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At least 1,045 records · Page 58
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Describing functional requirements for knowledge sharing communities

Human collaboration in distributed knowledge sharing groups depends on the functionality of information and communication technologies (ICT) to support performance. Since many of these dynamic environments are constrained by time limits, knowledge must be shared efficiently by adapting the level of information detail to the specific situation. This paper focuses on the process of knowledge and context sharing with and without mediation by ICT, as well as issues to be resolved when determining appropriate ICT channels. Both technology-rich and non-technology examples are discussed.

NASA Discipline Space Human Factors↗
NASA NTRS2016

Efficiency Management in Spaceflight Systems

Efficiency in spaceflight is often approached as “faster, better, cheaper – pick two”. The high levels of performance and reliability required for each mission suggest that planners can only control for two of the three. True efficiency comes by optimizing a system across all three parameters. The functional processes of spaceflight become technical requirements on three operational groups during mission planning: payload, vehicle, and launch operations. Given the interrelationships among the functions performed by the operational groups, optimizing function resources from one operational group to the others affects the efficiency of those groups and therefore the mission overall. This paper helps outline this framework and creates a context in which to understand the effects of resource trades on the overall system, improving the efficiency of the operational groups and the mission as a whole. This allows insight into and optimization of the controlling factors earlier in the mission planning stage.

Murphy, Karen↗
NASA NTRS2016

Efficiency Management in Spaceflight Systems

Efficiency in spaceflight is often approached as "faster, better, cheaper - pick two". The high levels of performance and reliability required for each mission suggest that planners can only control for two of the three. True efficiency comes by optimizing a system across all three parameters. The functional processes of spaceflight become technical requirements on three operational groups during mission planning: payload, vehicle, and launch operations. Given the interrelationships among the functions performed by the operational groups, optimizing function resources from one operational group to the others affects the efficiency of those groups and therefore the mission overall. This paper helps outline this framework and creates a context in which to understand the effects of resource trades on the overall system, improving the efficiency of the operational groups and the mission as a whole. This allows insight into and optimization of the controlling factors earlier in the mission planning stage.

Murphy, Karen↗
DOE OSTI2021

Spontaneous rearrangement of acetylated xylan on hydrophilic cellulose surfaces

The interaction of xylan, an abundant plant polysaccharide, with cellulose microfibrils is essential for secondary cell wall strength. A deeper understanding of these interactions is crucial both to improve our understanding of plant cell wall architecture and to design alternate strategies to overcome cellulose recalcitrance for the production of biofuels and sustainable biomaterials. Naturally occurring acetate or glucuronic acid substitutions on xylan have been shown to influence xylan-cellulose interactions. In this work, we use unrestrained molecular dynamics simulations to determine the interactions with the (110) hydrophilic face of cellulose fibers of four different xylans. In the absence of cellulose, all xylans, independent of the substitution pattern, adopt a highly flexible threefold helical screw conformation. However, when xylan is spatially close to a cellulose surface 1,2 linked acetyl xylans (2AcX) adopt rigid twofold helical screw conformations. The 2AcX conformations are primarily stabilized by interactions between the acetylated oxygen and the glycosidic linkage with C-O6 of cellulose. In contrast, the glycosidic oxygens and acetyl decorations for 1,3 linked acetyl groups (3AcX) are oriented away from the cellulose surface and the 3AcX xylans maintain threefold helical screw conformations on the cellulose surface. Our results show that evenly spaced chemical functionalization (with acetyl groups) and the position of substitution (1,2) on xylan backbone play key roles in tuning the xylan-cellulose interactions to stabilize the twofold helical screw conformations of xylan on the cellulose surface. A comparison with previous experimental findings further suggests that 1,2 substitutions induce twofold helical screw conformations of xylan on the cellulose surface irrespective of the chemical nature of the substituent, while 1,3 substitutions primarily bind lignin in threefold helical screw conformations rather than cellulose in plant cell walls.

1,2 Ac↗
DOE OSTI2026

Distinguishing Leptothrix and Sphaerotilus genera by an integrated genomic-phenotypic analysis supported by new Leptothrix genomes

The Sphaerotilus-Leptothrix group of bacteria includes one of the first described microorganisms, Leptothrix ochracea, an uncultured type strain, plus isolates of Leptothrix and Sphaerotilus. This group is unified by the ability to form sheaths and oxidize metals, although L. ochracea exhibits obvious ecological, morphological, and functional differences from the rest of Sphaerotilus-Leptothrix. Recently, there have been calls to combine the group into one genus, Sphaerotilus; however, these studies lacked adequate genomic representation of L. ochracea. Here, we present a comprehensive comparative genomic analysis of the Sphaerotilus-Leptothrix group, including expanded representation of L. ochracea, a closely related novel species, Leptothrix toolikensis, and two new isolates (Leptothrix mechoopdaensis). Analysis of 38 genomes resolves three phylogenetic and functional groups: the ochracea-type Leptothrix (Group 1), the mobilis-type Leptothrix (Group 2), and Sphaerotilus (Group 3). Group 1 genomes form a separate genus based on average nucleotide identity and alignment fraction. The genomes clearly diverge from the rest of Sphaerotilus-Leptothrix in phylogeny, size, and metabolic potential. Group 1 genomes are much smaller (2.59–3.04 Mb) than those of Groups 2 (4.55–6.06 Mb) and 3 (3.94–5.07 Mb), while encoding more metal oxidases and fewer carbohydrate-active enzymes. Group 2 clusters with Group 3 phylogenetically and is similar in organic carbon metabolisms but maintains more metal oxidation genes. Group 2 members lack homogeneity in phenotype and genotype, suggesting that additional isolates and genomes are needed for confident classification. However, Group 1 genomes (L. ochracea and L. toolikensis) show clear divergence, precluding their inclusion in Sphaerotilus and supporting the retention of the genus Leptothrix.

Leptothrix↗
DOE OSTI2020

The Bonding Nature and Adhesion of Polyacrylic Acid Coating on Li-Metal for Li Dendrite Prevention

The success of polyacrylic acid (PAA) to suppress Li dendrite growth suggests that the mechanical properties of polymer-based coatings, including the modulus, toughness, and interfacial adhesion are important design criteria. However, the measurement of the adhesion of thin PAA, as well as other polymer coatings to the reactive Li-metal anode surface is limited experimentally and challenging computationally. In this paper, a strategy was proposed to estimate the adhesion and delamination of the PAA(polymer)/Li interface, based on the bonding nature at the simpler PAA (oligomer)/Li interfaces using density functional theory calculations. It has been shown that the carboxylic acid groups in PAA reacted strongly with metallic Li, which significantly enhances the interfacial adhesion through the Li–O bonds formation, Li ionization and its incorporation into PAA, and –H or –OH termination of Li after decomposition of the COOH functional group. During delamination, it was found that the most likely PAA delamination route involved breaking partial Li–O bonds and lifting some ionized Li atoms from the Li-metal, especially for the Li atoms that showed a charge closer to +1 or are bonded with two O atoms from PAA. Based on the average bonding energies from PAA(oligomer)/Li interface delamination calculations, the work of separation, W sep , of the PAA(polymer)/Li interface was estimated to be ~1.0 (J/m 2 ). The high W sep of PAA (polymer)/Li was comparable with the Li 2 O/Li interface and higher than Li 2 CO 3 /Li and LiF/Li interfaces. This order correlated well with the areal density of Li–O bonds, which can serve as a descriptor for the interfacial adhesion. Furthermore, this computational approach can be applied to other interfaces with polymer-based coatings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Room temperature colossal superparamagnetic order in aminoferrocene–graphene molecular magnets

Intensive studies are published for graphene-based molecular magnets due to their remarkable electric, thermal, and mechanical properties. However, to date, most of all produced molecular magnets are ligand based and subject to challenges regarding the stability of the ligand(s). The lack of long-range coupling limits high operating temperature and leads to a short-range magnetic order. Herein, we introduce an aminoferrocene-based graphene system with room temperature superparamagnetic behavior in the long-range magnetic order that exhibits colossal magnetocrystalline anisotropy of 8 × 10 5 and 3 × 10 7 J/m 3 in aminoferrocene and graphene-based aminoferrocene, respectively. These values are comparable to and even two orders of magnitude larger than pure iron metal. Aminoferrocene [C 10 H 11 FeN] + is synthesized by an electrophilic substitution reaction. It was then reacted with graphene oxide that was prepared by the modified Hammers method. The phase structure and functionalization of surface groups were characterized and confirmed by XRD, FT-IR, and Raman spectroscopy. To model the behavior of the aminoferrocene between two sheets of hydroxylated graphene, we have used density functional theory by placing the aminoferrocene molecule between two highly ordered hydroxylated sheets and allowing the structure to relax. Here, the strong bowing of the isolated graphene sheets suggests that the charge transfer and resulting magnetization could be strongly influenced by pressure effects. In contrast to strategies based on ligands surface attachment, our present work that uses interlayer intercalated aminoferrocene opens routes for future molecular magnets as well as the design of qubit arrays and quantum systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1992

Chemical and physical studies of chondrites. X - Cathodoluminescence and phase composition studies of metamorphism and nebular processes in chondrules of type 3 ordinary chondrites

The cathodoluminescence (CL) characteristics of eight type-3 ordinary chondrites and one L5 chondrite were investigated with particular emphasis on detailed compositions of the relevant phases in four of these chondrites: Semarkona (type-3.0); Krymka (3.1); Allan Hills A77214 (3.5); and Dhajala (3.8). By sorting the chondrules into eight groups according to the CL of mesostasis and to certain compositional criteria and by determining the number of chondrules in these groups as a function of petrological type, it was possible to deduce genetic/evolutionary sequences of the chondrules. It is shown that there are major compositional differences in chondrules, which account for their CL properties and the chondrule groups.

Dehart, John M.↗
DOE OSTI2022

Conditional H I Mass Functions and the H I -to-halo Mass Relation in the Local Universe

We present a new H I mass estimator that relates log 10 (M HI /M * ) to a linear combination of four galaxy properties: stellar surface mass density, color index u - r, stellar mass, and concentration index, with the scatter of individual galaxies around the mean H I mass modeled with a Gaussian distribution function. We calibrate the estimator using the xGASS sample, including both H I detection and nondetection, and constrain the model parameters through Bayesian inferences. Tests with mock catalogs demonstrate that our estimator provides unbiased H I masses for optical samples like SDSS. We apply our estimator to the SDSS spectroscopic sample to estimate the H I mass function (HIMF) of local galaxies, as well as the conditional H I mass function in galaxy groups and the H I –halo mass relation. Our HIMF agrees with the ALFALFA measurements at M HI ≳ 5 × 10 9 M ⊙ , but with higher amplitude and a steeper slope at lower masses. We show that this discrepancy is caused primarily by the cosmic variance, which is corrected for the SDSS sample but not for ALFALFA. The total CHIMFs for all halo masses can be described by a single Schechter function, while those of central galaxies show a double-Gaussian profile. The total H I mass in a group increases monotonically with halo mass, but for central galaxies, the H I mass shows weak dependence on halo mass when M h ≳ 10 12 M ⊙ . The observed H I –halo mass relation is not reproduced by current hydrodynamic simulations and semianalytic models of galaxy formation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Linkage Transformations in a Three-Dimensional Covalent Organic Framework for High-Capacity Adsorption of Perfluoroalkyl Substances

Despite their many advantages, covalent organic frameworks (COFs) built from three-dimensional monomers are synthetically difficult to functionalize. Herein, we provide a new synthetic approach to the functionalization of a three-dimensional covalent organic framework (COF-300) by using a series of solid-state linkage transformations. By reducing the imine linkages of the framework to amine linkages, we produced a more hydrolytically stable material and liberated a nucleophilic amino group, poised for further functionalization. We then treated the amine-linked COF with diverse electrophiles to generate a library of functionalized materials, which we tested for their ability to adsorb perfluoroalkyl substances (PFAS) from water. The framework functionalized with dimethylammonium groups, COF-300-dimethyl, adsorbed more than 250 mg of perfluorooctanoic acid (PFOA) per 1 g of COF, which represents an approximately 14,500-fold improvement over that of COF-300 and underscores the importance of electrostatic interactions to PFAS adsorption performance. In conclusion, this work provides a conceptually new approach to the design and synthesis of functional three-dimensional COFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Measuring the X-ray luminosities of DESI groups from eROSITA Final Equatorial-Depth Survey – I. X-ray luminosity–halo mass scaling relation

ABSTRACT We use the eROSITA Final Equatorial-Depth Survey (eFEDS) to measure the rest-frame 0.1–2.4 keV band X-ray luminosities of ∼600 000 DESI groups using two different algorithms in the overlap region of the two observations. These groups span a large redshift range of 0.0 ≤ zg ≤ 1.0 and group mass range of $10^{10.76}\, h^{-1}\, \mathrm{M}_{\odot } \le M_h \le 10^{15.0}\, h^{-1}\, \mathrm{M}_{\odot }$. (1) Using the blind detection pipeline of eFEDS, we find that 10932 X-ray emission peaks can be cross-matched with our groups, ∼38 per cent of which have a signal-to-noise ratio $\rm {S}/\rm {N} \ge 3$ in X-ray detection. Comparing to the numbers reported in previous studies, this matched sample size is a factor of ∼6 larger. (2) By stacking X-ray maps around groups with similar masses and redshifts, we measure the average X-ray luminosity of groups as a function of halo mass in five redshift bins. We find that in a wide halo mass range, the X-ray luminosity, LX, is roughly linearly proportional to Mh and quite independent to the redshift of the groups. (3) We use a Poisson distribution to model the X-ray luminosities obtained using two different algorithms and obtain the best-fit $L_{\rm X}=10^{28.46\pm 0.03}M_{\rm h}^{1.024\pm 0.002}$ and $L_{\rm X}=10^{26.73 \pm 0.04}M_{\rm h}^{1.140 \pm 0.003}$ scaling relations, respectively. The best-fit slopes are flatter than the results previously obtained but closer to a self-similar prediction.

Astronomy & Astrophysics↗
NASA NTRS1980

Multispectral determination of soil moisture

The edited Guymon soil moisture data collected on August 2, 5, 14, 17, 1978 were grouped into four field cover types for statistical analysis. These are the bare, milo with rows parallel to field of view, milo with rows perpendicular to field of view and alfalfa cover groups. There are 37, 22, 24 and 14 observations respectively in each group for each sensor channel and each soil moisture layer. A subset of these data called the 'five cover set' (VEG5) limited the scatterometer data to the 15 deg look angle and was used to determine discriminant functions and combined group regressions.

Estes, J. E.↗
DOE OSTI2021

Controlled cyclization of peptoids to form chiral diketopiperazines

The present disclosure provides improved methods for controlled cyclization of peptoid dimers to form N,N′-2,5-diketopiperazines (N,N′-2,5-DKPs) with significant selectivity. In at least some examples, selectivity is based on a serendipitous conglomeration of slow exchange of amide rotamers, steric repulsion from the degree of α-substitution, and the geometric bulk of an amine nucleophile. By varying reaction conditions, the selectivity of the reaction and formation of a particular N,N′-2,5-DKP can be switched. The cyclization works in the presence of a variety of protection groups and diverse functionalities. The teachings herein provide techniques for synthesizing N,N′-2,5-DKPs that can be readily docked with drug candidates for shuttling across the blood brain barrier. This method provides a facile way to produce substituted DKPs containing groups ready for post-modification to include docking drug candidates.

Williams, Robert F.↗
DOE OSTI2025

Comparing the Effects of Side Chain Dipole–Dipole Interactions and Hydrogen Bonding on the Mechanical and Electrical Properties of Poly(3-hexylthiophene)

Poly(3-alkylthiophenes) are simple conjugated polymers with good electrical properties, but tend to be brittle, limiting their application. Here, we investigate how side chain modifications can improve their toughness without compromising their charge transport. Specifically, we compare a weak dipole–dipole interaction of ester groups with a stronger hydrogen-bonding interaction of the hydroxyl groups. Two copolymers with targeted 5 and 10 mol % ester-functionalized side chains were synthesized and hydrolyzed in the solid state to introduce hydroxyl groups. Both hydrolyzed polymers became insoluble in most organic solvents, providing a path to layer-by-layer solution processing. All polymers’ optical, thermal, structural, electrical, and mechanical properties were investigated. Optical spectroscopy revealed that functionalization at these low levels did not significantly affect aggregation or π–π stacking. Differential scanning calorimetry indicated reduced crystallinity in the functionalized copolymers compared to that of P3HT. Grazing-incidence wide-angle X-ray diffraction data showed that functionalization led to an increase in lamellar spacing without altering molecular orientation or π–π stacking. Mechanical testing highlighted that at the lower functionalization level, both ester and hydroxyl groups similarly enhanced toughness, suggesting that disorder, rather than the specific nature of the functional group, was responsible for these improvements. At the higher functionalization level, hydroxyl groups significantly increased the elastic modulus while also negatively impacting charge carrier mobility. This study suggests that with stronger hydrogen-bonding groups, only very small amounts can improve P3HT’s toughness. For a wider tunable range, it may be a better strategy to use weak interactions such as dipole–dipole interactions of ester groups.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Post-Modification of Crystalline Peptoid Nanomembranes with Active Nanoparticles for Efficient Photooxidation of a Mustard Gas Simulant

Peptoids (or poly-N-substituted glycines) hold immense potential for assembling into hierarchically structured functional materials via controlled molecular interactions. To create self-assembled materials with tailored functionalities, peptoid sequences are often conjugated with reactive or recognition motifs to enable applications including specific binding, biomimetic catalysis, and fluorescence imaging. However, the direct integration of bulky functional motifs into peptoid sequences can disrupt assembly processes and structural outcomes. Herein, we present a post-modification strategy for functionalizing pre-formed 2D crystalline assemblies. Through introducing clickable active sites, such as azide, alkyne, or thiol groups into a peptoid sequence, site-specific conjugation is achieved post-assembly via efficient “click”-type reactions. This strategy enables the ordered alignment of functional groups and gold nanoparticles (Au NPs) on the surface of 2D peptoid nanomaterials with controlled density, while preserving their high crystallinity and structural integrity. Furthermore, we demonstrated that nanomembranes functionalized with both Au NPs and porphyrins enhance the efficiency and selectivity of the photooxidation of 2-chloroethyl ethyl sulfide, a simulant of sulfur mustard. This innovative strategy lays the groundwork for advancing peptoid-based functional materials across diverse applications, from catalysis to biomedicine.

Chemistry↗
DOE OSTI2021

Maximized Hole Trapping in a Polystyrene Transistor Dielectric from a Highly Branched Iminobis(aminoarene) Side Chain

We synthesized highly branched and electron donating side chain subunits and attached them to polystyrene (PS) used as a dielectric layer in a pentacene field effect transistor. The influence of these groups on dielectric function, charge retention and threshold voltage shifts (ΔV th ) depending on their positions in dielectric multilayers was determined. We compared the observations made on an N-perphenylated iminobisaniline side chain with those from the same side chains modified with ZnO nanoparticles and with an adduct formed from tetracyanoethylene (TCNE). We also synthesized an analogue in which six methoxy groups are present instead of two amine nitrogens. At 6 mol % side chain, hopping transport was sufficient to cause shorting of the gate, while at 2 mol %, charge trapping was observable as transistor threshold voltage shifts (ΔV th ). Here, we created three types of devices: with the substituted PS layer as single layer dielectric, on top of a crosslinked PS layer but in contact with the pentacene (bilayers), and sandwiched between two PS layers in trilayers. Particularly large bias stress effects and ΔV th , larger than the hexamethoxy and previously studied dimethoxy analogs, were observed in the second case and the effects increased with the increasing electron donating properties of the modified side chains. The highest ΔV th was consistent with a majority of the side chains stabilizing trapped charge. Trilayer devices showed decreased charge storage capability compared to previous work in which we used less donating side chains but in higher concentrations. The ZnO and TCNE modifications resulted in slightly more and less negative ΔV th , respectively, when the side chain polystyrene was not in contact with the pentacene and isolated from the gate electrode. The results indicate a likely maximum combination of molecular charge stabilizing activity and side chain concentration that still allows gate dielectric function.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Aryl Diazonium-Assisted Amidoximation of MXene for Boosting Water Stability and Uranyl Sequestration via Electrochemical Sorption

Despite that two-dimensional transition metal carbides and carbonitrides (MXenes) are burgeoning candidates for remediation of environmental pollutants, the construction of robust functionalized MXene nanosheets with a high affinity for target heavy metal ions and radionuclides remains a challenge. Here we report the successful placement of amidoxime chelating groups on Ti 3 C 2 T x MXene surface by diazonium salt grafting. The introduction of amidoxime functional groups significantly enhances the selectivity of Ti 3 C 2 T x nanosheets for uranyl ions and also greatly improves their stability in aqueous solution, enabling efficient, rapid, and recyclable uranium extraction from aqueous solutions containing competitive metal ions. Benefiting from the excellent conductivity of MXenes, the amidoxime functionalized Ti 3 C 2 T x nanosheets show outstanding electrochemical performance such that when loaded on carbon cloth the application of an electric field increases the uranium adsorption capacity from 294 to 626 mg/g, outperforming all organic electrochemical sorption materials reported previously. Finally, the present work provides an effective strategy to functionalize MXene nanosheets with fundamental implications for the design of MXene-based selective electrosorption electrode materials.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries

Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si–R or Si–O–R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g –1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. In conclusion, the effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.

25 ENERGY STORAGE↗