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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Astatine partitioning between nitric acid and conventional solvents: indication of covalency in ketone complexation of AtO +

Astatine-211 has been produced at Texas A&M University on the K150 cyclotron, with a yield of 890 ± 80 MBq through the 209 Bi(α,2n) 211 At reaction via an 8 h bombardment with a beam current of 4–8 μA and an α-particle beam energy of 28.8 MeV. The target was then dissolved in HNO 3 and the extraction of 211 At was investigated into a variety of organic solvents in 1–3 M HNO 3 . Extraction of 211 At with distribution ratios as high as 11.3 ± 0.6, 12.3 ± 0.8, 42.2 ± 2.2, 69 ± 4, and 95 ± 6 were observed for diisopropyl ether, 1-decanol, 1-octanol, 3-octanone, and methyl isobutyl ketone, respectively, while the distribution ratios for 207 Bi were ≤0.05 in all cases. The extraction of 211 At into both methyl isobutyl ketone and 3-octanone showed a strong, linear dependence on the HNO 3 initial aqueous concentration and better extraction than other solvents. DFT calculations show stronger binding between the carbonyl oxygen of the ketone and the At metal center.

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

Eco-friendly, solution-processable and efficient low-energy lighting phosphors: copper halide based hybrid semiconductors Cu 4 X 6 (L) 2 (X = Br, I) composed of covalent, ionic and coordinate bonds

A series of copper halide based inorganic–organic hybrid semiconductors have been synthesized. Structural analysis confirms that all compounds are composed of one-dimensional Cu 4 X 6 2- anionic chains that coordinate to cationic ligands via Cu–N dative bonds. Different coordination affinities of the ligands lead to two types of ligand arrangements with various structural distortions. All compounds are highly resistant to heat and moisture as a result of the combination of coordinate and ionic bonds. Low energy emission with high efficiency is achieved for these compounds and the emission energy (~552–615 nm) and color (yellow-orange) can be tuned by varying the ligand and halogen element. The electronic structure and luminescence mechanism are examined by both experimental and theoretical methods. More importantly, all compounds demonstrate good solubility in polar aprotic solvents, a desired property that is absent in all other CuX hybrid families of extended structures, which is attributed primarily to the ionic nature of this material class. Furthermore, the good solution-processability, and cost effective and easily scalable synthesis coupled with high quantum efficiencies and framework stability make these hybrid materials promising phosphors for general lighting applications.

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

Covalently integrated silica nanoparticles in poly(ethylene glycol)-based acrylate resins: thermomechanical, swelling, and morphological behavior

Nanocomposites integrate functional nanofillers into viscoelastic matrices for electronics, lightweight structural materials, and tissue engineering. Herein, the effect of methacrylate-functionalized (MA-SiO 2 ) and vinyl-functionalized (V-SiO 2 ) silica nanoparticles on the thermal, mechanical, physical, and morphological characteristics of poly(ethylene glycol) (PEG) nanocomposites was investigated. The gel fraction of V-SiO 2 composites decreases upon addition of 3.8 wt% but increases with further addition (>7.4 wt%) until it reaches a plateau at 10.7 wt%. The MA-SiO 2 induced no significant changes in gel fraction and both V-SiO 2 and MA-SiO 2 nanoparticles had a negligible impact on the nanocomposite glass transition temperature and water absorption. The Young's modulus and ultimate compressive stress increased with increasing nanoparticle concentration for both nanoparticles. Due to the higher crosslink density, MA-SiO 2 composites reached a maximum mechanical stress at a concentration of 7.4 wt%, while V-SiO 2 composites reached a maximum at a concentration of 10.7 wt%. Scanning electron microscopy, transmission electron microscopy, and small-angle X-ray scattering revealed a bimodal size distribution for V-SiO 2 and a monomodal size distribution for MA-SiO 2 . Although aggregates were observed for both nanoparticle surface treatments, V-SiO 2 dispersion was poor while MA-SiO 2 were generally well-dispersed. Finally, these findings lay the framework for silica nanofillers in PEG-based nanocomposites for advanced manufacturing applications.

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

Engineering giant excitonic coupling in bioinspired, covalently bridged BODIPY dyads

Strong excitonic coupling in photosynthetic systems is believed to enable efficient light absorption and quantitative charge separation, motivating the development of artificial multi-chromophore arrays with equally strong or even stronger excitonic coupling. However, large excitonic coupling strengths have typically been accompanied by fast non-radiative recombination, limiting the potential of the arrays for solar energy conversion as well as other applications such as fluorescent labeling. Here, in this work, we report giant excitonic coupling leading to broad optical absorption in bioinspired BODIPY dyads that have high photostability, excited-state lifetimes at the nanosecond scale, and fluorescence quantum yields of nearly 50%. Through the synthesis, spectroscopic characterization, and computational modeling of a series of dyads with different linking moieties, we show that the strongest coupling is obtained with diethynylmaleimide linkers, for which the coupling occurs through space between BODIPY units with small separations and slipped co-facial orientations. Other linkers allow for broad tuning of both the relative through-bond and through-space coupling contributions and the overall strength of interpigment coupling, with a tradeoff observed in general between the strength of the two coupling mechanisms. These findings open the door to the synthesis of molecular systems that function effectively as light-harvesting antennas and as electron donors or acceptors for solar energy conversion.

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

Investigating trends in actinide covalency and magnetism with 35/37 Cl SSNMR spectroscopy and first-principles calculations

Solid-state NMR (SSNMR) spectroscopy is a powerful technique for studying actinide chemistry but has been significantly limited due to the complex paramagnetism, and radiological hazards presented by these materials. Lanthanide and actinide salts often feature magnetic ordering and can be paramagnetic, ferromagnetic, or antiferromagnetic depending on temperature and electronic structure. Paramagnetic interactions can manifest in SSNMR both as secular spectral shifts and/or couplings as well as contributions from non-secular relaxation. Both effects can be directly measured with NMR and used to extrapolate rich chemical information such as coordination environments, bonding characteristics, local molecular dynamics, and correlation times. Typically, these studies are carried out on high-γ and highly abundant NMR-active isotopes (e.g., 1 H, 6/7 Li, 19 F, 23 Na, etc.) or on enriched rare isotopes (e.g., 2 H and 17 O), which can be expensive. Herein, we present a facile methodology to measure the 35/37 Cl electric-field gradient (EFG) and paramagnetic shift anisotropy (SA) tensor components using static wideline SSNMR measurements of LaCl 3 , NdCl 3 , UCl 3 , and UCl 4 . The static powder spectra were measured with both 35 Cl and 37 Cl SSNMR to increase the fidelity of the extracted tensor parameters. Variable temperature NMR of a select case confirms the Curie–Weiss paramagnetism. Relaxation measurements of both nuclei further corroborate observations owing to the paramagnetic relaxation enhancement and reveal simultaneous quadrupolar relaxation mechanisms. Density functional theory (DFT) calculations using Hubbard U corrections to the uranium valence orbitals show excellent agreement with experimental EFG tensor parameters and help describe the bonding characteristics in these lanthanide and actinide systems.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Site-specific electronic structure of covalently linked bimetallic dyads from nitrogen K-edge x-ray absorption spectroscopy

A nitrogen K-edge x-ray absorption near-edge structure (XANES) survey is presented for tetrapyrido[3,2-a:',3'-c:3'',2''-h:2''',3'''-j]phenazine (tpphz)-bridged bimetallic assemblies that couple chromophore and catalyst transition metal complexes for light driven catalysis, as well as their individual molecular constituents. We demonstrate the high N site sensitivity of the N pre-edge XANES features, which are energetically well-separated for the phenazine bridge N atoms and for the individual metal-bound N atoms of the inner coordination sphere ligands. By comparison with the time-dependent density functional theory calculated spectra, we determine the origins of these distinguishable spectral features. We find that metal coordination generates large shifts toward higher energy for the metal-bound N atoms, with increasing shift for 3d < 4d < 5d metal bonding. This is attributed to increasing ligand-to-metal σ donation that increases the effective charge of the bound N atoms and stabilizes the N 1s core electrons. In contrast, the phenazine bridge N pre-edge peak is found at a lower energy due to stabilization of the low energy electron accepting orbital localized on the phenazine motif. While no sensitivity to ground state electronic coupling between the individual molecular subunits was observed, the spectra are sensitive to structural distortions of the tpphz bridge. Here these results demonstrate N K-edge XANES as a local probe of electronic structure in large bridging ligand motifs, able to distinctly investigate the ligand-centered orbitals involved in metal-to-ligand and ligand-to-ligand electron transfer following light absorption.

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

Erratum: “Breaking covalent bonds in the context of the many-body expansion (MBE). I. The purported ‘first row anomaly’ in XH n (X = C, Si, Ge, Sn; n = 1–4)” [J. Chem. Phys. 156, 244303 (2022)]

We have noted typographical errors in TABLE V of J. Chem. Phys. 156, 244303 (2022). Specifically, the values of the angles φ HχH for the XH 2 species in both the ( 3 B 1 ) and ( 1 A 1 ) states were incorrectly reported as half of the correct values. Additionally, the values of the same angles for the XH 3 and XH 4 species were reported correctly.

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

A bioactive supramolecular and covalent polymer scaffold for cartilage repair in a sheep model

Regeneration of hyaline cartilage in human-sized joints remains a clinical challenge, and it is a critical unmet need that would contribute to longer healthspans. Injectable scaffolds for cartilage repair that integrate both bioactivity and sufficiently robust physical properties to withstand joint stresses offer a promising strategy. We report here on a hybrid biomaterial that combines a bioactive peptide amphiphile supramolecular polymer that specifically binds the chondrogenic cytokine transforming growth factor β-1 (TGFβ-1) and crosslinked hyaluronic acid microgels that drive formation of filament bundles, a hierarchical motif common in natural musculoskeletal tissues. The scaffold is an injectable slurry that generates a porous rubbery material when exposed to calcium ions once placed in cartilage defects. The hybrid material was found to support in vitro chondrogenic differentiation of encapsulated stem cells in response to sustained delivery of TGFβ-1. Using a sheep model, we implanted the scaffold in shallow osteochondral defects and found it can remain localized in mechanically active joints. Evaluation of resected joints showed significantly improved repair of hyaline cartilage in osteochondral defects injected with the scaffold relative to defects injected with the growth factor alone, including implantation in the load-bearing femoral condyle. These results demonstrate the potential of the hybrid biomimetic scaffold as a niche to favor cartilage repair in mechanically active joints using a clinically relevant large-animal model.

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