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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Structural insights into RNase H catalytic mechanism from room-temperature X-ray and neutron crystallography of apo- and RNA/DNA hybrid-bound enzyme

RNase H enzymes are sequence-nonspecific endonucleases that cleave RNA strands in RNA/DNA hybrid duplexes, an enzymatic process essential in DNA replication and repair in both prokaryotes and eukaryotes. Also, RNase H activity of the reverse transcriptase in human immunodeficiency viruses (HIV-1 and HIV-2) is indispensable for the viral replication cycle. RNase H enzymes play an central role in the development of gene therapies and are targets for novel antivirals. It is therefore of great importance to gain a detailed understanding of the RNase H catalytic mechanism to improve drug design. We utilized Bacillus halodurans RNase H1 (BhRNase H1) to shed light on its function and catalytic mechanism. Room-temperature neutron crystallography of the wild-type and inactive D132N mutant enzymes revealed that E109, belonging to the catalytic DEDD motif, can change its protonation state, allowing us to propose its role in the protonation of the leaving O3′ hydroxyl group of RNA. X-ray crystallography has demonstrated the ability of the RNA/DNA duplex to slide along the protein surface upon metal ion binding at site M A , transforming a product mimic into a Michaelis-like complex, which confirms an essential role of the M A metal ion in catalysis.

Enzyme mechanisms↗
DOE OSTI2022

Hydrogen Atom Abstraction from an Os II (NH 3 ) 2 Complex Generates an Os IV (NH 2 ) 2 Complex: Experimental and Computational Analysis of the N–H Bond Dissociation Free Energies and Reactivity

We report double hydrogen atom abstraction from (TMP)Os II (NH 3 ) 2 (TMP = tetramesitylporphyrin) with phenoxyl or nitroxyl radicals leads to (TMP)Os IV (NH 2 ) 2 . This unusual bis(amide) complex is diamagnetic and displays an N-H resonance at 12.0 ppm in its 1 H NMR spectrum. 1 H- 15 N correlation experiments identified a 15 N NMR spectroscopic resonance at –267 ppm. Experimental reactivity studies and density functional theory calculations support relatively weak N-H bonds of 73.3 kcal/mol for (TMP)Os II (NH 3 ) 2 and 74.2 kcal/mol for (TMP)Os III (NH 3 )(NH 2 ). Cyclic voltammetry experiments provide an estimate of the pK a of [(TMP)Os III (NH 3 ) 2 ] + . In the presence of Barton’s base, a current enhancement is observed at the Os(III/II) couple, consistent with an ECE event. Spectroscopic experiments confirmed (TMP)Os IV (NH 2 ) 2 as the product of bulk electrolysis. Double hydrogen atom abstraction is influenced by π donation from the amides of (TMP)Os IV (NH 2 ) 2 into the d orbitals of the Os center, favoring the formation of (TMP)Os IV (NH 2 ) 2 over N-N coupling. This π donation leads to a Jahn-Teller distortion that splits the energy levels of the d xz and d yz orbitals of Os, results in a low spin electron configuration, and leads to minimal aminyl character on the N atoms, rendering (TMP)Os IV (NH 2 ) 2 unreactive towards amide-amide coupling.

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

Improving Carbonate-Promoted C–H Carboxylation Using Mesoporous Carbon Supports

C–H carboxylation is an attractive way to utilize CO 2 for chemical production provided that it does not consume resource-intensive reagents. Alkali carbonates dispersed into the pores of mesoporous supports display strongly basic reactivity under CO 2 , allowing them to be used as base promoters for C–H carboxylation of (hetero)arenes in the absence of other reagents or catalysts. Mesoporous oxides are convenient support materials, but only a relatively small fraction of the dispersed carbonate (ca. 10-20%) is converted to carboxylate products when metal oxide supports are used. Here we compare mesoporous oxide and carbon supports and investigate the dependence of carbonate reactivity on pore structure. We show that using mesoporous carbons supports can increase the carbonate conversion by 2–4x when compared to oxide supports. This improved carbonate reactivity is maintained across a variety of mesoporous carbons with different pore structures (ordered vs. disordered) and pore diameters, indicating that the dispersed carbonate is intrinsically more reactive on the surface of a carbon material compared to an oxide surface. Reaction of the carboxylate products with dimethyl carbonate yields isolable methyl esters as the final product and regenerates the dispersed carbonate. We show that mesoporous carbon supports are robust to at least 5 cycles of successive C–H carboxylation and methylation with dimethyl carbonate. Furthermore, understanding how the support structure affects dispersed carbonate reactivity is valuable for advancing C–H carboxylation toward practical application and utilizing these materials in other CO 2 transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Elucidating the Role of Water on Limonene Oxidation with H 2 O 2 over γ -Al 2 O 3

Limonene oxide, which is produced from limonene epoxidation, is a valuable molecule that can be applied in flavor, fragrance, and renewable polymer applications. A catalytic reaction system using H 2 O 2 with γ-Al 2 O 3 and ethyl acetate (EtOAc) as the solvent has been explored as an effective system for this reaction. In these previous studies, a number of postulates have been proposed as to how water affects the reaction; therefore, the focus of this work is to elucidate the role of water in limonene epoxidation. While not impacting the selectivity to limonene oxide, the amount of water in the reaction system is shown to significantly impact the limonene reactivity. Furthermore, through both addition of excess water and removal of water with a Dean–Stark apparatus, the control of the H 2 O 2 /H 2 O ratio is demonstrated to be the primary factor controlling reactivity. In contrast, changes in limonene concentrations for a specific H 2 O 2 /H 2 O ratio are shown to have little impact on the reaction rate. This study shows that the competitive adsorption of H 2 O 2 and water on the catalyst surface is key in explaining the water impact on the reaction performance.

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

Enzymatic Nitrogen Insertion into Unactivated C–H Bonds

Selective functionalization of aliphatic C–H bonds, ubiquitous in molecular structures, could allow ready access to diverse chemical products. While enzymatic oxygenation of C–H bonds is well established, the analogous enzymatic nitrogen functionalization is still unknown; nature is reliant on pre-oxidized compounds for nitrogen incorporation. Likewise, synthetic methods for selective nitrogen derivatization of unbiased C–H bonds remain elusive. In this work, new-to-nature heme-containing nitrene transferases were used as starting points for the directed evolution of enzymes to selectively aminate and amidate unactivated C(sp3)–H sites. The desymmetrization of methyl- and ethylcyclohexane with divergent site selectivity is offered as demonstration. The evolved enzymes in these lineages are highly promiscuous and show activity towards a wide array of substrates, providing a foundation for further evolution of nitrene transferase function. Computational studies and kinetic isotope effects (KIEs) are consistent with a stepwise radical pathway involving an irreversible, enantiodetermining hydrogen atom transfer (HAT), followed by a lower-barrier diastereoselectivity determining radical rebound step. In-enzyme molecular dynamics (MD) simulations reveal a predominantly hydrophobic pocket with favorable dispersion interactions with the substrate. Here, by offering a direct path from saturated precursors, these enzymes present a new biochemical logic for accessing nitrogen-containing compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Mechanistic Insights into the Origins of Selectivity in a Cu-Catalyzed C–H Amidation Reaction

The catalytic transformation of C-H to C-N bonds offers rapid access to fine chemicals and high-performance materials, but achieving high selectivity from undirected aminations of unactivated C(sp 3 )-H bonds remains an outstanding challenge. Here, we report the origins of the reactivity and selectivity of a Cu-catalyzed C-H amidation of simple alkanes. Using a combination of experimental and computational mechanistic studies and energy decomposition techniques, we uncover a switch in mechanism from inner-sphere to outer-sphere coupling between alkyl radicals and the active Cu(II) catalyst with increasing substitution of the alkyl radical. The combination of computational predictions and detailed experimental validation shows that simultaneous minimization of both Cu-C covalency and alkyl radical size increases the rate of reductive elimination and that both strongly electron-donating and electron-withdrawing substituents on the catalyst accelerate the selectivity-determining C-N bond formation process as a result of a change in mechanism. These findings offer design principles for the development of improved catalyst scaffolds for radical C-H functionalization reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Coordination-induced O-H/N-H bond weakening by a redox non-innocent, aluminum-containing radical

Abstract Several renewable energy schemes aim to use the chemical bonds in abundant molecules like water and ammonia as energy reservoirs. Because the O-H and N-H bonds are quite strong (>100 kcal/mol), it is necessary to identify substances that dramatically weaken these bonds to facilitate proton-coupled electron transfer processes required for energy conversion. Usually this is accomplished through coordination-induced bond weakening by redox-active metals. However, coordination-induced bond weakening is difficult with earth’s most abundant metal, aluminum, because of its redox inertness under mild conditions. Here, we report a system that uses aluminum with a redox non-innocent ligand to achieve significant levels of coordination-induced bond weakening of O-H and N-H bonds. The multisite proton-coupled electron transfer manifold described here points to redox non-innocent ligands as a design element to open coordination-induced bond weakening chemistry to more elements in the periodic table.

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

Turbulence driven widening of the near-SOL power width in ASDEX Upgrade H-Mode discharges

Divertor heat flux data from infra red (IR) from various tokamaks in H-Mode regime show that the power width, $\lambda_{q}$, scales approximately like 1.6 $(R/a) ρ_{s,pol}$. However, the IR based scaling comes with the restriction that only discharges were considered with attached divertor conditions. Here we set up a new data base covering low edge density data but also including high density plasmas reaching the H-mode density limit. We use Thomson-scattering to measure the electron temperature decay length which will set the near-SOL power width through parallel heat conduction. We present scaling results for the density, temperature and pressure separatrix fall-off lengths. As the principal result we derive a generalized power width scaling which reads as $\lambda_{q}\propto\,\rho_{s,pol}\cdot(1+2.1\alpha_{t}^{1.7})$ where $\alpha_{t}$ describes a normalized collisionality ($\alpha_{t} = 3\cdot\,10^{-18}\,R\,q^2\,n\,Z_{eff}T^{-2}$). The parameter $\alpha_{t}$ describes the relative importance of the interchange effect on drift-wave turbulence as proposed by Scott and is found to be closely linked to the diamagnetic parameter αd introduced by Rogers, Drake and Zeiler (RDZ). The edge operational space for ASDEX Upgrade displays a boundary qualitatively in agreement with the region labelled as density limit in the edge plasma phase space proposed by RDZ. The data base shows in the limit of low edge densities ($\alpha_{t}\simeq\,0.2$) accurate agreement to the IR based power width scaling. At elevated separatrix densities ($\alpha_{t}\simeq\,1$) the power width is broadened by a factor of up to about three accompanied by a reduction of the $\text{H}_{98,y2}$ confinement factor. Finally, plasmas with higher triangularity show higher values for $\text{H}_{98,y2}$ in the same range of normalized collisionality.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Non-linear dependence of ion heat flux on plasma density at the L–H transition of JET NBI-heated deuterium–tritium plasmas

Abstract Recent JET D–T campaigns opened the possibility of unique isotope studies to investigate the L–H transition physics in view of reactor plasmas and to study the origin of the observed power threshold minimum. In the present paper, we characterise L–H transitions in the low and high-density branches of JET NBI-heated D–T plasmas. As discussed in the paper, L–H transition has been hypothesised to be determined by the transport power losses of plasma ions, i.e. the so-called ion heat flux ( Q i ). We present the first power balance analysis of JET NBI-heated D–T plasmas to evaluate the ion heat flux at the transition. Due to the experimental setting being similar to previous JET D experiments, we also directly compare the results, discussing the isotope effect and similarities between datasets. First, we find an isotope effect between D and D–T Q i , with a lower Q i in D–T plasmas. We confirm that the ion heat flux deviates from density linearity compared to the linear trend observed in wave-heated D plasmas of other tokamaks. The deviation we observe in NBI-heated L–H transitions happens at an isotope-dependent density. Plasma edge rotation correlates with Q i deviation from density linearity in the low-density branch. However, further investigations would be required to assess the role of rotation on Q i and the power threshold minimum at JET. At low plasma density, NBI power dominates Q i , while increasing the density makes the equipartition power dominant. We finally compare our results with hypotheses proposed from evidence in other tokamaks to present a complete overview of ion heat flux analyses in D and D–T NBI-heated plasmas at JET.

Vincenzi, P. (ORCID:0000000251564354)↗
DOE OSTI2024

H - Ion Source RF Plasma Testing with 13 MHz and 27 MHz at the Spallation Neutron Source (SNS)

The baseline RF-driven H⁻ ion source configuration at the Spallation Neutron Source (SNS) facility uses a continuous wave (CW) 600 W 13 MHz RF system to ignite and maintain a low-density plasma inside the ion source vacuum chamber. After the continuous low-density 13 MHz plasma has been established, a pulsed (typical 1 ms pulse width and 60 Hz pulse repetition rate) 80 kW 2 MHz RF system is used to increase the plasma density to produce the pulsed H⁻ ion beam. Incremental upgrades and improvements to the SNS ion source systems have resulted in the ability to reliably operate an H⁻ ion source for SNS neutron production run cycles that can last up to four months. Conditions inside the SNS H⁻ ion source evolve throughout a four-month run cycle due to changes in impurity levels, sputtering, and erosion. As the internal ion source conditions change during the run cycle, there can also be changes in plasma stability and the 13 MHz RF power level required to ignite the plasma. This paper presents the preliminary results of testing performed on the SNS Ion Source Test Stand (ISTS) system where we looked at plasma ignition and plasma stability using 27 MHz RF in place of the baseline 13 MHz RF system.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Measurement of Λ b 0 , Λ c + , and Λ Decay Parameters Using Λ b 0 → Λ c + h − Decays

A comprehensive study of the angular distributions in the bottom-baryon decays Λ b 0 → Λ c + h − ( h = π , K ) , followed by Λ c + → Λ h + with Λ → p π − or Λ c + → p K S 0 decays, is performed using a data sample of proton-proton collisions corresponding to an integrated luminosity of 9 fb − 1 collected by the LHCb experiment at center-of-mass energies of 7, 8, and 13 TeV. The decay parameters and the associated charge-parity ( C P ) asymmetries are measured, with no significant C P violation observed. For the first time, the Λ b 0 → Λ c + h − decay parameters are measured. The most precise measurements of the decay parameters α , β , and γ are obtained for Λ c + decays and an independent measurement of the decay parameters for the strange-baryon Λ decay is provided. The results deepen our understanding of weak decay dynamics in baryon decays. © 2024 CERN, for the LHCb Collaboration 2024 CERN

Aaij, R. (ORCID:0000000305331952)↗
DOE OSTI2020

Simplified Two-Stage Model Predictive Control for a Hybrid Multilevel Converter With Floating H-Bridge

This paper proposes a simplified two-stage model predictive control (ST-MPC) for a hybrid multilevel converter, which is an active-neutral-point-clamped converter with floating H-bridge (ANPC-H). The objective of the first stage is to select the voltage vector that has the optimal current tracking performance by using a novel geometrical positioning approach in the complex plane. The second stage selects the best switching state among all the available switching states that belong to the same voltage vector obtained in the first stage, to balance dc capacitor voltages and reduce the common mode voltage. The proposed ST-MPC can dramatically reduce the computational burden and ensure the best current tracking by the two-stage structure, such that the execution time is much shorter compared with the conventional MPC. In addition, the geometrical positioning approach in the first stage is generic and can be applicable for any multilevel converters with N-level output; thus, this ST-MPC can be applied for both sevenand nine-level operation of the hybrid ANPC-H converter under different dc voltage ratios. Both simulation results and experimental results obtained on a silicon carbide hybrid ANPC-H converter prototype validate the feasibility and effectiveness of the proposed ST-MPC strategy.

42 ENGINEERING↗
DOE OSTI2022

Diamond formation kinetics in shock-compressed C$-$H$-$O samples recorded by small-angle x-ray scattering and x-ray diffraction

Extreme conditions inside ice giants such as Uranus and Neptune can result in peculiar chemistry and structural transitions, e.g., the precipitation of diamonds or superionic water, as so far experimentally observed only for pure C$-$H and H 2 O systems, respectively. Here, we investigate a stoichiometric mixture of C and H 2 O by shock-compressing polyethylene terephthalate (PET) plastics and performing in situ x-ray probing. We observe diamond formation at pressures between 72 ± 7 and 125 ± 13 GPa at temperatures ranging from ~3500 to ~6000 K. Combining x-ray diffraction and small-angle x-ray scattering, we access the kinetics of this exotic reaction. The observed demixing of C and H 2 O suggests that diamond precipitation inside the ice giants is enhanced by oxygen, which can lead to isolated water and thus the formation of superionic structures relevant to the planets’ magnetic fields. Moreover, our measurements indicate a way of producing nanodiamonds by simple laser-driven shock compression of cheap PET plastics.

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

Solvent Recovery and Management at the Savannah River Site H-Canyon Facility

NIOWAVE, Inc. is a domestic supplier of medical and industrial isotopes from uranium and radium. The Savannah River National laboratory (SRNL) is currently providing support to NIOWAVE, which plans to deploy a superconducting electron linear accelerator (LINAC) to fission uranium for Mo-99 production without the need for a nuclear reactor or HEU. The uranium from the Mo-99 production targets will be purified using a modified PUREX (Plutonium Uranium Reduction Extraction) solvent extraction process to recover the uranium in the product stream. The uranium will then be precipitated as an oxalate which is calcined to U 3 O 8 to fabricate pellets for new Mo-99 targets. In previous support provided to NIOWAVE, the SRNL demonstrated a solvent washing process to remove degradation products from the tributyl phosphate (TBP) solvent used in the modified PUREX process under development for uranium recovery. To supplement this technology demonstration, NIOWAVE requested the SRNL to provide summary information on the solvent recovery and management activities which are used at the Savannah River Site (SRS) H-Canyon facility. An existing reference document for the reprocessing of irradiated HEU fuels at the SRS was used as the primary reference for the solvent management activities; although, other reference documents were used to provide supplementary information. The information provided includes a brief summary of the solvent degradation issues which have been observed in the H-Canyon solvent extraction cycles and resulting process safety concerns. The solvent recovery processes for the three cycles of solvent extraction used in the H-Canyon were subsequently described including the process equipment which consists of the continuous and batch solvent washers, pumps, and tanks. A final section is provided on the monitoring and analysis of solvent quality based on the previous work performed at the SRNL for NIOWAVE and past research and development activities performed to support the solvent extraction processes in both the SRS F-Canyon and H-Canyon facilities.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2024

Probing room temperature indirect and minimum direct band gaps of h-BN

Abstract Hexagonal boron nitride (h-BN) has attracted considerable interest as an ultrawide bandgap (UWBG) semiconductor. Experimental studies focused on the detailed near band-edge structure of h-BN at room temperature are still lacking. We report a direct experimental measurement of the near band-edge structure performed on h-BN quasi-bulk wafers via photocurrent excitation spectroscopy (PES). PES resolved the band-to-band transitions near M- and K-points in the Brillion zone (BZ), from which the room temperature indirect band gap of E g M K ∼6.02 eV, minimum direct bandgap at M-point of E g M = 6.36 eV and next lowest direct energy bandgap at K-point of E g K = 6.56 eV , have been simultaneously determined for the first time experimentally. The measured energy differences between K- and M-points in the conduction band minimum (CBM) and valence band maximum (VBM) are Δ E C M K = 0.54 eV and Δ E V M K = 0.34 eV, respectively, in good agreement with the calculation results. Significantly differing from its III-nitride wurtzite counterparts, in which only electrons and holes in the conduction and valence band extremes at the Γ-point are predominantly involved in the optical and transport processes, the results highlighted that charge carriers associated with both M- and K-valleys control to the optical excitation, recombination and charge transport processes in h-BN.

Physics↗
DOE OSTI2021

Significant H i and Metal Differences around the z = 0.83 Lens Galaxy toward the Doubly Lensed Quasar SBS 0909+532

We report a large difference in neutral hydrogen (H i) and metal column densities between the two sight lines probing opposite sides of the lensing galaxy at z {sub lens} = 0.83 toward the doubly lensed quasar SBS 0909+532. Using archival HST-STIS and Keck HIRES spectra of the lensed quasar images, we measure log N {sub H I} = 18.77 ± 0.12 cm{sup −2} toward the brighter image (A) at an impact parameter of r {sub A} = 3.15 kpc and log N {sub H I} = 20.38 ± 0.20 cm{sup −2} toward the fainter image (B) at an impact parameter of r {sub B} = 5.74 kpc. This difference by a factor of ∼41 is the highest difference between sight lines for a lens galaxy in which H i has been measured, suggesting patchiness and/or anisotropy on these scales. We estimate an average Fe abundance gradient between the sight lines to be ≥+0.35 dex kpc{sup −1}. The N {sub Fe II}/N {sub Mg II} ratios for the individual components detected in the Keck HIRES spectra have supersolar values for all components in sight line A and for 11 out of 18 components in sight line B, suggesting that Type Ia supernovae may have contributed to the chemical enrichment of the galaxy’s environment. Additionally, these observations provide complementary information to detections of cold gas in early-type galaxies and the tension between these and some models of cloud survival.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1974

Multi-slit spectrograph and H alpha Doppler system

Description of the design and operation of a multiple-entrance-slit spectrograph, built for time-lapse photography of the spectra of flares and other transient solar phenomena. This spectrograph employs narrow-band filters to limit the wavelength range of the spectrograph to a few angstroms centered at H-alpha or other spectral lines. A polarizing beamsplitter, prior to the slits, provides a prefiltered second solar image to a narrow band H-alpha Doppler filter for simultaneous photography in the wings of the H-alpha line. The spectrograph and the H-alpha Doppler system constitute a flexible instrument in which components may be substituted to achieve different passband widths, image scales, dispersions, and corresponding numbers and spacings of adjacent spectra at a selected wavelength.

Martin, S. F.↗
NASA NTRS1979

H/+/ and He/2+/ in the dawnside magnetosheath

Mass and energy analyses of energetic ions in the dawnside magnetosheath have been made by the energetic ion composition experiment on the ISEE-1 spacecraft over the energy range 10 eV/e to 17 keV/e. The significant observations are: the bulk flows of the H(+) and He(2+) components determined from first moments of the distributions averaged over several minutes are equal within the uncertainties of the measurement. The H(+) and He(2+) distributions are similar in that they both show temperature anisotropies with perpendicular temperature not less than parallel temperature; however, the distributions are not well characterized by temperatures derived from second moments. In at least one case high energy tails of both distributions can be characterized by an additional higher temperature component. The major difference between the H(+) and He(2+) distributions is the depletion of the low velocity (in the center of mass frame) part of the He(2+) distributions, relative to the H(+) distributions.

Peterson, W. K.↗