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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Mesoscale characterization of local property distributions in heterogeneous electrodes

We report the performance of electrochemical devices depends on the three-dimensional (3D) distributions of microstructural features in their electrodes. Several mature methods exist to characterize 3D microstructures over the microscale (tens of microns), which are useful in understanding homogeneous electrodes. However, methods that capture mesoscale (hundreds of microns) volumes at appropriate resolution (tens of nm) are lacking, though they are needed to understand more common, less ideal electrodes. Using serial sectioning with a Xe plasma focused ion beam combined with scanning electron microscopy (Xe PFIB-SEM), two commercial solid oxide fuel cell (SOFC) electrodes are reconstructed over volumes of 126 × 73 × 12.5 and 124 × 110 × 8 μm 3 with a resolution on the order of ≈ 50 3 nm 3 . The mesoscale distributions of microscale structural features are quantified and both microscale and mesoscale inhomogeneities are found. We analyze the origin of inhomogeneity over different length scales by comparing experimental and synthetic microstructures, generated with different particle size distributions, with such synthetic microstructures capturing well the high-frequency heterogeneity. Effective medium theory models indicate that significant mesoscale variations in local electrochemical activity are expected throughout such electrodes. Finally, these methods offer improved understanding of the performance of complex electrodes in energy conversion devices.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2013

Two new polyoxometalate-based hybrids consisting of Keggin-type cluster modified by (Ag{sub 4}) group

Two new supramolecular polyoxometalate compounds [Ag{sub 2}(mbpy){sub 3}][Ag(mbpy){sub 2}][PW{sub 12}O{sub 40}] (1) and [Ag{sub 2}(mbpy){sub 3}]{sub 2}[SiW{sub 12}O{sub 40}] (2) (mbpy=4,4'-dimethyl-2,2'-dipyridyl), have been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. The structural feature of 1–2 is in the cationic moiety of a tetra-core (Ag{sub 4}) cluster through weak Ag…Ag interactions. The silver(I) centers show three-, four- and five-coordinated geometries. In 1 the tetrameric silver atoms in ([Ag{sub 2}(mbpy){sub 3}]{sub 2}){sup 4+} covalently bind to [PW{sub 12}O{sub 40}]{sup 3−} anion via Ag3O bonds, while there is only intermolecular hydrogen bonding between ([Ag{sub 2}(mbpy){sub 3}]{sub 2}){sup 4+} and [SiW{sub 12}O{sub 40}]{sup 4−} in 2. The coordination environments of the tetrameric silver cations have a great influence on the structure richness of the Keggin-based hybrids. The fluorescence properties of compounds 1 and 2 also have been discussed. - Graphical abstract: New polyoxometalate-based hybrids consisting of Keggin-type clusters modified by (Ag{sub 4}) groups had been synthesized and characterized, and their photoluminescence properties were also discussed. Display Omitted - Highlights: • Two Keggin-type polyoxometalates consisting of (Ag{sub 4}) clusters through weak Ag…Ag interactions have been synthesized. • There exist face-to-face and dot-to-face π…π interactions in (Ag-ligand){sub 4} fragment. • The fluorescence properties of (Ag{sub 4}) modified POMs are also discussed.

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

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M II (itao)(SO 4 )(H 2 O) 0,1 ] (M = Co, Ni, Cu) and [Cu(Me 6 tren)(SO 4 )] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal–sulfur bond, while the XAS preedge of [Zn(itao)(SO 4 )] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO 4 )] but not of [Cu(Me 6 tren)(SO 4 )] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M II (SO 4 )(H 2 O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5–2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal–absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which extends across a hydrogen-bond bridge between sulfate and the itao ligand and involves orbitals at energies below the frontier set. In conclusion, this electronic structure feature provides a direct spectroscopic confirmation of the through-bond electron-transfer mechanism of redox-active metalloproteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

The Solar-Stellar Connection (NAG5-6124: SOHO Guest Investigator Program)

The following is a final report from the SOHO Guest Investigator program to use the SUMER far-UV spectrometer to obtain imaging spectroscopy in support of the goals of the so-called "solar-stellar connection." In particular, a major emphasis was utilization of the long-slit time-resolved maps of the solar surface in bright far-UV emission lines to deduce how particular aspects of the temporally and spatially averaged line profiles trace back to individual structural features of the magnetically disturbed outer atmosphere; to help interpret the unresolved line profiles from high quality stellar observations (say, with the Space Telescope Imaging Spectrograph). The researchers served two tours of duty in the SOHO Operations Center as SUMER planners, during which time we conducted an extensive series of observing programs. These can be divided into three general categories: surface mapping, translimb spectroscopy, and active region diagnostics. We have analyzed some of the large volumes of data to the point where we have presented them in poster papers, and in invited papers at national and international meetings. Listed below are the titles of the preliminary publications we have written, including brief abstracts to indicate the main results. (1) Chromospheric structure and Dynamics-- Observations -- The chromosphere is a highly structured dynamic 'layer' of the solar outer atmosphere. Here, not only are the effects of mechanical heating first evident (moving upward in altitude from the deep photosphere), but also the amount of nonradiative energy deposited is far greater than in the albeit much hotter overlying transition region and corona. Further, the chromosphere is by far the thickest zone of the solar atmosphere with respect to the pressure scale height. A major goal of stellar astrophysics is to understand how the chromosphere is heated and why it adopts its peculiar structure. A cursory examination of solar filtergrams and high-resolution movies demonstrates that much of the chromospheric "action" must be occurring on fine spatial scales and short times; particularly in the cell interior transient brightenings, but also in the longer-lived network fragments. That regime of investigation is far removed from what one usually associates with "synoptic" measurements. Nevertheless, synoptic observations of chromospheric indices, filtergrams, and globally-averaged profile parameters not only can provide important insight concerning the crucial role of the cycle-variable part of the solar magnetic field; but they also can forge a key link with analogous measurements of the stars, where often the phenomena can be significantly exaggerated from the solar case, but high spatial resolution reconnaissance is not even a remote possibility. In addition to discussing the synoptic aspects of chromospheric structure and dynamics, I summarized new insights into the general problem of the solar chromosphere that have been obtained recently with the SUMER far-ultraviolet spectrometer on SOHO. (2) CO and the Temperature Structure of the Solar Atmosphere -- The surface layers of the Sun provide a crucial boundary condition for many of the processes that occur in the deep interior. The stratification of the outer solar atmosphere once was thought to be well understood. However, studies of thermally sensitive molecular absorptions in the infrared revealed puzzling anomalies. Strong lines of the CO fundamental vibration-rotation bands near 5 microns showed very cool temperatures at the extreme limb, and remarkable off-limb emissions extending well into the supposedly hot chromosphere. The conflicting pictures of the photosphere/chromosphere interface, from the widely separated wavelength regimes, has raised suspicions that those "layers" of the atmosphere are much more inhomogeneous than previously suspected. One proposal is that the low chromosphere is dominated by cool gas, the "COmosphere," which is threaded by a network of persistent small-scale hot magnetic filaments and occasionally disrupted by localized acoustic disturbances. The COmosphere is capped by the merged fields of the network elements in the chromospheric "canopy." (3) Translimb Spectroscopy with SOHO/SUMER -- We have used SUMER to obtain deep exposures of the 1300-1400 A spectrum, at the extreme limb and off-limb. Previous "translimb" studies in the thermal infrared had revealed remarkable extensions of cold material (T is approximately equal to 3000 K)-traced by carbon monoxide emission lines-into the heart of the hot chromosphere. A main objective of our program was to search for corresponding far-UV signatures of the "thermally-bifurcated" low chromosphere; for example, radiatively fluoresced emissions of the CO A-X 4th-positive system (collisional excitation would be negligible in cold gas). We conducted two separate observing programs with SUMER. Both made use of the 1 inch-diameter circular aperture, translated across the limb in the minimum motor step increments of 0."375, along the central meridian in the Northern polar coronal hole. The first program executed for nine hours beginning 19UT 25 Oct 1996. The full wavelength range was 1340-1400 A. It was recorded in two overlapping segments, placing key regions of the spectrum alternately on the KBr and bare parts of the detector, to help isolate 2nd-order features. Each segment was integrated for 500 s, and 32 pairs were obtained to span a 12" swath centered on the optical limb. The second program was conducted 00-09UT 01 Dec 1996. It consisted of a single wavelength setting (1300-1340 A) with exposure time 500 s, but twice the spatial coverage of the earlier series: 64 steps, for a total displacement of 24". The strong chromospheric resonance lines of atomic oxygen (1302-1305 A) and ionized carbon (1334-1335 A) were observed on the bare part of the MCP camera.

Ayres, Thomas R.↗
DOE OSTI2015

Syntheses, crystal structures, and NLO properties of the quaternary sulfides RE{sub 3}Sb{sub 0.33}SiS{sub 7} (RE=La, Pr)

Two quaternary sulfides RE{sub 3}Sb{sub 0.33}SiS{sub 7} (RE=La, Pr) have been prepared from stoichiometric mixtures of elements at 1223 K in an evacuated silica tube. They are the first examples of chalcogenides in the quaternary RE/Si/Sb/Q (RE=rare earth metal; Q=S, Se, Te) system. These two isostructural materials crystallize in the Ce{sub 3}Al{sub 1.67}S{sub 7} structure type in the hexagonal space group P6{sub 3}. Their structure features one-dimensional chains of face-sharing SbS{sub 6} octahedra running parallel to the c direction surrounded by the discrete SiS{sub 4} tetrahedra and RE cations. The La{sub 3}Sb{sub 0.33}SiS{sub 7} exhibits a SHG signal about 0.5 times that of the commercially used IR NLO material AgGaS{sub 2} at 2.05 μm laser. The optical gap of 1.92 eV for La{sub 3}Sb{sub 0.33}SiS{sub 7} was deduced from UV/Vis reflectance spectroscopy. - Graphical abstract: The RE{sub 3}Sb{sub 0.33}SiS{sub 7} (RE=La, Pr), crystalling in the Ce{sub 3}Al{sub 1.67}S{sub 7} structure type, have been prepared. The La{sub 3}Sb{sub 0.33}SiS{sub 7} exhibits a SHG signal about 0.5 times that of the IR NLO material AgGaS{sub 2}. - Highlights: • The RE{sub 3}Sb{sub 0.33}SiS{sub 7} (RE=La, Pr), crystalling in the Ce{sub 3}Al{sub 1.67}S{sub 7} structure type, have been prepared. • The La{sub 3}Sb{sub 0.33}SiS{sub 7} exhibits a SHG signal about 0.5 times that of the IR NLO material AgGaS{sub 2}. • The optical gap of 1.92 eV for La{sub 3}Sb{sub 0.33}SiS{sub 7} was deduced from UV/Vis reflectance spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structural and electrophysical properties of In{sub 0.52}Al{sub 0.48}As/In{sub 0.53}Ga{sub 0.47}As/In{sub 0.52}Al{sub 0.48}As/InP HEMT nanoheterostructures with different combinations of InAs and GaAs inserts in quantum well

A complex investigation of structural and electrical properties of In{sub 0.52}Al{sub 0.48}As/In{sub y}Ga{sub 1−y}As/In{sub 0.52}Al{sub 0.48}As nanoheterostructures on InP substrates containing thin InAs and GaAs inserts in a quantum well (QW) has been performed. The GaAs nanolayers are grown at the QW boundaries between InGaAs and InAlAs layers, while the double InAs inserts are grown in InGaAs layers symmetrically with respect to the QW center. The layer and interface structures have been studied by transmission electron microscopy. It is shown that, when using the proposed epitaxial growth conditions, the introduction of ∼1.2-nm-thick InAs nanoinserts into the InGaAs QW and a ∼1-nm-thick GaAs nanobarrier at the QW boundaries does not induce structural defects. The diffusion of the InAlAs/InGaAs interface (2–3 monolayers) and InAs/InGaAs nanoinsert interface (1–2 monolayers) has been estimated. Measured Hall mobilities and electron concentrations in structures with different combinations of InAs and GaAs inserts have been analyzed using calculated energy band diagrams and electron density distributions. It is found that the photoluminescence spectra of the structures under study have differences caused by specific structural features of coupled QWs (specifically, the change in the In molar fraction due to InAs inserts and the change in the QW thickness due to GaAs transition barriers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Structural basis for potency differences between GDF8 and GDF11

Background: Growth/differentiation factor 8 (GDF8) and GDF11 are two highly similar members of the transforming growth factor β (TGFβ) family. While GDF8 has been recognized as a negative regulator of muscle growth and differentiation, there are conflicting studies on the function of GDF11 and whether GDF11 has beneficial effects on age-related dysfunction. To address whether GDF8 and GDF11 are functionally identical, we compared their signaling and structural properties. Results: Here, in this paper, we show that, despite their high similarity, GDF11 is a more potent activator of SMAD2/3 and signals more effectively through the type I activin-like receptor kinase receptors ALK4/5/7 than GDF8. Resolution of the GDF11:FS288 complex, apo-GDF8, and apo-GDF11 crystal structures reveals unique properties of both ligands, specifically in the type I receptor binding site. Lastly, substitution of GDF11 residues into GDF8 confers enhanced activity to GDF8. Conclusions: These studies identify distinctive structural features of GDF11 that enhance its potency, relative to GDF8; however, the biological consequences of these differences remain to be determined.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1984

Fluvial erosion of impact craters: Earth and Mars

Geomorphic studies of impact structures in central Australia are being used to understand the complexities of fluvial dissection in the heavily cratered terrains of Mars. At Henbury, Northern Territory, approximately 12 small meteorite craters have interacted with a semiarid drainage system. The detailed mapping of the geologic and structural features at Henbury allowed this study to concentrate on degradational landforms. The breaching of crater rims by gullies was facilitated by the northward movement of sheetwash along an extensive pediment surface extending from the Bacon Range. South-facing crater rims have been preferentially breached because gullies on those sides were able to tap the largest amounts of runoff. At crater 6 a probable rim-gully system has captured the headward reaches of a pre-impact stream channel. The interactive history of impacts and drainage development is critical to understanding the relationships in the heavily cratered uplands of Mars. Whereas Henbury craters are younger than 4700 yrs. B.P., the Gosses Bluff structure formed about 130 million years ago. The bluff is essentially an etched central peak composed of resistant sandstone units. Fluvial erosion of this structure is also discussed.

Baker, V. R.↗
DOE OSTI2016

Improving gold catalysis of nitroarene reduction with surface Pd

Nitroarene reduction reactions are commercialized catalytic processes that play a key role in the synthesisof many products including medicines, rubbers, dyes, and herbicides. Whereas bimetallic compositionshave been studied, a better understanding of the bimetallic structure effects may lead to improved indus-trial catalysts. In this work, the influence of surface palladium atoms supported on 3-nm Au nanoparticles(Pd-on-Au NPs) on catalytic activity for 4-nitrophenol reduction is explored. Batch reactor studies indi-cate Pd-on-Au NPs exhibit maximum catalytic activity at a Pd surface coverage of 150 sc%, with aninitial turnover frequency of ~3.7 mol-nitrophenol/mol-metalsurface/s, which was ~5.5× and ~13× moreactive than pure Au NPs and Pd NPs, respectively. Pd NPs, Au NPs, and Pd-on-Au NPs below 175 sc%show compensation behavior. Three-dimensional Pd surface ensembles (with ~4–5 atoms) previouslyidentified through X-ray adsorption spectroscopy provide the active sites responsible for the catalyticmaximum. These results demonstrate the ability to adjust systematically a structural feature (i.e., Pdsurface coverage) to yield a more active material.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Wucherria bancrofti glutathione S-Transferase: Insights into the 2.3 Å resolution X-ray structure and function, a therapeutic target for human lymphatic filariasis

Highlights: • Crystal structure of W. bancrofti GST with its cofactor GSH at 2.3 Å resolution was determined. • Structural comparison against human GST reveals distinct differences in substrate binding sites. • GST xenobiotic binding site is more substrate accessible and reveals non-catalytic binding sites. • Enzyme kinetic assays reveal that antifilarial drug Diethyl carbamazine binds in an uncompetitive manner. • Structural features provide insights to support future design of parasite specific inhibitors. The notoriety of parasitic nematode survival is directly related to chronic pathogenicity, which is evident in human lymphatic filariasis. It is a disease of poverty which causes severe disability affecting more than 120 million people worldwide. These nematodes down-regulate host immune system through a myriad of strategies that includes secretion of antioxidant and detoxification enzymes like glutathione-S-transferases (GSTs). Earlier studies have shown Wuchereria bancrofti GST to be a potential therapeutic target. Parasite GSTs catalyse the conjugation of glutathione to xenobiotic and other endogenous electrophiles and are essential for their long-term survival in lymph tissues. Hence, the crystal structure of WbGST along with its cofactor GSH at 2.3 Å resolution was determined. Structural comparisons against host GST reveal distinct differences in the substrate binding sites. The parasite xenobiotic binding site is more substrate/solvent accessible. The structure also suggests the presence of putative non-catalytic binding sites that may permit sequestration of endogenous and exogenous ligands. The structure of WbGST also provides a case for the role of the π-cation interaction in stabilizing catalytic Tyr compared to stabilization interactions described for other GSTs. Hence, the obtained information regarding crucial differences in the active sites will support future design of parasite specific inhibitors. Further, the study also evaluates the inhibition of WbGST and its variants by antifilarial diethylcarbamazine through kinetic assays.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

How arsenic makes amorphous GeSe a robust chalcogenide glass for advanced memory integration

The 3D integration technology in semiconductor fabrication requires a key component, the ovonic threshold switching (OTS) selector, to suppress the current leakage. The As doped amorphous (a-) GeSe glass is a commercialized OTS material in 3D phase-change memory, but the understanding of such a doping mechanism is still inadequate. Here we systematically explore the effect of As doping on the structural, bonding, and dynamics properties of a-GeAsSe using ab initio molecular dynamics simulations. The results reveal that As atoms form strong bonds with both Ge and Se atoms. The distorted octahedral structures and the 5-fold rings linked by atoms are increased. All of these structural features lead to a more disordered configuration. Moreover, as atoms have notably slowed down the atomic mobility, rendering a-GeAsSe a high stability. Overall, our studies offer insightful understanding of As-doping in OTS materials, paving the way for the design and application of advanced selector devices.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Photosynthetic biohybrid systems for solar fuels catalysis

Photosynthetic reaction center (RC) proteins are finely tuned molecular systems optimized for solar energy conversion. RCs effectively capture and convert sunlight with near unity quantum efficiency utilizing light-induced directional electron transfer through a series of molecular cofactors embedded within the protein core to generate a long-lived charge separated state with a useable electrochemical potential. Of current interest are new strategies that couple RC chemistry to the direct synthesis of energy-rich compounds. This Feature Article highlights recent work from our lab on RC and RC-inspired hybrid systems that capture the Sun's energy and convert it to chemical energy in the form of H2, a carbon-neutral energy source derived from water. Further, biohybrids made from the Photosystem I (PSI) RC are among the best photocatalytic H2-producing protein hybrids to date. Targeted self-assembly strategies that couple abiotic catalysts to PSI translate to catalyst incorporation at intrinsic PSI sites within thylakoid membranes to achieve complete solar water-splitting systems. RC-inspired biohybrids interface synthetic photosensitizers and molecular catalysts with small proteins to create photocatalytic systems and enable the spectroscopic discernment of the structural features and electron transfer processes that underpin solar-driven proton reduction. In total, these studies showcase the incredible scientific opportunities photosynthetic biohybrid research provides for harnessing the optimal qualities of both artificial and natural photosynthetic systems and developing materials that capture, convert, and store solar energy as a fuel.

14 SOLAR ENERGY↗
DOE OSTI2018

Optimization of Advanced Steels for Cyclic Operation through an Integration of Material Testing, Modeling and Novel Component Test Validation

The efforts in this project were focused in three primary objectives, provided below: • To develop the needed microstructural processing and performance relationships and associated material models for specific constituents in fabricated weldments (such as the parent material, heat affected zone regions and weld metal), • Apply these metallurgical relationships through modeling of a welded pressure bearing power plant component subjected to cyclic operational conditions under both mechanical and thermal loading, and • Validate the model through novel structural feature and component tests. An attempt was made to optimize the heat treatment schedule to reduce or eliminate the presence of boron nitride (BN) in the matrix of the Grade 92 material. BN has been shown to be a primary nucleation source for creep damage. Proper evaluation of material behavior, and as assessed in this research, included the influence of geometric notches (such as those from poor fabrication or design) and metallurgical notches (such as weldments or poorly processed parent material). Better practice methodologies were implemented in the theoretical design of a high-temperature, critical component for cyclic operation. It was demonstrated that vessel testing can be reliably performed and provides a critical link between standard testing, structural assessment and validation. While the goal of an improved Grade 92 steel was not achieved in this project, there is considerable value in applying the documented testing and assessment methodologies to assess material and/or component behavior. This is especially true for materials and/or designs which are expected to be subjected to flexible operating modes. Design of a cycling state of the art thick wall steam header for long term operation with a state of the art ferritic steel was a task in this project. Implementation of that task showed how many factors including plant operating mode, creep strength, creep ductility, fatigue strength, and resistance to crack growth should be considered and evaluated to properly design high temperature components for long term service (200,000 operating hours or more) in a modern Fossil energy power plant. The current ASME non-nuclear boiler design code does not mandate this level of complex analysis nor does it provide all the metallurgical and mechanical properties data needed to perform this kind of design analysis.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2014

Electron scattering mechanisms in Cu-Mn films for interconnect applications

Electrical properties and corresponding structural features of Cu-Mn alloy films with potential application as barrier and interconnect layers were studied. Cu-Mn films were deposited by DC magnetron sputtering at room temperature on SiO{sub 2} substrates. Electrical resistivity measurements were made as a function of film composition and temperature. The specific resistivity varies linearly with the Mn content showing a maximum of 205 μΩcm at 80 at. % Mn. The temperature coefficient of resistance (TCR) of all alloy films is low, showing non-metallic conductivity for most compositions. Also a minimum TCR has been observed in the 40–80 at. % Mn range which was attributed to a magnetic transformation around 200–300 K. Electrical resistivity measurements are correlated with the film structure revealed by transmission electron microscopy to clarify the phase regions throughout the composition range. In the 20–40 at. % and 70–80 at. % Mn ranges, two-phase structures were identified, where Cu- or Mn-rich solid solution grains were surrounded by a thin amorphous covering layer. Based on the revealed phase regions and morphologies electron scattering mechanisms in the system were evaluated by combining the Matthiessen's rule and the Mayadas-Schatzkes theory. Grain boundary reflectivity coefficients (r = 0.6–0.8) were calculated from fitting the model to the measurements. The proposed model indicates that, in a binary system, the special arrangement of the two phases results in new scattering mechanisms. The results are of value in optimizing the various parameters needed to produce a suitable barrier layer.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Pyrrophens: Pyrrole-Based Hexadentate Ligands Tailor-Made for Uranyl (UO 2 2+ ) Coordination and Molecular Recognition

Derivatives of a novel pyrrole-containing Schiff base ligand system (called “pyrrophen”) are presented which feature substituted phenylene linkers (R 1 = R 2 = H (H 2 L 1 ); R 1 = R 2 = CH 3 (H 2 L 2 )) and a binding pocket modeled after macrocyclic species. These ligands bind neutral CH 3 OH in the solid state through pyrrolic hydrogen-bonding. Here, the interaction of the uranyl cation (UO 2 2+ ) and H 2 L 1–2 yields planar hexagonal bipyramdial uranyl complexes, while the Cu 2+ and Zn 2+ complexes were found to self-assemble as dinuclear helicate complexes (M 2 L 2 ) with H 2 L 1 under identical conditions. The favorable binding of UO 2 2+ over Zn 2+ provides insight into the molecular recognition of uranyl over other metal species. Structural features of these complexes are examined with special attention to features of the UO 2 2+ coordination environment which distinguish them from other related salophen and porphyrinoid complexes.

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

Native Top-Down Mass Spectrometry and Ion Mobility MS for Characterizing the Cobalt and Manganese Metal Binding of α-Synuclein Protein

Structural characterization of intrinsically disordered proteins (IDPs) has been a major challenge in the field of protein science due to limited capabilities to obtain full-length high-resolution structures. Native ESI-MS with top-down MS was utilized to obtain structural features of protein-ligand binding for the Parkinson’s disease-related protein, α-synuclein (αSyn), which is natively unstructured. Binding of heavy metals has been implicated in the accelerated formation of αSyn aggregation. Using high-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry, native top-down MS with various fragmentation methods, including electron capture dissociation (ECD), collisional activated dissociation (CAD), and multistage tandem MS (MS{sup 3}), deduced the binding sites of cobalt and manganese to the C-terminal region of the protein. Ion mobility MS (IM-MS) revealed a collapse toward compacted states of αSyn upon metal binding. The combination of native top-down MS and IM-MS provides structural information of protein-ligand interactions for intrinsically disordered proteins. .

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

Spatially confined protein assembly in hierarchical mesoporous metal-organic framework

Immobilization of biomolecules into porous materials could lead to significantly enhanced performance in terms of stability towards harsh reaction conditions and easier separation for their reuse. Metal-Organic Frameworks (MOFs), offering unique structural features, have emerged as a promising platform for immobilizing large biomolecules. Although many indirect methods have been used to investigate the immobilized biomolecules for diverse applications, understanding their spatial arrangement in the pores of MOFs is still preliminary due to the difficulties in directly monitoring their conformations. To gain insights into the spatial arrangement of biomolecules within the nanopores. We used in situ small-angle neutron scattering (SANS) to probe deuterated green fluorescent protein (d-GFP) entrapped in a mesoporous MOF. Our work revealed that GFP molecules are spatially arranged in adjacent nanosized cavities of MOF-919 to form “assembly” through adsorbate-adsorbate interactions across pore apertures. Our findings, therefore, lay a crucial foundation for the identification of proteins structural basics under confinement environment of MOFs.

59 BASIC BIOLOGICAL SCIENCES↗