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At least 1,495 records · Page 83
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Electron transfer in polysaccharide monooxygenase catalysis

Polysaccharide monooxygenase (PMO) catalysis involves the chemically difficult hydroxylation of unactivated C–H bonds in carbohydrates. The reaction requires reducing equivalents and will utilize either oxygen or hydrogen peroxide as a cosubstrate. Two key mechanistic questions are addressed here: 1) How does the enzyme regulate the timely and tightly controlled electron delivery to the mononuclear copper active site, especially when bound substrate occludes the active site? and 2) How does this electron delivery differ when utilizing oxygen or hydrogen peroxide as a cosubstrate? Using a computational approach, potential paths of electron transfer (ET) to the active site copper ion were identified in a representative AA9 family PMO from Myceliophthora thermophila ( Mt PMO9E). When Y62, a buried residue 12 Å from the active site, is mutated to F, lower activity is observed with O 2 . However, a WT-level activity is observed with H 2 O 2 as a cosubstrate indicating an important role in ET for O 2 activation. To better understand the structural effects of mutations to Y62 and axial copper ligand Y168, crystal structures were solved of the wild type Mt PMO9E and the variants Y62W, Y62F, and Y168F. A bioinformatic analysis revealed that position 62 is conserved as either Y or W in the AA9 family. The Mt PMO9E Y62W variant has restored activity with O 2 . Overall, the use of redox-active residues to supply electrons for the reaction with O 2 appears to be widespread in the AA9 family. Furthermore, the results provide a molecular framework to understand catalysis with O 2 versus H 2 O 2 .

Sayler, Richard I. (ORCID:000000017252707X)↗
NASA NTRS1989

Paradoxical monocular stereopsis and perspective vergence

The question of how to most effectively convey depth in a picture is a multifaceted problem, both because of potential limitations of the chosen medium (stereopsis, image motion), and because effectiveness can be defined in various ways. Practical applications usually focus on information transfer, i.e., effective techniques for evoking recognition of implied depth relationships, but this issue depends on subjective judgements which are difficult to scale when stimuli are above threshold. Two new approaches to this question are proposed here which are based on alternative criteria for effectiveness. Paradoxical monocular stereopsis is a remarkably compelling impression of depth which is evoked during one-eyed viewing of only certain illustrations; it can be unequivocally recognized because the feeling of depth collapses when one shifts to binocular viewing. An exploration of the stimulus properties which are effective for this phenomenon may contribute useful answers for the more general perceptual problem. Positive vergence is an eye-movement response associated with changes of fixation point within a picture which implies depth; it also arises only during monocular viewing. The response is directionally appropriate (i.e., apparently nearer objects evoke convergence, and vice versa), but the magnitude of the response can be altered consistently by making relatively minor changes in the illustration. The cross-subject agreement in changes of response magnitude would permit systematic exploration to determine which stimulus configurations are most effective in evoking perspective vergence, with quantitative answers based upon this involuntary reflex. It may well be that most effective pictures in this context will embody features which would increase effectiveness of pictures in a more general sense.

Enright, J. T.↗
NASA NTRS1999

Current and Future Plans of the NASA Data Assimilation Office (DAO)

The mission of the Data Assimilation Office (DAO) is to advance the state of the art of data assimilation and produce research-quality assimilated data sets which make optimal use of space-based observations. Development efforts over the last few years have focused on delivering a production data assimilation system in support of NASA's Terra platform. That system, called the Goddard Earth Observing System - version 2 or GEOS-2, represents a major upgrade to the baseline GEOS-1 system employed in NASA's first reanalysis effort. GEOS-2 includes a physical-space three dimensional variational analysis algorithm (the Physical-space Statistical Analysis System or PSAS) and numerous improvements to the general circulation model. The latter include a Soil-Vegetation-Atmosphere Transfer (SVAT) land surface scheme, a level 2.5 moist turbulence scheme and new Short Wave (SW) and Long Wave (LW) radiation code. The system also includes an off-line ozone assimilation system, and the capability to assimilate scatterometer surface winds, and TIROS Operational Vertical Sounder (TOVS) and Special Sensor Microwave Imager (SSM/I) moisture data. GEOS-2 is currently run at 1 degree horizontal resolution and 48 levels extending to O.Olmb. Experimental versions of GEOS-2 are run with a global stretched grid allowing enhanced (e.g. 1/4 deg) regional resolution. Other capabilities being developed include, the assimilation of Tropical Rainfall Measuring Mission (TRMM) precipitation and Global Positioning System (GPS) data, an off-line land surface assimilation system, and a retrospective analysis scheme. The DAO is also engaged in a number of collaborative efforts to help accelerate the development of the next generation data assimilation system. These include, a joint modeling effort between the DAO and NCAR/CGDD to develop a new Global Circulation Model (GCM), and a Department of Energy Lawrence Livermore National Laboratory (DOE/LLNL) collaboration on model parallelization. Plans for the next reanalysis will be discussed in the context of current and near term system quality and computing capabilities, and the need for multiple reanalysis products.

Atlas, Robert↗
NASA NTRS1999

Remote Sensing of Volcanic Clouds: Sulfur Gases and Plume Top Topography

New absorption line parameters for H2S were published and submitted to the Gestion et Etude des Informations Spectroscopiques Atmospheriques (GEISA) and high resolution transmission molecular absorption (HITRAN) databases. These new absorption line parameters will make it possible to use observations from the future Tropospheric Emission Spectrometer (TES) instrument [Earth Observing System (EOS) Chemistry Mission (CHEM) platform] to make more accurate H2S measurements if it observes an H2S-rich volcanic cloud. H2S is the second most abundant volcanic sulfur gas, and like SO2, it also converts to H2SO4 aerosols and can have a climate impact. A paper on the Moderate-resolution Imaging-Spectroradiometer (MODIS) SO2 alert is being revised. New aspects in the revision include verification of the SO2 alert during the EOS mission; factors affecting SO2 detection at thermal infrared, ultraviolet, and microwave wavelengths; radiative transfer tests; more description of satellite instruments; and thermal surface alert installed for MODIS. Her research involves the use of remote sensing to generate maps of plume top altitude. This parameter is important for models of volcanic eruption, aircraft hazards, and climate impact. The topographic shape of the top surface of a volcanic plume can provide information necessary to understand the physics controlling the injection and dispersal of a volcanic plume in the atmosphere. Glaze et al. describe the application of a photoclinometric technique to volcanic plumes. The software algorithm has been improved to account for more general plume and illumination geometries and for easily extracting position information directly from Advanced Very High-Resolution Radiometer (AVHRR) level 1B data. Testing of the algorithm has focused on acquiring AVHRR data for a variety of volcanic plumes in an effort to identify problems with the software as well as model sensitivities. The plumes chosen were erupted from volcanoes at a variety of latitudes, at different times of day, and in different seasons. Another important issue that is being investigated is the importance of plume opacity. A diagram illustrates the method for deriving phi, the angle a wind-blown plume makes with the horizontal, in the direction perpendicular to the remote sensing scan. A figure shows a sample output of the algorithm, a wire mesh map of plume top topography. Additional information is contained in the original.

Crisp, Joy A.↗
NASA NTRS2024

A Uniform Analysis of Debris Discs with the Gemini Planet Imager II: Constraints on Dust Density Distribution Using Empirically Informed Scattering Phase Functions

Spatially resolved images of debris discs are necessary to determine disc morphological properties and the scattering phase function (SPF) thatantifies the brightness of scattered light as a function of phase angle. Current high-contrast imaging instruments have successfully resolved several dozens of debris discs around other stars, but few studies have investigated trends in the scattered-light, resolved population of debris discs in a uniform and consistent manner. We have combined Karhunen-Loeve Image Projection (KLIP) with radiative-transfer disc forward modelling in order to obtain the highest-quality image reductions and constrain disc morphological properties of eight debris discs imaged by the Gemini Planet Imager at H -band with a consistent and uniformly applied approach. In describing the scattering properties of our models, we assume a common SPF informed from solar system dust scattering measurements and apply it to all systems. We identify a diverse range of dust density properties among the sample, including critical radius, radial width, and vertical width. We also identify radially narrow and vertically extended discs that may have resulted from substellar companion perturbations, along with a tentative positive trend in disc eccentricity with relative disc width. We also find that using a common SPF can achieve reasonable model fits for discs that are axisymmetric and asymmetric when fitting models to each side of the disc independently, suggesting that scattering behaviour from debris discs may be similar to Solar system dust.

scattering↗
NASA NTRS1996

High Precision Time Transfer in Space with a Hydrogen Maser on MIR

An atomic hydrogen maser clock system designed for long term operation in space will be installed on the Russian space station Mir, in late 1997. The H-maser's frequency stability will be measured using pulsed laser time transfer techniques. Daily time comparisons made with a precision of better than 100 picoseconds will allow an assessment of the long term stability of the space maser at a level on the order of 1 part in 10(sup 15) or better. Laser pulse arrival times at the spacecraft will be recorded with a resolution of 10 picoseconds relative to the space clock's time scale. Cube corner reflectors will reflect the pulses back to the Earth laser station to determine the propagation delay and enable comparison with the Earth-based time scale. Data for relativistic and gravitational frequency corrections will be obtained from a Global Positioning System (GPS) receiver.

Mattison, Edward M.↗
DOE OSTI2022

Polarized, V-Shaped, and Conjoined Biscoumarins: From Lack of Dipole Moment Alignment to High Brightness

Eleven conjoined coumarins possessing a chromeno[3,4-c]chromene-6,7-dione skeleton have been synthesized via the reaction of electron-rich phenols with esters of coumarin-3-carboxylic acids, catalyzed by either Lewis acids or 4-dimethylaminopyridine. Furthermore, Michael-type addition to angular benzo[f]coumarins is possible, leading to conjugated helical systems. Arrangement of the electron-donating amino groups at diverse positions on this heterocyclic skeleton makes it possible to obtain π-expanded coumarins with emission either sensitive to, or entirely independent of, solvent polarity with large Stokes shifts. Computational studies have provided a rationale for moderate solvatochromic effects unveiling the lack of collinearity of the dipole moments in the ground and excited states. Depending on the functional groups present, the obtained dyes are highly polarized with dipole moments of ~14 D in the ground state and ~20–25 D in the excited state. Strong emission in nonpolar solvents, in spite of the inclusion of a NO 2 group, is rationalized by the fact that the intramolecular charge transfer introduced into these molecules is strong enough to suppress intersystem crossing yet weak enough to prevent the formation of dark twisted intramolecular charge transfer states. Photochemical transformation of the dye possessing a chromeno[3,4-c]pyridine-4,5-dione scaffold led to the formation of a spirocyclic benzo[g]coumarin.

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

Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH 3 through Modification of the Hydrogen Atom Abstractor

We report that (TMP)Ru(NH 3 ) 2 (TMP = tetramesitylporphryin) is a molecular catalyst for oxidation of ammonia to dinitrogen. An aryloxy radical, tri-tert-butylphenoxyl (ArO•) abstracts H atoms from a bound ammonia ligand of (TMP)Ru(NH 3 ) 2 , leading to the discovery of a new catalytic C-N coupling to the para position of ArO•, forming 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to contain a trityl group at the para position, 2,6-di-tert-butyl-4-tritylphenoxyl radical, prevents C-N coupling and diverts the reaction to catalytic oxidation of ammonia to give N 2 . We achieve 125(±5) turnovers at 22 °C for oxidation of NH 3 , the highest reported to date for a molecular catalyst.

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

Hemodilution, vasopressin suppression, and diuresis during water immersion in man

The possible role of hemodilution in the early stages of water immersion in the suppression of antidiuretic hormone (vasopressin) and subsequent diuresis in man is investigated. Parameters characterizing hemodilution as well as water balance and intercompartmental fluid levels were measured before, during and after the immersion of ten subjects in a semireclining position in tap water up to their necks at 34.6 C for 8 hr. Results indicate that hemodilution and the suppression of vasopressin and plasma renin activity were present by the second hour of immersion, with the early hemodilution due to a slight increase in plasma volume with no change in plasma sodium or osmotic contents, even though urine volume and osmotic excretion rates increased significantly. Hyponatremia, hyposmotemia and plasma renin activity suppression are observed to continue to the end of immersion, resulting in final decreases of 15.6% in plasma volume, 18.8% in extracellular volume, 19.6% in interstitial volume and 10.7% in red cell volume. Findings suggest the transfer of hypotonic fluid into the vascular system, which contributes to vasopressin suppression observed during immersion.

Greenleaf, J. E.↗
NASA NTRSDate not supplied

Biosentinel: Update on Extended Mission Operations

BioSentinel has achieved unprecedented performance of an SLS secondary payload due to preparation, planning, and a robust design. Following the conclusion of the primary science mission in April 2023, the Linear Energy Transfer (LET) Spectrometer has continued to collect solar and galactic radiation data from its unique location in heliocentric orbit. The free space dataset offered by the BioSentinel LET is a valuable source of data for both model validation and future mission planning. As the spacecraft travels farther from Earth it is poised to provide longitudinally distributed measurements of solar particle events during solar maximum. Flight heritage has now been gained on many of the novel spacecraft components. The spacecraft bus continues to operate within the design envelope. The 3D-printed cold gas propulsion system provides momentum unloading from the reaction wheels. The power system has maintained power positive levels during flight. The IRIS radio communicates on a weekly basis with the Deep Space Network. The extended mission operations are allowing the team to characterize the performance of the spacecraft components over longer durations of operations. NASA Ames led development of the BioSentinel spacecraft and mission operations. The novel subsystems and COTS components that comprise the BioSentinel bus can serve as a template for future deep space missions. With over a year of continuous operations, the data will inform the next generation of interplanetary smallsat missions.

BioSentinel↗
DOE OSTI2024

LINAC Longitudinal Simulation and Measurement of Output Energy

The Linac at Fermilab, one of the oldest accelerators on-site, plays a crucial role in delivering 400 MeV proton beams to other accelerating facilities. The beam traveling through Linac needs to be carefully monitored for better accelerator operation. One of the key factors of efficient Linac operation is its longitudinal stability. The stability can minimize Linac loss and maximize beam current. For this purpose, I examined the beam's longitudinal profile, which is crucial for proper beam transfer between its two sections. After careful monitoring of the beam through Linac, we need to ensure that it leaves with desired parameters. The beam coming out from the Linac is subsequently injected into the Booster, a synchrotron that relies on dipole magnets to bend the beam at injection. If the output energy of the beam deviates from the expected value, the beam will bend at an incorrect radius, leading to potential beam loss. Therefore, precise regulation of the output energy is critical for the efficient operation of the accelerator. To address this, I have conducted a thorough examination of the Linac longitudinal simulations and data from Beam Position Monitors (BPMs). My objective is to measure and stabilize the output energy and verify its correspondence with the predicted simulation results. All these analyses are important for efficient operation of the accelerator.

Safaryan, Milena↗
DOE OSTI2023

Measurement of Beam Energy in the Fermilab's Linac taken at the transfer Line

Linac is the first machine in the Accelerator chain at Fermilab where 𝐻− particles are accelerated from 35 keV to 400 MeV and travel to the Booster where they are stripped. of the extra electrons to become protons. The Booster requires stable beam energy at injection. The Linac extraction energy tuning has been performed using two Beam Velocity Monitors (a.k.a Griffin detectors) to maintain stable relative energy between the Booster and the Linac. Our goal is to control the Linac energy parameters using Machine Learning techniques to increase reliability and quality of beam delivered from Linac. The first step is to understand the data from the Linac extraction diagnostics; and develop reliable, accurate methods for energy measurement and control before implementing machine learning. There were two methods of energy measurement implemented, and the results of these are compared. The first method was time of flight measurements using the Phase probes inside B eam Position Monitors (BPM) that provide the beam’s phase of arrival data. The second method used the relation between beam position data from the BPMs and dispersion values from the 400MeV MAD-X model to calculate momentum variation. The results of these two energy measurement methods compare well as the Linac energy is varied.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS2006

Correcting STIS CCD Point-Source Spectra for CTE Loss

We review the on-orbit spectroscopic observations that are being used to characterize the Charge Transfer Efficiency (CTE) of the STIS CCD in spectroscopic mode. We parameterize the CTE-related loss for spectrophotometry of point sources in terms of dependencies on the brightness of the source, the background level, the signal in the PSF outside the standard extraction box, and the time of observation. Primary constraints on our correction algorithm are provided by measurements of the CTE loss rates for simulated spectra (images of a tungsten lamp taken through slits oriented along the dispersion axis) combined with estimates of CTE losses for actual spectra of spectrophotometric standard stars in the first order CCD modes. For point-source spectra at the standard reference position at the CCD center, CTE losses as large as 30% are corrected to within approx.1% RMS after application of the algorithm presented here, rendering the Poisson noise associated with the source detection itself to be the dominant contributor to the total flux calibration uncertainty.

Goudfrooij, Paul↗
DOE OSTI2021

Importance of Superstructure in Stabilizing Oxygen Redox in P3‐Na 0.67 Li 0.2 Mn 0.8 O 2

Abstract Activation of oxygen redox represents a promising strategy to enhance the energy density of positive electrode materials in both lithium and sodium‐ion batteries. However, the large voltage hysteresis associated with oxidation of oxygen anions during the first charge represents a significant challenge. Here, P3‐type Na 0.67 Li 0.2 Mn 0.8 O 2 is reinvestigated and a ribbon superlattice is identified for the first time in P3‐type materials. The ribbon superstructure is maintained over cycling with very minor unit cell volume changes in the bulk while Li ions migrate reversibly between the transition metal and Na layers at the atomic scale. In addition, a range of spectroscopic techniques reveal that a strongly hybridized Mn 3d–O 2p favors ligand‐to‐metal charge transfer, also described as a reductive coupling mechanism, to stabilize reversible oxygen redox. By preparing materials under three different synthetic conditions, the degree of ordering between Li and Mn is varied. The sample with the maximum cation ordering delivers the largest capacity regardless of the voltage windows applied. These findings highlight the importance of cationic ordering in the transition metal layers, which can be tuned by synthetic control to enhance anionic redox and hence energy density in rechargeable batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The European wood pellets for heating market - Price developments, trade and market efficiency

Competitive international markets imply adjustments towards competitive spatial equilibrium in which excess from one market is transferred to another and prices are equilibrated except for remaining differences that can be assigned to transfer costs. The European market for wood pellets used in small-scale heating systems has been expanding significantly over the past decade. Small scale pellet heating is arguably a mature technology, but whether the market is mature is another question. In this paper we analyse recent data on trade flows and price developments between Italy, Austria, Germany and France to understand the developments of wood pellet market efficiency and to draw conclusions about market function. The objective of this study is to establish a framework to test the European residential wood pellet market for competitive spatial equilibrium using modern trade theory. We find mainly inefficiently integrated markets with remaining positive marginal profits and detectable arbitrageurs’ activity. Based on a thorough discussion of these findings and the underlying data we outline possible methodology advancements and list policy recommendations to secure access and affordability of this renewable heating commodity in the long run.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Fic Proteins Inhibit the Activity of Topoisomerase IV by AMPylation in Diverse Bacteria

The Fic (filamentation induced by cyclic AMP) domain is a widely distributed motif with a conserved sequence of HPFx[D/E]GN[G/K]R, some of which regulate cellular activity by catalyzing the transfer of the AMP moiety from ATP to protein substrates. Some Fic proteins, including Fic-1 from the soil bacterium Pseudomonas fluorescens strain 2P24, have been shown to inhibit bacterial DNA replication by AMPylating the subunit B of DNA gyrase (GyrB), but the biochemical activity and cellular target of most Fic proteins remain unknown. Here, we report that Fic-2, which is another Fic protein from strain 2P24 and Fic-1 AMPylate the topoisomerase IV ParE at Tyr 109 . We also examined Fic proteins from several phylogenetically diverse bacteria and found that those from Yersinia pseudotuberculosis and Staphylococcus aureus AMPylate ParE and GrlB, the counterpart of ParE in Gram-positive bacteria, respectively. Modification by Fic-1 of P. fluorescens and FicY of Y. pseudotuberculosis inhibits the relaxation activity of topoisomerase IV. Consistent with the inhibition of ParE activity, ectopic expression of these Fic proteins causes cell filamentation akin to the canonical par phenotype in which nucleoids are assembled in the center of elongated cells, a process accompanied by the induction of the SOS response. Our results establish that Fic proteins from diverse bacterial species regulate chromosome division and cell separation in bacteria by targeting ParE.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1971

Studies of positive-ion composition in the equatorial D-region ionosphere.

Evaluation of two daytime D-region positive-ion composition measurements performed at Thumba, India, for solar zenith angles of 53.2 and 27.8 deg. Comparison of upleg ram with downleg wake data shows a large increase in the concentration of heavy ions 48(+), NO(+) . H2O; 55(+), H3O(+) . (H2O)2; and M(+) greater than 65(+) for the downleg reduced shock condition. Peak concentrations of 48(+) and 55(+) occur at unit optical depth for Lyman alpha radiation. The ion 37(+), H3O(+) . H2O, is dominant for chi = 27.8 deg, but not for chi = 53.2 deg, consistent above 80 km with an origin from the X-ray production of O2(+). Laboratory measurements have shown that the ion, NO(+), can be transferred to heavy hydrates 48(+), 55(+), and M(+) greater than 65(+) by a reaction chain starting with NO(+) + X + M = NO(+) . X + M, where X can be O2, N2, CO2 or a combination of all three, depending on the rate of reaction. This chain, together with a similar reaction scheme starting with O2(+) and ending in 19(+), 37(+), and heavier clusters, is used to provide a consistent explanation for the hydrated ions observed in the D region.

Goldberg, R. A.↗
NASA NTRS1983

Spectral radiance errors in remote sensing ground studies due to nearby objects

Attention is given to the error that can occur in all radiometric measurements owing to the presence of nearby objects. When a researcher positions himself on the side of a target point opposite the sun, his body gives rise to two erroneous effects. First, it blocks a portion of the incoming diffuse sky radiance to the target point, and second, it reflects incoming diffuse and direct solar irradiance and ground exitance onto the target point. It is noted that the same phenomenon occurs for any nearby object, whether it be a field truck, a building structure, or a row of trees. This error deriving from nearby objects is often not recognized by researchers or is considered insignificant with no knowledge of its magnitude. The approach taken here is to mathematically model the radiant transfers that take place between the global irradiance, panel, or scene and the object and to report the magnitude of this error for various solar zenith angles, wavelengths, size and distances of objects (steradian blockage), and spectral reflectances of the scene and object. The scene, object, and panel are assumed to be Lambertian, and the object is always located on the side of the target point opposite the sun.

Kimes, D. S.↗