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At least 577 records · Page 32

Roles of Carburization and Oxidation on Transition-Metal Catalyzed Surface Reactions

Many industrial chemical transformation processes are based on reactions catalyzed by transition metals. In some cases the nano-size particles used as catalysts are synthesized simultaneously or right before the initiation of the main catalytic reaction. Synthesis treatments involve complex processes such as reductions followed by calcinations in oxygenated environments coupled to the presence of gases used for the main reaction. Synthesis details are crucial because they have important consequences on the catalyst shape, size, and chemical composition, and may also affect the structure and composition of the catalyst support. All these effects may alter the main catalyzed reaction in unexpected ways. This work focuses on the synthesis of the overall catalytic system that includes catalyst and support taking place in parallel with the initial stages of the main catalyzed reaction. Two important processes are characterized: carburization and oxidation of the transition metal catalyst during synthesis or initial stages of the main reaction. The objective is to understand how the coking mechanism coupled to surface oxidation and changes in the substrate influence the dry reforming of methane taken as a model reaction. The approach uses first principles computational methods to investigate the catalyst synthesis and characterization and catalytic reaction mechanisms. These studies are complemented with experimental characterization done by the group of Dr. Renu Sharma at the National Institute of Standards and Technology (unfunded collaborator) using high resolution transmission electron microscopy. Specific goals are to identify the role of the synthesis process on the initial nanocatalyst structure and composition, and to determine how that structure and composition may evolve after being exposed to the reactants atmosphere. These studies facilitate a systematic analysis of conditions where the nanoparticle composition can be optimized regarding activity and stability. Moreover, the fundamental study of catalyst/support interactions yields valuable insights for other catalytic processes and is a first step toward controlled nanocatalyst synthesis.

36 MATERIALS SCIENCE↗

Genomic variation across Chinook salmon populations reveals effects of a duplication on migration alleles and supports fine scale structure

Abstract The distribution of ecotypic variation in natural populations is influenced by neutral and adaptive evolutionary forces that are challenging to disentangle. This study provides a high‐resolution portrait of genomic variation in Chinook salmon ( Oncorhynchus tshawytscha ) with emphasis on a region of major effect for ecotypic variation in migration timing. With a filtered data set of ~13 million single nucleotide polymorphisms (SNPs) from low‐coverage whole genome resequencing of 53 populations (3566 barcoded individuals), we contrasted patterns of genomic structure within and among major lineages and examined the extent of a selective sweep at a major effect region underlying migration timing (GREB1L/ROCK1). Neutral variation provided support for fine‐scale structure of populations, while allele frequency variation in GREB1L/ROCK1 was highly correlated with mean return timing for early and late migrating populations within each of the lineages ( r 2 = .58–.95; p < .001). However, the extent of selection within the genomic region controlling migration timing was much narrower in one lineage (interior stream‐type) compared to the other two major lineages, which corresponded to the breadth of phenotypic variation in migration timing observed among lineages. Evidence of a duplicated block within GREB1L/ROCK1 may be responsible for reduced recombination in this portion of the genome and contributes to phenotypic variation within and across lineages. Lastly, SNP positions across GREB1L/ROCK1 were assessed for their utility in discriminating migration timing among lineages, and we recommend multiple markers nearest the duplication to provide highest accuracy in conservation applications such as those that aim to protect early migrating Chinook salmon. These results highlight the need to investigate variation throughout the genome and the effects of structural variants on ecologically relevant phenotypic variation in natural species.

Horn, Rebekah L.↗

Influence of 7 days of hindlimb suspension and intermittent weight support on rat muscle mechanical properties

The effect of intermittent periods of weight support on a decrease in mass of the soleus (Sol) and medial gastrocnemius (MG) muscles atrophied by hindlimb suspension (HS) was investigated in rats subjected to continuous HS for seven days or an HS plus intermittent (10 min every 6 hrs of slow walking on a treadmill) weight support (HS-WS). After 7 d HS, the Sol weight relative to body weight was 21 and 9 percent lower in Hs and HS-WS, respectively, than in control rats. Maximum tetanic tension/muscle mass ratio was significantly lower in HS than in controls; the HS-WS rats had values similar to controls, whereas the maximum tetanic tension/muscle weight was significantly elevated in HS-WS compared to controls. Contraction times were 25 percent faster in the Sol and unchanged in the MG of HS rats, indicating that a low-force short-duration exercise regime results in a significant functional recovery in the 'slow' Sol, whereas the 'fast' MG is less affected.

Pierotti, David J.↗

The RBE-LET relationship for rodent intestinal crypt cell survival, testes weight loss, and multicellular spheroid cell survival after heavy-ion irradiation

This report presents data for survival of mouse intestinal crypt cells, mouse testes weight loss as an indicator of survival of spermatogonial stem cells, and survival of rat 9L spheroid cells after irradiation in the plateau region of unmodified particle beams ranging in mass from 4He to 139La. The LET values range from 1.6 to 953 keV/microns. These studies examine the RBE-LET relationship for two normal tissues and for an in vitro tissue model, multicellular spheroids. When the RBE values are plotted as a function of LET, the resulting curve is characterized by a region in which RBE increases with LET, a peak RBE at an LET value of 100 keV/microns, and a region of decreasing RBE at LETs greater than 100 keV/microns. Inactivation cross sections (sigma) for these three biological systems have been calculated from the exponential terminal slope of the dose-response relationship for each ion. For this determination the dose is expressed as particle fluence and the parameter sigma indicates effect per particle. A plot of sigma versus LET shows that the curve for testes weight loss is shifted to the left, indicating greater radiosensitivity at lower LETs than for crypt cell and spheroid cell survival. The curves for cross section versus LET for all three model systems show similar characteristics with a relatively linear portion below 100 keV/microns and a region of lessened slope in the LET range above 100 keV/microns for testes and spheroids. The data indicate that the effectiveness per particle increases as a function of LET and, to a limited extent, Z, at LET values greater than 100 keV/microns. Previously published results for spread Bragg peaks are also summarized, and they suggest that RBE is dependent on both the LET and the Z of the particle.

Non-NASA Center↗

An Optothermal Raman Model Accounting for Convection, Radiation, and Substrate Effects for Evaluation of the Thermal Conductivity of Two‐Dimensional Coatings

Thermal conductivity of two‐dimensional (2D) materials is important to characterize as this will govern thermal transport physics in the various thermal and energy applications benefitting from the unique properties of these materials. Here, analytical and numerical techniques are presented to determine the thermal conductivity and interfacial conductance of a 2D material coating using confocal micro‐Raman spectroscopy as a noncontact diagnostic. While several methods have been proposed for calculating the values of thermal conductivity, interfacial conductance, and spatial temperature profile, these models often do not consider effects of radiation, convection, and substrate resistance on the temperature and heat flux profiles. We present a model to calculate the thermal conductivity and interfacial conductance which accounts for convection, radiation, and substrate effects to characterize a variety of 2D material coatings, which is demonstrated using large area graphene transferred onto copper and nickel substrates. Convection and radiation effects are found to have a negligible effect on the temperature profile of supported coatings, while the substrate effects have a considerable effect and therefore impact the quantification of thermal conductivity and interfacial conductance in addition to limiting the spatial resolution of the technique. These findings will allow for more accurate and reproducible extraction of the thermal conductivity of graphene and other 2D material coatings when employing noncontact optothermal Raman spectroscopy methods.

2D coatings↗

Evidence for long-term variability in the ultra high energy photon flux from Cygnus X-3

A time-correlation analysis of atmospheric Cerenkov pulses by a wide-angle photomultiplier system was previously shown to have present in it a nonrandom component which seemed associated with the Right Ascension (RA) range approx. 20+or-04h. A recent examination of multi-muon events recorded by a photon-decay detector shows a similar time-dependent effect, closely matching the previous results, supporting the suggestion that the effect is of cosmic origin. However, even though Cyg. X-3 lies well inside the region of peak intensity, it does not seem possible to ascribe to it the whole effect, for the implied photon flux appears too large to be reconciled to various gamma-ray measurements of Cyg. X-3. The original data were subjected to a phase-histogram analysis and it as found that only 2.5% of overall recorded data are compatible with a phase-dependent emission from Cyg. X-3. Assuming these events to be gamma rays yields a detected flux of (2.6 + or - 0.3) x 10 to the minus 12th power gamma cm -2s-1 above 5 x 10 to the 14th power eV. Comparing this value with more recent ultra high energy (UHE) photon data from the same source, it is suggested that the available data generally favor a long-term reduction in the Cyg. X-3 inferred luminosity ( 10 to the 13th power eV) by a factor of (1.8 + or - 0.3) per year.

Bhat, C. L.↗

Proposed Project Selection Method for Human Support Research and Technology Development (HSR&TD)

The purpose of HSR&TD is to deliver human support technologies to the Exploration Systems Mission Directorate (ESMD) that will be selected for future missions. This requires identifying promising candidate technologies and advancing them in technology readiness until they are acceptable. HSR&TD must select an may of technology development projects, guide them, and either terminate or continue them, so as to maximize the resulting number of usable advanced human support technologies. This paper proposes an effective project scoring methodology to support managing the HSR&TD project portfolio. Researchers strongly disagree as to what are the best technology project selection methods, or even if there are any proven ones. Technology development is risky and outstanding achievements are rare and unpredictable. There is no simple formula for success. Organizations that are satisfied with their project selection approach typically use a mix of financial, strategic, and scoring methods in an open, established, explicit, formal process. This approach helps to build consensus and develop management insight. It encourages better project proposals by clarifying the desired project attributes. We propose a project scoring technique based on a method previously used in a federal laboratory and supported by recent research. Projects are ranked by their perceived relevance, risk, and return - a new 3 R's. Relevance is the degree to which the project objective supports the HSR&TD goal of developing usable advanced human support technologies. Risk is the estimated probability that the project will achieve its specific objective. Return is the reduction in mission life cycle cost obtained if the project is successful. If the project objective technology performs a new function with no current cost, its return is the estimated cash value of performing the new function. The proposed project selection scoring method includes definitions of the criteria, a project evaluation questionnaire, and a scoring formula.

Jones, Harry↗

Life sciences and space research XXIII(3): Natural and artificial ecosystems; Proceedings of the Topical Meetings of the 27th COSPAR Plenary Meeting, Espoo, Finland, July 18-29, 1988

The present conference discusses topics in the fields of higher plant growth under controlled environmental conditions, waste oxidation, carbon cycling, and biofermentor design and operation. Attention is given to CO2 and O2 effects on the development and fructification of wheat in closed systems, transpiration during life cycle in controlled wheat growth, sources and processing of CELSS wastes, waste-recycling in bioregenerative life support, and the effect of iodine disinfection products on higher plants. Also discussed are carbon cycling by cellulose-fermenting nitrogen-fixing bacteria, a bioreactor design with sunlight supply and operations systems for use in the space environment, gas bubble coalescence in reduced gravity conditions, and model system studies of a phase-separated membrane bioreactor.

Macelroy, R. D.↗

Engineering a universal and efficient platform for terpenoid synthesis in yeast

Engineering microbes for the production of valuable natural products is often hindered by the regulation of native competing metabolic networks in host. This is particularly evident in the case of terpenoid synthesis in yeast, where the canonical terpenoid precursors are tightly coupled to the biosynthesis of sterols essential for yeast viability. One way to circumvent this limitation is by engineering product pathways less connected to the host native metabolism. Here, we introduce a two-step isopentenol utilization pathway (IUP) in Saccharomyces cerevisiae to augment the native mevalonate pathway by providing a shortcut to the synthesis of the common terpenoid precursors, isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP). As such, the IUP was capable of elevating the IPP/DMAPP pool by 147-fold compared with the native pathway. We further demonstrate that cofeeding isoprenol and prenol enhances geranyl diphosphate (GPP) content for monoterpene biosynthesis. More importantly, we established a synthetic three-step route for efficient synthesis of di-and tetraterpene precursor geranylgeranyl diphosphate (GGPP), circumventing the competition with farnesyl diphosphate (FPP) for sterol biosynthesis and elevating the GGPP level by 374-fold. We combine these IUP-supported precursor-forming platforms with downstream terpene synthases to harness their potential and improve the production of industrially relevant terpenoids by several fold. In conclusion, our exploration provides a universal and effective platform for supporting terpenoid synthesis in yeast.

59 BASIC BIOLOGICAL SCIENCES↗

The space shuttle ascent vehicle aerodynamic challenges configuration design and data base development

The phase B Space Shuttle systems definition studies resulted in a generic configuration consisting of a delta wing orbiter, and two solid rocket boosters (SRB) attached to an external fuel tank (ET). The initial challenge facing the aerodynamic community was aerodynamically optimizing, within limits, this configuration. As the Shuttle program developed and the sensitivities of the vehicle to aerodynamics were better understood the requirements of the aerodynamic data base grew. Adequately characterizing the vehicle to support the various design studies exploded the size of the data base to proportions that created a data modeling/management challenge for the aerodynamicist. The ascent aerodynamic data base originated primarily from wind tunnel test results. The complexity of the configuration rendered conventional analytic methods of little use. Initial wind tunnel tests provided results which included undesirable effects from model support tructure, inadequate element proximity, and inadequate plume simulation. The challenge to improve the quality of test results by determining the extent of these undesirable effects and subsequently develop testing techniques to eliminate them was imposed on the aerodynamic community. The challenges to the ascent aerodynamics community documented are unique due to the aerodynamic complexity of the Shuttle launch. Never before was such a complex vehicle aerodynamically characterized. The challenges were met with innovative engineering analyses/methodology development and wind tunnel testing techniques.

Dill, C. C.↗

Notable Contributions of Aerosols to the Predictability of Hail Precipitation

There is an increasing concern of the uncertainty produced by aerosols in forecasting precipitation including hail precipitation. This study provides an assessment of the uncertainties in hail and total precipitation by varying initial cloud condensation nuclei (CCN) number concentration (CCNC) and meteorological conditions based on 1200 cloud-resolving simulations of an idealized hailstorm. Although the meteorological perturbations produce large uncertainties in hail precipitation (including rate and maximum hail size) as well as total precipitation, varying CCNC by an order of magnitude can cause even larger uncertainties, especially pairing with the thermodynamics perturbation (i.e., potential temperature and water vapor). Changing CCNC modifies the predictability of hail precipitation, with a higher predictability in moderate polluted environments compared with the very clean and polluted environments. Increasing CCNC consistently leads a non-monotonic response of ensemble mean with an optimal CCNC for hail precipitation but a monotonic decreasing response of total precipitation with the various meteorological perturbations, meaning the initial meteorological perturbations does not qualitatively change the aerosol effects. Investigation with 10-fold reduced initial perturbation further supports the large CCN effects are not dependent of metrological perturbations. The findings suggest the importance of considering CCN effects in severe weather simulations and forecasting.

54 ENVIRONMENTAL SCIENCES↗

An evaluation of three experimental processes for two-dimensional transonic tests

The aerodynamic measurements in conventional wind tunnels usually suffer from the interference effects of the sting supporting the model and the test section walls. These effects are particularly severe in the transonic regime. Sting interference effects can be overcome through the Magnetic Suspension technique. Wall effects can be alleviated by: testing airfoils in conventional, ventilated tunnels at relatively small model to tunnel size ratios; treatment of the tunnel wall boundary layers; or by utilization of the Adaptive Wall Test Section (AWTS) concept. The operating capabilities and results from two of the foremost two-dimensional, transonic, AWTS facilities in existence are assessed. These facilities are the NASA 0.3-Meter Transonic Cryogenic Tunnel and the ONERA T-2 facility located in Toulouse, France. In addition, the results derived from the well known conventional facility, the NAE 5 ft x 5 ft Canadian wind tunnel will be assessed. CAST10/D0A2 Airfoil results will be used in all of the evaluations.

Zuppardi, Gennaro↗

Effects of Meteoroid Erosion in Planetary Rings

This grant supported continuing studies of the effects of ballistic transport on the evolution of Saturn's rings. Ballistic transport, as used in this context, refers to the net transport of mass and angular momentum caused by the exchange of meteoroid impact ejecta between neighboring ring regions (Ip 1983, 1984, Morfill et al. 1983, Lissauer 1984, Durisen 1984a,b). The characteristic time scale associated with this process is the gross erosion time t(sub g) the time it would take a ring region to be completed eroded if all impact ejecta were lost. This time scale is estimated to be about 10(exp 5) to 10(exp 6) years for a ring region with normal optical depth tau approximately 1. Earlier work by myself and collaborators developed the physical theory and simulation techniques to model this process (Durisen et al. 1989, Cuzzi and Durisen 1990). Detailed simulations, supported in part by this grant, have demonstrated that ballistic transport can produce observed structures in Saturn's rings, especially at and near the inner edges of the A and B Rings (Durisen et al. 1992, 1996). The structures of interest in the real rings are illustrated in Figures 1 and 2. Most of these structures were previously unexplained. The computational results plus analytic treatments place useful constraints on fundamental ring properties, including the indication of a relatively young ring age less than or equal 10(exp 8) years (see reviews by Nicholson and Dones 1991, Esposito 1993, Cuzzi 1995, and Porco 1995). This grant also supported development of the faster computational algorithms necessary to permit longer evolutions. Resulting simplications in the ballistic transport equations permitted an analytic linear stability analysis (Durisen 1995), which has provided considerable insight into ballistic transport processes and applications to Saturn's rings. All these accomplishments are described in more detail below.

Durisen, Richard H.↗

Marshall Space Flight Center's Virtual Reality Applications Program 1993

A Virtual Reality (VR) applications program has been under development at the Marshall Space Flight Center (MSFC) since 1989. Other NASA Centers, most notably Ames Research Center (ARC), have contributed to the development of the VR enabling technologies and VR systems. This VR technology development has now reached a level of maturity where specific applications of VR as a tool can be considered. The objectives of the MSFC VR Applications Program are to develop, validate, and utilize VR as a Human Factors design and operations analysis tool and to assess and evaluate VR as a tool in other applications (e.g., training, operations development, mission support, teleoperations planning, etc.). The long-term goals of this technology program is to enable specialized Human Factors analyses earlier in the hardware and operations development process and develop more effective training and mission support systems. The capability to perform specialized Human Factors analyses earlier in the hardware and operations development process is required to better refine and validate requirements during the requirements definition phase. This leads to a more efficient design process where perturbations caused by late-occurring requirements changes are minimized. A validated set of VR analytical tools must be developed to enable a more efficient process for the design and development of space systems and operations. Similarly, training and mission support systems must exploit state-of-the-art computer-based technologies to maximize training effectiveness and enhance mission support. The approach of the VR Applications Program is to develop and validate appropriate virtual environments and associated object kinematic and behavior attributes for specific classes of applications. These application-specific environments and associated simulations will be validated, where possible, through empirical comparisons with existing, accepted tools and methodologies. These validated VR analytical tools will then be available for use in the design and development of space systems and operations and in training and mission support systems.

Hale, Joseph P., II↗

An investigation of the physical and chemical changes of Pd nanoparticles on carbon supports in response to the release of hydrogen from aqueous formate solutions

Palladium nanoparticles on carbon supports (Pd/C) are effective for catalyzing hydrogen release from aqueous formate solutions but typically suffer from a gradual decrease of activity. This study finds two primary factors influencing activity: (i) the number of available surface Pd sites, and (ii) metal-support interactions which depend on the nature of the C support. We propose that the Pd/C catalyst is structure insensitive and undergoes Ostwald ripening to yield an active ‘conditioned’ catalyst with dispersion plateauing between ca. 15–20 %. Contrary to earlier studies, in-situ XANES experiments show that PdO is not an active catalyst for formate dehydrogenation. Calcination of Pd/C before dehydrogenation increases the catalytic activity which suggests a beneficial, albeit temporary, modification of the metal support interaction. N-containing supports minimize nanoparticle growth and also increase activity through a metal-support interaction. In conclusion, these findings advance our understanding of catalyst evolution and stability in formate dehydrogenation systems.

Formate dehydrogenation↗

In Situ Studies of the Formation of MoP Catalysts and Their Structure under Reaction Conditions for Higher Alcohol Synthesis: The Role of Promoters and Mesoporous Supports

Three formulations of a molybdenum phosphide (MoP) catalyst system were characterized for the higher alcohol synthesis (HAS) reaction using in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD), monitoring the chemical phase evolution during activation and under reaction conditions. Here, the in situ study herein provides important insights into the effect of the support and of K that lead to high performance in HAS for K-promoted MoP supported on carbon, as evidenced by previous studies (ethanol selectivity: 29%; conversion: 5%). During the activation process, XAS shows that the carbon-supported samples reduce and reach a highly crystalline state at a lower temperature than the SBA-15-supported sample, indicating a substantial difference in catalyst activation. After activation, the samples are introduced to relevant reaction conditions resulting in spectra fairly similar to one another. XRD results corroborate the difference in the degree of crystallinity of these samples, in alignment with the XAS, and reveal the formation of crystalline potassium pyrophosphate (K 4 P 2 O 7 ) during the activation period of the K-promoted samples. This K 4 P 2 O 7 phase remains present under reaction conditions. Taken together, these results provide insights into the roles played by the carbon support and K promotion, connecting activity to electronic and crystal structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A lunar base reference mission for the phased implementation of bioregenerative life support system components

Previous design efforts of a cost effective and reliable regenerative life support system (RLSS) provided the foundation for the characterization of organisms or 'biological processors' in engineering terms and a methodology was developed for their integration into an engineered ecological LSS in order to minimize the mass flow imbalances between consumers and producers. These techniques for the design and the evaluation of bioregenerative LSS have now been integrated into a lunar base reference mission, emphasizing the phased implementation of components of such a BLSS. In parallel, a designers handbook was compiled from knowledge and experience gained during past design projects to aid in the design and planning of future space missions requiring advanced RLSS technologies. The lunar base reference mission addresses in particular the phased implementation and integration of BLS parts and includes the resulting infrastructure burdens and needs such as mass, power, volume, and structural requirements of the LSS. Also, operational aspects such as manpower requirements and the possible need and application of 'robotics' were addressed.

Dittmer, Laura N.↗