Search NASA⌕ Search

SEARCH · Search NASA

Results for “NUCLEAR SPECTROSCOPY”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

57 Fe nuclear resonance vibrational spectroscopic studies of tetranuclear iron clusters bearing terminal iron( III )–oxido/hydroxido moieties

57 Fe nuclear resonance vibrational spectroscopy (NRVS) has been applied to study a series of tetranuclear iron ([Fe 4 ]) clusters based on a multidentate ligand platform (L 3− ) anchored by a 1,3,5-triarylbenzene linker and pyrazolate or (tertbutylamino)pyrazolate ligand (PzNH t Bu − ). These clusters bear a terminal Fe(III)–O/OH moiety at the apical position and three additional iron centers forming the basal positions. The three basal irons are connected with the apical iron center via a μ 4 -oxido ligand. Detailed vibrational analysis via density functional theory calculations revealed that strong NRVS spectral features below 400 cm −1 can be used as an oxidation state marker for the overall [Fe 4 ] cluster core. The terminal Fe(III)–O/OH stretching frequencies, which were observed in the range of 500–700 cm −1 , can be strongly modulated (energy shifts of 20–40 cm −1 were observed) upon redox events at the three remote basal iron centers of the [Fe 4 ] cluster without the change of the terminal Fe(III) oxidation state and its coordination environment. Therefore, the current study provides a quantitative vibrational analysis of how the remote iron centers within the same iron cluster exert exquisite control of the chemical reactivities and thermodynamic properties of the specific iron site that is responsible for small molecule activation.

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

Tailored polyMOFs for ion transport in lithium-based battery electrolyte

Owing to their low flammability, solid-state and quasi-solid-state electrolytes are safer alternatives to liquid organic electrolytes for energy storage applications. Metal–organic frameworks (MOFs), with facile functional tunability, long-range order, and rich host–guest interactions, have been implemented as electrolyte materials in a wide range of energy storage applications. In this work, we investigate a class of MOFs called polyMOFs as quasi-solid-state electrolyte materials. Unlike MOF–polymer composites, which are physical mixtures of MOF particles and polymers, polyMOFs are composed of polymeric linkers and metal ion nodes that self-assembled into crystalline and porous framework materials. PolyMOFs thus marry the ionic transport properties of liquid electrolyte and polymers with the synthetic versatility and host–guest interactions of MOFs. We demonstrate that the functionality of the polymer backbone of the polyMOF linker can improve room-temperature ion transport in the material. The polyMOF based on poly(ethylene glycol) (PEG) exhibits greater ionic conductivity, lithium transference number, and lower activation energy than its polyethylene (PE) analog. Supported by solid-state 7 Li nuclear magnetic resonance spectroscopy, we propose these improvements are due to stronger coordination of Li + to oxide sites in PEG, allowing for dissociation of Li and its associated anion. DFT studies further reveal that the confined solvent molecule mediates Li + transport in PEG-functionalized UiO-66 via a metastable adsorption and hopping mechanism. This work lies at the interface of inorganic and polymer electrolytes, unveiling fundamental insights into the design of next-generation ion conductive materials for energy technologies.

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

The surface chemistry of colloidal lead halide perovskite nanowires

This study explored the interplay between the ligand–surface chemistry of colloidal CsPbBr 3 nanowires (NWs) and their optical properties. The ligand equilibrium was probed using nuclear magnetic resonance spectroscopy, and by perturbing the equilibrium via dilution, the gradual removal of ligands from the CsPbBr 3 surface was observed. This removal was correlated with an increase in the surface defect density, as suggested by a broadening of the photoluminescence (PL) spectrum, a decrease in the PL quantum yield (PLQY), and quenching of the PL decay. These results highlight similar surface binding between the traditional CsPbBr 3 quantum dots and our NWs, thereby expanding the scope of well-established ligand chemistry to a relatively unexplored nanocrystal morphology. In conclusion, by controlling the dilution factor, it was revealed that CsPbBr 3 NWs achieve a PLQY of 72% ± 2% and a relatively long average PL lifetime of 400 ± 10 ns, without relying on additional surface passivation techniques, such as ligand exchange.

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

RCSB Protein Data Bank: powerful new tools for exploring 3D structures of biological macromolecules for basic and applied research and education in fundamental biology, biomedicine, biotechnology, bioengineering and energy sciences

Abstract The Research Collaboratory for Structural Bioinformatics Protein Data Bank (RCSB PDB), the US data center for the global PDB archive and a founding member of the Worldwide Protein Data Bank partnership, serves tens of thousands of data depositors in the Americas and Oceania and makes 3D macromolecular structure data available at no charge and without restrictions to millions of RCSB.org users around the world, including >660 000 educators, students and members of the curious public using PDB101.RCSB.org. PDB data depositors include structural biologists using macromolecular crystallography, nuclear magnetic resonance spectroscopy, 3D electron microscopy and micro-electron diffraction. PDB data consumers accessing our web portals include researchers, educators and students studying fundamental biology, biomedicine, biotechnology, bioengineering and energy sciences. During the past 2 years, the research-focused RCSB PDB web portal (RCSB.org) has undergone a complete redesign, enabling improved searching with full Boolean operator logic and more facile access to PDB data integrated with >40 external biodata resources. New features and resources are described in detail using examples that showcase recently released structures of SARS-CoV-2 proteins and host cell proteins relevant to understanding and addressing the COVID-19 global pandemic.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

The hTERT core promoter forms three parallel G-quadruplexes

The structure of the 68 nt sequence with G-quadruplex forming potential within the hTERT promoter is disputed. One model features a structure with three stacked parallel G-quadruplex units, while another features an unusual duplex hairpin structure adjoined to two stacked parallel and antiparallel quadruplexes. We report here the results of an integrated structural biology study designed to distinguish between these possibilities. As part of our study, we designed a sequence with an optimized hairpin structure and show that its biophysical and biochemical properties are inconsistent with the structure formed by the hTERT wild-type sequence. By using circular dichroism, thermal denaturation, nuclear magnetic resonance spectroscopy, analytical ultracentrifugation, small-angle X-ray scattering, molecular dynamics simulations and a DNase I cleavage assay we found that the wild type hTERT core promoter folds into a stacked, three-parallel G-quadruplex structure. The hairpin structure is inconsistent with all of our experimental data obtained with the wild-type sequence. All-atom models for both structures were constructed using molecular dynamics simulations. These models accurately predicted the experimental hydrodynamic properties measured for each structure. We found with certainty that the wild-type hTERT promoter sequence does not form a hairpin structure in solution, but rather folds into a compact stacked three-G-quadruplex conformation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Mechanistic studies of small molecule ligands selective to RNA single G bulges

Abstract Small-molecule RNA binders have emerged as an important pharmacological modality. A profound understanding of the ligand selectivity, binding mode, and influential factors governing ligand engagement with RNA targets is the foundation for rational ligand design. Here, we report a novel class of coumarin derivatives exhibiting selective binding affinity towards single G RNA bulges. Harnessing the computational power of all-atom Gaussian accelerated molecular dynamics simulations, we unveiled a rare minor groove binding mode of the ligand with a key interaction between the coumarin moiety and the G bulge. This predicted binding mode is consistent with results obtained from structure-activity relationship studies and transverse relaxation measurements by nuclear magnetic resonance spectroscopy. We further generated 444 molecular descriptors from 69 coumarin derivatives and identified key contributors to the binding events, such as charge state and planarity, by lasso (least absolute shrinkage and selection operator) regression. Our work deepened the understanding of RNA-small molecule interactions and integrated a new framework for the rational design of selective small-molecule RNA binders.

Biochemistry & Molecular Biology↗
DOE OSTI2026

Noncollinear spin order, field-induced transitions, and short-range correlations in Cu 4 ⁢SO 4 ⁢(OH) 6

We report a comprehensive study of spin-$\frac{1}{2}$ quantum magnet brochantite, Cu 4 ⁢SO 4 ⁢(OH) 6 , combining high-field thermodynamic measurements, polarized neutron diffraction, inelastic neutron scattering, and nuclear magnetic resonance spectroscopy. Using bulk magnetization and specific heat measurements we construct the magnetic 𝐻−𝑇 phase diagram for magnetic fields applied along main crystallographic directions up to 24.1 T. Polarized neutron diffraction reveals a noncollinear magnetic ground state confined to the 𝑎⁢𝑏 plane. A field-induced transition is observed for magnetic fields in the 𝑎⁢𝑏 plane whose critical field and character evolve continuously with field direction in the 𝑎⁢𝑏 plane. While the transition for 𝐻 ∥ 𝑏 might be a spin-flop-like transition, the one for 𝐻 ∥ 𝑎 resembles the short-range correlated state above 𝑇 N , suggesting a magnetic configuration related to the quasi-two-dimensional correlations in the 𝑏⁢𝑐 planes. The experimental results demonstrate that the ground-state and field-induced phases cannot be explained by a simple XXZ model with a single dominant exchange interaction and that weaker interchain and anisotropic interactions have to be taken into account. Our work establishes brochantite as a low-symmetry Cu-based quantum magnet with noncollinear order and complex field-induced behavior.

Prokhnenko, Oleksandr [Helmholtz-Zentrum Berlin (H↗
DOE OSTI2020

Evolution of nontrivial Fermi surface features in the band structures of the homologous members Pb 5 Bi 6 Se 14 and Pb 5 Bi 12 Se 23

High-quality single crystals of (PbSe) 5 (Bi 2 Se 3 ) 3m were grown and analyzed by nuclear magnetic resonance (NMR) spectroscopy. We report on 77 Se and 207 Pb NMR shifts and nuclear spin-lattice relaxation measurements in the naturally formed heterostructure homology (PbSe) 5 (Bi 2 Se 3 ) 3m with m = 1 (Pb 5 Bi 6 Se 14 ) and m = 2 (Pb 5 Bi 12 Se 23 ). A distinct site-specific contribution has been detected for both nuclei as a function of temperature, which reveals an electronic changeover from a semiconducting (Pb 5 Bi 6 Se 14 ) to a semimetalliclike (Pb 5 Bi 12 Se 23 ) system with nontrivial band structure features near the Fermi level. The temperature dependences of the relaxation rates are dominated by significant changes in the topology of energy dispersions accompanied with band edges and crossings in the region of the Fermi surface. These results, which interrogate nuclear spin interactions from selected atomic sites, clearly expose the effects of the added Bi 2 Se 3 layer on the crystal and electronic structure of (Pb 5 Bi 12 Se 23 ). These findings provide direct microscopic insight into the unconventional and dual nature of the electronic structure of these homologous thermoelectric and topologically nontrivial compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Delocalized polaron and Burstein-Moss shift induced by Li in α–V 2 O 5 : A DFT + DMFT study

For this work, we performed density functional theory (DFT)+U and dynamical mean field theory (DMFT) calculations with a continuous-time quantum Monte Carlo impurity solver to investigate the electronic properties of V 2 O 5 and Li x V 2 O 5 (x = 0.125 and 0.25). Pristine V 2 O 5 is a charge-transfer insulator with strong O p–V d hybridization, and it exhibits a large band gap (E gap ) as well as a nonzero conduction-band (CB) gap.We show that the band gap, the number of d electrons of vanadium, N d , and the CB gap for V 2 O 5 obtained from our DMFT calculations are in excellent agreement with the experimental values. While the DFT +U approach replicates the experimental band gap, it overestimates the value of N d and underestimates the CB gap. In the presence of low Li doping, the electronic properties of V 2 O 5 are mainly driven by a polaronic mechanism, and electron spin resonance and electron nuclear double resonance spectroscopies observed the coexistence of free and bound polarons. Notably, our DMFT results identify both polaron types, with the bound polaron being energetically preferred, while the DFT +U method only predicts the free polaron. Our DMFT analysis also reveals that increased Li doping leads to electron filling in the conduction band, shifting the Fermi level. This result is consistent with the observed Burstein-Moss shift upon enhanced Li doping, and we thus demonstrate that the DFT + DMFT approach can be used for an accurate and realistic description of strongly correlated materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

First observation of isomeric states in 111 Zr, 113 Nb, and 115 Mo

Isomeric states in the neutron-rich nuclei 111 Zr [T 1/2 =0.10 (7) μs] , 113 Nb [T 1/2 =0.7 (4) μs], 115 Mo [T 1/2 =46 (3) μs] were first identified at the Radioactive Ion Beam Factory (RIBF) of RIKEN by using in-flight fission and fragmentation of a 238 U beam at an energy of 345 MeV/u. Here is a brief report of the γ transitions de-exciting from isomeric states and half-lives measurements, which provides the first spectroscopy in the nuclear region of prolate-to-oblate shape-phase transition around mass A ≈110.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Polymorphism of Pb 5 (PO 4 ) 3 OH δ within the LK-99 mixture

During the synthetic exploration targeting the polycrystalline compound LK-99, an unexpected phase, Pb 5 (PO 4 ) 3 OH δ , was identified as a byproduct. We elucidated the composition of this compound through single-crystal X-ray diffraction analysis. Subsequent synthesis of the target compounds was achieved via high-temperature solid-state pellet reactions. The newly identified Pb 5 (PO 4 ) 3 OH δ has an orthorhombic crystal structure with space group Pnma , representing a unique structure differing from the hexagonal apatite phases of Pb 10 (PO 4 ) 6 O and Pb 5 (PO 4 ) 3 OH. Comprehensive temperature- and magnetic-field-dependent magnetization studies unveiled a temperature-independent magnetic characteristic of Pb 5 (PO 4 ) 3 OH δ . Solid-state nuclear magnetic resonance spectroscopy was employed to decipher the origins of the phase stability and confirm the presence of hydrogen atoms in Pb 5 (PO 4 ) 3 OH δ . These investigations revealed the presence of protonated oxygen sites, in addition to the interstitial water molecules within the structure, which may play critical roles in stabilizing the orthorhombic phase.

Xu, Mingyu (ORCID:0000000171386009)↗
DOE OSTI2023

Acetylation of homogalacturonan and rhamnogalacturonan‐I is catalyzed by a suite of trichome birefringence‐like proteins

SUMMARY Plant cell wall polysaccharides, including xylan, mannan, xyloglucan, and pectins, are often acetylated and members of the domain of unknown function 231 (DUF231)/trichome birefringence‐like (TBL) family have been shown to beO‐acetyltransferases mediating the acetylation of xylan, mannan, and xyloglucan. However, little is known about theO‐acetyltransferases responsible for pectin acetylation. In this report, we biochemically characterized a suite of Arabidopsis DUF231/TBL proteins for their roles in pectin acetylation. We generated 24 TBL recombinant proteins in mammalian cells and demonstrated that 10 of them were able to transfer acetyl groups from acetyl‐CoA onto the pectins homogalacturonan (HG) or rhamnogalacturonan‐I (RG‐I), and thus were named pectinO‐acetyltransferase 1 to 10 (POAT1 to 10). It was found that POAT2,4,9,10 specifically acetylated HG and POAT5,6 acetylated RG‐I, whereas POAT1,3,7,8 could act on both HG and RG‐I. The acetylation of HG and RG‐I by POATs was further corroborated by hydrolysis with pectin acetylesterases and by nuclear magnetic resonance spectroscopy. In addition, mutations of the conserved GDS and DXXH motifs in POAT3 and POAT8 were shown to lead to a loss of their ability to acetylate HG and RG‐I. Furthermore, simultaneous RNA interference downregulation ofPOAT1,3,6,7,8resulted in reduced cell expansion, impaired plant growth, and decreased pectin acetylation. Together, our findings indicate that these POATs are pectinO‐acetyltransferases involved in acetylation of the pectin polysaccharides HG and RG‐I.

Plant Sciences↗
DOE OSTI2022

Conserved conformational dynamics determine enzyme activity

Homologous enzymes often exhibit different catalytic rates despite a fully conserved active site. The canonical view is that an enzyme sequence defines its structure and function and, more recently, that intrinsic protein dynamics at different time scales enable and/or promote catalytic activity. Here, we show that, using the protein tyrosine phosphatase PTP1B, residues surrounding the PTP1B active site promote dynamically coordinated chemistry necessary for PTP1B function. However, residues distant to the active site also undergo distinct intermediate time scale dynamics and these dynamics are correlated with its catalytic activity and thus allow for different catalytic rates in this enzyme family. We identify these previously undetected motions using coevolutionary coupling analysis and nuclear magnetic resonance spectroscopy. Our findings strongly indicate that conserved dynamics drives the enzymatic activity of the PTP family. Characterization of these conserved dynamics allows for the identification of novel regulatory elements (therapeutic binding pockets) that can be leveraged for the control of enzymes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

A scalable solid-state nanoporous network with atomic-level interaction design for carbon dioxide capture

Carbon capture and sequestration reduces carbon dioxide emissions and is critical in accomplishing carbon neutrality targets. Here, we demonstrate new sustainable, solid-state, polyamine-appended, cyanuric acid–stabilized melamine nanoporous networks (MNNs) via dynamic combinatorial chemistry (DCC) at the kilogram scale toward effective and high-capacity carbon dioxide capture. Polyamine-appended MNNs reaction mechanisms with carbon dioxide were elucidated with double-level DCC where two-dimensional heteronuclear chemical shift correlation nuclear magnetic resonance spectroscopy was performed to demonstrate the interatomic interactions. We distinguished ammonium carbamate pairs and a mix of ammonium carbamate and carbamic acid during carbon dioxide chemisorption. The coordination of polyamine and cyanuric acid modification endows MNNs with high adsorption capacity (1.82 millimoles per gram at 1 bar), fast adsorption time (less than 1 minute), low price, and extraordinary stability to cycling by flue gas. This work creates a general industrialization method toward carbon dioxide capture via DCC atomic-level design strategies.

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

Deconvolution of metal apportionment in bulk metal-organic frameworks

We report a general route to decipher the apportionment of metal ions in bulk metal-organic frameworks (MOFs) by solid-state nuclear magnetic resonance spectroscopy. We demonstrate this route in Mg 1-x Ni x -MOF-74, where we uncover all eight possible atomic-scale Mg/Ni arrangements through identification and quantification of the distinct chemical environments of 13 C-labeled carboxylates as a function of the Ni content. Here, we use magnetic susceptibility, bond pathway, and density functional theory calculations to identify local metal bonding configurations. The results refute the notion of random apportionment from solution synthesis; rather, we reveal that only two of eight Mg/Ni arrangements are preferred in the Ni-incorporated MOFs. These preferred structural arrangements manifest themselves in macroscopic adsorption phenomena as illustrated by CO/CO 2 breakthrough curves. We envision that this nondestructive methodology can be further applied to analyze bulk assembly of other mixed-metal MOFs, greatly extending the knowledge on structure-property relationships of MOFs and their derived materials.

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

One-dimensional alignment of defects in a flexible metal-organic framework

Crystalline materials are often considered to have rigid periodic lattices, while soft materials are associated with flexibility and nonperiodicity. The continuous evolution of metal-organic frameworks (MOFs) has erased the boundaries between these two distinct conceptions. Flexibility, disorder, and defects have been found to be abundant in MOF materials with imperfect crystallinity, and their intricate interplay is poorly understood because of the limited strategies for characterizing disordered structures. Here, we apply advanced nuclear magnetic resonance spectroscopy to elucidate the mesoscale structures in a defective MOF with a semicrystalline lattice. We show that engineered defects can tune the degree of lattice flexibility by combining both ordered and disordered compartments. The one-dimensional alignment of correlated defects is the key for the reversible topological transition. The unique matrix is featured with both rigid framework of nanoporosity and flexible linkage of high swellability.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Molecular insights into the evolution of woody plant decay in the gut of termites

Plant cell walls represent the most abundant pool of organic carbon in terrestrial ecosystems but are highly recalcitrant to utilization by microbes and herbivores owing to the physical and chemical barrier provided by lignin biopolymers. Termites are a paradigmatic example of an organism’s having evolved the ability to substantially degrade lignified woody plants, yet atomic-scale characterization of lignin depolymerization by termites remains elusive. We report that the phylogenetically derived termite Nasutitermes sp. efficiently degrades lignin via substantial depletion of major interunit linkages and methoxyls by combining isotope-labeled feeding experiments and solution-state and solid-state nuclear magnetic resonance spectroscopy. Exploring the evolutionary origin of lignin depolymerization in termites, we reveal that the early-diverging woodroach Cryptocercus darwini has limited capability in degrading lignocellulose, leaving most polysaccharides intact. Conversely, the phylogenetically basal lineages of “lower” termites are able to disrupt the lignin-polysaccharide inter- and intramolecular bonding while leaving lignin largely intact. These findings advance knowledge on the elusive but efficient delignification in natural systems with implications for next-generation ligninolytic agents.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework

In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O 2 to form high-spin iron(IV) = O species remains an unrealized goal. Here, we report a metal–organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases. The framework reacts with O 2 at low temperatures to form high-spin iron(IV) = O species that are characterized using in situ diffuse reflectance infrared Fourier transform, in situ and variable-field Mössbauer, Fe Kβ x-ray emission, and nuclear resonance vibrational spectroscopies. In the presence of O 2 , the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗