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At least 955 records · Page 53

Video Image Stabilization and Registration

A method of stabilizing and registering a video image in multiple video fields of a video sequence provides accurate determination of the image change in magnification, rotation and translation between video fields, so that the video fields may be accurately corrected for these changes in the image in the video sequence. In a described embodiment, a key area of a key video field is selected which contains an image which it is desired to stabilize in a video sequence. The key area is subdivided into nested pixel blocks and the translation of each of the pixel blocks from the key video field to a new video field is determined as a precursor to determining change in magnification, rotation and translation of the image from the key video field to the new video field.

Hathaway, David H.↗

Precious Metal-Free Nickel Nitride Catalyst for the Oxygen Reduction Reaction

With promising activity and stability for the oxygen reduction reaction (ORR), transition metal nitrides are an interesting class of non-platinum group catalysts for polymer electrolyte membrane fuel cells. Here, we report an active thin-film nickel nitride catalyst synthesized through a reactive sputtering method. In rotating disk electrode testing in a 0.1 M HClO 4 electrolyte, the crystalline nickel nitride film achieved high activity and selectivity to four-electron ORR. It also exhibited good stability during 10 and 40 h chronoamperometry measurements in acid and alkaline electrolyte, respectively. A combined experiment-theory approach, with detailed ex situ materials characterization and density functional theory calculations, provides insight into the structure of the catalyst and its surface during catalysis. Design strategies for activity and stability improvement through alloying and nanostructuring are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identification, Characterization, and Optimization of Integrin αvβ6-Targeting Peptides from a One-Bead One-Compound (OBOC) Library: Towards the Development of Positron Emission Tomography (PET) Imaging Agents

The current translation of peptides identified through the one-bead one-compound (OBOC) technology into positron emission tomography (PET) imaging agents is a slow process, with a major delay between ligand identification and subsequent lead optimization. This work aims to streamline the development process of 18F-peptide based PET imaging agents to target the integrin αvβ6. By directly identify αvβ6–targeting peptides from a 9-mer 4-fluorobenzoyl peptide library using the on-bead two-color (OBTC) cell-screening assay, a total of 185 peptide beads were identified and 5 beads sequenced for further evaluation. The lead peptide 1 (VGDLTYLKK(FB), IC50 = 0.45 ± 0.06 μM, 25% stable in serum at 1 h) was further modified at the N-, C-, and bi-termini. C-terminal PEGylation increased the metabolic stability (>95% stable), but decreased binding affinity (IC50 = 3.7 ± 1 μM) was noted. C-terminal extension (1i, VGDLTYLKK(FB)KVART) significantly increased binding affinity for integrin αvβ6 (IC50 = 0.021 ± 0.002 μM), binding selectivity for αvβ6-expressing cells (3.1 ± 0.8:1), and the serum stability (>99% stable). Our results demonstrate the challenges in optimizing OBOC-derived peptides, indicate both termini of 1 are sensitive to modifications, and show that further modification of 1 is necessary to demonstrate utility as an 18F-peptide imaging agent.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Development of an Anode Stabilization Layer for High Energy Li-S Cells for Electric Vehicles

For lithium-Sulfur (Li-S) batteries to be practical, economic and safe for powering electric vehicles more than 300 miles between charges the energy and cycle life must be improved. Li- S’s theoretical specific energy and energy density are (2,550 Wh/kg, 2,860 Wh/l), compared to (~600 Wh/kg, 1,800 Wh/l) for Li-ion. At less than 25% of theoretical specific energy (~560 Wh/kg at the cell level), Li-S batteries could power a 1500 kg, 5 passenger vehicle, more than 300 miles between charges with a battery pack weighing less than 300 kg. For commercial viability these cells must be safe, low cost and exhibit more than 1,000 full depth of discharge cycles. By implementing unique new physical barrier technologies this work targets (500 Wh/kg, 500 cycles) at the cell level by late 2013. After this program, (600 Wh/kg, 1,000 cycles) cells are targeted in >40 kWh battery packs by 2018 at < $200/kWh. The present state-of-the-art Li-S cells developed at Sion Power, in current commercial format delivers (2.8 Ah, 5.8 Wh, 350 Wh/kg) and are limited to ~50 cycles. These cells deliver only 14% of theoretical specific energy. By retooling and optimizing cell design and packaging to rebalance materials, this chemistry can reach (350 Wh/kg, ~100 cycles) in commercial cells. Much more than 100 cycles, at >350 Wh/kg, is unlikely for the present chemistry-only Li-S cell paradigm. Cycle life is limited almost exclusively by reactions between the Li-metal anode and the solvents necessary to promote cathode function. To release the transformational energy of Li-S the anode must be decoupled from the cathode chemistry. Prospects to achieve this decoupling through chemistry alone are challenging, therefore this program is to accelerate efforts to decouple anode and cathode chemistries by separating the electrodes with ion selective, thin film multi-layer, physical barrier membranes stabilized by externally applied pressure. This report will focus on efforts of Battelle to develop an anode stabilization layer and method to measure the ionic conductivity of this thin vacuum deposited polymeric layer.

Gross, M. E.↗

The expression platform and the aptamer: cooperativity between Mg 2+ and ligand in the SAM-I riboswitch

Riboswitch operation involves the complex interplay between the aptamer domain and the expression platform. During transcription, these two domains compete against each other for shared sequence. In this study, we explore the cooperative effects of ligand binding and Magnesium interactions in the SAM-I riboswitch in the context of aptamer collapse and anti-terminator formation. Overall, our studies show the apo-aptamer acts as (i) a pre-organized aptamer competent to bind ligand and undergo structural collapse and (ii) a conformation that is more accessible to anti-terminator formation. We show that both Mg 2+ ions and SAM are required for a collapse transition to occur. We then use competition between the aptamer and expression platform for shared sequence to characterize the stability of the collapsed aptamer. We find that SAM and Mg 2+ interactions in the aptamer are highly cooperative in maintaining switch polarity (i.e. aptamer ‘off-state’ versus anti-terminator ‘onstate’). We further show that the aptamer off-state is preferentially stabilized by Mg 2+ and similar divalent ions. Furthermore, the functional switching assay was used to select for phosphorothioate interference, and identifies potential magnesium chelation sites while characterizing their coordinated role with SAM in aptamer stabilization. In addition, we find that Mg 2+ interactions with the apo-aptamer are required for the full formation of the anti-terminator structure, and that higher concentrations of Mg 2+ (>4 mM) shift the equilibrium toward the anti-terminator on-state even in the presence of SAM.

59 BASIC BIOLOGICAL SCIENCES↗

Cutting force and stability prediction for inserted cutters

Here, this paper presents an approach for inserted end/face mill force and stability predictions using a reverse engineering approach. Structured light scanning is implemented to identify the spatial coordinates of the points that define the multiple insert cutting edges. These points are analyzed to extract the cutting edge radius and angle values, which are then incorporated in a time domain simulation that predicts cutting force and tool/workpiece deflection for user-selected operating parameters. Good agreement between predicted and measured cutting forces is first demonstrated. The process stability is then predicted using the validated force model and measured structural dynamics. Observations about the stability dependence on insert geometry are finally presented for a selected end mill.

Machining↗

Selective and Stable In-Promoted Fe Catalyst for Syngas Conversion to Light Olefins

A selective and stable alumina-supported In-promoted Fe catalyst (10 mol % In based on Fe) was discovered for converting syngas (2:1 H 2 /CO ratio) to olefins with high selectivity (45% with CO 2 included) and a remarkable stability (72 h run) at a CO conversion of 10% at 400 °C and 5 bar. The X-ray photoelectron spectroscopy results indicated that incorporating In into Fe catalysts changed the chemical bonding state of Fe and Fe/In composition near the surface layers, which affected the catalytic reactivity. Steady-state isotopic transient kinetic analysis showed that more stable CHx fragments are present on the catalyst surface when incorporating In into Fe, which can promote C–C coupling reaction toward olefins. Our study demonstrates that introducing In into Fe catalysts on Al 2 O 3 support can lower CO activation abilities. It has more impacts on lowering hydrogenation activity, which permits more C–C couplings and like of “ene” hydrogenation. Furthermore, weakening CO adsorption both in terms of sites and strength encouraged CO toward hydrocarbons rather than CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Image Stability Requirements For a Geostationary Imaging Fourier Transform Spectrometer (GIFTS)

A Geostationary Imaging Fourier Transform Spectrometer (GIFTS) has been selected for the NASA New Millennium Program (NMP) Earth Observing-3 (EO-3) mission. Our paper will discuss one of the key GIFTS measurement requirements, Field of View (FOV) stability, and its impact on required system performance. The GIFTS NMP mission is designed to demonstrate new and emerging sensor and data processing technologies with the goal of making revolutionary improvements in meteorological observational capability and forecasting accuracy. The GIFTS payload is a versatile imaging FTS with programmable spectral resolution and spatial scene selection that allows radiometric accuracy and atmospheric sounding precision to be traded in near real time for area coverage. The GIFTS sensor combines high sensitivity with a massively parallel spatial data collection scheme to allow high spatial resolution measurement of the Earth's atmosphere and rapid broad area coverage. An objective of the GIFTS mission is to demonstrate the advantages of high spatial resolution (4 km ground sample distance - gsd) on temperature and water vapor retrieval by allowing sampling in broken cloud regions. This small gsd, combined with the relatively long scan time required (approximately 10 s) to collect high resolution spectra from geostationary (GEO) orbit, may require extremely good pointing control. This paper discusses the analysis of this requirement.

Bingham, G. E.↗

Anatase TiO 2 Surface Hydration: Infrared Vibrational Assignment and Facet-Specific Stability

Anatase TiO 2 nanoparticles support a subtle diversity of surface aqua and hydroxy coordination environments that are characteristic of distinct facets and defect sites. The disparate properties and stability of each molecularly or dissociatively absorbed water environment may provide unique reactivity for facet- and site-selective atomic layer deposition (ALD). Here we probe the temperature-dependent and facet-specific stretching frequency and stability of surface hydroxyls on faceted anatase TiO 2 nanoparticles via in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Well-defined truncated octahedra, disks, and rods fabricated through hydrothermal synthesis present dominant (101), (001), and (010) facets, respectively. The selective dehydration of discrete local coordination environments as a function of temperature provides a potential pathway to site-selective and facet-selective ALD on metal oxide nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-temperature Adhesive Development and Evaluation

High-temperature adhesive systems are evaluated for short and long-term stability at temperatures ranging from 232C to 427C. The resins selected for characterization include: NASA Langley developed polyphenylquinoxaline (PPQ), and commercially available polyimides (PI). The primary method of bond testing is single lap shear. The PPQ candidates are evaluated on 6A1-4V titanium adherends with chromic acid anodize and phosphate fluoride etch surface preparations. The remaining adhesives are evaluated on 15-5 PH stainless steel with a sulfuric acid anodize surface preparation. Preliminary data indicate that the PPQ adhesives tested have stability to 3000 hours at 450F with chromic acid anodize surface preparation. Additional studies are continuing to attempt to improve the PPQ's high-performance by formulating adhesive films with a boron filler and utilizing the phosphate fluoride surface preparation on titanium. Evaluation of the polyimide candidates on stainless-steel adherends indicates that the FM-35 (American Cyanamid), PMR-15 (U.S. Polymeric/Ferro), TRW partially fluorinated polyimide and NR 150B2S6X (DuPont) adhesives show sufficient promise to justify additional testing.

Hendricks, C. L.↗

Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks

Single-site catalysts with active species anchored over metal–organic framework (MOF) supports have garnered significant interest in recent years. Catalysts with vanadium oxide (VO x ) species immobilized over Zr-NU-1000 and Hf-MOF-808 (which have nodes containing six Zr (IV) or Hf (IV) ions, respectively) were recently characterized experimentally and were reported to be active for the selective oxidation of benzyl alcohol to benzaldehyde. Here, we report a detailed computational investigation of these VO x -incorporated MOF catalysts (V-MOF) by employing density functional theory. Based on the mode of VO x attachment, various structures are explored, and their relative stabilities and computed IR spectral features are reported. Mechanisms for the selective oxidation reaction are investigated. The analysis of electron flow in the turnover-limiting C–H activation step shows that the hydrogen-atom abstraction process involves a concerted proton-coupled electron-transfer mechanism. Here, the results of this study suggest that in addition to the identity of the metal in the node, the MOF node architecture plays a crucial role in driving the catalytic activities of V-MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vapor Phase Infiltration Improves Thermal Stability of Organic Layers in Perovskite Solar Cells

Despite the rapid increase in power conversion efficiency (PCE) of perovskite solar cells (PSCs) over the past decade, stability remains a major roadblock to commercialization. Here, this work shows vapor phase infiltration (VPI) as a tool to create hybrid organic–inorganic layers that improve the stability of organic charge transport layers, such as hole-selective spiro-OMeTAD in PSCs and in other organic electronic devices. Using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and grazing incident wide-angle X-ray scattering (GIWAXS), we identify that infiltration of TiO x via VPI hinders the crystallization of the spiro-OMeTAD layer by likely preventing the π–π stacking of the molecules. Infiltrated PSCs retained more than 80% of their original efficiency after an operando stability test of 200 h at 75 °C, double the efficiency retained by devices without infiltration, in which the efficiency rapidly decreases in the first 50 h. This work provides a blueprint for using VPI to stabilize organic charge transport layers via prevention of π–π stacking leading to deleterious crystallization that shortens device lifetimes.

14 SOLAR ENERGY↗

The Underlying Chemical Mechanism of Selective Chemical Etching in CsPbBr 3 Nanocrystals for Reliably Accessing Near-Unity Emitters

Reliably accessing nanocrystal luminophores with near-unity efficiencies aids in the ability to understand the upper performance limits in optoelectronic applications that require minimal nonradiative losses. Constructing structure-function relationships at the atomic level, while accounting for inevitable defects, allows for the development of robust strategies to achieve near-unity quantum yield luminophores. For CsPbBr 3 perovskite nanocrystals, bromine vacancies leave behind undercoordinated lead atoms that act as traps, limiting the achievable optical performance of the material. Here, we show that selective etching represents a promising path for mitigating the consequences of optical defects in CsPbBr 3 nanocrystals. A mechanistic understanding of the etching reaction is essential for developing strategies to finely control the reaction. We report a study of the selective etching mechanism of CsPbBr3 nanocrystal cubes by controlling the etchant chemical potential. We observe optical absorption and luminescence trajectories while varying the extent and rate of lead removal, removing in some cases up to 75% of the lead from the original nanocrystal ensemble. At modest etchant chemical potentials, the size and shape uniformity of the nanocrystal ensemble improves in addition to the quantum yield, proceeding through a layer-by-layer etching mechanism. Operating with excessively high etchant chemical potentials is detrimental to the overall optical performance as the etching transitions to nonselective, while too low of a chemical potential results in incomplete etching. Through this general approach, we show how to finely control selective etching to consistently access a steady state or chemical stability zone of near-unity quantum yield CsPbBr 3 nanocrystals postsynthetically, suggesting a practical framework to extend this treatment to other perovskite compositions and sizes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Amine-Containing Membranes with Functionalized Multi-Walled Carbon Nanotubes for CO2/H2 Separation

Amine-containing mixed-matrix membranes incorporated with amino-functionalized multi-walled carbon nanotubes (AF-MWNTs) were synthesized for CO2/H2 separation based on the facilitated transport mechanism. AF-MWNTs were chosen primarily as the mechanical reinforcing filler to enhance the membrane stability. At 107 °C and 0.2-MPa feed pressure, the membrane incorporated with 10 wt.% AF-MWNTs showed a CO2 permeability of 3196 Barrers and a CO2/H2 selectivity of 205. At the higher feed pressure of 1.5 MPa, owing to the carrier saturation phenomenon, the same membrane exhibited reduced transport performance with a CO2 permeability of 776 Barrers and a CO2/H2 selectivity of 31. These separation performances at both the low and high feed pressures were well above the theoretical upper bound. Furthermore, the incorporation of 10 wt.% AF-MWNTs led to a significant improvement on membrane stability. The transport performance and selective layer thickness of this membrane maintained for 100 h, which suggested that the incorporation of AF-MWNTs improved the resistance to membrane compaction upon a high feed pressure. Therefore, this work is considered as one of the crucial steps to enable the application of facilitated transport membranes to high-pressure gas processing such as syngas purification.

59 BASIC BIOLOGICAL SCIENCES↗

Controllable reductive method for synthesizing metal-containing particles

The invention is directed to a method for producing metal-containing particles, the method comprising subjecting an aqueous solution comprising a metal salt, E.sub.h, lowering reducing agent, pH adjusting agent, and water to conditions that maintain the E.sub.h value of the solution within the bounds of an E.sub.h-pH stability field corresponding to the composition of the metal-containing particles to be produced, and producing said metal-containing particles in said aqueous solution at a selected E.sub.h value within the bounds of said E.sub.h-pH stability field. The invention is also directed to the resulting metal-containing particles as well as devices in which they are incorporated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation-resistant, solution-processed plasmonic Ni nanochain-SiO{sub x} (x < 2) selective solar thermal absorbers

Metal oxidation at high temperatures has long been a challenge in cermet solar thermal absorbers, which impedes the development of atmospherically stable, high-temperature, high-performance concentrated solar power (CSP) systems. In this work, we demonstrate solution-processed Ni nanochain-SiO{sub x} (x < 2) and Ni nanochain-SiO{sub 2} selective solar thermal absorbers that exhibit a strong anti-oxidation behavior up to 600 °C in air. The thermal stability is far superior to previously reported Ni nanoparticle-Al{sub 2}O{sub 3} selective solar thermal absorbers, which readily oxidize at 450 °C. The SiO{sub x} (x < 2) and SiO{sub 2} matrices are derived from hydrogen silsesquioxane and tetraethyl orthosilicate precursors, respectively, which comprise Si-O cage-like structures and Si-O networks. Fourier transform infrared spectroscopy shows that the dissociation of Si-O cage-like structures and Si-O networks at high temperatures have enabled the formation of new bonds at the Ni/SiO{sub x} interface to passivate the surface of Ni nanoparticles and prevent oxidation. X-ray photoelectron spectroscopy and Raman spectroscopy demonstrate that the excess Si in the SiO{sub x} (x < 2) matrices reacts with Ni nanostructures to form silicides at the interfaces, which further improves the anti-oxidation properties. As a result, Ni-SiO{sub x} (x < 2) systems demonstrate better anti-oxidation performance than Ni-SiO{sub 2} systems. This oxidation-resistant Ni nanochain-SiO{sub x} (x < 2) cermet coating also exhibits excellent high-temperature optical performance, with a high solar absorptance of ∼90% and a low emittance ∼18% measured at 300 °C. These results open the door towards atmospheric stable, high temperature, high-performance solar selective absorber coatings processed by low-cost solution-chemical methods for future generations of CSP systems.

36 MATERIALS SCIENCE↗

Dynamics and statics of nonaxisymmetric liquid bridges

We finished the construction of the experimental apparatus and the design and testing of some of the visualization and data acquisition techniques. Experimental work focused on three areas: force measurements, loss of stability to nonaxisymmetric bridges, and vibration behavior. The experimental work is summarized in section 2. Selected results from our force measurement experiments are outlined in section 3. In addition we worked on the theory of the dynamic stability of axisymmetric bridges and undertook numerical simulation of the effects of inclined gravity vectors on the minimum volume stability limit for static bridges. The results and status of our theoretical work and numerical simulation are described in section 4. Papers published and in preparation, conference presentations, etc., are described in section 5. Work planned for the third year is discussed in section 6. References cited in the report are listed in section 7.

Alexander, J. Iwan D.↗

Tuning Metal–Organic Framework (MOF) Topology by Regulating Ligand and Secondary Building Unit (SBU) Geometry: Structures Built on 8-Connected M 6 (M = Zr, Y) Clusters and a Flexible Tetracarboxylate for Propane-Selective Propane/Propylene Separation

Topology evolution originating from variations of linker and SBU (Secondary Building Unit) geometries could largely enrich the chemistry of metal–organic frameworks (MOFs). Here we report the synthesis and characterization of three MOF structures built on the same organic linker, N,N,N',N'-Tetrakis(4-carboxyphenyl)-1,4-phenylenediamine (tcppda) and similar 8-connected M 6 (M = Zr or Y) clusters. The three compounds, HIAM-402, HIAM-403, and HIAM-311, feature 4,8-connected sqc, scu, and flu topology, respectively. Detailed structural analysis revealed that different geometries of the inorganic M 6 SBUs as well as the organic linker have led to the formation of distinct MOF nets. In particular, HIAM-402 features exceptional framework stability and high porosity and acts as a propane-selective adsorbent for the discrimination of propane and propylene. Its balanced adsorption selectivity (S propane/propylene = 1.43) and capacity (Q propane = 133.3 cm 3 /g, 298 K and 1 bar) endow it with the capability of separating propane and propylene mixtures and one-step production of highly pure propylene (purity >99.9%), as validated by column breakthrough measurements, with the presence of moisture or propyne. As a result, ab initio calculations further confirm that the propane-selective behavior of HIAM-402 is a result of its higher binding energy toward propane compared to that of propylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗