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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Mechanism of O 2 Activation and Cysteine Oxidation by the Unusual Mononuclear Cu(I) Active Site of the Formylglycine-Generating Enzyme

The formylglycine-generating enzyme (FGE) catalyzes the selective oxidation of a peptidyl-cysteine to form formylglycine, a critical cotranslational modification for type I sulfatase activation and a useful bioconjugation handle. Previous studies have shown that the substrate peptidyl-cysteine binds to the linear bis-thiolate Cu(I) site of FGE to form a trigonal planar tris-thiolate Cu(I) structure that activates O 2 for the oxidation of the C β –H of the cysteine substrate via an unknown mechanism. Here, we employed a combination of stopped-flow kinetic, spectroscopic (UV–vis absorption, XAS, and EPR), and computational (DFT/TD-DFT calculations) methods to observe and characterize the key intermediates in this reaction for FGE from Streptomyces coelicolor. Our results define the reaction coordinate of FGE, which involves H-atom abstraction from the C β –H bond of the cysteine substrate by a reactive Cu(II)–O 2 •– species to form the now experimentally observed Cu(I)–OOH intermediate bound to a peptidyl-thioaldehyde, which proceeds to oxidize one of the protein-derived cysteine residues to a sulfenate that is end-on O-coordinated to Cu(I). These results provide fundamental insights into how the unusual mononuclear Cu(I) site of FGE activates O 2 for cysteine oxidation and stores oxidizing equivalents during catalysis by employing a Cu(I)–sulfenate intermediate with an end-on O-coordination that is unprecedented in biology.

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

Cooperative Activation of CO 2 and Epoxide by a Heterobinuclear Al–Fe Complex via Radical Pair Mechanisms

Activation of inert molecules like CO 2 is often mediated by cooperative chemistry between two reactive sites within a catalytic assembly, the most common form of which is Lewis acid/base bifunctionality observed in both natural metalloenzymes and synthetic systems. Here, we disclose a heterobinuclear complex with an Al–Fe bond that instead activates CO 2 and other substrates through cooperative behavior of two radical intermediates. The complex L dipp (Me)AlFp (2, L dipp = HC{(CMe)(2,6- i Pr 2 C 6 H 3 N)} 2 , Fp = FeCp(CO) 2 , Cp = η 5 -C 5 H 5 ) was found to insert CO 2 and cyclohexene oxide, producing L dipp Al(Me)(μ:κ 2 -O 2 C)Fp (3) and L dipp Al(Me)(μ-OC 6 H 10 )Fp (4), respectively. Detailed mechanistic studies indicate unusual pathways in which (i) the Al–Fe bond dissociates homolytically to generate formally Al II and Fe I metalloradicals, then (ii) the metalloradicals add to substrate in a pairwise fashion initiated by O-coordination to Al. The accessibility of this unusual mechanism is aided, in part, by the redox noninnocent nature of L dipp that stabilizes the formally Al II intermediates, instead giving them predominantly Al III -like physical character. The redox noninnocent nature of the radical intermediates was elucidated through direct observation of L dipp Al(Me)(OCPh 2 ) (22), a metalloradical species generated by addition of benzophenone to 2. Complex 22 was characterized by X-band EPR, Q-band EPR, and ENDOR spectroscopies as well as computational modeling. As a result, the “radical pair” pathway represents an unprecedented mechanism for CO 2 activation.

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

Enhanced predictability of Eastern North Pacific Tropical cyclone activity using the ENSO Longitude Index

Past studies have indicated that El Nino-Southern Oscillation (ENSO) plays a major role in the interannual variability of Eastern Pacific hurricane activity. The primary mechanism being the eastward displacement of the warm pool during an El Nino, which carries warm water into that basin thereby creating favorable oceanic conditions. Despite this, the question of whether an accurate knowledge of ENSO enhances seasonal predictabiity of Eastern Pacific hurricanes has not been addressed specifically. In this study, we show that unlike traditional indices of ENSO, the ENSO Longitude Index (ELI) is able to predict Eastern Pacific hurricane activity at significant lead times. By capturing changes in the location of deep convection and associated thermocline processes more accurately, ELI explains the most variability in the upper-ocean heat content in the main development region of the Eastern Pacific basin compared to other ENSO indices. These results have substantial implications for operational seasonal forecasts of Eastern Pacific hurricanes.

Balaguru, Karthik↗
DOE OSTI2021

Direct methane activation by atomically thin platinum nanolayers on two-dimensional metal carbides

We report efficient and direct conversion of methane to value-added products has been a long-term challenge in shale gas applications. Here, we show that atomically thin nanolayers of Pt with a single or double atomic layer thickness, supported on a two-dimensional molybdenum titanium carbide (MXene), catalyse non-oxidative coupling of methane to ethane/ethylene (C 2 ). Kinetic and theoretical studies, combined with in-situ spectroscopic and microscopic characterizations, demonstrate that Pt nanolayers anchored at the hexagonal close-packed sites of the MXene support can activate the first C–H bond of methane to form methyl radicals that favour desorption over further dehydrogenation and thus suppress coke deposition. At 750 °C and 7% methane conversion, the catalyst runs for 72 hours of continuous operation without deactivation and exhibits >98% selectivity towards C 2 products, with a turnover frequency of 0.2–0.6 s -1 . Our findings provide insights into the design of highly active and stable catalysts for methane activation and create a platform for developing atomically thin supported metal catalysts.

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

Direct numerical simulations of activation and deactivation in turbulent atmospheric clouds

Significant knowledge gaps remain in our understanding of turbulence–cloud–aerosol interactions in the Earth's atmosphere, and direct numerical simulation (DNS) has increasingly become an indispensable tool to fill such critical knowledge gaps. Here, this study is an extension of our previous DNS model [Gao et al., J. Geophys. Res.: Atmos., 123(4), 2194–2214 (2018)], with a focus on the activation of aerosol particles into cloud droplets and deactivation of cloud droplets into aerosol particles in a microscale cloud environment. The effects of turbulence intensity, particle curvature, and solute, as well as the initial distributions of the aerosol particles (monodisperse or polydisperse) are investigated. The governing equations for the flow of air, temperature, and water vapor mixing ratio are solved numerically in the Eulerian fashion, assuming homogeneous and isotropic turbulence. The dynamics of the aerosol and cloud particles are calculated with the Lagrangian particle tracking method. The results show that the deviations of the thermodynamic variables from their respective means are significantly reduced, the activation process appears to be delayed, and the deactivation process occurs more rapidly, as the turbulence intensity is increased. The inclusion of particle curvature and solute effects, as well as polydispersity, tends to retard the activation of aerosols into cloud droplets. It is also observed that fluctuations in supersaturation broaden the spread of particle radii, and the broadening is followed by a narrowing as turbulent homogenization reduces thermodynamic fluctuations over time.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

The dimeric form of bacterial l ‐asparaginase YpAI is fully active

l ‐asparaginases from mesophilic bacteria (ASNases), including two enzymes very successfully used in the treatment of leukaemia, have been consistently described as homotetramers. On the contrary, structural studies show that homodimers of these enzymes should be sufficient to carry out the catalytic reaction. In this report, we investigated whether the type I Yersinia pestis asparaginase (YpAI) is active in a dimeric form or whether the tetrameric quaternary structure is critical for its activity. Using multiple biophysical techniques that investigate enzymatic properties and quaternary structure at either high or low protein concentration, we found that dimeric YpAI is fully active, suggesting that the tetrameric form of this subfamily of enzymes does not bear significant enzymatic relevance. In this process, we extensively characterized YpAI, showing that it is a cooperative enzyme, although the mechanism of allostery is still not definitely established. We showed that, like most type I ASNases, the substrate affinity of YpAI is low and this enzyme is very similar in terms of both the structure and enzymatic properties to homologous type I ASNase from Escherichia coli (EcAI). We extended these studies to more medically relevant type II ASNases, used as anti‐leukaemia drugs. We confirmed that type II ASNases are not allosteric, and that they might also be functional in a dimeric form. However, the determination of the accurate tetramer⇆dimer dissociation constants of these enzymes that most likely lie in the picomolar range is not possible with currently available biophysical techniques.

Biochemistry & Molecular Biology↗
DOE OSTI2021

Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity

A complex role for chlorine radicals Radicals are atoms or molecules that are highly reactive because they have an unpaired electron. A common means of investigating whether they are involved in a particular reaction is to try to trap them with an acceptor compound. Yang et al. reinvestigated a photoinduced alkane oxidation reaction for which a trapping study had previously implicated alkoxy radicals. Their spectroscopic, kinetic, and isotopic labeling studies revealed that chlorine, rather than alkoxy, was the key radical intermediate; the prior trapping results had stemmed from its complexation with alcohols. Science , abd8408, this issue p. 847

Science & Technology - Other Topics↗
DOE OSTI2023

Promising approaches for the assembly of the catalytically active, recombinant Desulfomicrobium baculatum hydrogenase with substitutions at the active site

Background: Hydrogenases (H2ases) are metalloenzymes capable of the reversible conversion of protons and electrons to molecular hydrogen. Exploiting the unique enzymatic activity of H2ases can lead to advancements in the process of biohydrogen evolution and green energy production. Results: Here we created of a functional, optimized operon for rapid and robust production of recombinant [NiFe] Desulfomicrobium baculatum hydrogenase (Dmb H2ase). The conversion of the [NiFeSe] Dmb H2ase to [NiFe] type was performed on genetic level by site-directed mutagenesis. The native dmb operon includes two structural H2ase genes, coding for large and small subunits, and an additional gene, encoding a specific maturase (protease) that is essential for the proper maturation of the enzyme. Dmb, like all H2ases, needs intricate bio-production machinery to incorporate its crucial inorganic ligands and cofactors. Strictly anaerobic, sulfate reducer D. baculatum bacteria are distinct, in terms of their biology, from E. coli. Thus, we introduced a series of alterations within the native dmb genes. As a result, more than 100 elements, further compiled into 32 operon variants, were constructed. The initial requirement for a specific maturase was omitted by the artificial truncation of the large Dmb subunit. The assembly of the produced H2ase subunit variants was investigated both, in vitro and in vivo. This approach resulted in 4 recombinant [NiFe] Dmb enzyme variants, capable of H 2 evolution. The aim of this study was to overcome the gene expression, protein biosynthesis, maturation and ligand loading bottlenecks for the easy, fast, and cost-effective delivery of recombinant [NiFe] H2ase, using a commonly available E. coli strains. Conclusion: The optimized genetic constructs together with the developed growth and purification procedures appear to be a promising platform for further studies toward fully-active and O 2 tolerant, recombinant [NiFeSe] Dmb H2ase, resembling the native Dmb enzyme. It could likely be achieved by selective cysteine to selenocysteine substitution within the active site of the [NiFe] Dmb variant.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Galactic Rain: Cool Gas Inflows in Red Geyser Galaxies and Their Connection to Active Galactic Nuclei Activity and Interactions

Red geysers are a population of massive (logM/M ⊙ ~ 10.5), quiescent galaxies with large-scale but weak, bisymmetric ionized gas outflows, interpreted as signatures of ongoing, low-level active galactic nucleus (AGN) feedback. We investigate the kinematics and prevalence of cool (T ∼ 100–1000 K) neutral gas traced by Na I D absorption, and its connection to galaxy environment and AGN activity. Using 140 red geyser galaxies from the Sloan Digital Sky Survey-IV Mapping Nearby Galaxies at Apache Point Observatory (or MaNGA), we measure spatially resolved velocities and dispersions via double-Gaussian fits to the Na I D doublet. We find that ∼70% of the cool gas is inflowing, with a median velocity of ∼47 km s −1 (∼10% of the expected freefall velocity), and that it also exhibits kinematically ordered motions with σ NaD /σ* ∼ 0.4. Additionally, the Na I D absorption is more prevalent in red geysers than in a matched control sample, with a higher detection fraction (63% versus 40%) and reservoir areas ∼1.6 times larger. Acceleration (∼1 Myr) and accretion (∼20 Myr) timescales indicate that the Na I D-absorbing clouds are likely young and short-lived. Another intriguing result is that radio-detected red geysers (30% of the sample) show inflowing gas reservoirs ∼7 times larger than in non-radio systems. Similarly, galaxies subject to environmental effects host inflowing gas reservoirs ∼2.7 times larger than isolated red geysers. We take this as evidence that galaxy environments play a key role in replenishing the cool gas reservoirs of red geysers, fueling central AGN activity, sustaining radio emission, and regulating long-term quiescence. These findings reveal that quiescent systems are governed by cycles of inflow, feedback, and regulation.

Moghni, Arian [Univ. of California, Santa Cruz, CA↗
NASA NTRS1973

Detailed correlation of type III radio bursts with H alpha activity. I - Active region of 22 May 1970.

Comparison of observations of type III impulsive radio bursts made at the Clark Lake Radio Observatory with high-spatial-resolution cinematographic observations taken at the Big Bear Solar Observatory. Use of the log-periodic radio interferometer makes it possible to localize the radio emission uniquely. This study concentrates on the particularly active region close to the limb on May 22, 1970. Sixteen of the 17 groups were associated with some H alpha activity, 11 of them with the start of such activity.

Kuiper, T. B. H.↗
NASA NTRS1975

A fuselage/tank structure study for actively cooled hypersonic cruise vehicles: Active cooling system analysis

The effects of fuselage cross section and structural arrangement on the performance of actively cooled hypersonic cruise vehicles are investigated. An active cooling system which maintains the aircraft's entire surface area at temperatures below 394 K at Mach 6 is developed along with a hydrogen fuel tankage thermal protection system. Thermodynamic characteristics of the actively cooled thermal protection systems established are summarized. Design heat loads and coolant flowrate requirements are defined for each major structural section and for the total system. Cooling system weights are summarized at the major component level. Conclusions and recommendations are included.

Stone, J. E.↗
NASA NTRS1974

Magnetic fields in flares and active prominences. II - The field configuration in some active prominences

Study of the longitudinal magnetic field in a number of active limb prominences showing fields in excess of 30 G. The objects fall into three groups: surges, caps, and active-region prominences. There appears to be an upper limit of 150 to 200 G for the field strength in prominences. A model of surges is presented in which a presurge axisymmetric magnetic field is established by a line current in the corona. Particle acceleration in surges is observed, which indicates that V x B is not equal to zero in these objects during periods comparable to the Alfven transit time. The strong fields observed in caps seem to run between parts of active regions in accordance with Hale's law of sunspot group polarities.

Tandberg-Hanssen, E.↗
NASA NTRS1982

Recurrence of solar activity - Evidence for active longitudes

It is pointed out that the autocorrelation coefficients of the daily Wolf sunspot numbers over a period of 128 years reveal a number of interesting features of the variability of solar activity. Besides establishing periodicities for the solar rotation, solar activity cycle, and, perhaps, the 'Gleissberg Cycle', they suggest that active longitudes do exist, but with much greater strength and persistence in some solar cycles than in others. Evidence is adduced for a variation in the solar rotation period, as measured by sunspot number, of as much as two days between different solar cycles.

Bogart, R. S.↗
NASA NTRS1984

Activity of calcium activated protease in skeletal muscles and its changes in atrophy and stretch

The reduction of protein content in skeletal muscle undergoing disuse-induced atrophy is correlated with accelerated rates of protein degradation and reduced rates of protein synthesis (Goldspink, 1977). It is not known in what manner myofibers are partially disassembled during disuse atrophy to fibers of smaller diameter; nor is it known which proteases are responsible for this morphological change in contractile protein mass. Dayton and colleagues (1975) have suggested that the Ca(2+)-activated protease (CaP) may initiate myofibril degradation. The discovery of a form of CaP that is activatable by nano-molar concentrations of Ca(2+) indicates that CaP activity may be regulated by physiological concentrations of Ca(2+) (Mellgren, 1980). The enhancement of proteolysis by the Ca(2+) ionophore A23187, reported by Etlinger (1979), is consistent with a significant role for CaP in protein degradation. It was of interest, therefore, to measure the levels of CaP activity and the CaP inhibitor in extracts obtained from skeletal muscles of rat and chicken limbs undergoing disuse atrophy or stretch hypertrophy, respectively.

Ellis, S.↗
NASA NTRS1989

Are low-activity comets intrinsically different from more active comets?

A group of comets defined as 'normal' by Cochran (1987) is compared with comets from which no C2 or C3 emissions have been detected and exhibit anomalously low activity. It is established that the low-activity comets are C2- and C3-depleted relative to CN, and that this depletion is not due to these comets' being low producers of all types of gases. A study of all the orbital parameters of the group of comets is conducted, but no parameter is found able to account for the observed difference between normal and low-activity types. Several alternative scenarios for the differences in question are proposed and discussed.

Cochran, Anita L.↗
NASA NTRS1990

Elementary bipoles of active regions and ephemeral active regions

The general properties of elementary bipoles (EBs), the class of moving magnetic features identified by Frazier (1972) as building blocks of new solar active regions, are described, and variations in their characteristics are illustrated with extensive videomagnetograms obtained at Big Bear Solar Observatory during 1984-1989. Consideration is given to ephemeral active regions consisting of EBs with only one positive and one negative pole, multiple-pole ephemeral regions, reversed-polarity EBs, interactions among EBs and adjacent magnetic features, and the EBs of small and medium active regions. The detection of EBs prior to the appearance of arch filaments confirms the relationship found by Frazier.

Martin, Sara F.↗