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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 1,225 records · Page 68
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Predicting peak spectral sensitivities of vertebrate cone visual pigments using atomistic molecular simulations

Vision is the dominant sensory modality in many organisms for foraging, predator avoidance, and social behaviors including mate selection. Vertebrate visual perception is initiated when light strikes rod and cone photoreceptors within the neural retina of the eye. Sensitivity to individual colors, i.e., peak spectral sensitivities (λ max ) of visual pigments, are a function of the type of chromophore and the amino acid sequence of the associated opsin protein in the photoreceptors. Large differences in peak spectral sensitivities can result from minor differences in amino acid sequence of cone opsins. To determine how minor sequence differences could result in large spectral shifts we selected a spectrally-diverse group of 14 teleost Rh2 cone opsins for which sequences and λ max are experimentally known. Classical molecular dynamics simulations were carried out after embedding chromophore-associated homology structures within explicit bilayers and water. These simulations revealed structural features of visual pigments, particularly within the chromophore, that contributed to diverged spectral sensitivities. Statistical tests performed on all the observed structural parameters associated with the chromophore revealed that a two-term, first-order regression model was sufficient to accurately predict λ max over a range of 452–528 nm. The approach was accurate, efficient and simple in that site-by-site molecular modifications or complex quantum mechanics models were not required to predict λ max . These studies identify structural features associated with the chromophore that may explain diverged spectral sensitivities, and provide a platform for future, functionally predictive opsin modeling.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Comparative Study on the Charge-Ordered and Mixed-Valence Phases of LuFe{sub 2}O{sub 4} via First-Principles Calculations

The first-principles density functional theory calculations have been used to investigate the relation between magnetic and structural properties of LuFe{sub 2}O{sub 4} for both the charge-ordered (CO) and the mixed-valence (MV) phases and also to compare the electronic properties for both phases. The computed structural parameters of rhombohedral and monoclinic systems are found to be in good agreement with experimental findings. An analysis of the magnetic properties is provided considering nonmagnetic, ferromagnetic, antiferromagnetic, and ferrimagnetic model orderings. In agreement with experimental results, CO modification of LuFe{sub 2}O{sub 4} is predicted to be ferrimagnetic. The GGA + U electronic structures show a semiconducting behavior of CO phase while a metallic character for MV LuFe{sub 2}O{sub 4} phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

GlcNAc-1-P-transferase–tunicamycin complex structure reveals basis for inhibition of N-glycosylation

N-linked glycosylation is a predominant post-translational modification of protein in eukaryotes, and its dysregulation is the etiology of several human disorders. The enzyme UDP-N-acetylglucosamine:dolichyl-phosphate N-acetylglucosaminephosphotransferase (GlcNAc-1-P-transferase or GPT) catalyzes the first and committed step of N-linked glycosylation in the endoplasmic reticulum membrane, and it is the target of the natural product tunicamycin. Tunicamycin has potent antibacterial activity, inhibiting the bacterial cell wall synthesis enzyme MraY, but its usefulness as an antibiotic is limited by off-target inhibition of human GPT. Our understanding of how tunicamycin inhibits N-linked glycosylation and efforts to selectively target MraY are hampered by a lack of structural information. Here we present crystal structures of human GPT in complex with tunicamycin. In conclusion, structural and functional analyses reveal the difference between GPT and MraY in their mechanisms of inhibition by tunicamycin. Here, we demonstrate that this difference could be exploited to design MraY-specific inhibitors as potential antibiotics.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Effect of X-ray beam on the molecular–topological structure of the surface of kynar® polyvinylidene fluoride resin

Thermomechanical analysis of poly(vinylidene fluoride) (PVDF) film shows that, unlike the completely amorphous structure of the native polymer, after irradiation with X-rays, the weight fraction of the crystalline modification in the polymer is 0.5. The initial PVDF film had a linear thermal expansion coefficient of α 1 = 11.33х10 5 K -1 and a glass transition temperature of T g =256 K. An efficient conversion of the amorphous structures of the polymer pseudo-network into crystalline networks occurs under X-ray irradiation. The irradiated polymer exhibits amorphous ( T g =239 K) and crystalline topological blocks ( T m =385 K). The presence of polyenyl and alkyl radicals is found in the electron paramagnetic resonance (EPR) spectra of the irradiated polymer. Lines with a splitting of 3.3 m T can be observed at the edges of the EPR spectra, consistent with radical centers like -CF 2 -C • H-CF 2 - . At high doses of radiolysis, polyenyl radicals are the main observed radicals. The macromolecular chains contain all three (α, β, γ) morphologies of the polymer. The Raman spectra show that X-ray irradiation can lead to carbonization and the formation of unsaturated bonds. Electronic structure calculations were used to aid in the analysis of the observed spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Boosting Cell Performance of LiNi 0.8 Co 0.15 A 0.05 O 2 via Surface Structure Design

Although the high energy density and environmental benignancy of LiNi 0.8 Co 0.15 A 0.05 O 2 (NCA) holds promise for use as cathode material in Li-ion batteries, present low rate capabilities, and fast capacity fade limit its broad commercial applications. Here, it is reported that surface modification of NCA cathode (R-3m) with 5 nm-thick nanopillar layers and Fm-3m structures significantly improves electrode structure, morphology, and electrochemical performance. The formation of nanopillar layers increases cycling and working voltage stability of NCA by shielding the host material from hydrofluoric acid and improves structural stability with the electrolyte. The modified NCA cathode exhibits an enhanced 89% capacity retention at a rate of 1 C over that of pristine NCA (75.2%) after 150 cycles and effectively suppresses working voltage fade (a drop of 0.025 V after 300 cycles) during repeated charge-discharge cycles. In addition, the diffusion barrier of Li ions in NCA crystals at 0.80 V is noticeably smaller than that of Li ions in pristine NCA (0.87 eV). These findings demonstrate that this unique surface structure design considerably enhances cycle and rate performance of NCA, which has potential applications in other Ni-rich layered cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Bioinspired Diversification Approach Toward the Total Synthesis of Lycodine-Type Alkaloids

Nitrogen heterocycles (azacycles) are common structural motifs in numerous pharmaceuticals, agrochemicals, and natural products. Many powerful methods have been developed and continue to be advanced for the selective installation and modification of nitrogen heterocycles through C–H functionalization and C–C cleavage approaches, revealing new strategies for the synthesis of targets containing these structural entities. Here, we report the first total syntheses of the lycodine-type Lycopodium alkaloids casuarinine H, lycoplatyrine B, lycoplatyrine A, and lycopladine F as well as the total synthesis of 8,15-dihydrohuperzine A through bioinspired late-stage diversification of a readily accessible common precursor, N-desmethyl-β-obscurine. Key steps in the syntheses include oxidative C–C bond cleavage of a piperidine ring in the core structure of the obscurine intermediate and site-selective C–H borylation of a pyridine nucleus to enable cross-coupling reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thermodynamically Driven Synthetic Optimization for Cation-Disordered Rock Salt Cathodes

Relating the synthesis conditions of materials to their functional performance has long been an experience-based trial-and-error process. However, this methodology is not always efficient in identifying an appropriate protocol and can lead to overlooked opportunities for the performance optimization of materials through simple modifications of the synthesis process. In this work, we systematically track the structural evolution in the synthesis of a representative disordered rocksalt (a promising next-generation Li-ion cathode material) at the scale of both the long-range crystal structure and the short-range atomic structure using various in situ and ex situ techniques, including transmission electron microscopy, X-ray diffraction, and pair distribution function analysis. Further, an optimization strategy is proposed for the synthesis protocol, leading to a remarkably enhanced capacity (specific energy) of 313 mAh g –1 (987 Wh kg –1 ) at a low rate (20 mA g –1 ), with a capacity of more than 140 mAh g –1 retained even at a very high cycling rate of 2,000 mA g –1 . This strategy is further rationalized using ab initio calculations, and important opportunities for synthetic optimization demonstrated in this study are highlighted.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Overcoming component limitations in synthetic biology through transposon-mediated protein engineering

Protein fission and fusion can be used to create biomolecules with new structures and functions, including circularly permuted proteins that require post-translational modifications for activity, split protein AND gates that require multiple inputs for activity, and fused domains that function as chemical-dependent protein switches. In this work, we describe how transposon mutagenesis can be used for protein design to create libraries of permuted, split, or domain-inserted proteins. Furthermore, when coupled with a functional screen or selection, these approaches can rapidly diversify the topologies and functions of natural proteins and create useful protein components for synthetic biology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Development and validation of an enhanced filtered drag model for simulating gas-solid fluidization of Geldart A particles in all flow regimes

Coarse-grid two-fluid simulation of gas-solid fluidized bed reactors based on the kinetic theory of granular flow exhibits a significant dependence on drag models, especially for Geldart A particles. Many drag models are available in the literature, which have been reported to work for different systems. This work focused on the evaluation of an enhanced filtered drag model along with other different drag models derived from different methods for three-dimensional two-fluid model simulations of gas-solid fluidized beds of Geldart A particles covering a broad range of fluidization regimes, including bubbling fluidization, turbulent fluidization, fast fluidization, and dilute phase transport regimes. Eight drag models were selected, which included five heterogeneous drag models and three homogeneous drag models. Comparison with the available experimental data demonstrates the need for modification of homogeneous drag models to account for the effect of mesoscale structures (i.e., bubbles and clusters). The enhanced filtered drag model and energy-minimization multi-scale (EMMS) drag models were found to achieve superior predictions in all fluidization regimes, while the other drag models were only capable of predicting certain fluidization regimes. Finally, the results of this work provide a guideline for choosing appropriate drag models for simulating Geldart A particles and suggestions on developing more reliable and general drag models applicable in all flow regimes.

42 ENGINEERING↗
DOE OSTI2025

Improving adhesive bonding of short carbon fiber thermoplastic composites to aluminum alloys with a hybrid laser-plasma surface modification strategy

This study investigates hybrid laser–plasma surface modification strategies for metal–CFRTP (carbon-fiber-reinforced thermoplastic polymer) dissimilar joints to improve their bonding performance, in contrast to existing literature that mostly focuses on either plasma or laser treatment alone. By conducting double cantilever beam (DCB) tests on adhesively-bonded AA5052 and CFRPA66 (carbon-fiber-reinforced polyamide 66) joints, as an example of metal–CFRTP joints, it was found that laser engraving on the metal surface combined with plasma treatment on the CFRTP surface significantly improved the specific fracture energy of the joint by 187% and 31% compared to as-received and plasma-treated-only joints, respectively. However, the hybrid treatment of laser engraving and plasma on the investigated CFRTP surface did not improve the bonding performance of the joints. The underlying mechanisms related to hybrid laser-plasma surface modification strategies were further investigated by examining the surface and cross-sectional morphologies after DCB testing using microscopy. Computational modeling was performed to elucidate the interaction between grooves on the metal substrate and the CFRTP–adhesive interfacial bonding in metal–CFRTP joints. This study provides new insights into developing surface modification methods for achieving strong metal–CFRTP adhesive joints, aimed at lightweighting structural components in automotive, aerospace, and other applications.

Adhesive bonding↗
DOE OSTI2018

Molecular Basis for Autocatalytic Backbone N -Methylation in RiPP Natural Product Biosynthesis

N-methylation of nucleic acids, proteins, and peptides is a chemical modification with significant impact on biological regulation. Despite the simplicity of the structural change, N-methylation can influence diverse functions including epigenetics, protein complex formation, and microtubule stability. While there are limited examples of N-methylation of the α-amino group of bacterial and eukaryotic proteins, there are no examples of catalysts that carry out post-translation methylation of backbone amides in proteins or peptides. Recent studies have identified enzymes that catalyze backbone N-methylation on a peptide substrate, a reaction with little biochemical precedent, in a family of ribosomally synthesized natural products produced in basidiomycetes. Here, we describe the crystal structures of Dendrothele bispora dbOphMA, a methyltransferase that catalyzes multiple N-methylations on the peptide backbone. We further carry out biochemical studies of this catalyst to determine the molecular details that promote this unusual chemical transformation. As a result, the structural and biochemical framework described here could facilitate biotechnological applications of catalysts for the rapid production of backbone N-methylated peptides.

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

Alternative splicing and allosteric regulation modulate the chromatin binding of UHRF1

UHRF1 is an important epigenetic regulator associated with apoptosis and tumour development. It is a multidomain protein that integrates readout of different histone modification states and DNA methylation with enzymatic histone ubiquitylation activity. Emerging evidence indicates that the chromatin-binding and enzymatic modules of UHRF1 do not act in isolation but interplay in a coordinated and regulated manner. Here, we compared two splicing variants (V1, V2) of murine UHRF1 (mUHRF1) with human UHRF1 (hUHRF1). We show that insertion of nine amino acids in a linker region connecting the different TTD and PHD histone modification-binding domains causes distinct H3K9me3-binding behaviour of mUHRF1 V1. Structural analysis suggests that in mUHRF1 V1, in contrast to V2 and hUHRF1, the linker is anchored in a surface groove of the TTD domain, resulting in creation of a coupled TTD-PHD module. This establishes multivalent, synergistic H3-tail binding causing distinct cellular localization and enhanced H3K9me3-nucleosome ubiquitylation activity. In contrast to hUHRF1, H3K9me3-binding of the murine proteins is not allosterically regulated by phosphatidylinositol 5-phosphate that interacts with a separate less-conserved polybasic linker region of the protein. Our results highlight the importance of flexible linkers in regulating multidomain chromatin binding proteins and point to divergent evolution of their regulation.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Electrochemical Probing of Steric, Electrostatic and Hydrophobic Interactions of Large Cations in Polymers of Intrinsic Microporosity

Porous membranes have been used for many applications, including separations in biotechnology, the food industry, water purification, and even energy storage devices. The benefit of polymers of intrinsic microporosity (PIMs) is their consistently sized nanopore channels. Inherent functionalities of the PIM structure not only create these channels but are also available for further modifications that can change the interactions of ions and molecules inside of the pore. Here we design solid state nanopores on which are drop-casted two different PIMs, functionalized with either a cyano group or a carboxylic acid. Ionic transport through the membranes is investigated based on pore size and charge-charge interactions, as well as steric and hydrophobic interactions. Achieving specific ion selectivity with easily processable porous membranes opens new avenues for water purification strategies and energy storage.

25 ENERGY STORAGE↗
DOE OSTI2018

Modified Slow Tuner Design for Cavity 1 Inside LCLS II Cryomodules

Initial LCLS-II cryomodule testing at Fermilab showed microphonics on the furthest upstream cavity (number 1) at least factor 2 larger than on the rest of the cavities. Testing indicated that this was a difference in the mechanical support of cavity 1, not a local acoustic source. Further investigation pointed to the upstream beam-pipe of the cavity 1. The upstream cavity flange has a solid spool piece connection to the beamline gate valve unlike the other cavities, which all connect through bellows. The gate valve's weight is supported by sliding system (free in z-axis) connected to large diameter Helium gas return pipe. The tuner design was modified to transform interface between cavity#1 and gate valve. Arms of the tuner for cavity 1 were extended and became the support structure for gate valve, eliminating the connection to the helium return pipe. Modification of the tuner design and results in microphonics mitigations will be presented.

43 PARTICLE ACCELERATORS↗
DOE OSTI2018

Fundamental Studies of Irradiation-Induced Modifications in Microstructural Evolution and Mechanical Properties of Advanced Alloys

This final technical report summarizes the research performed during October 2014 and December 2017, with a focus on investigating the radiation-induced microstructural and mechanical property modifications in optimized advanced alloys for sodium-cooled fast reactor (SFR) structural applications. To accomplish these objectives, the radiation responses of several different advanced alloys, including austenitic steel Alloy 709 (A709) and 316H, and ferritic/ martensitic Fe–9Cr steels T91 and G92, were investigated using a combination of microstructure characterizations and nanoindentation measurements. Different types of irradiation, including ex situ bulk ion irradiation and in situ transmission electron microscopy (TEM) ion irradiation, were employed in this study. Radiation-induced dislocations, precipitates, and voids were characterized by TEM. Scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (STEM-EDS) and/or atom probe tomography (APT) were used to study radiation-induced segregation and precipitation. Nanoindentation was used for hardness measurements to study irradiation hardening. Austenitic A709 and 316H was bulk-irradiated by 3.5 MeV Fe ++ ions to up to 150 peak dpa at 400, 500, and 600°. Compared to neutron-irradiated stainless steel (SS) 316, the Frank loop density of ion-irradiated A709 shows similar dose dependence at 400°, but very different temperature dependence. Due to the noticeable difference in the initial microstructure of A709 and 316H, no systematic comparison on the Frank loops in A709 vs 316H was made. It would be helpful that future ion irradiation study on 316 stainless steel could be conducted to directly compare the temperature dependence of Frank loop density in ion-irradiated 316 SS with that in neutron-irradiated 316 SS. In addition, future neutron irradiation on A709 at 400–600° at relative high dose (≥10 dpa) can be carried out to compare with ion-irradiated A709. The radiation-induced segregation (RIS) of Ni and Si was observed in both A709 and 316H in all irradiated conditions and was found at various sinks: line dislocations, dislocation loops, void surfaces, carbide-matrix interfaces, etc. Radiation also induced the formation of Ni,Si-rich precipitates. As suggested in a previous study on neutron-irradiated 316 stainless steel, one possible consequence of the significant RIS of Si is that the enrichment at defect sinks depletes the silicon in the matrix, which can lead to enhanced void nucleation rate. The enrichment of Ni and Si is accompanied by the depletion of Cr at defect sinks, which could also affect the corrosion resistance. Radiation-induced change in the orientation relationship of pre-existing MX precipitates was observed at 600°. It is believed that this change is associated with the network dislocations formed under irradiation. The underlying mechanism is still not well understood. This change could be a positive indication that the MX precipitates can survive high density network dislocations. It would be helpful if neutron irradiation at similar dose conditions could be carried out to verify that this effect is not unique for ion irradiation. Intragranular Cr-rich carbides with a core-shell structure, i.e. Cr-rich carbide core and Ni,Si-rich shell was found at 500° and 600° in the highest dose (150 peak dpa) specimens. Coarse voids (30 nm in diameter) were only commonly found at 500° in the 50 and 150 peak dpa specimens in regions less than 750 nm in depth. The highest swelling for A709 irradiated to 50 and 150 peak dpa at 500° is about 0.44% and 0.37%, respectively. Due to the choice of 100 degree temperature intervals, this study did not attempt to precisely identify peak void swelling conditions, merely the range of irradiation temperatures where this could be a concern. It is known high-dose ion irradiation can significantly suppress void nucleation. Future neutron irradiation in the 500–600° range (without considering the temperature shift) is needed to determine the onset of accelerated void swelling (possibly at lower dose).

36 MATERIALS SCIENCE↗
NASA NTRS1970

Applications of artificial intelligence for chemical inference. V.

Discussion of the modification of the DENDRAL computer program to extend the program to cyclic structures which exceed numerically the linear molecules of a given composition. IR, NMR and mass spectroscopy is used to develop a method for identification of each of the 27 possible ketones (exclusive of 5 cyclopropanones) of composition C6H10O.

Sheikh, Y. M.↗
NASA NTRS1974

The design and development of a space laboratory to conduct magnetospheric and plasma research

A design study was conducted concerning a proposed shuttle-borne space laboratory for research on magnetospheric and plasma physics. A worldwide survey found two broad research disciplines of interest: geophysical studies of the dynamics and structure of the magnetosphere (including wave characteristics, wave-particle interactions, magnetospheric modifications, beam-plasma interactions, and energetic particles and tracers) and plasma physics studies (plasma physics in space, wake and sheath studies, and propulsion and devices). The Plasma Physics and Environmental Perturbation Laboratory (PPEPL) designed to perform experiments in these areas will include two 50-m booms and two maneuverable subsatellites, a photometer array, standardized proton, electron, and plasma accelerators, a high-powered transmitter for frequencies above 100 kHz, a low-power transmitter for VLF and below, and complete diagnostic packages. Problem areas in the design of a space plasma physics laboratory are indicated.

Rosen, A.↗