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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 163 records · Page 9

The ALI-ARMS Code for Modeling Atmospheric non-LTE Molecular Band Emissions: Current Status and Applications

The Accelerated Lambda Iteration (ALI) technique was developed in stellar astrophysics at the beginning of 1990s for solving the non-LTE radiative transfer problem in atomic lines and multiplets in stellar atmospheres. It was later successfully applied to modeling the non-LTE emissions and radiative cooling/heating in the vibrational-rotational bands of molecules in planetary atmospheres. Similar to the standard lambda iterations ALI operates with the matrices of minimal dimension. However, it provides higher convergence rate and stability due to removing from the iterating process the photons trapped in the optically thick line cores. In the current ALI-ARMS (ALI for Atmospheric Radiation and Molecular Spectra) code version additional acceleration of calculations is provided by utilizing the opacity distribution function (ODF) approach and "decoupling". The former allows replacing the band branches by single lines of special shape, whereas the latter treats non-linearity caused by strong near-resonant vibration-vibrational level coupling without additional linearizing the statistical equilibrium equations. Latest code application for the non-LTE diagnostics of the molecular band emissions of Earth's and Martian atmospheres as well as for the non-LTE IR cooling/heating calculations are discussed.

Kutepov, A. A.↗

Targeted Adjusting Molecular Arrangement in Organic Solar Cells via a Universal Solid Additive

The incorporation of solid additive has been considered as an effective strategy for developing organic photovoltaics with multi-components, which is independent of dynamics, playing unique roles in morphology adjustment. However, their complex working mechanisms involving specific chemical structures are selective to material systems, hence limiting their university and flexibility in application. Herein, an inert small-molecular compound naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NT) is introduced into the bulk-heterojunction blend as the solid additive, which can function with various material systems and solvents, depending on its simple π-conjugated structure and S⋯N interaction for adjusting molecular alignment. It is interesting to note that the introduced NT can not only improve device performance, but also simplify complicated pre- or post-processing methods, reduce impact from batch-to-batch differences, construct sufficient energy transfer channel as well as improve device stability. The resulting devices based on PTzBI-dF:Y6-BO system show an impressive power conversion efficiency of 17.4% with obviously enhanced T 80 lifetime of >1200 h. These findings provide useful guidelines for exploring potential universal solid additives benefitting toward commercial application.

36 MATERIALS SCIENCE↗

Molecular-Based Optical Measurement Techniques for Transition and Turbulence in High-Speed Flow

High-speed laminar-to-turbulent transition and turbulence affect the control of flight vehicles, the heat transfer rate to a flight vehicle's surface, the material selected to protect such vehicles from high heating loads, the ultimate weight of a flight vehicle due to the presence of thermal protection systems, the efficiency of fuel-air mixing processes in high-speed combustion applications, etc. Gaining a fundamental understanding of the physical mechanisms involved in the transition process will lead to the development of predictive capabilities that can identify transition location and its impact on parameters like surface heating. Currently, there is no general theory that can completely describe the transition-to-turbulence process. However, transition research has led to the identification of the predominant pathways by which this process occurs. For a truly physics-based model of transition to be developed, the individual stages in the paths leading to the onset of fully turbulent flow must be well understood. This requires that each pathway be computationally modeled and experimentally characterized and validated. This may also lead to the discovery of new physical pathways. This document is intended to describe molecular based measurement techniques that have been developed, addressing the needs of the high-speed transition-to-turbulence and high-speed turbulence research fields. In particular, we focus on techniques that have either been used to study high speed transition and turbulence or techniques that show promise for studying these flows. This review is not exhaustive. In addition to the probe-based techniques described in the previous paragraph, several other classes of measurement techniques that are, or could be, used to study high speed transition and turbulence are excluded from this manuscript. For example, surface measurement techniques such as pressure and temperature paint, phosphor thermography, skin friction measurements and photogrammetry (for model attitude and deformation measurement) are excluded to limit the scope of this report. Other physical probes such as heat flux gauges, total temperature probes are also excluded. We further exclude measurement techniques that require particle seeding though particle based methods may still be useful in many high speed flow applications. This manuscript details some of the more widely used molecular-based measurement techniques for studying transition and turbulence: laser-induced fluorescence (LIF), Rayleigh and Raman Scattering and coherent anti-Stokes Raman scattering (CARS). These techniques are emphasized, in part, because of the prior experience of the authors. Additional molecular based techniques are described, albeit in less detail. Where possible, an effort is made to compare the relative advantages and disadvantages of the various measurement techniques, although these comparisons can be subjective views of the authors. Finally, the manuscript concludes by evaluating the different measurement techniques in view of the precision requirements described in this chapter. Additional requirements and considerations are discussed to assist with choosing an optical measurement technique for a given application.

Bathel, Brett F.↗

Multicopy suppressor screens reveal convergent evolution of single-gene lysis proteins

Single-strand RNA (ssRNA) Fiersviridae phages cause host lysis with a product of single gene (sgl for single-gene lysis; product Sgl) that induces autolysis. Many different Sgls have been discovered, but the molecular targets of only a few have been identified. In this study, we used a high-throughput genetic screen to uncover genome-wide host suppressors of diverse Sgls. In addition to validating known molecular mechanisms, we discovered that the Sgl of PP7, an ssRNA phage of Pseudomonas aeruginosa, targets MurJ, the flippase responsible for lipid II export, previously shown to be the target of the Sgl of coliphage M. These two Sgls, which are unrelated and predicted to have opposite membrane topology, thus represent a case of convergent evolution. We extended the genetic screens to other uncharacterized Sgls and uncovered a common set of multicopy suppressors, suggesting that these Sgls act by the same or similar mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of poly(ethylene glycol) hydrogel microstructures using photolithography

The fabrication of hydrogel microstructures based upon poly(ethylene glycol) diacrylates, dimethacrylates, and tetraacrylates patterned photolithographically on silicon or glass substrates is described. A silicon/silicon dioxide surface was treated with 3-(trichlorosilyl)propyl methacrylate to form a self-assembled monolayer (SAM) with pendant acrylate groups. The SAM presence on the surface was verified using ellipsometry and time-of-flight secondary ion mass spectrometry. A solution containing an acrylated or methacrylated poly(ethylene glycol) derivative and a photoinitiator (2,2-dimethoxy-2-phenylacetophenone) was spin-coated onto the treated substrate, exposed to 365 nm ultraviolet light through a photomask, and developed with either toluene, water, or supercritical CO2. As a result of this process, three-dimensional, cross-linked PEG hydrogel microstructures were immobilized on the surface. Diameters of cylindrical array members were varied from 600 to 7 micrometers by the use of different photomasks, while height varied from 3 to 12 micrometers, depending on the molecular weight of the PEG macromer. In the case of 7 micrometers diameter elements, as many as 400 elements were reproducibly generated in a 1 mm2 square pattern. The resultant hydrogel patterns were hydrated for as long as 3 weeks without delamination from the substrate. In addition, micropatterning of different molecular weights of PEG was demonstrated. Arrays of hydrogel disks containing an immobilized protein conjugated to a pH sensitive fluorophore were also prepared. The pH sensitivity of the gel-immobilized dye was similar to that in an aqueous buffer, and no leaching of the dye-labeled protein from the hydrogel microstructure was observed over a 1 week period. Changes in fluorescence were also observed for immobilized fluorophore labeled acetylcholine esterase upon the addition of acetyl acholine.

NASA Discipline Life Sciences Technologies↗

Motility of Synthetic Cells from Engineered Lipids

Synthetic cells are artificial systems that resemble natural cells. Significant efforts have been made over the years to construct synthetic protocells that can mimic biological mechanisms and perform various complex processes. These include compartmentalization, metabolism, energy supply, communication, and gene reproduction. Cell motility is also of great importance, as nature uses elegant mechanisms for intracellular trafficking, immune response, and embryogenesis. In this review, we discuss the motility of synthetic cells made from lipid vesicles and relevant molecular mechanisms. Synthetic cell motion may be classified into surface-based or solution-based depending on whether it involves interactions with surfaces or movement in fluids. Collective migration behaviors have also been demonstrated. The swarm motion requires additional mechanisms for intercellular signaling and directional motility that enable communication and coordination among the synthetic vesicles. In addition, intracellular trafficking for molecular transport has been reconstituted in minimal cells with the help of DNA nanotechnology. These efforts demonstrate synthetic cells that can move, detect, respond, and interact. Finally, we envision that new developments in protocell motility will enhance our understanding of biological processes and be instrumental in bioengineering and therapeutic applications.

59 BASIC BIOLOGICAL SCIENCES↗

High-Resolution Spectroscopic Database for the NASA Earth Observing System Program

The purpose of this project is to develop and enhance the HITRAN molecular spectroscopic database and associated software to support the observational programs of the Earth Observing System (EOS). In particular, the focus is on the EOS projects: the Atmospheric Infrared Sounder (AIRS), the High-Resolution Dynamics Limb Sounder (HIRDLS), Measurements of Pollution in the Troposphere (MOPITT), the Tropospheric Emission Spectrometer (TES), and the Stratospheric Aerosol and Gas Experiment (SAGE III). The data requirements of these programs in terms of spectroscopy are varied, but usually call for additional spectral parameters or improvements to existing molecular bands. In addition, cross-section data for heavier molecular species must be expanded and made amenable to modeling in remote sensing. The effort in the project also includes developing software and distribution to make access, manipulation, and use of HITRAN functional to the EOS program.

Rothman, Laurence S.↗

Data and scripts associated with a manuscript investigating impacts of solid phase extraction on freshwater organic matter optical signatures and mass spectrometry pairing

This data package is associated with the publication “Investigating the impacts of solid phase extraction on dissolved organic matter optical signatures and the pairing with high-resolution mass spectrometry data in a freshwater system” submitted to “Limnology and Oceanography: Methods.” This data is an extension of the River Corridor and Watershed Biogeochemistry SFA’s Spatial Study 2021 (https://doi.org/10.15485/1898914). Other associated data and field metadata can be found at the link provided. The goal of this manuscript is to assess the impact of solid phase extraction (SPE) on the ability to pair ultra-high resolution mass spectrometry data collected from SPE extracts with optical properties collected on ambient stream samples. Forty-seven samples collected from within the Yakima River Basin, Washington were analyzed dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC), absorbance, and fluorescence. Samples were subsequently concentrated with SPE and reanalyzed for each measurement. The extraction efficiency for the DOC and common optical indices were calculated. In addition, SPE samples were subject to ultra-high resolution mass spectrometry and compared with the ambient and SPE generated optical data. Finally, in addition to this cross-platform inter-comparison, we further performed and intra-comparison among the high-resolution mass spectrometry data to determine the impact of sample preparation on the interpretability of results. Here, the SPE samples were prepared at 40 milligrams per liter (mg/L) based on the known DOC extraction efficiency of the samples (ranging from ~30 to ~75%) compared to the common practice of assuming the DOC extraction efficiency of freshwater samples at 60%. This data package folder consists of one main data folder with one subfolder (Data_Input). The main data folder contains (1) readme; (2) data dictionary (dd); (3) file-level metadata (flmd); (4) final data summary output from processing script; and (5) the processing script. The R-markdown processing script (SPE_Manuscript_Rmarkdown_Data_Package.rmd) contains all code needed to reproduce manuscript statistics and figures (with the exception of that stated below). The Data_Input folder has two subfolders: (1) FTICR and (2) Optics. Additionally, the Data_Input folder contains dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data (SPS_NPOC_Summary.csv) and relevant supporting Solid Phase Extraction Volume information (SPS_SPE_Volumes.csv). Methods information for the optical and FTICR data is embedded in the header rows of SPS_EEMs_Methods.csv and SPS_FTICR_Methods.csv, respectively. In addition, the data dictionary (SPS_SPE_dd.csv), file level metadata (SPS_SPE_flmd.csv), and methods codes (SPS_SPE_Methods_codes.csv) are provided. The FTICR subfolder contains all raw FTICR data as well as instructions for processing. In addition, post processed FTICR molecular information (Processed_FTICRMS_Mol.csv) and sample data (Processed_FTICRMS_Data.csv) is provided that can be directly read into R with the associated R-markdown file. The Optics subfolder contains all Absorbance and Fluorescence Spectra. Fluorescence spectra have been blank corrected, inner filter corrected, and undergone scatter removal. In addition, this folder contains Matlab code used to make a portion of Figure 1 within the manuscript, derive various spectral parameters used within the manuscript, and used for parallel factor analysis (PARAFAC) modeling. Spectral indices (SPS_SpectralIndices.csv) and PARAFAC outputs (SPS_PARAFAC_Model_Loadings.csv and SPS_PARAFAC_Sample_Scores.csv) are directly read into the associated R-markdown file. We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected some of these data. We thank the Confederated Tribes and Bands of the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗

Polyphasic taxonomy of the genus Shewanella and description of Shewanella oneidensis sp. nov

The genus Shewanella has been studied since 1931 with regard to a variety of topics of relevance to both applied and environmental microbiology. Recent years have seen the introduction of a large number of new Shewanella-like isolates, necessitating a coordinated review of the genus. In this work, the phylogenetic relationships among known shewanellae were examined using a battery of morphological, physiological, molecular and chemotaxonomic characterizations. This polyphasic taxonomy takes into account all available phenotypic and genotypic data and integrates them into a consensus classification. Based on information generated from this study and obtained from the literature, a scheme for the identification of Shewanella species has been compiled. Key phenotypic characteristics were sulfur reduction and halophilicity. Fatty acid and quinone profiling were used to impart an additional layer of information. Molecular characterizations employing small-subunit 16S rDNA sequences were at the limits of resolution for the differentiation of species in some cases. As a result, DNA-DNA hybridization and sequence analyses of a more rapidly evolving molecule (gyrB gene) were performed. Species-specific PCR probes were designed for the gyrB gene and used for the rapid screening of closely related strains. With this polyphasic approach, in addition to the ten described Shewanella species, two new species, Shewanella oneidensis and 'Shewanella pealeana', were recognized; Shewanella oneidensis sp. nov. is described here for the first time.

NASA Discipline Exobiology↗

Molecular-orbital-based machine learning for open-shell and multi-reference systems with kernel addition Gaussian process regression

We introduce a novel machine learning strategy, kernel addition Gaussian process regression (KA-GPR), in molecular-orbital-based machine learning (MOB-ML) to learn the total correlation energies of general electronic structure theories for closed- and open-shell systems by introducing a machine learning strategy. The learning efficiency of MOB-ML(KA-GPR) is the same as the original MOB-ML method for the smallest criegee molecule, which is a closed-shell molecule with multi-reference characters. In addition, the prediction accuracies of different small free radicals could reach the chemical accuracy of 1 kcal/mol by training on one example structure. Accurate potential energy surfaces for the H10 chain (closed-shell) and water OH bond dissociation (open-shell) could also be generated by MOB-ML(KA-GPR). To explore the breadth of chemical systems that KA-GPR can describe, we further apply MOB-ML to accurately predict the large benchmark datasets for closed- (QM9, QM7b-T, and GDB-13-T) and open-shell (QMSpin) molecules.

Chemistry↗

Development of Processable PMR-Type Polymides with Star-Branched Structures

In the last two decades, high temperature polyimide matrix composites have found broad applications in aerospace structural components, due to their high specific modulus and high specific strength. As matrix resins, aromatic polyimides exhibit exceptional thermal stability and mechanical properties. However, their rodlike structures often result in poor solubility in most common organic solvents, as well as high melt temperature and melt viscosity, making them difficult to process. To overcome this difficulty, flexible linkages including O, SO2 or CH2 non coplanar biphenyl moieties, bulky lateral substituents, and crankshaft structures are often incorporated into the polymer backbones. Addition-curing of low molecular weight polyimides (resins) is another approach to improve processability. One of the most successfully developed materials has been PMR-15 (Polymerization of Monomer Reactants, molecular weight of 1500 g/mol), because of its good combination of thermal and mechanical properties and ease of processability. However, due to the high melt viscosity of PMR-type resins, use of more economical processing methods, such as resin transfer molding (RTM), is not possible. Recent research has focused on the incorporation of trifunctional monomers into addition-curing polyimides in an attempt to improve the processability of these polymers. The objective of this research is to use an aromatic triamine, 1,3,5 tris (4-aminophenoxy) benzene, to prepare new resin systems with starbranched structures. The glass transition temperatures (Tg's) and thermal oxidative stability TOS) of these polymers are compared to their linear counterparts and PMR-15.

Nguyen, Baochau N.↗

Releasing chemical energy in spatiallyprogrammed ferroelectrics

Chemical energy ferroelectrics are generally solid macromolecules showing spontaneous polarization and chemical bonding energy. These materials still suffer drawbacks, including the limited control of energy release rate, and thermal decomposition energy well below total chemical energy. To overcome these drawbacks, we report the integrated molecular ferroelectric and energetic material from machine learning-directed additive manufacturing coupled with the ice-templating assembly. The resultant aligned porous architecture shows a low density of 0.35 g cm -3 , polarization-controlled energy release, and an anisotropic thermal conductivity ratio of 15. Thermal analysis suggests that the chlorine radicals react with macromolecules enabling a large exothermic enthalpy of reaction (6180 kJ kg -1 ). In addition, the estimated detonation velocity of molecular ferroelectrics can be tuned from 6.69 ± 0.21 to 7.79 ± 0.25 km s -1 by switching the polarization state. These results provide a pathway toward spatially programmed energetic ferroelectrics for controlled energy release rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Blending block copolymers (BCP) with additives is a useful approach for controlling BCP morphology and properties. In athermal systems, blends of BCPs with polymer additives having very high molecular (M n ) mass generally result in macrophase separation. Bottlebrush polymers, which consist of a linear backbone and grafted side chains, present an interesting alternative where the overall M n of the system can be very large but the low M n side chains may drive miscibility with the BCP. Here, in this study, a bottlebrush with a polynorbornene backbone and polystyrene (PS) side chains is blended with PS-b-poly(methyl methacrylate) (PS-b-PMMA) of varying M n , and the resulting morphologies are examined in both the bulk and thin films. Two different M n of PS-b-PMMA were used in the bulk study, and the analysis of small-angle X-ray scattering data shows that the blends were miscible and lamellar at all concentrations. This deviates from reference series of both low and high M n linear polymer additives, which either showed morphological transitions from lamellae to cylinders (low M n ) or were immiscible at all mass fractions studied (high M n ). The relative molecular mass of the side chain (N SC ) and the corresponding component in the BCP (N A ) dictate the distribution of the bottlebrush throughout the BCP, analogous to BCP/linear blends or grafted nanoparticles in a homopolymer matrix. The studies on thin films show a thickness dependence for bottlebrush mass fractions at or above 0.17, a behavior which may be driven by conformational changes of the bottlebrush upon confinement.

36 MATERIALS SCIENCE↗

Rotationsal and vibrational spectra of molecular ions: Feasibility of laboratory and astrophysical observation

The rotational spectra of a number of small molecular ions should be detectable in the microwave or millimeter wave regions in laboratory experiments using currently available techniques. The dipole moments and absorption coefficients of polar diatomics CO(+) and NO(+) as well as asymmetric isotopically enriched species, like O-18O-16(+), NE-20NE-22(+), and OC-18 O-16(+) are calculated to be sufficiently large to allow observation of their spectra. In addition to the detailed molecular structure information which such spectral data would provide, precise knowledge of the transition frequencies would render likely the detection of certain of these ions in the interstellar sources or in planetary atmospheres. All of these ions also possess vibrational spectra which should be detectable in the infrared region in laboratory or astrophysical sources.

Woods, R. C.↗

A long-life lithium-oxygen battery via a molecular quenching/mediating mechanism

The advancement of lithium-oxygen (Li-O 2 ) batteries has been hindered by challenges including low discharge capacity, poor energy efficiency, severe parasitic reactions, etc. We report an Li-O 2 battery operated via a new quenching/mediating mechanism that relies on the direct chemical reactions between a versatile molecule and superoxide radical/Li 2 O 2 . The battery exhibits a 46-fold increase in discharge capacity, a low charge overpotential of 0.7 V, and an ultralong cycle life >1400 cycles. Featuring redox-active 2,2,6,6-tetramethyl-1-piperidinyloxy moieties bridged by a quenching-active perylene diimide backbone, the tailor-designed molecule acts as a redox mediator to catalyze discharge/charge reactions and serves as a reusable superoxide quencher to chemically react with superoxide species generated during battery operation. The all-in-one molecule can simultaneously tackle issues of parasitic reactions associated with superoxide radicals, singlet oxygen, high overpotentials, and lithium corrosion. The molecular design of multifunctional additives combining various capabilities opens a new avenue for developing high-performance Li-O 2 batteries.

25 ENERGY STORAGE↗

Molecularly Oriented Polymeric Thin Films for Space Applications

The increased commitment from NASA and private industry to the exploration of outer space and the use of orbital instrumentation to monitor the earth has focused attention on organic polymeric materials for a variety of applications in space. Some polymeric materials have exhibited short-term (3-5 yr) space environmental durability; however, future spacecraft are being designed with lifetimes projected to be 10-30 years. This gives rise to concern that material property change brought about during operation may result in unpredicted spacecraft performance. Because of their inherent toughness and flexibility, low density, thermal stability, radiation resistance and mechanical strength, aromatic polyimides have excellent potential use as advanced materials on large space structures. Also, there exists a need for high temperature (200-300 C) stable, flexible polymeric films that have high optical transparency in the 300-600nm range of the electromagnetic spectrum. Polymers suitable for these space applications were fabricated and characterized. Additionally, these polymers were molecularly oriented to further enhance their dimensional stability, stiffness, elongation and strength. Both unoriented and oriented polymeric thin films were also cryogenically treated to temperatures below -184 C to show their stability in cold environments and determine any changes in material properties.

Fay, Catharine C.↗

A Robotic High-Throughput Grid-Search Platform for Mapping Phase Behavior in Triblock Copolymer–Homopolymer Blends

We present a high-throughput experimental investigation of the phase behavior in triblock copolymers (PS-b-PB-b-PS and PS-b-PI-b-PS) and polystyrene (PS) homopolymer blends as a function of homopolymer molecular weight (MW) and blend ratio. Using a robotic thin-film processing platform (NOVA) integrated with Grazing Incidence Small-Angle X-ray Scattering (GISAXS) and Atomic Force Microscopy (AFM), we systematically mapped the order–disorder transition (ODT) boundaries and domain spacing evolution across a broad MW range (4.0–101.3 kDa) with varying homopolymer loadings (10% to 90%). The results reveal three distinct regimes: low-MW homopolymers, corresponding to the wet-brush regime produced only gradual domain swelling before disordering at high blend ratios (weight fraction); medium-MW homopolymers, corresponding to thedry-brush regime induced significant domain spacing increase up to 80% followed by earlier disordering, while high-MW homopolymers led to macrophase separation with minimal changes in domain spacing. Additionally, coarse-grained molecular dynamics simulations confirmed our experimental finding that in the low-MW region, the PS homopolymer uniformly distributed in the PS domain. These findings demonstrate that homopolymer molecular weight critically governs both the extent of domain swelling and the onset of disorder in triblock copolymer systems. This high-throughput platform enables the rapid mapping of composition–morphology relationships and can be integrated with AI/ML tools for designing next-generation nanostructured polymers.

36 MATERIALS SCIENCE↗