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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Structural Diversities in Heterometallic Mn–Ca Cluster Chemistry from the Use of Salicylhydroxamic Acid: {Mn III 4 Ca 2 }, {Mn II/III 6 Ca 2 }, {Mn III/IV 8 Ca}, and {Mn III 8 Ca 2 } Complexes with Relevance to Both High- and Low-Valent States of the Oxygen-Evolving Complex

We report that one-pot reactions between the [Mn 3 O(O 2 CPh) 6 (py) x ] +/o triangular precursors and either CaBr 2 ·xH 2 O or CaCl 2 ·6H 2 O, in the presence of salicylhydroxamic acid (shaH 2 ), have afforded the heterometallic complexes [MnIII 4 Ca 2 (O 2 CPh) 4 (shi) 4 (H 2 O) 3 (Me 2 CO)] ( 1 ) and (pyH)[Mn II 2 Mn III 4 Ca 2 Cl 2 (O 2 CPh) 7 (shi) 4 (py) 4 ] ( 2 ), respectively, in good yields. Further reactions but using a more flexible synthetic scheme comprising the Mn(NO 3 ) 2 · 4 H 2 O/Ca(NO 3 ) 2 · 4 H 2 O and Mn(O 2 CPh) 2 · 2 H 2 O/Ca(ClO 4 ) 2 · 4 H 2 O "metal blends" and shaH 2 , in the presence of external base NEt 3 , led to the new complexes (NHEt 3 ) 2 [Mn III 4 Mn IV 4 Ca(OEt) 2 (shi) 10 (EtOH) 2 ] ( 3 ) and (NHEt 3 ) 4 [Mn III 8 Ca 2 (CO 3 ) 4 (shi) 8 ] ( 4 ), respectively. In all reported compounds, the anion of the tetradentate (N,O,O,O)-chelating/bridging ligand salicylhydroxime (shi 3- ), resulting from the in situ metal-ion-assisted amide-iminol tautomerism of shaH 2 , was found to bridge both Mn and Ca atoms. Complexes 1-4 exhibit a variety of different structures, metal stoichiometries, and Mn oxidation-state descriptions; 1 possesses an overall octahedral metal arrangement, 2 can be described as a Mn 4 Ca 2 octahedron bound to an additional Mn 2 unit, 3 consists of a Mn 8 "ring" surrounding a Ca II atom, and 4 adopts a rectangular cuboidal motif of eight Mn atoms accommodating two CaIIatoms. Solid-state direct-current magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the Mn centers, leading to S = 0 spin ground-state values for all complexes. Lastly, from a bioinorganic chemistry perspective, the reported compounds may demonstrate some relevance to both high-valent scheme ( 3 ) and lower-oxidation-level species ( 1, 2, and 4 ) of the catalytic cycle of the oxygen-evolving complex.

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

M IV /Co –I (M = Zr, Hf) Bis(phosphinoamide) Complexes with η 6 - and η 4 -Arenes

Despite their relevance to catalysis, low-/subvalent cobalt complexes are difficult to synthesize and isolate. Consequently, very few “cobaltate” complexes are known and there is a lack of architectural diversity in this field. Lewis acidic d 0 group IV metals have been demonstrated to stabilize Co –I centers via metal–metal bonds. Herein, we report the synthesis of bis(phosphinoamide) heterobimetallic M IV /Co –I arene complexes (M = Zr, Hf). The driving force to maintain the aromaticity of the arenes dictates the hapticity of the Co-bound arene ligands and influences the binding arrangement of the phosphinoamide ligands. Benzene and toluene were observed to bind η 6 to the Co –I center, forcing dissociation of one of the phosphinoamide ligands, whereas η 4 -coordination of anthracene allows both phosphinoamide ligands to remain bound to the Co center. The identity of both the arene and the group IV metal ion starkly influence the lability of the arene. For instance, the Co-bound benzene ligand in the Zr IV /Co –I benzene complex rapidly exchanges with C 6 D 6 in solution, whereas toluene/C 6 D 6 exchange is much slower and appreciable C 6 H 6 /C 6 D 6 exchange is not observed for the Hf analogue. The Zr IV /Co –I benzene complex loses benzene upon repeated exposure to vacuum to form an arene-free tetrametallic dimer.

aromatic compounds↗
DOE OSTI2017

Reversible Heterolytic Cleavage of the H-H Bond by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and Hydride

Controlling the heterolytic cleavage of the H-H bond of dihydrogen is critically important in catalytic hydrogenations and in the catalytic oxidation of H2. We show how the rate of reversible heterolytic cleavage of H2 can be controlled over nearly four orders of magnitude at 25 °C, from 2.1 × 103 s-1 to ≥107 s-1. Bifunctional Mo complexes, [CpMo(CO)(κ3-P2N2)]+ (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane with alkyl/aryl groups on N and P), have been developed for heterolytic cleavage of H2 into a proton and a hydride, akin to Frustrated Lewis Pairs. The H-H bond cleavage is enabled by the basic amine in the second coordination sphere. The products of heterolytic cleavage of H2, Mo hydride complexes bearing protonated amines, [CpMo(H)(CO)(P2N2H)]+, were characterized by spectroscopic studies and by X-ray crystallography. Variable temperature 1H, 15N and 2-D 1H-1H ROESY NMR spectra indicated rapid exchange of the proton and hydride. The exchange rates are in the order [CpMo(H)(CO)(PPh2NPh2H)]+ > [CpMo(H)(CO)(PtBu2NPh2H)]+ > [CpMo(H)(CO)(PPh2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NtBu2H)]+. The pKa values determined in acetonitrile range from 9.3 to 17.7, and show a linear correlation with the logarithm of the exchange rates. Thus the exchange dynamics are controlled through the relative acidity of the [CpMo(H)(CO)(P2N2H)]+ and [CpMo(H2)(CO)(P2N2)]+ isomers, providing a design principle for controlling heterolytic cleavage of H2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry [Ephemeral collision complexes induce chemically termolecular transformations that affect global chemistry]

Termolecular association reactions involve ephemeral collision complexes—formed from the collision of two molecules—that collide with a third and chemically inert ‘bath gas’ molecule that simply transfers energy to/from the complex. These collision complexes are generally not thought to react chemically on collision with a third molecule in the gas-phase systems of combustion and planetary atmospheres. Such ‘chemically termolecular’ reactions, in which all three molecules are involved in bond making and/or breaking, were hypothesized long ago in studies establishing radical chain branching mechanisms, but were later concluded to be unimportant. Here, with data from ab initio master equation and kinetic-transport simulations, we reveal that reactions of H+O 2 collision complexes with other radicals constitute major kinetic pathways under common combustion situations. These reactions are also found to influence flame propagation speeds, a common measure of global reactivity. As a result, analogous chemically termolecular reactions mediated by ephemeral collision complexes are probably of significance in various combustion and planetary environments.

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

Evaluation of Attractive Interactions in the Second Coordination Sphere of Iron Complexes Containing Pendant Amines

The interactions between pendant amines in the second coordination sphere and ligands in the first coordination sphere are important for understanding the structures and reactivity of complexes containing PR2NR'2 ligands, which have been shown to be highly active H2 oxidation/production catalysts. A series of [Fe(PPh2NBn2)2(X)(Y)]n+ complexes have been prepared and structurally characterized. These complexes have two different ligands with which the pendant amines of the diphosphine ligand can interact. The solid state structure of cis-Fe(PPh2NBn2)2Cl2 reveals that the six-membered rings adjacent to the P atoms are in a boat confirmation, resulting in close N•••P distances that suggests the P atoms have a greater affinity for the lone pair of electrons on the N atom than chloride ligands. Similarly, boat conformations are observed for both rings adjacent to the hydride ligands of trans-[HFe(PPh2NBn2)2(CH3CN)]+ and trans-HFe(PPh2NBn2)2Cl, resulting in short N•••H distances. Spectroscopic and computational studies of trans-[HFe(PPh2NBn2)2(CO)]+, trans-[HFe(PPh2NBn2)(PPh2NBn2H)(CO)]2+, and trans-[HFe(PPh2NBn2)2(H2)]+ indicate the complexes are more stable when the pendant amines in boat conformations are adjacent to the hydride ligand. These data suggest an attractor ordering of H- > CO > H2 > PR3 > Cl- ~ CH3CN. This work was supported by 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 (PNNL) is operated by Battelle for the U.S. DOE. Computations were performed using the Cascade supercomputer at the Environmental Molecular Sciences Laboratory, a National Scientific User Facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL.

Liao, Qian↗
DOE OSTI2018

Stabilization of dinitrosyl iron complexes under matrix isolation conditions: solvent and polymer effects on the synthesis of composites based on poly(methyl methacrylate) and iron complexes [Fe{sub 2}(μ-NCS-R){sub 2}(NO){sub 4}]

Homogeneous composites based on poly(methyl methacrylate) and its copolymers with methacrylic acid and on the nitrosyl iron complexes with 2-mercaptobenzimidazole and 2-mercaptobenzthiazole were synthesized. An analysis of the experimental data obtained by the methods of small-angle X-ray diffraction and SQUID magnetometry in combination with the results of quantum chemical calculations showed that the nitrosyl complexes did not retain their initial binuclear structure under the matrix isolation conditions: some complexes decompose to mononuclear ones. The percentage ratio of the dimers and monomers depends on the fraction of the methacrylic acid copolymer in the polymeric matrix and is almost independent of the type of thiol ligand in the iron complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase, Mnx, from Bacillus sp. PL-12 has been successfully overexpressed in active form as a protein complex with a molecular mass of 211 kDa. We have recently used surface induced dissociation (SID) and ion mobility-mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data from the native mass spectrometry experiments led to a plausible structural model of this multicopper oxidase, which has been difficult to study by conventional structural biology methods. It was also revealed that each Mnx subunit binds a variable number of copper ions. Becasue of the heterogeneity of the protein and limited mass resolution, ambiguities in assigning some of the observed peaks remained as a barrier to fully understanding the role of metals and potential unknown ligands in Mnx. In this study, we performed SID in a modified Fourier transform-ion cyclotron resonance (FTICR) mass spectrometer. The high mass accuracy and resolution offered by FTICR unveiled unexpected artificial modifications on the protein that had been previously thought to be iron bound species based on lower resolution spectra. Additionally, isotopically resolved spectra of the released subcomplexes revealed the metal binding stoichiometry at different structural levels. This method holds great potential for in-depth characterization of metalloproteins and protein–ligand complexes. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Cryo-EM structures of engineered active bc 1- cbb 3 type CIII 2 CIV super-complexes and electronic communication between the complexes

Respiratory electron transport complexes are organized as individual entities or combined as large supercomplexes (SC). Gram-negative bacteria deploy a mitochondrial-like cytochrome (cyt) bc 1 (Complex III, CIII 2 ), and may have specific cbb 3 -type cyt c oxidases (Complex IV, CIV) instead of the canonical aa 3 -type CIV. Electron transfer between these complexes is mediated by soluble ( c 2 ) and membrane-anchored ( c y ) cyts. Here, we report the structure of an engineered bc 1 - cbb 3 type SC (CIII 2 CIV, 5.2Å resolution) and three conformers of native CIII 2 (3.3 Å resolution). The SC is active in vivo and in vitro, contains all catalytic subunits and cofactors, and two extra transmembrane helices attributed to cyt c y and the assembly factor CcoH. The cyt c y is integral to SC, its cyt domain is mobile and it conveys electrons to CIV differently than cyt c 2 . The successful production of a native-like functional SC and determination of its structure illustrate the characteristics of membrane-confined and membrane-external respiratory electron transport pathways in Gram-negative bacteria.

42 ENGINEERING↗
DOE OSTI2020

Deconstructing the Soil Microbiome into Reduced-Complexity Functional Modules

The soil microbiome is an invaluable component of the biosphere and critical for ecosystem functions, including biogeochemical cycling, soil-atmosphere gas exchange, degradation of toxic compounds, and promotion of plant growth and stress resistance/resilience. An improved understanding of the soil microbiome will help with predicting how these processes respond to external perturbations, and with harnessing beneficial aspects of the soil microbiome for agronomic applications such as crop amendments. However, the extensive taxonomic and functional diversity inherent within the soil microbiome hinders efficient analysis of this system. Microbial biodiversity in soils is orders of magnitude greater than other commonly studied systems such as the human gut microbiome (Blum, Zechmeister-Boltenstern, and Keiblinger 2019; Berendsen, Pieterse, and Bakker 2012). Thousands of microbial taxa may be found in a single gram of soil (Roesch et al. 2007), and high rates of gene flow and mutation further promote microbial diversification (Sergaki et al. 2018). Concomitantly, functional diversity in soil is similarly extensive. Soil is a heterogeneous mixture of microenvironments with defined physical and chemical attributes (Bach et al. 2018), within which numerous microbial guilds of distinct life-strategies and metabolic capacities can be found (Perez-Garcia, Lear, and Singhal 2016; H.-S. Song et al. 2014). Furthermore, the soil microbiome harbors a significant fraction of rare and/or quiescent members (Blagodatskaya and Kuzyakov 2013) that exist below the threshold of detection of current technologies. Such rare taxa may make significant contributions to process rates (Shade and Gilbert 2015; Dawson et al. 2017), but their scarcity complicates their identification and analysis. Finally, the vast amounts of information generated through holistic analyses of soil communities represent an intense computational burden (Scholz, Lo, and Chain 2012; Prosser 2015) that precludes assessment of the complete functional and taxonomic diversity contained in this ecosystem.

Naylor, Dan T.↗
DOE OSTI2021

Synthesis, structure, electronic characterization, and halogenation of gold(III) phlorin complexes

The metalation chemistry of the phlorin, which is a non-aromatic tetrapyrrole macrocycle containing a single sp 3 -hybridized meso-carbon has remained underdeveloped, as compared to that of more traditional tetrapyrroles such as porphyrins, corroles and phthalocyanines. There have been few prior efforts to prepare metallophlorins, and those that have been reported have relied on either reduction or nucleophilic attack of parent metalloporphyrins, rather than direct metalation of freebase phlorin constructs. In this work, an alternate synthetic approach for preparation of gold(III) phlorin complexes that involves the first direct metalation of two different freebase phlorin derivatives (3H(Phl tBu ) and 3H(Phl F )) with AuBr 3 to produce the stable and fully isolable gold(III) phlorin complexes Au(Phl tBu ) and Au(Phl F ) is reported. The first structural characterization of a metallophlorin bearing geminal dimethyl substituents at the sp 3 -hybridized meso-carbon via X-ray crystallography is also reported. In addition to the preparation of Au(Phl tBu ) and Au(Phl F ), the UV-vis absorption and redox properties of these two gold(III) phlorins in comparison to those of their freebase homologues is also detailed. Notably, the metallophlorins are characterized by panchromatic absorbance profiles and intense and broad bands that span the long-visible and into the near-IR regions, as well as two fully reversible oxidation and reduction waves as probed by cyclic voltammetry. Lastly, the chlorination of Au(Phl tBu ) using PhI(Cl 2 ) was probed and it was found that this regioslective reaction generates monochlorinated (Au(Phl tBu Cl)) and dichlorinated (Au(Phl tBu Cl 2 )) products, which were both structurally characterized by X-ray crystallography.

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

Siloxyaluminate and Siloxygallate Complexes as Models for Framework and Partially Hydrolyzed Framework Sites in Zeolites and Zeotypes.

Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu) 3 ] 4 - and HOM[OSi(OtBu) 3 ] 3 - (where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu) 3 ] 3 Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown-4 afforded charge-separated ion pairs composed of monomeric anions M[OSi(OtBu) 3 ] 4 - with outer-sphere [([12]crown-4) 2 Li] + cations, and hydroxides {HOM[OSi(OtBu) 3 ] 3 } with pendant [([12]crown-4)Li] + cations. These molecular models were characterized by single-crystal X-ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown-4)Li]{HOM[OSi(OtBu) 3 ] 3 } complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin-Ponndorf-Verley (MPV) transfer hydrogenations with Al/Ga-doped silica catalysts.

Dombrowski, James P↗
DOE OSTI2023

Ligand and Linkage Isomers of Bis(ethylthiocarbamato) Copper Complexes with Cyclic C 6 H 8 Backbone Substituents: Synthesis, Characterization, and Antiproliferation Activity

Abstract A series of isomeric bis(alkylthiocarbamate) copper complexes have been synthesized, characterized, and evaluated for antiproliferation activity. The complexes were derived from ligand isomers with 3‐methylpentyl (H 2 L 2 ) and cyclohexyl (H 2 L 3 ) backbone substituents, which each yield a pair of linkage isomers. The thermodynamic products CuL 2a/3a have two imino N and two S donors resulting in three five‐member chelate rings (555 isomers). The kinetic isomers CuL 2b/3b have one imino and one hydrazino N donor and two S donors resulting in four‐, six‐, and five‐member rings (465 isomers). The 555 isomers have more accessible Cu II/I potentials (E 1/2 =−811/−768 mV vs. ferrocenium/ferrocene) and lower energy charge transfer bands than their 465 counterparts (E 1/2 =−923/‐854 mV). Antiproliferation activities were evaluated against the lung adenocarcinoma cell line (A549) and nonmalignant lung fibroblast cell line (IMR‐90) using the MTT assay. CuL 2a was potent ( A549 EC 50 =0.080 μM) and selective ( IMR‐90 EC 50 / A549 EC 50 =25) for A549. Its linkage isomer CuL 2b had equivalent A549 activity, but lower selectivity ( IMR‐90 EC 50 / A549 EC 50 =12.5). The isomers CuL 3a and CuL 3b were less potent with A549 EC 50 values of 1.9 and 0.19 M and less selective with IMR‐90 EC 50 / A549 EC 50 ratios of 2.3 and 2.65, respectively. There was no correlation between reduction potential and A549 antiproliferation activity/selectivity.

Chemistry↗
DOE OSTI2016

Comparison of Measured and Numerically Simulated Turbulence Statistics in a Convective Boundary Layer Over Complex Terrain

High resolution numerical simulation can provide insight into important physical processes that occur within the planetary boundary layer (PBL). The present work employs large eddy simulation (LES) nested within the Weather Forecasting and Research (WRF) framework to simulate real conditions in the convective PBL over an area of complex terrain. A multiple nesting approach has been used to downsize the grid spacing size from 12.15 km (mesoscale) to 0.03 km (LES). To minimize artifacts in theWRF-LES solutions resulting from using an inappropriate grid spacing on the WRF-Meso domain, a careful selection of grid spacing has been conducted. The WRF-LES results have been evaluated with in situ and remote sensing observations collected during the US Department of Energy supported Columbia BasinWind Energy Study (CBWES). The comparison for the first and second order moments, turbulence spectrum, and probability density function (pdf) of wind speed show good agreement between the simulation and data. Furthermore, the WRF-LES variables show a great deal of variability in space and time caused by the complex topography in the LES domain. The WRF-LES results show that the flow structures, such as roll vortices and convective cells, over the domain vary depending on both the spatial location and time of the day. In addition to basic studies related to boundary-layer meteorology, results from these simulations can be used in other applications, such as studying the wind energy resources.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Predicting Deformation Limits of Dual-Phase Steels Under Complex Loading Paths

The deformation limits of various DP980 steels are examined in this study with deformation instability theory. Under uniaxial tension, overall stress-strain curves of the material are estimated based on simple rule of mixture (ROM) with both iso-strain and iso-stress assumptions. Under complex loading paths, actual microstructure-based finite element (FE) method is used to explicitly resolve the deformation incompatibilities between the soft ferrite and hard martensite phases. The results show that, for uniaxial tension, the deformation instability theory with iso-strain-based ROM can be used to provide the lower bound estimate of the uniform elongation (UE) for the various DP980 considered. Under complex loading paths, the deformation instability theory with microstructure-based FE method can be used in examining the effects of various microstructural features on the deformation limits of DP980 steels.

36 MATERIALS SCIENCE↗