Science.gov

Sample records for low-valence metal center

  1. Reforming catalyst comprising low valence TI, V or CR composited with non-oxidizing high surface area support

    SciTech Connect

    Gleim, W.K.T.

    1984-09-11

    This invention relates to a novel catalyst for reforming gasoline comprising a low valence titanium, vanadium and/or chromium metallic component composited with a non-oxidizing high surface area support. The low valence metallic component is present in divalent form or as a combination of the metallic state and the divalent form - preferably as a chloride and/or bromide. The preferred support is a high surface area coke.

  2. Method of reforming gasoline to raise the octane thereof utilizing low valence chromium composited with non-oxidizing high surface area support

    SciTech Connect

    Gleim, W.K.T.

    1984-05-15

    This invention relates to a method of reforming gasoline to raise the octane number thereof utilizing a novel catalyst comprising a low valence chromium metallic component composited with a non-oxidizing high surface area support. The low valence metallic component is present in divalent form or as a combination of the metallic state and the divalent form-preferably as a chloride and/or bromide. The preferred support is a high surface area coke.

  3. Metal Atomization (Materials Preparation Center)

    SciTech Connect

    2010-01-01

    The following video is a slow motion capture of an atomization event. Atomization of metal requires high pressure gas and specialized chambers for cooling and collecting the powders without contamination. The critical step for morphological control is the impingement of the gas on the melt stream. This material was cast at the Ames Laboratorys Materials Preparation Center http://www.mpc.ameslab.gov

  4. Metals Processing Laboratory User Center (MPLUS)

    SciTech Connect

    Mackiewicz-Ludtka, G.; Hayden, H.W.

    1997-04-01

    The Metals Processing Laboratory User (MPLUS) Center was officially designated as a DOE User Facility in February, 1996. It`s primary purpose is to assist researchers in key U.S. industries, universities, and federal laboratories in improving energy efficiency and enhancing U.S. competitiveness in the world market. The MPLUS Center provides users the unique opportunity to address technology-related issues to solve metals-processing problems from a fully integrated approach. DOE facilitates the process and catalyzes industrial interactions that enables technical synergy and financial leveraging to take place between the industrial sector identifying and prioritizing their technological needs, and MPLUS, which provides access to the technical expertise and specialized facilities to address these needs. MPLUS is designed to provide U.S. industries with access to the specialized technical expertise and equipment needed to solve metals-processing issues that limit the development and implementation of emerging metals-processing technologies. As originated, MPLUS includes the following four primary user centers: Metals Processing, Metals Joining, Metals Characterization, and Metals Process Modeling. These centers are devoted to assisting U.S. industries in adjusting to rapid changes in the marketplace and in improving products and processes. This approach optimizes the complementary strengths of industry and government. Tremendous industrial response, has resulted in MPLUS expanding to meet the ever-growing technical needs and requests initiated by U.S. industry.

  5. Metallicity of the Stars at the Galactic Center

    NASA Astrophysics Data System (ADS)

    Kohler, Susanna

    2015-08-01

    A recent study suggests that the stars in the central parsec of our galaxy are not a single, roughly solar-metallicity population, as previously thought. Instead, these stars have a large variation in metallicities which has interesting implications for the formation history of the Milky Ways nuclear star cluster.Clues from AbundancesWhy do we care about the metallicity of stars and stellar populations? Metallicity measurements can help us to separate multiple populations of stars and figure out when and where they were formed.Measurements of the chemical abundances of stars in the Milky Way have demonstrated that theres a metallicity gradient in the galaxy: on average, its below solar metallicity at the outer edges of the disk and increases to above solar metallicity within the central 5 kpc of the galaxy.So far, measurements of stars in the very center of the galaxy are consistent with this galactic trend: theyre all slightly above solar metallicity, with little variation between them. But these measurements exist for only about a dozen stars within the central 10 pc of the galaxy! Due to the high stellar density in this region, a larger sample is needed to get a complete picture of the abundances and thats what this study set out to find.Different PopulationsLed by Tuan Do (Dunlap Fellow at the University of Toronto and member of the Galactic Center Group at UCLA), the authors of this study determined the metallicities of 83 late-type giant stars within the central parsec of the galaxy. The metallicities were found by fitting the stars K-band spectra from observations by the NIFS instrument on the Gemini North telescope.In contrast to the previous studies, the authors found that the 83 stars exhibited a wide range of metallicities, from a tenth of solar metallicity all the way to super-solar metallicities.The abundances of the low-metallicity stars they found are consistent with globular cluster metallicities, suggesting that these stars (about 6% of the sample

  6. MCPB.py: A Python Based Metal Center Parameter Builder.

    PubMed

    Li, Pengfei; Merz, Kenneth M

    2016-04-25

    MCPB.py, a python based metal center parameter builder, has been developed to build force fields for the simulation of metal complexes employing the bonded model approach. It has an optimized code structure, with far fewer required steps than the previous developed MCPB program. It supports various AMBER force fields and more than 80 metal ions. A series of parametrization schemes to derive force constants and charge parameters are available within the program. We give two examples (one metalloprotein example and one organometallic compound example), indicating the program's ability to build reliable force fields for different metal ion containing complexes. The original version was released with AmberTools15. It is provided via the GNU General Public License v3.0 (GNU_GPL_v3) agreement and is free to download and distribute. MCPB.py provides a bridge between quantum mechanical calculations and molecular dynamics simulation software packages thereby enabling the modeling of metal ion centers. It offers an entry into simulating metal ions in a number of situations by providing an efficient way for researchers to handle the vagaries and difficulties associated with metal ion modeling. PMID:26913476

  7. 75 FR 76037 - General Motors Corporation Grand Rapids Metal Center Metal Fabricating Division Including On-Site...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-12-07

    ... published in the Federal Register on April 23, 2010 (75 FR 21356). At the request of the State agency, the... Employment and Training Administration General Motors Corporation Grand Rapids Metal Center Metal Fabricating..., applicable to workers of General Motors Corporation, Grand Rapids Metal Center, Metal Fabricating...

  8. Density Functional Theory of Biologically Relevant Metal Centers

    NASA Astrophysics Data System (ADS)

    Siegbahn, Per E. M.; Blomberg, Margareta R. A.

    1999-10-01

    Recent applications of density functional theory to biologically relevant metal centers are reviewed. The emphasis is on reaction mechanisms, structures, and modeling. The accuracy of different functionals is discussed for standard benchmark tests of first- and second-row molecules and for transition metal systems. Modeling aspects of the protein metal complexes are discussed regarding both the size of the model being treated quantum mechanically and the treatment of the protein surrounding it. To illustrate the effects, structures computed without the effects of the protein are compared with experimental structures from enzymes, and results from simple dielectric models of the protein for electron transfer processes are described. The choice of spin state is discussed for multimetal complexes. Examples of mechanisms studied recently by density functional theory are described, such as O2 and methane activation in methane monooxygenase and O2 formation in photosystem II.

  9. Emission properties of body-centered cubic elemental metal photocathodes

    SciTech Connect

    Li, Tuo; Rickman, Benjamin L. Schroeder, W. Andreas

    2015-04-07

    A first principles analysis of photoemission is developed to explain the lower than expected rms transverse electron momentum measured using the solenoid scan technique for the body-centered cubic Group Vb (V, Nb, and Ta) and Group VIb (Cr, Mo, and W) metallic photocathodes. The density functional theory based analysis elucidates the fundamental role that the electronic band structure (and its dispersion) plays in determining the emission properties of solid-state photocathodes and includes evaluation of work function anisotropy using a thin-slab method.

  10. Rationalization of interactions in precious metal/ceria catalysts using the d-band center model.

    PubMed

    Acerbi, N; Tsang, S C Edman; Jones, G; Golunski, S; Collier, P

    2013-07-22

    A correlation between ceria reducibility and the precious-metal d-band center is reported for ceria-supported precious-metal catalysts. The results could provide the missing link to fully explain the occurrence of strong metal-support interaction (SMSI) and hydrogen spillover in catalysts that consist of dispersed metals in contact with reducible metal oxides. PMID:23780919

  11. Final report for the DOE Metal Hydride Center of Excellence.

    SciTech Connect

    Keller, Jay O.; Klebanoff, Leonard E.

    2012-01-01

    This report summarizes the R&D activities within the U.S. Department of Energy Metal Hydride Center of Excellence (MHCoE) from March 2005 to June 2010. The purpose of the MHCoE has been to conduct highly collaborative and multi-disciplinary applied R&D to develop new reversible hydrogen storage materials that meet or exceed DOE 2010 and 2015 system goals for hydrogen storage materials. The MHCoE combines three broad areas: mechanisms and modeling (which provide a theoretically driven basis for pursuing new materials), materials development (in which new materials are synthesized and characterized) and system design and engineering (which allow these new materials to be realized as practical automotive hydrogen storage systems). This Final Report summarizes the organization and execution of the 5-year research program to develop practical hydrogen storage materials for light duty vehicles. Major results from the MHCoE are summarized, along with suggestions for future research areas.

  12. 5-year review of Metal Hydride Center of Excellence.

    SciTech Connect

    Keller, Jay O.; Klebanoff, Leonard E.

    2010-05-01

    The purpose of the DOE Metal Hydride Center of Excellence (MHCoE) is to develop hydrogen storage materials with engineering properties that allow the use of these materials in a way that satisfies the DOE/FreedomCAR Program system requirements for automotive hydrogen storage. The Center is a multidisciplinary and collaborative effort with technical interactions divided into two broad areas: (1) mechanisms and modeling (which provide a theoretically driven basis for pursuing new materials) and (2) materials development (in which new materials are synthesized and characterized). Driving all of this work are the hydrogen storage system specifications outlined by the FreedomCAR Program for 2010 and 2015. The organization of the MHCoE during the past year is show in Figure 1. During the past year, the technical work was divided into four project areas. The purpose of the project areas is to organize the MHCoE technical work along appropriate and flexible technical lines. The four areas summarized are: (1) Project A - Destabilized Hydrides, The objective of this project is to controllably modify the thermodynamics of hydrogen sorption reactions in light metal hydrides using hydride destabilization strategies; (2) Project B - Complex Anionic Materials, The objective is to predict and synthesize highly promising new anionic hydride materials; (3) Project C - Amides/Imides Storage Materials, The objective of Project C is to assess the viability of amides and imides (inorganic materials containing NH{sub 2} and NH moieties, respectively) for onboard hydrogen storage; and (4) Project D - Alane, AlH{sub 3}, The objective of Project D is to understand the sorption and regeneration properties of AlH{sub 3} for hydrogen storage.

  13. Metal forming at the center of excellence for the synthesis and processing of advanced materials

    NASA Astrophysics Data System (ADS)

    Hughes, D. A.; Kassner, M. E.; Stout, M. G.; Vetrano, J. S.

    1998-06-01

    The U.S. Department of Energy’s Office of Basic Energy Sciences recently established the Center for Excellence in the Synthesis and Processing of Advanced Materials. Projects at the center typically include several national laboratories, industrial partners, and universities; metal forming is one of eight projects within the center. This article describes the center’s metal forming project, which emphasizes aluminum alloy forming, particularly as applicable to the automotive industry.

  14. Economizer Based Data Center Liquid Cooling with Advanced Metal Interfaces

    SciTech Connect

    Timothy Chainer

    2012-11-30

    A new chiller-less data center liquid cooling system utilizing the outside air environment has been shown to achieve up to 90% reduction in cooling energy compared to traditional chiller based data center cooling systems. The system removes heat from Volume servers inside a Sealed Rack and transports the heat using a liquid loop to an Outdoor Heat Exchanger which rejects the heat to the outdoor ambient environment. The servers in the rack are cooled using a hybrid cooling system by removing the majority of the heat generated by the processors and memory by direct thermal conduction using coldplates and the heat generated by the remaining components using forced air convection to an air- to- liquid heat exchanger inside the Sealed Rack. The anticipated benefits of such energy-centric configurations are significant energy savings at the data center level. When compared to a traditional 10 MW data center, which typically uses 25% of its total data center energy consumption for cooling this technology could potentially enable a cost savings of up to $800,000-$2,200,000/year (assuming electricity costs of 4 to 11 cents per kilowatt-hour) through the reduction in electrical energy usage.

  15. Stable singlet carbenes as mimics for transition metal centers

    PubMed Central

    Martin, David; Soleilhavoup, Michele

    2011-01-01

    This perspective summarizes recent results, which demonstrate that stable carbenes can activate small molecules (CO, H2, NH3 and P4) and stabilize highly reactive intermediates (main group elements in the zero oxidation state and paramagnetic species). These two tasks were previously exclusive for transition metal complexes. PMID:21743834

  16. Layer-by-layer synthesis of metal-containing conducting polymers: caged metal centers for interlayer charge transport.

    PubMed

    Liu, Wenjun; Huang, Weijie; Pink, Maren; Lee, Dongwhan

    2010-09-01

    Metal-templated [2 + 3]-type cocondensation of a pi-extended boronic acid and nioxime furnished a series of cage molecules, which were electropolymerized to prepare metal-containing conducting polymers (MCPs). Despite sharing essentially isostructural organic scaffolds, these materials display metal-dependent electrochemical properties as evidenced by different redox windows observed for M = Co, Fe, Ru. Consecutive electropolymerization using two different monomers furnished bilayer MCPs having different metals in each layer. In addition to functioning as heavy atom markers in cross-sectional analysis by FIB and EDX, redox-active metal centers participate in voltage-dependent interlayer electron transport to give rise to cyclic voltammograms that are distinctively different from those of each layer alone or random copolymers. A simple electrochemical technique can thus be used as a straightforward diagnostic tool to investigate the structural ordering of electrically conductive layered materials. PMID:20690667

  17. U.S. Department of Energy National Center of Excellence for Metals Recycle

    SciTech Connect

    Adams, V.; Bennett, M.; Bishop, L.

    1998-05-01

    The US Department of Energy (DOE) National Center of Excellence for Metals Recycle has recently been established. The vision of this new program is to develop a DOE culture that promotes pollution prevention by considering the recycle and reuse of metal as the first and primary disposition option and burial as a last option. The Center of Excellence takes the approach that unrestricted release of metal is the first priority because it is the most cost-effective disposition pathway. Where this is not appropriate, restricted release, beneficial reuse, and stockpile of ingots are considered. Current recycling activities include the sale of 40,000 tons of scrap metal from the East Tennessee Technology Park (formerly K-25 Plant) K-770 scrap yard, K-1064 surplus equipment and machinery, 7,000 PCB-contaminated drums, 12,000 tons of metal from the Y-l2 scrap yard, and 1,000 metal pallets. In addition, the Center of Excellence is developing a toolbox for project teams that will contain a number of specific tools to facilitate metals recycle. This Internet-based toolbox will include primers, computer programs, and case studies designed to help sites to perform life cycle analysis, perform ALARA (As Low As is Reasonably Achievable) analysis for radiation exposures, provide pollution prevention information and documentation, and produce independent government estimates. The use of these tools is described for two current activities: disposition of scrap metal in the Y-12 scrapyard, and disposition of PCB-contaminated drums.

  18. Highly active, low-valence molybdenum- and tungsten-amide catalysts for bifunctional imine-hydrogenation reactions.

    PubMed

    Chakraborty, Subrata; Blacque, Olivier; Fox, Thomas; Berke, Heinz

    2014-01-01

    The reactions of [M(NO)(CO)4(ClAlCl3)] (M=Mo, W) with (iPr2PCH2CH2)2NH, (PN(H)P) at 90 °C afforded [M(NO)(CO)(PN(H)P)Cl] complexes (M=Mo, 1a; W, 1b). The treatment of compound 1a with KOtBu as a base at room temperature yielded the alkoxide complex [Mo(NO)(CO)(PN(H)P)(OtBu)] (2a). In contrast, with the amide base Na[N(SiMe3 )2 ], the PN(H) P ligand moieties in compounds 1a and 1b could be deprotonated at room temperature, thereby inducing dehydrochlorination into amido complexes [M(NO)(CO)(PNP)] (M=Mo, 3a; W, 3b; PNP=(iPr2PCH2CH2)2N)). Compounds 3a and 3b have pseudo-trigonal-bipyramidal geometries, in which the amido nitrogen atom is in the equatorial plane. At room temperature, compounds 3a and 3b were capable of adding dihydrogen, with heterolytic splitting, thereby forming pairs of isomeric amine-hydride complexes [Mo(NO)(CO)H(PN(H)P)] (4a(cis) and 4a(trans)) and [W(NO)(CO)H(PN(H)P)] (4b(cis) and 4b(trans); cis and trans correspond to the position of the H and NO groups). H2 approaches the Mo/W=N bond in compounds 3a,b from either the CO-ligand side or from the NO-ligand side. Compounds 4a(cis) and 4a(trans) were only found to be stable under a H2 atmosphere and could not be isolated. At 140 °C and 60 bar H2 , compounds 3a and 3b catalyzed the hydrogenation of imines, thereby showing maximum turnover frequencies (TOFs) of 2912 and 1120 h(-1), respectively, for the hydrogenation of N-(4-methoxybenzylidene)aniline. A Hammett plot for various para-substituted imines revealed linear correlations with a negative slope of -3.69 for para substitution on the benzylidene side and a positive slope of 0.68 for para substitution on the aniline side. Kinetics analysis revealed the initial rate of the hydrogenation reactions to be first order in c(cat.) and zeroth order in c(imine). Deuterium kinetic isotope effect (DKIE) experiments furnished a low kH /kD value (1.28), which supported a Noyori-type metal-ligand bifunctional mechanism with H2 addition as the rate

  19. Activation of the binuclear metal center through formation of phosphotriesterase-inhibitor complexes.

    PubMed

    Samples, Cynthia R; Raushel, Frank M; DeRose, Victoria J

    2007-03-20

    Phosphotriesterase (PTE) from Pseudomonas diminuta is a binuclear metalloenzyme that catalyzes the hydrolysis of organophosphate nerve agents at rates approaching the diffusion-controlled limit. The proposed catalytic mechanism postulates the interaction of the substrate with the metal center and subsequent nucleophilic attack by the bridging hydroxide. X-band EPR spectroscopy was utilized to monitor the active site of Mn/Mn-substituted PTE upon addition of two inhibitors, diisopropyl methyl phosphonate and triethyl phosphate, and the product of hydrolysis, diethyl phosphate. The effects of inhibitor and product binding on the magnetic properties of the metal center and the hydroxyl bridge were evaluated by measuring changes in the features of the EPR spectra. The EPR spectra support the proposal that the binding of substrate analogues to the binuclear metal center diminishes the population of hydroxide-bridged species. These results, in conjunction with previously published kinetic and crystallographic data, suggest that substrate binding via the phosphoryl oxygen at the beta-metal weakens the coordination of the hydroxide bridge to the beta-metal. The weakened coordination to the beta-metal ion increases the nucleophilic character of the hydroxide and is coupled to the increase in the electrophilic character of the substrate. PMID:17315951

  20. X-ray crystallography and biological metal centers: is seeing believing?

    SciTech Connect

    Sommerhalter, M.; Lieberman, R.L.; Rosenzweig, A.C.

    2010-03-08

    Metalloenzyme crystal structures have a major impact on our understanding of biological metal centers. They are often the starting point for mechanistic and computational studies and inspire synthetic modeling chemistry. The strengths and limitations of X-ray crystallography in determining properties of biological metal centers and their corresponding ligand spheres are explored through examples, including ribonucleotide reductase R2 and particulate methane monooxygenase. Protein crystal structures locate metal ions within a protein fold and reveal the identities and coordination geometries of amino acid ligands. Data collection strategies that exploit the anomalous scattering effect of metal ions can establish metal ion identity. The quality of crystallographic data, particularly the resolution, determines the level of detail that can be extracted from a protein crystal structure. Complementary spectroscopic techniques can provide crucial information regarding the redox state of the metal center as well as the presence, type, and protonation state of exogenous ligands. The final result of the crystallographic characterization of a metalloenzyme is a model based on crystallographic data, supported by information from biophysical and modeling studies, influenced by sample handling, and interpreted carefully by the crystallographer.

  1. The Metal Centers of Particulate Methane Monooxygenase from Methylosinus trichosporium OB3b

    SciTech Connect

    Hakemian,A.; Kondapalli, K.; Telser, J.; Hoffman, B.; Stemmler, T.; Rosenzweig, A.

    2008-01-01

    Particulate methane monooxygenase (pMMO) is a membrane-bound metalloenzyme that oxidizes methane to methanol in methanotrophic bacteria. The nature of the pMMO active site and the overall metal content are controversial, with spectroscopic and crystallographic data suggesting the presence of a mononuclear copper center, a dinuclear copper center, a trinuclear center, and a diiron center or combinations thereof. Most studies have focused on pMMO from Methylococcus capsulatus (Bath). pMMO from a second organism, Methylosinus trichosporium OB3b, has been purified and characterized by spectroscopic and crystallographic methods. Purified M. trichosporium OB3b pMMO contains 2 copper ions per 100 kDa protomer. Electron paramagnetic resonance (EPR) spectroscopic parameters indicate that type 2 Cu(II) is present as two distinct species. Extended X-ray absorption fine structure (EXAFS) data are best fit with oxygen/nitrogen ligands and reveal a Cu-Cu interaction at 2.52 Angstroms. Correspondingly, X-ray crystallography of M. trichosporium OB3b pMMO shows a dinuclear copper center, similar to that observed previously in the crystal structure of M. capsulatus (Bath) pMMO. There are, however, significant differences between the pMMO structures from the two organisms. A mononuclear copper center present in M. capsulatus (Bath) pMMO is absent in M. trichosporium OB3b pMMO, whereas a metal center occupied by zinc in the M. capsulatus (Bath) pMMO structure is occupied by copper in M. trichosporium OB3b pMMO. These findings extend previous work on pMMO from M. capsulatus (Bath) and provide new insight into the functional importance of the different metal centers.

  2. The metal centers of particulate methane monooxygenase from Methylosinus trichosporium OB3b.

    PubMed

    Hakemian, Amanda S; Kondapalli, Kalyan C; Telser, Joshua; Hoffman, Brian M; Stemmler, Timothy L; Rosenzweig, Amy C

    2008-07-01

    Particulate methane monooxygenase (pMMO) is a membrane-bound metalloenzyme that oxidizes methane to methanol in methanotrophic bacteria. The nature of the pMMO active site and the overall metal content are controversial, with spectroscopic and crystallographic data suggesting the presence of a mononuclear copper center, a dinuclear copper center, a trinuclear center, and a diiron center or combinations thereof. Most studies have focused on pMMO from Methylococcus capsulatus (Bath). pMMO from a second organism, Methylosinus trichosporium OB3b, has been purified and characterized by spectroscopic and crystallographic methods. Purified M. trichosporium OB3b pMMO contains approximately 2 copper ions per 100 kDa protomer. Electron paramagnetic resonance (EPR) spectroscopic parameters indicate that type 2 Cu(II) is present as two distinct species. Extended X-ray absorption fine structure (EXAFS) data are best fit with oxygen/nitrogen ligands and reveal a Cu-Cu interaction at 2.52 A. Correspondingly, X-ray crystallography of M. trichosporium OB3b pMMO shows a dinuclear copper center, similar to that observed previously in the crystal structure of M. capsulatus (Bath) pMMO. There are, however, significant differences between the pMMO structures from the two organisms. A mononuclear copper center present in M. capsulatus (Bath) pMMO is absent in M. trichosporium OB3b pMMO, whereas a metal center occupied by zinc in the M. capsulatus (Bath) pMMO structure is occupied by copper in M. trichosporium OB3b pMMO. These findings extend previous work on pMMO from M. capsulatus (Bath) and provide new insight into the functional importance of the different metal centers. PMID:18540635

  3. [Water treatment systems of hemodialysis centers in Lithuania and trace metals in purified water in 2002].

    PubMed

    Skarupskiene, Inga; Kuzminskis, Vytautas; Abdrachmanovas, Olegas; Ryselis, Stanislovas; Smalinskiene, Alina; Naginiene, Rima

    2003-01-01

    The objective of this survey was to obtain information on hemodialysis chemical water quality and on water treatment systems of hemodialysis centers in Lithuania. Five trace metals (Al, Pb, Cd, Zn, Cu) were examined in the purified water (sample from a point after the water treatment system) of 28 hemodialysis centers. Atomic absorption spectrophotometry was applied to measure water trace metals levels. All hemodialysis centers in Lithuania used treated water. Softeners were used by 100%, reverse osmosis by 86.2% of the centers. Concomitant use of sand filter, softeners, activated carbon, reverse osmosis was found in 72.4% of the centers. The age of the water treatment system varied from 1 to 117 months (mean=39.7+/-30.4). Concentrations of Al, Pb, Cd, Zn, Cu in the purified water of 28 hemodialysis centers did not exceed standards of the European Pharmacopoeia. There was significant decrease in the mean levels of investigated trace elements in the treated water in Lithuania in 2002 compared with examined in 1998. PMID:12761429

  4. Synthesis and microstructure of electrodeposited and sputtered nanotwinned face-centered-cubic metals

    DOE PAGESBeta

    Bufford, Daniel C.; Wang, Morris; Liu, Yue; Lu, Lei

    2016-04-01

    The remarkable properties of nanotwinned (NT) face-centered-cubic (fcc) metals arise directly from twin boundaries, the structures of which can be initially determined by growth twinning during the deposition process. When we understand the synthesis process and its relation to the resulting microstructure, and ultimately to material properties, we realize how key it is to understanding and utilizing these materials. Furthermore, our article presents recent studies on electrodeposition and sputtering methods that produce a high density of nanoscale growth twins in fcc metals. Nanoscale growth twins tend to form spontaneously in monolithic and alloyed fcc metals with lower stacking-fault energies, whilemore » engineered approaches are necessary for fcc metals with higher stacking-fault energies. Finally, growth defects and other microstructural features that influence nanotwin behavior and stability are introduced here, and future challenges in fabricating NT materials are highlighted.« less

  5. Photochemical reactions of metal nitrosyl complexes. Mechanisms of NO reactions with biologically relevant metal centers

    DOE PAGESBeta

    Ford, Peter C.

    2001-01-01

    Tmore » he discoveries that nitric oxide (a.k.a. nitrogen monoxide) serves important roles in mammalian bioregulation and immunology have stimulated intense interest in the chemistry and biochemistry of NO and derivatives such as metal nitrosyl complexes. Also of interest are strategies to deliver NO to biological targets on demand. One such strategy would be to employ a precursor which displays relatively low thermal reactivity but is photochemically active to release NO.his proposition led us to investigate laser flash and continuous photolysis kinetics of nitrosyl complexes such as the Roussin's iron-sulfur-nitrosyl cluster anions Fe 2 S 2 ( NO ) 4 2 − and Fe 4 S 3 ( NO ) 7 − and several ruthenium salen and porphyrin nitrosyls.hese include studies using metal-nitrosyl photochemistry as a vehicle for delivering NO to hypoxic cell cultures in order to sensitize γ -radiation damage. Also studied were the rates and mechanisms of NO “on” reactions with model water soluble heme compounds, the ferriheme protein met-myoglobin and various ruthenium complexes using ns laser flash photolysis techniques. An overview of these studies is presented.« less

  6. Development of Li-Metal Battery Cell Chemistries at NASA Glenn Research Center

    NASA Technical Reports Server (NTRS)

    Lvovich, Vadim F.

    2015-01-01

    State-of-the-Art lithium-ion battery technology is limited by specific energy and thus not sufficiently advanced to support the energy storage necessary for aerospace needs, such as all-electric aircraft and many deep space NASA exploration missions. In response to this technological gap, our research team at NASA Glenn Research Center has been active in formulating concepts and developing testing hardware and components for Li-metal battery cell chemistries. Lithium metal anodes combined with advanced cathode materials could provide up to five times the specific energy versus state-of-the-art lithium-ion cells (1000 Whkg versus 200 Whkg). Although Lithium metal anodes offer very high theoretical capacity, they have not been shown to successfully operate reversibly.

  7. Beyond Metal-Hydrides: Non-Transition-Metal and Metal-Free Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation.

    PubMed

    Haddad, Andrew Z; Garabato, Brady D; Kozlowski, Pawel M; Buchanan, Robert M; Grapperhaus, Craig A

    2016-06-29

    A new pathway for homogeneous electrocatalytic H2 evolution and H2 oxidation has been developed using a redox active thiosemicarbazone and its zinc complex as seminal metal-free and transition-metal-free examples. Diacetyl-bis(N-4-methyl-3-thiosemicarbazone) and zinc diacetyl-bis(N-4-methyl-3-thiosemicarbazide) display the highest reported TOFs of any homogeneous ligand-centered H2 evolution catalyst, 1320 and 1170 s(-1), respectively, while the zinc complex also displays one of the highest reported TOF values for H2 oxidation, 72 s(-1), of any homogeneous catalyst. Catalysis proceeds via ligand-centered proton-transfer and electron-transfer events while avoiding traditional metal-hydride intermediates. The unique mechanism is consistent with electrochemical results and is further supported by density functional theory. The results identify a new direction for the design of electrocatalysts for H2 evolution and H2 oxidation that are not reliant on metal-hydride intermediates. PMID:27326672

  8. Two-Center/Three-Electron Sigma Half-Bonds in Main Group and Transition Metal Chemistry.

    PubMed

    Berry, John F

    2016-01-19

    First proposed in a classic Linus Pauling paper, the two-center/three-electron (2c/3e) σ half-bond challenges the extremes of what may or may not be considered a chemical bond. Two electrons occupying a σ bonding orbital and one electron occupying the antibonding σ* orbital results in bond orders of ∼0.5 that are characteristic of metastable and exotic species, epitomized in the fleetingly stable He2(+) ion. In this Account, I describe the use of coordination chemistry to stabilize such fugacious three-electron bonded species at disparate ends of the periodic table. A recent emphasis in the chemistry of metal-metal bonds has been to prepare compounds with extremely short metal-metal distances and high metal-metal bond orders. But similar chemistry can be used to explore metal-metal bond orders less than one, including 2c/3e half-bonds. Bimetallic compounds in the Ni2(II,III) and Pd2(II,III) oxidation states were originally examined in the 1980s, but the evidence collected at that time suggested that they did not contain 2c/3e σ bonds. Both classes of compounds have been re-examined using EPR spectroscopy and modern computational methods that show the unpaired electron of each compound to occupy a M-M σ* orbital, consistent with 2c/3e Ni-Ni and Pd-Pd σ half-bonds. Elsewhere on the periodic table, a seemingly unrelated compound containing a trigonal bipyramidal Cu3S2 core caused a stir, leaving prominent theorists at odds with one another as to whether the compound contains a S-S bond. Due to my previous experience with 2c/3e metal-metal bonds, I suggested that the Cu3S2 compound could contain a 2c/3e S-S σ half-bond in the previously unknown oxidation state of S2(3-). By use of the Cambridge Database, a number of other known compounds were identified as potentially containing S2(3-) ligands, including a noteworthy set of cyclopentadienyl-supported compounds possessing diamond-shaped Ni2E2 units with E = S, Se, and Te. These compounds were subjected to

  9. High dose effects in neutron irradiated face-centered cubic metals

    SciTech Connect

    Garner, F.A.; Toloczko, M.B.

    1993-06-01

    During neutron irradiation, most face-centered cubic metals and alloys develop saturation or quasi-steady state microstructures. This, in turn, leads to saturation levels in mechanical properties and quasi-steady state rates of swelling and creep deformation. Swelling initially plays only a small role in determining these saturation states, but as swelling rises to higher levels, it exerts strong feedback on the microstructure and its response to environmental variables. The influence of swelling, either directly or indirectly via second order mechanisms, such as elemental segregation to void surfaces, eventually causes major changes, not only in irradiation creep and mechanical properties, but also on swelling itself. The feedback effects of swelling on irradiation creep are particularly complex and lead to problems in applying creep data derived from highly pressurized creep tubes to low stress situations, such as fuel pins in liquid metal reactors.

  10. Flux-Pinning Centers In Metal-Organic Deposited YBCO Coated Conductors

    SciTech Connect

    Strickland, N. M.; Long, N. J.; Talantsev, E. F.; Xia, J. A.; Kennedy, J.; Markwitz, A.; Zondervan, A.; Rupich, M. W.; Zhang, W.; Li, X.; Sathyamurthy, S.

    2009-07-23

    We present our recent results in introducing artificial flux-pinning centers in metal-organic deposited YBa{sub 2}Cu{sub 3}O{sub 7} coated conductors. In particular, we describe methods for creating point-like and planar defects through precursor and process modifications, and linear defects using post-process heavy-ion irradiation. We observe these defects through transmission-electron microscopy. Each type of defect contributes a particular critical-current signature and combinations of defects can be used to tailor the superconductor for specific applications.

  11. Metal-centered polymers: Using controlled polymerization methodologies for the generation of responsive materials

    NASA Astrophysics Data System (ADS)

    Johnson, Robert Matthew

    Controlled polymerization methods were used to prepare highly modular polymeric metal complexes via convergent and divergent strategies. In these materials, the metal center provides a versatile hub for preparing diverse architectures through coordinative bonds. Moreover, the metal complex introduces various properties to the polymer such as luminescence, magnetism, or electroactivity. Suitably functionalized metal complexes have been used for the atom transfer radical polymerization of acrylate and methacrylate monomers by metalloinitiation to generate luminescent biocompatible materials through a divergent synthesis. By cleaving the tert-butyl groups from poly(tert -butyl acrylate), water soluble [Ru(bpyPAA2)3] 2+ has been prepared as well as the amphiphilic star block copolymer [Ru{bpy(PLA-PAA)2}3]2+ (PLA = poly(lactic acid), PAA = poly(acrylic acid) Bipyridine-centered polymeric macroligands may be chelated to a variety of metal salts. The polymer size greatly influences the formation of [Fe(bpy) 3]2+ centered polymers. As the molecular weight increases (> ˜25 kDa) tris complex formation decreases. Tris(bpy) synthesis is also impacted by chemical composition. BpyPtBA2 (PtBA = poly(tert-butyl acrylate) generates an iron mono(bpy) complex before giving rise to the bis(bpy) iron complex; no tris complex is observed. In contrast, the combination of bpyPEG2 (3 equiv) (PEG = (poly(ethylene glycol)) results in the formation of some iron tris(bpy) compound; however, complete tris(bpy) product formation is suppressed, presumably because of the chelating ability of the PEG chains. These examples contrast with other polymeric macroligands such as bpyPS2, bpyPMMA2, bpyPCL2 and bpyPLA 2 (PS = polystyrene; PMMA = poly(methyl methacrylate); PCL = poly(epsilon-caprolactone); PLA = poly(DL-lactic acid)) for which chelation reactions are facile for low molecular weight macroligands (<15 kDa), with chelation efficiencies (defined as (epsilonPMC/epsilonbpy) x 100%) only declining

  12. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    PubMed Central

    Sainna, Mala A.; de Visser, Sam P.

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)2(μ2-H)(μ2-NHCH3)(μ3-C)PtCH3(P(CH3)3)2](CO)n+ with n = 0, 2 and Cp = η5-C5(CH3)5, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  13. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    PubMed

    Sainna, Mala A; de Visser, Sam P

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)₂(μ²-H) (μ²-NHCH₃)(μ³-C)PtCH₃(P(CH₃)₃)₂](CO)n⁺ with n=0, 2 and Cp=η⁵-C₅(CH₃)₅, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  14. The Systematic Study of the Organotransition Metal Compounds.

    ERIC Educational Resources Information Center

    Carriedo, Gabino A.

    1990-01-01

    Discussed is an extension of the conventional method for studying the organometallic chemistry of transition metals that may be useful to show how the various existing types of low-valence complexes can be constructed. This method allows students to design new types of complexes that may still be nonexistent. (CW)

  15. Experimental study of grain interactions on rolling texture development in face-centered cubic metals

    NASA Astrophysics Data System (ADS)

    Kumar Ray, Atish

    There exists considerable debate in the texture community about whether grain interactions are a necessary factor to explain the development of deformation textures in polycrystalline metals. Computer simulations indicate that grain interactions play a significant role, while experimental evidence shows that the material type and starting orientation are more important in the development of texture and microstructure. A balanced review of the literature on face-centered cubic metals shows that the opposing viewpoints have developed due to the lack of any complete experimental study which considers both the intrinsic (material type and starting orientation) and extrinsic (grain interaction) factors. In this study, a novel method was developed to assemble ideally orientated crystalline aggregates in 99.99% aluminum (Al) or copper (Cu) to experimentally evaluate the effect of grain interactions on room temperature deformation texture. Ideal orientations relevant to face-centered cubic rolling textures, Cube {100} <001>, Goss {110} <001>, Brass {110} <11¯2> and Copper {112} <111¯> were paired in different combinations and deformed by plane strain compression to moderate strain levels of 1.0 to 1.5. Orientation dependent mechanical behavior was distinguishable from that of the neighbor-influenced behavior. In interacting crystals the constraint on the rolling direction shear strains (gammaXY , gammaXZ) was found to be most critical to show the effect of interactions via the evolution of local microstructure and microtexture. Interacting crystals with increasing deformations were observed to gradually rotate towards the S-component, {123} <634>. Apart from the average lattice reorientations, the interacting crystals also developed strong long-range orientation gradients inside the bulk of the crystal, which were identified as accumulating misorientations across the deformation boundaries. Based on a statistical procedure using quaternions, the orientation and

  16. Metal centers in the anaerobic microbial metabolism of CO and CO2

    PubMed Central

    Bender, Güneş; Pierce, Elizabeth; Hill, Jeffrey A.; Darty, Joseph E.

    2014-01-01

    Carbon dioxide and carbon monoxide are important components of the carbon cycle. Major research efforts are underway to develop better technologies to utilize the abundant greenhouse gas, CO2, for harnessing ‘green’ energy and producing biofuels. One strategy is to convert CO2 into CO, which has been valued for many years as a synthetic feedstock for major industrial processes. Living organisms are masters of CO2 and CO chemistry and, here, we review the elegant ways that metalloenzymes catalyze reactions involving these simple compounds. After describing the chemical and physical properties of CO and CO2, we shift focus to the enzymes and the metal clusters in their active sites that catalyze transformations of these two molecules. We cover how the metal centers on CO dehydrogenase catalyze the interconversion of CO and CO2 and how pyruvate oxidoreductase, which contains thiamin pyrophosphate and multiple Fe4S4 clusters, catalyzes the addition and elimination of CO2 during intermediary metabolism. We also describe how the nickel center at the active site of acetyl-CoA synthase utilizes CO to generate the central metabolite, acetyl-CoA, as part of the Wood-Ljungdahl pathway, and how CO is channelled from the CO dehydrogenase to the acetyl-CoA synthase active site. We cover how the corrinoid iron–sulfur protein interacts with acetyl-CoA synthase. This protein uses vitamin B12 and a Fe4S4 cluster to catalyze a key methyltransferase reaction involving an organometallic methyl-Co3+ intermediate. Studies of CO and CO2 enzymology are of practical significance, and offer fundamental insights into important biochemical reactions involving metallocenters that act as nucleophiles to form organometallic intermediates and catalyze C–C and C–S bond formations. PMID:21647480

  17. Metal centers in the anaerobic microbial metabolism of CO and CO2.

    PubMed

    Bender, Güneş; Pierce, Elizabeth; Hill, Jeffrey A; Darty, Joseph E; Ragsdale, Stephen W

    2011-08-01

    Carbon dioxide and carbon monoxide are important components of the carbon cycle. Major research efforts are underway to develop better technologies to utilize the abundant greenhouse gas, CO(2), for harnessing 'green' energy and producing biofuels. One strategy is to convert CO(2) into CO, which has been valued for many years as a synthetic feedstock for major industrial processes. Living organisms are masters of CO(2) and CO chemistry and, here, we review the elegant ways that metalloenzymes catalyze reactions involving these simple compounds. After describing the chemical and physical properties of CO and CO(2), we shift focus to the enzymes and the metal clusters in their active sites that catalyze transformations of these two molecules. We cover how the metal centers on CO dehydrogenase catalyze the interconversion of CO and CO(2) and how pyruvate oxidoreductase, which contains thiamin pyrophosphate and multiple Fe(4)S(4) clusters, catalyzes the addition and elimination of CO(2) during intermediary metabolism. We also describe how the nickel center at the active site of acetyl-CoA synthase utilizes CO to generate the central metabolite, acetyl-CoA, as part of the Wood-Ljungdahl pathway, and how CO is channelled from the CO dehydrogenase to the acetyl-CoA synthase active site. We cover how the corrinoid iron-sulfur protein interacts with acetyl-CoA synthase. This protein uses vitamin B(12) and a Fe(4)S(4) cluster to catalyze a key methyltransferase reaction involving an organometallic methyl-Co(3+) intermediate. Studies of CO and CO(2) enzymology are of practical significance, and offer fundamental insights into important biochemical reactions involving metallocenters that act as nucleophiles to form organometallic intermediates and catalyze C-C and C-S bond formations. PMID:21647480

  18. Optically Detected Ferromagnetic Resonance in Metallic Ferromagnets Via Off-Resonant Detection of Nitrogen Vacancy Centers in Diamond

    NASA Astrophysics Data System (ADS)

    Page, Michael R.; Bhallamudi, Vidya P.; Schulze, Joe; Purser, Carola M.; Manuilov, Sergei; Wolfe, Christopher; Brangham, Jack T.; Yang, Fengyuan; Hammel, P. Chris

    We report optical detection of ferromagnetic resonance in thin film metallic ferromagnets using a recently discovered approach employing nitrogen vacancy centers in nanodiamonds. While conventional optically detected magnetic resonance measures magnetic fields through their impact on the magnetic resonance frequency of the nitrogen vacancy center, we measure a change in the nitrogen vacancy center photoluminescence at the ferromagnet's resonance condition without need to work at the NV resonance frequency. This measurement technique allows sensitive, local detection of ferromagnetic resonance and can enable the study of magnetic dynamics at the nanoscale in a wide range of materials. While this measurement protocol was first reported in the study of ferromagnetic resonance in YIG, here we demonstrate the measurement in commonly used metallic ferromagnets to establish the generality of the technique and open the possibility of measuring nanoscale patterned devices and magnetic textures based on metallic ferromagnets of both commercial and scientific interest.

  19. Stacking fault energy of face-centered cubic metals: thermodynamic and ab initio approaches.

    PubMed

    Li, Ruihuan; Lu, Song; Kim, Dongyoo; Schönecker, Stephan; Zhao, Jijun; Kwon, Se Kyun; Vitos, Levente

    2016-10-01

    The formation energy of the interface between face-centered cubic (fcc) and hexagonal close packed (hcp) structures is a key parameter in determining the stacking fault energy (SFE) of fcc metals and alloys using thermodynamic calculations. It is often assumed that the contribution of the planar fault energy to the SFE has the same order of magnitude as the bulk part, and thus the lack of precise information about it can become the limiting factor in thermodynamic predictions. Here, we differentiate between the interfacial energy for the coherent fcc(1 1 1)/hcp(0 0 0 1) interface and the 'pseudo-interfacial energy' that enters the thermodynamic expression for the SFE. Using first-principles calculations, we determine the coherent and pseudo-interfacial energies for six elemental metals (Al, Ni, Cu, Ag, Pt, and Au) and three paramagnetic Fe-Cr-Ni alloys. Our results show that the two interfacial energies significantly differ from each other. We observe a strong chemistry dependence for both interfacial energies. The calculated pseudo-interfacial energies for the Fe-Cr-Ni steels agree well with the available literature data. We discuss the effects of strain on the description of planar faults via thermodynamic and ab initio approaches. PMID:27484794

  20. Evaluation of leakage from a metal machining center using tracer gas methods: a case study.

    PubMed

    Heitbrink, W A; Earnest, G S; Mickelsen, R L; Mead, K R; D'Arcy, J B

    1999-01-01

    To evaluate the efficacy of engineering controls in reducing worker exposure to metalworking fluids, an evaluation of an enclosure for a machining center during face milling was performed. The enclosure was built around a vertical metal machining center with an attached ventilation system consisting of a 25-cm diameter duct, a fan, and an air-cleaning filter. The evaluation method included using sulfur hexafluoride (SF6) tracer gas to determine the ventilation system's flow rate and capture efficiency, a respirable aerosol monitor (RAM) to identify aerosol leak locations around the enclosure, and smoke tubes and a velometer to evaluate air movement around the outside of the enclosure. Results of the tracer gas evaluation indicated that the control system was approximately 98% efficient at capturing tracer gas released near the spindle of the machining center. This result was not significantly different from 100% efficiency (p = 0.2). The measured SF6 concentration when released directly into the duct had a relative standard deviation of 2.2%; whereas, when releasing SF6 at the spindle, the concentration had a significantly higher relative standard deviation of 7.8% (p = 0.016). This increased variability could be due to a cyclic leakage at a small gap between the upper and lower portion of the enclosure or due to cyclic stagnation. Leakage also was observed with smoke tubes, a velometer, and an aerosol photometer. The tool and fluid motion combined to induce a periodic airflow in and out of the enclosure. These results suggest that tracer gas methods could be used to evaluate enclosure efficiency. However, smoke tubes and aerosol instrumentation such as optical particle counters or aerosol photometers also need to be used to locate leakage from enclosures. PMID:10635544

  1. Methane activation by metal-free Lewis acid centers only - a computational design and mechanism study.

    PubMed

    Ma, Gongli; Li, Zhen Hua

    2016-04-20

    In the present computational study by using the density functional theory (DFT) method, we found that silylboranes, which have metal-free Lewis acid centers only, can break the C-H bond of the exceedingly unreactive methane. The study shows that, unlike the activation mechanism of small molecules by the frustrated Lewis pairs (FLPs), the Lewis acidic boron center plays a key role in breaking the C-H bond of methane. Detailed analyses indicate that in the transition state the C-H bond is substantially activated by the empty 2p orbital of boron (2pB) primarily due to the orbital interaction between the C-H σ-bonding orbital and 2pB. On the other hand, the orbital interaction between the C-H σ-anti-bonding orbital and the B-Si σ-bonding orbital also contributes to the activation but plays a minor role. A statistical method was used to find the relationship between the reactivity of 57 silylboranes and their electronic properties. The results indicate that the boron center does have more prominent effect on the reactivity, especially the occupancy (n) and energy (ε) of 2pB, where lowering n and ε will increase the reactivity of the silylboranes. Based on the activation mechanism and taking kinetic and thermodynamic possibilities, as well as the possible side reactions, into consideration, three silylboranes suitable for methane activation under mild experimental conditions were designed. The analogous line of thought can be used as a hint for further experimental realizations, even under ambient conditions. This strategy can also be expected to be transplanted to more extensive C-H activation of hydrocarbons. PMID:27064140

  2. Grain-boundary strengthening in nanocrystalline chromium and the Hall- Petch coefficient of body-centered cubic metals

    SciTech Connect

    Wu, Dong; Junyan, Zhang; Huang, J C; Bei, Hongbin; Nieh, Tai-Gang

    2013-01-01

    Nanocrystalline Cr (nc-Cr) was synthesized by electrodeposition. Samples with various grain sizes (19 57 nm) were prepared by annealing the as-deposited sample. Microstructures were examined using X-ray and electron microscopy, and the mechanical prop- erties were evaluated using nanoindentation. The strength of nc-Cr samples apparently obeyed the classical Hall Petch relationship. It was found that hardening potency caused by grain refinement was generally higher in body-centered cubic metals than that in face-centered cubic and hexagonal close-packed metals. A possible explanation was offered.

  3. Structural and binding studies of the three-metal center in two mycobacterial PPM Ser/Thr protein phosphatases.

    PubMed

    Wehenkel, Annemarie; Bellinzoni, Marco; Schaeffer, Francis; Villarino, Andrea; Alzari, Pedro M

    2007-12-01

    Phospho-Ser/Thr protein phosphatases (PPs) are dinuclear metalloenzymes classed into two large families, PPP and PPM, on the basis of sequence similarity and metal ion dependence. The archetype of the PPM family is the alpha isoform of human PP2C (PP2Calpha), which folds into an alpha/beta domain similar to those of PPP enzymes. The recent structural studies of three bacterial PPM phosphatases, Mycobacterium tuberculosis MtPstP, Mycobacterium smegmatis MspP, and Streptococcus agalactiae STP, confirmed the conservation of the overall fold and dinuclear metal center in the family, but surprisingly revealed the presence of a third conserved metal-binding site in the active site. To gain insight into the roles of the three-metal center in bacterial enzymes, we report structural and metal-binding studies of MtPstP and MspP. The structure of MtPstP in a new trigonal crystal form revealed a fully active enzyme with the canonical dinuclear metal center but without the third metal ion bound to the catalytic site. The absence of metal correlates with a partially unstructured flap segment, indicating that the third manganese ion contributes to reposition the flap, but is dispensable for catalysis. Studies of metal binding to MspP using isothermal titration calorimetry revealed that the three Mn(2+)-binding sites display distinct affinities, with dissociation constants in the nano- and micromolar range for the two catalytic metal ions and a significantly lower affinity for the third metal-binding site. In agreement, the structure of inactive MspP at acidic pH was determined at atomic resolution and shown to lack the third metal ion in the active site. Structural comparisons of all bacterial phosphatases revealed positional variations in the third metal-binding site that are correlated with the presence of bound substrate and the conformation of the flap segment, supporting a role of this metal ion in assisting enzyme-substrate interactions. PMID:17961594

  4. Driving forces of heavy metal changes in agricultural soils in a typical manufacturing center.

    PubMed

    Qiu, Menglong; Li, Fangbai; Wang, Qi; Chen, Junjian; Yang, Guoyi; Liu, Liming

    2015-05-01

    Heavy metal concentrations in 2002 and 2012 in agricultural soils in Dongguan, a manufacturing center in southern China, were analyzed to determine the impact of rapid economic development on soil pollution. The level of pollution was assessed using the Nemerow synthetic pollution index (NPI), and its changing characteristics and driving forces were analyzed using multivariate statistical and geostatistical methods. The results indicate that the mean NPI was 0.79 in 2002 and 0.84 in 2012, which indicates aggravated heavy metal contamination in the agricultural soils. The concentrations of Cd and Zn increased 54.7 and 20.8 %, respectively, whereas Hg and Pb decreased 35.3 and 24.5 %, respectively. Cr, As, Cu, and Ni remained relatively stable. The Hg and Cd concentrations were highly correlated with soil types (P < 0.01), the secondary industrial output per unit of land (P < 0.01), proportion of cereal fields (P < 0.01), proportion of vegetable fields (P < 0.01), population density (P < 0.05), and road density (P < 0.05). The Pb and As concentrations were greatly influenced by soil types (P < 0.01), river density (P < 0.01), fertilizer rate (P < 0.01), and road density (P < 0.05). Cr, Zn, Cu, and Ni concentrations were primarily driven by soil types (P < 0.01), river density (P < 0.01), and fertilizer rate (P < 0.05). PMID:25861902

  5. Numerical Modeling of the Stability of Face-Centered Cubic Metals with High Vacancy Concentration

    SciTech Connect

    Brian P. Somerday; M. I. Baskes

    1998-12-01

    The objective of this research is to assess the possibility of forming an atomically porous structure in a low-density metal, e.g., Al with vacancies up to 0.20/lattice site; and to examine the effects of hydrogen and vacancy concentration on the stability of an atomically porous structure that has been experimentally produced in nickel. The approach involves numerical modeling using the Embedded-Atom Method (EAM). High vacancy concentrations cause the Al lattice to disorder at 300K. In contrast, Ni retains the face-centered-cubic structure at 300K for vacancy concentrations up to 0.15 Vac/lattice site. Unexpectedly, the lattice with 0.15 Vac/lattice site is more stable than the lattice with 0.10 or 0.20 Vac/lattice site. The Ni systems with 0.10 and 0.15 Vac/lattice site exhibit domains consisting of uniform lattice rotations. The Ni lattice with 0.15 Vac/lattice site is more stable with an initial distribution of random vacancies compared to ordered vacancies. The equilibrium lattice structures of Ni a d Al containing vacancies and H are less ordered to structures with vacancies only at 300K.

  6. Geometrical requirements for transition-metal-centered aromatic boron wheels: the case of VB10(-).

    PubMed

    Li, Wei-Li; Romanescu, Constantin; Piazza, Zachary A; Wang, Lai-Sheng

    2012-10-21

    A class of transition-metal-centered aromatic boron wheels (D(nh)-M©B(n)(q-)) have been recently produced and characterized according to an electronic design principle. Here we investigate the interplay between electronic and geometric requirements for the molecular wheels using the case of VB(10)(-), which is isoelectronic to the decacoordinated molecular wheels, Ta©B(10)(-) and Nb©B(10)(-). Photoelectron spectra of VB(10)(-) are observed to be broad and complicated with relatively low electron binding energies, in contrast to the simple and high electron binding energies observed for the molecular wheels of its heavier congeners. An unbiased global minimum search found the most stable isomer of VB(10)(-) to be a singlet "boat"-like structure (C(2)), in which the V atom is coordinated to a quasi-planar B(10) unit. A similar triplet C(2v) boat-like isomer is found to be almost degenerate to the C(2) structure, whereas the beautiful molecular wheel structure, D(10h)-V©B(10)(-), is significantly higher in energy on the potential energy surface. Therefore, even though the VB(10)(-) system fulfills the electronic requirement to form a D(10h)-M©B(10)(-) aromatic molecular wheel, the V atom is too small to stabilize the ten-membered boron ring. PMID:22968622

  7. (BB)-Carboryne Complex of Ruthenium: Synthesis by Double B-H Activation at a Single Metal Center.

    PubMed

    Eleazer, Bennett J; Smith, Mark D; Popov, Alexey A; Peryshkov, Dmitry V

    2016-08-24

    The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B-H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B-Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne-carboranyl transformations reported herein represent a new mode of cooperative metal-ligand reactivity of boron-based complexes. PMID:27526855

  8. Using NV centers to probe magnetization dynamics in normal metal/magnetic insulator hybrid system at the nanoscale

    NASA Astrophysics Data System (ADS)

    Zhang, Huiliang; Ku, Mark J. H.; Han, Minyong; Casola, Francesco; van der Sar, Toeno; Yacoby, Amir; Walsworth, Ronald L.

    2016-05-01

    Understanding magnetization dynamics induced by electric current is of great interest for both fundamental and practical reasons. Great endeavor has been dedicated to spin-orbit torques (SOT) in metallic structures, while quantitative study of analogous phenomena in magnetic insulators remains challenging where transport measurements are not feasible. Recently we have developed techniques using nitrogen vacancy (NV) centers in diamond to probe few-nanometre-scale correlated-electron magnetic excitations (i.e., spin waves). Here we demonstrate how this powerful tool can be implemented to study magnetization dynamics inside ferromagnetic insulator, Yttrium iron garnet (YIG) with spin injection from electrical current through normal metal (Platinum in our case). Particularly our work will focus on NV magnetic detection, imaging, and spectroscopy of coherent auto-oscillations in Pt/YIG microdisc. Magnetic fluctuations and local temperature measurements, both with nearby NV centers, will also be interesting topics relevant to SOT physics in Pt/YIG hybrid system.

  9. (BB)-Carboryne Complex of Ruthenium: Synthesis by Double B–H Activation at a Single Metal Center

    PubMed Central

    2016-01-01

    The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B–H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B–Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne–carboranyl transformations reported herein represent a new mode of cooperative metal–ligand reactivity of boron-based complexes. PMID:27526855

  10. Incoherent Bi off-centering in Bi₂Ti₂O₆O' and Bi₂Ru₂O₆O': Insulator versus metal

    DOE PAGESBeta

    Shoemaker, Daniel P.; Seshadri, Ram; Tachibana, Makoto; Hector, Andrew L.

    2011-08-24

    In the cubic, stoichiometric oxide compounds Bi₂Ti₂O₆O' (also written as Bi₂Ti₂O₇) and Bi₂Ru₂O₆O' (also written as Bi₂Ru₂O₇) Bi³⁺ ions on the pyrochlore A site display a propensity to off-center. Unlike Bi₂Ti₂O₆O', Bi₂Ru₂O₆O' is a metal, so it is of interest to ask whether conduction electrons and/or involvement of Bi 6s states at the Fermi energy influence Bi³⁺ displacements. The Bi³⁺ off-centering in Bi₂Ti₂O₆O' has previously been revealed to be incoherent from detailed reverse Monte Carlo analysis of total neutron scattering. Similar analysis of Bi₂Ru₂O₆O' reveals incoherent off-centering as well, but of smaller magnitude and with distinctly different orientational preference. Analysismore » of the distributions of metal to oxygen distances presented suggests that Bi in both compounds is entirely Bi³⁺. Disorder in Bi₂Ti₂O₆O' has the effect of stabilizing valence while simultaneously satisfying the steric constraint imposed by the presence of the lone pair of electrons. In Bi₂Ru₂O₆O', off-centering is not required to satisfy valence and seems to be driven by the lone pair. Decreased volume of the lone pair may be a result of partial screening by conduction electrons.« less

  11. Incoherent Bi off-centering in Bi₂Ti₂O₆O' and Bi₂Ru₂O₆O': Insulator versus metal

    SciTech Connect

    Shoemaker, Daniel P.; Seshadri, Ram; Tachibana, Makoto; Hector, Andrew L.

    2011-08-24

    In the cubic, stoichiometric oxide compounds Bi₂Ti₂O₆O' (also written as Bi₂Ti₂O₇) and Bi₂Ru₂O₆O' (also written as Bi₂Ru₂O₇) Bi³⁺ ions on the pyrochlore A site display a propensity to off-center. Unlike Bi₂Ti₂O₆O', Bi₂Ru₂O₆O' is a metal, so it is of interest to ask whether conduction electrons and/or involvement of Bi 6s states at the Fermi energy influence Bi³⁺ displacements. The Bi³⁺ off-centering in Bi₂Ti₂O₆O' has previously been revealed to be incoherent from detailed reverse Monte Carlo analysis of total neutron scattering. Similar analysis of Bi₂Ru₂O₆O' reveals incoherent off-centering as well, but of smaller magnitude and with distinctly different orientational preference. Analysis of the distributions of metal to oxygen distances presented suggests that Bi in both compounds is entirely Bi³⁺. Disorder in Bi₂Ti₂O₆O' has the effect of stabilizing valence while simultaneously satisfying the steric constraint imposed by the presence of the lone pair of electrons. In Bi₂Ru₂O₆O', off-centering is not required to satisfy valence and seems to be driven by the lone pair. Decreased volume of the lone pair may be a result of partial screening by conduction electrons.

  12. Rapid, sensitive, and selective fluorescent DNA detection using iron-based metal-organic framework nanorods: Synergies of the metal center and organic linker.

    PubMed

    Tian, Jingqi; Liu, Qian; Shi, Jinle; Hu, Jianming; Asiri, Abdullah M; Sun, Xuping; He, Yuquan

    2015-09-15

    Considerable recent attention has been paid to homogeneous fluorescent DNA detection with the use of nanostructures as a universal "quencher", but it still remains a great challenge to develop such nanosensor with the benefits of low cost, high speed, sensitivity, and selectivity. In this work, we report the use of iron-based metal-organic framework nanorods as a high-efficient sensing platform for fluorescent DNA detection. It only takes about 4 min to complete the whole "mix-and-detect" process with a low detection limit of 10 pM and a strong discrimination of single point mutation. Control experiments reveal the remarkable sensing behavior is a consequence of the synergies of the metal center and organic linker. This work elucidates how composition control of nanostructures can significantly impact their sensing properties, enabling new opportunities for the rational design of functional materials for analytical applications. PMID:25879891

  13. A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal-Organic Framework.

    PubMed

    Johnson, Jacob A; Petersen, Brenna M; Kormos, Attila; Echeverría, Elena; Chen, Yu-Sheng; Zhang, Jian

    2016-08-17

    We describe a new strategy to generate non-coordinating anions using zwitterionic metal-organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO2)4](-)) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of Mn(III)- and Fe(III)-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels-Alder cycloaddition of aldehydes with dienes. This work paves a new way to design functional MOFs for tunable chemical catalysis. PMID:27435751

  14. Characterization of the particulate methane monooxygenase metal centers in multiple redox states by X-ray absorption spectroscopy.

    PubMed

    Lieberman, Raquel L; Kondapalli, Kalyan C; Shrestha, Deepak B; Hakemian, Amanda S; Smith, Stephen M; Telser, Joshua; Kuzelka, Jane; Gupta, Rajeev; Borovik, A S; Lippard, Stephen J; Hoffman, Brian M; Rosenzweig, Amy C; Stemmler, Timothy L

    2006-10-01

    The integral membrane enzyme particulate methane monooxygenase (pMMO) converts methane, the most inert hydrocarbon, to methanol under ambient conditions. The 2.8-A resolution pMMO crystal structure revealed three metal sites: a mononuclear copper center, a dinuclear copper center, and a nonphysiological mononuclear zinc center. Although not found in the crystal structure, solution samples of pMMO also contain iron. We have used X-ray absorption spectroscopy to analyze the oxidation states and coordination environments of the pMMO metal centers in as-isolated (pMMO(iso)), chemically reduced (pMMO(red)), and chemically oxidized (pMMO(ox)) samples. X-ray absorption near-edge spectra (XANES) indicate that pMMO(iso) contains both Cu(I) and Cu(II) and that the pMMO Cu centers can undergo redox chemistry. Extended X-ray absorption fine structure (EXAFS) analysis reveals a Cu-Cu interaction in all redox forms of the enzyme. The Cu-Cu distance increases from 2.51 to 2.65 A upon reduction, concomitant with an increase in the average Cu-O/N bond lengths. Appropriate Cu2 model complexes were used to refine and validate the EXAFS fitting protocols for pMMO(iso). Analysis of Fe EXAFS data combined with electron paramagnetic resonance (EPR) spectra indicates that Fe, present as Fe(III), is consistent with heme impurities. These findings are complementary to the crystallographic data and provide new insight into the oxidation states and possible electronic structures of the pMMO Cu ions. PMID:16999437

  15. Manganese-centered tubular boron cluster - MnB16-: A new class of transition-metal molecules

    NASA Astrophysics Data System (ADS)

    Jian, Tian; Li, Wan-Lu; Popov, Ivan A.; Lopez, Gary V.; Chen, Xin; Boldyrev, Alexander I.; Li, Jun; Wang, Lai-Sheng

    2016-04-01

    We report the observation of a manganese-centered tubular boron cluster (MnB16-), which is characterized by photoelectron spectroscopy and ab initio calculations. The relatively simple pattern of the photoelectron spectrum indicates the cluster to be highly symmetric. Ab initio calculations show that MnB16- has a Mn-centered tubular structure with C4v symmetry due to first-order Jahn-Teller effect, while neutral MnB16 reduces to C2v symmetry due to second-order Jahn-Teller effect. In MnB16-, two unpaired electrons are observed, one on the Mn 3dz2 orbital and another on the B16 tube, making it an unusual biradical. Strong covalent bonding is found between the Mn 3d orbitals and the B16 tube, which helps to stabilize the tubular structure. The current result suggests that there may exist a whole class of metal-stabilized tubular boron clusters. These metal-doped boron clusters provide a new bonding modality for transition metals, as well as a new avenue to design boron-based nanomaterials.

  16. Manganese-centered tubular boron cluster - MnB16 (-): A new class of transition-metal molecules.

    PubMed

    Jian, Tian; Li, Wan-Lu; Popov, Ivan A; Lopez, Gary V; Chen, Xin; Boldyrev, Alexander I; Li, Jun; Wang, Lai-Sheng

    2016-04-21

    We report the observation of a manganese-centered tubular boron cluster (MnB16 (-)), which is characterized by photoelectron spectroscopy and ab initio calculations. The relatively simple pattern of the photoelectron spectrum indicates the cluster to be highly symmetric. Ab initio calculations show that MnB16 (-) has a Mn-centered tubular structure with C4v symmetry due to first-order Jahn-Teller effect, while neutral MnB16 reduces to C2v symmetry due to second-order Jahn-Teller effect. In MnB16 (-), two unpaired electrons are observed, one on the Mn 3dz(2) orbital and another on the B16 tube, making it an unusual biradical. Strong covalent bonding is found between the Mn 3d orbitals and the B16 tube, which helps to stabilize the tubular structure. The current result suggests that there may exist a whole class of metal-stabilized tubular boron clusters. These metal-doped boron clusters provide a new bonding modality for transition metals, as well as a new avenue to design boron-based nanomaterials. PMID:27389223

  17. Metal-ion-center assembly of ferredoxin and plastocyanin in isolated chloroplasts

    SciTech Connect

    Li, Hsoumin; Theg, S.M.; Bauerle, C.M.; Keegstra, K. )

    1990-09-01

    Most chloroplastic proteins are cytosolically synthesized andposttranslationally transported to their proper locations. Two examples of this group of proteins are ferredoxin and plastocyanin, both of which are metal-containing components of the photosynthetic electron-transport chain. The import process for these two proteins includes the insertion of the metal ions to produce the holo forms of the proteins. The authors show here that in vitro translated precursor proteins of ferredoxin and plastocyanin are synthesized as apo forms and are assembled into their respective holo forms after being imported into isolated chloroplasts. They also provide evidence that only mature-sized proteins are competent to be assembled into holo forms.

  18. Proposed Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation at a Noninnocent Mononuclear Metal-Thiolate.

    PubMed

    Haddad, Andrew Z; Kumar, Davinder; Ouch Sampson, Kagna; Matzner, Anna M; Mashuta, Mark S; Grapperhaus, Craig A

    2015-07-29

    The noninnocent coordinatively saturated mononuclear metal-thiolate complex ReL3 (L = diphenylphosphinobenzenethiolate) serves as an electrocatalyst for hydrogen evolution or hydrogen oxidation dependent on the presence of acid or base and the applied potential. ReL3 reduces acids to H2 in dichloromethane with an overpotential of 380 mV and a turnover frequency of 32 ± 3 s(-1). The rate law displays a second-order dependence on acid concentration and a first-order dependence on catalyst concentration with an overall third-order rate constant (k) of 184 ± 2 M(-2) s(-1). Reactions with deuterated acid display a kinetic isotope effect of 9 ± 1. In the presence of base, ReL3 oxidizes H2 with a turnover frequency of 4 ± 1 s(-1). The X-ray crystal structure of the monoprotonated species [Re(LH)L2](+), an intermediate in both catalytic H2 evolution and oxidation, has been determined. A ligand-centered mechanism, which does not require metal hydride intermediates, is suggested based on similarities to the redox-regulated, ligand-centered binding of ethylene to ReL3. PMID:26161802

  19. Inorganic–organic hybrids presenting high basic center content: SBA-15 incorporation, toxic metals sorption and energetic behavior

    SciTech Connect

    Oliveira, Fernando J.V.E.; Melo, Maurício A.; Airoldi, Claudio

    2013-03-15

    Highlights: ► Mesoporous SBA-15 silicas were organofunctionalized with new silylant agents. ► Thiocarbamate was used to enhance the silylating agent chains and basic centers. ► The synthesized pendant chains contain nitrogen and sulfur basic centers. ► The new hybrids sorb toxic cations from aqueous solutions with high efficiency. ► The thermodynamic data demonstrated favorable cation/basic center interactions. - Abstract: Mesoporous SBA-15 samples were organofunctionalized with mono, di- and tri-aminosilanes that previously reacted with thiocarbamide to enhance the organic chains and attach nitrogen and sulfur basic centers to the surface of the solids. These new organosilanes were synthesized through a non-solvent approach to reduce both cost and hazardous wastes. The high affinities for both hard and soft Lewis acids due to the combination of nitrogen and sulfur atoms attached to the same pendant chain enabled favorable sorption capacities for Cu{sup 2+}, Cd{sup 2+} and Pb{sup 2+} cations, with maximum capacities of 1.90, 3.48 and 5.30 mmol g{sup −1}, respectively, for the most efficient mesoporous silica. Microcalorimetric investigations allowed the calculation of the thermodynamic data at the solid/liquid interface. All Gibbs energy are negative as expected for spontaneous cation/basic center interactions and the positive entropic values from 49 ± 3 to 108 ± 5 J K{sup −1} mol{sup −1}, also reinforced this favorable interactive process in heterogeneous system. The designed organosilanes covalently bonded to the inorganic siliceous skeleton can be suggested as new materials for toxic metal removal from a wastewater with high efficiency.

  20. In situ observation of deformation processes in nanocrystalline face-centered cubic metals

    PubMed Central

    Kobler, Aaron; Brandl, Christian; Hahn, Horst

    2016-01-01

    Summary The atomistic mechanisms active during plastic deformation of nanocrystalline metals are still a subject of controversy. The recently developed approach of combining automated crystal orientation mapping (ACOM) and in situ straining inside a transmission electron microscope was applied to study the deformation of nanocrystalline PdxAu1− x thin films. This combination enables direct imaging of simultaneously occurring plastic deformation processes in one experiment, such as grain boundary motion, twin activity and grain rotation. Large-angle grain rotations with ≈39° and ≈60° occur and can be related to twin formation, twin migration and twin–twin interaction as a result of partial dislocation activity. Furthermore, plastic deformation in nanocrystalline thin films was found to be partially reversible upon rupture of the film. In conclusion, conventional deformation mechanisms are still active in nanocrystalline metals but with different weighting as compared with conventional materials with coarser grains. PMID:27335747

  1. In situ observation of deformation processes in nanocrystalline face-centered cubic metals.

    PubMed

    Kobler, Aaron; Brandl, Christian; Hahn, Horst; Kübel, Christian

    2016-01-01

    The atomistic mechanisms active during plastic deformation of nanocrystalline metals are still a subject of controversy. The recently developed approach of combining automated crystal orientation mapping (ACOM) and in situ straining inside a transmission electron microscope was applied to study the deformation of nanocrystalline Pd x Au1- x thin films. This combination enables direct imaging of simultaneously occurring plastic deformation processes in one experiment, such as grain boundary motion, twin activity and grain rotation. Large-angle grain rotations with ≈39° and ≈60° occur and can be related to twin formation, twin migration and twin-twin interaction as a result of partial dislocation activity. Furthermore, plastic deformation in nanocrystalline thin films was found to be partially reversible upon rupture of the film. In conclusion, conventional deformation mechanisms are still active in nanocrystalline metals but with different weighting as compared with conventional materials with coarser grains. PMID:27335747

  2. Two Isostructural Metal-Organic Frameworks Directed by the Different Center Metal Ions, Exhibiting the Ferrimagnetic Behavior and Slow Magnetic Relaxation.

    PubMed

    Wu, Yun-Long; Guo, Fu-Sheng; Yang, Guo-Ping; Wang, Lu; Jin, Jun-Cheng; Zhou, Xiang; Zhang, Wen-Yan; Wang, Yao-Yu

    2016-07-01

    Two 3D isostructural metal-organic frameworks with 1D ferrimagnetic chains, formulated as [M3(L)(μ3-OH)2(H2O)4] [H4L = (1,1':4',1″-terphenyl)-2',3,3″,5'-tetracarboxylic acid, where M = Mn for 1 and Co for 2], have been successfully synthesized by employing different center metal ions and a multicarboxylate ligand under identical reaction conditions in this work. The single-crystal X-ray diffraction data of 1 and 2 reveal that the complexes are two 3D isostructural frameworks based on 1D [M3(OH)2]n chains composed of triangular subunits as rod-shaped secondary building units, which are classified as binodal 4,6-connected fry nets with the point symbol (5(10)·6(3)·7(8))(5(4)·6(2)). The magnetic properties revealed that complexes 1 and 2 exhibit ferrimagnetic behavior. Also, the alternating-current susceptibility of 2 displays slow magnetic relaxation, showing interesting magnetic behavior of a single-chain magnet with an effective energy barrier of 32 K. PMID:27327901

  3. Molecular dynamic simulation for nanometric cutting of single-crystal face-centered cubic metals

    PubMed Central

    2014-01-01

    In this work, molecular dynamics simulations are performed to investigate the influence of material properties on the nanometric cutting of single crystal copper and aluminum with a diamond cutting tool. The atomic interactions in the two metallic materials are modeled by two sets of embedded atom method (EAM) potential parameters. Simulation results show that although the plastic deformation of the two materials is achieved by dislocation activities, the deformation behavior and related physical phenomena, such as the machining forces, machined surface quality, and chip morphology, are significantly different for different materials. Furthermore, the influence of material properties on the nanometric cutting has a strong dependence on the operating temperature. PMID:25426007

  4. Molecular dynamic simulation for nanometric cutting of single-crystal face-centered cubic metals.

    PubMed

    Huang, Yanhua; Zong, Wenjun

    2014-01-01

    In this work, molecular dynamics simulations are performed to investigate the influence of material properties on the nanometric cutting of single crystal copper and aluminum with a diamond cutting tool. The atomic interactions in the two metallic materials are modeled by two sets of embedded atom method (EAM) potential parameters. Simulation results show that although the plastic deformation of the two materials is achieved by dislocation activities, the deformation behavior and related physical phenomena, such as the machining forces, machined surface quality, and chip morphology, are significantly different for different materials. Furthermore, the influence of material properties on the nanometric cutting has a strong dependence on the operating temperature. PMID:25426007

  5. Insights on activation enthalpy for non-Schmid slip in body-centered cubic metals

    SciTech Connect

    Hale, Lucas M.; Lim, Hojun; Zimmerman, Jonathan A.; Battaile, Corbett C.; Weinberger, Christopher R.

    2014-12-18

    We use insights gained from atomistic simulation to develop an activation enthalpy model for dislocation slip in body-centered cubic iron. Furthermore, using a classical potential that predicts dislocation core stabilities consistent with ab initio predictions, we quantify the non-Schmid stress-dependent effects of slip. The kink-pair activation enthalpy is evaluated and a model is identified as a function of the general stress state. Thus, our model enlarges the applicability of the classic Kocks activation enthalpy model to materials with non-Schmid behavior.

  6. Effects of stacking fault energy on defect formation process in face-centered cubic metals

    NASA Astrophysics Data System (ADS)

    Okita, Taira; Yang, Yingjuan; Hirabayashi, Junichi; Itakura, Mitsuhiro; Suzuki, Katsuyuki

    2016-05-01

    To elucidate the effect of stacking fault energies (SFEs) on defect formation by the collision cascade process for face-centred cubic metals, we used six sets of interatomic potentials with different SFEs while keeping the other properties almost identical. Molecular dynamic simulations of the collision cascade were carried out using these potentials with primary knock-on atom energies (EPKA) of 10 and 20 keV at 100 K. Neither the number of residual defects nor the size distributions for both self-interstitial atom (SIA) type and vacancy type clusters were affected by the difference in the SFE. In the case of EPKA = 20 keV, the ratio of glissile SIA clusters increased as the SFE decreased, which was not expected by a prediction based on the classical dislocation theory. The trend did not change after annealing at 1100 K for 100 ps. For vacancy clusters, few stacking fault tetrahedrons (SFTs) formed before the annealing. However, lower SFEs tended to increase the SFT fraction after the annealing, where large vacancy clusters formed at considerable densities. The findings of this study can be used to characterise the defect formation process in low SFE metals such as austenitic stainless steels.

  7. High-Frequency (13)C and (29)Si NMR Chemical Shifts in Diamagnetic Low-Valence Compounds of Tl(I) and Pb(II): Decisive Role of Relativistic Effects.

    PubMed

    Vícha, Jan; Marek, Radek; Straka, Michal

    2016-02-15

    The (13)C and (29)Si NMR signals of ligand atoms directly bonded to Tl(I) or Pb(II) heavy-element centers are predicted to resonate at very high frequencies, up to 400 ppm for (13)C and over 1000 ppm for (29)Si, outside the typical experimental NMR chemical-shift ranges for a given type of nuclei. The large (13)C and (29)Si NMR chemical shifts are ascribed to sizable relativistic spin-orbit effects, which can amount to more than 200 ppm for (13)C and more than 1000 ppm for (29)Si, values unexpected for diamagnetic compounds of the main group elements. The origin of the vast spin-orbit contributions to the (13)C and (29)Si NMR shifts is traced to the highly efficient 6p → 6p* metal-based orbital magnetic couplings and related to the 6p orbital-based bonding together with the low-energy gaps between the occupied and virtual orbital subspaces in the subvalent Tl(I) and Pb(II) compounds. New NMR spectral regions for these compounds are suggested based on the fully relativistic density functional theory calculations in the Dirac-Coulomb framework carefully calibrated on the experimentally known NMR data for Tl(I) and Pb(II) complexes. PMID:26820039

  8. Low-temperature thermostatics of face-centered-cubic metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Caron, L. G.

    1974-01-01

    The thermostatic properties of a high-symmetry phase of metallic hydrogen with atomic sphere radius between 0.1 and 1.5 bohr are studied, with special emphasis accorded to electronic screening and quantum proton motion. The electron-proton and proton-proton interactions receive a perturbation treatment based on the Singwi dielectric function, while the proton motion is handled by self-consistent harmonic approximation. Quantum behavior is found to be less pronounced than expected, and nuclear magnetism is absent. The phonon spectrum is, however, affected by screening and large proton motion. The zero-point vibrational energy and the superconducting critical temperature are below previous estimates. The crystalline-defect formation energies are a few times the Debye energy, which implies that defects contribute significantly to melting at the lower particle densities.

  9. Sulfide oxidation by hydrogen peroxide catalyzed by iron complexes: two metal centers are better than one.

    PubMed

    Mekmouche, Yasmina; Hummel, Helga; Ho, Raymond Y N; Que, Lawrence; Schünemann, Volker; Thomas, Fabrice; Trautwein, Alfred X; Lebrun, Colette; Gorgy, Karine; Leprêtre, Jean-Claude; Collomb, Marie-Noëlle; Deronzier, Alain; Fontecave, Marc; Ménage, Stéphane

    2002-03-01

    Peroxoiron species have been proposed to be involved in catalytic cycles of iron-dependent oxygenases and in some cases as the active intermediates during oxygen-transfer reactions. The catalytic properties of a mononuclear iron complex, [Fe(II)(pb)(2)(CH(3)CN)(2)] (pb=(-)4,5-pinene-2,2'-bipyridine), have been compared to those of its related dinuclear analogue. Each system generates specific peroxo adducts, which are responsible for the oxidation of sulfides to sulfoxides. The dinuclear catalyst was found to be more reactive and (enantio)selective than its mononuclear counterpart, suggesting that a second metal site affords specific advantages for stereoselective catalysis. These results might help for the design of future enantioselective iron catalysts. PMID:11891908

  10. Oxidative addition of C--H bonds in organic molecules to transition metal centers

    SciTech Connect

    Bergman, R.G.

    1989-04-01

    Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs.

  11. Platinum trans-Bis(borirene) complexes displaying coplanarity and communication across a platinum metal center.

    PubMed

    Braunschweig, Holger; Damme, Alexander; Dewhurst, Rian D; Kelch, Hauke; Macha, Bret B; Radacki, Krzysztof; Vargas, Alfredo; Ye, Qing

    2015-02-01

    Ambient-temperature photolysis of the aminoborylene complex [(OC)5 Cr=B=N(SiMe3 )2 ] in the presence of a series of trans-bis(alkynyl)platinum(II) precursors of the type trans-[Pt(CCAr)2 (PEt3 )2 ] (Ar=Ph, p-C6 H4 OMe, and p-C6 H4 CF3 ) successfully leads to twofold transfer of the borylene moiety [:B=N(SiMe3 )2 ] onto the alkyne functionalities. The alkynyl precursors and resultant bis(borirene)platinum(II) complexes formed are of the type trans-[Pt(B{=N(SiMe3 )2 }C=CAr)2 (PEt3 )2 ] (Ar=Ph, p-C6 H4 OMe, and p-C6 H4 CF3 ). These species have all been successfully characterized by NMR, IR, and UV/Vis spectroscopy as well as by elemental analysis. Single-crystal X-ray diffraction has verified that these trans-bis(borirene)platinum(II) complexes display coplanarity between the twin three-membered rings across the platinum core in the solid state and stand as the first examples of coplanar conformations of twin borirene systems. These complexes were modeled using density functional theory (DFT), providing information helpful in determining the ability of the transition metal core to interact with each individual borirene ring system and allowing for the observed coplanarity of these rings in the solid state. This proposed transition metal interaction with the twin borirene systems is manifested in the electronic characterization of these borirene species, which display divergent photophysical UV/Vis spectroscopic profiles compared to a previously published mono(borirene)platinum(II) complex. PMID:25430871

  12. Formation of recrystallization cube texture in high purity face-centered cubic metal sheets

    SciTech Connect

    Mao, W.

    1999-10-01

    An investigation on recrystallization textures in high purity face-centered cubic (fcc) aluminum, copper, and nickel indicated that the cube texture is a unique dominant final texture. In a macroview of rolling deformation, a balanced activation of four slip systems can result in certain stability of some substructure with cube orientation in the deformed matrix. In the stable substructure the dislocation density is very low, and the dislocation configuration is rather simple in comparison to other orientations so that the cube substructure can easily be transformed into cube recrystallization nuclei by a recovery process. A high orientation gradient and correspondingly high angle boundaries to the deformed matrix are usually expected around the cube nuclei, which, therefore, grow rapidly. After the primary recrystallization, the size of cube grains is much larger than the grains with other orientations, which will be expensed as the cube grains grow further, so that the cube texture can finally become a dominant texture component.

  13. Fatigue damage in cross-ply titanium metal matrix composites containing center holes

    NASA Technical Reports Server (NTRS)

    Bakuckas, J. G., Jr.; Johnson, W. S.; Bigelow, C. A.

    1992-01-01

    The development of fatigue damage in (0/90) sub SCS-6/TI-15-3 laminates containing center holes was studied. Stress levels required for crack initiation in the matrix were predicted using an effective strain parameter and compared to experimental results. Damage progression was monitored at various stages of fatigue loading. In general, a saturated state of damage consisting of matrix cracks and fiber matrix debonding was obtained which reduced the composite modulus. Matrix cracks were bridged by the 0 deg fibers. The fatigue limit (stress causing catastrophic fracture of the laminates) was also determined. The static and post fatigue residual strengths were accurately predicted using a three dimensional elastic-plastic finite element analysis. The matrix damage that occurred during fatigue loading significantly reduced the notched strength.

  14. Liquid Metal Processing and Casting Experiences at the U.S. Department of Energy's Albany Research Center

    SciTech Connect

    Jablonski, Paul D.; Turner, Paul C.

    2005-09-01

    In this paper we will discuss some of the early pioneering work as well as some of our more recent research. The Albany Research Center (ARC) has been involved with the melting and processing of metals since it was established in 1942. In the early days, hardly anything was known about melting refractory or reactive metals and as such, virtually everything had to be developed in-house. Besides the more common induction heated air-melt furnaces, ARC has built and/or utilized a wide variety of furnaces including vacuum arc remelt ingot and casting furnaces, cold wall induction furnaces, electric arc furnaces, cupola furnaces and reverberatory furnaces. The melt size of these furnaces range from several grams to a ton or more. We have used these furnaces to formulate custom alloys for wrought applications as well as for such casting techniques as spin casting, investment casting and lost foam casting among many. Two early spin-off industrializations were Wah Chang (wrought zirconium alloys for military and commercial nuclear applications) and Oremet (both wrought and cast Ti). Both of these companies are now part of the ATI Allegheny Ludlum Corporation.

  15. Mechanism-based crystal plasticity modeling of twin boundary migration in nanotwinned face-centered-cubic metals

    NASA Astrophysics Data System (ADS)

    Mirkhani, Hamidreza; Joshi, Shailendra P.

    2014-08-01

    Nanotwinned (nt) metals are an important subset of nanostructured materials because they exhibit impressive strength and ductility. Several recent investigations on nt face-centered-cubic (FCC) metals indicate that their macroscopic responses emerge from complex microscopic mechanisms that are dominated by dislocation-TB interactions. Under applied stimulus, nt microstructures evolve through migration of twin boundaries (TBs) that may have implications on the material strength and stability. This work focuses on modeling TB migration within finite element framework in an explicit manner and studying its effects on the micromechanics of twinned FCC metals under quasi-static loading conditions. The theoretical setting is developed using three-dimensional single crystal plasticity as a basis wherein the plastic slip on the {111}<1bar10> slip systems in an FCC crystal structure is modeled as visco-plastic behavior. Owing to their governing role, twins are modeled as discrete lamellas with full crystallographic anisotropy. To model TB migration, an additional visco-plastic slip-law for twinning partial systems ({111}<112bar>) based on the nucleation and motion of twin partial dislocations is introduced. This size-dependent constitutive law is presumed to prevail in the vicinity of the TB and naturally facilitates TB migration when combined with a twinning condition that is based on the accrual of the necessary shear strain. The constitutive development is implemented within a finite element framework through a User Material (UMAT) facility within ABAQUS/STANDARD®. Detailed micromechanics simulations on model microstructures involving single-grained and polycrystalline topologies are presented.

  16. Multifunctional, defect-engineered metal-organic frameworks with ruthenium centers: sorption and catalytic properties.

    PubMed

    Kozachuk, Olesia; Luz, Ignacio; Llabrés i Xamena, Francesc X; Noei, Heshmat; Kauer, Max; Albada, H Bauke; Bloch, Eric D; Marler, Bernd; Wang, Yuemin; Muhler, Martin; Fischer, Roland A

    2014-07-01

    A mixed-linker solid-solution approach was employed to modify the metal sites and introduce structural defects into the mixed-valence Ru(II/III) structural analogue of the well-known MOF family [M3(II,II)(btc)2] (M=Cu, Mo, Cr, Ni, Zn; btc=benzene-1,3,5-tricarboxylate), with partly missing carboxylate ligators at the Ru2 paddle-wheels. Incorporation of pyridine-3,5-dicarboxylate (pydc), which is the same size as btc but carries lower charge, as a second, defective linker has led to the mixed-linker isoreticular derivatives of Ru-MOF, which display characteristics unlike those of the defect-free framework. Along with the creation of additional coordinatively unsaturated sites, the incorporation of pydc induces the partial reduction of ruthenium. Accordingly, the modified Ru sites are responsible for the activity of the "defective" variants in the dissociative chemisorption of CO2, the enhanced performance in CO sorption, the formation of hydride species, and the catalytic hydrogenation of olefins. PMID:24838592

  17. Elastic-plastic deformation of a metal-matrix composite coupon with a center slot

    NASA Technical Reports Server (NTRS)

    Post, D.; Czarnek, R.; Joh, D.; Jo, J.; Guo, Y.

    1985-01-01

    A comprehensive experimental analysis of deformations of the surface of a metal-matrix specimen is reported. The specimen is a 6-ply 0 + or - 45 sub s boron-aluminum tensile coupon with a central slot. Moire interferometry is used for high-sensitivity whole-field measurements of in-plane displacements. Normal and shear strains are calculated from displacement gradients. Displacement fields are analyzed at various load levels from 15% to 95% of the failure load. Deformations of the boron fibers could be distinguished from those of the matrix. Highly localized plastic slip zones occur tangent to the ends of the slot. Shear strains and concurrent transverse compressive strains in the slip zones reach approximately 10% and 1%, respectively. Upon unloading, elastic recovery in surrounding regions causes a reverse plastic shear strain in the slip zone of about 4%. Longitudinal normal strains on the unslotted ligament peak at the slot boundary at about 1% strain. The strain concentration factor at the end of the slot decreases with load level and the advance of plasticity.

  18. Elastic-plastic deformation of a metal-matrix composite coupon with a center slot

    SciTech Connect

    Post, D.; Czarnek, R.; Joh, D.; Jo, J.; Guo, Y.

    1985-11-01

    A comprehensive experimental analysis of deformations of the surface of a metal-matrix specimen is reported. The specimen is a 6-ply 0 + or - 45 sub s boron-aluminum tensile coupon with a central slot. Moire interferometry is used for high-sensitivity whole-field measurements of in-plane displacements. Normal and shear strains are calculated from displacement gradients. Displacement fields are analyzed at various load levels from 15% to 95% of the failure load. Deformations of the boron fibers could be distinguished from those of the matrix. Highly localized plastic slip zones occur tangent to the ends of the slot. Shear strains and concurrent transverse compressive strains in the slip zones reach approximately 10% and 1%, respectively. Upon unloading, elastic recovery in surrounding regions causes a reverse plastic shear strain in the slip zone of about 4%. Longitudinal normal strains on the unslotted ligament peak at the slot boundary at about 1% strain. The strain concentration factor at the end of the slot decreases with load level and the advance of plasticity. 1 ref.

  19. Extended Peierls-Nabarro model for cross slip in face centered cubic metals

    NASA Astrophysics Data System (ADS)

    Ramirez, Benjamin R.

    Recent improvements in the dislocation dynamics modeling of work hardening has triggered a new interest in the calculation of the cross-slip activation energy, which is responsible for the dynamic recovery in f.c.c. metals. Early attempts to model cross-slip, which were based on either continuum theory or atomistic modeling, had varying degrees of success in the prediction of the reaction path and activation energy, Thus, methods based on classical continuum theory with concept of the Volterra dislocations were limited to describing the strain field outside of the dislocation core due to the singularity problem of the elastic solution. On the other hand, atomistic models are still limited by the use of ad-hoc potentials, which are at the present time unable to reliably predict the energies for atomic displacements far from equilibrium. Therefore, a very critical shortcoming in both elasticity-based and atomistic (MD) models is that both do not include quantum mechanics into their calculations. This aspect limits their use to situations where the material parameters are all known, and does not allow for studies of the influence of local chemistry (e.g. presence of impurities and solutes) on cross-slip. The objective of the present work is to develop a cross-slip model that takes into account most of the atomistic characteristics of the cross-slip mechanism, and is capable of simulating any complex 3-dimensional configuration without the computational cost of current atomistic models. Thus, a hybrid ab-initio continuum approach is developed for the determination of the dislocation cross-slip configuration and the energy barrier for cross-slip in f.c.c. metals. Quantum mechanics information is introduced into the model through the lattice restoring force calculated using ab-inito methods (gamma-surface). Thus, this force is balanced against the elastic interaction force on the dislocation configuration, which is obtained from a full 3-dimensional interaction. All

  20. Molecular anatomy of tyrosinase and its related proteins: beyond the histidine-bound metal catalytic center.

    PubMed

    García-Borrón, José C; Solano, Francisco

    2002-06-01

    The structure of tyrosinase (Tyr) is reviewed from a double point of view. On the one hand, by comparison of all Tyr found throughout nature, from prokaryotic organisms to mammals and on the other, by comparison with the tyrosinase related proteins (Tyrps) that appeared late in evolution, and are only found in higher animals. Their structures are reviewed as a whole rather than focused on the histidine (His)-bound metal active site, which is the part of the molecule common to all these proteins. The availability of crystallographic data of hemocyanins and recently of sweet potato catechol oxidase has improved the model of the three-dimensional structure of the Tyr family. Accordingly, Tyr has a higher structural disorder than hemocyanins, particularly at the CuA site. The active site seems to be characterized by the formation of a hydrophobic pocket with a number of conserved aromatic residues sited close to the well-known His. Other regions specific of the mammalian enzymes, such as the cytosolic C-terminal tail, the cysteine clusters, and the N-glycosylation sequons, are also discussed. The complete understanding of the Tyr copper-binding domain and the characterization of the residues determinant of the relative substrate affinities of the Tyrps will improve the design of targeted mutagenesis experiments to understand the different catalytic capabilities of Tyr and Tyrps. This may assist future aims, from the design of more efficient bacterial Tyr for biotechnological applications to the design of inhibitors of undesirable fruit browning in vegetables or of color skin modulators in animals. PMID:12028580

  1. Examination of metals from aerospace-related activity in surface water samples from sites surrounding the Kennedy Space Center (KSC), Florida.

    PubMed

    Bowden, John A; Cantu, Theresa M; Scheidt, Douglas M; Lowers, Russell H; Nocito, Brian A; Young, Vaneica Y; Guillette, Louis J

    2014-05-01

    Metal contamination from Space Shuttle launch activity was examined using inductively coupled plasma-atomic emission spectroscopy in a two-tier study sampling surface water collected from several sites at the Kennedy Space Center (KSC) and associated Merritt Island National Wildlife Refuge in east central Florida. The primary study examined both temporal changes in baseline metal concentrations (19 metals) in surface water (1996 to 2009, 11 sites) samples collected at specific long-term monitoring sites and metal deposition directly associated with Space Shuttle launch activity at two Launch Complexes (LC39A and LC39B). A secondary study examined metal concentrations at additional sites and increased the amount of elements measured to 48 elements. Our examination places a heavy focus on those metals commonly associated with launch operations (e.g., Al, Fe, Mn, and Zn), but a brief discussion of other metals (As, Cu, Mo, Ni, and Pb) is also included. While no observable accumulation of metals occurred during the time period of the study, the data obtained postlaunch demonstrated a dramatic increase for Al, Fe, Mn, and Zn. Comparing overall trends between the primary and secondary baseline surface water concentrations, elevated concentrations were generally observed at sampling stations located near the launch complexes and from sites isolated from major water systems. While there could be several natural and anthropogenic sources for metal deposition at KSC, the data in this report indicate that shuttle launch events are a significant source. PMID:24738662

  2. EPR investigation of Cu2+-substituted photosynthetic bacterial reaction centers: evidence for histidine ligation at the surface metal site.

    PubMed

    Utschig, L M; Poluektov, O; Tiede, D M; Thurnauer, M C

    2000-03-21

    The coordination environments of two distinct metal sites on the bacterial photosynthetic reaction center (RC) protein were probed with pulsed electron paramagnetic resonance (EPR) spectroscopy. For these studies, Cu2+ was bound specifically to a surface site on native Fe2+-containing RCs from Rhodobacter sphaeroides R-26 and to the native non-heme Fe site in biochemically Fe-removed RCs. The cw and pulsed EPR results clearly indicate two spectroscopically different Cu2+ environments. In the dark, the RCs with Cu2+ bound to the surface site exhibit an axially symmetric EPR spectrum with g(parallel) = 2.24, A(parallel) = 160 G, g(perpendicular) = 2.06, whereas the values g(parallel) = 2.31, A(parallel) = 143 G, and g(perpendicular) = 2.07 were observed when Cu(2+) was substituted in the Fe site. Examination of the light-induced spectral changes indicate that the surface Cu2+ is at least 23 A removed from the primary donor (P+) and reduced quinone acceptor (QA-). Electron spin-echo envelope modulation (ESEEM) spectra of these Cu-RC proteins have been obtained and provide the first direct solution structural information about the ligands in the surface metal site. From these pulsed EPR experiments, modulations were observed that are consistent with multiple weakly hyperfine coupled 14N nuclei in close proximity to Cu2+, indicating that two or more histidines ligate the Cu2+ at the surface site. Thus, metal and EPR analyses confirm that we have developed reliable methods for stoichiometrically and specifically binding Cu2+ to a surface site that is distinct from the well characterized Fe site and support the view that Cu2+ is bound at or near the Zn site that modulates electron transfer between the quinones QA and QB (QA-QB --> QAQB-) (Utschig, L. M., Ohigashi, Y., Thurnauer, M. C., and Tiede, D. M (1998) Biochemistry 37, 8278-8281) and proton uptake by QB- (Paddock, M. L., Graige, M. S., Feher, G., and Okamura, M. Y. (1999) Proc. Natl. Acad. Sci. U.S.A. 96, 6183

  3. Kinetic and Mechanistic Studies of Carbon-to-Metal Hydrogen Atom Transfer Involving Os-Centered Radicals: Evidence for Tunneling

    SciTech Connect

    Lewandowska-Androlojc, Anna; Grills, David C.; Zhang, Jie; Bullock, R. Morris; Miyazawa, Akira; Kawanishi, Yuji; Fujita, Etsuko

    2014-03-05

    We have investigated the kinetics of novel carbon-to-metal hydrogen atom transfer reactions, in which homolytic cleavage of a C-H bond is accomplished by a single metal-centered radical. Studies by means of time-resolved IR spectroscopic measurements revealed efficient hydrogen atom transfer from xanthene, 9,10-dihydroanthracene and 1,4-cyclohexadiene to Cp(CO)2Os• and (n5-iPr4C5H)(CO)2Os• radicals, formed by photoinduced homolysis of the corresponding osmium dimers. The rate constants for hydrogen abstraction from these hydrocarbons were found to be in the range 1.54 × 105 M 1 s 1 -1.73 × 107 M 1 s-1 at 25 °C. For the first time, kinetic isotope effects for carbon-to-metal hydrogen atom transfer were determined. Large primary kinetic isotope effects of 13.4 ± 1.0 and 16.6 ± 1.4 were observed for the hydrogen abstraction from xanthene to form Cp(CO)2OsH and (n5-iPr4C5H)(CO)2OsH, respectively, at 25 °C. Temperature-dependent measurements of the kinetic isotope effects over a 60 -C temperature range were carried out to obtain the difference in activation energies and the pre-exponential factor ratio. For hydrogen atom transfer from xanthene to (n5-iPr4C5H)(CO)2Os•, the (ED - EH) = 3.25 ± 0.20 kcal/mol and AH/AD = 0.056 ± 0.018 values are greater than the semi-classical limits and thus suggest a quantum mechanical tunneling mechanism. The work at BNL was carried out under contract DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Geosciences & Biosciences, Office of Basic Energy Sciences. RMB also thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  4. Large Amplitude Oscillatory Shear of Block Copolymer Spheres on a Body-Centered Cubic Lattice: Are Micelles Like Metals?

    SciTech Connect

    Torija, Maria A.; Choi, Soo-Hyung; Lodge, Timothy P.; Bates, Frank S.

    2013-03-07

    Small-angle X-ray diffraction experiments have uncovered a remarkable mechanism of grain alignment during plastic deformation of ordered sphere-forming diblock copolymer micelles when subjected to large amplitude dynamic shearing. A nearly monodisperse poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymer with block molecular weights of 42,000 and 60,000 was mixed with squalane (C{sub 30}H{sub 62}), an EP selective solvent, at a concentration of 10 wt %. After high temperature annealing, the sample formed an ordered polydomain morphology containing glassy S cores at room temperature. SAXS powder patterns confirm body-centered cubic (BCC) symmetry and reveal the development of a complex array of two-dimensionally resolved Bragg reflections following the application, and cessation, of oscillatory shearing. These diffraction results are interpreted on the basis of the classic mechanism of crystalline slip, which accounts for plastic deformation of ductile materials such as metals. Four distinct slip systems are shown to be active in this work, suggesting a robust basis for deforming and mixing of soft ordered solids.

  5. First-principles path-integral molecular dynamics study of diffusion process of hydrogen in face-centered cubic metals

    NASA Astrophysics Data System (ADS)

    Kimizuka, Hajime; Ogata, Shigenobu

    We investigated the H diffusivity in face-centered cubic Pd and Al by performing path-integral molecular dynamics (PIMD) modeling in the framework of density functional theory (DFT); in our calculations, we took nuclear quantum effects into consideration. The DFT results showed that the H-migration barriers (Em) in Pd and Al exhibited similar values (approximately 0.16 eV), while the H atoms were stable at octahedral (O) sites for Pd and at tetrahedral (T) sites for Al. The PIMD-based free-energy profiles for H migration between the O-site and T-site were evaluated using the thermodynamic integration of the centroid forces at 150-600 K. We confirmed that the quantum effects significantly affected the Em and the difference between the energies of the H atom at the O-site and the T-site (EO - T); The Em and EO - T values in Pd at 300 K increased by 32% and 98%, respectively, relative to the classical limit. On the other hand, the Em and ET - O (i.e., -EO - T) values in Al at 300 K decreased by 3% and 41%, respectively. This suggested that the quantum nature of H nuclei was essential for understanding the H-diffusion kinetics in these metals even above ambient temperature.

  6. First-principles calculation of the ultrafast spin manipulation of two-center metallic clusters with a CO molecule attached to one center as an infrared marker

    NASA Astrophysics Data System (ADS)

    Li, Chun; Hartenstein, Tobias; Lefkidis, Georgios; Hübner, Wolfgang

    2009-05-01

    We present a fully ab initio ultrafast spin manipulation calculation in two-magnetic-center clusters with CO attached to one of the magnetic centers. CO serves as an experimental marker for certain magnetic states between which spin flip and transfer can be achieved. The predicted spin-state-dependent CO vibrational frequencies indicate that spin manipulation can be readily monitored through the infrared spectrum. The feasibility is demonstrated by two charged clusters [CoMg2Ni-CO]+ and [NiCo-CO]+ . Spin transfer between magnetic centers is achieved with a fidelity of 99.8%.

  7. Final Technical Report on DE-SC00002460 [Bimetallic or trimetallic materials with structural metal centers based on Mn, Fe or V

    SciTech Connect

    Takeuchi, Esther Sans; Takeuchi, Kenneth James; Marschilok, Amy Catherine

    2013-07-26

    Bimetallic or trimetallic materials with structural metal centers based on Mn, Fe or V were investigated under this project. These metal centers are the focus of this research as they have high earth abundance and have each shown success as cathode materials in lithium batteries. Silver ion, Ag{sup +}, was initially selected as the displacement material as reduction of this center should result in increased conductivity as Ag{sup 0} metal particles are formed in-situ upon electrochemical reduction. The in-situ formation of metal nanoparticles upon electrochemical reduction has been previously noted, and more recently, we have investigated the resulting increase in conductivity. Layered materials as well as materials with tunnel or channel type structures were selected. Layered materials are of interest as they can provide 2-dimensional ion mobility. Tunnel or channel structures are also of interest as they provide a rigid framework that should remain stable over many discharge/charge cycles. We describe some examples of materials we have synthesized that demonstrate promising electrochemistry.

  8. Purification, substrate range, and metal center of AtzC: the N-isopropylammelide aminohydrolase involved in bacterial atrazine metabolism.

    PubMed

    Shapir, Nir; Osborne, Jeffrey P; Johnson, Gilbert; Sadowsky, Michael J; Wackett, Lawrence P

    2002-10-01

    N-Isopropylammelide isopropylaminohydrolase, AtzC, the third enzyme in the atrazine degradation pathway in Pseudomonas sp. strain ADP, catalyzes the stoichiometric hydrolysis of N-isopropylammelide to cyanuric acid and isopropylamine. The atzC gene was cloned downstream of the tac promoter and expressed in Escherichia coli, where the expressed enzyme comprised 36% of the soluble protein. AtzC was purified to homogeneity by ammonium sulfate precipitation and phenyl column chromatography. It has a subunit size of 44,938 kDa and a holoenzyme molecular weight of 174,000. The K(m) and k(cat) values for AtzC with N-isopropylammelide were 406 micro M and 13.3 s(-1), respectively. AtzC hydrolyzed other N-substituted amino dihydroxy-s-triazines, and those with linear N-alkyl groups had higher k(cat) values than those with branched alkyl groups. Native AtzC contained 0.50 eq of Zn per subunit. The activity of metal-depleted AtzC was restored with Zn(II), Fe(II), Mn(II), Co(II), and Ni(II) salts. Cobalt-substituted AtzC had a visible absorbance band at 540 nm (Delta epsilon = 84 M(-1) cm(-1)) and exhibited an axial electron paramagnetic resonance (EPR) signal with the following effective values: g((x)) = 5.18, g((y)) = 3.93, and g((z)) = 2.24. Incubating cobalt-AtzC with the competitive inhibitor 5-azacytosine altered the effective EPR signal values to g((x)) = 5.11, g((y)) = 4.02, and g((z)) = 2.25 and increased the microwave power at half saturation at 10 K from 31 to 103 mW. Under the growth conditions examined, our data suggest that AtzC has a catalytically essential, five-coordinate Zn(II) metal center in the active site and specifically catalyzes the hydrolysis of intermediates generated during the metabolism of s-triazine herbicides. PMID:12218024

  9. Electron work function and surface energy of body-centered and face-centered cubic modifications of 4 d- and 5 d-metals

    NASA Astrophysics Data System (ADS)

    Aref'eva, L. P.; Shebzukhova, I. G.

    2016-07-01

    A technique for the evaluation of the electron work function of metallic single crystals and the electron work function anisotropy has been developed in the framework of the electron-statistical method. The surface energy and the electron work function have been calculated for crystal faces of allotropic modifications of 4 d- and 5 d-metals. A change in the electron work function due to the allotropic transformations has been estimated, and the periodic dependence of the electron work function has been determined. It has been shown that the results obtained using the proposed technique correlate with the available experimental data for polycrystals.

  10. Binding of Copper and Silver to Single-Site Variants of Peptidylglycine Monooxygenase Reveals the Structure and Chemistry of the Individual Metal Centers

    PubMed Central

    2015-01-01

    Peptidylglycine monooxygenase (PHM) catalyzes the final step in the biosynthesis of amidated peptides that serve as important signaling molecules in numerous endocrine pathways. The catalytic mechanism has attracted much attention because of a number of unique attributes, including the presence of a pair of uncoupled copper centers separated by 11 Å (termed CuH and CuM), an unusual Cu(I)SMet interaction at the oxygen binding M-site, and the postulated Cu(II)–superoxo intermediate. Understanding the mechanism requires determining the catalytic roles of the individual copper centers and how they change during catalysis, a task made more difficult by the overlapping spectral signals from each copper center in the wild-type (WT) protein. To aid in this effort, we constructed and characterized two PHM variants that bound metal at only one site. The H242A variant bound copper at the H-center, while the H107AH108A double mutant bound copper at the M-center; both mutants were devoid of catalytic activity. Oxidized Cu(II) forms showed electron paramagnetic resonance and extended X-ray absorption fine structure (EXAFS) spectra consistent with their previously determined Cu(II)His3O and Cu(II)His2O2 ligand sets for the H- and M-centers, respectively. Cu(I) forms, on the other hand, showed unique chemistry. The M-center bound two histidines and a methionine at all pHs, while the H-center was two-coordinate at neutral pH but coordinated a new methionine S ligand at low pH. Fourier transform infrared studies confirmed and extended previous assignments of CO binding and showed unambiguously that the 2092 cm–1 absorbing species observed in the WT and many variant forms is an M-site Cu(I)–CO adduct. Silver binding was also investigated. When H107AH108A and M109I (a WT analogue with both sites intact) were incubated with excess AgNO3, each variant bound a single Ag(I) ion, from which it was inferred that Ag(I) binds selectively at the M-center with little or no affinity for

  11. Transition-Metal-Free Cyclopropanation of 2-Aminoacrylates with N-Tosylhydrazones: A General Route to Cyclopropane α-Amino Acid with Contiguous Quaternary Carbon Centers.

    PubMed

    Zhu, Chuanle; Li, Jiawei; Chen, Pengquan; Wu, Wanqing; Ren, Yanwei; Jiang, Huanfeng

    2016-03-18

    Cyclopropanation of 2-aminoacrylates with N-tosylhydrazones could proceed smoothly under transition-metal-free conditions via a [3 + 2] cycloaddition process. This robust protocol exhibits excellent generality, delivering a wide spectrum of cyclopropane α-amino acid esters bearing contiguous quaternary carbon centers in high yields and diastereoselectivities. With these readily available products, the steric convergence of cyclopropane α-amino acids could be readily obtained. PMID:26958741

  12. Double aromaticity in transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8)

    NASA Astrophysics Data System (ADS)

    Xu, Chang; Cheng, Longjiu; Yang, Jinlong

    2014-09-01

    It is well known that double-ring boron clusters have got the special double aromaticity with delocalized π orbitals in two directions (tangential and radial), which are potential ligands centered by a transition metal. In this article, the transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8) are theoretically investigated by density functional theory calculations. These endohedral compounds have also got double aromaticity in both tangential and radial directions. Interestingly, the tangential delocalized π orbitals of boron ligands following the Huckle's (4n + 2) rule do not interact with the central metal, while the radial π orbitals of boron ligands are bonded with the central mental to form spd-π endohedral bonding. The spd-π endohedral bonding follows the 18e-principle in Ni@B14 and Fe@B16. However, due to the flat shape of the compounds, 14e (Cr@B14) and 16e (Ni@B12) can also be electronically very stable where the energy levels of the spd-π orbitals delocalized in z-direction rise up. This intriguing bonding model makes sense in further study of the boron chemistry.

  13. Squeezing and Heating Rock to Scope Out How Metallic Iron Dribbled to the Center of the Earth

    NASA Astrophysics Data System (ADS)

    Taylor, G. J.

    2005-07-01

    Formation of Earth's metallic core was one of the most important events in the history of the planet. Metallic iron is much denser than rock, so it sank to the middle, taking other elements that concentrate in metal rather than silicate (rock) with it. However, we do not understand everything about core formation. One particularly niggling puzzle is why cobalt (Co) and nickel (Ni) have the same concentration (relative to primitive carbonaceous chondrites) as one another in Earth's mantle. At low pressure these elements concentrate in metallic iron to different extents. Calculations show that if metal segregated from silicate at low pressure, nickel ought to be 100 times less abundant (normalized to chondrites) than cobalt, not equal. Cosmochemists have tackled this problem by doing experiments at high pressure and temperature to map out how cobalt and nickel partitioning between metal and silicate differs compared to low pressure. However, the studies differ in their predictions of the behavior because of differences in the assumed pressure, temperature, and oxidation state during core formation. Nancy Chabot (Case Western Reserve University, now at the Johns Hopkins Applied Physics Laboratory), and David Draper and Carl Agee from the University of New Mexico addressed the discrepancies by designing a series of experiments over a wide range in temperature. Their results plot out the conditions under which metal can sink to the core while leading to the observed cobalt and nickel concentrations in the mantle. While the results do not lead to a unique solution, they point the way for further studies of other elements that tend to concentrate in metallic iron, and they show clearly that the equal nickel and cobalt concentrations in the mantle can be the product of core formation in the early Earth.

  14. Metal-Metal Bonds in Biology

    PubMed Central

    Lindahl, Paul A.

    2011-01-01

    Nickel-containing carbon monoxide dehydrogenases, acetyl-CoA synthases, nickel-iron hydrogenases, and diron hydrogenases are distinct metalloenzymes yet they share a number of important characteristics. All are O2-sensitive, with active-sites composed of iron and/or nickel ions coordinated primarily by sulfur ligands. In each case, two metals are juxtaposed at the “heart” of the active site, within range of forming metal-metal bonds. These active-site clusters exhibit multielectron redox abilities and must be reductively activated for catalysis. Reduction potentials are milder than expected based on formal oxidation state changes. When reductively activated, each cluster attacks an electrophilic substrate via an oxidative addition reaction. This affords a two-electron-reduced substrate bound to one or both metals of an oxidized cluster. M-M bonds have been established in hydrogenases where they serve to initiate the oxidative addition of protons and perhaps stabilize active sites in multiple redox states. The same may be true of the CODH and ACS active sites – Ni-Fe and Ni-Ni bonds in these sites may play critical roles in catalysis, stabilizing low-valence states and initiating oxidative addition of CO2 and methyl group cations, respectively. In this article, the structural and functional commonalities of these metalloenzyme active sites are described, and the case is made for the formation and use of metal-metal bonds in each enzyme mentioned. As a post-script, the importance of Fe-Fe bonds in the nitrogenase FeMoco active site is discussed. PMID:22119810

  15. High-temperature fatigue in metals - A brief review of life prediction methods developed at the Lewis Research Center of NASA

    NASA Technical Reports Server (NTRS)

    Halford, G. R.

    1983-01-01

    The presentation focuses primarily on the progress we at NASA Lewis Research Center have made. The understanding of the phenomenological processes of high temperature fatigue of metals for the purpose of calculating lives of turbine engine hot section components is discussed. Improved understanding resulted in the development of accurate and physically correct life prediction methods such as Strain-Range partitioning for calculating creep fatigue interactions and the Double Linear Damage Rule for predicting potentially severe interactions between high and low cycle fatigue. Examples of other life prediction methods are also discussed. Previously announced in STAR as A83-12159

  16. [CrF(O2 C(t) Bu)2 ]9 : Synthesis and Characterization of a Regular Homometallic Ring with an Odd Number of Metal Centers and Electrons.

    PubMed

    Woolfson, Robert J; Timco, Grigore A; Chiesa, Alessandro; Vitorica-Yrezabal, Inigo J; Tuna, Floriana; Guidi, Tatiana; Pavarini, Eva; Santini, Paolo; Carretta, Stefano; Winpenny, Richard E P

    2016-07-25

    The first regular homometallic ring containing an odd number of metal centers is reported. The ring was synthesized by means of amine-templated self-assembly. Extensive physical characterization studies, including magnetic measurements, powder inelastic neutron scattering (INS), and DFT calculations, show that the molecule has a near perfect match to the expected behavior for a frustrated system with the lowest energy pair of S=1/2 spin states separated by only 0.1 meV (0.8 cm(-1) ). PMID:27294807

  17. Structure of a Novel Phosphotriesterase from Sphingobium sp. TCM1: A Familiar Binuclear Metal Center Embedded in a Seven-Bladed β-Propeller Protein Fold.

    PubMed

    Mabanglo, Mark F; Xiang, Dao Feng; Bigley, Andrew N; Raushel, Frank M

    2016-07-19

    A novel phosphotriesterase was recently discovered and purified from Sphingobium sp. TCM1 (Sb-PTE) and shown to catalyze the hydrolysis of a broad spectrum of organophosphate esters with a catalytic efficiency that exceeds 10(6) M(-1) s(-1) for the hydrolysis of triphenyl phosphate. The enzyme was crystallized and the three-dimensional structure determined to a resolution of 2.1 Å using single-wavelength anomalous diffraction (Protein Data Bank entry 5HRM ). The enzyme adopts a seven-bladed β-propeller protein fold, and three disulfide bonds were identified between Cys-146 and Cys-242, Cys-411 and Cys-443, and Cys-542 and Cys-559. The active site of Sb-PTE contains a binuclear manganese center that is nearly identical to that of the structurally unrelated phosphotriesterase from Pseudomonas diminuta (Pd-PTE). The two metal ions in the active site are bridged to one another by Glu-201 and a water molecule. The α-metal ion is further coordinated to the protein by interactions with His-389, His-475, and Glu-407, whereas the β-metal ion is further liganded to His-317 and His-258. Computational docking of mimics of the proposed pentavalent reaction intermediates for the hydrolysis of organophosphates was used to provide a model for the binding of chiral substrates in the active site of Sb-PTE. The most striking difference in the catalytic properties of Sb-PTE, relative to those of Pd-PTE, is the enhanced rate of hydrolysis of organophosphate esters with substantially weaker leaving groups. The structural basis for this difference in the catalytic properties between Sb-PTE and Pd-PTE, despite the nearly identical binuclear metal centers for the activation of the substrate and nucleophilic water molecule, is at present unclear. PMID:27353520

  18. Analysis of the twin spacing and grain size effects on mechanical properties in hierarchically nanotwinned face-centered cubic metals based on a mechanism-based plasticity model

    NASA Astrophysics Data System (ADS)

    Zhu, Linli; Qu, Shaoxing; Guo, Xiang; Lu, Jian

    2015-03-01

    Hierarchical twin lamellae in polycrystalline face-centered cubic (fcc) metals possess a possibility to achieve higher strength with keeping an acceptable elongation. The present work is concerned with the analysis of twin spacing and grain size-dependent plastic performance in hierarchically nanotwinned fcc metals using a generalized strain-gradient plasticity model. The dislocation density-based physical model for constitutive description of nanotwinned fcc metals is expanded for the hierarchical structures of nanotwins. The strengthening mechanism and the failure behavior in these hierarchical nanostructures are studied to evaluate the strength and ductility. Moreover, the transition twin spacing between the strengthening and softening is obtained in different order of twin lamellae. A dislocation-based model on nucleating deformation twins is presented to predict the critical twin spacing in the lowest twin lamellae for generating the subordinate twin lamellae. Our simulation results demonstrate that the existence of the hierarchical nanotwins gives rise to a significant enhancement in the strength, and the resulting global flow stresses are sensitive to the twin spacings of the hierarchical twin lamellae and the grain size. Two softening stages are observed with variation of twin spacing, and the relevant transition twin spacing depends on the microstructural size in hierarchically nanotwinned metals. We further find that the predicted failure strain decreases with decreasing the twin spacing, which is quite different from the case of the individually nanotwinned fcc metals. The critical twin spacing for generating subordinate twins also depends on the twin spacing of superordinate twin lamellae and the grain size. These findings suggest that the high yield strength and good ductility can be achieved by optimizing the grain size and the twin spacings in the hierarchical twins.

  19. Biological effects of anionic meso-tetrakis (para-sulfonatophenyl) porphyrins modulated by the metal center. Studies in rat liver mitochondria.

    PubMed

    Pessoto, Felipe Samuel; Inada, Natalia Mayumi; Nepomuceno, Maria de Fátima; Ruggiero, Ana Célia; Nascimento, Otaciro R; Vercesi, Anibal E; Nantes, Iseli L

    2009-10-30

    In this paper, we present a study about the influence of the porphyrin metal center and meso ligands on the biological effects of meso-tetrakis porphyrins. Different from the cationic meso-tetrakis 4-N-methyl pyridinium (Mn(III)TMPyP), the anionic Mn(III) meso-tetrakis (para-sulfonatophenyl) porphyrin (Mn(III)TPPS4) exhibited no protector effect against Fe(citrate)-induced lipid oxidation. Mn(III)TPPS4 did not protect mitochondria against endogenous hydrogen peroxide and only delayed the swelling caused by tert-BuOOH and Ca2+. Fe(III)TPPS4 exacerbated the effect of the tert-BuOOH, and both porphyrins did not significantly affect Fe(II)citrate-induced swelling. Consistently, Fe(III)TPPS4 predominantly promotes the homolytic cleavage of peroxides and exhibits catalytic efficiency ten-fold higher than Mn(III)TPPS4. For Mn(III)TPPS4, the microenvironment of rat liver mitochondria favors the heterolytic cleavage of peroxides and increases the catalytic efficiency of the manganese porphyrin due to the availability of axial ligands for the metal center and reducing agents such as glutathione (GSH) and proteins necessary for Compound II (oxomanganese IV) recycling to the initial Mn(III) form. The use of thiol reducing agents for the recycling of Mn(III)TPPS4 leads to GSH depletion and protein oxidation and consequent damages in the organelle. PMID:19631199

  20. Metal-Centered 17-Electron Radicals CpM(CO)3• (M = Cr, Mo, W): A Combined Negative Ion Photoelectron Spectroscopic and Theoretical Study

    SciTech Connect

    van der Eide, Edwin F.; Hou, Gao-Lei; Deng, Shihu; Wen, Hui; Yang, Ping; Bullock, R. Morris; Wang, Xue B.

    2013-04-08

    Despite the importance of group VI metal-centered 17-electron radicals CpM(CO)3 (Cp = 5-C5H5, M = Cr, Mo, W) in establishing many of the fundamental reactions now known for metal-centered radicals, spectroscopic characterization of their electronic properties and structures has been very challenging due to their high reactivity. Here we report a gas-phase study of these species by means of photodetachment photoelectron spectroscopy (PES) of their corresponding 18-electron anions and theoretical electronic structure calculations. Three well-separated spectral features are observed by PES for each anionic species. Electron affinities (EAs) of CpM(CO)3 were experimentally measured from the threshold of each spectrum to be 2.38 ± 0.02 (M = Cr), 2.63 ± 0.02 (Mo), and 2.63 ± 0.01 eV for (W), well correlated with the reported redox potentials measured in solution. Theoretical calculations for all anionic and neutral (radical) species gave calculated EAs and band gaps that are in good agreement with the experimental data. Molecular orbital (MO) analyses for each anion indicate that the top three occupied MOs are mainly metal-based and contribute to the first spectral feature, whereas the next two MOs are largely from C5H5 moiety and contribute to the second spectral feature. The calculations further exhibit appreciable anion-to-neutral structural changes for all three species but with the change for the W species being the smallest, consistent with the W spectra being better resolved than the other two.

  1. Metal-Ion Effects on the Polarization of Metal-Bound Water and Infrared Vibrational Modes of the Coordinated Metal Center of Mycobacterium tuberculosis Pyrazinamidase via Quantum Mechanical Calculations

    PubMed Central

    2014-01-01

    Mycobacterium tuberculosis pyrazinamidase (PZAse) is a key enzyme to activate the pro-drug pyrazinamide (PZA). PZAse is a metalloenzyme that coordinates in vitro different divalent metal cofactors in the metal coordination site (MCS). Several metals including Co2+, Mn2+, and Zn2+ are able to reactivate the metal-depleted PZAse in vitro. We use quantum mechanical calculations to investigate the Zn2+, Fe2+, and Mn2+ metal cofactor effects on the local MCS structure, metal–ligand or metal–residue binding energy, and charge distribution. Results suggest that the major metal-dependent changes occur in the metal–ligand binding energy and charge distribution. Zn2+ shows the highest binding energy to the ligands (residues). In addition, Zn2+ and Mn2+ within the PZAse MCS highly polarize the O–H bond of coordinated water molecules in comparison with Fe2+. This suggests that the coordination of Zn2+ or Mn2+ to the PZAse protein facilitates the deprotonation of coordinated water to generate a nucleophile for catalysis as in carboxypeptidase A. Because metal ion binding is relevant to enzymatic reaction, identification of the metal binding event is important. The infrared vibrational mode shift of the C=Nε (His) bond from the M. tuberculosis MCS is the best IR probe to metal complexation. PMID:25055049

  2. Simulation of changes in heavy metal contamination in farmland soils of a typical manufacturing center through logistic-based cellular automata modeling.

    PubMed

    Qiu, Menglong; Wang, Qi; Li, Fangbai; Chen, Junjian; Yang, Guoyi; Liu, Liming

    2016-01-01

    A customized logistic-based cellular automata (CA) model was developed to simulate changes in heavy metal contamination (HMC) in farmland soils of Dongguan, a manufacturing center in Southern China, and to discover the relationship between HMC and related explanatory variables (continuous and categorical). The model was calibrated through the simulation and validation of HMC in 2012. Thereafter, the model was implemented for the scenario simulation of development alternatives for HMC in 2022. The HMC in 2002 and 2012 was determined through soil tests and cokriging. Continuous variables were divided into two groups by odds ratios. Positive variables (odds ratios >1) included the Nemerow synthetic pollution index in 2002, linear drainage density, distance from the city center, distance from the railway, slope, and secondary industrial output per unit of land. Negative variables (odds ratios <1) included elevation, distance from the road, distance from the key polluting enterprises, distance from the town center, soil pH, and distance from bodies of water. Categorical variables, including soil type, parent material type, organic content grade, and land use type, also significantly influenced HMC according to Wald statistics. The relative operating characteristic and kappa coefficients were 0.91 and 0.64, respectively, which proved the validity and accuracy of the model. The scenario simulation shows that the government should not only implement stricter environmental regulation but also strengthen the remediation of the current polluted area to effectively mitigate HMC. PMID:26341341

  3. UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation.

    PubMed

    Luo, Feng; Yan, Changsheng; Dang, Lilong; Krishna, Rajamani; Zhou, Wei; Wu, Hui; Dong, Xinglong; Han, Yu; Hu, Tong-Liang; O'Keeffe, Michael; Wang, Lingling; Luo, Mingbiao; Lin, Rui-Biao; Chen, Banglin

    2016-05-01

    A new metal-organic framework Zn2(H2O)(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 Å. Unlike metal sites in the well-established MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn(2+) sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm(3)/cm(3)) to Zn-MOF-74. Interestingly, the accessible Zn(2+) sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm(3)/cm(3)) than Zn-MOF-74 (146 cm(3)/cm(3)) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result. PMID:27113684

  4. 3d-4f Metal-Organic Framework with Dual Luminescent Centers That Efficiently Discriminates the Isomer and Homologues of Small Organic Molecules.

    PubMed

    Zeng, Guang; Xing, Shanghua; Wang, Xiuru; Yang, Yulin; Ma, Dingxuan; Liang, Hongwei; Gao, Lu; Hua, Jia; Li, Guanghua; Shi, Zhan; Feng, Shouhua

    2016-02-01

    A 3d-4f luminescent metal-organic framework (MOF), [Tb2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (4), and three analogues {[La2(Cu8I8)(C12H8NO2)6(C4H8O2)2(H2O)2]·3C4H8O2·2H2O (1), [Ce2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (2), and [Eu2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (3)}, were self-assembled from copper(I) halide clusters and lanthanide metal ions with an organic linker [3-(pyridin-4-yl)benzoic acid] under solvothermal conditions. Compound 4 with high quantum yield (Φ = 68%) exhibits reversible luminescence behavior, accompanying the removal and recovery of guest molecules (1,4-dioxane). Because of the unique porous structure and dual luminescent centers of compound 4, it can efficiently differentiate benzene series with different sizes and provide readouts in corresponding optical signals. Furthermore, it also can unambiguously discriminate the isomers, homologues, and other small molecules with similar structural motifs from one another. The luminescent color of the MOF sensor in different guest solvents has obvious changes that can be clearly distinguished by the naked eye. This multicolor luminescence originates from emissions of the dual luminescent centers, and the emissions have shifted, enhanced, weakened, or quenched to different degrees. PMID:26756250

  5. Ames Research Center cryogenic mirror testing program - A comparison of the cryogenic performance of metal and glass mirrors with different types of mounts

    NASA Technical Reports Server (NTRS)

    Miller, Jacob H.; Melugin, Ramsey K.; Augason, Gordon C.; Howard, Steven D.; Pryor, G. Mark

    1989-01-01

    A summary of the cryogenic testing of glass and metal mirrors performed at NASA Ames Research Center (ARC) and two other places is presented. Recent improvements to the ARC Cryogenic Optics Test Facility are described. The purposes of the tests were to determine: (1) how glass mirrors would perform at cryogenic temperatures compared with metal mirrors and (2) how various mirror mounts would affect the cryogenic performance of mirrors. Details of a cryogenic test of a 50 cm 'double arch', fused-silica mirror with a three-point mount and with a radially-compliant, flexured mount are given. Within the accuracy of the measurements, it was determined that the flexured mount did not induce appreciable distortion in the double arch mirror. Results of the cryogenic tests of a number of glass mirrors and two beryllium mirrors are included. The cryogenic distortion of the glass mirrors was found to be less than that for the beryllium mirrors. Within the accuracy of the measurements, no hysteresis was found in the glass mirrors. It was possible to measure hysteresis in one of the beryllium mirrors.

  6. Three-dimensional nonlinear optical chromophores based on metal-to-ligand charge-transfer from ruthenium(II) or iron(II) centers.

    PubMed

    Coe, Benjamin J; Harris, James A; Brunschwig, Bruce S; Asselberghs, Inge; Clays, Koen; Garín, Javier; Orduna, Jesús

    2005-09-28

    In this article, we describe a series of new complex salts in which electron-rich transition-metal centers are coordinated to three electron-accepting N-methyl/aryl-2,2':4,4' ':4',4' ''-quaterpyridinium ligands. These complexes contain either Ru(II) or Fe(II) ions and have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d --> pi* metal-to-ligand charge-transfer bands. The latter experiments reveal that these putatively octupolar D(3) chromophores exhibit two substantial components of the beta tensor which are associated with transitions to dipolar excited states. Computations involving time-dependent density-functional theory and the finite field method serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts. PMID:16173774

  7. Unusual non-bifunctional mechanism for Co-PNP complex catalyzed transfer hydrogenation governed by the electronic configuration of metal center.

    PubMed

    Hou, Cheng; Jiang, Jingxing; Li, Yinwu; Zhang, Zhihan; Zhao, Cunyuan; Ke, Zhuofeng

    2015-10-01

    The mimic of hydrogenases has unleashed a myriad of bifunctional catalysts, which are widely used in the catalytic hydrogenation of polar multiple bonds. With respect to ancillary ligands, the bifunctional mechanism is generally considered to proceed via the metal-ligand cooperation transition state. Inspired by the interesting study conducted by Hanson et al. (Chem Commun., 2013, 49, 10151), we present a computational study of a distinctive example, where a Co(II)-PNP catalyst with an ancillary ligand exhibits efficient transfer hydrogenation through a non-bifunctional mechanism. Both the bifunctional and non-bifunctional mechanisms are discussed. The calculated results, which are based on a full model of the catalyst, suggest that the inner-sphere non-bifunctional mechanism is more favorable (by ∼11 kcal mol(-1)) than the outer-sphere bifunctional mechanism, which is in agreement with the experimental observations. The origin of this mechanistic preference of the Co(II)-PNP catalyst can be attributed to its preference for the square planar geometry. A traditional bifunctional mechanism is less plausible for Co(II)-PNP due to the high distortion energy caused by the change in electronic configuration with the varied ligand field. Considering previous studies that focus on the development of ligands more often, this computational study indicates that the catalytic hydrogenation mechanism is controlled not only by the structure of the ligand but also by the electronic configuration of the metal center. PMID:26332273

  8. Mechanistic Insight into the Intramolecular Benzylic C-H Nitrene Insertion Catalyzed by Bimetallic Paddlewheel Complexes: Influence of the Metal Centers.

    PubMed

    Zhang, Xuepeng; Xu, Huiying; Liu, Xueping; Phillips, David Lee; Zhao, Cunyuan

    2016-05-17

    The intramolecular benzylic C-H amination catalyzed by bimetallic paddlewheel complexes was investigated by using density functional theory calculations. The metal-metal bonding characters were investigated and the structures featuring either a small HOMO-LUMO gap or a compact SOMO energy scope were estimated to facilitate an easier one-electron oxidation of the bimetallic center. The hydrogen-abstraction step was found to occur through three manners, that is, hydride transfer, hydrogen migration, and proton transfer. The imido N species are more preferred in the Ru-Ru and Pd-Mn cases whereas coexisting N species, namely, singlet/triplet nitrene and imido, were observed in the Rh-Rh and Pd-Co cases. On the other hand, the triplet nitrene N species were found to be predominant in the Pd-Ni and Pd-Zn systems. A concerted asynchronous mechanism was found to be modestly favorable in the Rh-Rh-catalyzed reactions whereas the Pd-Co-catalyzed reactions demonstrated a slight preference for a stepwise pathway. Favored stepwise pathways were seen in each Ru-Ru- and Pd-Mn-catalyzed reactions and in the triplet nitrene involved Pd-Ni and Pd-Zn reactions. The calculations suggest the feasibility of the Pd-Mn, Pd-Co, and Pd-Ni paddlewheel complexes as being economical alternatives for the expensive dirhodium/diruthenium complexes in C-H amination catalysis. PMID:27061588

  9. The surface metal site in Blc. viridis photosynthetic bacterial reaction centers: Cu{sup 2+} as a probe of structure, location, and flexibility.

    SciTech Connect

    Utschig, L. M.; Dalosto, S. D.; Thurnauer, M. C.; Poluektov, O. G.

    2010-01-01

    Metal ion binding to a surface site on photosynthetic reaction centers (RCs) modulates light-induced electron and proton transfer events in the RC. Whereas many studies have elucidated aspects of metal ion modulation events in Rhodobacter sphaeroides RCs, much less is understood about the surface site in Blastochloris viridis (Blc. viridis) RCs. Interestingly, electron paramagnetic resonance studies revealed two spectroscopically distinct Cu{sup 2+} surface site environments in Blc. viridis RCs. Herein, Cu{sup 2+} has been used to spectroscopically probe the structure of these Cu{sup 2+} site(s) in response to freezing conditions, temperature, and charge separation. One Cu{sup 2+} environment in Blc. viridis RCs, termed CuA, exhibits temperature-dependent conformational flexibility. Different conformation states of the CuA{sup 2+} site are trapped when the RC is frozen in the dark either by fast-freeze or slow-freeze procedure. The second Cu{sup 2+} environment, termed CuB, is structurally invariant to different freezing conditions and shows resolved hyperfine coupling to three nitrogen atoms. Cu{sup 2+} is most likely binding at the same location on the RC, but in different coordination environments which may reflect two distinct conformational states of the isolated Blc. viridis RC protein.

  10. Self-assembly of cobalt-centered metal organic framework and multiwalled carbon nanotubes hybrids as a highly active and corrosion-resistant bifunctional oxygen catalyst

    NASA Astrophysics Data System (ADS)

    Fang, Yiyun; Li, Xinzhe; Li, Feng; Lin, Xiaoqing; Tian, Min; Long, Xuefeng; An, Xingcai; Fu, Yan; Jin, Jun; Ma, Jiantai

    2016-09-01

    Metal organic frameworks (MOF) derived carbonaceous materials have emerged as promising bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts for electrochemical energy conversion and storage. But previous attempts to overcome the poor electrical conductivity of MOFs hybrids involve a harsh high-template pyrolytic process to in situ form carbon, which suffer from extremely complex operation and inevitable carbon corrosion at high positive potentials when OER is operated. Herein, a self-assembly approach is presented to synthesize a non-precious metal-based, high active and strong durable Co-MOF@CNTs bifunctional catalyst for OER and ORR. CNTs not only improve the transportation of the electrons but also can sustain the harsh oxidative environment of OER without carbon corrosion. Meanwhile, the unique 3D hierarchical structure offers a large surface area and stable anchoring sites for active centers and CNTs, which enables the superior durability of hybrid. Moreover, a synergistic catalysis of Co(II), organic ligands and CNTs will enhance the bifunctional electrocatalytic performance. Impressively, the hybrid exhibits comparable OER and ORR catalytic activity to RuO2 and 20 wt% Pt/C catalysts and superior stability. This facile and versatile strategy to fabricating MOF-based hybrids may be extended to other electrode materials for fuel cell and water splitting applications.

  11. Friction Stir Welding for Aluminum Metal Matrix Composites (MMC's) (Center Director's Discretionary Fund, Project No. 98-09)

    NASA Technical Reports Server (NTRS)

    Lee, J. A.; Carter, R. W.; Ding, J.

    1999-01-01

    This technical memorandum describes an investigation of using friction stir welding (FSW) process for joining a variety of aluminum metal matrix composites (MMC's) reinforced with discontinuous silicon-carbide (SiC) particulate and functional gradient materials. Preliminary results show that FSW is feasible to weld aluminum MMC to MMC or to aluminum-lithium 2195 if the SiC reinforcement is <25 percent by volume fraction. However, a softening in the heat-affected zone was observed and is known to be one of the major limiting factors for joint strength. The pin tool's material is made from a low-cost steel tool H-13 material, and the pin tool's wear was excessive such that the pin tool length has to be manually adjusted for every 5 ft of weldment. Initially, boron-carbide coating was developed for pin tools, but it did not show a significant improvement in wear resistance. Basically, FSW is applicable mainly for butt joining of flat plates. Therefore, FSW of cylindrical articles such as a flange to a duct with practical diameters ranging from 2-5 in. must be fully demonstrated and compared with other proven MMC joining techniques for cylindrical articles.

  12. Hydrolysis mechanisms of BNPP mediated by facial copper(II) complexes bearing single alkyl guanidine pendants: cooperation between the metal centers and the guanidine pendants.

    PubMed

    Zhang, Xuepeng; Liu, Xueping; Phillips, David Lee; Zhao, Cunyuan

    2016-01-28

    The hydrolysis mechanisms of DNA dinucleotide analogue BNPP(-) (bis(p-nitrophenyl) phosphate) catalyzed by mononuclear/dinuclear facial copper(ii) complexes bearing single alkyl guanidine pendants were investigated using density functional theory (DFT) calculations. Active catalyst forms have been investigated and four different reaction modes are proposed accordingly. The [Cu2(L(1))2(μ-OH)](3+) (L(1) is 1-(2-guanidinoethyl)-1,4,7-triazacyclononane) complex features a strong μ-hydroxo mediated antiferromagnetic coupling between the bimetallic centers and the corresponding more stable open-shell singlet state. Three different reaction modes involving two catalysts and a substrate were proposed for L(1) entries and the mode 1 in which an inter-complex nucleophilic attack by a metal bound hydroxide was found to be more favorable. In the L(3)-involved reactions (L(3) is 1-(4-guanidinobutyl)-1,4,7-triazacyclononane), the reaction mode in which an in-plane intracomplex scissoring-like nucleophilic attack by a Cu(ii)-bound hydroxide was found to be more competitive. The protonated guanidine pendants in each proposed mechanism were found to play crucial roles in stabilizing the reaction structures via hydrogen bonds and in facilitating the departure of the leaving group via electrostatic attraction. The calculated results are consistent with the experimental observations that the Cu(ii)-L(3) complexes are hydrolytically more favorable than their L(1)-involved counterparts. PMID:26688285

  13. Theoretical models of catalytic domains of protein phosphatases 1 and 2A with Zn2+ and Mn2+ metal dications and putative bioligands in their catalytic centers.

    PubMed

    Woźniak-Celmer, E; Ołdziej, S; Ciarkowski, J

    2001-01-01

    The oligomeric metalloenzymes protein phosphatases dephosphorylate OH groups of Ser/Thr or Tyr residues of proteins whose actions depend on the phosphorus signal. The catalytic units of Ser/Thr protein phosphatases 1, 2A and 2B (PP1c, PP2Ac and PP2Bc, respectively), which exhibit about 45% sequence similarity, have their active centers practically identical. This feature strongly suggests that the unknown structure of PP2Ac could be successfully homology-modeled from the known structures of PP1c and/or PP2Bc. Initially, a theoretical model of PP1c was built, including a phosphate and a metal dication in its catalytic site. The latter was modeled, together with a structural hydroxyl anion, as a triangular pseudo-molecule (Zno or Mno), composed of two metal cations (double Zn2+ or Mn2+, respectively) and the OH- group. To the free PP1c two inhibitor sequences R29RRRPpTPAMLFR40 of DARPP-32 and R30RRRPpTPATLVLT42 of Inhibitor-1, and two putative substrate sequences LRRApSVA and QRRQRKpRRTI were subsequently docked. In the next step, a free PP2Ac model was built via homology re-modeling of the PP1c template and the same four sequences were docked to it. Thus, together, 20 starting model complexes were built, allowing for combination of the Zno and Mno pseudo-molecules, free enzymes and the peptide ligands docked in the catalytic sites of PP1c and PP2Ac. All models were subsequently subjected to 250-300 ps molecular dynamics using the AMBER 5.0 program. The equilibrated trajectories of the final 50 ps were taken for further analyses. The theoretical models of PP1c complexes, irrespective of the dication type, exhibited increased mobilities in the following residue ranges: 195-200, 273-278, 287-209 for the inhibitor sequences and 21-25, 194-200, 222-227, 261, 299-302 for the substrate sequences. Paradoxically, the analogous PP2Ac models appeared much more stable in similar simulations, since only their "prosegment" residues 6-10 and 14-18 exhibited an increased mobility

  14. Transition-Metal-Centered Nine-Membered Boron Rings: M©B 9 and M©B 9 (M = Rh, Ir)

    SciTech Connect

    Li, Wei-Li; Romanescu, Constantin; Galeev, Timur R.; Piazza, Zachary A.; Boldyrev, Alexander I.; Wang, Lai-Sheng

    2012-01-11

    We report the observation of two transition-metal-centered nine-atom boron rings, Rh©B9 - and Ir©B9-. These two doped-boron clusters are produced in a laser-vaporization supersonic molecular beam and characterized by photoelectron spectroscopy and ab initio calculations. Large HOMO-LUMO gaps are observed in the anion photoelectron spectra, suggesting that neutral Rh©B9 and Ir©B9 are highly stable, closed shell species. Theoretical calculations show that Rh©B9 and Ir©B9 are of D9h symmetry. Chemical bonding analyses reveal that these complexes are doubly aromatic, each with six completely delocalized π and σ electrons, which describe the bonding between the central metal atom and the boron ring. This work establishes firmly the metal-doped B rings as a new class of novel aromatic molecular wheels.

  15. VVV SURVEY NEAR-INFRARED PHOTOMETRY OF KNOWN BULGE RR LYRAE STARS: THE DISTANCE TO THE GALACTIC CENTER AND ABSENCE OF A BARRED DISTRIBUTION OF THE METAL-POOR POPULATION

    SciTech Connect

    Dékány, I.; Minniti, D.; Catelan, M.; Zoccali, M.; Hempel, M.; Saito, R. K.

    2013-10-20

    We have combined optical and near-infrared data of known RR Lyrae (RRL) stars in the bulge in order to study the spatial distribution of its metal-poor component by measuring precise reddening values and distances of 7663 fundamental-mode RRL stars with high-quality photometry. We obtain a distance to the Galactic center of R {sub 0} = 8.33 ± 0.05 ± 0.14 kpc. We find that the spatial distribution of the RRL stars differs from the structures traced by the predominantly metal-rich red clump (RC) stars. Unlike the RC stars, the RRL stars do not trace a strong bar, but have a more spheroidal, centrally concentrated distribution, showing only a slight elongation in its very center. We find a hint of bimodality in the density distribution at high southern latitudes (b < –5°), which needs to be confirmed by extending the areal coverage of the current census. The different spatial distributions of the metal-rich and metal-poor stellar populations suggest that the Milky Way has a composite bulge.

  16. Halocuprate(I) zigzag chain structures with N-methylated DABCO cations--bright metal-centered luminescence and thermally activated color shifts.

    PubMed

    Maderlehner, Sebastian; Leitl, Markus J; Yersin, Hartmut; Pfitzner, Arno

    2015-11-28

    Two compounds 1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane catena-tetra-μ-halo-dicuprate(I) with DABCOMe2 Cu2X4 (1: X = Br, 2: X = I) were synthesized by hydrothermal reaction of copper(I) halides with the corresponding 1,4-diazoniabicyclo[2.2.2]octane (DABCO) dihydrohalides in an acetonitrile/methanol mixture. Both compounds crystallize monoclinically, 1 with a = 9.169(4) Å, b = 10.916(6) Å, c = 15.349(6) Å, β = 93.93(2)°, V = 1533(1) Å(3), Z = 4, space group P2(1)/n (no. 14) and 2 with a = 15.826(9) Å, b = 9.476(5) Å, c = 22.90(2) Å, β = 90.56(5)°, V = 3434(5) Å(3), Z = 8, space group P2(1) (no. 4), respectively (lattice constants refined from powder diffraction data measured at 293 K). The cations in both compounds are formed by in situ N-methylation of DABCOH2(2+) cations by methanol in a S(N)2 reaction. Both compounds contain an anionic copper(I) halide chain structure consisting of trans edge-sharing CuX4 tetrahedra. The chains are strongly kinked at every 2(nd) junction thus forming a zigzag structure. The shortest halide-halide distances are observed between the halide ions of adjacent tetrahedra which are approaching each other due to the kinking. This structure type shows a specific luminescence behavior. Under optical excitation, the compounds exhibit yellow (1) and green (2) emission with photoluminescence quantum yields of Φ(PL) = 52 and 4%, respectively, at ambient temperature. According to DFT and TDDFT calculations, the emission is assigned to be a phosphorescence essentially involving a metal centered transition between the HOMO consisting mainly of copper 3d and halide p orbitals and the LUMO consisting mainly of copper 4s and 4p orbitals. The temperature dependence of the emission spectra, decay times, and quantum yields has been investigated in detail, especially for 1. From the resulting trends it can be concluded that the emission for T≤ 100 K stems from energetically lower lying copper halide segments. Such segments represent

  17. Electronic Structure of the Metal Center in the Cd[superscript 2+], Zn[superscript 2+], and Cu[superscript 2+] Substituted Forms of KDO8P Synthase: Implications for Catalysis

    SciTech Connect

    Kona, Fathima; Tao, Peng; Martin, Philip; Xu, Xingjue; Gatti, Domenico L.

    2009-07-31

    Aquifex aeolicus 3-deoxy-D-manno-octulosonate 8-phosphate synthase (KDO8PS) is active with a variety of different divalent metal ions bound in the active site. The Cd{sup 2+}, Zn{sup 2+}, and Cu{sup 2+} substituted enzymes display similar values of k{sub cat} and similar dependence of K{sub m}{sup PEP} and K{sub m}{sup A5P} on both substrate and product concentrations. However, the flux-control coefficients for some of the catalytically relevant reaction steps are different in the presence of Zn{sup 2+} or Cu{sup 2+}, suggesting that the type of metal bound in the active site affects the behavior of the enzyme in vivo. The type of metal also affects the rate of product release in the crystal environment. For example, the crystal structure of the Cu{sup 2+} enzyme incubated with phosphoenolpyruvate (PEP) and arabinose 5-phosphate (A5P) shows the formed product, 3-deoxy-D-manno-octulosonate 8-phosphate (KDO8P), still bound in the active site in its linear conformation. This observation completes our structural studies of the condensation reaction, which altogether have provided high-resolution structures for the reactants, the intermediate, and the product bound forms of KDO8PS. The crystal structures of the Cd{sup 2+}, Zn{sup 2+}, and Cu{sup 2+} substituted enzymes show four residues (Cys-11, His-185, Glu-222, and Asp-233) and a water molecule as possible metal ligands. Combined quantum mechanics/molecular mechanics (QM/MM) geometry optimizations reveal that the metal centers have a delocalized electronic structure, and that their true geometry is square pyramidal for Cd{sup 2+} and Zn{sup 2+} and distorted octahedral or distorted tetrahedral for Cu{sup 2+}. These geometries are different from those obtained by QM optimization in the gas phase (tetrahedral for Cd{sup 2+} and Zn{sup 2+}, distorted tetrahedral for Cu{sup 2+}) and may represent conformations of the metal center that minimize the reorganization energy between the substrate-bound and product-bound states

  18. Metal-organic framework based upon the synergy of a Brønsted acid framework and Lewis acid centers as a highly efficient heterogeneous catalyst for fixed-bed reactions.

    PubMed

    Li, Baiyan; Leng, Kunyue; Zhang, Yiming; Dynes, James J; Wang, Jian; Hu, Yongfeng; Ma, Dingxuan; Shi, Zhan; Zhu, Liangkui; Zhang, Daliang; Sun, Yinyong; Chrzanowski, Matthew; Ma, Shengqian

    2015-04-01

    We report a strategy of combining a Brønsted acid metal-organic framework (MOF) with Lewis acid centers to afford a Lewis acid@Brønsted acid MOF with high catalytic activity, as exemplified in the context of MIL-101-Cr-SO3H·Al(III). Because of the synergy between the Brønsted acid framework and the Al(III) Lewis acid centers, MIL-101-Cr-SO3H·Al(III) demonstrates excellent catalytic performance in a series of fixed-bed reactions, outperforming two benchmark zeolite catalysts (H-Beta and HMOR). Our work therefore not only provides a new approach to achieve high catalytic activity in MOFs but also paves a way to develop MOFs as a new type of highly efficient heterogeneous catalysts for fixed-bed reactions. PMID:25773275

  19. Synthesis of the First Example of the 12-Vertex-closo/12-Vertex-nido Biscarborane Cluster by a Metal-Free B-H Activation at a Phosphorus(III) Center.

    PubMed

    Wong, Yuen Onn; Smith, Mark D; Peryshkov, Dmitry V

    2016-05-10

    An unusual 12-vertex-closo-C2 B10 /12-vertex-nido-C2 B10 biscarborane cluster was synthesized through an unprecedented regioselective metal-free B-H activation by a sterically hindered P(III) center under mild conditions accompanied by cage-opening rearrangement. A combination of the electron-accepting properties of a carborane cage and steric enforcement of close interatomic contacts represent a new synthetic strategy for the activation of strong B-H bonds in carboranes. PMID:26990216

  20. Schottky barrier height reduction for holes by Fermi level depinning using metal/nickel oxide/silicon contacts

    SciTech Connect

    Islam, Raisul Shine, Gautam; Saraswat, Krishna C.

    2014-11-03

    We report the experimental demonstration of Fermi level depinning using nickel oxide (NiO) as the insulator material in metal-insulator-semiconductor (M-I-S) contacts. Using this contact, we show less than 0.1 eV barrier height for holes in platinum/NiO/silicon (Pt/NiO/p-Si) contact. Overall, the pinning factor was improved from 0.08 (metal/Si) to 0.26 (metal/NiO/Si). The experimental results show good agreement with that obtained from theoretical calculation. NiO offers high conduction band offset and low valence band offset with Si. By reducing Schottky barrier height, this contact can be used as a carrier selective contact allowing hole transport but blocking electron transport, which is important for high efficiency in photonic applications such as photovoltaics and optical detectors.

  1. METALS (Minority Education Through Traveling and Learning in the Sciences) and the Value of Collaborative Field-centered Experiences in the Geosciences (Invited)

    NASA Astrophysics Data System (ADS)

    White, L. D.

    2013-12-01

    METALS (Minority Education Through Traveling and Learning in the Sciences) is a field-based, geoscience diversity program developed by a collaborative venture among San Francisco State University, the University of Texas at El Paso, the University of New Orleans, and Purdue University. Since 2010, this program has created meaningful geoscience experiences for underrepresented minorities by engaging 30 high school students in experiential learning opportunities each year. During METALS field trips, the primarily urban students observe natural landforms, measure water quality, conduct beach profiles, and interpret stratigraphic and structural features in locations that have included southern Utah, southern Louisiana, central Wyoming, and northern California. In these geological settings participants are also able to focus on societally relevant, community-related issues. Results from program evaluation suggest that student participants view METALS as: (1) opening up new opportunities for field-based science not normally available to them, (2) engaging in a valuable science-based field experience, (3) an inspirational, but often physically challenging, undertaking that combines high-interest geology content with an exciting outdoor adventure, and (4) a unique social experience that brings together people from various parts of the United States. Further evaluation findings from the four summer trips completed thus far demonstrate that active learning opportunities through direct interaction with the environment is an effective way to engage students in geoscience-related learning. Students also seem to benefit from teaching strategies that include thoughtful reflection, journaling, and teamwork, and mentors are positive about engaging with these approaches. Participants appear motivated to explore geoscience topics further and often discuss having new insights and new perspectives leading to career choices in geosciences. Additionally, students who had a prior and

  2. Assemblies of a new flexible multicarboxylate ligand and d10 metal centers toward the construction of homochiral helical coordination polymers: structures, luminescence, and NLO-active properties.

    PubMed

    Zang, Shuangquan; Su, Yang; Li, Yizhi; Ni, Zhaoping; Meng, Qingjin

    2006-01-01

    Hydro(solvo)thermal reactions between a new flexible multicarboxylate ligand of 2,2',3,3'-oxydiphthalic acid (2,2',3,3'-H(4)ODPA) and M(NO(3))(2).xH(2)O (M = Zn, x = 6; M = Cd, x = 4) in the presence of 4,4'-bipyridine (bpy) afford two novel homochiral helical coordination polymers [[Zn(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 1 and [Cd(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 2]. Though having almost the same chemical formula, they have different space groups (P2(1)2(1)2(1) for 1 and P2(1) for 2) and different bridging modes of the 2,2',3,3'-ODPA ligand. Two kinds of homochiral helices (right-handed) are found in both 1 and 2, each of which discriminates only one kind of crystallographical nonequivalent metal atom. 1 has a 2D metal-organic framework and can be seen as the unity of two parallel homochiral Zn1 and Zn2 helices, in which the nodes are etheric oxygen atoms. In contrast, 2 has a 3D metal-organic framework and consists of two partially overlapped homochiral Cd1 and Cd2 helices in the two dimensions. Moreover, metal-ODPA helices give a 2D chiral herringbone structural motif in both 1 and 2 in the two dimensions, which are further strengthened by the second ligand of bpy. Bulk materials for 1 and 2 all have good second-harmonic generation activity, approximately 1 and 0.8 times that of urea. PMID:16390053

  3. Asymmetric Desymmetrization via Metal-Free C-F Bond Activation: Synthesis of 3,5-Diaryl-5-fluoromethyloxazolidin-2-ones with Quaternary Carbon Centers.

    PubMed

    Tanaka, Junki; Suzuki, Satoru; Tokunaga, Etsuko; Haufe, Günter; Shibata, Norio

    2016-08-01

    We disclose the first asymmetric activation of a non-activated aliphatic C-F bond in which a conceptually new desymmetrization of 1,3-difluorides by silicon-induced selective C-F bond scission is a key step. The combination of a cinchona alkaloid based chiral ammonium bifluoride catalyst and N,O-bis(trimethylsilyl)acetoamide (BSA) as the silicon reagent enabled the efficient catalytic cycle of asymmetric Csp3 -F bond cleavage under mild conditions with high enantioselectivities. The ortho effect of the aryl group at the prostereogenic center is remarkable. This concept was applied for the asymmetric synthesis of promising agrochemical compounds, 3,5-diaryl-5-fluoromethyloxazolidin-2-ones bearing a quaternary carbon center. PMID:27332650

  4. Metal Preferences and Metallation*

    PubMed Central

    Foster, Andrew W.; Osman, Deenah; Robinson, Nigel J.

    2014-01-01

    The metal binding preferences of most metalloproteins do not match their metal requirements. Thus, metallation of an estimated 30% of metalloenzymes is aided by metal delivery systems, with ∼25% acquiring preassembled metal cofactors. The remaining ∼70% are presumed to compete for metals from buffered metal pools. Metallation is further aided by maintaining the relative concentrations of these pools as an inverse function of the stabilities of the respective metal complexes. For example, magnesium enzymes always prefer to bind zinc, and these metals dominate the metalloenzymes without metal delivery systems. Therefore, the buffered concentration of zinc is held at least a million-fold below magnesium inside most cells. PMID:25160626

  5. Hastings Center

    MedlinePlus

    ... Events October 19, Hastings Center Seminar, Garrison : Human Genetic Engineering: Wh at Can We Do? What Should We ... Events October 19, Hastings Center Seminar, Garrison : Human Genetic Engineering: Wh at Can We Do? What Should We ...

  6. First-principles calculations of the twin boundary energies and adhesion energies of interfaces for cubic face-centered transition-metal nitrides and carbides

    NASA Astrophysics Data System (ADS)

    Li, Tengfei; Liu, Tianmo; Wei, Hongmei; Hussain, Shahid; Wang, Jinxing; Zeng, Wen; Peng, Xianghe; Wang, Zhongchang

    2015-11-01

    The twin boundary energies of TiN, ZrN, HfN, TiC, ZrC, HfC, VC, NbC and TaC and the adhesion energies of twin interfaces and interfaces of TiN/ZrN, VC/TiC and TiN/TiC were calculated using first-principles methods. A new route in the preparation of mechanically superhard films has been proposed by introducing twin into the multilayer of transition-metal nitrides and carbides.

  7. Visible-light-mediated, nitrogen-centered radical amination of tertiary alkyl halides under metal-free conditions to form α-tertiary amines.

    PubMed

    Brueckner, Alexander C; Hancock, Erin N; Anders, Evan J; Tierney, Matthew M; Morgan, Heather R; Scott, Kristina A; Lamar, Angus A

    2016-05-11

    A mild and operationally convenient amino-functionalization of a range of tertiary alkyl halides by reaction with iminoiodinanes (PhI[double bond, length as m-dash]NNs) and I2 has been developed. According to the mechanistic experiments described within, the reaction is speculated to proceed through a light-promoted, N-centered radical pathway involving a N,N-diiodosulfonamide reactive species. This method of direct N-incorporation offers an attractive alternative to the production of α-tertiary amines, a synthetically challenging structural class found in a variety of bioactive molecules. PMID:27113972

  8. Introduction of Artificial Pinning Center into PLD-YBCO Coated Conductor on IBAD and Self-Epitaxial CeO2 Buffered Metal Substrate

    SciTech Connect

    Kobayashi, H.; Yamada, Y.; Ishida, S.; Takahashi, K.; Konishi, M.; Ibi, A.; Miyata, S.; Kato, T.; Hirayama, T.; Shiohara, Y.

    2006-03-31

    In order to fabricate YBa2Cu3O7-x (YBCO) coated conductors with high critical current density Jc in magnetic fields, we fabricated YBCO coated conductors with artificial pinning centers by the pulsed laser deposition (PLD) method on a self epitaxial PLD-CeO2 layer and ion-beam assisted deposition (IBAD)-Gd2Zr2O7 (GZO) buffered Hastelloy tape. Artificial pinning centers were introduced by the PLD deposition using the yttria-stabilized zirconia (YSZ) oxide target (nano-dot method) and YBCO target including YSZ particles (mixed target method). In the experiments using YSZ oxide target, YSZ nano-dots were observed. They were approximately 15 nm in height and 10 nm to 70 nm in diameter. We found that the density of nano-dots was controlled by the number of laser pulses. These samples exhibited higher Jc than YBCO films in magnetic fields. Furthermore, a similar improvement of Jc was observed in the experiments using YBCO target including YSZ particles. TEM observation revealed that columnar nano-structure made of BaZrO3 was formed during YBCO deposition and it was effective for pinning. We call this new epitaxial nano-structure 'bamboo structure' from its anisotropic growth and morphology.

  9. Job center

    NASA Astrophysics Data System (ADS)

    To better meet the needs of AGU members, a program has been started to increase the effectiveness of the Job Center activity at the Spring and Fall Meetings. As a result, participation in the Job Center at the 1988 AGU Spring Meeting in Baltimore increased substantially compared to previous Spring Meetings. The number of employers, applicants, and interviews scheduled more than doubled compared to the 1987 Spring Job Center.In order to make the meeting Job Centers even better, a survey is being conducted of employers and applicants who participated in the 1988 Spring Job Center. Evaluation of this survey will be useful in continuing increased participation in and the effectiveness of the Job Center at the 1988 Fall Meeting. Past participants and those interested in the future of the Job Center are encouraged to forward comments and suggestions to AGU, Member Programs Division, 2000 Florida Ave., N.W., Washington, DC 20009.

  10. Orange Zinc Germanate with Metallic Ge-Ge Bonds as a Chromophore-Like Center for Visible-Light-Driven Water Splitting.

    PubMed

    Qian, Ling; Chen, Jian Fu; Li, Yu Hang; Wu, Long; Wang, Hai Feng; Chen, Ai Ping; Hu, P; Zheng, Li Rong; Yang, Hua Gui

    2015-09-21

    The efficiency of solar-energy-conversion devices depends on the absorption region and intensity of the photon collectors. Organic chromophores, which have been widely stabilized on inorganic semiconductors for light trapping, are limited by the interface between the chromophore and semiconductor. Herein we report a novel orange zinc germanate (Zn-Ge-O) with a chromophore-like structure, by which the absorption region can be dramatically expanded. Structural characterizations and theoretical calculations together reveal that the origin of visible-light response can be attributed to the unusual metallic Ge-Ge bonds which act in a similar way to organic chromophores. Benefiting from the enhanced light harvest, the orange Zn-Ge-O demonstrates superior capacity for solar-driven hydrogen production. PMID:26291331

  11. 2,5-dimethylthiophene coordination to three metal centers in (. eta. sup 4 ,S-. mu. sub 3 -2,5-Me sub 2 T)(IrCp sup * )(Mo(CO) sub 2 Cp) sub 2

    SciTech Connect

    Chen, Jiabi; Angelici, R.J. )

    1990-03-01

    The reaction of Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T), where {eta}{sup 4}-2,5-Me{sub 2}T is 2,5-dimethylthiophene coordinated through the four ring carbons, with Cp(CO){sub 2}Mo{triple bond}Mo(CO){sub 2}Cp gives ({eta}{sup 4},S-{mu}{sub 3}-2,5-Me{sub 2}T)(IrCp{sup *})(Mo(CO){sub 2}Cp){sub 2}, in which the bridging thiophene is {eta}{sup 4}-coordinated to the Ir and bonded via the sulfur to both Mo atoms. The same product is obtained from the ring-opened isomer of Cp{sup *}Ir(2,5-Me{sub 2}T). The structure of the product, which is the first example of a thiophene coordinated to three metal centers, was established by X-ray crystallography.

  12. Metal-ligand cooperation.

    PubMed

    Khusnutdinova, Julia R; Milstein, David

    2015-10-12

    Metal-ligand cooperation (MLC) has become an important concept in catalysis by transition metal complexes both in synthetic and biological systems. MLC implies that both the metal and the ligand are directly involved in bond activation processes, by contrast to "classical" transition metal catalysis where the ligand (e.g. phosphine) acts as a spectator, while all key transformations occur at the metal center. In this Review, we will discuss examples of MLC in which 1) both the metal and the ligand are chemically modified during bond activation and 2) bond activation results in immediate changes in the 1st coordination sphere involving the cooperating ligand, even if the reactive center at the ligand is not directly bound to the metal (e.g. via tautomerization). The role of MLC in enabling effective catalysis as well as in catalyst deactivation reactions will be discussed. PMID:26436516

  13. Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

    NASA Technical Reports Server (NTRS)

    Tatarenko, Valentine A.; Tsysman, Constantin L.; Oltarzhevskaya, Yelena T.

    1995-01-01

    The calculations in a majority of previous works for the fulleride (AqC-60) crystals were performed within the framework of the rigid-lattice model, neglecting the distortion relaxation of the host fullerene (C-60) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distortion field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. The given paper seeks to find a functional relation between the amplitudes of the doping-induced structure-distortion waves and of static concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method(*). In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the static inherent reorientation and/or displacements of the solvent molecules from the 'average-lattice' sites' as well as on the lattice parameter a of a elastically-anysotropic 'cubic' C-60 crystal are taken into account.

  14. Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

    SciTech Connect

    Tatarenko, V.A.; Tsysman, C.L.; Oltarzhevskaya, Y.T.

    1994-12-31

    The calculations in a majority of previous works for the fulleride (AqC{sub 60}) crystals were performed within the framework of the rigid-lattice model, neglecting the distoration relaxation of the host fullerene (C{sub 60}) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distoration field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. This paper seeks to find a functional relation between the amplitudes of the doping-induced structure-distortion waves and of statistic concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method. In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the statistic inherent reorientation and/or displacements of the solvent molecules from the average-lattice sites as well as on the lattice parameter a of the elastically-anysotropic cubic C{sub 60} crystal are taken into account.

  15. Materials Characterization Center state-of-the-art report on corrosion data pertaining to metallic barriers for nuclear-waste repositories

    SciTech Connect

    Merz, M.D.

    1982-10-01

    A compilation of published corrosion data on metals that have been suggested as canisters and overpack materials is presented. The data were categorized according to the solutions used in testing and divided into two parts: high-ionic strength solutions (such as seawater and brine) and low-ionic-strength waters (such as basalt and tuff waters). This distinction was made primarily because of the general difference in aggressiveness of these solutions with respect to general corrosion. A considerable amount of data indicated that titanium alloys have acceptably low uniform corrosion rates in anticipated repository sites; the other possible corrosion failure modes for titanium alloys, such as stress corrosion cracking and delayed failure due to hydrogen, have not been sufficiently studied to make any similar conclusions about lifetime with respect to these particular degradation processes. Other data suggested that iron-base alloys are sufficiently resistant to corrosion in basalt and tuff waters, although the effects of radiation and radiation combined with elevated temperature have not been reported in enough detail to conclusively qualify iron-base alloys for any particular barrier thickness in regard to uniform corrosion rate. The effect of overpack size on corrosion rate has been given little attention. A review of long-term underground data indicated that temperature and accessibility to oxygen were too different for deep geologic repositories to make the underground corrosion data directly applicable. However, the characteristics of corrosion attack, statistical treatment of data, and kinetics of corrosion showed that corrosion proceeds in a systematic and predictable way.

  16. Why Is There an “Inert” Metal Center in the Active Site of Nitrile Hydratase? Reactivity and Ligand Dissociation from a Five-Coordinate Co(III) Nitrile Hydratase Model

    PubMed Central

    Shearer, Jason; Kung, Irene Y.; Lovell, Scott; Kaminsky, Werner; Kovacs, Julie A.

    2015-01-01

    To determine how a substitutionally inert metal can play a catalytic role in the metalloenzyme nitrile hydratase (NHase), a reactive five-coordinate CoIII thiolate complex ([CoIII(S2Me2N3(Pr,Pr))](PF6) (1)) that resembles the active site of cobalt containing nitrile hydratase (Co NHase) was prepared. This was screened for reactivity, by using low-temperature electronic absorption spectroscopy, toward a number of biologically relevant “substrates”. It was determined 1 will react with azide, thiocyanate, and ammonia, but is unreactive toward nitriles, NO, and butyrate. Substrate-bound 1 has similar spectroscopic and structural properties as [CoIII(ADIT2)](PF6) (2). Complex 2 is a six-coordinate CoIII complex containing cis-thiolates and imine nitrogens, and has properties similar to the cobalt center of Co NHase. Substrate binding to 1 is reversible and temperature-dependent, allowing for the determination of the thermodynamic parameters of azide and thiocyanate binding and the rates of ligand dissociation. Azide and thiocyanate bind trans to a thiolate, and with similar entropies and enthalpies (thiocyanate: ΔH = −7.5 ± 1.1 kcal/mol, ΔS = −17.2 ± 3.2 eu; azide: ΔH = −6.5 ± 1.0 kcal/mol, ΔS = −12.6 ± 2.4 eu). The rates of azide and thiocyanate displacement from the metal center are also comparable to one another (kd = (7.22 ± 0.04) × 10−1 s−1 for thiocyanate and kd = 2.14 ± 0.50) × 10−2 s−1 for azide), and are considerably faster than one would expect for a low-spin d6 six-coordinate CoIII complex. These rates are comparable to those of an analogous Fe(III) complex, demonstrating that Co(III) and Fe(III) react at comparable rates when in this ligand environment. This study therefore indicates that ligand displacement from a low-spin CoIII center in a ligand environment that resembles NHase is not prohibitivly slow so as to disallow catalytic action in nonredox active cobalt metalloenzymes. PMID:11456548

  17. Development of new transition metal oxide catalysts for the destruction of PCDD/Fs.

    PubMed

    Yu, Ming-Feng; Li, Wen-Wei; Li, Xiao-Dong; Lin, Xiao-Qing; Chen, Tong; Yan, Jian-Hua

    2016-08-01

    Various transition metal oxide and vanadium-containing multi-metallic oxide catalysts were developed for the destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans). A stable PCDD/Fs generating system was installed to support the catalytic destruction tests in this study. Nano-titania supported vanadium catalyst (VOx/TiO2) showed the highest activity, followed by CeOx, MnOx, WOx and finally MoOx. Multi-metallic oxide catalysts, prepared by doping WOx, MoOx, MnOx and CeOx into VOx/TiO2 catalysts, showed different activities on the decomposition of PCDD/Fs. The highest destruction efficiency of 92.5% was observed from the destruction test over VOxCeOx/TiO2 catalyst. However, the addition of WOx and MoOx even played a negative role in multi-metallic VOx/TiO2 catalysts. Characterizations of transition metal oxides and multi-metallic VOx/TiO2 catalysts were also investigated with XRD and TPR. After the catalysts were used, the conversion from high valent metals to low valence states was observed by XPS. PMID:27186687

  18. Skills Center.

    ERIC Educational Resources Information Center

    Canter, Patricia; And Others

    The services of the Living Skills Center for the Visually Handicapped, a habilitative service for blind young adults, are described. It is explained that the Center houses its participants in their own apartments in a large complex and has served over 70 young people in 4 years. The evaluation section describes such assessment instruments as an…

  19. Endoscopic treatment of large pancreatic fluid collections (PFC) using self-expanding metallic stents (SEMS) – a two-center experience

    PubMed Central

    Chaves, Dalton Marques; Mönkemüller, Klaus; Carneiro, Fred; Medrado, Bruno; dos Santos, Marcos; Wodak, Stephanie; Reimão, Sílvia; Sakai, Paulo; de Moura, Eduardo

    2014-01-01

    Background/study aim: During the last several years, endoscopic ultrasound (EUS)-guided pancreatic fluid collections’ (PFC) drainage has evolved into the preferred drainage technique. Recently, self-expanding metallic stents (SEMS) have been used as an alternative to double pigtail stents, with the advantage of providing a larger diameter fistula, thereby decreasing the risk of early obstruction and also allowing for direct endoscopic exploration of the cavity. The aim of this study was to evaluate the technical and clinical success, safety, and outcome of patients undergoing EUS-guided drainage of complex PFC using SEMS. Patients/materials and methods: The study was conducted at two tertiary hospitals from January 2010 to January 2013. All patients with PFC referred for endoscopic drainage were enrolled in a prospective database. The inclusion criteria were: (1) patients with pseudocysts or walled-off necrosis based on the revised Atlanta classification; (2) symptomatic patients with thick PFC; (3) PFC that persisted more than 6 weeks; and (4) large PFC diameter (≥ 9 cm). The exclusion criteria consisted of coagulation disorders, PFC bleeding or infection, and failure-to-inform written consent. Results: A total of 16 patients (9 females, 7 males; mean age 52.6, range 20 – 82) underwent EUS drainage with SEMS. There were 14 cases of pseudocysts and 2 cases of walled-off necrosis. The etiologies of the PFC were mainly gallstones (8 of 16 patients, 50 %) and alcohol (5 of 16 patients, 31 %). Technical success was achieved in 100 % of the cases. All patients had a complete resolution of the PFC. Conclusion: Transmural EUS-guided drainage of complex PFC using SEMS is feasible, appears safe, and is efficacious. However, the exchange of the UC (uncovered)-SEMS for plastic stents is mandatory within 1 week. Future prospective studies, preferably multicenter studies, comparing SEMS versus traditional plastic stents for the drainage of PFC are

  20. Intramolecular coupling of eta/sup 2/-iminoacyl groups at group 4 metal centers: a kinetic study of the carbon-carbon double-bond-forming reaction

    SciTech Connect

    Durfee, L.D.; McMullen, A.K.; Rothwell, I.P.

    1988-03-02

    The series of bis(eta/sup 2/-iminoacyl) compounds of general formula M(OAr)/sub 2/(eta/sup 2/-R'NCR)/sub 2/ (M = Ti, Zr, Hf; OAr = 2,6-diisopropyl- and 2,6-di-tert-butylphenoxide; R = CH/sub 3/, CH/sub 2/Ph; R' = various substituted phenyls) undergo intramolecular coupling on thermolysis to produce the corresponding enediamide derivatives M(OAr)/sub 2/(R'NC(R) = C(R)NR'). A kinetic study of the reaction in hydrocarbon solvents has shown it to be first order. The reaction is metal dependent with the rate decreasing in the order Ti > Zr > Hf. The rate of the reaction is also dependent on the steric and electronic nature of the nitrogen substituent (R'). The use of the bulky aryl group 2,6-dimethylphenyl retards the reaction, while the use of various 3- and 4-substituted phenyls (3-F, 3-OMe, 4-OMe, 4-Cl, 4-NMe/sub 2/) shows the reaction to be accelerated by electron-withdrawing substituents. A sigma plot based on kinetic data obtained at 67/sup 0/C and 77/sup 0/C yielded rho values of 0.83 (R = 0.97) and 0.84 (R = 0.95), respectively. Both the steric and electronic dependence of the reactivity on the nitrogen substituents is discussed mechanistically and used to rationalize the much more facile intramolecular coupling observed for the related eta/sup 2/-acyl (eta/sup 2/-OCR) functionalities.

  1. Site-isolated luminescent europium complexes with polyester macroligands: metal-centered heteroarm stars and nanoscale assemblies with labile block junctions.

    PubMed

    Bender, Jessica L; Corbin, Perry S; Fraser, Cassandra L; Metcalf, David H; Richardson, Frederick S; Thomas, Edwin L; Urbas, Augustine M

    2002-07-24

    The synthesis of a series of polymeric Eu(III) complexes with polyester ligands, along with supporting emission spectra, luminescence lifetimes, and, for a Eu block copolymer film, atomic force microscopy (AFM) data, is presented. Dibenzoylmethane was derivatized with a hydroxyl initiator site (dbmOH, 1) for tin octoate catalyzed ring opening polymerization of dl-lactide. The resulting poly(lactic acid) macroligand, dbmPLA (2), was combined with EuCl3 to generate Eu(dbmPLA)3 (3). Chelation of both dbmPLA and a polycaprolactone-functionalized bipyridine ligand (bpyPCL2) led to the Eu(III)-centered heteroarm star Eu(dbmPLA)3(bpyPCL2) (4). Unpolarized emission spectra and luminescence lifetimes were recorded for the Eu polymers in CH2Cl2 and for Eu(dbmPLA)3, as a film. Solution data for Eu(dbm)3 and Eu(dbm)3(bpy) were collected for comparison. For Eu tris(dbm) complexes, data were fit to a double exponential decay, indicating the presence of multiple species. Relative amounts of the longer lifetime component increase in the series Eu(dbm)3 solutions to Eu(dbmPLA)3 solutions to Eu(dbmPLA)3 films, perhaps suggesting benefits of the "polymer shell effect" and the diminishment of aquo adducts known to shorten lifetimes. As with the nonpolymeric analogue, data for Eu(dbmPLA)3(bpyPCL2) fit to a single-exponential decay. The sharpness of the feature at 579.7 nm, attributable to the 5D0 --> 7F0 transition in the emission spectrum of 4, lends further support for a homogeneous sample. AFM studies of "as cast" thin films of 4 reveal a lamellar structure with a 17.5 nm repeat. These microstructures, inferred to contain Eu luminophores at the glassy PLA-crystalline PCL domain interfaces, are modified by thermal treatment. PMID:12121083

  2. Structure of a conserved hypothetical protein SA1388 from S. aureus reveals a capped hexameric toroid with two PII domain lids and a dinuclear metal center

    SciTech Connect

    Saikatendu, Kumar Singh; Zhang, Xuejun; Kinch, Lisa; Leybourne, Matthew; Grishin, Nick V.; Zhang, Hong

    2009-01-26

    The protein encoded by the SA1388 gene from Staphylococcus aureus was chosen for structure determination to elucidate its domain organization and confirm our earlier remote homology based prediction that it housed a nitrogen regulatory PII protein-like domain. SA1388 was predicted to contain a central PII-like domain and two flanking regions, which together belong to the NIF3-like protein family. Proteins like SA1388 remain a poorly studied group and their structural characterization could guide future investigations aimed at understanding their function. The structure of SA1388 has been solved to 2.0{angstrom} resolution by single wavelength anomalous dispersion phasing method using selenium anomalous signals. It reveals a canonical NIF3-like fold containing two domains with a PII-like domain inserted in the middle of the polypeptide. The N and C terminal halves of the NIF3-like domains are involved in dimerization, while the PII domain forms trimeric contacts with symmetry related monomers. Overall, the NIF3-like domains of SA1388 are organized as a hexameric toroid similar to its homologs, E. coli ybgI and the hypothetical protein SP1609 from Streptococcus pneumoniae. The openings on either side of the toroid are partially covered by trimeric 'lids' formed by the PII domains. The junction of the two NIF3 domains has two zinc ions bound at what appears to be a histidine rich active site. A well-defined electron density corresponding to an endogenously bound ligand of unknown identity is observed in close proximity to the metal site. SA1388 is the third member of the NIF3-like family of proteins to be structurally characterized, the other two also being hypothetical proteins of unknown function. The structure of SA1388 confirms our earlier prediction that the inserted domain that separates the two NIF3 domains adopts a PII-like fold and reveals an overall capped toroidal arrangement for the protein hexamer. The six PII-like domains form two trimeric 'lids' that

  3. Individual and competitive removal of heavy metals using capacitive deionization.

    PubMed

    Huang, Zhe; Lu, Lu; Cai, Zhenxiao; Ren, Zhiyong Jason

    2016-01-25

    This study presents the viability and preference of capacitive deionization (CDI) for removing different heavy metal ions in various conditions. The removal performance and mechanisms of three ions, cadmium (Cd(2+)), lead (Pb(2+)) and chromium (Cr(3+)) were investigated individually and as a mixture under different applied voltages and ion concentrations. It was found that CDI could effectively remove these metals, and the performance was positively correlated with the applied voltage. When 1.2 V was applied into solution containing 0.5mM individual ions, the Cd(2+), Pb(2+), and Cr(3+) removal was 32%, 43%, and 52%, respectively, and the electrosorption played a bigger role in Cd(2+) removal than for the other two ions. Interestingly, while the removal of Pb(2+) and Cr(3+) remained at a similar level of 46% in the mixture of three ions, the Cd(2+) removal significantly decreased to 14%. Similar patterns were observed when 0.05 mM was used to simulate natural contaminated water condition, but the removal efficiencies were much higher, with the removal of Pb(2+), Cr(3+), and Cd(2+) increased to 81%, 78%, and 42%, respectively. The low valence charge and lack of physical sorption of Cd(2+) were believed to be the reason for the removal behavior, and advanced microscopic analysis showed clear deposits of metal ions on the cathode surface after operation. PMID:26476320

  4. Increasing Metal Fracture Toughness

    NASA Technical Reports Server (NTRS)

    Lawing, P. L.; Wood, W. H.; Sandefur, P. G. J.

    1982-01-01

    In technique developed at Langley Research Center several thin sheets of metal are diffusion-brazed together in vacuum furnace to create thick piece of metal that retains much of fracture toughness of its thin components. Technique is expected to make many of high-strength stainless steels, not currently suitable, usable at cryogenic temperatures.

  5. Senior Centers

    MedlinePlus Videos and Cool Tools

    ... something many older adults would like to do as long as they can. Senior centers, adult day care, transportation, ... adults who live independently can go to find a variety of social and recreational activities. [Karen Albers] ...

  6. Heteroleptic Ir(iii) and Pt(ii) complexes based on 2-(2,4-difluorophenyl)-pyridine and bisthienylethene BrLH: the influence of the metal center on structures, luminescence and photochromism.

    PubMed

    Gong, Dan-Ping; Cao, Deng-Ke

    2016-05-31

    Heteroleptic complexes [Ir(dfppy)2(BrL)]·3CH3OH () and [Pt(dfppy)(BrL)]·CH3OH () have been prepared based on the same ligands including bisthienylethene BrLH and dfppyH = (2-(2,4-difluorophenyl)-pyridine). Complexes and reveal distinct crystal structures. The BrL(-) anion uses its phenol-imidazole moiety to coordinate with an {Ir(dfppy)2}(+) unit in the former, while with a {Pt(dfppy)}(+) unit in the latter. Neighboring [Ir(dfppy)2(BrL)]/[Pt(dfppy)(BrL)] molecules are connected through extensive hydrogen bonds and aromatic stacking interactions, thus forming a supramolecular chain structure in , and a layer structure in . Upon irradiation with 380 nm light, compound shows photochromic behavior in CH2Cl2, with a color change from nearly colorless to light green. However, no photochromism was observed in compound . At room temperature, compound reveals phosphorescence with a predominant (3)MLCT character both in CH2Cl2 solution (emissions at 495 and 513 nm) and in the solid state (emission at 524 nm). Compound exhibits phosphorescence with a predominant (3)LC character in CH2Cl2 solution (emission at 508 nm), but it is almost non-luminescent in the solid state. Our experimental results demonstrate that the metal centers in and could significantly influence their structures, photochromism, and luminescence behaviors. PMID:27184525

  7. Children's cancer centers

    MedlinePlus

    Pediatric cancer center; Pediatric oncology center; Comprehensive cancer center ... from getting the care your child needs. The Pediatric Oncology Resource Center has links and contact information ...

  8. The materials processing research base of the Materials Processing Center

    NASA Technical Reports Server (NTRS)

    Flemings, M. C.; Bowen, H. K.; Kenney, G. B.

    1980-01-01

    The goals and activities of the center are discussed. The center activities encompass all engineering materials including metals, ceramics, polymers, electronic materials, composites, superconductors, and thin films. Processes include crystallization, solidification, nucleation, and polymer synthesis.

  9. Comparative Evaluation of Friction Resistance of Titanium, Stainless Steel, Ceramic and Ceramic with Metal Insert Brackets with Varying Dimensions of Stainless Steel Wire: An In vitro Multi-center Study

    PubMed Central

    Kumar, B Sunil; Miryala, Suresh; Kumar, K Kiran; Shameem, K; Regalla, Ravindra Reddy

    2014-01-01

    Background: The orthodontist seeks an archwire–bracket combination that has both good biocompatibility and low friction. Hence, the aim of this multicenter in vitro study was to evaluate and compare the frictional resistance generated between titanium (Ti), stainless steel (SS), ceramic and ceramic with metal insert (CMI) brackets with SS wires of varying dimensions in a specially designed apparatus. Materials and Methods: The material used in this study were Ti, SS, Ceramic and CMI with 0.018″ slot manufactured with zero degree tip and −7° torque premolar brackets (3M, Unitek) and SS wires of varying dimensions (0.016″ round, 0.016 × 0.016″ square, 0.016 × 0.022″ rectangular and 0.017 × 0.025″ rectangular) used. The frictional resistance was measured using Instron Universal testing machine (Model no. 4301). The specimen population in each center composed each of 160 brackets and wires. Differences among the all bracket/wire combinations were tested using (one-way) ANOVA, followed by the student Newman Keuls multiple comparisons of means ranking (at P < 0.05) for the determination of differences among the groups. Results: Ti bracket in combination with 0.017 × 0.025″ SS rectangular wire produced significant force levels for an optimum orthodontic movement with least frictional resistance. Conclusion: Ti brackets have least resistance and rectangular wires produced significant force. These can be used to avoid hazards of Nickel. SS brackets revealed higher static frictional force values as the wire dimension increased and showed lower static friction than Ti brackets for all wires except the thicker wire. Our study recommends the preclusion of brackets with rough surface texture (Ti brackets) with SS ligature wire for ligating bracket and archwire are better to reduce friction. PMID:25395796

  10. National Health Information Center

    MedlinePlus

    ... About ODPHP National Health Information Center National Health Information Center The National Health Information Center (NHIC) is ... of interest View the NHO calendar . Federal Health Information Centers and Clearinghouses Federal Health Information Centers and ...

  11. Low valency in lanthanides: A theoretical study of NdF and LuF

    SciTech Connect

    Schoendorff, George; Wilson, Angela K.

    2014-06-14

    The ground and low-lying excited state potential energy curves of neodymium monofluoride were calculated using multireference (CASSCF) and single reference (EOM-CR-CCSD(T)) methods. Optimized bond lengths were obtained and accurate bond dissociation energies were computed. The EOM-CR-CCSD(T) method was used to determine the bond dissociation energy of lutetium monofluoride, and it is shown that core correlation is required to produce bond dissociation energies in agreement with experiment.

  12. Homochiral metal phosphonate nanotubes.

    PubMed

    Liu, Xun-Gao; Bao, Song-Song; Huang, Jian; Otsubo, Kazuya; Feng, Jian-Shen; Ren, Min; Hu, Feng-Chun; Sun, Zhihu; Zheng, Li-Min; Wei, Shiqiang; Kitagawa, Hiroshi

    2015-10-21

    A new type of homochiral metal-organic nanotubular structures based on metal phosphonates are reported, namely, (R)- or (S)-[M(pemp)(H2O)2][M = Co(II) (1), Ni(II) (2)] [pemp(2-) = (R)- or (S)-(1-phenylethylamino)methylphosphonate]. In these compounds, the tube-walls are purely inorganic, composed of metal ions and O-P-O bridges. The cavity of the nanotube is hydrophilic with one coordination water pointing towards the center, while the outer periphery of the nanotube is hydrophobic, decorated by the phenylethyl groups of pemp(2-). The thermal stabilities, adsorption and proton conductivity properties are investigated. PMID:26324662

  13. Concurrent engineering research center

    NASA Technical Reports Server (NTRS)

    Callahan, John R.

    1995-01-01

    The projects undertaken by The Concurrent Engineering Research Center (CERC) at West Virginia University are reported and summarized. CERC's participation in the Department of Defense's Defense Advanced Research Project relating to technology needed to improve the product development process is described, particularly in the area of advanced weapon systems. The efforts committed to improving collaboration among the diverse and distributed health care providers are reported, along with the research activities for NASA in Independent Software Verification and Validation. CERC also takes part in the electronic respirator certification initiated by The National Institute for Occupational Safety and Health, as well as in the efforts to find a solution to the problem of producing environment-friendly end-products for product developers worldwide. The 3M Fiber Metal Matrix Composite Model Factory Program is discussed. CERC technologies, facilities,and personnel-related issues are described, along with its library and technical services and recent publications.

  14. Metal aminoboranes

    DOEpatents

    Burrell, Anthony K.; Davis, Benjamin J.; Thorn, David L.; Gordon, John C.; Baker, R. Thomas; Semelsberger, Troy Allen; Tumas, William; Diyabalanage, Himashinie Vichalya Kaviraj; Shrestha, Roshan P.

    2010-05-11

    Metal aminoboranes of the formula M(NH.sub.2BH.sub.3).sub.n have been synthesized. Metal aminoboranes are hydrogen storage materials. Metal aminoboranes are also precursors for synthesizing other metal aminoboranes. Metal aminoboranes can be dehydrogenated to form hydrogen and a reaction product. The reaction product can react with hydrogen to form a hydrogen storage material. Metal aminoboranes can be included in a kit.

  15. General Preparation of Three-Dimensional Porous Metal Oxide Foams Coated with Nitrogen-Doped Carbon for Enhanced Lithium Storage.

    PubMed

    Lu, Ke; Xu, Jiantie; Zhang, Jintao; Song, Bin; Ma, Houyi

    2016-07-13

    Porous metal oxide architectures coated with a thin layer of carbon are attractive materials for energy storage applications. Here, a series of porous metal oxide (e.g., vanadium oxides, molybdenum oxides, manganese oxides) foams with/without nitrogen-doped carbon (N-C) coating have been synthesized via a general surfactant-assisted template method, involving the formation of porous metal oxides coated with 1-hexadecylamine (HDA) and a subsequent thermal treatment. The presence of HDA is of importance for the formation of a porous structure, and the successive pyrolysis of such a nitrogen-containing surfactant generates nitrogen-doped carbon (N-C) coated on the surface of metal oxides, which also provides a facile way to adjust the valence states of metal oxides via the carbothermal reduction reaction. When used as electrode materials, the highly porous metal oxides with N-C coating exhibited enhanced performance for lithium ion storage, thanks to the unique 3D structures associated with highly porous structure and thin N-C coating. Typically, the porous metal oxides (V2O5, MoO3, MnO2) exhibited discharge capacities of 286, 303, and 463 mAh g(-1) at current densities of 30 and 100 mA g(-1), respectively. In contrast, the metal oxides with low valences and carbon coating (VO2@N-C, MoO2@N-C, and MnO@N-C) exhibited improved capacities of 461, 613, and 892 mAh g(-1). The capacity retentions of about 87.5, 80.2, and 85.0% for VO2@N-C, MoO2@N-C, and MnO@N-C were achieved after 600 cycles, suggesting the acceptable cycling stability. The present strategy would provide general guidance for preparing porous metal oxide foams with enhanced lithium storage performances. PMID:27322176

  16. Bond-Energy and Surface-Energy Calculations in Metals

    ERIC Educational Resources Information Center

    Eberhart, James G.; Horner, Steve

    2010-01-01

    A simple technique appropriate for introductory materials science courses is outlined for the calculation of bond energies in metals from lattice energies. The approach is applied to body-centered cubic (bcc), face-centered cubic (fcc), and hexagonal-closest-packed (hcp) metals. The strength of these bonds is tabulated for a variety metals and is…

  17. Children's cancer centers

    MedlinePlus

    Pediatric cancer center; Pediatric oncology center; Comprehensive cancer center ... Treating childhood cancer is not the same as treating adult cancer. The cancers are different. So are the treatments and the ...

  18. Fireworks Information Center

    MedlinePlus

    ... Home / Safety Education / Safety Education Centers En Español Fireworks Information Center This is an information center on ... Video Put Safety First This Fourth of July Fireworks Information What are consumer fireworks and where are ...

  19. The Watergate Learning Center

    ERIC Educational Resources Information Center

    Training in Business and Industry, 1971

    1971-01-01

    The Watergate Learning Center, recently opened by Sterling Learning Center in Washington, D. C., blueprints the plan established by Sterling and Marriott Hotels for a national chain of learning centers with much the same facilities. (EB)

  20. Alkali-metal azides interacting with metal-organic frameworks.

    PubMed

    Armata, Nerina; Cortese, Remedios; Duca, Dario; Triolo, Roberto

    2013-01-14

    Interactions between alkali-metal azides and metal-organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η(2) coordination mode are more favored. PMID:23161861

  1. Casimir Repulsion between Metallic Objects in Vacuum

    SciTech Connect

    Levin, Michael; McCauley, Alexander P.; Rodriguez, Alejandro W.; Reid, M. T. Homer; Johnson, Steven G.

    2010-08-27

    We give an example of a geometry in which two metallic objects in vacuum experience a repulsive Casimir force. The geometry consists of an elongated metal particle centered above a metal plate with a hole. We prove that this geometry has a repulsive regime using a symmetry argument and confirm it with numerical calculations for both perfect and realistic metals. The system does not support stable levitation, as the particle is unstable to displacements away from the symmetry axis.

  2. Design of dinuclear manganese cofactors for bacterial reaction centers.

    PubMed

    Olson, Tien L; Espiritu, Eduardo; Edwardraja, Selvakumar; Simmons, Chad R; Williams, JoAnn C; Ghirlanda, Giovanna; Allen, James P

    2016-05-01

    A compelling target for the design of electron transfer proteins with novel cofactors is to create a model for the oxygen-evolving complex, a Mn4Ca cluster, of photosystem II. A mononuclear Mn cofactor can be added to the bacterial reaction center, but the addition of multiple metal centers is constrained by the native protein architecture. Alternatively, metal centers can be incorporated into artificial proteins. Designs for the addition of dinuclear metal centers to four-helix bundles resulted in three artificial proteins with ligands for one, two, or three dinuclear metal centers able to bind Mn. The three-dimensional structure determined by X-ray crystallography of one of the Mn-proteins confirmed the design features and revealed details concerning coordination of the Mn center. Electron transfer between these artificial Mn-proteins and bacterial reaction centers was investigated using optical spectroscopy. After formation of a light-induced, charge-separated state, the experiments showed that the Mn-proteins can donate an electron to the oxidized bacteriochlorophyll dimer of modified reaction centers, with the Mn-proteins having additional metal centers being more effective at this electron transfer reaction. Modeling of the structure of the Mn-protein docked to the reaction center showed that the artificial protein likely binds on the periplasmic surface similarly to cytochrome c2, the natural secondary donor. Combining reaction centers with exogenous artificial proteins provides the opportunity to create ligands and investigate the influence of inhomogeneous protein environments on multinuclear redox-active metal centers. This article is part of a Special Issue entitled Biodesign for Bioenergetics - the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson. PMID:26392146

  3. Metal inks

    DOEpatents

    Ginley, David S; Curtis, Calvin J; Miedaner, Alex; van Hest, Marinus Franciscus Antonius Maria; Kaydanova, Tatiana

    2014-02-04

    Self-reducing metal inks and systems and methods for producing and using the same are disclosed. In an exemplary embodiment, a method may comprise selecting metal-organic (MO) precursor, selecting a reducing agent, and dissolving the MO precursor and the reducing agent in an organic solvent to produce a metal ink that remains in a liquid phase at room temperature. Metal inks, including self-reducing and fire-through metal inks, are also disclosed, as are various applications of the metal inks.

  4. AFRD WAREHOUSE, SOUTH SIDE. FACING NORTH. METAL AWNING ALONG LENGTH ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    AFRD WAREHOUSE, SOUTH SIDE. FACING NORTH. METAL AWNING ALONG LENGTH OF BUILDING AND VERTICAL METAL SIDING ARE ALTERATIONS MAD BY THE AFRD. - Minidoka Relocation Center Warehouse, 111 South Fir Street, Shoshone, Lincoln County, ID

  5. Adsorption of two gas molecules at a single metal site in a metal-organic framework.

    PubMed

    Runčevski, Tomče; Kapelewski, Matthew T; Torres-Gavosto, Rodolfo M; Tarver, Jacob D; Brown, Craig M; Long, Jeffrey R

    2016-07-01

    One strategy to markedly increase the gas storage capacity of metal-organic frameworks is to introduce coordinatively-unsaturated metal centers capable of binding multiple gas molecules. Herein, we provide an initial demonstration that a single metal site within a framework can support the terminal coordination of two gas molecules-specifically hydrogen, methane, or carbon dioxide. PMID:27284590

  6. Metallization failures

    NASA Technical Reports Server (NTRS)

    Beatty, R.

    1971-01-01

    Metallization-related failure mechanisms were shown to be a major cause of integrated circuit failures under accelerated stress conditions, as well as in actual use under field operation. The integrated circuit industry is aware of the problem and is attempting to solve it in one of two ways: (1) better understanding of the aluminum system, which is the most widely used metallization material for silicon integrated circuits both as a single level and multilevel metallization, or (2) evaluating alternative metal systems. Aluminum metallization offers many advantages, but also has limitations particularly at elevated temperatures and high current densities. As an alternative, multilayer systems of the general form, silicon device-metal-inorganic insulator-metal, are being considered to produce large scale integrated arrays. The merits and restrictions of metallization systems in current usage and systems under development are defined.

  7. Remote Operations Control Center (ROCC)

    NASA Technical Reports Server (NTRS)

    1997-01-01

    Undergraduate students Kristina Wines and Dena Renzo at Rensselaer Poloytech Institute (RPI) in Troy, NY, monitor the progress of the Isothermal Dendritic Growth Experiment (IDGE) during the U.S. Microgravity Payload-4 (USMP-4) mission (STS-87), Nov. 19 - Dec.5, 1997). Remote Operations Control Center (ROCC) like this one will become more common during operations with the International Space Station. The Isothermal Dendritic Growth Experiment (IDGE), flown on three Space Shuttle missions, is yielding new insights into virtually all industrially relevant metal and alloy forming operations. Photo credit: Rensselaer Polytechnic Institute (RPI)

  8. Dryden Flight Research Center: Center Overview

    NASA Technical Reports Server (NTRS)

    Ratnayake, Nalin

    2009-01-01

    This viewgraph presentation describes a general overview of Dryden Flight Research Center. Strategic partnerships, Dryden's mission activity, exploration systems and aeronautics research programs are also described.

  9. METAL PHTHALOCYANINES

    DOEpatents

    Frigerio, N.A.

    1962-03-27

    A process is given for preparing heavy metal phthalocyanines, sulfonated or not. The process comprises mixing an inorganic metal salt with dimethyl formamide or methyl sulfoxide; separating the metal complex formed from the solution; mixing the complex with an equimolar amount of sodium, potassium, lithium, magnesium, or beryllium sulfonated or unsulfonated phthalocyanine whereby heavy-metal phthalocyanine crystals are formed; and separating the crystals from the solution. Uranyl, thorium, lead, hafnium, and lanthanide rare earth phthalocyanines can be produced by the process. (AEC)

  10. Student Success Center Toolkit

    ERIC Educational Resources Information Center

    Jobs For the Future, 2014

    2014-01-01

    "Student Success Center Toolkit" is a compilation of materials organized to assist Student Success Center directors as they staff, launch, operate, and sustain Centers. The toolkit features materials created and used by existing Centers, such as staffing and budgeting templates, launch materials, sample meeting agendas, and fundraising…

  11. Opportunities Center. Concept Paper.

    ERIC Educational Resources Information Center

    Kimeldorf, Martin

    The opportunities center is a new school service concept that can help students find opportunities related to their talents and interests in work, education, leisure, small business, or community service. The opportunities center model expands the career center model into an information search center offering multiple services that link academic…

  12. PRB CHEMISTRY CASE STUDY: DENVER FEDERAL CENTER

    EPA Science Inventory

    The Denver Federal Center permeable reactive barrier is a funnel-and-gate system with four reactive gates, each separated by up to about 120 m of metal sheet pile. In this study, ground water sampling, core collection, and solid phase characterization studies were carried out in...

  13. Silicone metalization

    DOEpatents

    Maghribi, Mariam N.; Krulevitch, Peter; Hamilton, Julie

    2006-12-05

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  14. Silicone metalization

    DOEpatents

    Maghribi, Mariam N.; Krulevitch, Peter; Hamilton, Julie

    2008-12-09

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  15. Alkali Metal Handling Practices at NASA MSFC

    NASA Technical Reports Server (NTRS)

    Salvail, Patrick G.; Carter, Robert R.

    2002-01-01

    NASA Marshall Space Flight Center (MSFC) is NASA s principle propulsion development center. Research and development is coordinated and carried out on not only the existing transportation systems, but also those that may be flown in the near future. Heat pipe cooled fast fission cores are among several concepts being considered for the Nuclear Systems Initiative. Marshall Space Flight Center has developed a capability to handle high-purity alkali metals for use in heat pipes or liquid metal heat transfer loops. This capability is a low budget prototype of an alkali metal handling system that would allow the production of flight qualified heat pipe modules or alkali metal loops. The processing approach used to introduce pure alkali metal into heat pipe modules and other test articles are described in this paper.

  16. ACTS data center

    NASA Astrophysics Data System (ADS)

    Syed, Ali; Vogel, Wolfhard J.

    1993-08-01

    Viewgraphs on ACTS Data Center status report are included. Topics covered include: ACTS Data Center Functions; data flow overview; PPD flow; RAW data flow; data compression; PPD distribution; RAW Data Archival; PPD Audit; and data analysis.

  17. Taking Center Stage.

    ERIC Educational Resources Information Center

    Cohen, Andrew

    1995-01-01

    Describes Ohio's 390,000 square-foot Perry High School and Community Fitness Center and its ability to accommodate all segments of both school and community group activities. A list of companies that supply the center is included. (GR)

  18. Marketing Your Advising Center.

    ERIC Educational Resources Information Center

    Flickinger, Jan

    1989-01-01

    A tour of centralized university advising centers revealed that the busiest centers had done an excellent job of marketing themselves to their campus clientele. Factors affecting successful marketing include image, location, service, advertising, and innovative problem-solving. (MSE)

  19. BKG Data Center

    NASA Technical Reports Server (NTRS)

    Thorandt, Volkmar; Wojdziak, Reiner

    2013-01-01

    This report summarizes the activities and background information of the IVS Data Center for the year 2012. Included is information about functions, structure, technical equipment, and staff members of the BKG Data Center.

  20. ACTS data center

    NASA Technical Reports Server (NTRS)

    Syed, Ali; Vogel, Wolfhard J.

    1993-01-01

    Viewgraphs on ACTS Data Center status report are included. Topics covered include: ACTS Data Center Functions; data flow overview; PPD flow; RAW data flow; data compression; PPD distribution; RAW Data Archival; PPD Audit; and data analysis.

  1. Regional Instrumentation Centers.

    ERIC Educational Resources Information Center

    Cromie, William J.

    1980-01-01

    Focuses on the activities of regional instrumentation centers that utilize the state-of-the-art instruments and methodology in basic scientific research. The emphasis is on the centers involved in mass spectroscopy, magnetic resonance spectroscopy, lasers, and accelerators. (SA)

  2. NIST Diffusion Data Center

    National Institute of Standards and Technology Data Gateway

    NIST Diffusion Data Center (Web, free access)   The NIST Diffusion Data Center is a collection of over 14,100 international papers, theses, and government reports on diffusion published before 1980.

  3. Tornadoes: A Center Approach.

    ERIC Educational Resources Information Center

    Christman-Rothlein, Liz; Meinbach, Anita M.

    1981-01-01

    Information is given on how to put together a learning center. Discusses information and activity packets for a complete learning center on tornadoes including objectives, directions, materials, photographs of physical arrangements, and posttest. (DC)

  4. National Health Information Center

    MedlinePlus

    ... About ODPHP Dietary Guidelines Physical Activity Guidelines Health Literacy and Communication Health Care Quality and Patient Safety Healthy People healthfinder health.gov About ODPHP National Health Information Center National Health Information Center The National Health ...

  5. Data Center Tasking.

    ERIC Educational Resources Information Center

    Temares, M. Lewis; Lutheran, Joseph A.

    Operations tasking for data center management is discussed. The original and revised organizational structures of the data center at the University of Miami are also described. The organizational strategy addresses the functions that should be performed by the data center, anticipates the specialized skills required, and addresses personnel…

  6. Center for Instructional Computing.

    ERIC Educational Resources Information Center

    American Association of State Colleges and Universities, Washington, DC.

    The Center for Instructional Computing (CIC) at Eastern Michigan University is described in this report. The center serves as a model for making the infusion of innovative uses of microcomputers within instruction a faculty-centered effort. CIC provides a physical facility with IBM and Apple microcomputers dedicated to faculty use, both as a…

  7. Nuclear Reaction Data Centers

    SciTech Connect

    McLane, V.; Nordborg, C.; Lemmel, H.D.; Manokhin, V.N.

    1988-01-01

    The cooperating Nuclear Reaction Data Centers are involved in the compilation and exchange of nuclear reaction data for incident neutrons, charged particles and photons. Individual centers may also have services in other areas, e.g., evaluated data, nuclear structure and decay data, reactor physics, nuclear safety; some of this information may also be exchanged between interested centers. 20 refs., 1 tab.

  8. Language Resource Centers Program

    ERIC Educational Resources Information Center

    Office of Postsecondary Education, US Department of Education, 2012

    2012-01-01

    The Language Resource Centers (LRC) program provides grants to institutions of higher education to establish, strengthen, and operate resource centers that serve to improve the nation's capacity to teach and learn foreign languages. Eligible applicants are institutions of higher education. Duration of the grant is four years. Center activities…

  9. Data center cooling method

    DOEpatents

    Chainer, Timothy J.; Dang, Hien P.; Parida, Pritish R.; Schultz, Mark D.; Sharma, Arun

    2015-08-11

    A method aspect for removing heat from a data center may use liquid coolant cooled without vapor compression refrigeration on a liquid cooled information technology equipment rack. The method may also include regulating liquid coolant flow to the data center through a range of liquid coolant flow values with a controller-apparatus based upon information technology equipment temperature threshold of the data center.

  10. CNC electrical discharge machining centers

    SciTech Connect

    Jaggars, S.R.

    1991-10-01

    Computer numerical control (CNC) electrical discharge machining (EDM) centers were investigated to evaluate the application and cost effectiveness of establishing this capability at Allied-Signal Inc., Kansas City Division (KCD). In line with this investigation, metal samples were designed, prepared, and machined on an existing 15-year-old EDM machine and on two current technology CNC EDM machining centers at outside vendors. The results were recorded and evaluated. The study revealed that CNC EDM centers are a capability that should be established at KCD. From the information gained, a machine specification was written and a shop was purchased and installed in the Engineering Shop. The older machine was exchanged for a new model. Additional machines were installed in the Tool Design and Fabrication and Precision Microfinishing departments. The Engineering Shop machine will be principally used for the following purposes: producing deep cavities in small corner radii, machining simulated casting models, machining difficult-to-machine materials, and polishing difficult-to-hand polish mold cavities. 2 refs., 18 figs., 3 tabs.

  11. Human Motion Tracking at Marshall Space Flight Center's Collaborative Engineering Center ANVIL

    NASA Technical Reports Server (NTRS)

    Henderson, Steven J.; Hamilton, George S.

    2004-01-01

    The installation and use of electromagnetic human motion trackers requires a specially designed and metal-free environment for optimal performance. Such an area is not readily available at the Marshall Space Flight Center Collaborative Engineering Center ANVIL. Our paper details a systems engineering approach to installing and operating Ascension Technologies Ethernet MotionStar tracking system in a sub-optimal environment, used with the JACK human computer model's motion capture capabilities. We also discuss how this system is integrated into the Marshall Space Flight Center's Human Engineering process.

  12. Plasmonic Roche lobe in metal-dielectric-metal structure

    SciTech Connect

    Shiu, Ruei-Cheng; Lan, Yung-Chiang

    2013-07-15

    This study investigates a plasmonic Roche lobe that is based on a metal-dielectric-metal (MDM) structure using finite-difference time-domain simulations and theoretical analyses. The effective refractive index of the MDM structure has two centers and is inversely proportional to the distance from the position of interest to the centers, in a manner that is analogous to the gravitational potential in a two-star system. The motion of surface plasmons (SPs) strongly depends on the ratio of permittivities at the two centers. The Lagrange point is an unstable equilibrium point for SPs that propagate in the system. After the SPs have passed through the Lagrange point, their spread drastically increases.

  13. Metal Detectors.

    ERIC Educational Resources Information Center

    Harrington-Lueker, Donna

    1992-01-01

    Schools that count on metal detectors to stem the flow of weapons into the schools create a false sense of security. Recommendations include investing in personnel rather than hardware, cultivating the confidence of law-abiding students, and enforcing discipline. Metal detectors can be quite effective at afterschool events. (MLF)

  14. Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal {beta} Double-Prime -(BEDT-TTF){sub 4}H{sub 3}O[Fe(C{sub 2}O{sub 4}){sub 3}] {center_dot} C{sub 6}H{sub 4}Cl{sub 2}

    SciTech Connect

    Zorina, L. V.; Prokhorova, T. G.; Simonov, S. V. Khasanov, S. S.; Shibaeva, R. P.; Manakov, A. I.; Zverev, V. N.; Buravov, L. I.; Yagubskii, E. B.

    2008-02-15

    The {beta} Double-Prime -(BEDT-TTF){sub 4}A{sup I}[M{sup III}(C{sub 2}O{sub 4}){sub 3}] {center_dot} G(A{sup I}=NH{sub 4}{sup +}, H{sub 3}O{sup +}, K{sup +}, Rb{sup +}; M{sup III}=Fe, Cr; G = 'guest' solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C{sub 6}H{sub 4}Cl{sub 2})-containing conductor of this family, namely, {beta} Double-Prime -(BEDT-TTF){sub 4}H{sub 3}O[Fe(C{sub 2}O{sub 4}){sub 3}] {center_dot} C{sub 6}H{sub 4}Cl{sub 2}, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) A, b= 19.991(2) A, c= 35.441(3) A, {beta} = 92.87(1) Degree-Sign , V= 7374(1) A{sup 3}, space groupC2/c, and Z = 4. In the temperature range 0.5 and 2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the {beta} Double-Prime -(BEDT-TTF){sub 4}A{sup I}[M{sup III}(C{sub 2}O{sub 4}){sub 3}] {center_dot} G crystals are analyzed.

  15. Comparison of Bare-Metal Stent and Drug-Eluting Stent for the Treatment of Patients Undergoing Percutaneous Coronary Intervention for Unprotected Left Main Coronary Artery Disease – Long-Term Result from a Single Center Experience

    PubMed Central

    Lai, Chih-Hung; Lee, Wen-Lieng; Sung, Shih-Hsien; Hsu, Pai-Feng; Chen, Ying-Hwa; Chan, Wan-Leong; Lin, Shing-Jong; Lu, Tse-Min

    2015-01-01

    Background Percutaneous coronary intervention (PCI) has become an alternative treatment for left main (LM) coronary artery disease. The aim of our study was to compare long-term clinical outcomes of patients undergoing unprotected LM PCI with bare-metal stent (BMS) or drug-eluting stent (DES) in a high-risk population. Methods and Results We enrolled 223 consecutive patients with unprotected LM coronary artery disease undergoing PCI (mean age: 71.1 ± 11.2 years, 187 male), including 94 patients receiving BMS and 129 patients receiving DES. The patients receiving DES had a significantly higher SYNTAX score (p = 0.05). During the mean follow-up period of 2.5 years, there were 31 cardiovascular deaths (BMS: 21 cases, DES: 10 cases, p = 0.04 by log-rank test), 56 major adverse cardiovascular events (MACE, including cardiovascular death, non-fatal myocardial infarction (MI) and clinical-driven target lesion revascularization; BMS: 33 cases, DES: 23 cases, p = 0.03 by log-rank test) and 6 cases with definite/probable stent thrombosis (BMS: 5 cases, DES: 1 cases, p = 0.09). In multivariate Cox analysis, the use of DES was identified as an independent protective factor against cardiovascular death [hazard ratio (HR) = 0.34, 95% confidence interval (Cl) = 0.15-0.79, p = 0.01] and MACE (HR = 0.50, 95% CI = 0.28-0.88, p = 0.02). The clinical outcome analyses in propensity-score matched the cohort (87 matched pair of patients receiving BMS and DES) and yielded similar results. Conclusions In the general practice among a high-risk population undergoing unprotected LM PCI, the use of DES appeared to be beneficial in reducing the risk of long-term cardiovascular death and MACE. PMID:27122897

  16. Emergency Operations Center at Johnson Space Center

    NASA Technical Reports Server (NTRS)

    Caylor, Gary C.

    1997-01-01

    In June 1966, at the start of the Gulf Coast hurricane season, the Johnson Space Center (JSC) celebrated the opening of its new 4,000-square foot, state-of-the-art Emergency Operations Center (EOC). The new EOC has been upgraded and enhanced to support a wide spectrum of emergencies affecting JSC and neighboring communities. One of the main features of the EOC is its premier computerized dispatch center. The new system unites many of JSC's critical emergency functions into one integrated network. It automatically monitors fire alarms, security entrances, and external cameras. It contains the JSC inventory of hazardous materials, by building and room, and can call up Material Safety Data Sheets for most of the generic hazardous materials used on-site. The EOC is available for community use during area emergencies such as hurricanes and is a welcome addition to the Clear Lake/Galveston Bay Area communities' emergency response resources.

  17. Spin-lattice relaxation of coupled metal-radical spin-dimers in proteins: application to Fe(2+)-cofactor (Q(A)(-.), Q(B)(-.), phi(-.)) dimers in reaction centers from photosynthetic bacteria.

    PubMed Central

    Calvo, Rafael; Isaacson, Roger A; Abresch, Edward C; Okamura, Melvin Y; Feher, George

    2002-01-01

    The spin-lattice relaxation times (T(1)) for the reduced quinone acceptors Q(A)(-.) and Q(B)(-.), and the intermediate pheophytin acceptor phi(-.), were measured in native photosynthetic reaction centers (RC) containing a high spin Fe(2+) (S = 2) and in RCs in which Fe(2+) was replaced by diamagnetic Zn(2+). From these data, the contribution of the Fe(2+) to the spin-lattice relaxation of the cofactors was determined. To relate the spin-lattice relaxation rate to the spin-spin interaction between the Fe(2+) and the cofactors, we developed a spin-dimer model that takes into account the zero field splitting and the rhombicity of the Fe(2+) ion. The relaxation mechanism of the spin-dimer involves a two-phonon process that couples the fast relaxing Fe(2+) spin to the cofactor spin. The process is analogous to the one proposed by R. Orbach (Proc. R. Soc. A. (Lond.). 264:458-484) for rare earth ions. The spin-spin interactions are, in general, composed of exchange and dipolar contributions. For the spin dimers studied in this work the exchange interaction, J(o), is predominant. The values of J(o) for Q(A)(-.)Fe(2+), Q(B)(-.)Fe(2+), and phi(-.)Fe(2+) were determined to be (in kelvin) -0.58, -0.92, and -1.3 x 10(-3), respectively. The |J(o)| of the various cofactors (obtained in this work and those of others) could be fitted with the relation exp(-beta(J)d), where d is the distance between cofactor spins and beta(J) had a value of (0.66-0.86) A(-1). The relation between J(o) and the matrix element |V(ij)|(2) involved in electron transfer rates is discussed. PMID:12414679

  18. Spin-lattice relaxation of coupled metal-radical spin-dimers in proteins: application to Fe(2+)-cofactor (Q(A)(-.), Q(B)(-.), phi(-.)) dimers in reaction centers from photosynthetic bacteria.

    PubMed

    Calvo, Rafael; Isaacson, Roger A; Abresch, Edward C; Okamura, Melvin Y; Feher, George

    2002-11-01

    The spin-lattice relaxation times (T(1)) for the reduced quinone acceptors Q(A)(-.) and Q(B)(-.), and the intermediate pheophytin acceptor phi(-.), were measured in native photosynthetic reaction centers (RC) containing a high spin Fe(2+) (S = 2) and in RCs in which Fe(2+) was replaced by diamagnetic Zn(2+). From these data, the contribution of the Fe(2+) to the spin-lattice relaxation of the cofactors was determined. To relate the spin-lattice relaxation rate to the spin-spin interaction between the Fe(2+) and the cofactors, we developed a spin-dimer model that takes into account the zero field splitting and the rhombicity of the Fe(2+) ion. The relaxation mechanism of the spin-dimer involves a two-phonon process that couples the fast relaxing Fe(2+) spin to the cofactor spin. The process is analogous to the one proposed by R. Orbach (Proc. R. Soc. A. (Lond.). 264:458-484) for rare earth ions. The spin-spin interactions are, in general, composed of exchange and dipolar contributions. For the spin dimers studied in this work the exchange interaction, J(o), is predominant. The values of J(o) for Q(A)(-.)Fe(2+), Q(B)(-.)Fe(2+), and phi(-.)Fe(2+) were determined to be (in kelvin) -0.58, -0.92, and -1.3 x 10(-3), respectively. The |J(o)| of the various cofactors (obtained in this work and those of others) could be fitted with the relation exp(-beta(J)d), where d is the distance between cofactor spins and beta(J) had a value of (0.66-0.86) A(-1). The relation between J(o) and the matrix element |V(ij)|(2) involved in electron transfer rates is discussed. PMID:12414679

  19. Study of high-temperature hydrogen reduced Pt0/TiO2 by X-ray photoelectron spectroscopy combined with argon ion sputtering—Diffusion-encapsulation effect in relation to strong metal-support interaction

    NASA Astrophysics Data System (ADS)

    Zhang, Jingwei; Zhang, Min; Jin, Zhensheng; Wang, Jingju; Zhang, Zhijun

    2012-02-01

    X-ray photoelectron spectroscopy combined with Ar+ ion sputtering has been used to analyze the variation in the valence and concentration of Pt, Ti, and O of Pt0/TiO2 reduced by H2 at elevated temperature. It is confirmed that titanium oxide of low-valence is transferred onto the surface of Pt0 particulates to encapsulate the surface via a strong metal-support interaction under reducing atmosphere. It is also found for the first time that Pt0 atom is diffused into the lattice of TiO2 to occupy the oxygen vacancy (VOrad rad ) and accept one electron from adjacent Ti3+ forming a localized Pt-sbnd Ti4+ bond. This differs from the strong metal-support interaction under oxidizing atmosphere. Namely, although the Pt0 atom is also diffused into the lattice of TiO2 under oxidizing atmosphere, it replaces Ti atom and forms a Pt2+sbnd O2- bond. Moreover, the strong metal-support interaction under oxidizing atmosphere results in increased photocatalytic activity of Pt0/TiO2, while the strong metal-support interaction under reducing atmosphere leads to decreased photocatalytic activity of Pt0/TiO2.

  20. Metal oxide films on metal

    DOEpatents

    Wu, Xin D.; Tiwari, Prabhat

    1995-01-01

    A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

  1. Noble metals in oncology

    PubMed Central

    Markowska, Anna; Jaszczyńska-Nowinka, Karolina; Lubin, Jolanta; Markowska, Janina

    2015-01-01

    Worldwide research groups are searching for anticancer compounds, many of them are organometalic complexes having platinum group metals as their active centers. Most commonly used cytostatics from this group are cisplatin, carboplatin and oxaliplatin. Cisplatin was used fot the first time in 1978, from this time many platinum derivatives were created. In this review we present biological properties and probable future clinical use of platinum, gold, silver, iridium and ruthenium derivatives. Gold derivative Auranofin has been studied extensively. Action of silver nanoparticles on different cell lines was analysed. Iridium isotopes are commonly used in brachyterapy. Ruthenium compound new anti-tumour metastasis inhibitor (NAMI-A) is used in managing lung cancer metastases. Electroporation of another ruthenium based compound KP1339 was also studied. Most of described complexes have antiproliferative and proapoptotic properties. Further studies need to be made. Nevertheless noble metal based chemotherapheutics and compounds seem to be an interesting direction of research. PMID:26557773

  2. Metal Coatings

    NASA Technical Reports Server (NTRS)

    1994-01-01

    During the Apollo Program, General Magnaplate Corporation developed process techniques for bonding dry lubricant coatings to space metals. The coatings were not susceptible to outgassing and offered enhanced surface hardness and superior resistance to corrosion and wear. This development was necessary because conventional lubrication processes were inadequate for lightweight materials used in Apollo components. General Magnaplate built on the original technology and became a leader in development of high performance metallurgical surface enhancement coatings - "synergistic" coatings, - which are used in applications from pizza making to laser manufacture. Each of the coatings is designed to protect a specific metal or group of metals to solve problems encountered under operating conditions.

  3. 13. SAC command center, weather center, underground structure, building 501, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    13. SAC command center, weather center, underground structure, building 501, undated - Offutt Air Force Base, Strategic Air Command Headquarters & Command Center, Command Center, 901 SAC Boulevard, Bellevue, Sarpy County, NE

  4. Test Control Center exhibit

    NASA Technical Reports Server (NTRS)

    2000-01-01

    Have you ever wondered how the engineers at John C. Stennis Space Center in Hancock County, Miss., test fire a Space Shuttle Main Engine? The Test Control Center exhibit at StenniSphere can answer your questions by simulating the test firing of a Space Shuttle Main Engine. A recreation of one of NASA's test control centers, the exhibit explains and portrays the 'shake, rattle and roar' that happens during a real test firing.

  5. Relativistic Guiding Center Equations

    SciTech Connect

    White, R. B.; Gobbin, M.

    2014-10-01

    In toroidal fusion devices it is relatively easy that electrons achieve relativistic velocities, so to simulate runaway electrons and other high energy phenomena a nonrelativistic guiding center formalism is not sufficient. Relativistic guiding center equations including flute mode time dependent field perturbations are derived. The same variables as used in a previous nonrelativistic guiding center code are adopted, so that a straightforward modifications of those equations can produce a relativistic version.

  6. Forensic Science Center

    SciTech Connect

    Andresen, B.; Grant, P.M.

    1994-03-01

    Since 1991, the Laboratory's Forensic Science Center has focused a comprehensive range of analytical expertise on issues related to non proliferation, counterterrorism, and domestic law enforcement. During this short period, LLNL's singular combination of human and technological resources has made the Center among the best of its kind in the world. The Forensic Science Center houses a variety of state-of-the-art analytical tools ranging from gas chromatograph/mass spectrometers to ultratrace DNA detection techniques. The Center's multidisciplinary staff provides expertise in organic and inorganic analytical chemistry, nuclear science, biochemistry, and genetics useful for supporting law enforcement and for verifying compliance with international treaties and agreements.

  7. Data Center at NICT

    NASA Technical Reports Server (NTRS)

    Ichikawa, Ryuichi; Sekido, Mamoru

    2013-01-01

    The Data Center at the National Institute of Information and Communications Technology (NICT) archives and releases the databases and analysis results processed at the Correlator and the Analysis Center at NICT. Regular VLBI sessions of the Key Stone Project VLBI Network were the primary objective of the Data Center. These regular sessions continued until the end of November 2001. In addition to the Key Stone Project VLBI sessions, NICT has been conducting geodetic VLBI sessions for various purposes, and these data are also archived and released by the Data Center.

  8. Metals 2000

    SciTech Connect

    Allison, S.W.; Rogers, L.C.; Slaughter, G.; Boensch, F.D.; Claus, R.O.; de Vries, M.

    1993-05-01

    This strategic planning exercise identified and characterized new and emerging advanced metallic technologies in the context of the drastic changes in global politics and decreasing fiscal resources. In consideration of a hierarchy of technology thrusts stated by various Department of Defense (DOD) spokesmen, and the need to find new and creative ways to acquire and organize programs within an evolving Wright Laboratory, five major candidate programs identified are: C-17 Flap, Transport Fuselage, Mach 5 Aircraft, 4.Fighter Structures, and 5. Missile Structures. These results were formed by extensive discussion with selected major contractors and other experts, and a survey of advanced metallic structure materials. Candidate structural applications with detailed metal structure descriptions bracket a wide variety of uses which warrant consideration for the suggested programs. An analysis on implementing smart skins and structures concepts is given from a metal structures perspective.

  9. Arc Casting Intermetallic Alloy (Materials Preparation Center)

    SciTech Connect

    2010-01-01

    Arc casting of intermetallic (La-Ni-Sn) AB5 alloy used for metal hydride hydrogen storage. Upon solidification the Sn is partially rejected and increases in concentration in the remaining liquid. Upon completing solidification there is a great deal of internal stress in the ingot. As the ingot cools further the stress is relieved. This material was cast at the Ames Laboratorys Materials Preparation Center http://www.mpc.ameslab.gov

  10. Funding Opportunity: Genomic Data Centers

    Cancer.gov

    Funding Opportunity CCG, Funding Opportunity Center for Cancer Genomics, CCG, Center for Cancer Genomics, CCG RFA, Center for cancer genomics rfa, genomic data analysis network, genomic data analysis network centers,

  11. Dialysis centers - what to expect

    MedlinePlus

    ... treatment. Many people have dialysis in a treatment center. This article focuses on hemodialysis at a treatment center. ... Artificial kidneys - dialysis centers - what to expect; Dialysis - what to expect; Renal replacement therapy - dialysis centers - what to expect

  12. Learner-Centered Education.

    ERIC Educational Resources Information Center

    O'Neil, Robert M.

    There is no clear consensus of the term "learner-centered reform." Learner-centered reform has become by implication either the cause or the consequence of inflated grades, lowered admission requirements, affirmative action, elimination of language and other requirements, student evaluation of teaching, abandonment of research, and many other ills…

  13. Finding Treatment Centers

    MedlinePlus

    ... to pull together and focus many kinds of research approaches on the cancer problem. The National Cancer Institute (NCI) Cancer Center Program has chosen more than 65 cancer centers that take part in research to help reduce cancer rates and deaths from ...

  14. Johnson Space Center

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    The Johnson Space Center (JSC) in Houston is NASA's lead center for the space shuttle and the International Space Station programs and for biomedical research. Areas of study include Earth sciences and solar system exploration, astromaterials and space medicine. About 14 000 people, including 3000 civil servants, work at JSC....

  15. Developing a Teacher Center.

    ERIC Educational Resources Information Center

    Parsons, Theodore W.

    This paper begins by outlining six functions of a teacher center that are seen as generally accepted and by remarking on certain realities, like the overworked teacher and dearth of funds, that are pertinent to establishing a teacher center. The majority of the text is devoted to an explanation of a large number of specific principles that should…

  16. Learning Resources Centers

    ERIC Educational Resources Information Center

    Powell, Len S.

    1974-01-01

    A learning resources center has three roles: storage and retrieval of learning media, creation and production of learning materials, and instruction and advice in the utilization of the facilities available. The design, purpose, and staffing of a resources center are discussed in detail in this article. (DS)

  17. Simple Machine Science Centers

    ERIC Educational Resources Information Center

    Chessin, Debby

    2007-01-01

    Science centers can engage students; accommodate different learning styles and individual interests; help students become independent and confident learners; and encourage social skills among students. In this article, the author worked with third-grade students as they completed activities at learning centers during a week-long unit on simple…

  18. GSFC VLBI Analysis center

    NASA Technical Reports Server (NTRS)

    Gordon, David; Ma, Chopo; MacMillan, Dan; Petrov, Leonid; Baver, Karen

    2005-01-01

    This report presents the activities of the GSFC VLBI Analysis Center during 2004. The GSFC Analysis Center analyzes all IVS sessions, makes regular IVS submissions of data and analysis products, and performs research and software development activities aimed at improving the VLBI technique.

  19. GSFC VLBI Analysis Center

    NASA Technical Reports Server (NTRS)

    Gordon, David; Ma, Chopo; MacMillan, Dan; Gipson, John; Bolotin, Sergei; Le Bail, Karine; Baver, Karen

    2013-01-01

    This report presents the activities of the GSFC VLBI Analysis Center during 2012. The GSFC VLBI Analysis Center analyzes all IVS sessions, makes regular IVS submissions of data and analysis products, and performs research and software development aimed at improving the VLBI technique.

  20. National Resource Centers Program

    ERIC Educational Resources Information Center

    Office of Postsecondary Education, US Department of Education, 2012

    2012-01-01

    The National Resource Centers Program provides grants to institutions of higher education to establish, strengthen, and operate comprehensive and undergraduate centers that are national resources for: (1) Teaching modern foreign languages, especially the less and least commonly taught languages; (2) Disciplinary instruction to provide a thorough…

  1. About the ADEAR Center

    MedlinePlus

    ... and news updates How to Contact the ADEAR Center Call toll-free at: 1-800-438-4380 (8: ... To give you the best possible service, ADEAR Center staff abide by the following customer service standards: We will answer your telephone calls promptly between 8:30 a.m. and 5: ...

  2. URBAN STUDIES CENTER.

    ERIC Educational Resources Information Center

    HEBOUT, JOHN E.

    THE CENTER WORKS WITH RUTGERS UNIVERSITY TO MAKE USE OF URBAN STUDIES IN APPROPRIATE RESEARCH AND TEACHING PROGRAMS AND IN OTHER INTELLECTUAL SERVICES TO THE COMMUNITY. THE FIVE MAIN RESPONSIBILITIES OF THE CENTER - EXTENSION, RESEARCH AND EDUCATION, LIBRARY SERVICES, OPPORTUNITIES EXPANSION PROJECT, AND THE URBAN FELLOWSHIP PROGRAM - ARE…

  3. National Technology Transfer Center

    NASA Technical Reports Server (NTRS)

    Rivers, Lee W.

    1992-01-01

    Viewgraphs on the National Technology Transfer Center (NTTC) are provided. The NTTC mission is to serve as a hub for the nationwide technology-transfer network to expedite the movement of federally developed technology into the stream of commerce. A description of the Center is provided.

  4. Early Childhood Centers

    ERIC Educational Resources Information Center

    Butin, Dan; Woolums, Jennifer

    2009-01-01

    Early childhood centers have become a common and necessary part of millions of Americans' lives. More women in the workforce, longer workweeks, and educational research supporting the importance of early education have all contributed to the rise of early childhood centers throughout the United States. Today, more than 30 percent of children under…

  5. NASA Propagation Information Center

    NASA Technical Reports Server (NTRS)

    Smith, Ernest K.; Flock, Warren L.

    1989-01-01

    The NASA Propagation Information Center became formally operational in July 1988. It is located in the Department of Electrical and Computer Engineering of the University of Colorado at Boulder. The Center is several things: a communications medium for the propagation with the outside world, a mechanism for internal communication within the program, and an aid to management.

  6. NASA propagation information center

    NASA Technical Reports Server (NTRS)

    Smith, Ernest K.; Flock, Warren L.

    1990-01-01

    The NASA Propagation Information Center became formally operational in July 1988. It is located in the Department of Electrical and Computer Engineering of the University of Colorado at Boulder. The center is several things: a communications medium for the propagation with the outside world, a mechanism for internal communication within the program, and an aid to management.

  7. Science Center and Attitude

    ERIC Educational Resources Information Center

    Daneshamooz, Saeed; Alamolhodaei, Hassan; Darvishian, Saeed; Daneshamooz, Soniya

    2013-01-01

    The project team gathered data with the assistance of Recreational and Cultural Organization of Mashhad Municipality, Organization of Mashhad Municipality and Science and Astronomy Science Center of Mashhad Municipality, Khorasan Razavi, Islamic Republic of Iran. This paper discusses the effect of science center on attitude of students who visit…

  8. Natural Science Centers: Directory.

    ERIC Educational Resources Information Center

    Natural Science for Youth Foundation, Roswell, GA.

    A nature center is defined as an organized and permanent nonprofit institution which is essentially educational, scientific, and cultural in purpose with professional staff, and open to the public on some regular schedule. A nature center manages and interprets its lands, native plants and animals and facilities to promote an understanding of…

  9. Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

    2015-03-01

    Hydrogen is the simplest and most abundant element in the Universe. At high pressure it is predicted to transform to a metal with remarkable properties: room temperature superconductivity, a metastable metal at ambient conditions, and a revolutionary rocket propellant. Both theory and experiment have been challenged for almost 80 years to determine its condensed matter phase diagram, in particular the insulator-metal transition. Hydrogen is predicted to dissociate to a liquid atomic metal at multi-megabar pressures and T =0 K, or at megabar pressures and very high temperatures. Thus, its predicted phase diagram has a broad field of liquid metallic hydrogen at high pressure, with temperatures ranging from thousands of degrees to zero Kelvin. In a bench top experiment using static compression in a diamond anvil cell and pulsed laser heating, we have conducted measurements on dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K. We observe a first-order phase transition in the liquid phase, as well as sharp changes in optical transmission and reflectivity when this phase is entered. The optical signature is that of a metal. The mapping of the phase line of this transition is in excellent agreement with recent theoretical predictions for the long-sought plasma phase transition to metallic hydrogen. Research supported by the NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H.

  10. Isolation and Structural Characterization of a Mackay 55-Metal-Atom Two-Shell Icosahedron of Pseudo-Ih Symmetry, Pd55L12(μ3-CO)20 (L = PR3, R = Isopropyl): Comparative Analysis with Interior Two-Shell Icosahedral Geometries in Capped Three-Shell Pd145, Pt-Centered Four-Shell Pd-Pt M165, and Four-Shell Au133 Nanoclusters.

    PubMed

    Erickson, Jeremiah D; Mednikov, Evgueni G; Ivanov, Sergei A; Dahl, Lawrence F

    2016-02-10

    We present the first successful isolation and crystallographic characterization of a Mackay 55-metal-atom two-shell icosahedron, Pd55L12(μ3-CO)20 (L = PPr(i)3) (1). Its two-shell icosahedron of pseudo-Ih symmetry (without isopropyl substituents) enables a structural/bonding comparison with interior 55-metal-atom two-shell icosahedral geometries observed within the multi-shell capped 145-metal-atom three-shell Pd145(CO)72(PEt3)30 and 165-metal-atom four-shell Pt-centered (μ12-Pt)Pd164-xPtx(CO)72(PPh3)20 (x ≈ 7) nanoclusters, and within the recently reported four-shell Au133(SC6H4-p-Bu(t))52 nanocluster. DFT calculations carried out on a Pd55(CO)20(PH3)12 model analogue, with triisopropyl phosphine substituents replaced by H atoms, revealed a positive +0.84 e charge for the entire Pd55 core, with a highly positive second-shell Pd42 surface of +1.93 e. PMID:26790717

  11. The MSFC complementary metal oxide semiconductor (including multilevel interconnect metallization) process handbook

    NASA Technical Reports Server (NTRS)

    Bouldin, D. L.; Eastes, R. W.; Feltner, W. R.; Hollis, B. R.; Routh, D. E.

    1979-01-01

    The fabrication techniques for creation of complementary metal oxide semiconductor integrated circuits at George C. Marshall Space Flight Center are described. Examples of C-MOS integrated circuits manufactured at MSFC are presented with functional descriptions of each. Typical electrical characteristics of both p-channel metal oxide semiconductor and n-channel metal oxide semiconductor discrete devices under given conditions are provided. Procedures design, mask making, packaging, and testing are included.

  12. Energy efficient data centers

    SciTech Connect

    Tschudi, William; Xu, Tengfang; Sartor, Dale; Koomey, Jon; Nordman, Bruce; Sezgen, Osman

    2004-03-30

    Data Center facilities, prevalent in many industries and institutions are essential to California's economy. Energy intensive data centers are crucial to California's industries, and many other institutions (such as universities) in the state, and they play an important role in the constantly evolving communications industry. To better understand the impact of the energy requirements and energy efficiency improvement potential in these facilities, the California Energy Commission's PIER Industrial Program initiated this project with two primary focus areas: First, to characterize current data center electricity use; and secondly, to develop a research ''roadmap'' defining and prioritizing possible future public interest research and deployment efforts that would improve energy efficiency. Although there are many opinions concerning the energy intensity of data centers and the aggregate effect on California's electrical power systems, there is very little publicly available information. Through this project, actual energy consumption at its end use was measured in a number of data centers. This benchmark data was documented in case study reports, along with site-specific energy efficiency recommendations. Additionally, other data center energy benchmarks were obtained through synergistic projects, prior PG&E studies, and industry contacts. In total, energy benchmarks for sixteen data centers were obtained. For this project, a broad definition of ''data center'' was adopted which included internet hosting, corporate, institutional, governmental, educational and other miscellaneous data centers. Typically these facilities require specialized infrastructure to provide high quality power and cooling for IT equipment. All of these data center types were considered in the development of an estimate of the total power consumption in California. Finally, a research ''roadmap'' was developed through extensive participation with data center professionals, examination of case

  13. Photobiomolecular metallic particles and films

    DOEpatents

    Hu, Zhong-Cheng

    2003-05-06

    The method of the invention is based on the unique electron-carrying function of a photocatalytic unit such as the photosynthesis system I (PSI) reaction center of the protein-chlorophyll complex isolated from chloroplasts. The method employs a photo-biomolecular metal deposition technique for precisely controlled nucleation and growth of metallic clusters/particles, e.g., platinum, palladium, and their alloys, etc., as well as for thin-film formation above the surface of a solid substrate. The photochemically mediated technique offers numerous advantages over traditional deposition methods including quantitative atom deposition control, high energy efficiency, and mild operating condition requirements.

  14. Metal nanoshells.

    PubMed

    Hirsch, Leon R; Gobin, Andre M; Lowery, Amanda R; Tam, Felicia; Drezek, Rebekah A; Halas, Naomi J; West, Jennifer L

    2006-01-01

    Metal nanoshells are a new class of nanoparticles with highly tunable optical properties. Metal nanoshells consist of a dielectric core nanoparticle such as silica surrounded by an ultrathin metal shell, often composed of gold for biomedical applications. Depending on the size and composition of each layer of the nanoshell, particles can be designed to either absorb or scatter light over much of the visible and infrared regions of the electromagnetic spectrum, including the near infrared region where penetration of light through tissue is maximal. These particles are also effective substrates for surface-enhanced Raman scattering (SERS) and are easily conjugated to antibodies and other biomolecules. One can envision a myriad of potential applications of such tunable particles. Several potential biomedical applications are under development, including immunoassays, modulated drug delivery, photothermal cancer therapy, and imaging contrast agents. PMID:16528617

  15. Visitors Center activities

    NASA Technical Reports Server (NTRS)

    1997-01-01

    More than 2,000 children and adults from Mississippi, Louisiana and Alabama recently build a 12-foot tall Space Shuttle made entirely from tiny LEGO bricks at the John C. Stennis Space Center Visitors Center in South Mississippi. The shuttle was part of an exhibit titled 'Travel in Space' World Show which depicts the history of flight and space travel from the Wright brothers to future generations of space vehicles. For more information concerning hours of operation or Visitors Center educational programs, call 1-800-237-1821 in Mississippi and Louisiana or (601) 688-2370.

  16. Visitors Center activities

    NASA Technical Reports Server (NTRS)

    1997-01-01

    Astronaut Katherine Hire and LEGO-Master Model Builders assisted children from Mississippi, Louisiana and Mississippi in the building of a 12-foot tall Space Shuttle made entirely from tiny LEGO bricks at the John C. Stennis Space Center Visitors Center in South Mississippi. The shuttle was part of an exhibit titled ' Travel in Space' World Show which depicts the history of flight and space travel from the Wright brothers to future generations of space vehicles. For more information concerning hours of operation or Visitors Center educational programs, call 1-800-237-1821 in Mississippi and Louisiana or (601) 688-2370.

  17. Metallized Products

    NASA Technical Reports Server (NTRS)

    1980-01-01

    Since the early 1960's, virtually all NASA spacecraft have used metallized films for a variety of purposes, principally thermal radiation insulation. King Seeley manufactures a broad line of industrial and consumer oriented metallized film, fabric, paper and foam in single layer sheets and multi-layer laminates. A few examples, commercialized by MPI Outdoor Safety Products, are the three ounce Thermos Emergency Blanket which reflects and retains up to 80 percent of the user's body heat helping prevent post accident shock or keeping a person warm for hours under emergency cold weather conditions.

  18. Precision Joining Center

    NASA Technical Reports Server (NTRS)

    Powell, John W.

    1991-01-01

    The establishment of a Precision Joining Center (PJC) is proposed. The PJC will be a cooperatively operated center with participation from U.S. private industry, the Colorado School of Mines, and various government agencies, including the Department of Energy's Nuclear Weapons Complex (NWC). The PJC's primary mission will be as a training center for advanced joining technologies. This will accomplish the following objectives: (1) it will provide an effective mechanism to transfer joining technology from the NWC to private industry; (2) it will provide a center for testing new joining processes for the NWC and private industry; and (3) it will provide highly trained personnel to support advance joining processes for the NWC and private industry.

  19. Carbon Monoxide Information Center

    MedlinePlus Videos and Cool Tools

    ... Center The Invisible Killer Carbon monoxide, also known as CO, is called the "Invisible Killer" because it's ... used or incorrectly-vented fuel-burning appliances such as furnaces, stoves, water heaters and fireplaces. Watch This ...

  20. Fermi Galactic Center Zoom

    NASA Video Gallery

    This animation zooms into an image of the Milky Way, shown in visible light, and superimposes a gamma-ray map of the galactic center from NASA's Fermi. Raw data transitions to a view with all known...

  1. NCI Designated Cancer Centers

    MedlinePlus

    ... Laboratory for Cancer Research Partners & Collaborators Spotlight on Scientists Research Areas Cancer Biology Cancer Genomics Causes of Cancer ... Cancer Center History Frederick National Laboratory for Cancer Research Partners ... Profiles in Cancer Research Outstanding Investigator Award Recipients ...

  2. Accredited Birth Centers

    MedlinePlus

    ... 59803 406-541-7115 Accredited Since February 2010 60 Interior Birthing Center Accredited 1636 30th Avenue, Suite ... Boulder Accredited 2800 Folsom Street, Suite C Boulder, CO 80304 303-443-3993 Accredited since July 2014 ...

  3. Reliability Centered Maintenance - Methodologies

    NASA Technical Reports Server (NTRS)

    Kammerer, Catherine C.

    2009-01-01

    Journal article about Reliability Centered Maintenance (RCM) methodologies used by United Space Alliance, LLC (USA) in support of the Space Shuttle Program at Kennedy Space Center. The USA Reliability Centered Maintenance program differs from traditional RCM programs because various methodologies are utilized to take advantage of their respective strengths for each application. Based on operational experience, USA has customized the traditional RCM methodology into a streamlined lean logic path and has implemented the use of statistical tools to drive the process. USA RCM has integrated many of the L6S tools into both RCM methodologies. The tools utilized in the Measure, Analyze, and Improve phases of a Lean Six Sigma project lend themselves to application in the RCM process. All USA RCM methodologies meet the requirements defined in SAE JA 1011, Evaluation Criteria for Reliability-Centered Maintenance (RCM) Processes. The proposed article explores these methodologies.

  4. Kennedy Space Center

    NASA Technical Reports Server (NTRS)

    Simpkins, Patrick A.

    2010-01-01

    This slide presentation reviews the importance of the Kennedy Space Center both in terms to the economy of Florida and to spaceflight. It reviews the general NASA direction,the challenges of the coming year and the accomplishments.

  5. Soviet Mission Control Center

    NASA Technical Reports Server (NTRS)

    2003-01-01

    This photo is an overall view of the Mission Control Center in Korolev, Russia during the Expedition Seven mission. The Expedition Seven crew launched aboard a Soyez spacecraft on April 26, 2003. Photo credit: NASA/Bill Ingalls

  6. Mental Health Screening Center

    MedlinePlus

    ... Center For Clinicians resources, publications Publications for Your Office Resources for Your Patients Information about Depression Information about Bipolar Disorder Wellness Tools DBSA Support Groups Active Research Studies Mood Disorders ...

  7. Proteome Characterization Centers - TCGA

    Cancer.gov

    The centers, a component of NCI’s Clinical Proteomic Tumor Analysis Consortium, will analyze a subset of TCGA samples to define proteins translated from cancer genomes and their related biological processes.

  8. NMA Analysis Center

    NASA Technical Reports Server (NTRS)

    Kierulf, Halfdan Pascal; Andersen, Per Helge

    2013-01-01

    The Norwegian Mapping Authority (NMA) has during the last few years had a close cooperation with Norwegian Defence Research Establishment (FFI) in the analysis of space geodetic data using the GEOSAT software. In 2012 NMA has taken over the full responsibility for the GEOSAT software. This implies that FFI stopped being an IVS Associate Analysis Center in 2012. NMA has been an IVS Associate Analysis Center since 28 October 2010. NMA's contributions to the IVS as an Analysis Centers focus primarily on routine production of session-by-session unconstrained and consistent normal equations by GEOSAT as input to the IVS combined solution. After the recent improvements, we expect that VLBI results produced with GEOSAT will be consistent with results from the other VLBI Analysis Centers to a satisfactory level.

  9. Tsukuba VLBI Analysis Center

    NASA Technical Reports Server (NTRS)

    Kurihara, Shinobu; Nozawa, Kentaro

    2013-01-01

    The Tsukuba Analysis Center is funded by the Geospatial Information Authority of Japan (GSI). The c5++ analysis software is regularly used for the IVS-INT2 analysis and the ultra-rapid EOP experiments.

  10. Science Center Goes Underground

    ERIC Educational Resources Information Center

    Modern Schools, 1977

    1977-01-01

    A unique underground science center at Bluffton College, designed to save energy and preserve trees, rolling landscape, and other environmental features of the campus, is under construction in Bluffton, Ohio. (Author)