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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 1,315 records · Page 73
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Solvent Extraction: Structure of the Liquid-Liquid Interface Containing a Diamide Ligand

Knowledge of the (supra)molecular structure of an interface that contains amphiphilic ligand molecules is necessary for a full understanding of ion transfer during solvent extraction. Even if molecular dynamics already yield some insight in the molecular configurations in solution, hardly any experimental data giving access to distributions of both extractant molecules and ions at the liquid–liquid interface exist. Here, the combined application of X-ray and neutron reflectivity measurements represents a key milestone in the deduction of the interfacial structure and potential with respect to two different lipophilic ligands. Indeed, we show for the first time that hard trivalent cations can be repelled or attracted by the extractant-enriched interface according to the nature of the ligand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Nitrosylation of Nitric-Oxide-Sensing Regulatory Proteins Containing [4Fe-4S] Clusters Gives Rise to Multiple Iron-Nitrosyl Complexes

The reaction of protein-bound iron–sulfur (Fe-S) clusters with nitric oxide (NO) plays key roles in NO-mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe-S clusters has been hampered by a lack of information about the nature of the iron-nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe-4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe 2 (NO) 4 (Cys) 2 ]) and Roussin's Black Salt (RBS, [Fe 4 (NO) 7 S 3 ]. In the latter case, the absence of 32 S/ 34 S shifts in the Fe-S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates.

Serrano, Pauline N.↗
DOE OSTI2017

Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers

Template–free fabrication of non–spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self–assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self–assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solid cubic particle formation. An approach for preserving the structures of these cubes in water by thiol– or photo–induced crosslinking was developed. In conclusion, the ability to solubilize a model hydrophobic drug, curcumin, was also explored.

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

Site-Selective Functionalization of (sp 3 )C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor

The selective functionalization of one C-H bond over others in nearly identical steric and electronic environments can facilitate the construction of complex molecules. We report site-selective functionalizations of C-H bonds, differentiated solely by remote substituents, catalyzed by artificial metalloenzymes (ArMs) that are generated from the combination of an evolvable P450 scaffold and an iridium-porphyrin cofactor. The generated systems catalyze the insertion of carbenes into the C-H bonds of a range of phthalan derivatives containing substituents that render the two methylene positions in each phthalan inequivalent. These reactions occur with site-selectivity ratios of up to 17.8:1 and, in most cases, with pairs of enzyme mutants that preferentially form each of the two constitutional isomers. This study demonstrates the potential of abiotic reactions catalyzed by metalloenzymes to functionalize C-H bonds with site selectivity that is difficult to achieve with small-molecule catalysts.

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

Analysis of Powders Containing Illicit Drugs Using Magnetic Levitation

Magneto-Archimedes levitation (MagLev) enables the separation of powdered mixtures of illicit drugs (cocaine, methamphetamine, heroin, fentanyl, and its analogues), adulterants, and diluents based on density, and allows the presumptive identification of individual components. Small samples (mass <50 mg), with low concentrations of illicit drugs, present a particular challenge to analysis for forensic chemists. The MagLev device, a cuvette containing a solution of paramagnetic gadolinium(III) chelate in a non-polar solvent, placed between two like-poles-facing NdFeB magnets, allowed separation of seven relevant compounds simultaneously. In particular, initial separation with MagLev, followed by characterization by FTIR-ATR, enabled identification of fentanyl in a sample of fentanyl-laced heroin (1.3 wt % fentanyl, 2.6 wt % heroin, and 96.1 wt % lactose). MagLev allows identification of unknown powders in mixtures and enables confirmatory identification based on structure-specific techniques.

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

Heterometallic Actinide-Containing Photoresponsive Metal-Organic Frameworks: Dynamic and Static Tuning of Electronic Properties

Acquiring fundamental knowledge of properties of actinide-based materials is a necessary step to create new possibilities for addressing the current challenges in the nuclear energy and nuclear waste sectors. Here in this report, we established a photophysics–electronics correlation for actinide-containing metal-organic frameworks (An-MOFs) as a function of excitation wavelength, for the first time. A stepwise approach for dynamically modulating electronic properties was applied for the first time towards actinide-based heterometallic MOFs through integration of photochromic linkers. Optical cycling, modeling of density of states near the Fermi edge, conductivity measurements, and photoisomerization kinetics were employed to shed light on the process of tailoring optoelectronic properties of An-MOFs. Furthermore, the first photochromic MOF-based field-effect transistor, in which the field-effect response could be changed through light exposure, was constructed. As a demonstration, the change in current upon light exposure was sufficient to operate a two-LED fail-safe indicator circuit.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Matrix Extension Validation of AOCS Ce 2c‐11 for Omega‐3 Polyunsaturated Fatty Acids in Conventional Foods and Dietary Supplements Containing Added Marine Oil

Abstract Marine oils are commonly added to conventional foods and dietary supplements to enhance their contents of omega‐3 polyunsaturated fatty acids (PUFA), including eicosapentaenoic acid (EPA; 20:5n‐3) and docosahexaenoic acid (DHA; 22:6n‐3), which have been associated with numerous potential health benefits. This study compared American Oil Chemists’ Society (AOCS) Official Methods Ce 2b‐11 and Ce 2c‐11 for determining EPA and DHA in foods and dietary supplements and found that AOCS Ce 2c‐11 produces significantly higher analyzed values, which could be attributed to a more comprehensive breakdown of the sample matrix and derivatization of fatty acids. Our subsequent food matrix extension validation of AOCS Ce 2c‐11 demonstrated that the method produces true, accurate, sensitive, and precise determinations of EPA, DHA, and total omega‐3 PUFA in foods and dietary supplements containing added marine oil, including those formulated with emulsified and microencapsulated oils. The method detection limits for EPA and DHA were 0.012 ± 0.002 and 0.011 ± 0.003 mg g −1 , respectively (means ± SD). The analyzed contents of EPA (1.26–386 mg serving −1 ), DHA (1.37–563 mg serving −1 ), and total omega‐3 PUFA (2.69–1270 mg serving −1 ) were reported for 27 conventional food and dietary supplement products. Eighteen products declared contents of DHA, EPA + DHA, or total omega‐3 PUFA on product labels, and the analyzed contents of those fatty acids varied from 95 to 162% of label declarations for all but two of the products.

Li, Ziyi↗
DOE OSTI2022

Interlaminar improvement of carbon fiber/epoxy composites via fluorine‐containing high‐epoxy‐value sizing agent

Abstract To improve the interfacial bonding effect of carbon fibers (CFs) and epoxy resins, we prepared a fluorine‐containing high‐epoxy‐value sizing agent (named TS) in this article. It is an emulsion with a more uniform particle size distribution and higher stability better than a commercial Takemoto sizing agent. In addition, sulfonic acid groups can improve the hydrophilicity of the TS, and the presence of epoxy groups enhances the wettability between CFs and the matrix. The properties of the sizing agents were examined by Fourier transform infrared spectroscopy, dynamic light scattering, and thermogravimetric analysis. The sized CFs were evaluated by scanning electron microscopy, x‐ray photoelectron spectroscopy, monofilament tensile test, and dynamic contact angle. Afterward, CF/epoxy composites were prepared, and their fracture morphology and interlaminar shear strength (ILSS) were examined. Results indicated that the TS sizing significantly increased the content of activated carbon on the surface of the CFs and improved the bonding effect between the fiber and the matrix. After TS was sized, the ILSS increased from 49.64 to 58.74 MPa, 18.34% higher than unsized CF/epoxy composites, showing the prominent interfacial reinforcement better than commercial Takemoto.

Qiu, Zhijie↗
DOE OSTI2015

Neighbor-directed histidine N(τ) alkylation. A route to imidazolium-containing phosphopeptide macrocycles

Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. These cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Furthermore, neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts.

cationic dialkyl histidine↗
DOE OSTI2018

Partial Oxidation of Methane to Synthesis Gas Using Supported Ga-Containing Bimetallic Catalysts and a Ti-Promoter

A series of bimetallic Ga-containing materials using TiO 2 and TiO 2 -promoted SiO 2 supports have been prepared. Rhodium, palladium, and platinum have been used as additional metals in this system. The materials are characterized and used as catalysts for the partial oxidation of methane into synthesis gas (H 2 and CO). The presence of a low quantity of titanium in the form of anatase TiO 2 was shown to improve the overall activity of catalytic methane oxidation and to strongly increase the selectivity of partial oxidation products over the total oxidation of methane to carbon dioxide and water. Here, particular attention is paid to the formation of gallium-metal alloys on the surface of the catalyst supports. Rh-Ga-Ti-SiO 2 was found to be the most active and selective catalyst, giving 89 % conversion of methane and 99 % selectivity to synthesis gas at 750 °C, as well as exhibiting catalytic activity and preferential conversion to partial oxidation products at temperatures as low as 350 °C.

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

Fast Correction of Errors in the DFT‐Calculated Energies of Gaseous Nitrogen‐Containing Species

Abstract Modeling adsorption phenomena on surfaces by DFT calculations often involves substantial errors, resulting in inaccurate predictions of catalytic activities. Such errors partly stem from the inaccurate description of the energetics of free molecules. Herein, we use a semiempirical group‐additivity method to correct the DFT‐calculated heats of formation of 106 carbon‐ and nitrogen‐containing gaseous compounds belonging to 15 different chemical families. PBE, PW91, RPBE and BEEF‐vdW initially yield mean absolute errors (MAEs) with respect to experiments in the range of 0.32–0.75 eV. After correcting the systematic errors, the overall MAEs decrease to ∼0.05 eV. Additionally, upon applying the corrections to three types of reaction enthalpies, the resulting MAEs are below 0.10 eV. These functional‐group corrections can be used in (electro)catalysis to correct the gas‐phase references necessary to evaluate equilibrium potentials and adsorption energies, predict error cancellation, and assess conflicting experimental data.

Urrego‐Ortiz, Ricardo↗
DOE OSTI2020

Effect of Electrochemical Oxidation on Physicochemical Properties of Fe-Containing Single-Walled Carbon Nanotubes

Metal catalysts are necessary for fabricating carbon nanotubes, but are often considered impurities in the end products, and arduous steps are used to remove catalyst residues from the nanotube structure. However, as metals can be electrocatalytic, instead of removing them we can utilize their role in detection of analgesics. Herein, we study the physicochemical properties of Fe-containing single-walled carbon nanotubes (SWCNTs), and the effect of simple oxidative pretreatment on them. We show that a gentle anodic pretreatment i) increased the amount of oxidized Fe nanoparticles, most likely exhibiting phases Fe3O4 and Fe2O3 and ii) effectively removed disordered carbonaceous material from SWCNT bundles surfaces. Pretreatment had only a marginal effect on sensitivity towards analgesics. However, interestingly, selectivity of Fe-SWCNTs towards paracetamol and morphine could be modified with pretreatment. Through this kind of in-depth investigation, we can, to a certain extent, correlate various material properties of SWCNTs with the observed electrochemical performance. We show this approach allows us to evaluate what factors in SWCNTs truly affect the electrochemical detection of biomolecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Probing Effects of Electron Addition to Polycyclic Conjugated Hydrocarbons Containing Four‐Membered Rings

The rectangular cyclobutadiene (CBD, C 4 H 4 ) is a unique moiety for building nonbenzenoid polycyclic conjugated hydrocarbons with interesting electron‐accepting properties. Herein, the investigation on chemical reduction of several CBD‐containing polycyclic hydrocarbons with increasing conjugation length is reported: biphenylene (C 12 H 8 ), dimethyl[2]naphthalene (C 22 H 16 ), and tetramethyl‐dibenzo‐[3]phenylene (C 30 H 22 ). The two‐step sequential reduction is first demonstrated by in situ spectroscopic investigation and then confirmed by the isolation of single crystals of the reduced products. The X‐ray crystallographic analysis reveals the formation of several mono‐ and doubly reduced products in solvent‐separated and complexed forms. The crystal structures for both neutral parents and corresponding reduced products unravel the changes in bond alternation in each ring of the fused systems. Density functional theory (DFT) and nucleus‐independent chemical shift (NICS) scan calculations reveal that the two‐electron addition reduces the aromatic character in the benzenoid rings but has minor influence on the antiaromatic CBD rings.

Zhu, Yikun [Department of Chemistry University at ↗
DOE OSTI2015

A Metal-Organic Framework Containing Unusual Eight-Connected Zr–-Oxo Secondary Building Units and Orthogonal Carboxylic Acids for Ultra-sensitive Metal Detection

Two metal-organic frameworks (MOFs) with Zr-oxo secondary building units (SBUs) were prepared by using p,p'-terphenyldicarboxylate (TPDC) bridging ligands pre-functionalized with orthogonal succinic acid (MOF-1) and maleic acid groups (MOF-2). Single-crystal X-ray structure analysis of MOF-1 provides the first direct evidence for eight-connected SBUs in UiO-type MOFs. In contrast, MOF-2 contains twelve-connected SBUs as seen in the traditional UiO MOF topology. These structural assignments were confirmed by extended X-ray absorption fine structure (EXAFS) analysis. The highly porous MOF-1 is an excellent fluorescence sensor for metal ions with the detection limit of <0.5 ppb for Mn 2+ and three to four orders of magnitude greater sensitivity for metal ions than previously reported luminescent MOFs.

Carboni, Michaël↗
DOE OSTI2023

Crystallization of a Neptunyl Oxalate Hydrate from Solutions Containing Np V and the Uranyl Peroxide Nanocluster U 60 Ox 30

Uranyl peroxide nanoclusters are an evolving family of materials with potential applications throughout the nuclear fuel cycle. While several studies have investigated their interactions with alkali and alkaline earth metals, no studies have probed their interactions with the actinide elements. This work describes a system containing U 60 Ox 30 , [((UO 2 )(O 2 )) 60 (C 2 O 4 ) 30 ] 60- , and neptunium(V) as a function of neptunium concentration. Ultra-small and small angle X-ray scattering were used to observe these interactions in the aqueous phase, and X-ray diffraction was used to observe solid products. The results show that neptunium induces aggregation of U 60 Ox 30 when the neptunium concentration is ≤ 10 mM, whereas (NpO 2 ) 2 C 2 O 4 ·6H 2 O(cr) and studtite ultimately form at 15–25 mM neptunium. Finally, the latter result suggests that neptunium coordinates with the bridging oxalate ligands in U 60 Ox 30 , leaving metastable uranyl peroxide species in solution, and is an important finding given the potential application of uranyl peroxide nanoclusters in the recycling of used nuclear fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2014

Selective Hydrogenation of Furan-Containing Condensation Products as a Source of Biomass-Derived Diesel Additives

Here, we demonstrate that while the energy density and lubricity of the C 15 and C 16 products of furan condensation of biomass-derived aldehydes with 2-methylfuran are consistent with requirements for diesel, these products do not meet specifications for cetane number and pour point due to their aromatic furan rings. However, a novel class of products that fully meet or exceed most specifications for diesel can be produced by converting the furan rings in these compounds to cyclic ether moieties. Full hydrodeoxygenation of furan condensation products to alkanes would require 55-60% higher hydrogen demand, starting from biomass, compared to the products of furan ring saturation, providing an additional incentive to support the saturated products. We also report here on a tunable class of catalysts that contain Pd nanoparticles supported on ionic liquid-modified SiO 2 that can achieve complete saturation of the furan rings in yields of 95% without opening these rings. Furans to fuels: Production of diesel fuels from lignocellulosic feedstocks has largely relied on hydrodeoxygenation of oxygenates to alkanes. However, the products of selective ring saturation have been demonstrated herein to provide diesel additives of exceptional quality with minimal H 2 input. Further, a new class of heterogeneous palladium catalysts with tunable surface properties achieves excellent yields to cyclic ethers without hydrogenolysis.

biomass↗
DOE OSTI2016

Synthesis and Structure of Vanadium Halide Complexes Containing Diphosphine Ligands with Pendant Amines

A series of vanadium(III) diiodide complexes of the formula CpV(P R N R' P R )I 2 (Cp = 5-C 5 H 5 ; P R N R' P R = (R 2 PCH 2 ) 2 N(R)), where R = Et, R = Me (1a), R = Ph (1b); R = Ph, R = Me (1c)) is reported. The corresponding vanadium(II) monoiodide complexes of the formula CpV(P R N R' PR )I, where R = Et, R = Me (2a), R = Ph (2b); R = Ph, R = Me (2c)) were prepared in THF by reduction of 1a-c with Zn powder. The paramagnetic complexes 1a-c and 2a-c are characterized by elemental analysis, 1H NMR spectroscopy, and by cyclic voltammetry for complexes 2b and 4b. Complexes 1c and 2a-c were also characterized in the single crystal by X-ray crystallography. We report the preparation of the vanadium(II) complexes CpV(P Ph 2 N Ph 2 )I (3) (P Ph 2 N Ph 2 = 1,5-diphenyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) and trans-[VCl 2 (PEtNMePEt)2] (4a) and trans-[VCl 2 (PEtNPhPEt) 2 ] (4b). These complexes represent initial coordination chemistry of vanadium complexes with P R N R' P R and P Ph 2 N Ph 2 diphosphine ligands, which contain a pendant amine in the second coordination sphere. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

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

Behavior of copper‐containing high‐entropy alloys in harsh metal‐dusting environments

Abstract Metal dusting is still an unresolved issue at high temperatures. Currently, two material‐related strategies to mitigate metal dusting are described in the literature. On the one hand, highly alloyed materials are used, which contain large amounts of protective oxide‐forming elements, such as Cr, Al, and Si. The second mitigation strategy is based on inhibiting the catalytic effect of Fe, Ni, and Co. These elements all strongly catalyze the formation of solid carbon from the gas phase. Combining the catalytic protection of Cu alloying for metal dusting with protection by a classical alumina/chromia barrier is a native feature that high‐entropy alloys (HEAs) can offer. In this study, the behavior of different equiatomic HEAs with and without Al and/or Cu are studied when exposed at 620°C in a highly aggressive metal‐dusting environment.

36 MATERIALS SCIENCE↗