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At least 919 records · Page 51

Grafting metal complexes onto amorphous supports: from elementary steps to catalyst site populations via kernel regression

Ab initio computational studies have made tremendous progress in describing the behavior of molecular (homogeneous) catalysts and crystalline versions of heterogeneous catalysts, but not for amorphous heterogeneous catalysts. Even widely used industrial amorphous catalysts like atomically dispersed Cr on silica remain poorly understood and largely intractable to computational investigation. The central problems are that (i) the amorphous support presents an unknown quenched disordered structure, (ii) metal atoms attach to various surface grafting sites with different rates, and (iii) the resulting grafted sites have different activation and catalytic reaction kinetics. This study combines kernel regression and importance sampling techniques to efficiently model grafting of metal ions onto a non-uniform ensemble of support environments. Our analysis uses a simple model of the quenched disordered support environment, grafting chemistry, and catalytic activity of the resulting grafted sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of Pitting Corrosion on Wrought and Additively Manufactured 316L Stainless Steel in Atmospheric Environments

Additive manufacturing of metal components enables rapid fabrication of complex geometries. However, metal additive manufacturing also introduces new morphological and microstructural characteristics which might be detrimental to component performance. Here we report the pitting corrosion properties of wrought and additively manufactured 316L stainless steel after atmospheric exposure to coastal environments and laboratory-created environments. Qualitative visualization in combination with quantitative analysis of resulting pits provided an in-depth understanding of pitting differences between wrought and additively manufactured 316L stainless steel and between coastal and laboratory-based exposure. Optical and scanning electron microscopy were utilized for visualization, while white light interferometry measured pits across approximately 5mm x 5mm areas on each sample. Post-processing of the interferometry data enables quantification of pitting attack for each sample in terms of both pit depth and pit volume. The pitting analysis introduced herein offers a new technique to compare pitting attack between different manufacturing processes and materials.

36 MATERIALS SCIENCE↗

Design, execution, and interpretation of plant RNA-seq analyses

Genomics has transformed our understanding of the genetic architecture of traits and the genetic variation present in plants. Here, we present a review of how RNA-seq can be performed to tackle research challenges addressed by plant sciences. We discuss the importance of experimental design in RNA-seq, including considerations for sampling and replication, to avoid pitfalls and wasted resources. Approaches for processing RNA-seq data include quality control and counting features, and we describe common approaches and variations. Though differential gene expression analysis is the most common analysis of RNA-seq data, we review multiple methods for assessing gene expression, including detecting allele-specific gene expression and building co-expression networks. With the production of more RNA-seq data, strategies for integrating these data into genetic mapping pipelines is of increased interest. Finally, special considerations for RNA-seq analysis and interpretation in plants are needed, due to the high genome complexity common across plants. By incorporating informed decisions throughout an RNA-seq experiment, we can increase the knowledge gained.

59 BASIC BIOLOGICAL SCIENCES↗

Uranium (VI) Adsorbate Structures on Portlandite [Ca(OH)2] Type Surfaces Determined by Computational Modelling and X-ray Absorption Spectroscopy

Portlandite [Ca(OH) 2 ] is a potentially dominant solid phase in the high pH fluids expected within the cementitious engineered barriers of Geological Disposal Facilities (GDF). This study combined X-ray Absorption Spectroscopy with computational modelling in order to provide atomic-scale data which improves our understanding of how a critically important radionuclide (U) will be adsorbed onto this phase under conditions relevant to a GDF environment. Such data are fundamental for predicting radionuclide mass transfer. Surface coordination chemistry and speciation of uranium with portlandite [Ca(OH) 2 ] under alkaline groundwater conditions (ca. pH 12) were determined by both in situ and ex situ grazing incidence extended X-ray absorption fine structure analysis (EXAFS) and by computational modelling at the atomic level. Free energies of sorption of aqueous uranyl hydroxides, [UO 2 (OH) n ] 2–n (n = 0–5) with the (001), (100) and (203) or (101) surfaces of portlandite are predicted from the potential of mean force using classical molecular umbrella sampling simulation methods and the structural interactions are further explored using fully periodic density functional theory computations. Although uranyl is predicted to only weakly adsorb to the (001) and (100) clean surfaces, there should be significantly stronger interactions with the (203/101) surface or at hydroxyl vacancies, both prevalent under groundwater conditions. The uranyl surface complex is typically found to include four equatorially coordinated hydroxyl ligands, forming an inner-sphere sorbate by direct interaction of a uranyl oxygen with surface calcium ions in both the (001) and (203/101) cases. In contrast, on the (100) surface, uranyl is sorbed with its axis more parallel to the surface plane. The EXAFS data are largely consistent with a surface structural layer or film similar to calcium uranate, but also show distinct uranyl characteristics, with the uranyl ion exhibiting the classic dioxygenyl oxygens at 1.8 Å and between four and five equatorial oxygen atoms at distances between 2.28 and 2.35 Å from the central U absorber. These experimental data are wholly consistent with the adsorbate configuration predicted by the computational models. These findings suggest that, under the strongly alkaline conditions of a cementitious backfill engineered barrier, there would be significant uptake of uranyl by portlandite to inhibit the mobility of U(VI) from the near field of a geological disposal facility.

36 MATERIALS SCIENCE↗

Fluid Phase Separation (FPS) experiment for flight on the shuttle in a Get Away Special (GAS) canister: Design and fabrication

The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid that will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The phase separation experiment is totally self-contained, with three levels of containment on all fluids, and provides all necessary electrical power and control. The controller regulates the temperature of the fluid and controls data logging and sampling. An astronaut-activated switch will initiate the experiment and an unmaskable interrupt is provided for shutdown. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS 42 in April 1991. Presented here are the design and the production of a fluid phase separation experiment for rapid implementation at low cost.

Source record↗

Modeling and Analysis of the Reverse Water Gas Shift Process for In-Situ Propellant Production

This report focuses on the development of mathematical models and simulation tools developed for the Reverse Water Gas Shift (RWGS) process. This process is a candidate technology for oxygen production on Mars under the In-Situ Propellant Production (ISPP) project. An analysis of the RWGS process was performed using a material balance for the system. The material balance is very complex due to the downstream separations and subsequent recycle inherent with the process. A numerical simulation was developed for the RWGS process to provide a tool for analysis and optimization of experimental hardware, which will be constructed later this year at Kennedy Space Center (KSC). Attempts to solve the material balance for the system, which can be defined by 27 nonlinear equations, initially failed. A convergence scheme was developed which led to successful solution of the material balance, however the simplified equations used for the gas separation membrane were found insufficient. Additional more rigorous models were successfully developed and solved for the membrane separation. Sample results from these models are included in this report, with recommendations for experimental work needed for model validation.

Whitlow, Jonathan E.↗

Early and Late Chromosome Damages in Human Lymphocytes Induced by Gamma Rays and Fe Ions

Chromosomal translocations and inversions are considered stable, and cells containing these types of chromosome aberrations can survive multiple cell divisions. An efficient method to detect an inversion is multi-color banding fluorescent in situ hybridization (mBAND) which allows identification of both inter- and intrachromosome aberrations simultaneously. Post irradiation, chromosome aberrations may also arise after multiple cell divisions as a result of genomic instability. To investigate the stable or late-arising chromosome aberrations induced after radiation exposure, we exposed human lymphocytes to gamma rays and Fe ions ex vivo, and cultured the cells for multiple generations. Chromosome aberrations were analyzed in cells collected at first mitosis and at several time intervals during the culture period post irradiation. With gamma irradiation, about half of the damages observed at first mitosis remained after 7 day- and 14 day- culture, suggesting the transmissibility of damages to the surviving progeny. Detailed analysis of chromosome break ends participating in exchanges revealed a greater fraction of break ends involved in intrachromosome aberrations in the 7- and 14-day samples in comparison to the fraction at first mitosis. In particular, simple inversions were found at 7 and 14 days, but not at the first mitosis, suggesting that some of the aberrations might be formed days post irradiation. In contrast, at the doses that produced similar frequencies of gamma-induced chromosome aberrations as observed at first mitosis, a significantly lower yield of aberrations remained at the same population doublings after Fe ion exposure. At these equitoxic doses, more complex type aberrations were observed for Fe ions, indicating that Fe ion-induced initial chromosome damages are more severe and may lead to cell death. Comparison between low and high doses of Fe ion irradiation in the induction of late damages will also be discussed.

Sunagawa, Mayumi↗

mBAND Analysis of Late Chromosome Aberrations in Human Lymphocytes Induced by Gamma Rays and Fe Ions

Chromosomal translocations and inversions are considered stable, and cells containing these types of chromosome aberrations can survive multiple cell divisions. An efficient method to detect an inversion is multi-color banding fluorescent in situ hybridization (mBAND) which allows identification of both inter- and intrachromosome aberrations simultaneously. Post irradiation, chromosome aberrations may also arise after multiple cell divisions as a result of genomic instability. To investigate the stable or late-arising chromosome aberrations induced after radiation exposure, we exposed human lymphocytes to gamma rays and Fe ions ex vivo, and cultured the cells for multiple generations. Chromosome aberrations were analyzed in cells collected at first mitosis and at several time intervals during the culture period post irradiation. With gamma irradiation, about half of the damages observed at first mitosis remained after 7 day- and 14 day- culture, suggesting the transmissibility of damages to the surviving progeny. Detailed analysis of chromosome break ends participating in exchanges revealed a greater fraction of break ends involved in intrachromosome aberrations in the 7- and 14-day samples in comparison to the fraction at first mitosis. In particular, simple inversions were found at 7 and 14 days, but not at the first mitosis, suggesting that some of the aberrations might be formed days post irradiation. In contrast, at the doses that produced similar frequencies of gamma-induced chromosome aberrations as observed at first mitosis, a significantly lower yield of aberrations remained at the same population doublings after Fe ion exposure. At these equitoxic doses, more complex type aberrations were observed for Fe ions, indicating that Fe ion-induced initial chromosome damages are more severe and may lead to cell death. Comparison between low and high doses of Fe ion irradiation in the induction of late damages will also be discussed.

Sunagawa, Mayumi↗

Heterogeneity in small aliquots of Apolllo 15 olivine-normative basalt: Implications for breccia clast studies

Most of the recent advances in lunar petrology are the direct result of breccia pull-apart studies, which have identified a wide array of new highland and mare basalt rock types that occur only as clasts within the breccias. These rocks show that the lunar crust is far more complex than suspected previously, and that processes such as magma mixing and wall-rock assimilation were important in its petrogenesis. These studies are based on the implicit assumption that the breccia clasts, which range in size from a few mm to several cm across, are representative of the parent rock from which they were derived. In many cases, the aliquot allocated for analysis may be only a few grain diameters across. While this problem is most acute for coarse-grained highland rocks, it can also cause considerable uncertainty in the analysis of mare basalt clasts. Similar problems arise with small aliquots of individual hand samples. Our study of sample heterogeneity in 9 samples of Apollo 15 olivine normative basalt (ONB) which exhibit a range in average grain size from coarse to fine are reported. Seven of these samples have not been analyzed previously, one has been analyzed by INAA only, and one has been analyzed by XRF+INAA. Our goal is to assess the effects of small aliquot size on the bulk chemistry of large mare basalt samples, and to extend this assessment to analyses of small breccia clasts.

Lindstrom, Marilyn M.↗

Modernization of the Radiation Measurements Laboratory at the Advanced Test Reactor Complex

The Advanced Test Reactor (ATR) at the Idaho National Laboratory (INL) is a unique, water-cooled, high-flux test reactor capable of performing tests prototypical of PWR operating conditions. The Radiation Measurements Laboratory (RML) was founded in the 1960s to support reactor operations and to conduct independent scientific research. For nearly six decades RML has performed four primary functions: monitoring of radioactivity by gamma-ray spectroscopy of routine reactor samples, fluence rate determinations for irradiation cycles, fission-rate measurements for the ATR-Critical (ATR-C) Facility, and independent research and development of radiation detection systems and applications. Through the decades, RML has seen technological advancements that have been integrated into each of the critical functions of the laboratory. However, many of the measurement and analysis systems employed to this day can be improved by modernization. Recent progess at RML are improving reliability and accuracy of the radiation measurements performed in support of nuclear energy research for the U.S.A. Department of Energy. The control and data collection systems supporting ATR-C have been upgraded. New High-Purity Germanium (HPGe) spectrometers have been procured with liquid nitrogen recycling capabilities to improve up-time and reduce measurement uncertainties. Fluence-rate measurement techniques are also being improved to ensure accuracy, avoid systemic errors, and identify biases. In a parallel effort, new scientific research avenues are being explored which will provide an opportunity to further enhance the utilization of ATR and ensure the sustainability of the RML as nuclear research continues to evolve. The RML is improving the effectiveness of irradiation services provided by ATR while ensuring a sustainable future for nuclear energy research.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Modernization of the Radiation Measurements Laboratory at the Advanced Test Reactor Complex

The Advanced Test Reactor (ATR) at the Idaho National Laboratory (INL) is a unique, water-cooled, high-flux test reactor capable of performing tests prototypical of PWR operating conditions. The Radiation Measurements Laboratory (RML) was founded in the 1960s to support reactor operations and to conduct independent scientific research. For nearly six decades RML has performed four primary functions: monitoring of radioactivity by gamma-ray spectroscopy of routine reactor samples, fluence rate determinations for irradiation cycles, fission-rate measurements for the ATR-Critical (ATR-C) Facility, and independent research and development of radiation detection systems and applications. Through the decades, RML has seen technological advancements that have been integrated into each of the critical functions of the laboratory. However, many of the measurement and analysis systems employed to this day can be improved by modernization. Recent progress at RML is improving reliability and accuracy of the radiation measurements performed in support of nuclear energy research for the U.S.A. Department of Energy. The control and data collection systems supporting ATR-C have been upgraded. New High-Purity Germanium (HPGe) spectrometers have been procured with liquid nitrogen recycling capabilities to improve up-time and reduce measurement uncertainties. Fluence-rate measurement techniques are also being improved to ensure accuracy, avoid systemic errors, and identify biases. In a parallel effort, new scientific research avenues are being explored which will provide an opportunity to further enhance the utilization of ATR and ensure the sustainability of the RML as nuclear research continues to evolve. The RML is improving the effectiveness of irradiation services provided by ATR while ensuring a sustainable future for nuclear energy research.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Complex deuteron NMR signals

To determine the spin polarization of deuterons, nuclear magnetic resonance (NMR) is used. This is necessary for polarized targets, such as for the upcoming A zz and b 1 experiment at Jefferson Lab. NMR measures the impedance of a solenoid around a deuterated sample. Although the impedance is a complex value, conventionally only the real part of the impedance has been used for this purpose. However, often the tune is not precisely real, meaning the signal has at least some small imaginary portion. This conventionally has been dealt with by an offset parameter, such as Dulya’s false asymmetry method. For vector polarization, this suffices, as the tuning is factored into the overall error of the results, and for a small phase angle doesn’t make much of a difference. However, for tensor polarization, the exact lineshape of the signal is quite significant, and treating the impedance as complex during analysis removes the need for an offset parameter. As a result, it also provides more accurate results, as the conventional false asymmetry method over- or underestimates polarization, depending on the sign of the phase angle.

McClellan, Michael [University of New Hampshire, D↗

Structural Polymorphism of Chitin and Chitosan in Fungal Cell Walls From Solid-State NMR and Principal Component Analysis

Chitin is a major carbohydrate component of the fungal cell wall and a promising target for novel antifungal agents. However, it is technically challenging to characterize the structure of this polymer in native cell walls. Here, we recorded and compared 13 C chemical shifts of chitin using isotopically enriched cells of six Aspergillus, Rhizopus, and Candida strains, with data interpretation assisted by principal component analysis (PCA) and linear discriminant analysis (LDA) methods. The structure of chitin is found to be intrinsically heterogeneous, with peak multiplicity detected in each sample and distinct fingerprints observed across fungal species. Fungal chitin exhibits partial similarity to the model structures of α- and γ-allomorphs; therefore, chitin structure is not significantly affected by interactions with other cell wall components. Addition of antifungal drugs and salts did not significantly perturb the chemical shifts, revealing the structural resistance of chitin to external stress. In addition, the structure of the deacetylated form, chitosan, was found to resemble a relaxed two-fold helix conformation. This study provides high-resolution information on the structure of chitin and chitosan in their cellular contexts. The method is applicable to the analysis of other complex carbohydrates and polymer composites.

59 BASIC BIOLOGICAL SCIENCES↗

A general multiblock Euler code for propulsion integration. Volume 3: User guide for the Euler code

This manual explains the procedures for using the general multiblock Euler (GMBE) code developed under NASA contract NAS1-18703. The code was developed for the aerodynamic analysis of geometrically complex configurations in either free air or wind tunnel environments (vol. 1). The complete flow field is divided into a number of topologically simple blocks within each of which surface fitted grids and efficient flow solution algorithms can easily be constructed. The multiblock field grid is generated with the BCON procedure described in volume 2. The GMBE utilizes a finite volume formulation with an explicit time stepping scheme to solve the Euler equations. A multiblock version of the multigrid method was developed to accelerate the convergence of the calculations. This user guide provides information on the GMBE code, including input data preparations with sample input files and a sample Unix script for program execution in the UNICOS environment.

Chen, H. C.↗

Effect of scanline orientation on ventricular flow propagation: assessment using high frame-rate color Doppler echocardiography

Color M-mode echocardiography has recently been utilized to describe diastolic flow propagation velocity (Vp) in the left ventricle. While increasing temporal resolution from 15 to 200 Hz, this M-mode technique requires the user to select a single scanline, potentially limiting quantification of Vp due to the complex three-dimensional inflow pattern. We previously performed computational fluid dynamics simulations to demonstrate the insignificance of the scanline orientation, however geometric complexity was limited. The purpose of this study was to utilize high frame-rate 2D color Doppler images to investigate the importance of scanline selection in patients for the quantification of Vp. 2D color Doppler images were digitally acquired at 50 frames/s in 6 subjects from the apical 4-chamber window (System 5, GE/Vingmed, Milwaukee, WI). Vp was determined for a set of scanlines positioned through 5 locations across the mitral annulus (from the anterior to posterior mitral annulus). An analysis of variance was performed to examine the differences in Vp as a function of scanline position. Vp was not effected by scanline position in sampled locations from the center of the mitral valve towards the posterior annulus. Although not statistically significant, there was a trend to slower propagation velocities on the anterior side of the valve (60.8 +/- 16.7 vs. 54.4 +/- 13.6 cm/s). This study clinically validates our previous numerical experiment showing that Vp is insensitive to small perturbations of the scanline through the mitral valve. However, further investigation is necessary to examine the impact of ventricular geometry in pathologies including dilated cardiomyopathy.

Non-NASA Center↗

NM-Scale Anatomy of an Entire Stardust Carrot Track

Comet Wild-2 samples collected by NASA s Stardust mission are extremely complex, heterogeneous, and have experienced wide ranges of alteration during the capture process. There are two major types of track morphologies: "carrot" and "bulbous," that reflect different structural/compositional properties of the impactors. Carrot type tracks are typically produced by compact or single mineral grains which survive essentially intact as a single large terminal particle. Bulbous tracks are likely produced by fine-grained or organic-rich impactors [1]. Owing to their challenging nature and especially high value of Stardust samples, we have invested considerable effort in developing both sample preparation and analytical techniques tailored for Stardust sample analyses. Our report focuses on our systematic disassembly and coordinated analysis of Stardust carrot track #112 from the mm to nm-scale.

Nakamura-Messenger, K.↗

Low Temperature Regolith Bricks for In-Situ Structural Material

Current technology for producing in-situ structural materials on future missions to Mars or the moon relies heavily on energy-intensive sintering processes to produce solid bricks from regolith. This process requires heating the material up to temperatures in excess of 1000 C and results in solid regolith pieces with compressive strengths in the range of 14000 to 28000 psi, but are heavily dependent on the porosity of the final material and are brittle. This method is currently preferred over a low temperature cementation process to prevent consumption of precious water and other non-renewable materials. A high strength structural material with low energy requirements is still needed for future colonization of other planets. To fulfill these requirements, a nano-functionalization process has been developed to produce structural bricks from regolith simulant and shows promising mechanical strength results. Functionalization of granular silicate particles into alkoxides using a simple low temperature chemical process produces a high surface area zeolite particles that are held together via inter-particle oxygen bonding. Addition of water in the resulting zeolite particles produces a sol-gel reaction called "inorganic polymerization" which gives a strong solid material after a curing process at 60 C. The aqueous solution by-product of the reaction is currently being investigated for its reusability; an essential component of any ISRU technology. For this study, two batches of regolith bricks are synthesized from JSC-1A; the first batch from fresh solvents and chemicals, the second batch made from the water solution by-product of the first batch. This is done to determine the feasibility of recycling necessary components of the synthesis process, mainly water. Characterization including BET surface area, SEM, and EDS has been done on the regolith bricks as well as the constituent particles,. The specific surface area of 17.53 sq m/g (average) of the granular regolith material was obtained from nitrogen adsorption isotherm measurement. The size, shape and textures of regolith from SEM shows that the particles are 25-50 micrometers in size and mostly irregular in shape (Figure 1a). The elemental composition of regolith was identified from EDS analysis showed the presence of Si, Al, Fe, Na, Mg, Ca, Ti, O and C (see figure 1b). Each set of cylindrical brick samples were prepared by low energy process, and cured for 21 and 28 days, respectively to compare their compressive strength. Figure 1c, and d shows the JSC-1A brick and the compressive strength measurements. The results from the 21 day cured bricks (2 bricks) have been done and yielded an aver-age strength of 3050 psi, considerably higher than Portland cement mortars (Type IV and V). This promising technology provides the benefits of construction material similar to concrete, with a low complexity, low energy synthesis process and the likelihood of complete reusability of precious resources. Compressive strength using this method can be improved by increasing the surface area of the particles, using bi-modal particle size distribution, and adding certain additives to increase inter-particle forces.

ISRU↗

Molecular Dynamics Simulation of Complex Reactivity with the Rapid Approach for Proton Transport and Other Reactions (RAPTOR) Software Package

Simulating chemically reactive phenomena such as proton transport on nanosecond to microsecond and beyond time scales is a challenging task. Ab initio methods are unable to currently access these time scales routinely, and traditional molecular dynamics methods feature fixed bonding arrangements that cannot account for changes in the system’s bonding topology. The Multiscale Reactive Molecular Dynamics (MS-RMD) method, as implemented in the Rapid Approach for Proton Transport and Other Reactions (RAPTOR) software package for the LAMMPS molecular dynamics code, offers a method to routinely sample longer time scale reactive simulation data with statistical precision. RAPTOR may also be interfaced with enhanced sampling methods to drive simulations toward the analysis of reactive rare events, and a number of collective variables (CVs) have been developed to facilitate this. Key advances to this methodology, including GPU acceleration efforts and novel CVs to model water wire formation are reviewed, along with recent applications of the method which demonstrate its versatility and robustness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗