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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

The yeast ALA synthase C‐terminus positively controls enzyme structure and function

Abstract 5‐Aminolevulinic acid synthase (ALAS) is a pyridoxal 5′‐phosphate (PLP)‐dependent enzyme that catalyzes the first and rate‐limiting step of heme biosynthesis in α‐proteobacteria and several non‐plant eukaryotes. All ALAS homologs contain a highly conserved catalytic core, but eukaryotes also have a unique C‐terminal extension that plays a role in enzyme regulation. Several mutations in this region are implicated in multiple blood disorders in humans. In Saccharomyces cerevisiae ALAS (Hem1), the C‐terminal extension wraps around the homodimer core to contact conserved ALAS motifs proximal to the opposite active site. To determine the importance of these Hem1 C‐terminal interactions, we determined the crystal structure of S. cerevisiae Hem1 lacking the terminal 14 amino acids (Hem1 ΔCT). With truncation of the C‐terminal extension, we show structurally and biochemically that multiple catalytic motifs become flexible, including an antiparallel β‐sheet important to Fold‐Type I PLP‐dependent enzymes. The changes in protein conformation result in an altered cofactor microenvironment, decreased enzyme activity and catalytic efficiency, and ablation of subunit cooperativity. These findings suggest that the eukaryotic ALAS C‐terminus has a homolog‐specific role in mediating heme biosynthesis, indicating a mechanism for autoregulation that can be exploited to allosterically modulate heme biosynthesis in different organisms.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Morphology engineering of iridium electrodes via modifying titanium substrates with controllable pillar structures for highly efficient oxygen evolution reaction

Nowadays, Ti is the well-chosen anode substrate material for proton exchange membrane electrolyzer cells (PEMECs) and modifications of the substrate surfaces are essential for the fabrication of highly efficient electrodes. Herein, we introduce the morphology engineering of Ir/Ti electrodes with different acid treatments of hydrochloric acid (HCl) and oxalic acid (OA), and the comparative benefits of these two acid treatment methods are studied from the aspects of their impacts on the morphology, interfacial contact resistance (ICR), and oxygen evolution reaction (OER) performances of resultant electrodes. Notably, compared to the flat surface from OA treatment, Ti substrates with the pillar structure could be successfully achieved via HCl etching. Further, the HCl and the oxalic acid (OA) treatments would reduce the interfacial contact resistance (ICR) to 15.2% and 5.5% of the pristine Ti substrate at 1.38 MPa, respectively. By iridium electrodeposition on Ti substrates, Ir/Ti electrodes with different catalyst loadings are fabricated. With similar low-loadings of about 0.05 mgIr cm –2 , an Ir/Ti electrode with HCl treated substrate exhibits a lower overpotential of ~283 mV at 10 mA cm –2 current density than 305 mV from OA treatment, due to the boosted reaction areas from HCl treatment.

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

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO 2 or Al 2 O 3 . NH 3 -TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO 2 gives softer coke and increases cumulative benzene yields by 25%, while Al 2 O 3 strongly decreases yields. H 2 -TPR and UV-visible and Raman spectroscopy show how the overcoats redisperse the MoO x precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with 27 Al-MAS NMR, MoO x redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Altogether, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.

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

Sequence-Controlled Secondary Structures and Stimuli Responsiveness of Bioinspired Polyampholytes

In this work, a comprehensive study focusing on the influence of the sequence charge pattern on the secondary structure preferences of annealed polyampholytes and their responsiveness to external stimuli is presented. Two sequences are designed composed entirely of ionizable amino acids (charge fraction f=1), and an equal number of positive and negative charges (f + =f - =0.5) with distinct charge-patterns consisting of lysine and glutamic acid monomers. The study reveals that the sequence charge pattern has a significant influence on the secondary structure preferences of polyampholytes at physiological pH. Furthermore, it shows that external stimuli such as pH, ionic strength and solvent dielectric constant can be used to modulate the secondary structure of the two designed sequences. The observed secondary structure transformations for the two sequences are also substantially different from those determined for uniformly charged polypeptides-homo-polypeptides under matching conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Ligand Control of Structural Diversity in Luminescent Hybrid Copper(I) Iodides

Copper(I) iodide hybrids are of interest for next-generation lighting technologies because of their efficient luminescence in the absence of rare-earth elements. Here, we report 10 structurally diverse hybrid copper(I) iodides that emit in the green–red region with quantum yields reaching 67%. The compounds display a diversity of structures including ones with one-dimensional (1D) Cu–1 chains, Cu 2 I 2 rhomboid dimers, and structures with two different arrangements of Cu 4 I 4 tetramers. The compounds with Cu 2 I 2 rhomboid dimers or Cu 4 I 4 cubane tetramers have higher photoluminescence quantum yields than those with Cu–I 1D chains and octahedral Cu 4 I 4 tetramers, owing to the optimal degree of condensation of the inorganic motifs, which suppresses nonradiative processes. Electronic structure calculations on these compounds point out the critical influence of the inorganic motif and organic ligand on the nature of the band gaps and thus the excitation characteristics. Temperature-dependent photoluminescence spectra are presented to better understand the nature of luminescence in compounds with different inorganic motifs. Here. the emerging understanding of composition–structure–property correlations in this family provides inspiration for the rational design of hybrid phosphors for general lighting applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Controlling the Structure of MoS 2 Membranes via Covalent Functionalization with Molecular Spacers

Restacked two-dimensional (2D) materials represent a new class of membranes for water-ion separations. Understanding the interplay between the 2D membrane’s structure and the constituent material’s surface chemistry to its ion sieving properties is crucial for further membrane development. In this paper, we reveal, and tune via covalent functionalization, the structure of MoS 2 -based membranes. We find features on both the ~1 nm (interlayer spacing) and ~100 nm (mesoporous voids between layers) length scales that evolve with the hydration level. The functional groups act as permanent molecular spacers, preventing local impermeability caused by irreversible restacking and promoting the uniform rehydration of the membrane. Molecular dynamics simulations show that the choice of functional group tunes the structure of water within the MoS 2 channel and consequently determines the hydrated interlayer spacing. We demonstrate that MoS 2 membranes functionalized with acetic acid have consistently ~92% rejection of Na 2 SO 4 with a flux of ~1.5 lm -2 hr -1 bar -1 .

2D channel↗
DOE OSTI2025

Crystalline Peptoid Nanofibers with a Single-Unit Cell Cross Section

Ultranarrow crystalline one-dimensional nanostructures formed from soft materials facilitate precise structural control in nanomaterial design, which is essential for biomedicine and nanotechnology applications. Systematic control of their hierarchical structure is challenging due to the complexities of simultaneously manipulating multiple noncovalent interactions at such small scales. We employed a polypeptoid crystal motif as a supramolecular synthon to engineer ultranarrow crystalline nanofibers constrained to a single lattice axis by incorporating a single ionizable side chain into the hydrophobic core of a nanosheet-forming peptoid. Cryogenic transmission electron microscopy of the nanofibers revealed detailed molecular arrangements of a unit-cell cross-section and the presence of distinct pH-dependent lattice isoforms that resulted in morphological transformations. Molecular dynamics simulations demonstrated that the ionizable side chain plays a critical role in changing the local conformation of the unit cell, which further impacts the dimensionality of hierarchical structures. Moreover, these fibers were readily functionalized with biological ligands to afford one-dimensional (1D) protein arrays. This approach for the high-precision bottom-up assembly of ultranarrow 1D nanostructures offers significant potential for developing novel biomimetic nanostructures.

Lee, Yen Jea↗
DOE OSTI2019

Controlling the structure and photophysics of fluorophore dimers using multiple cucurbit[8]uril clampings

A modular strategy has been employed to develop a new class of fluorescent molecules, which generates discrete, dimeric stacked fluorophores upon complexation with multiple cucurbit[8]uril macrocycles. The multiple constraints result in a “static” complex (remaining as a single entity for more than 30 ms) and facilitate fluorophore coupling in the ground state, showing a significant bathochromic shift in absorption and emission. This modular design is surprisingly applicable and flexible and has been validated through an investigation of nine different fluorophore cores ranging in size, shape, and geometric variation of their clamping modules. All fluorescent dimers evaluated can be photo-excited to atypical excimer-like states with elongated excited lifetimes (up to 37 ns) and substantially high quantum yields (up to 1). This strategy offers a straightforward preparation of discrete fluorophore dimers, providing promising model systems with explicitly stable dimeric structures and tunable photophysical features, which can be utilized to study various intermolecular processes.

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

Anisotropy and Controllable Band Structure in Suprawavelength Polaritonic Metasurfaces

In this Letter, we exploit the extended coherence length of mixed plasmon-exciton states to generate active metasurfaces. For this purpose, periodic stripes of organic dye are deposited on a continuous silver film. Typical metasurface effects, such as effective behavior and geometry sensitivity, are measured for periods exceeding the polaritonic wavelength by more than one order of magnitude. Here, by adjusting the metasurface geometry, anisotropy, modified band structure, and unidimensional polaritons are computationally simulated and experimentally observed in reflectometry as well as in emission.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Sequence Impedance Modeling of Grid-Forming Inverters

Grid-forming control of inverter-based resources has been identified as a critical technology for operating power systems with high levels of inverter-based resources. This paper presents the sequence impedance modeling of a grid-forming inverter to evaluate its small-signal stability properties. Droop control structure is implemented to control the inverter in grid-forming mode, and the impact of individual controller on the inverter impedance characteristics is discussed. The developed sequence impedance model is compared with that of the grid-following inverter. It is found from the developed sequence impedance models that grid-forming inverters are less prone to harmonic resonance problems during operation with weaker grids. The developed models are validated using PSCAD simulations.

grid- following inverter↗
DOE OSTI2020

A Station-hybrid HVDC System Structure and Control Strategies for Cross-seam Power Transmission

Cross-seam high voltage DC (HVDC) transmission in the United States can provide an efficient and flexible bulk power delivery highway between the interconnections. Recent studies have shown significant economic benefits of cross-seam HVDC transmission systems by taking the advantages of load diversity, frequency response, renewable energy diversity, and energy arbitrage in the different interconnections. This paper introduces a station-hybrid system scheme for cross-seam interconnections. Here, the proposed station-hybrid system combines the advantages of line commutated converter (LCC) and voltage source converter (VSC) technologies, thus enabling reliable and flexible bidirectional power flows across the interconnections. Control strategies of the station-hybrid system are investigated with a focus on power flow reversal control under normal operation conditions and grid support control under emergency conditions. The feasibility and effectiveness of the proposed station-hybrid system and corresponding control strategies are verified by simulations in PSCAD/EMTDC.

Station-hybrid system↗
DOE OSTI2019

Identification of key parameters controlling demographically structured vegetation dynamics in a Land Surface Model

This dataset includes outputs of 5000 simulations of CLM4.5(ED) to quantify the sensitivity of the model outputs to changes in model parameters using the Fourier Amplitude Sensitivity Test (FAST). Each simulation is generated by simultaneously sampling from 15% deviations of the default values of >80 vegetation parameters. This dataset includes 1) model codes of CLM4.5(ED) used for the sensitivity analysis; 2) the parameter samples; and 3) the corresponding model outputs of vegetation status (e.g., Gross Primary Production, Leaf Area Index and Biomass) and demography (e.g., diameter growth and mortality rates). The outputs are organized to the format of the FAST toolbox (https://sites.google.com/site/xuchongang/uasatoolbox).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Controlling Molecular Structure and Spin with Multiconfigurational Quantum Chemistry (Final Technical Report)

For many first-row transition metal complexes, structure-property relationships can be obtained from high-level molecular geometry optimizations and subsequent electronic structure studies. The project funded under this award utilized newly implemented fully internally contracted (FIC) nuclear gradients for extended multi-state (XMS) complete active space second-order multireference perturbation theory (CASPT2) to explore geometry changes in first-row transition metal coordination complexes. At the start of the project, only one full geometry optimization using FIC-CASPT2 analytical gradients had been reported (J. Chem. Theory Comput., 2016, 12 (8), 3781), and many open-questions regarding the performance and achievable accuracy in applying such computations to larger complexes persisted. Key deliverables in the report include the implementation of the numerical Hessian and subsequent vibrational analysis in the BAGEL program package. This includes both full Hessian vibrational analysis (FHVA) and a partial Hessian vibrational analysis (PHVA). The latter of which allows us to reduce the significant cost of computing the vibrational frequencies in a large molecule by focusing on the modes of highest interest. The gradient code also proved useful in the development of an approach to improve the Hubbard-U correction by removing bias in predicting spin-splitting in Fe(II) complexes via plane-wave density functional theory (DFT). Finally, we showed for three families of complexes (spin-crossover (SCO) complexes, metallocorroles complexes, and those with metal-metal bonds) that CASPT2 can result in good molecular geometries and established best practices in undertaking this work. We are now using this approach in collaborative projects with experimental groups, which would not have been possible at the start of this project. A common theme also arose through this work that static and dynamic correlation must be recovered in a balanced way to yield quantitative results. By systematically varying how both effects were included, we were able to make key chemical insights. This work supported the training of two postdoctoral scholars, one graduate student, and one undergraduate student in applying high-level wavefunction based methods to challenging systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗