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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 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Catalytic conversion of cellulose and its derived sugars to 5-Hydroxymethylfurfural, levulinate esters, and sorbitol: a comprehensive review

Cellulose, an abundant, renewable, and sustainable non-edible carbon source from agriculture and forestry, has attracted great attention for producing diverse value-added chemicals and fuels. However, the rigid 3D structure of cellulose, maintained by an extensive hydrogen bonding network, hinders chemical conversion, requiring effective pretreatment to break down the crystalline structure. High-value cellulose-derived compounds such as 5-hydroxymethylfurfural (5-HMF), levulinate esters, and sorbitol, recognized as critical platform chemicals by the U.S. Department of Energy, are particularly attractive for versatile applications. This review provides a comprehensive overview of methodologies for the chemical synthesis of 5-HMF, levulinate esters, and sorbitol, focusing on direct catalytic conversion of cellulose. It delves into recent advancements in reaction systems and catalysts, highlighting catalytic pathways, selectivity, strategies for process optimization, and computational approaches, while discussing the challenges associated with the catalytic conversion of cellulose into these high-value products and offering potential strategies for enhancing future catalytic processes.

Huang, Kaixuan [Yancheng Teachers Univ. (China); N↗
DOE OSTI2022

Intramolecular hydrogen bonding analysis

The quasi-atomic orbital (QUAO) bonding analysis is used to study intramolecular hydrogen bonding (IMHB) in salicylic acid and an intermediate that is crucial to the synthesis of aspirin. The bonding analysis rigorously explores IMHB through directly accessing information that is intrinsic to the molecular wave function, thereby bypassing the need for intrinsically biased methods. The variables that affect the strength of IMHB are determined using kinetic bond orders, QUAO populations, and QUAO hybridizations. Important properties include both the interatomic distance between hydrogen and oxygen participating in the IMHB and the hybridization on the oxygen. The bonding analysis further shows that each intramolecular hydrogen bond is a four-electron three-center bond. Here, the bonding analysis is used to understand how aromatic reactivity changes due to the effect of functional groups on the aromatic ring.

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

Facet-selective etching trajectories of individual semiconductor nanocrystals

The size and shape of semiconductor nanocrystals govern their optical and electronic properties. Liquid cell transmission electron microscopy (LCTEM) is an emerging tool that can directly visualize nanoscale chemical transformations and therefore inform the precise synthesis of nanostructures with desired functions. However, it remains difficult to controllably investigate the reactions of semiconductor nanocrystals with LCTEM, because of the highly reactive environment formed by radiolysis of liquid. Here, we harness the radiolysis processes and report the single-particle etching trajectories of prototypical semiconductor nanomaterials with well-defined crystalline facets. Lead selenide nanocubes represent an isotropic structure that retains the cubic shape during etching via a layer-by-layer mechanism. The anisotropic arrow-shaped cadmium selenide nanorods have polar facets terminated by either cadmium or selenium atoms, and the transformation trajectory is driven by etching the selenium-terminated facets. LCTEM trajectories reveal how nanoscale shape transformations of semiconductors are governed by the reactivity of specific facets in liquid environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1981

Integrated Application of Active Controls (IAAC) technology to an advanced subsonic transport project: Current and advanced act control system definition study, volume 1

An active controls technology (ACT) system architecture was selected based on current technology system elements and optimal control theory was evaluated for use in analyzing and synthesizing ACT multiple control laws. The system selected employs three redundant computers to implement all of the ACT functions, four redundant smaller computers to implement the crucial pitch-augmented stability function, and a separate maintenance and display computer. The reliability objective of probability of crucial function failure of less than 1 x 10 to the -9th power per flight of 1 hr can be met with current technology system components, if the software is assumed fault free and coverage approaching 1.0 can be provided. The optimal control theory approach to ACT control law synthesis yielded comparable control law performance much more systematically and directly than the classical s-domain approach. The ACT control law performance, although somewhat degraded by the inclusion of representative nonlinearities, remained quite effective. Certain high-frequency gust-load alleviation functions may require increased surface rate capability.

Hanks, G. W.↗
NASA NTRS1986

A silane-based polysilicon process

A silane based polysilicon process plant was constructed in Miami, Oklahoma. The processes included: the synthesis of crude silane gas, ultrapurification of the gas, and direct pyrolysis to product silicon. Features of the process provided for direct continuous operation from process feed to final product, without the requirement to store intermediates or even convert the silane to a liquid phase. Semiconductor product quality as analyzed internally was demonstrated by the first integrated operation of the plant.

Grayson, P. E.↗
NASA NTRS1986

System identification for modeling for control of flexible structures

The major components of a design and operational flight strategy for flexible structure control systems are presented. In this strategy an initial distributed parameter control design is developed and implemented from available ground test data and on-orbit identification using sophisticated modeling and synthesis techniques. The reliability of this high performance controller is directly linked to the accuracy of the parameters on which the design is based. Because uncertainties inevitably grow without system monitoring, maintaining the control system requires an active on-line system identification function to supply parameter updates and covariance information. Control laws can then be modified to improve performance when the error envelopes are decreased. In terms of system safety and stability the covariance information is of equal importance as the parameter values themselves. If the on-line system ID function detects an increase in parameter error covariances, then corresponding adjustments must be made in the control laws to increase robustness. If the error covariances exceed some threshold, an autonomous calibration sequence could be initiated to restore the error enveloped to an acceptable level.

Mettler, Edward↗
NASA NTRS1991

Kinetics of the template-directed oligomerization of guanosine 5'-phosphate-2-methylimidazolide: Effect of temperature on individual steps of reactionion

Non-enzymatic, template-directed reactions have been proposed as models for prebiological polynucleotide synthesis. Chemically activated mononucleotides react in the presence of a polynucleotide, acting as the template in a Watson-Crick base-pairing fashing, and form the complementary daughter polynucleotide. Phosphoimidazolide-activated nucleotides have been used successfully as substrates in these reactions. The kinetics of the guanosine 5'-monophosphate-2-methylimidazolide (2-MelmpG) reaction in aqueous pH 8.0 solutions in the presence and in the absence of polycytidylate (poly(C)) were studied, acting as the template at 6, 23, and 37 C. In the absence of the template, the major reaction pathway of 2-MelmpG is hydrolysis of the P-N bond to form the unreactive guanosine 5'-monophosphate (5'-GMP) and 2-methylimidazole. Concentrated solution of 2-MelmpG (greater than 0.02 M) in the absence of the template form only a small amount dinucleotide, (pG)2, but in the presence of poly(C), oligoguanylates, (pG)n with 2 less than or = n less than or = 40, can be detected. We were able to determine the rate constants for individual steps of this reaction. A summary of the conclusions is presented.

Kanavarioti, A.↗
NASA NTRS1992

Reaction-bonded Si3N4 and SiC matrix composites

A development status evaluation is presented for the reaction-bonded SiC- and Si3N4-matrix types of fiber-reinforced ceramic-matrix composite (FRCMC). A variety of reaction-bonding methods are being pursued for FRCMC fabrication: CVI, CVD, directed metal oxidation, and self-propagating high-temperature synthesis. Due to their high specific modulus and strength, toughness, and fabricability, reaction-bonded FRCMC are important candidate materials for such heat-engine components as combustor liners, nozzles, and turbine and stator blading. The improvement of long-term oxidative stability in these composites is a major goal of current research.

Bhatt, Ramakrishna T.↗
NASA NTRS1999

Tissue Engineered Skeletal Myofibers can Directly "Sense" Gravitational Force Changes

Long-term manned space flight requires a better understanding of skeletal muscle atrophy resulting from microgravity. Atrophy most likely results from changes at both the systemic level (e.g. decreased circulating growth hormone, increased circulating glucocorticoids) and locally (e.g. decreased myofiber resting tension). Differentiated skeletal myofibers in tissue culture have provided a model system over the last decade for gaining a better understanding of the interactions of exogenous growth factors, endogenous growth factors, and muscle fiber tension in regulating protein turnover rates and muscle cell growth. Tissue engineering these cells into three dimensional bioartificial muscle (BAM) constructs has allowed us to extend their use to Space flight studies for the potential future development of countermeasures. Embryonic avian muscle cells were isolated and BAMs tissue engineered as described previously. The myoblasts proliferate and fuse into aligned postmitotic myofibers after ten to fourteen days in vitro. A cylindrical muscle-like structure containing several thousand myofibers is formed which is approximately 30 mm in length, 2-3 mm in diameter, and attached at each end. For the Space Shuttle experiments, the BAMs were transferred to 55 mL bioreactor cartridges (6 BAMs/cartridge). At Kennedy Space Center, the cartridges were mounted in two Space Tissue Loss (STL) Modules (three to four cartridges per Module) and either maintained as ground controls or loaded in a Mid-Deck locker of the Space Shuttle. The BAM cartridges were continuously perfused during the experiment at 1.5 mL/ min with tissue culture medium. Eighteen BAMs were flown for nine days on Mission STS66 while eighteen BAMs served as ground controls. The complete experiment was repeated on Mission STS77 with twenty four BAMs in each group. BAMs could be maintained in a healthy state for at least 30 days in the perfusion bioreactor cartridges. The BAM muscle fibers directly detected both the loss of gravity and the reloading effects of 1 x g. While total cellular metabolism and total protein degradation rates were not altered during 9 to 10 days in Space, protein synthesis rates were significantly reduced and resulted in significant myofiber atrophy compared to ground controls. One g reloading of the flight muscle cells post-flight significantly increased protein synthesis rates and the synthesis rates of myosin heavy chain, fibronectin, and collagen. Tissue cultured muscle cells can directly "sense" changes in gravity and provide a valid model to begin the study of countermeasures. Based on our ground based experiments, and the experiments of others, growth hormone and/or insulin-like growth factors are attractive protein therapeutics which may assisting attenuating skeletal muscle wasting in space. Our laboratory is developing a new cell-based delivery system for this and other potential therapeutic factors for attenuating muscle and bone wasting.

Vandenburgh, Herman H.↗
NASA NTRS2004

Automating Traceability for Generated Software Artifacts

Program synthesis automatically derives programs from specifications of their behavior. One advantage of program synthesis, as opposed to manual coding, is that there is a direct link between the specification and the derived program. This link is, however, not very fine-grained: it can be best characterized as Program is-derived- from Specification. When the generated program needs to be understood or modified, more $ne-grained linking is useful. In this paper, we present a novel technique for automatically deriving traceability relations between parts of a specification and parts of the synthesized program. The technique is very lightweight and works -- with varying degrees of success - for any process in which one artifact is automatically derived from another. We illustrate the generality of the technique by applying it to two kinds of automatic generation: synthesis of Kalman Filter programs from speci3cations using the Aut- oFilter program synthesis system, and generation of assembly language programs from C source code using the GCC C compilel: We evaluate the effectiveness of the technique in the latter application.

Richardson, Julian↗
NASA NTRS1978

Trends in computerized structural analysis and synthesis; Proceedings of the Symposium, Washington, D.C., October 30-November 1, 1978

The subjects considered are related to future directions of structural applications and potential of new computing systems, advances and trends in data management and engineering software development, advances in applied mathematics and symbolic computing, computer-aided instruction and interactive computer graphics, nonlinear analysis, dynamic analysis and transient response, structural synthesis, structural analysis and design systems, advanced structural applications, supercomputers, numerical analysis, and trends in software systems. Attention is given to the reliability and optimality of the finite element method, computerized symbolic manipulation in structural mechanics, a standard computer graphics subroutine package, and a drag method as a finite element mesh generation scheme.

Noor, A. K.↗
DOE OSTI2021

Click-Chemistry-Based Free Azide versus Azido Sugar Detection Enables Rapid In Vivo Screening of Glycosynthase Activity

Engineering of carbohydrate-active enzymes such as glycosynthases to enable chemoenzymatic synthesis of bespoke oligosaccharides has been limited by the lack of suitable ultrahigh-throughput screening methods capable of robustly detecting either starting substrates or end-products of the glycosidic bond formation reaction. Currently, there are limited screening methods available for rapid and highly sensitive single-cell-based screening of glycosynthase enzymes employing azido sugars as activated donor glycosyl substrates. Here, we report a fluorescence-based approach employing click-chemistry for the selective detection of glycosyl azides as substrates versus free inorganic azides as reaction products that facilitated an ultrahigh-throughput in vivo single-cell-based assay of glycosynthase activity. This assay was developed based on the distinct differences observed in relative fluorescence intensity of the triazole-containing fluorophore product formed during the click-chemistry reaction of organic glycosyl azides versus inorganic azides. This discovery formed the basis for proof of concept validation of a directed evolution methodology for screening and sorting glycosynthase mutants capable of synthesis of targeted fucosylated oligosaccharides. Our screening approach facilitated fluorescence-activated cell sorting of an error-prone polymerase chain reaction-based mutant library of fucosynthases expressed in Escherichia coli to identify several novel mutants that showed increased activity for ß-fucosyl azide-activated donor sugars toward desired acceptor sugars (e.g., pNP-xylose and lactose). Finally, we discuss avenues for improving this proof of concept in vivo assay method to identify better glycosynthase mutants and further demonstrate the broader applicability of this screening methodology for synthesis of bespoke glycans.

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

A detailed genome-scale metabolic model of Clostridium thermocellum investigates sources of pyrophosphate for driving glycolysis

Lignocellulosic biomass is an abundant and renewable source of carbon for chemical manufacturing, yet it is cumbersome in conventional processes. A promising, and increasingly studied, candidate for lignocellulose bioprocessing is the thermophilic anaerobe Clostridium thermocellum given its potential to produce ethanol, organic acids, and hydrogen gas from lignocellulosic biomass under high substrate loading. Possessing an atypical glycolytic pathway which substitutes GTP or pyrophosphate (PP i ) for ATP in some steps, including in the energy-investment phase, identification, and manipulation of PP i sources are key to engineering its metabolism. Previous efforts to identify the primary pyrophosphate have been unsuccessful. Here, we explore pyrophosphate metabolism through reconstructing, updating, and analyzing a new genome-scale stoichiometric model for C. thermocellum, iCTH669. Hundreds of changes to the former GEM, iCBI655, including correcting cofactor usages, addressing charge and elemental balance, standardizing biomass composition, and incorporating the latest experimental evidence led to a MEMOTE score improvement to 94%. We found agreement of iCTH669 model predictions across all available fermentation and biomass yield datasets. The feasibility of hundreds of PP i synthesis routes, newly identified and previously proposed, were assessed through the lens of the iCTH669 model including biomass synthesis, tRNA synthesis, newly identified sources, and previously proposed PP i -generating cycles. In all cases, the metabolic cost of PP i synthesis is at best equivalent to investment of one ATP suggesting no direct energetic advantage for the cofactor substitution in C. thermocellum. Even though no unique source of PP i could be gleaned by the model, by combining with gene expression data two most likely scenarios emerge. First, previously investigated PP i sources likely account for most PP i production in wild-type strains. Second, alternate metabolic routes as encoded by iCTH669 can collectively maintain PP i levels even when previously investigated synthesis cycles are disrupted. Model iCTH669 is available at github.com/maranasgroup/iCTH669.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1971

Program on application of communications satellites to educational development

Interdisciplinary research in needs analysis, communications technology studies, and systems synthesis is reported. Existing and planned educational telecommunications services are studied and library utilization of telecommunications is described. Preliminary estimates are presented of ranges of utilization of educational telecommunications services for 1975 and 1985; instructional and public television, computer-aided instruction, computing resources, and information resource sharing for various educational levels and purposes. Communications technology studies include transmission schemes for still-picture television, use of Gunn effect devices, and TV receiver front ends for direct satellite reception at 12 GHz. Two major studies in the systems synthesis project concern (1) organizational and administrative aspects of a large-scale instructional satellite system to be used with schools and (2) an analysis of future development of instructional television, with emphasis on the use of video tape recorders and cable television. A communications satellite system synthesis program developed for NASA is now operational on the university IBM 360-50 computer.

Morgan, R. P.↗
NASA NTRS2022

GBaTSv2: a revised synthesis of the likely basal thermal state of the Greenland Ice Sheet

The basal thermal state (frozen or thawed) of the Greenland Ice Sheet is under-constrained due to few direct measurements, yet knowledge of this state is becoming increasingly important to interpret modern changes in ice flow. The first synthesis of this state relied on inferences from widespread airborne and satellite observations and numerical models, for which most of the underlying datasets have since been updated. Further, new and independent constraints on the basal thermal state have been developed from analysis of basal and englacial reflections observed by airborne radar sounding. Here we synthesize constraints on the Greenland Ice Sheet's basal thermal state from boreholes, thermomechanical ice-flow models that participated in the Ice Sheet Model Intercomparison Project for CMIP6 (ISMIP6; Coupled Model Intercomparison Project Phase 6), IceBridge BedMachine Greenland v4 bed topography, Making Earth Science Data Records for Use in Research Environments (MEaSUREs) Multi-Year Greenland Ice Sheet Velocity Mosaic v1 and multiple inferences of a thawed bed from airborne radar sounding. Most constraints can only identify where the bed is likely thawed rather than where it is frozen. This revised synthesis of the Greenland likely Basal Thermal State version 2 (GBaTSv2) indicates that 33 % of the ice sheet's bed is likely thawed, 40 % is likely frozen and the remainder (28 %) is too uncertain to specify. The spatial pattern of GBaTSv2 is broadly similar to the previous synthesis, including a scalloped frozen core and thawed outlet-glacier systems. Although the likely basal thermal state of nearly half (46 %) of the ice sheet changed designation, the assigned state changed from likely frozen to likely thawed (or vice versa) for less than 6 % of the ice sheet. This revised synthesis suggests that more of northern Greenland is likely thawed at its bed and conversely that more of southern Greenland is likely frozen, both of which influence interpretation of the ice sheet's present subglacial hydrology and models of its future evolution. The GBaTSv2 dataset, including both code that performed the analysis and the resulting datasets, is freely available at https://doi.org/10.5281/zenodo.6759384 (MacGregor, 2022).

Joseph A. MacGregor↗
DOE OSTI2020

Carbohydrate‐binding domains facilitate efficient oligosaccharides synthesis by enhancing mutant catalytic domain transglycosylation activity

Abstract Chemoenzymatic approaches using carbohydrate‐active enzymes (CAZymes) offer a promising avenue for the synthesis of glycans like oligosaccharides. Here, we report a novel chemoenzymatic route for cellodextrins synthesis employed by chimeric CAZymes, akin to native glycosyltransferases, involving the unprecedented participation of a “non‐catalytic” lectin‐like domain or carbohydrate‐binding modules (CBMs) in the catalytic step for glycosidic bond synthesis using β‐cellobiosyl donor sugars as activated substrates. CBMs are often thought to play a passive substrate targeting role in enzymatic glycosylation reactions mostly via overcoming substrate diffusion limitations for tethered catalytic domains (CDs) but are not known to participate directly in any nucleophilic substitution mechanisms that impact the actual glycosyl transfer step. This study provides evidence for the direct participation of CBMs in the catalytic reaction step for β‐glucan glycosidic bonds synthesis enhancing activity for CBM‐based CAZyme chimeras by >140‐fold over CDs alone. Dynamic intradomain interactions that facilitate this poorly understood reaction mechanism were further revealed by small‐angle X‐ray scattering structural analysis along with detailed mutagenesis studies to shed light on our current limited understanding of similar transglycosylation‐type reaction mechanisms. In summary, our study provides a novel strategy for engineering similar CBM‐based CAZyme chimeras for the synthesis of bespoke oligosaccharides using simple activated sugar monomers.

Bandi, Chandra Kanth↗
DOE OSTI2022

Peptoid-Directed Formation of Five-Fold Twinned Au Nanostars through Particle Attachment and Facet Stabilization

While bio-inspired synthesis offers great potential for controlling nucleation and growth of inorganic particles, precisely tuning biomolecule-particle interactions is a long-standing challenge. Herein, we used variations in peptoid sequence to manipulate peptoid-Au interaction, leading to synthesis of concave five-fold twinned, five-pointed Au nanostars via a process of repeated particle attachment and facet stabilization. Ex situ and liquid-phase TEM observations show that a balance between particle attachment biased to occur near the star points, preferential growth along the [100] direction, and stabilization of (111) facets is critical to forming star-shaped particles. Molecular simulations predict that interaction strengths between peptoids and distinct Au facets differ significantly and thus can alter attachment kinetics and surface energies to form the stars. This work provides new insights into how sequence-defined ligands affect particle growth to regulate crystal morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗