer, V5-dependent plasma neutralization for a Tier-2 autologous TF evolved mutant virus. Structural analysis of autologous nAb DH427 revealed binding to V5, demonstrating the source of narrow nAb specificity and explaining the failure to acquire breadth. Thus, oligomeric TF Envs can elicit autologous nAbs to Tier-2 HIVs, but induction of bnAbs will require targeting of precursors of B cell lineages that can mature to heterologous neutralization.

59 BASIC BIOLOGICAL SCIENCES↗

A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization

Carbene polymerization provides polyolefins that cannot be readily prepared from olefin monomers; however, controlled and living carbene polymerization has been a long-standing challenge. Here we report a new class of initiators, (π-allyl)palladium carboxylate dimers, which polymerize ethyl diazoacetate, a carbene precursor in a controlled and quasi-living manner, with nearly quantitative yields, degrees of polymerization >100, molecular weight dispersities 1.2–1.4, and well-defined, diversifiable chain ends. This method also provides block copolycarbenes that undergo microphase segregation. Experimental and theoretical mechanistic analysis supports a new dinuclear mechanism for this process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructure and Raman Scattering of Cu{sub 2}ZnSnSe{sub 4} Thin Films Deposited onto Flexible Metal Substrates

Cu{sub 2}ZnSnSe{sub 4} thin films are produced by selenizing electrochemically layer-by-layer deposited and preliminarily annealed Cu–Zn–Sn precursors. For flexible metal substrates, Mo and Ta foils are used. The morphology, elemental and phase compositions, and crystal structure of Cu{sub 2}ZnSnSe{sub 4} films are studied by scanning electron microscopy, X-ray spectral microanalysis, X-ray phase analysis, and Raman spectroscopy.

36 MATERIALS SCIENCE↗

Development of an arcjet nuclear electric propulsion system for a 1993 flight demonstration

The design and performance of an arcjet NEP spacecraft, suitable for use in the Space Nuclear Power System (SNPS) Reference Mission, are outlined. Several arcjet technology levels were considered in this study, and the vehicle design was based on an 30 kW ammonia arcjet system operating at an Isp of 1000 s and an efficiency of 45 percent. The arcjet/gimbal system, PPU and propellant feed-system are described. A 100 kWe SNPS was assumed and the spacecraft mass was baselined at 5500 kg excluding the propellant feed system. A radiation/arcjet efflux diagnostics package was included in the performance analysis. This spacecraft, launched from Kennedy, can perform a 50 degree inclination change and reach a final orbit of GEO with a 180 day trip time providing a six month active load for the SNPS. Advanced ammonia and hydrogen systems were examined for precursor SDI platform applications.

Deininger, W. D.↗

NanoSIMS Reveals New Structural and Elemental Signatures of Early Life

The young technology of NanoSIMS is unlocking new information from organic matter in ancient sediments. We have used this technique to characterize sub-micron scale element composition of Proterozoic organics that are clearly biogenic as a guide for interpreting problematic structures in terrestrial or extraterrestrial samples. We used the NanoSIMS 50 of the National Museum of Natural History in Paris to map carbon, nitrogen (as CN), and sulfur in organic structures from the approximately 0.8 Ga Bitter Springs Formation. We analyzed spheroidal and filamentous microfossils as well as organic laminae that appeared amorphous by optical and scanning electron microscopy. In clear-cut microfossils, a coincidence between optical images and NanoSIMS element maps suggests a biological origin for the mapped carbon, sulfur, and nitrogen; this conclusion is supported by high resolution NanoSIMS maps showing identical spatial distributions of C, CN and S. High resolution images also demonstrate distinctive nano structure of the filaments and spheroids. In the amorphous laminae, NanoSIMS reveals morphologies reminiscent of compressed microfossils. Distinct CN/C ratios of the spheroids, filaments, and laminae may reflect their biological precursors (cell walls, cyanobacterial sheaths, and microbial communities/biofilms, respectively). Similar amorphous laminae comprise a preponderance of the organic matter in many Precambrian deposits. Thus it is possible that NanoSIMS will provide fresh insight into a large body of previously uninterpretable material. Additionally, NanoSIMS analysis may establish new biosignatures that will be helpful for assessing the origin and biogenicity of controversial Archean structures and any organic materials that may occur in Martian or other extraterrestrial samples.

Oehler, Dorothy Z.↗

Feasibility Study of Interstellar Missions Using Laser Sail Probes Ranging in Size from the Nano to the Macro

This paper presents the analysis examining the feasibility of interstellar travel using laser sail probes ranging in size from the nano to the macro. The relativistic differential equations of motion for a laser sail are set up and solved using the Pasic Method. The limitations of the analysis are presented and discussed. The requirements for the laser system are examined, including the thermal analysis of the laser sails. Black holes, plasma fields, atmospheric collisions and sun light are several methods discussed to enable the deceleration of the interstellar probe. A number of novel mission scenarios are presented including the embryonic transport of plant life as a precursor to the arrival of space colonies

Malroy, Eric T.↗

Global and Regional Temperature-change Potentials for Near-term Climate Forcers

We examine the climate effects of the emissions of near-term climate forcers (NTCFs) from 4 continental regions (East Asia, Europe, North America and South Asia) using results from the Task Force on Hemispheric Transport of Air Pollution Source-Receptor global chemical transport model simulations. We address 3 aerosol species (sulphate, particulate organic matter and black carbon) and 4 ozone precursors (methane, reactive nitrogen oxides (NOx), volatile organic compounds and carbon monoxide). We calculate the global climate metrics: global warming potentials (GWPs) and global temperature change potentials (GTPs). For the aerosols these metrics are simply time-dependent scalings of the equilibrium radiative forcings. The GTPs decrease more rapidly with time than the GWPs. The aerosol forcings and hence climate metrics have only a modest dependence on emission region. The metrics for ozone precursors include the effects on the methane lifetime. The impacts via methane are particularly important for the 20 yr GTPs. Emissions of NOx and VOCs from South Asia have GWPs and GTPs of higher magnitude than from the other Northern Hemisphere regions. The analysis is further extended by examining the temperature-change impacts in 4 latitude bands, and calculating absolute regional temperature-change potentials (ARTPs). The latitudinal pattern of the temperature response does not directly follow the pattern of the diagnosed radiative forcing. We find that temperatures in the Arctic latitudes appear to be particularly sensitive to BC emissions from South Asia. The northern mid-latitude temperature response to northern mid-latitude emissions is approximately twice as large as the global average response for aerosol emission, and about 20-30% larger than the global average for methane, VOC and CO emissions.

North America↗

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe 2 O 3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. Furthermore, we confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fechemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Block copolymer-mediated synthesis of TiO2/RuO2 nanocomposite for efficient oxygen evolution reaction

Abstract An amphiphilic block copolymer, poly (styrene-2-polyvinyl pyridine-ethylene oxide), was used as a structure-directing and stabilizing agent to synthesize TiO 2 /RuO 2 nanocomposite. The strong interaction of polymers with metal precursors led to formation of a porous heterointerface of TiO 2 /RuO 2 . It acted as a bridge for electron transport, which can accelerate the water splitting reaction. Scanning electron microscopy, energy-dispersive X -ray spectroscopy, transmission electron microscopy, and X -ray diffraction analysis of TiO 2 /RuO 2 samples revealed successful fabrication of TiO 2 /RuO 2 nanocomposites. The TiO 2 /RuO 2 nanocomposites were used to measure electrochemical water splitting in three-electrode systems in 0.1-M KOH. Electrochemical activities unveil that TiO 2 /RuO 2 -150 nanocomposites displayed superior oxygen evolution reaction activity, having a low overpotential of 260 mV with a Tafel slope of 80 mVdec −1 . Graphical abstract

36 MATERIALS SCIENCE↗

Dye sensitized solar cell applications of CdTiO{sub 3}–TiO{sub 2} composite thin films deposited from single molecular complex

A heterobimetallic complex [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO{sub 3}–TiO{sub 2} composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity, phase identification and chemical composition of microspherical architectured CdTiO{sub 3}–TiO{sub 2} composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application. - Graphical abstarct: Microspherical designed CdTiO{sub 3}–TiO{sub 2} composite oxides photoanode film has been fabricated from single source precursor [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF via aerosol assisted chemical vapor deposition technique for dye sensitized solar cell application. - Highlights: • Synthesis and characterization of a heterobimetallic Cd–Ti complex. • Fabrication of CdTiO{sub 3}–TiO{sub 2} thin film photoelectrode. • Application as dye sensitized photoanode for solar application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The 2.1 Å structure of protein F9 and its comparison to L1, two components of the conserved poxvirus entry-fusion complex

The poxvirus F9 protein is a component of the vaccinia virus entry fusion complex (EFC) which consists of 11 proteins. The EFC forms a unique apparatus among viral fusion proteins and complexes. We solved the atomic structure of the F9 ectodomain at 2.10Å. A structural comparison to the ectodomain of the EFC protein L1 indicated a similar fold and organization, in which a bundle of fve α-helices is packed against two pairs of β-strands. However, instead of the L1 myristoylation site and hydrophobic cavity, F9 possesses a protruding loop between α-helices α3 and α4 starting at Gly90. Gly90 is conserved in all poxviruses except Salmon gill poxvirus (SGPV) and Diachasmimorpha longicaudata entomopoxvirus. Phylogenetic sequence analysis of all Poxviridae F9 and L1 orthologs revealed the SGPV genome to contain the most distantly related F9 and L1 sequences compared to the vaccinia proteins studied here. The structural diferences between F9 and L1 suggest functional adaptations during evolution from a common precursor that underlie the present requirement for each protein.

59 BASIC BIOLOGICAL SCIENCES↗