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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Proximal Galerkin: A Structure-Preserving Finite Element Method for Pointwise Bound Constraints

The proximal Galerkin finite element method is a high-order, low iteration complexity, nonlinear numerical method that preserves the geometric and algebraic structure of pointwise bound constraints in infinite-dimensional function spaces. This paper introduces the proximal Galerkin method and applies it to solve free boundary problems, enforce discrete maximum principles, and develop a scalable, mesh-independent algorithm for optimal design with pointwise bound constraints. This paper also introduces the latent variable proximal point (LVPP) algorithm, from which the proximal Galerkin method derives. When analyzing the classical obstacle problem, we discover that the underlying variational inequality can be replaced by a sequence of second-order partial differential equations (PDEs) that are readily discretized and solved with, e.g., the proximal Galerkin method. Throughout this work, we arrive at several contributions that may be of independent interest. These include (1) a semilinear PDE we refer to as the entropic Poisson equation; (2) an algebraic/geometric connection between high-order positivity-preserving discretizations and certain infinite-dimensional Lie groups; and (3) a gradient-based, bound-preserving algorithm for two-field, density-based topology optimization. The complete proximal Galerkin methodology combines ideas from nonlinear programming, functional analysis, tropical algebra, and differential geometry and can potentially lead to new synergies among these areas as well as within variational and numerical analysis. Open-source implementations of our methods accompany this work to facilitate reproduction and broader adoption.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Synthesis of Ln II ‐in‐Cryptand Complexes by Chemical Reduction of Ln III ‐in‐Cryptand Precursors: Isolation of a Nd II ‐in‐Cryptand Complex

Abstract Lanthanide triflates have been used to incorporate Nd III and Sm III ions into the 2.2.2‐cryptand ligand (crypt) to explore their reductive chemistry. The Ln(OTf) 3 complexes (Ln=Nd, Sm; OTf=SO 3 CF 3 ) react with crypt in THF to form the THF‐soluble complexes [Ln III (crypt)(OTf) 2 ][OTf] with two triflates bound to the metal encapsulated in the crypt. Reduction of these Ln III ‐in‐crypt complexes using KC 8 in THF forms the neutral Ln II ‐in‐crypt triflate complexes [Ln II (crypt)(OTf) 2 ]. DFT calculations on [Nd II (crypt)] 2+ ], the first Nd II cryptand complex, assign a 4f 4 electron configuration to this ion.

Huh, Daniel N.↗
DOE OSTI2024

Clustering and Cliques in Preferential Attachment Random Graphs with Edge Insertion

In this paper, we investigate the global clustering coefficient (a.k.a transitivity) and clique number of graphs generated by a preferential attachment random graph model with an additional feature of allowing edge connections between existing vertices. Specifically, at each time step t, either a new vertex is added with probability f(t), or an edge is added between two existing vertices with probability 1 – f(t). We establish concentration inequalities for the global clustering and clique number of the resulting graphs under the assumption that f(t) is a regularly varying function at infinity with index of regular variation –$\gamma$, where $\gamma$ $\in$ [0, 1). Finally, we also demonstrate an inverse relation between these two statistics: the clique number is essentially the reciprocal of the global clustering coefficient.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Structure of a dimeric photosystem II complex from a cyanobacterium acclimated to far-red light

Photosystem II (PSII) is the water-splitting enzyme central to oxygenic photosynthesis. To drive water oxidation, light is harvested by accessory pigments, mostly chlorophyll (Chl) a molecules, which absorb visible light (400–700 nm). Some cyanobacteria facultatively acclimate to shaded environments by altering their photosynthetic machinery to additionally absorb far-red light (FRL, 700–800 nm), a process termed far-red light photoacclimation or FaRLiP. During far-red light photoacclimation, FRL-PSII is assembled with FRL-specific isoforms of the subunits PsbA, PsbB, PsbC, PsbD, and PsbH, and some Chl-binding sites contain Chls d or f instead of the usual Chl a. The structure of an apo-FRL-PSII monomer lacking the FRL-specific PsbH subunit has previously been determined, but visualization of the dimeric complex has remained elusive. Here, we report the cryo-EM structure of a dimeric FRL–PSII complex. The site assignments for Chls d and f are consistent with those assigned in the previous apo-FRL-PSII monomeric structure. All sites that bind Chl d or Chl f at high occupancy exhibit a FRL-specific interaction of the formyl moiety of the Chl d or Chl f with the protein environment, which in some cases involves a phenylalanine sidechain. The structure retains the FRL-specific PsbH2 subunit, which appears to alter the energetic landscape of FRL-PSII, redirecting energy transfer from the phycobiliprotein complex to a Chl f molecule bound by PsbB2 that acts as a bridge for energy transfer to the electron transfer chain. Collectively, these observations extend our previous understanding of the structure-function relationship that allows PSII to function using lower energy FRL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Structural Characterization of the Human Cytosolic Malate Dehydrogenase I

The first crystal structure of the human cytosolic malate dehydrogenase I (MDH1) is described. Structure determination at a high resolution (1.65 Å) followed production, isolation, and purification of human MDH1 using a bacterial expression system. The structure is a binary complex of MDH1 with only a bound malonate molecule in the substrate binding site. Comparisons of this structure with malate dehydrogenase enzymes from other species confirm that the human enzyme adopts similar secondary, tertiary, and quaternary structures and that the enzyme retains a similar conformation even when nicotinamide adenine dinucleotide (NAD + ) is not bound. A comparison to the highly homologous porcine (sus scrofa) MDH1 ternary structures leads to the conclusion that only small conformational differences are needed to accommodate binding by NAD + or other NAD + mimetics. Conformational differences observed in the second subunit show that the NAD + binding elements are nevertheless quite flexible. Comparison of hMDH1 to the human mitochondrial malate dehydrogenase (hMDH2) reveals some key differences in the α7–α8 loop, which lies directly beneath the substrate binding pocket. These differences might be exploited in the structure-assisted design of selective small molecule inhibitors of hMDH1, an emerging target for the development of anticancer therapeutics.

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

Challenges of conventional iterative all-atom and coarse-grained multiscale molecular dynamics

In this work, we evaluate the biomolecular dynamics behaviors when conventionally iterating between all-atom (AA) and coarse-grained (CG) molecular dynamics (MD) simulations over multiple cycles. We implemented the workflow to iterate between AA and CG in OpenMM, namely the iterative multiscale MD (iMMD) simulation workflow. In particular, we aim to identify practical applications for iterating between AA and CG simulations in a conventional manner without any constraints or model modifications. We evaluate the iMMD workflow on four representative systems, spanning folding of two soluble proteins and protein-protein as well as protein-lipid interactions of two membrane proteins. We observe that iteration between AA and CG representations could help the soluble proteins exit undesirable metastable states to fold, resulting from random protein structural distortions due to cycling. Consequently, the most reliable use of iterative AA and CG simulations appears to be to accelerating complex lipid mixing for membrane-bound protein systems rather than sampling protein conformational space. Our work explores the practical usages and limitations for iterative AA and CG simulations using readily available AA and CG force fields. The evaluated iMMD workflow in OpenMM is made available at https://github.com/lanl/iMMD.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Genetic switching by the Lac repressor is based on two-state Monod–Wyman–Changeux allostery

High-resolution NMR spectroscopy enabled us to characterize allosteric transitions between various functional states of the dimeric Escherichia coli Lac repressor. In the absence of ligands, the dimer exists in a dynamic equilibrium between DNA-bound and inducer-bound conformations. Binding of either effector shifts this equilibrium toward either bound state. Analysis of the ternary complex between repressor, operator DNA, and inducer shows how adding the inducer results in allosteric changes that disrupt the interdomain contacts between the inducer binding and DNA binding domains and how this in turn leads to destabilization of the hinge helices and release of the Lac repressor from the operator. Based on our data, the allosteric mechanism of the induction process is in full agreement with the well-known Monod–Wyman–Changeux model.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Lattice QCD study of π Σ − K ¯ N scattering and the Λ ( 1405 ) resonance

A lattice QCD computation of the coupled channel π Σ – K ¯ N scattering amplitudes in the Λ ( 1405 ) region is detailed. Results are obtained using a single ensemble of gauge field configurations with N f = 2 + 1 dynamical quark flavors and m π ≈ 200 MeV and m K ≈ 487 MeV . Hermitian correlation matrices using both single baryon and meson-baryon interpolating operators for a variety of different total momenta and irreducible representations are used. Several parametrizations of the two-channel scattering K -matrix are utilized to obtain the scattering amplitudes from the finite-volume spectrum. The amplitudes, continued to the complex energy plane, exhibit a virtual bound state below the π Σ threshold and a resonance pole just below the K ¯ N threshold. Published by the American Physical Society 2024

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

In-Situ Species Concentration Measurements In Ammonia-Mix Flames Using Ftir Spectroscopy

Hydrogen and ammonia represent two carbon-free fuel sources that could be used in place of current fossil energy sources in combustion systems. To develop optimized ammonia combustion systems, validated modeling tools are needed. In the open literature, it has been shown that the complex chemistry associated with fuel-bound nitrogen contained in ammonia differs greatly from natural gas or hydrogen combustion. As a result, several new chemical kinetic mechanisms have been developed. Many of these mechanisms have been validated experimentally, however this has primarily focused on bulk parameters such as laminar flame speed and ignition delay time. Critically, high quality measurements of species concentrations are needed under controlled conditions which are easily represented by simple models. In this paper, direct, in-situ measurements of species concentrations and gas temperature are performed in a laminar flat-flame burner. This arrangement enables comparison with 1D model predictions, better isolating chemical kinetics from the fluid dynamics. Quantitative species concentrations are determined by absorption spectroscopy using an FTIR spectrometer. Fuel compositions representative of cracked ammonia (NH 3 /H 2 ) and ammonia-natural gas (NH 3 /CH 4 ) are considered for rich and lean equivalence ratios. A major focus of the paper is on the selection of spectral features for nitric oxide and ammonia and correcting for large amounts of baseline H 2 O absorption.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Optical-Gating of Spin-based Quantum States (Final Report)

This project developed a generalizable strategy for optical control of spin-based quantum states through the Photoisomerization-Induced Spin–Charge Excited State (PISCES) process, in which a photochromic spirooxazine ligand bound to an electronically bistable metal complex enables reversible, room-temperature optical switching of spin states in both dilute matrices and the solid state. A multidisciplinary team integrated synthesis, spectroscopy, theory, and surface science to establish design principles for opto-spintronic quantum materials. Systematic structure–property studies across four spirooxazine series revealed that donor–π–acceptor interactions govern thermal isomerization, which proceeds via a rotational pathway. Pulsed EPR measurements demonstrated millisecond-scale coherence times in cobalt-dioxolene-spirooxazine complexes, establishing their promise as optically addressable molecular qubits; the approach was extended to Cu(II), Ni(II), and lanthanide complexes, including optical modulation of zero-field splittings and clock transitions. Two-dimensional IR spectroscopy resolved picosecond ground-state population exchange dynamics, while ab initio calculations elucidated photoisomerization mechanisms and parametrized Hamiltonians for spin relaxation and decoherence. Toward device integration, the team fabricated 2D polymer scaffolds for covalent qubit organization, developed tip-enhanced Raman imaging of molecular monolayers, and demonstrated optical gating of gate voltage in spirooxazine-graphene field-effect transistors. The project produced numerous publications, dissertations, and presentations, and trained over 30 researchers.

2D polymers↗
NASA NTRS1974

Optimal space communications techniques

Digital multiplication of two waveforms using delta modulation (DM) is discussed. It is shown that while conventional multiplication of two N bit words requires N2 complexity, multiplication using DM requires complexity which increases linearly with N. Bounds on the signal-to-quantization noise ratio (SNR) resulting from this multiplication are determined and compared with the SNR obtained using standard multiplication techniques. The phase locked loop (PLL) system, consisting of a phase detector, voltage controlled oscillator, and a linear loop filter, is discussed in terms of its design and system advantages. Areas requiring further research are identified.

Schilling, D. L.↗
NASA NTRS2003

EAGLE can do Efficient LTL Monitoring

We briefly present a rule-based framework, called EAGLE, that has been shown to be capable of defining and implementing finite trace monitoring logics, including future and past time temporal logic, extended regular expressions, real-time logics, interval logics, forms of quantified temporal logics, and so on. In this paper we show how EAGLE can do linear temporal logic (LTL) monitoring in an efficient way. We give an upper bound on the space and time complexity of this monitoring.

Barringer, Howard↗
NASA NTRS2004

Lipid Biomarkers for a Hypersaline Microbial Mat Community

The use of lipid biomarkers and their carbon isotopic compositions are valuable tools for establishing links to ancient microbial ecosystems. Various lipids associated with specific microbial groups can serve as biomarkers for establishing organism source and function in contemporary microbial ecosystems (membrane lipids), and by analogy, potential relevance to ancient organic-rich sedimentary rocks (geolipids). As witnessed by the stromatolite record, benthic microbial mats grew in shallow water lagoonal environments. Our recent work has focused on lipid biomarker analysis of a potential analogue for such ancient mats growing in a set of hypersaline evaporation ponds at Guerrero Negro, Baja California Sur, Mexico. The aerobic, surface layer of this mat (0 to 1 mm) contained a variety of ester-bound fatty acids (FA) representing a diverse bacterial population including cyanobacteria, sulphate reducers (SRB) and heterotrophs. Biomarkers for microeukaryotes detected in this layer included sterols, C-20 polyunsaturated FA and a highly branched isoprenoid, diagnostic for diatoms. Cyanobacteria were also indicated by the presence of a diagnostic set of mid-chain methylalkanes. C-28, to C-34 wax esters (WXE) present in relatively small amounts in the upper 3 mm of the mat are considered biomarkers for green non-sulphur bacteria. Ether-bound isoprenoids were also identified although in considerably lower abundance than ester-bound FA (approx. 1:l0). These complex ether lipids included archatol, hydroxyarchaeol and a C-40 tetraether, all in small amounts. After ether cleavage with boron tribromide, the major recovered isoprenyl was a C-30:1. This C(sub 30;1) yelded squalane after hydrogenation, a known geobiomarker for hypersaline environments in ancient oils and sediments. In this mat, it represents the dominant Archaeal population. The carbon isotopic composition of biomarker lipids were generally depleted relative to the bulk organic material (delta C-13 TOC -10%). Most depleted were the cyanobacterial methylalkanes at -27% with FA such as the SRB biomarker, 10- methyl C-I6, somewhat heavier at -16%, and WXE at -17%. The C-30:1 isoprenyl was most enriched with delta C-13 in the -7 to -11% range, much too heavy to represent the methanogen population responsible for mat methane values measured at -60%.

Jahnke, Linda↗
NASA NTRS1992

An assay for intermolecular exchange of alpha crystallin

An affinity column of alpha crystallin linked to cyanogen bromide-activated Sepharose was developed to study the exchange of alpha subunits. Alpha crystallin bound to the Sepharose-alpha complex was dissociated with 8 mol/l urea, followed by quantitation using high-performance reverse-phase liquid chromatography. The time course of binding at 37 degrees C showed a hyperbolic binding pattern reaching equilibrium between 6-18 hr. Under these conditions, binding of beta and gamma crystallins to the same matrix was less than 10% of the alpha values, as was binding of alpha to glycine-coupled Sepharose. This assay was used to demonstrate changes in the subunit exchange of alpha crystallins present in high molecular weight versus lower molecular weight aggregates of the human lens. These results show that this binding procedure was a specific reproducible assay that might be used to study intermolecular interactions of the alpha crystallins.

NASA Discipline Cell Biology↗
DOE OSTI2024

In-Situ Species Concentration Measurements in Ammonia-Mix Flames Using FTIR Spectroscopy

Hydrogen and ammonia represent two carbon-free fuel sources that could be used in place of current fossil energy sources in combustion systems. To develop optimized ammonia combustion systems, validated modeling tools are needed. In the open literature, it has been shown that the complex chemistry associated with fuel-bound nitrogen contained in ammonia differs greatly from natural gas or hydrogen combustion. As a result, several new chemical kinetic mechanisms have been developed. Many of these mechanisms have been validated experimentally, however this has primarily focused on bulk parameters such as laminar flame speed and ignition delay time. Critically, high quality measurements of species concentrations are needed under controlled conditions which are easily represented by simple models. In this paper, direct, in-situ measurements of species concentrations and gas temperature are performed in a laminar flat-flame burner. This arrangement enables comparison with 1D model predictions, better isolating chemical kinetics from the fluid dynamics. Quantitative species concentrations are determined by absorption spectroscopy using an FTIR spectrometer. Fuel compositions representative of cracked ammonia (NH3/H2) and ammonia-natural gas (NH3/CH4) are considered for rich and lean equivalence ratios. A major focus of the paper is on the selection of spectral features for nitric oxide and ammonia and correcting for large amounts of baseline H2O absorption.

Bedick, Clinton↗
DOE OSTI2026

The high-valent vanadium chemistry of isoindoline chelates

Isoindoline-based chelates, in particular bis(arylimino)isoindolines, have shown extensive metal binding chemistry. Although this chemistry has been explored for the middle and late transition metal ions, little work has been carried out on early transition metal complexes. In this article, we present the first examples of vanadium coordinated using four bis(arylimino)isoindolines, in which the aryl groups are pyrazole, indazole, benzimidazole, and pyridine (ligands 1–4 , respectively). We isolated five complexes using vanadyl sulfate or vanadyl acetylacetonate as the vanadium source. In all cases, the ligands bound in a meridional mode, and for four of the complexes, the vanadium ion was observed in the V(v) oxidation state. Three of the ligands ( 1–3 ) formed VO 2 complexes with vanadyl sulfate and vanadyl acetylacetonate, but the bis(pyridylimino)isoindoline (ligand 4 ) formed a V(v) oxosulfonato complex with the former starting material and a vanadyl V(iv) acetylacetonate with the latter starting material. All metal compounds were structurally elucidated by X-ray crystallographic methods, and we probed their electronic structures using DFT methods.

Bore, Joan C. [Univ. of Akron, OH (United States)]↗
DOE OSTI2024

Synthesis, Isolation, and Study of Heterobimetallic Uranyl Crown Ether Complexes

Although crown ethers can selectively bind many metal cations, little is known regarding the solution properties of crown ether complexes of the uranyl dication, UO 2 2+ . Here, in this work, the synthesis and characterization of isolable complexes in which the uranyl dication is bound in an 18-crown-6-like moiety are reported. A tailored macrocyclic ligand, templated with a Pt(II) center, captures UO 2 2+ in the crown moiety, as demonstrated by results from single-crystal X-ray diffraction analysis. The U(V) oxidation state becomes accessible at a quite positive potential (E 1/2 ) of –0.18 V vs Fc +/0 upon complexation, representing the most positive U VI /U V potential yet reported for the UO 2 n+ core. Isolation and characterization of the U(V) form of the crown complex are also reported here; there are no prior reports of reduced uranyl crown ether complexes, but U(V) is clearly stabilized by crown chelation. Joint computational studies show that the electronic structure of the U(V) form results in significant weakening of U–O oxo bonding despite the quite positive reduction potential at which this species can be accessed, underscoring that crown-ligated uranyl species could demonstrate unique reactivity under only modestly reducing conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗