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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The generation of gridded emissions data for CMIP6

Abstract. Spatially distributed anthropogenic and open burning emissions are fundamental data needed by Earth system models. We describe the methods used for generating gridded datasets produced for use by the modeling community, particularly for the Coupled Model Intercomparison Project Phase 6. The development of three sets of gridded data for historical open burning, historical anthropogenic, and future scenarios was coordinated to produce consistent data over 1750–2100. Historical data up to 2014 were provided with annual resolution and future scenario data in 10-year intervals. Emissions are provided on a sectoral basis, along with additional files for speciated non-methane volatile organic compounds (NMVOCs). An automated framework was developed to produce these datasets to ensure that they are reproducible and facilitate future improvements. We discuss the methodologies used to produce these data along with limitations and potential for future work.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1997

New Anti-Corrosive Coatings with Resin-Bonded Polyaniline and Related Electroactive Groups

It is already known that polyaniline (an electroactive polymer) functions as a corrosion inhibitor for steel and in view of the fact that it is known to perform in the presence of hydrochloric acid, it has been considered likely that it may be useful to NASA for protecting launch structures at KSC which are exposed to not only continual ocean-side salt spray but also to hydrochloric acid at the times that solid-fuel boosters are fired. The currently used zinc-rich silicate-bonded coating is not wholly protective against the hydrochloric acid. Water pollution from zinc salts is another concern. Other earlier and concurrent NASA sponsored projects have been focussed on polyaniline specifically. Our project, administered for NASA by Dr. K. Thompson of KSC and these more-specifically polyaniline-related projects are included in a CRADA coordinated by Dr. F. Via of Akzo Nobel. A parallel project at Polytechnic under Prof K. Levon concentrated more specifically on polyaniline with various dopants. Our exploratory project reported herein was aimed at broadening the range of such corrosion inhibitors, to give protective paint compounders a wider latitude for adding corrosion inhibitors having polyaniline-like performance, and thus we diverged in several probing directions from polyaniline. Our working hypothesis was that physical variants of polyaniline, such as supported formulations on pigments or carriers, and chemical variants of polyaniline, including those having no electroconductive character, may have enhanced anticorrosion activity. We also hypothesized that small (non-polymeric) molecules having structures related to those occurring in polyaniline, may be active as corrosion inhibitors. We did preliminary testing, using an ASTM salt spray method at a nearby commercial paint testing laboratory. Our most interesting findings were that a non-electroconductive meta-isomer of polyaniline showed some corrosion activity, suggesting that the features of the polyaniline molecule associated with conductivity are not necessary for the anticorrosion action. Also, signtficantly, small molecular weight aromatic diamines and diimines resembling the reduced and the oxidized repeating unit in polyaniline showed an interesting degree of anticorrosive activity, suggesting that the polymeric feature of polyaniline is not necessary for anticorrosion action.

Weil, Edward D.↗
DOE OSTI2023

Cluster-Spin-Glass Magnetic Behavior and Morphology in the Coordination Polymer Alloys Fe y Co 1– y BTT

We report the synthesis of a series of pseudo-1D coordination polymer (CP) materials with the formula Fe y Co 1–y BTT (BTT = 1,3,5-benzenetrithiolate). These materials were structurally characterized by PXRD Rietveld, EXAFS, and PDF analyses, revealing that the CP superstructure enables a continuous and isomorphous alloy between the two homometallic compounds. Lower Fe loadings exhibit emergent spin glass magnetic behavior, such as memory effects and composition-dependent spin glass response time constants ranging from 6.9 × 10 –9 s to 1.8 × 10 –6 s. These data are consistent with the formation of spin clusters within the lattice. The magnetic behavior in these materials was modeled via replica exchange Monte Carlo simulation, which provides a good match for the experimentally measured spin glassing and magnetic phase transitions. Furthermore, these findings underscore how the rigid superstructure of CP and MOF scaffolds can enable the systematic tuning of physical properties, such as the spin glass behavior described here.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Synthesis of Ionic Ultramicroporous Polymers for Selective Separation of Acetylene from Ethylene

The design of highly stable and efficient porous materials is essential for developing breakthrough hydrocarbon separation methods based on physisorption to replace currently used energy-intensive distillation/absorption technologies. Efforts to develop advanced porous materials such as zeolites, coordination frameworks, and organic polymers have met with limited success. Here, a new class of ionic ultramicroporous polymers (IUPs) with high-density inorganic anions and narrowly distributed ultramicroporosity is reported, which are synthesized by a facile free-radical polymerization using branched and amphiphilic ionic compounds as reactive monomers. A covalent and ionic dual-crosslinking strategy is proposed to manipulate the pore structure of amorphous polymers at the ultramicroporous scale. The IUPs exhibit exceptional selectivity (286.1–474.4) for separating acetylene from ethylene along with high thermal and water stability, collaboratively demonstrated by gas adsorption isotherms and experimental breakthrough curves. Modeling studies unveil the specific binding sites for acetylene capture as well as the interconnected ultramicroporosity for size sieving. Finally, the porosity-engineering protocol used in this work can also be extended to the design of other ultramicroporous materials for the challenging separation of other key gas constituents.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Single-Crystal Optical Actuation Generated by 100% SO 2 Linkage Photoisomerization in a Ruthenium-Based Coordination Complex

Single-crystal optical actuators are emerging as a new field of materials chemistry because of their wide-ranging potential applications, from light-induced molecular motors to photosensing technologies. Ruthenium-based coordination complexes that contain sulfur dioxide linkage photoisomers have shown particular promise as optical actuators, given that they may exhibit either optical switching or nano-optomechanical transduction in their single-crystal form. The type of single-crystal optical actuation observed in a specific compound within this family of complexes depends upon the nature of the ligand that lies trans to this SO 2 linkage photoisomer, since this governs the type and extent of photoisomer (η 2 -(OS)O or η 1 -OSO) that will form upon the application of light. We report the discovery of a new complex, trans-[Ru(SO 2 )(NH 3 ) 4 (3-iodopyridine)]tosylate 2 (1), which forms an η 1 -OSO photoisomer with 100% photoconversion upon the application of 505 nm light. The photoisomerization process in the ruthenium-based cation of 1 stimulates rotation and translation of the toluenic constituent of its neighboring anion, thereby affording nano-optomechnical transduction. We show that this η 1 -OSO photoisomer transitions to its more thermally stable η 2 -(OS)O photoisomer with an activation energy, E a , of 11(2) kJ/mol using thermally activated single-crystal optical absorption spectroscopy. The application of external light with different wavelengths to 1 is also shown to cause a variation in its optical absorption spectral characteristics. Here, this suggests that the photophysical properties of 1 may be tunable with light.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Ultrafast Relaxation of MLCT Excited States in Manganese Tricarbonyl Complexes: Insights from Polarization-Resolved Femtosecond X-ray Absorption Spectroscopy at the Mn and Br K-Edges

Optical absorption features that are often described as metal-to-ligand charge transfer (MLCT) bands underlie the utility of many metal coordination complexes by harnessing the energy of light to drive otherwise inaccessible chemical reactions. Excitation of these bands triggers rapid electronic dynamics that can be challenging to understand, due to complicated potential energy landscapes and highly correlated electronic and nuclear degrees of freedom in metal-containing compounds. The lowest-energy absorption bands in Mn complexes containing alpha-diimine, carbonyl, and halide ligands are particularly interesting, due to the delocalized nature of charge transfer upon excitation. Here, in this study, we report experimental ultrafast dynamics measurements for the series of compounds Mn­(CO) 3 ( R bpy)Br ( R bpy = 4,4′-disubstituted-2,2′-bipyridine; R = H, CF 3 , or NO 2 ) using polarization-resolved, femtosecond X-ray absorption spectroscopy (XAS) at both the Mn and Br K edges. The appearance of a new absorption feature in the Br pre-edge spectrum upon optical excitation reveals the instantaneous formation of an electronic hole that is partially localized on the Br atom and has a lifetime that depends on the electron withdrawing character of the R bpy ligand. For two of the complexes (R = H or CF 3 ), a large expansion of the Mn–Br distance results in a rapid redistribution of the hole and a corresponding decrease in anisotropy of the absorption feature within 50 fs, after which the absorption into the hole disappears on a time scale shorter than 300 fs. We observe a different result for the NO 2 substituted compound, for which the Mn–Br bond contracts and the absorption into the Br-centered hole persists beyond the 2 ps time scale of our measurement. The Mn pre-edge spectrum also reveals structural changes for these three complexes, but the new Mn absorption features become evident only after the nuclei respond to the initial excitation, which allows mixing of Mn 3d and 4p orbitals. The combined use of ultrafast Mn and Br K-edge spectroscopy provides unique insight into the ways in which bipyridine substitution alters the excited-state dynamics, including a very different structural response for the most strongly electron withdrawing substituent.

Otolski, Christopher J. [Univ. of Kansas, Lawrence↗
DOE OSTI2023

Americium Oxalate: An Experimental and Computational Investigation of Metal–Ligand Bonding

A novel actinide-containing coordination polymer, [Am(C 2 O 4 )(H 2 O) 3 Cl] (Am-1), has been synthesized and structurally characterized. The crystallographic analysis reveals that the structure is two-dimensional and comprised of pseudo-dimeric Am 3+ nodes that are bridged by oxalate ligands to form sheets. Each metal center is nine-coordinate, forming a distorted capped square antiprism geometry with a C 1 symmetry, and features bound oxalate, aqua, and chloro ligands. The Am 3+ –ligand bonds were probed computationally using the quantum theory of atoms in molecules nd natural localized molecular orbital approaches to investigate the underlying mechanisms and hybrid atomic orbital contributions therein. The analyses indicate that the bonds within Am-1 are predominantly ionic and the 5f shell of the Am 3+ metal centers does not add a significant covalent contribution to the bonds. Further, our bonding assessment is supported by measurements on the optical properties of Am-1 using diffuse reflectance and photoluminescence spectroscopies. The position of the principal absorption band at 507 nm ( 5 L 6' ← 7 F 0' ) is notable because it is consistent with previously reported americium oxalate complexes in solution, indicating similarities in the electronic structure and ionic bonding. Compound Am-1 is an active phosphor, featuring strong bright-blue oxalate-based luminescence with no evidence of metal-centered emission.

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

Off-axis representation of hyperbolic mirror shapes for X-ray beamlines

Mirror-centered, closed-form expressions for hyperbolic surfaces used in X-ray beamlines have been derived. Hyperbolic mirrors create a virtual focus or source point and can be used to lengthen or shorten the effective focal distance of a compound optical system. The derivations here express off-axis segments of a hyperbolic surface in terms of the real and virtual focal distances and the incident glancing angle at the center of the mirror. Conventional mathematical expressions of hyperbolic shapes describe the surfaces in Cartesian or polar coordinates centered on an axis of symmetry, necessitating cumbersome rotation and translation to mirror-centered coordinates. The representation presented here, with zero slope and the origin at the central point, is most convenient for modeling, metrology, aberration correction, and general surface analysis of off-axis configurations. The direct derivation avoids the need for nested coordinate transforms. A series expansion provides a helpful approximation; the coefficients of the implicit equation are also provided.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Solution Chemistry of Copper(II) Binding to Substituted 8-Hydroxyquinolines

8-Hydroxyquinolines (8HQs) are a family of lipophilic metal ion chelators that have been used in a range of analytical and pharmaceutical applications over the last 100 years. More recently, CQ (clioquinol; 5-chloro-7-iodo-8-hydroxyquinoline) and PBT2 (5,7-dichloro-2-[(dimethylamino)methyl]-8-hydroxyquinoline) have undergone clinical trials for the treatment of Alzheimer’s disease and Huntington’s disease. Because CQ and PBT2 appear to redistribute metals into cells, these compounds have been redefined as copper and zinc ionophores. Despite the attention surrounding the clinical trials and the clear link between 8HQs and metals, the fundamental solution chemistry of how these compounds bind divalent metals such as copper and zinc, as well as their mechanism(s) of action in mammalian systems, remains poorly understood. Here, we used a combination of X-ray absorption spectroscopy (XAS), high-energy resolution fluorescence detected (HERFD) XAS, electron paramagnetic resonance (EPR), and UV–visible absorption spectroscopies to investigate the aqueous solution chemistry of a range of 8HQ derivatives. To circumvent the known solubility issues with 8HQ compounds and their complexes with Cu(II), and to avoid the use of abiological organic solvents, we have devised a surfactant buffer system to investigate these Cu(II) complexes in aqueous solution. Our study comprises the first comprehensive investigation of the Cu(II) complexes formed with many 8HQs of interest in aqueous solution, and it provides the first structural information on some of these complexes. We find that halogen substitutions in 8HQ derivatives appear to have little effect on the Cu(II) coordination environment; 5,7-dihalogenated 8HQ conformers all have a pseudo square planar Cu(II) bound by two quinolin-8-olate anions, in agreement with previous studies. Conversely, substituents in the 2-position of the 8HQ moiety appear to cause significant distortions from the typical square-planar-like coordination of most Cu(II)-bis-8HQ complexes, such that the 8HQ moieties in the Cu(II)-bis-8HQ complex are rotated approximately 30–40° apart in a “propeller-like” arrangement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Molecular Origins of Near-Infrared Luminescence in Molybdenum and Tungsten Oxyhalide Perovskites

Materials with near-infrared (near-IR) luminescence are desirable for applications in communications and sensing, as well as biomedical diagnostics and imaging. The most used inorganic near-IR emitters rely on precise doping of host crystal structures with select rare-earth or transition metal ions. Recently, another class of materials with intrinsic near-IR emission has been reported. The compositions of these materials were initially described as vacancy-ordered halide double perovskites Cs 2 MoCl 6 and Cs 2 WCl 6 , but further investigation by some of us on the compound reported as Cs2WCl6 revealed an oxyhalide instead, with a composition Cs 2 WO x Cl 6–x , where 1 < x < 2. Here we demonstrate that the Mo compounds similarly possess the composition Cs 2 MoO x Cl 6–x or Cs 2 MoO x Br 6–x where 1 < x < 2. Preparing the pure halide appears harder for Mo than for W, and we have not succeeded in doing so. The distinctly different composition requires the coordination environment and oxidation state for the Mo and W centers to be reconsidered from what was assumed for the pure halides. In this work, we examine the mechanism for near-IR emission in these materials given their true structures and compositions. We demonstrate that the luminescence is due to the specific d-orbital splitting caused by the presence of oxygen in the distorted [MOX 5 ] 2– octahedra (X is Cl or Br). The fine structure in the emission spectra at low temperatures has been resolved and is attributed to vibronic coupling to the Mo–O and W–O bond stretches. Understanding the true structure and composition of these interesting materials, besides explaining the near-IR luminescence, suggests how this desirable emission can be realized and manipulated.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The seventh blind test of crystal structure prediction: structure generation methods

A seventh blind test of crystal structure prediction was organized by the Cambridge Crystallographic Data Centre featuring seven target systems of varying complexity: a silicon and iodine-containing molecule, a copper coordination complex, a near-rigid molecule, a cocrystal, a polymorphic small agrochemical, a highly flexible polymorphic drug candidate, and a polymorphic morpholine salt. In this first of two parts focusing on structure generation methods, many crystal structure prediction (CSP) methods performed well for the small but flexible agrochemical compound, successfully reproducing the experimentally observed crystal structures, while few groups were successful for the systems of higher complexity. A powder X-ray diffraction (PXRD) assisted exercise demonstrated the use of CSP in successfully determining a crystal structure from a low-quality PXRD pattern. The use of CSP in the prediction of likely cocrystal stoichiometry was also explored, demonstrating multiple possible approaches. Crystallographic disorder emerged as an important theme throughout the test as both a challenge for analysis and a major achievement where two groups blindly predicted the existence of disorder for the first time. Additionally, large-scale comparisons of the sets of predicted crystal structures also showed that some methods yield sets that largely contain the same crystal structures.

Chemistry↗
DOE OSTI2024

Manipulating Photoconduction in Cu–Pyrene 1-D Coordination Nanosheets by Modulating Interlayer π–π Stacking

2D conductive metal organic frameworks (MOFs) have become promising candidates for applications in electronic and photoelectronic devices. However, the lack of a fundamental understanding of the charge transport mechanism and synthetic design to alter their conductivity limits their potential applications. In this work, we report the design and synthesis of two 1D Cu–pyrene coordination nanosheets, Cu–pyrene-4,5,9,10 tetrathiol (Cu-PTT) and Cu–2,7-di-tert-butylpyrene-4,5,9,10-tetrathiol (Cu– tBu PTT), as models of 2D conductive MOFs, where the introduction of two different functional groups (H and tert-butyl groups) at the 2 and 7 positions of the PTT ligands is used to tune the interlayer distance and π–π stacking of MOFs. Using optical pump terahertz probe spectroscopy, we show that both nanosheets exhibit appreciable photoconduction, but the photoconduction in Cu– tBu PTT is reduced with respect to that in Cu–PTT, which can be attributed to the larger interlayer distance in the former leading to the decoupling of the interlayer charge transport pathway. Furthermore, these results demonstrate a unique strategy to investigate the impact of out-of-plane extended conjugation on photoconduction in conductive conjugated polymers, MOFs, or coordination nanosheets through adjusting their interlayer spacing.

14 SOLAR ENERGY↗
DOE OSTI2024

Supramolecular Metal Halide Complexes for High-Temperature Nonlinear Optical Switches

Nonlinear optical (NLO) switching materials, which exhibit reversible intensity modulation in response to thermal stimuli, have found extensive applications across diverse fields, including sensing, photoelectronics, and photonic applications. While significant progress has been made in solid-state NLO switching materials, these materials typically showcase their highest NLO performance near room temperature. However, this performance drastically deteriorates upon heating, primarily due to the phase transition undergone by the materials from non-centrosymmetric to centrosymmetric phase. Here, we introduce a new class of NLO switching materials, solid-state supramolecular compounds 18-Crown-6 ether@Cu 2 Cl 4 ·4H 2 O (1·4H 2 O), exhibiting reversible and stable NLO switching when subjected to near-infrared (NIR) photoexcitation and/or thermal stimuli. The reversible crystal structure in response to external stimuli is attributed to the presence of a weakly coordinated bridging water molecule, facilitated by hydrogen bonding/chelation interactions between the metal halide and crown-ether supramolecules. We observed an exceptionally high second-harmonic generation (SHG) signal under continuous photoexcitation, even at temperatures exceeding 110°C. In addition, the bridging water molecules within the complex can be released and recaptured in a fully reversible manner, all without requiring excessive energy input. This feature allows for precise control of SHG signal activation and deactivation through structural transformations, resulting in a high-contrast off/on ratio, reaching values in the million-fold range.

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

Synthesis, characterization, and structure determination of bis-oxazolidine complexes of rhenium

A tetradentate fused bis-oxazolidine ligand (FOX) is used to coordinate to rhenium carbonyl. The ligand binds in a κ 3 -NNN fashion to a Re(CO) 3 + fragment, giving an octahedral complex. The hydroxymethyl group can be deprotonated with CsOH, leading to a κ 3 -ONN variation in the binding of the ligand. Furthermore, loss of CO from this compound proved difficult, impeding further reactivity.

09 BIOMASS FUELS↗
NASA NTRS1995

Coordinated Control Of Mobile Robotic Manipulators

Computationally efficient scheme developed for on-line coordinated control of both manipulation and mobility of robots that include manipulator arms mounted on mobile bases. Applicable to variety of mobile robotic manipulators, including robots that move along tracks (typically, painting and welding robots), robots mounted on gantries and capable of moving in all three dimensions, wheeled robots, and compound robots (consisting of robots mounted on other robots). Theoretical basis discussed in several prior articles in NASA Tech Briefs, including "Increasing the Dexterity of Redundant Robots" (NPO-17801), "Redundant Robot Can Avoid Obstacles" (NPO-17852), "Configuration-Control Scheme Copes With Singularities" (NPO-18556), "More Uses for Configuration Control of Robots" (NPO-18607/NPO-18608).

Seraji, Homayoun↗
NASA NTRS2001

The Crystal and Molecular Structure of Acetatochlorobis(4-methylpyridine)oxovanadium (IV)

The crystal and molecular structure of the title compound, VOCl(O2CCH3)(4-CH3C5H4N)2, has been determined by single-crystal x-ray diffraction. The material crystallizes in the space group P 1(bar) (#2) with a = 7.822(2), b = 8.023(l), c = 14.841(2) Angstroms, alpha = 99.73(l), beta = 91.41(l), and gamma = 117.13(l). The coordination geometry around the vanadium is a highly distorted octahedron. The molecule is remarkable for being a monomeric oxovanadium (IV) carboxylate. A generalized synthetic strategy is proposed for the preparation of oxovanadium (IV) monomers.

Schupp, John D.↗
NASA NTRS1993

Cell proliferation and differentiation in chemical leukemogenesis

In tissues such as bone marrow with normally high rates of cell division, proliferation is tightly coordinated with cell differentiation. Survival, proliferation and differentiation of early hematopoietic progenitor cells depend on the growth factors, interleukin 3 (IL-3) and/or granulocyte-macrophage colony stimulating factor (GM-CSF) and their synergism with other cytokines. We provide evidence that a characteristic shared by a diverse group of compounds with demonstrated leukemogenic potential is the ability to act synergistically with GM-CSF. This results in an increase in recruitment of a resting population of hematopoietic progenitor cells normally unresponsive to the cytokine and a twofold increase in the size of the proliferating cell population normally regarded to be at risk of transformation in leukemogenesis. These findings support the possibility that transient alterations in hematopoietic progenitor cell differentiation may be an important factor in the early stages of development of leukemia secondary to chemical or drug exposure.

Non-NASA Center↗
DOE OSTI2022

Pd and octahedra do not get along: Square planar [PdS 4 ] units in non-centrosymmetric La 6 PdSi 2 S 14

Non-linear optical (NLO) materials require a balance of high second-harmonic generation (SHG) signal and laser damage threshold (LDT), as well as phase matchable behavior. Herein, we report a new member of the (RE) 6 (TM) x (Tt) 2 Q 14 family of compounds, La 6 PdSi 2 S 14 , which, unlike all other reported TM analogues crystallizing in hexagonal P6 3 space group, crystallizes in the non-centrosymmetric monoclinic P2 1 space group. The crystal structure contains chains of edge-sharing distorted square planar [PdS 4 ] units. The square-planar coordination of Pd in La 6 PdSi 2 S 14 exhibits remarkable NLO properties with high SHG (3.7 × AgGaS 2 ) and LDT (3 × AgGaS 2 ) values as well as phase matchability. This shows the promise of novel materials with distorted structural motifs for enhanced NLO properties. Further, upon formation of bimetallic chiral sulfides containing both Cu and Pd, Cu occupies the opposite faces of the octahedra forming [CuS 3 ] units while Pd can be stabilized in the center of PdS 6 octahedra in the hexagonal P6 3 crystal structure of La 6 Pd 0.5 CuSi 2 S 14 . This suggests that it is possible to form mixed metal systems which could further enhance NLO properties by incorporation of additional structural distortions.

36 MATERIALS SCIENCE↗