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At least 739 records · Page 41

Screening and Discovery of Metal Compound Active Sites for Strong and Selective Adsorption of N 2 in Air

Photocatalytic nitrogen fixation has the potential to provide a greener route for producing nitrogen-based fertilizers under ambient conditions. Computational screening is a promising route to discover new materials for the nitrogen fixation process, but requires identifying “descriptors” that can be efficiently computed. In this work, we argue that selectivity toward the adsorption of molecular nitrogen and oxygen can act as a key descriptor. A catalyst that can selectively adsorb nitrogen and resist poisoning of oxygen and other molecules present in air has the potential to facilitate the nitrogen fixation process under ambient conditions. Here we provide a framework for active site screening based on multifidelity density functional theory (DFT) calculations for a range of metal oxides, oxyborides, and oxyphosphides. The screening methodology consists of initial low-fidelity fixed geometry calculations and a second screening in which more expensive geometry optimizations were performed. The approach identifies promising active sites on several TiO 2 polymorph surfaces and a VBO 4 surface, and the full nitrogen reduction pathway is studied with the BEEF-vdW and HSE06 functionals on two active sites. The findings suggest that metastable TiO 2 polymorphs may play a role in photocatalytic nitrogen fixation, and that VBO 4 may be an interesting material for further studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis and effects of the advanced solid rocket motor on the Space Shuttle elements

This interim final report summarizes the activities and major accomplishments under NASA/MSFC Contract NAS8-39235 for the initial two year contractual effort beginning October 1, 1991, and ending September 30, 1993. It is not intended as an exhaustive treatment or review of any particular technical issue which was addressed during this two-year period, but does provide an overview of the many induced environment studies and test support activities undertaken by REMTECH and its subcontractors during this two-year period. The initial scope of work has been pursued vigorously through this two-year period by separating the effort into five functional areas. The five functional areas are ascent plume radiation, ascent plume convection, ascent aerodynamic heating, launch stand environments, and reentry heating. A work breakdown structure (WBS) for each functional area was devised to permit nearly autonomous activities within each functional responsibility while maintaining commonality in reporting procedures and cost accounting. The contract was modified 11 times to provide incremental funding and to expand the scope of work. Additional work breakdown structure was incorporated to meet the expanded scope. A contract chronology is provided in Section 2. The initial scope of work, expanded scope, and corresponding WBS designation are described in Section 3. A summary review of major accomplishments is also provided in Section 4 to show the breadth of activities and extent of reporting. Reports, meetings, test activities, and other accomplishments within each functional area are also summarized by WBS heading in the appendices.

Source record↗

Space station Platform Management System (PMS) replanning using resource envelopes

One of the responsibilities of the Space Station Platform Management System (PMS) is to maintain constraint-free, short-term plans for platform and free-flyer activities. Both the replanning function and the associated constraint-checking function are viewed as potentially requiring expert system assistance. The PMS Resource Envelope Scheduling System (PRESS) expert system, which is currently under development, is described. The PRESS capabilities will include the following: plan, replan, and perform constraint checking using resource envelopes resembling those required for telescience; initialize itself using the results fo a previous run; infer the replanning needs associated with a change in resource availability; allow the user to determine the level of interaction (including an advisory capability) with the system during execution; and generate both a graphic timeline and a report as output. The PRESS is being developed on an IBM PC/AT using TeKnowledge, Inc.'s M.1 expert system shell. The PRESS activity definitions and constraints are based on those defined for the Cosmic Background Explorer (COBE) mission scheduled for launch in early 1989.

Bush, Joy Lee↗

Uncrewed Lunar Surface Operations and Support Activities

A sustained human presence on the surface of the Moon and future missions to Mars require increased independence from surface crews and Earth-based mission control to operate efficiently, safely, and reliably. The number of astronauts and the availability of the surface crew to perform tasks will be limited, and extravehicular activities are burdensome and time-consuming. A balance of crewed and uncrewed surface operations will maximize crew exploration time by reducing their time dedicated to routine maintenance and support tasks. Certain sustaining activities that consume valuable crew time and preparation tasks such as staging and prepositioning equipment and materials can be performed without the crew, either before their arrival on the lunar surface or after their departure, thus improving task efficiency and mission effectiveness. This paper will define uncrewed operations and support activities and examine the functions, features, and capabilities that support sustained human and robotic surface operations. It will also discuss the extreme environmental challenges and the complexities associated with the development and operation of autonomous systems, as well as some suggested methods, techniques, and tools to overcome these challenges.

Lunar↗

Pr-specific phytochrome phosphorylation in vitro by a protein kinase present in anti-phytochrome maize immunoprecipitates

Protein kinase activity has repeatedly been found to co-purify with the plant photoreceptor phytochrome, suggesting that light signals received by phytochrome may be transduced or modulated through protein phosphorylation. In this study immunoprecipitation techniques were used to characterize protein kinase activity associated with phytochrome from maize (Zea mays L.). A protein kinase that specifically phosphorylated phytochrome was present in washed anti-phytochrome immunoprecipitates of etiolated coleoptile proteins. No other substrate tested was phosphorylated by this kinase. Adding salts or detergents to disrupt low-affinity protein interactions reduced background phosphorylation in immunoprecipitates without affecting phytochrome phosphorylation, indicating that the protein kinase catalytic activity is either intrinsic to the phytochrome molecule or associated with it by high-affinity interactions. Red irradiation (of coleoptiles or extracts) sufficient to approach photoconversion saturation reduced phosphorylation of immunoprecipitated phytochrome. Subsequent far-red irradiation reversed the red-light effect. Phytochrome phosphorylation was stimulated about 10-fold by a co-immunoprecipitated factor. The stimulatory factor was highest in immunoprecipitates when Mg2+ was present in immunoprecipitation reactions but remained in the supernatant in the absence of Mg2+. These observations provide strong support for the hypothesis that phytochrome-associated protein kinase modulates light responses in vivo. Since only phytochrome was found to be phosphorylated, the co-immunoprecipitated protein kinase may function to regulate receptor activity.

NASA Discipline Plant Biology↗

Prediction of Geomagnetic Activity and Key Parameters in High-latitude Ionosphere

Prediction of geomagnetic activity and related events in the Earth's magnetosphere and ionosphere are important tasks of US Space Weather Program. Prediction reliability is dependent on the prediction method, and elements included in the prediction scheme. Two of the main elements of such prediction scheme are: an appropriate geomagnetic activity index, and an appropriate coupling function (the combination of solar wind parameters providing the best correlation between upstream solar wind data and geomagnetic activity). We have developed a new index of geomagnetic activity, the Polar Magnetic (PM) index and an improved version of solar wind coupling function. PM index is similar to the existing polar cap PC index but it shows much better correlation with upstream solar wind/IMF data and other events in the magnetosphere and ionosphere. We investigate the correlation of PM index with upstream solar wind/IMF data for 10 years (1995-2004) that include both low and high solar activity. We also have introduced a new prediction function for the predicting of cross-polar-cap voltage and Joule heating based on using both PM index and upstream solar wind/IMF data. As we show such prediction function significantly increase the reliability of prediction of these important parameters. The correlation coefficients between the actual and predicted values of these parameters are approx. 0.9 and higher.

Khazanov, George V.↗

The release of alginate lyase from growing Pseudomonas syringae pathovar phaseolicola

Pseudomonas syringae pathovar phaseolicola, which produces alginate during stationary growth phase, displayed elevated extracellular alginate lyase activity during both mid-exponential and late-stationary growth phases of batch growth. Intracellular activity remained below 22% of the total activity during exponential growth, suggesting that alginate lyase has an extracellular function for this organism. Extracellular enzyme activity in continuous cultures, grown in either nutrient broth or glucose-simple salts medium, peaked at 60% of the washout rate, although nutrient broth-grown cultures displayed more than twice the activity per gram of cell mass. These results imply that growth rate, nutritional composition, or both initiate a release of alginate lyase from viable P. syringae pv. phaseolicola, which could modify its entrapping biofilm.

Polysaccharide-Lyases/secretion↗

Leveraging Existing Mission Tools in a Re-Usable, Component-Based Software Environment

Emerging methods in component-based software development offer significant advantages but may seem incompatible with existing mission operations applications. In this paper we relate our positive experiences integrating existing mission applications into component-based tools we are delivering to three missions. In most operations environments, a number of software applications have been integrated together to form the mission operations software. In contrast, with component-based software development chunks of related functionality and data structures, referred to as components, can be individually delivered, integrated and re-used. With the advent of powerful tools for managing component-based development, complex software systems can potentially see significant benefits in ease of integration, testability and reusability from these techniques. These benefits motivate us to ask how component-based development techniques can be relevant in a mission operations environment, where there is significant investment in software tools that are not component-based and may not be written in languages for which component-based tools even exist. Trusted and complex software tools for sequencing, validation, navigation, and other vital functions cannot simply be re-written or abandoned in order to gain the advantages offered by emerging component-based software techniques. Thus some middle ground must be found. We have faced exactly this issue, and have found several solutions. Ensemble is an open platform for development, integration, and deployment of mission operations software that we are developing. Ensemble itself is an extension of an open source, component-based software development platform called Eclipse. Due to the advantages of component-based development, we have been able to vary rapidly develop mission operations tools for three surface missions by mixing and matching from a common set of mission operation components. We have also had to determine how to integrate existing mission applications for sequence development, sequence validation, and high level activity planning, and other functions into a component-based environment. For each of these, we used a somewhat different technique based upon the structure and usage of the existing application.

Greene, Kevin↗

Catalytic consequences of hydrogen addition events and solvent-adsorbate interactions during guaiacol-H 2 reactions at the H 2 O-Ru(0 0 0 1) interface

Catalytic reactions of biomass-derived phenolics and H 2 occur on transition metal surfaces via competitive C–O cleavage and ring saturation pathways, with both requiring multiple hydrogen addition events before forming their respective rate limiting transition states. These events are markedly affected by solvent chemical identity, with polar protic solvents ionizing hydrogen adatoms (H*) to interfacial protons (H + ) and opening up new catalytic routes. Here, we establish the reaction coordinate space for guaiacol-H 2 reactions on Ru(0 0 0 1) using density functional theory and describe the atomic-scale effect of a polar protic solvent, H 2 O. Coupled H + and H* attack leads to quasi-equilibrated enol and keto intermediates as the precursors for C–O cleavage and ring saturation, respectively. For C–O cleavage, H 2 O solvent enables a lower energy pathway via concomitant transfer of the hydroxyl H + to the methoxy oxygen during C–OCH 3 cleavage, forming a charge separated [Ru(s)–(C 6 H 5 O – )…(H + )…OCH 3 ] transition state and reducing the barrier by up to 0.8 eV as compared to unassisted C–OCH 3 cleavage. For ring saturation, H* attack onto an unsaturated meta carbon is rate limiting with no direct solvent participation, suggesting that protic polar solvents selectively promote the C–O cleavage pathway. Taken together, we show that activating guaiacol for either C–O bond cleavage or ring saturation product formation depends on the reactive hydrogen identity (H* or H + ), enol/keto isomerization equilibrium, and accessibility of the proton assisted Car–OCH 3 cleavage transition state. Here, all such factors are tunable via changes to the solvent or metal identity.

09 BIOMASS FUELS↗

Conservation and Expansion of Transcriptional Factor Repertoire in the Fusarium oxysporum Species Complex

The Fusarium oxysporum species complex (FOSC) includes both plant and human pathogens that cause devastating plant vascular wilt diseases and threaten public health. Each F. oxysporum genome comprises core chromosomes (CCs) for housekeeping functions and accessory chromosomes (ACs) that contribute to host-specific adaptation. This study inspects global transcription factor profiles (TFomes) and their potential roles in coordinating CC and AC functions to accomplish host-specific interactions. Remarkably, we found a clear positive correlation between the sizes of TFomes and the proteomes of an organism. With the acquisition of ACs, the FOSC TFomes were larger than the other fungal genomes included in this study. Among a total of 48 classified TF families, 14 families involved in transcription/translation regulations and cell cycle controls were highly conserved. Among the 30 FOSC expanded families, Zn2-C6 and Znf_C2H2 were most significantly expanded to 671 and 167 genes per family including well-characterized homologs of Ftf1 (Zn2-C6) and PacC (Znf_C2H2) that are involved in host-specific interactions. Manual curation of characterized TFs increased the TFome repertoires by 3% including a disordered protein Ren1. RNA-Seq revealed a steady pattern of expression for conserved TF families and specific activation for AC TFs. Functional characterization of these TFs could enhance our understanding of transcriptional regulation involved in FOSC cross-kingdom interactions, disentangle species-specific adaptation, and identify targets to combat diverse diseases caused by this group of fungal pathogens.

59 BASIC BIOLOGICAL SCIENCES↗

A common network of functional areas for attention and eye movements

Functional magnetic resonance imaging (fMRI) and surface-based representations of brain activity were used to compare the functional anatomy of two tasks, one involving covert shifts of attention to peripheral visual stimuli, the other involving both attentional and saccadic shifts to the same stimuli. Overlapping regional networks in parietal, frontal, and temporal lobes were active in both tasks. This anatomical overlap is consistent with the hypothesis that attentional and oculomotor processes are tightly integrated at the neural level.

Non-NASA Center↗

Identification of Cardiometabolic Vulnerabilities Caused by Effects of Synergistic Stressors that are Commonly Encountered During Space Missions

Microgravity is a physiologically challenging state even when at rest. Astronauts experience additional physical and mental stresses, such as prolonged exertion, sleep loss and circadian misalignment, that could impact cardiovascular function. The main goals of this four year NASA project are to characterize the independent and synergistic effects on cardiovascular and immune function of: (1) circadian misalignment; (2) sleep loss; and (3) varied physical and mental stressors, mimicking some of the synergistic stressors experienced by astronauts. Sixteen healthy volunteers, aged 35-55 years, will be studied with standardized behavioral stressors occurring across all circadian phases, both with and without accruing sleep loss, achieved via two 11-day "forced desynchrony" protocols performed in each subject (randomized, within-subject design), where wake periods are advanced 4-h each "day" (i.e. recurring 20-h "days"). One protocol permits 8.33 h sleep opportunity per 20-h "day" (=10 h sleep per 24-h), and the other permits 5 h sleep per 20-h "day" (=6 h sleep per 24-h; matching the reported sleep duration of astronauts). In both protocols, subjects will perform a standardized stress battery including a cognitively challenging task; bicycle exercise, and passive 60deg head up tilt. Outcome variables include blood pressure, heart rate, arrhythmia frequency, cardiac vagal tone (from heart rate variability), sympathetic activity (catecholamines), and endothelial function. Additional measures of cardiac function (echocardiography), responses to a passive 80deg head up tilt, maximal oxygen uptake, and immune function will be assessed at the beginning and at the end of each protocol (i.e., without and with sleep loss, and before and after circadian misalignment). We hope to identify the relative impact on cardiovascular risk markers of varied behavioural stressors while subjects experience circadian misalignment and sleep loss, mimicking some of the synergistic stressors experienced by astronauts. Supported by NASANNX1 OAR 1 OG.

Ruger, M.↗

Crosslinked Polyethyleneimine Gel Polymer Interface to Improve Cycling Stability of RFBs

Redox flow batteries are considered a promising technology for grid energy storage. However, capacity decay caused by crossover of active materials is a universal challenge for many flow battery systems, which are based on various chemistries. In this paper, using the vanadium redox flow battery as an example, we demonstrate a new gel polymer interface (GPI) consisting of crosslinked polyethyleneimine with a large amount of amino and carboxylic acid groups introduced between the positive electrode and the membrane. The GPI functions as a key component to prevent vanadium ions from crossing the membrane, thus supporting stable long-term cycling. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted to investigate the effect of GPI on the electrochemical properties of graphitic carbon electrodes (GCFs) and redox reaction of catholyte. X-ray photoelectron spectroscopy (XPS) and 1 H nuclear magnetic resonance (NMR) spectra demonstrated that the crosslinked GPI is chemically stable for 100 cycles without dissolution of polymers and swelling in the strong acidic electrolytes. Results from inductively coupled plasma mass spectrometry (ICP-MS), Fourier-transform infrared (FTIR) spectroscopy, and energy-dispersive X-ray (EDX) spectroscopy proved that the GPI is effective in maintaining the concentration of vanadium species in their respective half-cells, resulting in improved cycling stability because of it prevents active species from crossing the membrane and stabilizes the oxidation states of active species.

Lim, Hyung-Seok↗

Badhwar-O'Neill 2011 Galactic Cosmic Ray Model Update and Future Improvements

The Badhwar-O'Neill Galactic Cosmic Ray (GCR) Model based on actual GCR measurements is used by deep space mission planners for the certification of microelectronic systems and the analysis of radiation health risks to astronauts in space missions. The BO GCR Model provides GCR flux in deep space (outside the earth's magnetosphere) for any given time from 1645 to present. The energy spectrum from 50 MeV/n - 20 GeV/n is provided for ions from hydrogen to uranium. This work describes the most recent version of the BO GCR model (BO'11). BO'11 determined the GCR flux at a given time applying an emperical time delay function to past sunspot activity. We describe the GCR measurement data used in the BO'11 update - modern data from BESS, PAMELA, CAPRICE, and ACE emphasized more than the older balloon data used for the previous BO model (BO'10). We look at the GCR flux for the last 24 solar minima and show how much greater the flux was for the cycle 24 minimum in 2010. The BO'11 Model uses the traditional, steady-state Fokker-Planck differential equation to account for particle transport in the heliosphere due to diffusion, convection, and adiabatic deceleration. It assumes a radially symmetrical diffusion coefficient derived from magnetic disturbances caused by sunspots carried outward by a constant solar wind. A more complex differential equation is now being tested to account for particle transport in the heliosphere in the next generation BO model. This new model is time-dependent (no longer a steady state model). In the new model, the dynamics and anti-symmetrical features of the actual heliosphere are accounted for so emperical time delay functions will no longer be required. The new model will be capable of simulating the more subtle features of modulation - such as the Sun's polarity and modulation dependence on gradient and curvature drift. This improvement is expected to significantly improve the fidelity of the BO GCR model. Preliminary results of its performance will be presented.

O'Neill, Pat M.↗

Badhwar-O'Neill 2011 Galactic Cosmic Ray Model Update and Future Improvements

The Badhwar-O'Neill Galactic Cosmic Ray (GCR) Model based on actual GR measurements is used by deep space mission planners for the certification of micro-electronic systems and the analysis of radiation health risks to astronauts in space missions. The BO GCR Model provides GCR flux in deep space (outside the earth's magnetosphere) for any given time from 1645 to present. The energy spectrum from 50 MeV/n-20 GeV/n is provided for ions from hydrogen to uranium. This work describes the most recent version of the BO GCR model (BO'11). BO'11 determines the GCR flux at a given time applying an empirical time delay function to past sunspot activity. We describe the GCR measurement data used in the BO'11 update - modern data from BESS, PAMELA, CAPRICE, and ACE emphasized for than the older balloon data used for the previous BO model (BO'10). We look at the GCR flux for the last 24 solar minima and show how much greater the flux was for the cycle 24 minimum in 2010. The BO'11 Model uses the traditional, steady-state Fokker-Planck differential equation to account for particle transport in the heliosphere due to diffusion, convection, and adiabatic deceleration. It assumes a radially symmetrical diffusion coefficient derived from magnetic disturbances caused by sunspots carried onward by a constant solar wind. A more complex differential equation is now being tested to account for particle transport in the heliosphere in the next generation BO model. This new model is time-dependent (no longer a steady state model). In the new model, the dynamics and anti-symmetrical features of the actual heliosphere are accounted for so empirical time delay functions will no longer be required. The new model will be capable of simulating the more subtle features of modulation - such as the Sun's polarity and modulation dependence on the gradient and curvature drift. This improvement is expected to significantly improve the fidelity of the BO GCR model. Preliminary results of its performance will be presented.

O'Neill, Pat M.↗

CO 2 Methanation on Cu-Cluster Decorated Zirconia Supports with Different Morphology: A Combined Experimental In Situ GIXANES/GISAXS, Ex Situ XPS and Theoretical DFT Study

We report that subnanometer copper tetramer-zirconia catalysts turn out to be highly efficient for CO 2 hydrogenation and its conversion to methane. The cluster size and substrate morphology are controlled to optimize the catalytic performance. The two types of zirconia supports investigated are prepared by atomic layer deposition (~ 3 nm thick film) and supersonic cluster beam deposition (nanostructured film, ~ 100 nm thick). The substrate plays a crucial role in determining the activity of the catalyst as well as its cyclability over repeated thermal ramps. A temperature-programmed reaction combined with in situ X-ray characterization reveals the correlation between the evolution in the oxidation state and catalytic activity. Ex situ photoelectron spectroscopy indicates Cu clusters with stronger interactions with the nanostructured film, which can be the cause for the higher activity of this catalyst. Density functional theory calculations based on the Cu 4 O 2 cluster supported on a ZrOx subunit reveal low activation barriers and provide mechanism for CO 2 hydrogenation and its conversion to methane. Altogether, the results show a new way to tune the catalytic activity of CO 2 hydrogenation catalysts through controlling the morphology of the support at the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Space-based multifunctional end effector systems functional requirements and proposed designs

The end effector is an essential element of teleoperator and telerobot systems to be employed in space in the next decade. The report defines functional requirements for end effector systems to perform operations that are currently only feasible through Extra-Vehicular Activity (EVA). Specific tasks and functions that the end effectors must be capable of performing are delineated. Required capabilities for forces and torques, clearances, compliance, and sensing are described, using current EVA requirements as guidelines where feasible. The implications of these functional requirements on the elements of potential end effector systems are discussed. The systems issues that must be considered in the design of space-based manipulator systems are identified; including impacts on subsystems tightly coupled to the end effector, i.e., control station, information processing, manipulator arm, tool and equipment stowage. Possible end effector designs are divided into three categories: single degree-of-freedom end effectors, multiple degree of freedom end effectors, and anthropomorphic hands. Specific design alternatives are suggested and analyzed within the individual categories. Two evaluations are performed: the first considers how well the individual end effectors could substitute for EVA; the second compares how manipulator systems composed of the top performers from the first evaluation would improve the space shuttle Remote Manipulator System (RMS) capabilities. The analysis concludes that the anthropomorphic hand is best-suited for EVA tasks. A left- and right-handed anthropomorphic manipulator arm configuration is suggested as appropriate to be affixed to the RMS, but could also be used as part of the Smart Front End for the Orbital Maneuvering Vehicle (OMV). The technical feasibility of the anthropomorphic hand and its control are demonstrated. An evolutionary development approach is proposed and approximate scheduling provided for implementing the suggested manipulator systems in time for space stations operations in the early 1990s.

Mishkin, A. H.↗