WorldWideScience

Sample records for non-radioactive bonding metal

  1. Development of materials for the removal of metal ions from radioactive and non-radioactive waste streams

    Science.gov (United States)

    Hasan, Md. Shameem

    Nuclear wastes that were generated during cold-war era from various nuclear weapon programs are presently stored in hundreds of tanks across the United States. The composition of these wastes is rather complex containing both radionuclides and heavy metals, such as 137Cs, 90Sr, Al, Pb, Cr, and Cd. In this study, chitosan based biosorbents were prepared to adsorb some of these metal ions. Chitosan is a partially acetylated glucosamine biopolymer encountered in the cell walls of fungi. In its natural form this material is soft and has a tendency to agglomerate or form gels. Various methods were used to modify chitosan to avoid these problems. Chitosan is generally available commercially in the form of flakes. For use in an adsorption system, chitosan was made in the form of beads to reduce the pressure drop in an adsorption column. In this research, spherical beads were prepared by mixing chitosan with perlite and then by dropwise addition of the slurry mixture into a NaOH precipitation bath. Beads were characterized using Fourier Transform InfraRed Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy dispersive spectroscopy (EDS), Tunneling Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric Analysis (TGA). The SEM, EDS, and TEM data indicated that the beads were porous in nature. The TGA data showed that bead contained about 32% chitosan. The surface area, pore volume, and porosity of the beads were determined from the BET surface area that was measured using N2 as adsorbate at 77K. Adsorption and desorption of Cr(VI), Cr(III), Cd(II), U(VI), Cu(II), from aqueous solutions of these metal ions were studied to evaluate the adsorption capacities of the beads for these metals ions. Equilibrium adsorption data of these metals on the beads were found to correlate well with the Langmuir isotherm equation. Chitosan coated perlite beads had negligible adsorption capacity for Sr(II) and Cs(I). It was found that Fullers earth

  2. Bonding Elastomers To Metal Substrates

    Science.gov (United States)

    Dickerson, George E.; Kelley, Henry L.

    1990-01-01

    Improved, economical method for bonding elastomers to metals prevents failures caused by debonding. In new technique, vulcanization and curing occur simultaneously in specially designed mold that acts as form for desired shape of elastomer and as container that positions and supports metal parts. Increases interface adhesion between metal, adhesive, and elastomer.

  3. Metallic bonding and cluster structure

    Energy Technology Data Exchange (ETDEWEB)

    Soler, Jose M. [Department of Physics, Lyman Laboratory, Harvard University, Cambridge, Massachusetts 02138 (United States); Departamento de Fisica de la Materia Condensada, Universidad Autonoma de Madrid, E-28049 Madrid, (Spain); Beltran, Marcela R. [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Apartado Postal 70-360, Mexico Distrito Federal, 01000 Mexico (Mexico); Michaelian, Karo [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, Apartado Postal 20-364, Mexico Distrito Federal, 01000 Mexico (Mexico); Garzon, Ignacio L. [Departamento de Fisica de la Materia Condensada, Universidad Autonoma de Madrid, E-28049 Madrid, (Spain); Instituto de Fisica, Universidad Nacional Autonoma de Mexico, Apartado Postal 20-364, Mexico Distrito Federal, 01000 Mexico (Mexico); Ordejon, Pablo [Institut de Ciencia de Materials de Barcelona-CSIC, Campus de la U.A.B., 08193 Bellaterra, Barcelona, (Spain); Sanchez-Portal, Daniel [Department of Physics and Materials Research Laboratory, University of Illinois, Urbana, Illinois 61801 (United States); Artacho, Emilio [Departamento de Fisica de la Materia Condensada, Universidad Autonoma de Madrid, E-28049 Madrid, (Spain)

    2000-02-15

    Knowledge of the structure of clusters is essential to predict many of their physical and chemical properties. Using a many-body semiempirical Gupta potential (to perform global minimizations), and first-principles density functional calculations (to confirm the energy ordering of the local minima), we have recently found [Phys. Rev. Lett. 81, 1600 (1998)] that there are many intermediate-size disordered gold nanoclusters with energy near or below the lowest-energy ordered structure. This is especially surprising because we studied ''magic'' cluster sizes, for which very compact-ordered structures exist. Here, we show how the analysis of the local stress can be used to understand the physical origin of this amorphization. We find that the compact ordered structures, which are very stable for pair potentials, are destabilized by the tendency of metallic bonds to contract at the surface, because of the decreased coordination. The amorphization is also favored by the relatively low energy associated to bondlength and coordination disorder in metals. Although these are very general properties of metallic bonding, we find that they are especially important in the case of gold, and we predict some general trends in the tendency of metallic clusters towards amorphous structures. (c) 2000 The American Physical Society.

  4. Valence-Bond Concepts in Coordination Chemistry and the Nature of Metal-Metal Bonds.

    Science.gov (United States)

    Pauling, Linus; Herman, Zelek S.

    1984-01-01

    Discusses the valence-bond method, applying it to some coordination compounds of metals, especially those involving metal-metal bonds. Suggests that transition metals can form as many as nine covalent bonds, permitting valence-theory to be extended to transition metal compounds in a more effective way than has been possible before. (JN)

  5. Complete Non-Radioactive Operability Tests for Cladding Hull Chlorination

    Energy Technology Data Exchange (ETDEWEB)

    Collins, Emory D [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Johnson, Jared A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Hylton, Tom D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Brunson, Ronald Ray [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Hunt, Rodney Dale [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); DelCul, Guillermo Daniel [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bradley, Eric Craig [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Spencer, Barry B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-04-01

    Non-radioactive operability tests were made to test the metal chlorination reactor and condenser and their accessories using batch chlorinations of non-radioactive cladding samples and to identify optimum operating practices and components that need further modifications prior to installation of the equipment into the hot cell for tests on actual used nuclear fuel (UNF) cladding. The operability tests included (1) modifications to provide the desired heating and reactor temperature profile; and (2) three batch chlorination tests using, respectively, 100, 250, and 500 g of cladding. During the batch chlorinations, metal corrosion of the equipment was assessed, pressurization of the gas inlet was examined and the best method for maintaining solid salt product transfer through the condenser was determined. Also, additional accessing equipment for collection of residual ash and positioning of the unit within the hot cell were identified, designed, and are being fabricated.

  6. Graphene composites containing chemically bonded metal oxides

    Indian Academy of Sciences (India)

    K Pramoda; S Suresh; H S S Ramakrishna Matte; A Govindaraj

    2013-08-01

    Composites of graphene involving chemically bonded nano films of metal oxides have been prepared by reacting graphene containing surface oxygen functionalities with metal halide vapours followed by exposure to water vapour. The composites have been characterized by electron microscopy, atomic force microscopy and other techniques. Magnetite particles chemically bonded to graphene dispersible in various solvents have been prepared and they exhibit fairly high magnetization.

  7. Bonding theory for metals and alloys

    CERN Document Server

    Wang, Frederick E

    2005-01-01

    Bonding Theory for Metals and Alloys exhorts the potential existence of covalent bonding in metals and alloys. Through the recognition of the covalent bond in coexistence with the 'free' electron band, the book describes and demonstrates how the many experimental observations on metals and alloys can all be reconciled. Subsequently, it shows how the individual view of metals and alloys by physicists, chemists and metallurgists can be unified. The physical phenomena of metals and alloys covered in this book are: Miscibility Gap between two liquid metals; Phase Equilibrium Diagrams; Phenomenon of Melting. Superconductivity; Nitinol; A Metal-Alloy with Memory; Mechanical Properties; Liquid Metal Embrittlement; Superplasticity; Corrosion; The author introduces a new theory based on 'Covalon' conduction, which forms the basis for a new approach to the theory of superconductivity. This new approach not only explains the many observations made on the phenomenon of superconductivity but also makes predictions that ha...

  8. Progress in cold roll bonding of metals

    Energy Technology Data Exchange (ETDEWEB)

    Li Long; Nagai, Kotobu; Yin Fuxing [Innovative Materials Engineering Laboratory, National Institute for Materials Science, Tsukuba 305-0047 (Japan)], E-mail: LI.Long@nims.go.jp

    2008-04-01

    Layered composite materials have become an increasingly interesting topic in industrial development. Cold roll bonding (CRB), as a solid phase method of bonding same or different metals by rolling at room temperature, has been widely used in manufacturing large layered composite sheets and foils. In this paper, we provide a brief overview of a technology using layered composite materials produced by CRB and discuss the suitability of this technology in the fabrication of layered composite materials. The effects of process parameters on bonding, mainly including process and surface preparation conditions, have been analyzed. Bonding between two sheets can be realized when deformation reduction reaches a threshold value. However, it is essential to remove surface contamination layers to produce a satisfactory bond in CRB. It has been suggested that the degreasing and then scratch brushing of surfaces create a strong bonding between the layers. Bonding mechanisms, in which the film theory is expressed as the major mechanism in CRB, as well as bonding theoretical models, have also been reviewed. It has also been showed that it is easy for fcc structure metals to bond compared with bcc and hcp structure metals. In addition, hardness on bonding same metals plays an important part in CRB. Applications of composites produced by CRB in industrial fields are briefly reviewed and possible developments of CRB in the future are also described. Corrections were made to the abstract and conclusion of this article on 18 June 2008. The corrected electronic version is identical to the print version. (topical review)

  9. Atomic bonding between metal and graphene

    KAUST Repository

    Wang, Hongtao

    2013-03-07

    To understand structural and chemical properties of metal-graphene composites, it is crucial to unveil the chemical bonding along the interface. We provide direct experimental evidence of atomic bonding between typical metal nano structures and graphene, agreeing well with density functional theory studies. Single Cr atoms are located in the valleys of a zigzag edge, and few-atom ensembles preferentially form atomic chains by self-assembly. Low migration barriers lead to rich dynamics of metal atoms and clusters under electron irradiation. We demonstrate no electron-instigated interaction between Cr clusters and pristine graphene, though Cr has been reported to be highly reactive to graphene. The metal-mediated etching is a dynamic effect between metal clusters and pre-existing defects. The resolved atomic configurations of typical nano metal structures on graphene offer insight into modeling and simulations on properties of metal-decorated graphene for both catalysis and future carbon-based electronics. © 2013 American Chemical Society.

  10. Metal-metal bonding using silver/copper nanoparticles

    Science.gov (United States)

    Kobayashi, Y.; Maeda, T.; Yasuda, Y.; Morita, T.

    2016-08-01

    A method for producing nanoparticles composed of silver and copper and a metal-metal bonding technique using the silver/copper nanoparticles are proposed. The method consists of three steps. First, copper oxide nanoparticles are produced by mixing Cu(NO3)2 aqueous solution and NaOH aqueous solution. Second, copper metal nanoparticles are fabricated by reducing the copper oxide nanoparticles with hydrazine in the presence of poly(vinylpyrrolidone) (PVP). Third, silver/copper nanoparticles are synthesized by reducing Ag+ ions with hydrazine in the presence of the copper metal nanoparticles. Initial concentrations in the final silver/copper particle colloid, composed of 0.0075 M Cu2+, 0.0025 M Ag+, 1.0 g/L PVP, and 0.6 M hydrazine, produced silver/copper nanoparticles with an average size of 49 nm and a crystal size of 16.8 nm. Discs of copper metal were successfully bonded by the silver/copper nanoparticles under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in not only hydrogen gas but also nitrogen gas. The shear force required to separate the bonded discs was 22.3 MPa for the hydrogen gas annealing and 14.9 MPa for the nitrogen gas annealing (namely, 66.8 % of that for hydrogen gas annealing).

  11. Cooperativity in Surface Bonding and Hydrogen Bonding of Water and Hydroxyl at Metal Surfaces

    DEFF Research Database (Denmark)

    Schiros, T.; Ogasawara, H.; Naslund, L. A.;

    2010-01-01

    of the mixed phase at metal surfaces. The surface bonding can be considered to be similar to accepting a hydrogen bond, and we can thereby apply general cooperativity rules developed for hydrogen-bonded systems. This provides a simple understanding of why water molecules become more strongly bonded...... to the surface upon hydrogen bonding to OH and why the OH surface bonding is instead weakened through hydrogen bonding to water. We extend the application of this simple model to other observed cooperativity effects for pure water adsorption systems and H3O+ on metal surfaces.......We examine the balance of surface bonding and hydrogen bonding in the mixed OH + H2O overlayer on Pt(111), Cu(111), and Cu(110) via density functional theory calculations. We find that there is a cooperativity effect between surface bonding and hydrogen bonding that underlies the stability...

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

    Science.gov (United States)

    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…

  13. Interplay of metal-allyl and metal-metal bonding in dimolybdenum allyl complexes

    Energy Technology Data Exchange (ETDEWEB)

    John, Kevin D [Los Alamos National Laboratory; Martin, Richard L [Los Alamos National Laboratory; Obrey, Steven J [Los Alamos National Laboratory; Scott, Brian L [Los Alamos National Laboratory

    2008-01-01

    Addition of PMe{sub 3} to Mo{sub 2}(allyl){sub 4} afforded Mo{sub 2}(allyl){sub 4}(PMe{sub 3}){sub 2}, in which two of the allyl groups adopt an unprecedented {mu}{sub 2{sup -}}{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the role sof the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  14. Reactive Bonding Film for Bonding Carbon Foam Through Metal Extrusion

    CERN Document Server

    Chertok, Maxwell; Irving, Michael; Neher, Christian; Tripathi, Mani; Wang, Ruby; Zheng, Gayle

    2016-01-01

    Future tracking detectors, such as those under development for the High Luminosity LHC, will require mechanical structures employing novel materials to reduce mass while providing excellent strength, thermal conductivity, and radiation tolerance. Adhesion methods for such materials are under study at present. This paper demonstrates the use of reactive bonding film as an adhesion method for bonding carbon foam.

  15. Understanding metallic bonding: Structure, process and interaction by Rasch analysis

    Science.gov (United States)

    Cheng, Maurice M. W.; Oon, Pey-Tee

    2016-08-01

    This paper reports the results of a survey of 3006 Year 10-12 students on their understandings of metallic bonding. The instrument was developed based on Chi's ontological categories of scientific concepts and students' understanding of metallic bonding as reported in the literature. The instrument has two parts. Part one probed into students' understanding of metallic bonding as (a) a submicro structure of metals, (b) a process in which individual metal atoms lose their outermost shell electrons to form a 'sea of electrons' and octet metal cations or (c) an all-directional electrostatic force between delocalized electrons and metal cations, that is, an interaction. Part two assessed students' explanation of malleability of metals, for example (a) as a submicro structural rearrangement of metal atoms/cations or (b) based on all-directional electrostatic force. The instrument was validated by the Rasch Model. Psychometric assessment showed that the instrument possessed reasonably good properties of measurement. Results revealed that it was reliable and valid for measuring students' understanding of metallic bonding. Analysis revealed that the structure, process and interaction understandings were unidimensional and in an increasing order of difficulty. Implications for the teaching of metallic bonding, particular through the use of diagrams, critiques and model-based learning, are discussed.

  16. Comparisons between radioactive and non-radioactive gas lantern mantles.

    Science.gov (United States)

    Furuta, E; Yoshizawa, Y; Aburai, T

    2000-12-01

    Gas lantern mantles containing radioactive thorium have been used for more than 100 years. Although thorium was once believed to be indispensable for giving a bright light, non-radioactive mantles are now available. From the radioactivities of the daughter nuclides, we estimated the levels of radioactivity of 232Th and 228Th in 11 mantles. The mantles contained various levels of radioactivity from background levels to 1410 +/- 140 Bq. Our finding that radioactive and non-radioactive mantles are equally bright suggests that there is no advantage in using radioactive mantles. A remaining problem is that gas lantern mantles are sold without any information about radioactivity.

  17. TOPICAL REVIEW: Progress in cold roll bonding of metals

    Science.gov (United States)

    Li, Long; Nagai, Kotobu; Yin, Fuxing

    2008-04-01

    Layered composite materials have become an increasingly interesting topic in industrial development. Cold roll bonding (CRB), as a solid phase method of bonding same or different metals by rolling at room temperature, has been widely used in manufacturing large layered composite sheets and foils. In this paper, we provide a brief overview of a technology using layered composite materials produced by CRB and discuss the suitability of this technology in the fabrication of layered composite materials. The effects of process parameters on bonding, mainly including process and surface preparation conditions, have been analyzed. Bonding between two sheets can be realized when deformation reduction reaches a threshold value. However, it is essential to remove surface contamination layers to produce a satisfactory bond in CRB. It has been suggested that the degreasing and then scratch brushing of surfaces create a strong bonding between the layers. Bonding mechanisms, in which the film theory is expressed as the major mechanism in CRB, as well as bonding theoretical models, have also been reviewed. It has also been showed that it is easy for fcc structure metals to bond compared with bcc and hcp structure metals. In addition, hardness on bonding same metals plays an important part in CRB. Applications of composites produced by CRB in industrial fields are briefly reviewed and possible developments of CRB in the future are also described. Corrections were made to the abstract and conclusion of this article on 18 June 2008. The corrected electronic version is identical to the print version.

  18. TOPICAL REVIEW Progress in cold roll bonding of metals

    Directory of Open Access Journals (Sweden)

    Long Li, Kotobu Nagai and Fuxing Yin

    2008-01-01

    Full Text Available Layered composite materials have become an increasingly interesting topic in industrial development. Cold roll bonding (CRB, as a solid phase method of bonding same or different metals by rolling at room temperature, has been widely used in manufacturing large layered composite sheets and foils. In this paper, we provide a brief overview of a technology using layered composite materials produced by CRB and discuss the suitability of this technology in the fabrication of layered composite materials. The effects of process parameters on bonding, mainly including process and surface preparation conditions, have been analyzed. Bonding between two sheets can be realized when deformation reduction reaches a threshold value. However, it is essential to remove surface contamination layers to produce a satisfactory bond in CRB. It has been suggested that the degreasing and then scratch brushing of surfaces create a strong bonding between the layers. Bonding mechanisms, in which the film theory is expressed as the major mechanism in CRB, as well as bonding theoretical models, have also been reviewed. It has also been showed that it is easy for fcc structure metals to bond compared with bcc and hcp structure metals. In addition, hardness on bonding same metals plays an important part in CRB. Applications of composites produced by CRB in industrial fields are briefly reviewed and possible developments of CRB in the future are also described.

  19. Metalmetal multiple bonded intermediates in catalysis

    Indian Academy of Sciences (India)

    John F Berry

    2015-02-01

    Metal–metal bonded Rh2 and Ru2 complexes having a paddlewheel-type structure are exceptional catalysts for a broad range of organic transformations. I review here the recent efforts towards the observation and characterization of intermediates in these reactions that have previously eluded detection. Specifically, mechanistic investigations of carbenoid and nitrenoid reactions of Rh2(II,II)-tetracarboxylate compounds have led to the observation of a metastable Rh2(II,II) carbene complex as well as a mixed-valent Rh2(II,III)-amido intermediate. Related Ru2 nitrido compounds have been studied and found to undergo intramolecular C–H amination reactions as well as intermolecular reaction with triphenylphosphine

  20. Comparison of Shear Bond Strengths of three resin systems for a Base Metal Alloy bonded to

    Directory of Open Access Journals (Sweden)

    Jlali H

    1999-12-01

    Full Text Available Resin-bonded fixed partial dentures (F.P.D can be used for conservative treatment of partially edentulous"npatients. There are numerous studies regarding the strength of resin composite bond to base meta! alloys. Shear bond"nstrength of three resin systems were invistigated. In this study these systems consisted of: Panavia Ex, Mirage FLC and"nMarathon V. Thirty base metal specimens were prepared from rexillium III alloy and divided into three groups. Then each"ngroup was bonded to enamel of human extracted molar teeth with these systems. All of specimens were stored in water at"n37ac for 48 hours. A shear force was applied to each specimen by the instron universal testing machine. A statistical"nevaluation of the data using one-way analysis of variance showed that there was highly significant difference (P<0.01"nbetween the bond strengths of these three groups."nThe base metal specimens bonded with panavia Ex luting agent, exhibited the highest mean bond strength. Shear bond"nstrength of the specimens bonded to enamel with Mirage F1C showed lower bond strenght than panavia EX. However, the"nlowest bond strength was obtained by the specimens bonded with Marathon V.

  1. Shear bond strength of ceramic and metallic orthodontic brackets bonded with self-etching primer and conventional bonding adhesives

    Science.gov (United States)

    Arash, Valiollah; Naghipour, Fatemeh; Ravadgar, Mehdi; Karkhah, Ahmad; Barati, Mohammad Saleh

    2017-01-01

    Introduction Adult patients typically require high-quality orthodontic treatment for ceramic brackets, but some clinicians remain concerned about the bond strength of these brackets. Therefore, the aim of this study was to determine the shear bond strength and de-bonding characteristics of metallic and ceramic brackets bonded with two types of bonding agents. Methods In an experimental study done in 2013 in Babol, Iran, 120 extracted human maxillary premolar teeth were randomly divided into four groups as follows: HM group: metallic bracket/conventional bonding agent; SM group: metallic bracket/Transbond self-etching primer; HC group: ceramic bracket/conventional bonding agent; SC group: ceramic bracket/Transbond self-etching primer. Twenty-four hours after thermocycling (1000 cycle, 5 °C–55 °C), the shear bond strength values were measured. The amount of resin remaining on the tooth surface (adhesive remnant index: ARI) was determined under a stereomicroscope. Enamel detachment index was evaluated under a scanning electron microscope. To perform statistical analysis, ANOVA, Kruskal–Wallis, and Tukey post-hoc tests were applied. The level of significance was set at p ceramic brackets. In addition, self-etching primer was able to produce fewer bonds compared with the conventional technique. Many samples showed the bracket-adhesive interface failure or failure inside the adhesive. PMID:28243410

  2. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

    Science.gov (United States)

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

    Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in

  3. Sensitive non-radioactive detection of HIV-1

    DEFF Research Database (Denmark)

    Teglbjærg, Lars Stubbe; Nielsen, C; Hansen, J E

    1992-01-01

    This report describes the use of the polymerase chain reaction (PCR) for the non-radioactive detection of HIV-1 proviral genomic sequences in HIV-1 infected cells. We have developed a sensitive assay, using three different sets of nested primers and our results show that this method is superior t...... genomic copies often are present at such low numbers that they are otherwise undetectable....

  4. Metal-Free Oxidative C-C Bond Formation through C-H Bond Functionalization.

    Science.gov (United States)

    Narayan, Rishikesh; Matcha, Kiran; Antonchick, Andrey P

    2015-10-12

    The formation of C-C bonds embodies the core of organic chemistry because of its fundamental application in generation of molecular diversity and complexity. C-C bond-forming reactions are well-known challenges. To achieve this goal through direct functionalization of C-H bonds in both of the coupling partners represents the state-of-the-art in organic synthesis. Oxidative C-C bond formation obviates the need for prefunctionalization of both substrates. This Minireview is dedicated to the field of C-C bond-forming reactions through direct C-H bond functionalization under completely metal-free oxidative conditions. Selected important developments in this area have been summarized with representative examples and discussions on their reaction mechanisms. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Unique chemical properties of metal-carbon bonds in metal-carboranyl and metal-carboryne complexes

    Institute of Scientific and Technical Information of China (English)

    QIU ZaoZao; XIE ZuoWei

    2009-01-01

    The metal-carbon bonds in metal-carboranyl and metal-carboryne complexes behave very differently from those in classical organometallic complexes. The unique electronic and steric properties of icosahedral carboranyl moiety make the M-C bond in metal-carboranyl complexes inert toward unsaturated molecules, and on the other hand, the sterically demanding carborane cage can induce unexpected C-C coupling reactions. The M-C bonds in metal-carboryne complexes are, however, active toward various kinds of unsaturated molecules and the reactivity patterns are dependent upon the electronic configurations of the metal ions. This account provides an overview of our recent work in this area.

  6. Unique chemical properties of metal-carbon bonds in metal-carboranyl and metal-carboryne complexes

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The metal-carbon bonds in metal-carboranyl and metal-carboryne complexes behave very differently from those in classical organometallic complexes. The unique electronic and steric properties of ico-sahedral carboranyl moiety make the M-C bond in metal-carboranyl complexes inert toward unsaturated molecules, and on the other hand, the sterically demanding carborane cage can induce unexpected C-C coupling reactions. The M-C bonds in metal-carboryne complexes are, however, active toward various kinds of unsaturated molecules and the reactivity patterns are dependent upon the electronic configurations of the metal ions. This account provides an overview of our recent work in this area.

  7. Metallic Thin-Film Bonding and Alloy Generation

    Science.gov (United States)

    Fryer, Jack Merrill (Inventor); Campbell, Geoff (Inventor); Peotter, Brian S. (Inventor); Droppers, Lloyd (Inventor)

    2016-01-01

    Diffusion bonding a stack of aluminum thin films is particularly challenging due to a stable aluminum oxide coating that rapidly forms on the aluminum thin films when they are exposed to atmosphere and the relatively low meting temperature of aluminum. By plating the individual aluminum thin films with a metal that does not rapidly form a stable oxide coating, the individual aluminum thin films may be readily diffusion bonded together using heat and pressure. The resulting diffusion bonded structure can be an alloy of choice through the use of a carefully selected base and plating metals. The aluminum thin films may also be etched with distinct patterns that form a microfluidic fluid flow path through the stack of aluminum thin films when diffusion bonded together.

  8. Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides.

    Science.gov (United States)

    Belkova, Natalia V; Epstein, Lina M; Filippov, Oleg A; Shubina, Elena S

    2016-08-10

    The dihydrogen bond-an interaction between a transition-metal or main-group hydride (M-H) and a protic hydrogen moiety (H-X)-is arguably the most intriguing type of hydrogen bond. It was discovered in the mid-1990s and has been intensively explored since then. Herein, we collate up-to-date experimental and computational studies of the structural, energetic, and spectroscopic parameters and natures of dihydrogen-bonded complexes of the form M-H···H-X, as such species are now known for a wide variety of hydrido compounds. Being a weak interaction, dihydrogen bonding entails the lengthening of the participating bonds as well as their polarization (repolarization) as a result of electron density redistribution. Thus, the formation of a dihydrogen bond allows for the activation of both the MH and XH bonds in one step, facilitating proton transfer and preparing these bonds for further transformations. The implications of dihydrogen bonding in different stoichiometric and catalytic reactions, such as hydrogen exchange, alcoholysis and aminolysis, hydrogen evolution, hydrogenation, and dehydrogenation, are discussed.

  9. Metallic and intermetallic-bonded ceramic composites

    Energy Technology Data Exchange (ETDEWEB)

    Plucknett, K.P.; Tiegs, T.N.; Alexander, K.B. [Oak Ridge National Laboratory, TN (United States)] [and others

    1995-05-01

    The purpose of this task is to establish a framework for the development and fabrication of metallic-phase-reinforced ceramic matrix composites with improved fracture toughness and damage resistance. The incorporation of metallic phases that plastically deform in the crack tip region, and thus dissipate strain energy, will result in an increase in the fracture toughness of the composite as compared to the monolithic ceramic. It is intended that these reinforced ceramic matrix composites will be used over a temperature range from 20{degrees}C to 800-1200{degrees}C for advanced applications in the industrial sector. In order to systematically develop these materials, a combination of experimental and theoretical studies must be undertaken.

  10. Simulation research on ultrasonic guided waves detection of metal rod buffer system bonding quality

    Directory of Open Access Journals (Sweden)

    Yang Hu

    2013-01-01

    Full Text Available The judgment of metal rod buffer system bonding quality depends on the bond of the metal rods with the surrounding medium. System bonding area will lead to different reflection amplitude. Compared the simulation with the experiment, it can be concluded that different bonding area can measure bond quality, i.e, the greater the bonding area is the more excellent bonding quality will be. This conclusion provides the basis for the system ultrasonic testing.

  11. Carbon Nanotube Bonding Strength Enhancement Using Metal "Wicking" Process

    Science.gov (United States)

    Lamb, James L.; Dickie, Matthew R.; Kowalczyk, Robert S.; Liao, Anna; Bronikowski, Michael J.

    2012-01-01

    Carbon nanotubes grown from a surface typically have poor bonding strength at the interface. A process has been developed for adding a metal coat to the surface of carbon nano tubes (CNTs) through a wicking process, which could lead to an enhanced bonding strength at the interface. This process involves merging CNTs with indium as a bump-bonding enhancement. Classical capillary theory would not normally allow materials that do not wet carbon or graphite to be drawn into the spacings by capillary action because the contact angle is greater than 90 degrees. However, capillary action can be induced through JPL's ability to fabricate oriented CNT bundles to desired spacings, and through the use of deposition techniques and temperature to control the size and mobility of the liquid metal streams and associated reservoirs. A reflow and plasma cleaning process has also been developed and demonstrated to remove indium oxide, and to obtain smooth coatings on the CNT bundles.

  12. Shear bond strength of metallic brackets: influence of saliva contamination

    Directory of Open Access Journals (Sweden)

    Luciana Borges Retamoso

    2009-06-01

    Full Text Available OBJECTIVE: To evaluate the influence of saliva contamination on shear bond strength and the bond failure pattern of 3 adhesive systems (Transbond XT, AdheSE and Xeno III on orthodontic metallic brackets bonded to human enamel. MATERIAL AND METHODS: Seventy-two permanent human molars were cut longitudinally in a mesiodistal direction, producing seventy-two specimens randomly divided into six groups. Each system was tested under 2 different enamel conditions: no contamination and contaminated with saliva. In T, A and X groups, the adhesive systems were applied to the enamel surface in accordance with manufacturer's instructions. In TS, AS and XS groups, saliva was applied to enamel surface followed by adhesive system application. The samples were stored in distilled water at 37ºC for 24 h, and then tested for shear bond strength in a universal testing machine (Emic, DL 2000 running at a crosshead speed of 1 mm/min. After bond failure, the enamel surfaces were observed under an optical microscope at 40x magnification. RESULTS: The control and contaminated groups showed no significant difference in shear bond strength for the same adhesive system. However, shear bond strength of T group (17.03±4.91 was significantly higher than that of AS (8.58±1.73 and XS (10.39±4.06 groups (p<0.05. Regarding the bond failure pattern, TS group had significantly higher scores of no adhesive remaining on the tooth in the bonding area than other groups considering the adhesive remnant index (ARI used to evaluate the amount of adhesive left on the enamel. CONCLUSIONS: Saliva contamination showed little influence on the 24-h shear bond strength of orthodontic brackets.

  13. Designer Metallic Acceptor-Containing Halogen Bonding: General Strategies.

    Science.gov (United States)

    Zhang, Xinxing; Bowen, Kit H

    2017-03-13

    Being electrostatic interactions in nature, hydrogen bonding (HB) and halogen bonding (XB) are considered to be two parallel worlds. In principle, all the applications that HB has could also be applied to XB. However, there has been no report on a metallic XB acceptor but metal anions have been observed to be good HB acceptors. This missing mosaic piece of XB is because common metal anions are reactive for XB donors. In view of this, we propose two strategies for designing metallic acceptor-containing XB using ab initio calculations. The first one is to utilize a metal cluster anion with a high electron detachment energy, such as the superatom, Al13- as the XB acceptor. The second strategy is to design a ligand passivated/protected metal core while it still can maintain the negative charge; several exotic clusters, such as PtH5-, PtZnH5- and PtMgH5-, are utilized as examples. Based on these two strategies, we anticipate that more metallic acceptor-containing XB will be discovered.

  14. Effects of tin plating on base metal alloy-ceramic bond strength.

    Science.gov (United States)

    Değer, S; Caniklioglu, M B

    1998-01-01

    This study investigated the metal-ceramic bonding of treated metal surfaces. The study was divided into two parts. In Part I, the depth of tin diffusion from a tin-plated bone metal alloy surface was measured using an energy-dispersive spectrometer. In Part II the metal-ceramic bond strength was determined using a shear test. The weakest bonding was observed in the directly tin-plated group, and the strongest metal-ceramic bonding was maintained in the tin-diffused group. A controlled oxidation produced the greatest bond strengths. With the base metal alloys tested, diffusion under the argon environment was conducive to a stronger metal-ceramic bond. The metal oxidation rate should approximate the ceramic vitrification rate, and the diffusion rate of the metal elements should be slower than the vitrification rate to obtain the strongest metal-ceramic bond.

  15. Tensile Bond Strength of Metal Bracket Bonding to Glazed Ceramic Surfaces With Different Surface Conditionings

    Directory of Open Access Journals (Sweden)

    M. Imani

    2011-12-01

    Full Text Available Objective: The objective of this study was to compare the tensile bond strength of metal brackets bonding to glazed ceramic surfaces using three various surface treatments.Materials and Methods: Forty two glazed ceramic disks were assigned to three groups. In the first and second groups the specimens were etched with 9.5% hydrofluoric acid (HFA. Subsequently in first group, ceramic primer and adhesive were applied, but in second group a bonding agent alone was used. In third group, specimens were treated with 35% phosphoric acid followed by ceramic primerand adhesive application. Brackets were bonded with light cure composites. The specimens were stored in distilled water in the room temperature for 24 hours and thermocycled 500 times between 5°C and 55°C. The universal testing machine was used to test the tensile bond strength and the adhesive remenant index scores between three groups was evaluated. The data were subjected to one-way ANOVA, Tukey and Kruskal-Wallis tests respectively.Results: The tensile bond strength was 3.69±0.52 MPa forfirst group, 2.69±0.91 MPa for second group and 3.60±0.41 MPa for third group. Group II specimens showed tensile strength values significantly different from other groups (P<0.01.Conclusion: In spite of limitations in laboratory studies it may be concluded that in application of Scotch bond multipurpose plus adhesive, phosphoric acid can be used instead of HFA for bonding brackets to the glazed ceramic restorations with enough tensile bond strength.

  16. Spectroscopic monitoring of metallic bonding in laser metal deposition

    NARCIS (Netherlands)

    Ya, Wei; Konuk, A.R.; Aarts, R.G.K.M.; Pathiraj, B.; Huis in 't Veld, A.J.

    2015-01-01

    A new approach is presented in this paper to link optical emission spectrum analysis to the quality of clad layers produced with laser metal deposition (LMD). A Nd:YAG laser (λ = 1.064 μm) was used to produce clad tracks with Metco 42C powder on AISI 4140 steel substrate. The laser power was ramped

  17. Composite rebonding to stainless steel metal using different bonding agents.

    Science.gov (United States)

    al-Shalan, T A; Till, M J; Feigal, R J

    1997-01-01

    The purpose of this study was to determine the in vitro bond strengths of composite rebonded to stainless steel crown metal (SS) using five different bonding agents after composite to SS bond failure had been produced. The adhesive systems were applied to the failed bonds following the manufacturers' instructions and, as a control, composite was bonded to SS without using a bonding agent. Each group was then divided into two subgroups: mechanically prepared (MP), in which the SS was roughened by a diamond bur, and unprepared (NMP), in which no modification of the SS was done. ESPE VISIO-GEM composite was placed in a plastic mold and light cured to the treated SS. Samples were stored in water at 37 degrees C for 72 hr, thermocycled for 500 cycles between 5 and 55 degrees C, and mounted in an Instron Universal Testing Machine. Caulk's Adhesive System provided significantly higher rebond strength (228.97 +/- 106.9 kg/cm2) than the other materials, and mechanical surface preparation offered no significant advantages.

  18. Ceramic susceptor for induction bonding of metals, ceramics, and plastics

    Science.gov (United States)

    Fox, Robert L.; Buckley, John D.

    1991-01-01

    A thin (.005) flexible ceramic susceptor (carbon) was discovered. It was developed to join ceramics, plastics, metals, and combinations of these materials using a unique induction heating process. Bonding times for laboratory specimens comparing state of the art technology to induction bonding were cut by a factor of 10 to 100 times. This novel type of carbon susceptor allows for applying heat directly and only to the bondline without heating the entire structure, supports, and fixtures of a bonding assembly. The ceramic (carbon film) susceptor produces molten adhesive or matrix material at the bond interface. This molten material flows through the perforated susceptor producing a fusion between the two parts to be joined, which in many instances has proven to be stronger than the parent material. Bonding can be accomplished in 2 minutes on areas submitted to the inductive heating. Because a carbon susceptor is used in bonding carbon fiber reinforced plastics and ceramics, there is no radar signature or return making it an ideal process for joining advanced aerospace composite structures.

  19. Fluorine substituent effects on dihydrogen bonding of transition metal hydrides.

    Science.gov (United States)

    Jacobsen, Heiko

    2009-09-07

    Hydrogen and dihydrogen bonding of the fluorinated alcohol (CF(3))(2)CHOH with the transition metal complex WH(CO)(2)(NO)(PMe(3))(2) has been explored by a set of four exemplary density functional theory methods that comprises the BP86, PBE, B3LYP and TPSS functionals. The hydride, nitrosyl and carbonyl ligands of the tungsten complex have been considered as sites of protonation. The main effect of fluorination is an increased dihydrogen bond strength by about 15 kJ mol(-1). The [see equation in text] dihydrogen bond is about 10 kJ mol(-1) stronger than the [W]-NOH-OR hydrogen bond. Of the four DFT methods investigated, the BP86 functional provides the most satisfying quantitative as well as qualitative agreement with experiment. The geometry of the [see equation in text] linkage is significantly influenced by secondary dispersive intermolecular bonding. Linear and bent dihydrogen bonds are separated in energy only by about 1 kJ mol(-1), and represent local minima on the corresponding energy hypersurface.

  20. Students' Visualization of Metallic Bonding and the Malleability of Metals

    Science.gov (United States)

    Cheng, Maurice M. W.; Gilbert, John K.

    2014-01-01

    This study investigated the mental representations of metallic bonding and the malleability of metals held by three male students aged 14-15 (Year 10) who were attending a Hong Kong school. One student was selected by their chemistry teacher as representing each of the highest, the medium, and the lowest level of attainment in chemistry in a…

  1. Alkali metal mediated C-C bond coupling reaction.

    Science.gov (United States)

    Tachikawa, Hiroto

    2015-02-14

    Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2](-) was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.

  2. Bonds between metals and nanocomposites created by explosion welding

    Science.gov (United States)

    Bondar', M. P.; Karpov, E. V.; Lukyanov, Ya. L.

    2016-09-01

    This paper describes the study of the influence of a microstructure characterized by directed or chaotic distribution of nanoinclusions and strain rate on the deformability of nanocomposites. It is revealed that, under identical loading conditions, cracks are formed in nanocomposites whose structural elements are mostly directed in the same way at lower strain rates than in nanocomposites with chaotic distribution of the reinforcer. It is shown that, as the strain rate increases, the influence of the structural order on the limiting deformation reduces due to transition from shear strain to rotational strain. No cracks are formed in the creation of bonds between metals and nanocomposites by explosion welding. The experimental results obtained in the study of transverse bending of two-layer welded beams and the structure in the vicinity of the weld reveal that the obtained metal-nanocomposite bond has a uniform structure retained in deformation, with fracture occurring in the nanocomposite.

  3. Elastic properties and atomic bonding character in metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Rouxel, T., E-mail: tanguy.rouxel@univ-rennes1.fr [Institut de Physique de Rennes, IPR, UMR-CNRS 6251, Université de Rennes, campus de Beaulieu, 35042 Rennes cedex (France); Yokoyama, Y. [Cooperative Research and Development Center for Advanced Materials, Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)

    2015-07-28

    The elastic properties of glasses from different metallic systems were studied in the light of the atomic packing density and bonding character. We found that the electronegativity mismatch (Δe{sup −}) between the host- and the major solute-elements provides a plausible explanation to the large variation observed for Poisson's ratio (ν) among metallic glasses (MGs) (from 0.28 for Fe-based to 0.43 for Pd-based MGs), notwithstanding a similar atomic packing efficiency (C{sub g}). Besides, it is found that ductile MGs correspond to Δe{sup −} smaller than 0.5 and to a relatively steep atomic potential well. Ductility is, thus, favored in MGs exhibiting a weak bond directionality on average and opposing a strong resistance to volume change.

  4. Bump Bonding Using Metal-Coated Carbon Nanotubes

    Science.gov (United States)

    Lamb, James L.; Dickie, Matthew R.; Kowalczyk, Robert S.; Liao, Anna; Bronikowski, Michael J.

    2012-01-01

    Bump bonding hybridization techniques use arrays of indium bumps to electrically and mechanically join two chips together. Surface-tension issues limit bump sizes to roughly as wide as they are high. Pitches are limited to 50 microns with bumps only 8-14 microns high on each wafer. A new process uses oriented carbon nanotubes (CNTs) with a metal (indium) in a wicking process using capillary actions to increase the aspect ratio and pitch density of the connections for bump bonding hybridizations. It merges the properties of the CNTs and the metal bumps, providing enhanced material performance parameters. By merging the bumps with narrow and long CNTs oriented in the vertical direction, higher aspect ratios can be obtained if the metal can be made to wick. Possible aspect ratios increase from 1:1 to 20:1 for most applications, and to 100:1 for some applications. Possible pitch density increases of a factor of 10 are possible. Standard capillary theory would not normally allow indium or most other metals to be drawn into the oriented CNTs, because they are non-wetting. However, capillary action can be induced through the ability to fabricate oriented CNT bundles to desired spacings, and the use of deposition techniques and temperature to control the size and mobility of the liquid metal streams and associated reservoirs. This hybridization of two technologies (indium bumps and CNTs) may also provide for some additional benefits such as improved thermal management and possible current density increases.

  5. Some Approaches of Ultrasonic Evaluation of Metal Sheets Adhesive Bonds

    Science.gov (United States)

    Maeva, E. Yu.; Severina, I. A.; O'Neill, B.; Severin, F. M.; Maev, R. Gr.

    2004-02-01

    Proper interpretation of ultrasonic inspection results for adhesive bonding of thin metal sheets is discussed. Several approaches including pulse-echo imaging, resonance spectrometry and Lamb wave technique are compared. New method of signal processing based on estimation of cross-correlation function is proposed. Theoretical speculations are supported by experiments with plane and spherically focused acoustic beams. The practical aspects of discussed methods as well as technical recommendations are provided for developing a specialized inspection system.

  6. Metallic bond effects on mean excitation energies for stopping powers

    Science.gov (United States)

    Wilson, J. W.; Xu, Y. J.

    1982-01-01

    Mean excitation energies for first row metals are evaluated by means of the local plasma approximation. Particle corrections based on Pines' (1953) procedure and the Wigner Seitz (1934) model of the metallic state are included. The agreement with experimental values is remarkably good. In contrast to previous work, the calculations given here estimate shifts in the plasma frequency according to the theory for plane wave states in an extended plasma as calculated by Pines. It is demonstrated that the effects of the metallic bond in lithium and beryllium are quite large and that they appear mainly as a result of collective oscillations in the 'free' electron gas formed from the valence electrons. The usefulness of the plasma frequency shift derived for a degenerate electron gas in predicting the plasma frequency shift within the ion core is considered surprising.

  7. Transition-Metal-Catalyzed C-H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds.

    Science.gov (United States)

    Hummel, Joshua R; Boerth, Jeffrey A; Ellman, Jonathan A

    2016-12-12

    The transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom-substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functional group compatibility and without the production of waste byproducts. Additionally, many transition-metal-catalyzed C-H bond additions to polarized π bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds.

  8. Bonding, aromaticity and reactivity patterns in some all-metal and non-metal clusters

    Indian Academy of Sciences (India)

    S Duley; S Giri; A Chakraborty; P K Chattaraj

    2009-09-01

    Several sandwich-like metal clusters have been studied at the B3LYP/6-311 + G∗ level of theory. Bonding and reactivity have been analysed through various geometrical parameters and conceptual density functional theory based global reactivity descriptors. Aromaticity patterns have been understood in terms of the associated nucleus independent chemical shift values. Possibility of bond-stretch isomerism in some doped clusters is explored. Preferable sites for electrophilic and nucleophilic attacks have been identified using different local reactivity descriptors.

  9. Electrostatically enhanced FF interactions through hydrogen bonding, halogen bonding and metal coordination: an ab initio study.

    Science.gov (United States)

    Bauzá, Antonio; Frontera, Antonio

    2016-07-27

    In this manuscript the ability of hydrogen and halogen bonding interactions, as well as metal coordination to enhance FF interactions involving fluorine substituted aromatic rings has been studied at the RI-MP2/def2-TZVPD level of theory. We have used 4-fluoropyridine, 4-fluorobenzonitrile, 3-(4-fluorophenyl)propiolonitrile and their respective meta derivatives as aromatic compounds. In addition, we have used HF and IF as hydrogen and halogen bond donors, respectively, and Ag(i) as the coordination metal. Furthermore, we have also used HF as an electron rich fluorine donor entity, thus establishing FF interactions with the above mentioned aromatic systems. Moreover, a CSD (Cambridge Structural Database) search has been carried out and some interesting examples have been found, highlighting the impact of FF interactions involving aromatic fluorine atoms in solid state chemistry. Finally, cooperativity effects between FF interactions and both hydrogen and halogen bonding interactions have been analyzed and compared. We have also used Bader's theory of "atoms in molecules" to further describe the cooperative effects.

  10. A fluorescence based non-radioactive electrophoretic mobility shift assay.

    Science.gov (United States)

    Ruscher, K; Reuter, M; Kupper, D; Trendelenburg, G; Dirnagl, U; Meisel, A

    2000-03-10

    Electrophoretic mobility shift assay (EMSA) or gel shift assay is one of the most powerful methods for studying protein-DNA interactions. Typically, 32P-labeled DNA probes containing the sequence bound by the protein of interest are used in EMSA (rEMSA). Although rEMSA is sensitive and practicable, it relies on the handling of hazardous radioisotopes, and does not easily allow quantification. We developed a non-radioactive procedure using fluorescence (Cyano dye Cy5) labeled oligodeoxynucleotide duplexes as specific probes (fEMSA) and an automatic DNA sequencer for analysis. Testing different DNA-binding proteins (restriction endonuclease EcoRII, transcription factor NFkappaB and it's subunit p50) the results in fEMSA and rEMSA are similar in regard to quality, reproducibility, and sensitivity. fEMSA allows a semiquantitative screening of large amounts of samples for specific DNA binding activities and is, therefore, a high throughput technology for semiquantitative analysis of DNA-protein interaction.

  11. Is it True That the Normal Valence-Length Correlation Is Irrelevant for Metal-Metal Bonds?

    Science.gov (United States)

    Singh, Vijay; Dixit, Mudit; Kosa, Monica; Major, Dan Thomas; Levi, Elena; Aurbach, Doron

    2016-04-04

    The most intriguing feature of metal-metal bonds in inorganic compounds is an apparent lack of correlation between the bond order and the bond length. In this study, we combine a variety of literature data obtained by quantum chemistry and our results based on the empirical bond valence model (BVM), to confirm for the first time the existence of a normal exponential correlation between the effective bond order (EBO) and the length of the metal-metal bonds. The difference between the EBO and the formal bond order is attributed to steric conflict between the (TM)n cluster (TM=transition metal) and its environment. This conflict, affected mainly by structural type, should cause high lattice strains, but electron redistribution around TM atoms, evident from the BVM calculations, results in a full or partial strain relaxation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Integration of robust fluidic interconnects using metal to glass anodic bonding

    Science.gov (United States)

    Briand, Danick; Weber, Patrick; de Rooij, Nicolaas F.

    2005-09-01

    This paper reports on the encapsulation of a piezoresistive silicon/Pyrex liquid flow sensor using metal to glass anodic bonding. The bonding technique allowed integrating robust metallic microfluidic interconnects and eliminating the use of glue and O-rings. The bonding parameters of a silicon/Pyrex/metal triple stack were chosen to minimize the residual stress and to obtain a strong and liquid tight bonding interface. The silicon/Pyrex liquid flow sensor was successfully bonded to metallic plates of Kovar and Alloy 42, on which tubes were fixed and a printed circuit board (PCB) was integrated. A post-bonding annealing procedure was developed to reduce the residual bonding stress. The characteristics of the encapsulated liquid flow sensor, such as the temperature coefficient of sensitivity, fulfilled the specifications. Wafer level packaging using metal to glass anodic bonding was considered to reduce the packaging size and cost.

  13. Covalent bonds against magnetism in transition metal compounds.

    Science.gov (United States)

    Streltsov, Sergey V; Khomskii, Daniel I

    2016-09-20

    Magnetism in transition metal compounds is usually considered starting from a description of isolated ions, as exact as possible, and treating their (exchange) interaction at a later stage. We show that this standard approach may break down in many cases, especially in 4d and 5d compounds. We argue that there is an important intersite effect-an orbital-selective formation of covalent metal-metal bonds that leads to an "exclusion" of corresponding electrons from the magnetic subsystem, and thus strongly affects magnetic properties of the system. This effect is especially prominent for noninteger electron number, when it results in suppression of the famous double exchange, the main mechanism of ferromagnetism in transition metal compounds. We study this mechanism analytically and numerically and show that it explains magnetic properties of not only several 4d-5d materials, including Nb2O2F3 and Ba5AlIr2O11, but can also be operative in 3d transition metal oxides, e.g., in CrO2 under pressure. We also discuss the role of spin-orbit coupling on the competition between covalency and magnetism. Our results demonstrate that strong intersite coupling may invalidate the standard single-site starting point for considering magnetism, and can lead to a qualitatively new behavior.

  14. Damage tolerance of bonded composite aircraft repairs for metallic structures

    Science.gov (United States)

    Clark, Randal John

    This thesis describes the development and validation of methods for damage tolerance substantiation of bonded composite repairs applied to cracked plates. This technology is used to repair metal aircraft structures, offering improvements in fatigue life, cost, manufacturability, and inspectability when compared to riveted repairs. The work focuses on the effects of plate thickness and bending on repair life, and covers fundamental aspects of fracture and fatigue of cracked plates and bonded joints. This project falls under the UBC Bonded Composite Repair Program, which has the goal of certification and widespread use of bonded repairs in civilian air transportation. This thesis analyses the plate thickness and transverse stress effects on fracture of repaired plates and the related problem of induced geometrically nonlinear bending in unbalanced (single-sided) repairs. The author begins by developing a classification scheme for assigning repair damage tolerance substantiation requirements based upon stress-based adhesive fracture/fatigue criteria and the residual strength of the original structure. The governing equations for bending of cracked plates are then reformulated and line-spring models are developed for linear and nonlinear coupled bending and extension of reinforced cracks. The line-spring models were used to correct the Wang and Rose energy method for the determination of the long-crack limit stress intensity, and to develop a new interpolation model for repaired cracks of arbitrary length. The analysis was validated using finite element models and data from mechanical tests performed on hybrid bonded joints and repair specimens that are representative of an in-service repair. This work will allow designers to evaluate the damage tolerance of the repaired plate, the adhesive, and the composite patch, which is an airworthiness requirement under FAR (Federal Aviation Regulations) 25.571. The thesis concludes by assessing the remaining barriers to

  15. Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes

    NARCIS (Netherlands)

    Jongbloed, L.S.

    2016-01-01

    The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Car

  16. Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes

    NARCIS (Netherlands)

    L.S. Jongbloed

    2016-01-01

    The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Car

  17. Theoretical determination of the alkali-metal superoxide bond energies

    Science.gov (United States)

    Partridge, Harry; Bauschlicher, Charles W., Jr.; Sodupe, Mariona; Langhoff, Stephen R.

    1992-01-01

    The bond dissociation energies for the alkali-metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional level. Our computed D0 values are 61.4, 37.2, 40.6, and 38.4 kcal/mol for LiO2, NaO2, KO2, and RbO2, respectively. These values, which are expected to be lower bounds and accurate to 2 kcal/mol, agree well with some of the older flame data, but rule out several recent experimental measurements.

  18. Unveiling nickelocene bonding to a noble metal surface

    Science.gov (United States)

    Bachellier, N.; Ormaza, M.; Faraggi, M.; Verlhac, B.; Vérot, M.; Le Bahers, T.; Bocquet, M.-L.; Limot, L.

    2016-05-01

    The manipulation of a molecular spin state in low-dimensional materials is central to molecular spintronics. The designs of hybrid devices incorporating magnetic metallocenes are very promising in this regard, but are hampered by the lack of data regarding their interaction with a metal. Here, we combine low-temperature scanning tunneling microscopy and density functional theory calculations to investigate a magnetic metallocene at the single-molecule level—nickelocene. We demonstrate that the chemical and electronic structures of nickelocene are preserved upon adsorption on a copper surface. Several bonding configurations to the surface are identified, ranging from the isolated molecule to molecular layers governed by van der Waals interactions.

  19. INVESTIGATION OF BONDING IN OXIDE-FIBER (WHISKER) REINFORCED METALS.

    Science.gov (United States)

    CERAMIC FIBERS , BONDING), (*COMPOSITE MATERIALS, BONDING), (*BONDING, CERAMIC FIBERS ), ALUMINUM COMPOUNDS, OXIDES, ZIRCONIUM, NICKEL, TITANIUM, CHROMIUM, SINGLE CRYSTALS, VACUUM, SHEAR STRESSES, SURFACE PROPERTIES, ADDITIVES.

  20. ELECTRONIC AND CHEMICAL PROPERTIES OF PD IN BIMETALLIC SYSTEMS: HOW MUCH DO WE KNOW ABOUT HETERONUCLEAR METAL-METAL BONDING?

    Energy Technology Data Exchange (ETDEWEB)

    RODRIGUEZ,J.A.

    2001-09-27

    The experimental and theoretical studies described above illustrate the complex nature of the heteronuclear metal-metal bond. In many cases, bimetallic bonding induces a significant redistribution of charge around the bonded metals. This redistribution of charge is usually linked to the strength of the bimetallic bond, affects the position of the core and valence levels of the metals, and can determine the chemical reactivity of the system under study. New concepts are emerging [22,23,34,36] and eventually the coupling of experiment and theory can be useful for designing more efficient bimetallic catalysts [98,106,107].

  1. Evaluation of shear bond strength of metallic and ceramic brackets bonded to enamel prepared with self-etching primer.

    Science.gov (United States)

    Uysal, Tancan; Ustdal, Ayca; Kurt, Gokmen

    2010-04-01

    The aim of this in vitro study was to evaluate the shear bond strength (SBS) of different metallic and ceramic bracket bonding combinations using self-etching primers (SEPs). Eighty freshly extracted human premolar teeth were randomly divided into four equal groups for bonding with ceramic or metallic brackets as follows: group 1, metallic brackets bonded with conventional acid etching; group 2, metallic brackets bonded with Transbond Plus Self-Etching primer (TPSEP); group 3, ceramic brackets bonded as per group 1; group 4, ceramic brackets bonded as per group 2. The SBS of these brackets was measured and recorded in megapascals (MPa). The adhesive remnant index (ARI) scores were determined after bracket failure. Data were analyzed with the analysis of variance, Tukey, and chi-square tests. The bond strength of group 3 (mean: 36.7 +/- 11.8 MPa) was significantly higher than group 4 (mean: 26.6 +/- 8.9 MPa; P 0.05). Compared with conventional acid etching, SEPs significantly decreased the SBS of ceramic orthodontic brackets.

  2. Glass-to-metal bonding process improves stability and performance of semiconductor devices

    Science.gov (United States)

    Trent, R. L.

    1970-01-01

    Anodic bonding of glass coverslips to photodiodes and photovoltaic devices eliminates the need for adhesive. The process requires relatively low temperatures /less than 560 degrees C/ and the metals and glass remain solid throughout the bonding process.

  3. Synthesis and characterization of metal--metal bonded dimers of tantalum and tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Templeton, Joseph Leslie [Iowa State Univ., Ames, IA (United States)

    1975-12-01

    A search for innovative synthetic routes to new metal-metal bonded metal-halide clusters resulted in isolation of two completely independent dimeric species. The syntheses and characterizations of Ta2X6(SC4H8)3 (X = Cl, Br) and ((n-C3H7)4N)2(W2Br9) followed entirely different experimental routes, yet occasionally similar properties linked the two projects.

  4. Shear strength of resin developed by four bonding agents used with cast metal restorations.

    Science.gov (United States)

    Reilly, B; Davis, E L; Joynt, R B; Quevedo, J

    1992-07-01

    The evolution of the acid etch technique has made possible a more conservative approach to the fabrication of cast metal restorations. The resin bonding technique, however, places a greater burden for success on the selection of a bonding agent. This study examined the shear bond strength durability of cast metal restorations bonded to tooth structure with one of four metal adhesive bonding agents. Results indicated stronger bonds for restorations cemented with Panavia EX bonding agent than with any of the other bonding agents tested, both with and without exposure to thermal stress. Although it was one of the easier materials with which to work, Panavia EX bonding agent requires the additional step of applying an agent to prevent oxygen contact in the setting process.

  5. Microstructure and properties of hot roll bonding layer of dissimilar metals. 2. Bonding interface microstructure of Zr/stainless steel by hot roll bonding and its controlling

    Energy Technology Data Exchange (ETDEWEB)

    Yasuyama, Masanori; Ogawa, Kazuhiro; Taka, Takao; Nakasuji, Kazuyuki [Sumitomo Metal Industries Ltd., Osaka (Japan); Nakao, Yoshikuni; Nishimoto, Kazutoshi

    1996-07-01

    The hot roll bonding of zirconium and stainless steel inserted with tantalium was investigated using the newly developed rolling mill. The effect of hot rolling temperatures of zirconium/stainless steel joints on bonding interface structure was evaluated. Intermetallic compound layer containing cracks was observed at the bonding interface between stainless steel and tantalium when the rolling temperature was above 1373K. The hardness of the bonding layer of zirconium and tantalium bonded above 1273K was higher than tantalium or zirconium base metal in spite of absence of intermetallic compound. The growth of reaction layer at the stainless steel and tantalium interface and at the tantalium and zirconium interface was conforming a parabolic low when that was isothermally heated after hot roll bonding, and the growth rate was almost same as that of static diffusion bonding without using hot roll bonding process. It is estimated that the strain caused by hot roll bonding gives no effect on the growth of reaction layer. It was confirmed that the dissimilar joint of zirconium and stainless steel with insert of tantalium having the sound bonding interface were obtained at the suitable bonding temperature of 1173K by the usage of the newly developed hot roll bonding process. (author)

  6. An in vitro Comparative Evaluation of Micro Tensile Bond Strength of Two metal bonding Resin Cements bonded to Cobalt Chromium alloy

    Science.gov (United States)

    Musani, Smita; Musani, Iqbal; Dugal, Ramandeep; Habbu, Nitin; Madanshetty, Pallavi; Virani, Danish

    2013-01-01

    Background: The purpose of this study was to evaluate and compare the micro tensile bond strength of two metal bonding resin cements to sandblasted cobalt chromium alloy. Materials & Methods: Eight, Cobalt chromium alloy blocks of dimensions 10x5x5 mm were cast, finished and polished. One of the faces of each alloy block measuring 5x5mm was sandblasted with 50 μm grit alumina particles. The alloy blocks were then cleaned in an ultrasonic cleaner for 1 min and then air dried with an air stream. The Sandblasted surfaces of the two alloy blocks were bonded together with 2 different metal bonding resin systems (Panavia F Kuraray and DTK Kleber – Bredent). The samples were divided into 2 groups (n=4). Group 1- Two Co-Cr blocks were luted with Panavia cement. Group 2- Two Co-Cr blocks were luted with DTK Kleber-Bredent cement. The bonded samples were cut with a diamond saw to prepare Microtensile bars of approximately 1mm x 1mm x 6mm. Thirty bars from each group were randomly separated into 2 subgroups (n=15) and left for 3hrs (baseline) as per manufacturer's instructions while the other group was aged for 24hrs in 370C water, prior to loading to failure under tension at a cross head speed of 1mm/min. Failure modes were determined by means of stereomicroscopy (sm). Statistical analysis was performed through one way – ANOVA. Results: Significant variation in micro-tensile bond strength was observed between the two metal bonding resin systems. Conclusion: DTK showed higher mean bond strength values than Panavia F cement both at baseline and after aging. How to cite this article: Musani S, Musani I, Dugal R, Habbu N, Madanshetty P, Virani D. An in vitro Comparative Evaluation of Micro Tensile Bond Strength of Two metal bonding Resin Cements bonded to Cobalt Chromium alloy. J Int Oral Health 2013;5(5):73-8. PMID:24324308

  7. Direct bonding for dissimilar metals assisted by carboxylic acid vapor

    Science.gov (United States)

    Song, Jenn-Ming; Huang, Shang-Kun; Akaike, Masatake; Suga, Tadatomo

    2015-03-01

    This study developed a low-temperature low-vacuum direct bonding process for dissimilar metals via surface modification with formic acid vapor. Robust Cu/Ag and Cu/Zn bonding with a shear strength higher than 25 MPa can be achieved by thermal compression at 275 and 300 °C, respectively. CuZn5 and Cu5Zn8 formed at the interface of Cu/Zn joints, while no distinct interdiffusion layers appeared at the Cu/Ag interface. At elevated temperatures, the shear strength of Cu/Zn joints decreased significantly and turned to be weaker than Cu/Ag at 250 °C due to the softening of Zn. All the joints performed well subjected to thermal cycling up to 1000 times. However, compared with Cu/Ag joints with stable mechanical performance suffering aging at 250 °C, the shear strength of Cu/Zn degraded drastically up to 200 h, and after that it remained almost constant, which can be ascribed to the competitive growth between CuZn5 and Cu5Zn8, resulting in collapse and oxidation of CuZn5.

  8. Metal hydrides form halogen bonds: measurement of energetics of binding.

    Science.gov (United States)

    Smith, Dan A; Brammer, Lee; Hunter, Christopher A; Perutz, Robin N

    2014-01-29

    The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η(5)-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η(5)-cyclopentadienyl) is demonstrated by (1)H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = -10.9 ± 0.4 and -11.8 ± 0.3 kJ/mol; ΔS° = -38 ± 2 and -34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH° = -7.3 ± 0.1 kJ/mol, ΔS° = -24 ± 1 J/(mol·K)). For the more reactive complexes 2-5, measurements are limited to determination of their low-temperature (212 K) association constants with C6F5I as 2.9 ± 0.2, 2.5 ± 0.1, <1.5, and 12.5 ± 0.3 M(-1), respectively.

  9. JOINING MECHANISM OF FIELD-ASSISTED BONDING OF ELECTROLYTE GLASS TO METALS

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Investigations of technological characteristics and bonding mechanism of field-assisted bonding are done, which are for bonding of electrolytes (Pyrex glass) to monocrystal silicon and aluminum. The features of microstructure and the distribution of the diffused elements in the bonding interface area are studied by means of SEM, EDX and XRD, and the influence of the technological factors on the bonding process is also studied. The model of"metal-oxides-glass"of bonding structure and ions diffusion and bonding in the condition of electrical field-assisted are indicated.

  10. Technetium dichloride: a new binary halide containing metal-metal multiple bonds.

    Science.gov (United States)

    Poineau, Frederic; Malliakas, Christos D; Weck, Philippe F; Scott, Brian L; Johnstone, Erik V; Forster, Paul M; Kim, Eunja; Kanatzidis, Mercouri G; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2011-06-15

    Technetium dichloride has been discovered. It was synthesized from the elements and characterized by several physical techniques, including single crystal X-ray diffraction. In the solid state, technetium dichloride exhibits a new structure type consisting of infinite chains of face sharing [Tc(2)Cl(8)] rectangular prisms that are packed in a commensurate supercell. The metal-metal separation in the prisms is 2.127(2) Å, a distance consistent with the presence of a Tc≡Tc triple bond that is also supported by electronic structure calculations.

  11. A RhIII-N-heterocyclic carbene complex from metal-metal singly bonded [RhII−RhII] precursor

    Indian Academy of Sciences (India)

    Arup Sinha; Abir Sarbajna; Shrabani dinda; Jitendra K Bera

    2011-11-01

    Metal-metal singly bonded [Rh2(CO)4(acac)2][OTf]2 (1) has been synthesized and characterized by spectroscopic and analytical techniques. A density functional theory (DFT) optimized structure has been computed for the unbridged centro-symmetric structure. Reaction of 1 with PIN.HBr results in the [Rh(PIN)2(H2O)Br][OTf]2 (2) in high yield. The reaction involves metal-oxidation from RhII to RhIII accompanied by the metal-metal bond cleavage. The X-ray structure of 2 has been determined which reveals the incorporation of two N-heterocyclic carbene (NHC) ligands to each rhodium. This work demonstrates the general utility of the metal-metal bonded compounds for the easy synthesis of metal-NHC compounds.

  12. GaN/metal/Si heterostructure fabricated by metal bonding and laser lift-off

    Institute of Scientific and Technical Information of China (English)

    Zhang Xiaoying; Ruan Yujiao; Chen Songyan; Li Cheng

    2009-01-01

    A process methodology has been adopted to transfer GaN thin films grown on sapphire substrates to Si substrates using metal bonding and laser lift-off techniques. After bonding, a single KrF (248 nm) excimer laser pulse was directed through the transparent sapphire substrates followed by low-temperature heat treatment to remove the substrates. The influence of bonding temperature and energy density of the excimer laser on the structure and optical properties of GaN films were investigated systemically. Atomic force microscopy, X-ray diffraction and photolumi-nescence measurements showed that (1) the quality of the GaN film was higher at a lower bonding temperature and lower energy density; (2) the threshold of the energy density of the excimer laser lift-off GaN was 300 mJ/cm~2. The root-mean-square roughness of the transferred GaN surface was about 50 nm at a bonding temperature of 400 ℃.

  13. Influence of metal bonding layer on strain transfer performance of FBG

    Science.gov (United States)

    Liu, Hao; Chen, Weimin; Zhang, Peng; Liu, Li; Shu, Yuejie; Wu, Jun

    2013-01-01

    Metal bonding layer seriously affects the strain transfer performance of Fiber Bragg Grating (FBG). Based on the mode of FBG strain transfer, the influence of the length, the thickness, Poisson's ratio, elasticity modulus of metal bonding layer on the strain transfer coefficient of FBG is analyzed by numerical simulation. FBG is packaged to steel wire using metal bonding technology of FBG. The tensile tests of different bonding lengths and elasticity modulus are carried out. The result shows the strain transfer coefficient of FBGs are 0.9848,0.962 and their average strain sensitivities are 1.076 pm/μɛ,1.099 pm/μɛ when the metal bonding layer is zinc, whose lengths are 15mm, 20mm, respectively. The strain transfer coefficient of FBG packaged by metal bonding layer raises 8.9 percent compared to epoxy glue package. The preliminary experimental results show that the strain transfer coefficient increases with the length of metal bonding layer, decreases with the thickness of metal bonding layer and the influence of Poisson's ratio can be ignored. The experiment result is general agreement with the analysis and provides guidance for metal package of FBG.

  14. Evaluation of shear bond strength of composite resin to nonprecious metal alloys with different surface treatments

    OpenAIRE

    Yassini E.; Almasi S

    2007-01-01

    Background and Aim: Replacing fractured ceramometal restorations may be the best treatment option, but it is costly. Many different bonding systems are currently available to repair the fractured ceramometal restorations. This study compared the shear bond strength of composite to a base metal alloy using 4 bonding systems.Materials and Methods: In this experimental in vitro study, fifty discs, casted in a Ni-Cr-Be base metal alloy (Silvercast, Fulldent),were ground with 120, 400 and 600 grit...

  15. Experimental Investigations on the Influence of Adhesive Oxides on the Metal-Ceramic Bond

    Directory of Open Access Journals (Sweden)

    Susanne Enghardt

    2015-01-01

    Full Text Available The objective of this study was to test the influence of selected base metals, which act as oxide formers, on the metal-ceramic bond of dental veneer systems. Using ion implantation techniques, ions of Al, In and Cu were introduced into near-surface layers of a noble metal alloy containing no base metals. A noble metal alloy with base metals added for oxide formation was used as a reference. Both alloys were coated with a low-temperature fusing dental ceramic. Specimens without ion implantation or with Al2O3 air abrasion were used as controls. The test procedures comprised the Schwickerath shear bond strength test (ISO 9693-1, profile height (surface roughness measurements (ISO 4287; ISO 4288; ISO 25178, scanning electron microscopy (SEM imaging, auger electron spectroscopy (AES and energy dispersive X-ray analysis (EDX. Ion implantation resulted in no increase in bond strength. The highest shear bond strengths were achieved after oxidation in air and air abrasion with Al2O3 (41.5 MPa and 47.8 MPa respectively. There was a positive correlation between shear bond strength and profile height. After air abrasion, a pronounced structuring of the surface occurred compared to ion implantation. The established concentration shifts in alloy and ceramic could be reproduced. However, their positive effects on shear bond strength were not confirmed. The mechanical bond appears to be of greater importance for metal-ceramic bonding.

  16. Unwilling U-U bonding in U2@C80: cage-driven metal-metal bonds in di-uranium fullerenes.

    Science.gov (United States)

    Foroutan-Nejad, Cina; Vícha, Jan; Marek, Radek; Patzschke, Michael; Straka, Michal

    2015-10-07

    Endohedral actinide fullerenes are rare and a little is known about their molecular properties. Here we characterize the U2@C80 system, which was recently detected experimentally by means of mass spectrometry (Akiyama et al., JACS, 2001, 123, 181). Theoretical calculations predict a stable endohedral system, (7)U2@C80, derived from the C80:7 IPR fullerene cage, with six unpaired electrons. Bonding analysis reveals a double ferromagnetic (one-electron-two-center) U-U bond at an rU-U distance of 3.9 Å. This bonding is realized mainly via U(5f) orbitals. The U-U interaction inside the cage is estimated to be about -18 kcal mol(-1). U-U bonding is further studied along the U2@Cn (n = 60, 70, 80, 84, 90) series and the U-U bonds are also identified in U2@C70 and U2@C84 systems at rU-U∼ 4 Å. It is found that the character of U-U bonding depends on the U-U distance, which is dictated by the cage type. A concept of unwilling metal-metal bonding is suggested: uranium atoms are strongly bound to the cage and carry a positive charge. Pushing the U(5f) electron density into the U-U bonding region reduces electrostatic repulsion between enclosed atoms, thus forcing U-U bonds.

  17. Dihydrogen bonding vs metal-σ interaction in complexes between H2 and metal hydride.

    Science.gov (United States)

    Alkorta, Ibon; Elguero, Jose; Solimannejad, Mohammad; Grabowski, Sławomir J

    2011-01-20

    The complexes formed by hydrogen with metal hydrides (LiH, NaH, BeH(2), MgH(2), BH(3), AlH(3), Li(2)H(2), Na(2)H(2), Be(2)H(4), and Mg(2)H(4)) have been theoretically studied at the MP2/aug-cc-pVTZ, MP2/aug-cc-pVQZ and CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ levels of theory. The hydrogen molecule can act as a Lewis acid or base. In the first case, a dihydrogen bonded complex is obtained and in the second an interaction between the σ-bond of the hydrogen molecule and an empty orbital of the metal atoms is found. Quantum theory of atoms in molecules and natural bond orbitals methods have been applied to analyze the intermolecular interactions. Additionally, the cooperativity effects are analyzed for selected complexes with two H(2) molecules where both kinds of interactions exist simultaneously.

  18. Effect of layered manufacturing techniques, alloy powders, and layer thickness on metal-ceramic bond strength.

    Science.gov (United States)

    Ekren, Orhun; Ozkomur, Ahmet; Ucar, Yurdanur

    2017-07-06

    Direct metal laser sintering (DMLS) and direct metal laser melting (DMLM) have become popular for fabricating the metal frameworks of metal-ceramic restorations. How the type of layered manufacturing device, layer thickness, and alloy powder may affect the bond strength of ceramic to metal substructure is unclear. The purpose of this in vitro study was to evaluate the bond strength of dental porcelain to metal frameworks fabricated using different layered manufacturing techniques (DMLS and DMLM), Co-Cr alloy powders, and layer thicknesses and to evaluate whether a correlation exists between the bond strength and the number of ceramic remnants on the metal surface. A total of 75 bar-shaped metal specimens (n=15) were fabricated using either DMLS or DMLM. The powder alloys used were Keramit NP-S and EOS-Cobalt-Chrome SP-2 with layer thicknesses of 20 μm and 30 μm. After ceramic application, the metal-ceramic bond strength was evaluated with a 3-point-bend test. Three-way ANOVA followed by the Tukey honest significance difference test were used for statistical analysis (α=.05). De-bonding surface microstructure was observed with scanning electron microscopy. Energy dispersive spectroscopy analysis was conducted to evaluate the correlation between ceramic remnants on the metal surface and bond strength values. The mean bond strength value of DMLS was significantly higher than that of DMLM. While no statistically significant difference was found between layer thicknesses, alloy powders closely affected bond strength. Statistical comparisons revealed that the highest bond strength could be achieved with DMLS-Cobalt-Chrome SP2-20μm, and the lowest bond strength was observed in DMLS-Keramit NP-S-20μm (P≤.05). No correlation was found between porcelain remnants on the metal surface and bond strength values. The layered manufacturing device and the alloy powders evaluated in the current study closely affected the bond strength of dental porcelain to a metal framework

  19. Bonding Interface and Bending Deformation of Al/316LSS Clad Metal Prepared by Explosive Welding

    Science.gov (United States)

    Guo, Xunzhong; Fan, Minyu; Wang, Liuan; Ma, Fuye

    2016-06-01

    The morphology, elemental distribution, and phase analysis of the bonding interface were investigated by means of SEM, EDS, and XRD to evaluate the interface bonding properties of Al/316LSS clad metal prepared by explosive welding method. Furthermore, the micro-hardness and bending properties were also investigated. The results indicated that the linear and wavy bonding interfaces coexisted and intermetallic phases were present in the local interfacial zone. Moreover, the micro-hardness value at the bonding interface with intermetallic phases was higher than that at the interface without any intermetallic phases. In addition, bulk metal compounds could easily lead to the generation of micro-cracks during the bending forming process.

  20. Molecular Adsorption Bond Lengths at Metal Oxide Surfaces: Failure of Current Theoretical Methods

    Energy Technology Data Exchange (ETDEWEB)

    Hoeft, J.-T.; Kittel, M.; Polcik, M.; Bao, S.; Toomes, R. L.; Kang, J.-H.; Woodruff, D. P.; Pascal, M.; Lamont, C. L. A.

    2001-08-20

    New experimental structure determinations for molecular adsorbates on NiO(100) reveal much shorter Ni-C and Ni-N bond lengths for adsorbed CO and NH{sub 3} as well as NO (2.07, 1.88, 2.07{angstrom}) than previously computed theoretical values, with discrepancies up to 0.79{angstrom}, highlighting a major weakness of current theoretical descriptions of oxide-molecule bonding. Comparisons with experimentally determined bond lengths of the same species adsorbed atop Ni on metallic Ni(111) show values on the oxide surface that are consistently larger (0.1--0.3{angstrom}) than on the metal, indicating somewhat weaker bonding.

  1. Metal-Organic Frameworks (MOFs) of a Cubic Metal Cluster with Multicentered Mn(I)-Mn(I) Bonds.

    Science.gov (United States)

    Hu, Huan-Cheng; Hu, Han-Shi; Zhao, Bin; Cui, Ping; Cheng, Peng; Li, Jun

    2015-09-28

    MOFs with both multicentered metal-metal bonds and low-oxidation-state (LOS) metal ions have been underexplored hitherto. Here we report the first cubic [Mn(I) 8 ] cluster-based MOF (1) with multicentered Mn(I)-Mn(I) bonds and +1 oxidation state of manganese (Mn(I) or Mn(I)), as is supported by single-crystal structure determination, XPS analyses, and quantum chemical studies. Compound 1 possesses the shortest Mn(I)-Mn(I) bond of 2.372 Å. Theoretical studies with density functional theory (DFT) reveal extensive electron delocalization over the [Mn(I) 8 ] cube. The 48 electrons in the [Mn(I) 8 ] cube fully occupy half of the 3d-based and the lowest 4s-based bonding orbitals, with six electrons lying at the nonbonding 3d-orbitals. This bonding feature renders so-called cubic aromaticity. Magnetic properties measurements show that 1 is an antiferromagnet. This work is expected to inspire further investigation of cubic metal-metal bonding, MOF materials with LOS metals, and metalloaromatic theory.

  2. Bond length and local energy density property connections for non-transition-metal oxide-bonded interactions.

    Science.gov (United States)

    Gibbs, G V; Spackman, M A; Jayatilaka, D; Rosso, K M; Cox, D F

    2006-11-01

    For a variety of molecules and earth materials, the theoretical local kinetic energy density, G(r(c)), increases and the local potential energy density, V(r(c)), decreases as the M-O bond lengths (M = first- and second-row metal atoms bonded to O) decrease and the electron density, rho(r(c)), accumulates at the bond critical points, r(c). Despite the claim that the local kinetic energy density per electronic charge, G(r(c))/rho(r(c)), classifies bonded interactions as shared interactions when less than unity and closed-shell when greater, the ratio was found to increase from 0.5 to 2.5 au as the local electronic energy density, H(r(c)) = G(r(c)) + V(r(c)), decreases and becomes progressively more negative. The ratio appears to be a measure of the character of a given M-O bonded interaction, the greater the ratio, the larger the value of rho(r(c)), the smaller the coordination number of the M atom and the more shared the bonded interaction. H(r(c))/rho(r(c)) versus G(r(c))/rho(r(c)) scatter diagrams categorize the M-O bonded interactions into domains with the local electronic energy density per electron charge, H(r(c))/rho(r(c)), tending to decrease as the electronegativity differences for the bonded pairs of atoms decrease. The values of G(r(c)) and V(r(c)), estimated with a gradient-corrected electron gas theory expression and the local virial theorem, are in good agreement with theoretical values, particularly for the bonded interactions involving second-row M atoms. The agreement is poorer for shared C-O and N-O bonded interactions.

  3. Comparison of shear bond strengths of two resin luting systems for a base and a high noble metal alloy bonded to enamel.

    Science.gov (United States)

    Dixon, D L; Breeding, L C; Hughie, M L; Brown, J S

    1994-11-01

    Researchers are investigating the use of noble metals for the fabrication of resin-bonded prostheses because of concerns about health hazards of nickel and beryllium in base metal alloys. Tin-plating has been advocated to improve the bond of resin luting agents to noble metal alloys. Some manufacturers have suggested that tin-plating is unnecessary to bond noble metal alloys to etched enamel with their products. In this study, Rexillium base metal and Olympia noble metal alloy specimens were bonded to extracted human teeth with the use of two resin luting agents (F21 and Panavia OP). One third of the noble metal specimens were tin-plated, one third were oxidized, and one third were oxidized and sandblasted. Each of the bonded specimens were thermocycled and subjected to a shear force until bond failure. The base metal specimens bonded with Panavia OP luting agent exhibited the greatest mean shear bond strengths. The tin-plating surface treatment significantly increased the mean shear bond strengths of Olympia noble metal specimens.

  4. Metal-activated histidine carbon donor hydrogen bonds contribute to metalloprotein folding and function.

    Science.gov (United States)

    Schmiedekamp, Ann; Nanda, Vikas

    2009-07-01

    Carbon donor hydrogen bonds are typically weak interactions that contribute less than 2 kcal/mol, and provide only modest stabilization in proteins. One exception is the class of hydrogen bonds donated by heterocyclic side chain carbons. Histidine is capable of particularly strong interactions through the Cepsilon(1) and Cdelta(2) carbons when the imidazole is protonated or bound to metal. Given the frequent occurrence of metal-bound histidines in metalloproteins, we characterized the energies of these interactions through DFT calculations on model compounds. Imidazole-water hydrogen bonding could vary from -11.0 to -17.0 kcal/mol, depending on the metal identity and oxidation state. A geometric search of metalloprotein structures in the PDB identified a number of candidate His C-H...O hydrogen bonds which may be important for folding or function. DFT calculations on model complexes of superoxide reductase show a carbon donor hydrogen bond positioning a water molecule above the active site.

  5. Effect of Adhesive Type on the Shear Bond Strength of Metal Brackets to Two Ceramic Substrates

    Directory of Open Access Journals (Sweden)

    Mohammad Sadegh Ahmad Akhoundi

    2014-04-01

    Full Text Available Increased number of adult patients requesting orthodontic treatment result in bonding bracket to ceramic restorations more than before. The aim of this study was to evaluate and compare the shear bond strength of orthodontic brackets bonded to two types of ceramic bases with conventional orthodontic bonding resin and a new nano-filled composite resin.Twenty four feldespathic porcelain and 24 lithium disilicate ceramic disks were fabricated. All of the samples were conditioned by sandblasting, hydrofluoric acid and silane. Maxillary incisor metal brackets were bonded to half of the disks in each group by conventional orthodontic bonding resin and the other half bonded with a nano-filled composite. The samples then were thermocycled for 2000 cycle between 5-55° C. Shear bond strength was measured and the mode of failure was examined. Randomly selected samples were also evaluated by SEM.The lowest bond strength value was found infeldespathic ceramic bonded by nano-filled composite (p<0.05. There was not any statistically significant difference between other groups regarding bond strength. The mode of failure in the all groups except group 1 was cohesive and porcelain damages were detected.Since less damages to feldspathic porcelain was observed when the nano-filled composite was used to bond brackets, the use of nano-filled composite resins can be suggested for bonding brackets to feldspathic porcelain restorations.

  6. Oxidative cleavage of benzylic C-N bonds under metal-free conditions.

    Science.gov (United States)

    Gong, Jin-Long; Qi, Xinxin; Wei, Duo; Feng, Jian-Bo; Wu, Xiao-Feng

    2014-10-14

    An interesting procedure for the oxidative cleavage of benzylic C-N bonds has been developed. Using TBAI as the catalyst and H2O2 as the oxidant, various benzylamines were transformed into their corresponding aromatic aldehydes in moderate to good yields. Notably, this is the first example of an oxidative cleavage of benzylic C-N bonds under metal-free conditions.

  7. Metal-organic framework catalysts for selective cleavage of aryl-ether bonds

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Stavila, Vitalie

    2017-08-01

    The present invention relates to methods of employing a metal-organic framework (MOF) as a catalyst for cleaving chemical bonds. In particular instances, the MOF results in selective bond cleavage that results in hydrogenolyzis. Furthermore, the MOF catalyst can be reused in multiple cycles. Such MOF-based catalysts can be useful, e.g., to convert biomass components.

  8. The effect of enamel bleaching on the shear bond strengths of metal and ceramic brackets.

    Science.gov (United States)

    Oztaş, E; Bağdelen, G; Kiliçoğlu, H; Ulukapi, H; Aydin, I

    2012-04-01

    The aim of this study was to evaluate the effects of bleaching and delayed bonding on the shear bond strengths of metal and ceramic brackets bonded with light and chemically cure composite resin to human enamel. One hundred and twenty extracted human premolar teeth were randomly divided into three groups of 40 each. The first two groups were bleached with 20 per cent carbamide peroxide (CP) at-home bleaching agent. No bleaching procedures were applied to the third group and served as control. The first two and control groups were divided into equal subgroups according to different adhesive-bracket combinations. Specimens in group 1 (n = 40) were bonded 24 hours after bleaching process was completed while the specimens in group 2 (n = 40) were bonded 14 days after. The specimens in all groups were debonded with a Universal testing machine while the modified adhesive remnant index was used to evaluate fracture properties. No statistically significant differences were found between the shear bond strengths of metal and ceramic brackets bonded to bleached enamel after 24 hours, 14 days, and unbleached enamel with light or chemical cure adhesives (P > 0.05). The mode of failure was mostly at the bracket/adhesive interface and cohesive failures within the resin were also observed. Our findings indicated that at-home bleaching agents that contain 20 per cent CP did not significantly affect the shear bond strength of metal and ceramic orthodontic brackets to enamel when bonding is performed 24 hours or 14 days after bleaching.

  9. Use of sampling based correction for non-radioactivity X-ray energy calibration

    Institute of Scientific and Technical Information of China (English)

    CHENG Cheng; WEI Yong-Bo; JIANG Da-Zhen

    2005-01-01

    As the requirement of non-radioactivity measurement has increased in recent years, various energy calibration methods applied in portable X-ray fluorescence (XRF) spectrometers have been developed. In this paper, a sampling based correction energy calibration has been discussed. In this method both history information and current state of the instrument are considered and relative high precision and reliability can be obtained.

  10. On the structure and bonding of first row transition metal ozone carbonyl hydrides.

    Science.gov (United States)

    Venter, Gerhard A; Raubenheimer, Helgard G; Dillen, Jan

    2007-08-23

    Model complexes of the general form M(CO)m(H)n(O3) (m = 1-5, n = 0 or 1) between ozone and the transition metals Ti to Cu were studied by density functional theory (DFT) calculations. The CDA charge decomposition method was used to analyze the interaction between the metal atom and the ozone ligand in terms of the traditional donation-back-donation mechanisms. Information about bond strengths was extracted from an analysis of the electron density in terms of the theory of atoms in molecules (AIM). The bonding in the ozone-metal complex was also studied within the NBO paradigm. Bond dissociation energies were calculated to be positive for all the complexes studied. Considering all the criteria employed in this study to analyze the interaction between the ozone and the transition metal, the Fe-complex is predicted to be the most stable, whereas the copper complex has the weakest metal-ozone interaction.

  11. Thin Films from Solvated Metal Atoms and Metal-Metal Bonded Compounds

    Science.gov (United States)

    1988-07-01

    Departamento de Quimica , Universidad de Con- palladium colloids. cepcion, Casilla 3-C, Concepcion, Chile. (2) Department of Physics. (3) Turkevich, J.; Stevenson... change would be the period before particle stabilization that is important. realized. Indeed, with this procedure the resulting Pd And if metal...case controlled by concentration effects. 21 With palladium we electrophoretic behavior changed markedly, and mea- , invariably obtained particle sizes

  12. Using Alloys of Cr-Ni-Co system as metallic bond in powder metallurgy products

    Directory of Open Access Journals (Sweden)

    A. M. Gazaliyev

    2015-10-01

    Full Text Available There is studied the possibility of using alloys of the Cr-Ni-Cо system as a metallic bond in producing ceramet. As the basic material there was used titanium carbide. There were measured such mechanical properties as bending strength, tensile strength, impact viscosity. There is considered a possibility of using ceramet with a metallic bond of the Cr-Ni-Co system as a refractory material. As a heat resistance indicator there was estimated the limit of long durability. It is established that in the studied range of temperatures the material properties are the function of the bond content.

  13. Shear bond strength of metallic and ceramic brackets using color change adhesives

    Directory of Open Access Journals (Sweden)

    Aisha de Souza Gomes Stumpf

    2013-04-01

    Full Text Available OBJECTIVE: To determine the shear bond strength of orthodontic brackets using color change adhesives that are supposed to aid in removing excess of bonding material and compare them to a traditional adhesive. METHODS: Ninety metallic and ninety ceramic brackets were bonded to bovine incisors using two color change adhesives and a regular one. A tensile stress was applied by a universal testing machine. The teeth were observed in a microscope after debonding in order to determine the Adhesive Remnant Index (ARI. RESULTS: The statistical analysis (ANOVA, Tukey, and Kruskall-Wallis tests demonstrated that the mean bond strength presented no difference when metallic and ceramic brackets were compared but the bond resistance values were significantly different for the three adhesives used. The most common ARI outcome was the entire adhesive remaining on the enamel. CONCLUSIONS: The bond strength was similar for metallic and ceramic brackets when the same adhesive system was used. ARI scores demonstrated that bonding with these adhesives is safe even when ceramic brackets were used. On the other hand, bond strength was too low for orthodontic purposes when Ortho Lite Cure was used.

  14. Effect of Repeated Firings of Porcelain on Bond Strength of Two Base Metal Alloys

    Directory of Open Access Journals (Sweden)

    Gerami Panah F

    2001-05-01

    Full Text Available The formation of oxides on the surface of the metal are proven to contribute to the formation of strong bonding. However, The base metal alloys are expected to exhibit more oxidation than high gold alloys, increase in oxide layer thickness due to repeated firing in them can reduce the bond strength. The aim of this study was to compare the effect of repeated porcelain firing on the bond strength of two base metal alloys (Minalux and Verabond II. Sixteen metal plates (20x5x0.5 from each alloy were cast and prepared according to the manufacturers' instruction. Porcelain with uniform thickness (Imm was applied on the middle one third of metal plates. After this stage, each alloy group divided to three subgroups. Group I was fired for the second time to form the final glaze, group II and III were fired two and four more times respectively. Specimens were subjected to 3-point flexural test in a digital tritest machine. Results showed no significant differences between bond strength of two alloys. Also results showed repeated firing had no significant effect on bond strength. Due to these findings, this study support similarity of two alloys (Minalux and Verabond II in their bond strength with porcelain.

  15. Development of dissimilar metal transition joint by hot roll bonding technique

    Energy Technology Data Exchange (ETDEWEB)

    Nagai, Takayuki; Takeda, Seiichiro; Tanaka, Yasumasa (Power Reactor and Nuclear Fuel Development Corp., Tokai, Ibaraki (Japan). Tokai Works); Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Ikenaga, Yoshiaki

    1994-12-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by the hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author).

  16. Development of dissimilar metal transition joint by hot roll bonding technique

    Energy Technology Data Exchange (ETDEWEB)

    Nagai, Takayuki; Takeuchi, Masayuki; Takeda, Seiichiro; Shikakura, Sakae [Power Reactor and Nuclear Fuel Development Corp., Tokai, Ibaraki (Japan). Tokai Works; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Kajimura, Haruhiko

    1995-12-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called `rotary reduction mill`. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author).

  17. Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

    Science.gov (United States)

    Humphries, T D; Sheppard, D A; Buckley, C E

    2015-06-30

    For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

  18. A new, peroral non-radioactive vitamin B{sub 12} absorption test compared with the Schilling test

    Energy Technology Data Exchange (ETDEWEB)

    Magnus, E.; Mueller, C. [Ullevaal Hospital, Dept. of Haematology and Dept. of Nuclear Medicine, Oslo (Norway)

    1995-02-01

    The results of a non-radioactive, peroral absorption test have been compared with the results of the traditional Schilling test in 31 cobalamin-deficient patients. The non-radioactive test is simple to perform, is less costly than the Schilling test and seems to give reliable results. The non-radioactive test should be performed after cobalamin treatment, but not until the plasma cobalamin value has declined to below 450 pmol/l. Normal Schilling test was noted in one-third of the patients, while normal non-radioactive test was noted in only one-fifth of the patients. The results reveal some discrepancies between the two tests regarding the response to intrinsic factor. In the non-radioactive test without intrinsic factor, the great variation in values may reflect varying secretion of intrinsic factor, possibly secondary to infestation with Helicobacter pylori. `False normal` Schilling test seems to be more common than previously believed. (au) (12 refs.).

  19. Evaluation of shear bond strength of composite resin to nonprecious metal alloys with different surface treatments

    Directory of Open Access Journals (Sweden)

    Yassini E.

    2007-07-01

    Full Text Available Background and Aim: Replacing fractured ceramometal restorations may be the best treatment option, but it is costly. Many different bonding systems are currently available to repair the fractured ceramometal restorations. This study compared the shear bond strength of composite to a base metal alloy using 4 bonding systems.Materials and Methods: In this experimental in vitro study, fifty discs, casted in a Ni-Cr-Be base metal alloy (Silvercast, Fulldent,were ground with 120, 400 and 600 grit sandpaper and divided equally into 5 groups receiving 5 treatments for veneering. Conventional feldspathic porcelain (Ceramco2, Dentsply Ceramco was applied on control group (PFM or group1 and the remaining metal discs were air- abraded for 15 seconds with 50 mm aluminum oxide at 45 psi and washed for 5 seconds under tap water.Then the specimens were dried by compressed air and the  groups were treated with one of the bonding systems as follows: All-Bond 2 (AB, Ceramic Primer (CP, Metal Primer II (MP and Panavia F2 (PF. An opaque composite (Foundation opaque followed by a hybrid composite (Gradia Direct was placed on the treated metal surface and light cured separately. Specimens were stored in distilled water at 370C and thermocycled prior to shear strength testing. Fractured specimens were evaluated under a stereomicroscope. Statistical analysis was performed with one way ANOVA and Tukey HSD tests. P<0.05 was considered as the level of significance.Results: Mean shear bond strengths of the groups in MPa were as follows: PFM group 38.6±2, All-Bond 2 17.06±2.85, Ceramic Primer 14.72±1.2, Metal Primer II 19.04±2.2 and Panavia F2 21.37±2.1. PFM group exhibited the highest mean shear bond strength and Ceramic Primer showed the lowest. Tukey's HSD test revealed the mean bond strength of the PFM group to be significantly higher than the other groups (P<0.001. The data for the PF group was significantly higher than AB and CP groups (P<0.05 and the shear

  20. Theoretical study of the bonding of the first- and second-row transition-metal positive ions to acetylene

    Science.gov (United States)

    Sodupe, M.; Bauschlicher, Charles W., Jr.

    1991-01-01

    The bonding of transition-metal ions to acetylene is studied by using a theoretical treatment that includes electron correlation. The ions on the left side of the first and second transition rows insert into the pi bond to form a three-membered ring. On the right side of the row the bonding is electrostatic. The trends in bonding are discussed.

  1. Oxidation study on as-bonded intermetallic of copper wire-aluminum bond pad metallization for electronic microchip

    Energy Technology Data Exchange (ETDEWEB)

    Joseph Sahaya Anand, T., E-mail: anand@utem.edu.my [Faculty of Manufacturing Engineering, University Technical Malaysia Melaka, Hang Tuah Jaya, 76100 Durian Tunggal, Melaka (Malaysia); Yau, Chua Kok [Faculty of Manufacturing Engineering, University Technical Malaysia Melaka, Hang Tuah Jaya, 76100 Durian Tunggal, Melaka (Malaysia); University of Technical Malaysia Supported by Infineon Technology - Malaysia - Sdn. Bhd., Melaka (Malaysia); Huat, Lim Boon [Department of Innovation, Infineon Technology - Malaysia - Sdn. Bhd., FTZ Batu Berendam, 75350 Melaka (Malaysia)

    2012-10-15

    In this work, influence of Copper free air ball (FAB) oxidation towards Intermetallic Compound (IMC) at Copper wire-Aluminum bond pad metallization (Cu/Al) is studied. Samples are synthesized with different Copper FAB oxidation condition by turning Forming Gas supply ON and OFF. Studies are performed using Optical Microscope (OM), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and line-scan Energy Dispersive X-ray (EDX). SEM result shows there is a cross-sectional position offset from center in sample synthesized with Forming Gas OFF. This is due to difficulty of determining the position of cross-section in manual grinding/polishing process and high occurrence rate of golf-clubbed shape of oxidized Copper ball bond. TEM inspection reveals that the Copper ball bond on sample synthesized with Forming Gas OFF is having intermediate oxidation. Besides, the presence of IMC at the bonding interface of Cu/Al for both samples is seen. TEM study shows voids form at the bonding interface of Forming Gas ON sample belongs to unbonded area; while that in Forming Gas OFF sample is due to volume shrinkage of IMC growth. Line-scan EDX shows the phases present in the interfaces of as-bonded samples are Al{sub 4}Cu{sub 9} ({approx}3 nm) for sample with Forming Gas ON and mixed CuAl and CuAl{sub 2} ({approx}15 nm) for sample with Forming Gas OFF. Thicker IMC in sample with Forming Gas OFF is due to cross-section is positioned at high stress area that is close to edge of ball bond. Mechanical ball shear test shows that shear strength of sample with Forming Gas OFF is about 19% lower than that of sample with Forming Gas ON. Interface temperature is estimated at 437 Degree-Sign C for as-bonded sample with Forming Gas ON by using empirical parabolic law of volume diffusion. -- Highlights: Black-Right-Pointing-Pointer 3 nm Al{sub 4}Cu{sub 9} are found in sample prepared with Forming Gas ON. Black-Right-Pointing-Pointer 15 nm mixed CuAl + CuAl{sub 2} are found

  2. Saturated bonds and anomalous electronic transport in transition-metal aluminides

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, T.

    2006-05-22

    This thesis deals with the special electronic properties of the transition-metal aluminides. Following quasicrystals and their approximants it is shown that even materials with small elementary cells exhibit the same surprising effects. So among the transition-metal aluminides also semi-metallic and semiconducting compounds exist, although if they consist of classic-metallic components like Fe, Al, or Cr. These properties are furthermore coupled with a deep pseusogap respectively gap in the density of states and strongly covalent bonds. Bonds are described in this thesis by two eseential properties. First by the bond charge and second by the energetic effect of the bond. It results that in the caes of semiconducting transition-metal aluminides both a saturation of certain bonds and a bond-antibond alteration in the Fermi level is present. By the analysis of the near-order in form of the so-calles coordination polyeders it has been succeeded to establish a simple rule for semiconductors, the five-fold coordination for Al. This rule states that aluminium atoms with their three valence electrons are not able to build more than five saturated bonds to their nearest transition-metal neighbours. In excellent agreement with the bond angles predicted theoretically under assumption of equal-type bonds it results that all binary transition-element aluminide semiconductors exhibit for the Al atoms the same near order. Typical values for specific resistances of the studied materials at room temperature lie in the range of some 100 {mu}{omega}cm, which is farly larger than some 10 {mu}{omega}cm as in the case of the unalloyed metals. SUrprising is furthermore a high transport anisotropy with a ratio of the specific resistances up to 3.0. An essential result of this thesis can be seen in the coupling of the properties of the electronic transport and the bond properties. The small conducitivities could be explained by small values in the density of states and a bond

  3. Mixed-Mode Fatigue Disbond on Metallic Bonded Joints

    NARCIS (Netherlands)

    Bürger, D.B.

    2015-01-01

    Aerospace structures have been long dealing with the safety versus weight issue. Lighter airplanes are cheaper to operate, however, they may face a safety issue because of the reduced fatigue life. Consequently, a heavier/safer structure is designed. Adhesive bonding is a joining technique that offe

  4. Microleakage under Orthodontic Metal Brackets Bonded with Three Different Bonding Techniques with/without Thermocycling

    Directory of Open Access Journals (Sweden)

    Berahman Sabzevari

    2013-12-01

    Full Text Available Introduction: The aim of this study was to compare the microleakage of beneath the orthodontic brackets bonded with 3 different bonding techniques and evaluate the effect of thermocycling. Methods: One hundred and twenty premolars were randomly divided into 6 groups, received the following treatment: group 1: 37% phosphoric acid gel+Unite primer+Unite adhesive, group 2: 37% phosphoric acid gel+ Transbond XT primer+Transbond XT adhesive, group 3: Transbond plus Self Etching Primer (TSEP+Transbond XT adhesive. Groups 4, 5, and 6 were similar to groups 1, 2, and 3, respectively. Evaluation of microleakage was done following to thermocycling test. After bonding, the specimens were sealed with nail varnish except for 1 mm around the brackets and then stained with 0.5% basic fuchsine. The specimens were sectioned at buccolingual direction in 2 parallel planes and evaluated under a stereomicroscope to determine the amount of microleakage at bracket-adhesive and adhesive-enamel interfaces from gingival and occlusal margins. Results: Microleakage was observed in all groups, and increased significantly after thermocycling at some interfaces of Unite adhesive group and conventional etching+Transbond XT adhesive group, but the increase was not significant in any interface of TSEP group. With or without thermocycling, TSEP displayed more microleakage than other groups. In most groups, microleakage at gingival margin was significantly higher than occlusal margin. Conclusion: Thermocycling and type of bonding technique significantly affect the amount of microleakage.

  5. USE OF NUCLEOTIDES AS AN ALTERNATIVE TO FORMAMIDE IN NON-RADIOACTIVE IN SITU HYBRIDIZATION

    OpenAIRE

    Koji, Takehiko; Nakane, Paul K.

    1990-01-01

    To analyze the expression of specific mRNA at the level of individual cells, non-radioactive in situ hybridization has been a most powerful technique. In the process of in situ hybridization, the use of formamide is usually required in order to reduce the melting temperature (Tm) of nucleic acids. However, formamide is an expensive and unstable reagent, and more importantly, formamide in itself has some deteriorative effects such as nonspecific staining and morphological damage on the results...

  6. Non-radioactive waste management in a Nuclear Energy Research Institution

    Energy Technology Data Exchange (ETDEWEB)

    Furusawa, Helio A.; Martins, Elaine A.J.; Cotrim, Marycel E.B.; Pires, Maria A. F., E-mail: helioaf@ipen.br, E-mail: elaine@ipen.br, E-mail: mecotrim@ipen.br, E-mail: mapires@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEM-SP), Sao Paulo, SP (Brazil). Centro de Quimica e Meio Ambiente

    2013-07-01

    For more than 50 years, non-radioactive materials have been used in processes at IPEN to support the nuclear fuel development and all related activities. Reagents, raw materials, products and by-products have been stored. Many of these are hazardous highly toxic or reactants materials. Some years ago actions sent part of these non-radioactive waste materials to proper disposal (technical incineration) resulting in an Institutional Non-Radioactive Waste Management Program. In 2005, an internal set of procedures and information entitled - Guia de Procedimentos para Armazenamento, Tratamento e Descarte de Residuos de Laboratorio Quimico - (Guide of Procedures for Storage, Treatment, and Disposal of Chemistry Laboratory Wastes) - was published to be used at the IPEN's facilities. A data base managed by software was created in order to allow the Units to input data and information about the routinely generated wastes and those already existing. Even after disposing so huge amount of wastes, a latent demand still exists. Several goals were achieved notably a well-organized and roomy space; safer storage places; local, state, and nationwide laws enforcement (for radioactive and non-radioactive materials); and improvement in chemicals control as hazardous and aged materials are more frequently disposed. A special stress was conducted to know and follow laws, regulations, and technical norms as the entire process is very detailed and this is not a day-by-day routine for the IPEN's technical personnel. The immediate consequence is that the safer the workplace the safer the nuclear related activities are done. (author)

  7. Bonding of metal oxides in sodium silicate glass

    Energy Technology Data Exchange (ETDEWEB)

    Lam, D.J.; Veal, B.W.; Chen, H.; Knapp, G.S.

    1978-01-01

    X-ray photoelectron spectroscopy (XPS) and extended x-ray absorption fine structure (EXAFS) studies have been undertaken on sodium disilicate glasses containing varying amounts of Fe/sub 2/O/sub 3/ and UO/sub 2/. The XPS results enable one to distinguish the different bonding characteristics of iron and uranium in these glasses. A three dimensional model for the iron coordination in the sodium disilicate glass is inferred from the combined XPS and EXAFS results.

  8. Adhesive Bonding of Neoprene to Metals in Sonar Devices

    Science.gov (United States)

    1989-08-31

    primers. However, the most effective primers contained an epoxy resin similar to the diglycidyl ether of bisphenol-A ( DGEBA ) and 7-AEAPS. In a few cases...289.2 291.2 Table V. Non-Proprietary Primer for Bonding Neoprene to Steel. DGEBA 7.90 grams Carbon Black 2.25 7-AEAPS 1.50 Dowanol PM 45.00 Toluene

  9. Factors affecting the bond strength of denture base and reline acrylic resins to base metal materials

    Directory of Open Access Journals (Sweden)

    Naomi Tanoue

    2013-07-01

    Full Text Available OBJECTIVE: The shear bond strengths of two hard chairside reline resin materials and an auto-polymerizing denture base resin material to cast Ti and a Co-Cr alloy treated using four conditioning methods were investigated. MATERIAL AND METHODS: Disk specimens (diameter 10 mm and thickness 2.5 mm were cast from pure Ti and Co-Cr alloy. The specimens were wet-ground to a final surface finish of 600 grit, air-dried, and treated with the following bonding systems: 1 air-abraded with 50-70-µm grain alumina (CON; 2 1 + conditioned with a primer, including an acidic phosphonoacetate monomer (MHPA; 3 1 + conditioned with a primer including a diphosphate monomer (MDP; 4 treated with a tribochemical system. Three resin materials were applied to each metal specimen. Shear bond strengths were determined before and after 10,000 thermocycles. RESULTS: The strengths decreased after thermocycling for all combinations. Among the resin materials assessed, the denture base material showed significantly (p<0.05 greater shear bond strengths than the two reline materials, except for the CON condition. After 10,000 thermocycles, the bond strengths of two reline materials decreased to less than 10 MPa for both metals. The bond strengths of the denture base material with MDP were sufficient: 34.56 MPa for cast Ti and 38.30 for Co-Cr alloy. CONCLUSION: Bonding of reline resin materials to metals assessed was clinically insufficient, regardless of metal type, surface treatment, and resin composition. For the relining of metal denture frameworks, a denture base material should be used.

  10. Comparative evaluation of the shear bond strength of metal brackets bonded to porcelain using different porcelain surface treatments

    Directory of Open Access Journals (Sweden)

    Eslami Amirabadi GH

    2011-02-01

    Full Text Available "nBackground and Aims: The aim of this in vitro study was to compare shear bond strength of metal brackets bonded to dental porcelain on the basis of presence or absence of silane, type of acid [hydrofluoric acid (HF or phosphoric acid (H3PO4] and roughness of porcelain surface (glazed or deglazed within mouth-like environment."nMaterials and Methods: Eighty glazed ceramic disks were randomly divided into 8 groups of 10 disks: group 1 [HF+silane], group 2 [deglazed+HF+silane], group 3 [HF], group 4 [deglazed+HF], group 5 [H3PO4+silane], group 6 [deglazed+H3PO4+silane], group 7 [H3PO4], group 8 [deglazed+H3PO4]. Then the brackets were bonded and thermocycled. After that, shear bond strength test was done using the Zwick device and the type of bond failure was determined under stereomicroscope at 4X magnification. 3-way ANOVA and Kruskal-Wallis were used for statistical analyses."nResults: The shear bond strength for the test groups were as follows: group (1:13.05±7.7 MPa , group (2:25.16±10.66 MPa, group (3:6.7±5.86 MPa, group (4:15.39±8.97 MPa, group (5:12.76±7.91 MPa, group (6:13.57±7.85 MPa, group (7:0.54±0.67 MPa, group (8: 9.34±6.52 MPa. The type of bond failure in all groups was adhesive failure except for group 2. No significant difference in the interaction between (glazed or deglazed, (presence or absence of silane, and type of acid was found (P>0.05."nConclusion: Under the conditions of this study, the best clinical method was the use of 37% phosphoric acid and silane that resulted in the optimal clinical strength and adhesive bond failure.

  11. Divergent reactivity of nitric oxide with metal-metal quintuple bonds.

    Science.gov (United States)

    Wu, Pei-Fang; Liu, Shih-Cheng; Shieh, Yun-Jen; Kuo, Ting-Shen; Lee, Gene-Hsiang; Wang, Yu; Tsai, Yi-Chou

    2013-05-14

    Reactions of NO with the quintuple bonded chromium and molybdenum amidinate dimers, respectively, gave dichromium nitrosyl nitrito amidinato complexes, and the quadruple bonded dimolybdenum nitrito amidinato species with a paddlewheel configuration.

  12. Shear bond strength of a ceromer to noble and base metal alloys

    Directory of Open Access Journals (Sweden)

    Dorriz H.

    2006-08-01

    Full Text Available Background and Aim: The improvement of the physical and chemical properties of resins as well as great advances achieved in the field of chemical bonding of resin to metal has changed the trend of restorative treatments. Today the second generation of laboratory resins have an important role in the restoration of teeth. The clinical bond strength should be reliable in order to gain successful results. In this study the shear bond strength (SBS between targis (a ceromer and two alloys (noble and base metal was studied and the effect of thermocycling on the bond investigated. Materials and Methods: In this experimental study, alloys samples were prepared according to the manufacturer. After sandblasting of bonding surfaces with 50µ AI2o3 Targis was bonded to the alloy using Targis I link. All of the samples were placed in 37°C water for a period of 24 hours. Then half of the samples were subjected to 1000 cycles of thermocycling at temperatures of 5°C and 55°C. Planear shear test was used to test the bond strength in the Instron machine with the speed rate of 0.5mm/min. Data were analyzed by SPSS software. Two-way analysis of variance was used to compare the bond strength among the groups. T test was used to compare the alloys. The influence of thermocycling and alloy type on bond strength was studied using Mann Whitney test. P<0.05 was considered as the limit of significance. Result: The studied alloys did not differ significantly, when the samples were not thermocycled (P=0.136 but after thermocycling a significant difference was observed in SBS of resin to different alloys (P=000.1. Thermal stress and alloy type had significant interaction, with regard to shear bond strength (P=0.003. There was a significant difference in SBS before and after thermocycling in noble alloys (P=0.009, but this was not true in base metals (P=0.29. Maximum SBS (19.09 Mpa belonged to Degubond 4, before thermocycling. Minimum SBS (8.21 Mpa was seen in Degubond 4

  13. Metal-Ligand Bonds of Second- and Third-Row d-Block Metals Characterized by Density Functional Theory

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2009-01-01

    This paper presents systematic data for 200 neutral diatomic molecules ML (M is it second- or third-row d-block metal and L = H, F, Cl, Br, I, C, N, O, S, or Se) Computed with the density functionals TPSSh and BP86. With experimental Structures and bond enthalpies available for many of these mole......This paper presents systematic data for 200 neutral diatomic molecules ML (M is it second- or third-row d-block metal and L = H, F, Cl, Br, I, C, N, O, S, or Se) Computed with the density functionals TPSSh and BP86. With experimental Structures and bond enthalpies available for many...... of these molecules, the computations first document the high accuracy of TPSSh, giving metal-ligand bond lengths with a mean absolute error of similar to 0.01 angstrom for the second row and 0.03 angstrom for the third row. TPSSh provides metal-ligand bond enthalpies with mean absolute errors of 37 and 44 k.......99. Equally important, TPSSh provides uniform accuracy across all three rows of the d-block, which is unprecedented and due to the 10% exact exchange, which is close to optimal for the d-block as a whole. This work provides an accurate and systematic prediction of electronic ground-state spins, characteristic...

  14. Joining mechanism of field-assisted diffusion bonding of solid electrolyte ceramic to metals

    Institute of Scientific and Technical Information of China (English)

    孟庆森; 薛锦

    2003-01-01

    Field-assisted diffusion bonding applied in the joining of solid electrolyte borosilicate glass, β″-Al2O3, Y2O-ZrO2 to monocrystal silicate and aluminum were proceeded with bonding machine in the assistance of static electric field. TEM, SEM, XRD and other means were applied to investigate and analyze microstructure of interface. It is supposed that the interfacial area is a model of metal-oxides-ceramic, and the joining mechanism is solid diffusion joining and static electric bonding. The process of ions migration and accumulation under electric field is the most essential factor for the anodic oxidation and interfacial joining. Temperature and voltage are the basic factors of the solid diffusion bonding of interfacial oxidation. And voltage, temperature, pressure and the condition of surface are the most important factors that govern the bonding process.

  15. An In vitro Evaluation of Flexural Bond Strength of Indirect Composites Fused to Metal.

    Science.gov (United States)

    Sunitha, N; Ariga, Padma; Jain, Ashish R; Philip, Jacob Mathew

    2013-06-01

    With the advent of newer indirect composite resin materials for crown and bridge prosthesis, it has become imperative to evaluate their strength to serve as long term replacements as a substitute to metal ceramic restorations. This study aimed to evaluate and compare the flexural bond strength of three composite resin veneering material to metal, cured by different methods. Specimen were fabricated with pattern resin by duplicating it with machined metal die and divided into three groups. Three composite resin materials were used in this study. Group (A) received Adoro, Group (B) received Targis and Group (C) received Tescera. The bond strength of all specimens was tested with Lloyd's universal testing machine under three point loading. The highest values for fracture resistance were displayed by light, heat and pressure cured composites followed by composites cured using a temperature of 104 °C and composites with curing temperature of 95 °C. The results indicate that there is a significant difference between the three groups, with the Tescera group specimens exhibiting the highest flexural bond strength. Of the other two groups, Adoro group exhibited higher flexural bond strength than Targis group. The results of this study suggest that Tescera group with curing temperature of 130 °C and pressure of 80 Psi, cured with metal halide unit exhibited the highest flexural bond strength when compared to Adoro and Targis groups.

  16. Identification of the Molecule-Metal Bonding Geometries of Molecular Nanowires

    CERN Document Server

    Demir, Firuz

    2011-01-01

    Molecular nanowires in which a single molecule bonds chemically to two metal electrodes and forms a stable electrically conducting bridge between them have been studied intensively for more than a decade. However the experimental determination of the bonding geometry between the molecule and electrodes has remained elusive. Here we demonstrate by means of ab initio calculations that inelastic tunneling spectroscopy (IETS) can determine these geometries. We identify the bonding geometries at the gold-sulfur interfaces of propanedithiolate molecules bridging gold electrodes that give rise to the specific IETS signatures that were observed in recent experiments.

  17. Carbon-to-metal bonds: Electrochemical reduction of 2-butenenitrile

    Science.gov (United States)

    Deniau, Guy; Azoulay, Laurent; Jégou, Pascale; Le Chevallier, Gilles; Palacin, Serge

    2006-02-01

    2-Butenenitrile belongs to the large family of electron deficient vinylic monomers that usually form 100 to 500 nm thick grafted polymer films by electroreduction. However, 2-butenenitrile exhibits a slightly acidic hydrogen atom on its CH 3 group that inhibits the anionic polymerization usually observed with 'classical' organic monomers such as its isomer methacrylonitrile. 2-Butenenitrile thus gives nanometer thick grafted film by electroreduction, essentially composed of a mixture of monomers, dimers and trimers and in the same way, allows an easy observation by XPS of the chemical signature of the grafting, i.e. the carbon-to-nickel bond, observed at 283.6 eV.

  18. Transition-Metal-Catalyzed Redox-Neutral and Redox-Green C-H Bond Functionalization.

    Science.gov (United States)

    Wang, Hongli; Huang, Hanmin

    2016-08-01

    Transition-metal-catalyzed C-H bond functionalization has become one of the most promising strategies to prepare complex molecules from simple precursors. However, the utilization of environmentally unfriendly oxidants in the oxidative C-H bond functionalization reactions reduces their potential applications in organic synthesis. This account describes our recent efforts in the development of a redox-neutral C-H bond functionalization strategy for direct addition of inert C-H bonds to unsaturated double bonds and a redox-green C-H bond functionalization strategy for realization of oxidative C-H functionalization with O2 as the sole oxidant, aiming to circumvent the problems posed by utilizing environmentally unfriendly oxidants. In principle, these redox-neutral and redox-green strategies pave the way for establishing new environmentally benign transition-metal-catalyzed C-H bond functionalization strategies. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Effect of metal primers and tarnish treatment on bonding between dental alloys and veneer resin

    OpenAIRE

    Choo, Seung-Sik; Huh, Yoon-Hyuk; Cho, Lee-Ra; Park, Chan-Jin

    2015-01-01

    PURPOSE The aim of this study was to evaluate the effect of metal primers on the bonding of dental alloys and veneer resin. Polyvinylpyrrolidone solution's tarnish effect on bonding strength was also investigated. MATERIALS AND METHODS Disk-shape metal specimens (diameter 8 mm, thickness 1.5 mm) were made from 3 kinds of alloy (Co-Cr, Ti and Au-Ag-Pd alloy) and divided into 4 groups per each alloy. Half specimens (n=12 per group) in tarnished group were immersed into polyvinylpyrrolidone solu...

  20. The effect of furcated hydrogen bond and coordination bond on luminescent behavior of metal-organic framework [CuCN·EIN]: a TDDFT study.

    Science.gov (United States)

    Wu, Danyang; Mi, Weihong; Ji, Min; Hao, Ce; Qiu, Jieshan

    2012-11-01

    The hydrogen bonding in electronically excited-state of the metal-organic framework [CuCN·EIN] was studied using time-dependent density functional theory (TDDFT). The representative fragment of [CuCN·EIN] was employed for the computation. The geometric structures, binding energies and IR spectra in both ground state and electronically excited state S(1) of the complex were computed using DFT and TDDFT methods to investigate excited-state hydrogen-bonding and coordination bonding, respectively. Based on the analysis of the frontier molecular orbitals and the electronic configuration of the complex, the ligand-to-metal charge transfer (LMCT) luminescence was confirmed. Furthermore, furcated hydrogen bonds are both strengthened in the S(1) state slightly. And then, the strengthening of the hydrogen bonds in the S(1) state goes against the charge transfer from ligand to metal and then should be in favor of the luminescence. In particular, we also discuss strengthening or weakening behavior of the coordination bonds in the S(1) state for the first time. Based on the results of the bond lengths and vibration frequency of the coordination bond, we can conclude that the coordination bond Cu(7)-N(8) is strengthened in the S(1) state. And the strengthening of the coordination bond Cu(7)-N(8) should also be in favor of the luminescence.

  1. Effect of self-etching primer/adhesive and conventional bonding on the shear bond strength in metallic and ceramic brackets

    Science.gov (United States)

    Kimyai, Soodabeh; Hydari, Mahboubeh; Shahrbaf, Shirin; Mirzakouchaki-Boroujeni, Parvin

    2012-01-01

    Introduction: Bracket debonding from the tooth surface is a common problem in fixed orthodontics. The aims of the present study were to assess the bond strength and failure sites in two ways of bonding technique, with metallic and ceramic brackets. Material and Methods: One hundred premolars were assigned to 4 groups of 25 each: Group A, metallic brackets/ conventional procedure; Group B, metallic brackets/Transbond XT; Group C, ceramic brackets/conventional procedure; and Group D, ceramic brackets/Transbond XT. Transbond XT composite paste was used for bracket bonding and cured by conventional light-cure device. Specimens were subjected to thermocycling. One week after bonding shearing force was applied to the bracket-tooth interface. Bonding failure site optically examined using a stereomicroscope under 10 × magnifications and scoring was done using the adhesive remnant index (ARI). Data were subjected to analysis of One-way variance, Tukey post hoc, Chi-square and Spearman’s tests. Results: Mean bond strength (in MPa) were: group A=9.2, group B=8.5, group C=6.2 and group D=5.7. Bond strength differences between groups A and B, and between C and D were not significant, (pceramic ones and the selfetching primer produce fewer bonds than the conventional method (clinically acceptable). A positive correlation found between changes in shearing bond strength and ARI. Key words: Acid etching, adhesive remnant index, orthodontic brackets, self-etching primer, shearing bond strength. PMID:21743430

  2. Spin, Charge, and Bonding in Transition Metal Mono Silicides

    NARCIS (Netherlands)

    Marel, D. van der; Damascelli, A.; Schulte, K.; Menovsky, A. A.

    1997-01-01

    Published in: Physica B 244 (1998) 138-147 citations recorded in [Science Citation Index] Abstract: We review some of the relevant physical properties of the transition metal mono-silicides with the FeSi structure (CrSi, MnSi, FeSi, CoSi, NiSi, etc) and explore the relation between their structural

  3. Probing the bonding of CO to heteronuclear group 4 metal-nickel clusters by photoelectron spectroscopy.

    Science.gov (United States)

    Zou, Jinghan; Xie, Hua; Yuan, Qinqin; Zhang, Jumei; Dai, Dongxu; Fan, Hongjun; Tang, Zichao; Jiang, Ling

    2017-04-12

    A series of heterobinuclear group 4 metal-nickel carbonyls MNi(CO)n(-) (M = Ti, Zr, Hf; n = 3-7) has been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectroscopy. Quantum chemical calculations have been carried out to elucidate the geometric and electronic structures and support the spectral assignments. The n = 3 cluster is determined to be capable of simultaneously accommodating three different types of CO bonds (i.e., side-on-bonded, bridging, and terminal modes), resulting in a MNi[η(2)(μ2-C, O)](μ-CO)(CO)(-) structure, which represents the smallest metal carbonyl with the involvement of all the main modes of metal-CO coordination to date. The building block of three bridging CO molecules is favored at n = 4, the structure of which persists up to n = 7. The additional CO ligands are bonded terminally to the metal atoms. The present findings provide important new insight into the structure and bonding mechanisms of CO molecules with heteronuclear transition metals, which would have important implications for understanding chemisorbed CO molecules on alloy surfaces.

  4. S-S bond reactivity in metal-perthiocarboxylato compounds.

    Science.gov (United States)

    Mas-Ballesté, Rubén; Guijarro, Alejandro; González-Prieto, Rodrigo; Castillo, Oscar; Sanz Miguel, Pablo J; Zamora, Félix

    2010-02-14

    While M-percarboxylato species are elusive intermediates, their sulfur containing analogues are known in some cases. The feasibility of isolation of M-perthioacetato compounds allowed, in this work, to obtain new insights into the pathways that follow the reactivity of M-E-ER (E = O, S) fragments. Herein we report on the isolation of two new M-perthioacetato compounds: trans-[Pt(CH(3)CS(2)S)(2)] () and [Ni(CH(3)CSS)(CH(3)CS(2)S)] (), which have been fully characterized, including X-ray structures. Reactivity of these compounds towards PPh(3) has been studied combining UV-vis monitorization and NMR measurements. Overall the accumulated data suggest that the evolution of the perthioacetato ligand in complexes and by reaction with PPh(3) consists of a complex multistep pathway in which the sulfur transfer is preceded by electron transfer. Cyclic voltammetry measurements indicate that the transference of two electrons from the phosphorus to the sulfur atom is not concerted, suggesting that the first step of the reaction with PPh(3) is the monoelectronic electron transfer followed by P-S bond formation. The results presented here show a novel pathway in the field of S-S bond reactivity processes relevant in biological, synthetic systems and in hydrocarbon desulfurization processes.

  5. Bad metal behaviour in the new Hg-rich amalgam KHg{sub 6} with polar metallic bonding

    Energy Technology Data Exchange (ETDEWEB)

    Tambornino, Frank; Hoch, Constantin, E-mail: constantin.hoch@cup.uni-muenchen.de

    2015-01-05

    Highlights: • The novel Hg-rich amalgam KHg{sub 6} was synthesised by electrocrystallisation. • The structure was investigated by single crystal and powder diffraction. • Thermal decomposition, electric resistance and magnetic susceptibiliy were examined. • Band structure, total and partial density of states and Bader charges were calculated. • Bad metal behaviour results from ionic, metallic and covalent bonding contributions. - Abstract: The new mercury-rich amalgam KHg{sub 6} crystallises with the BaHg{sub 6} structure type (orthorhombic, space group Pnma (No. 62), a = 13.394(9) Å, b = 5.270(3) Å, c = 10.463 Å). It was prepared by electrolysis of a solution of KI in N,N′-Dimethylformamide at 343 K at a reactive Hg cathode. The structure of KHg{sub 6} shows motifs of ionic packing, covalent Hg cluster formation and metallic properties. KHg{sub 6} decomposes peritectically at 443 K. The combination of alkali metals with a noble metal with moderate electron affinity results in the formation of polar metal–metal bonding with considerable but incomplete electron transfer from the electropositive to the electronegative sublattice, resulting in typical “bad metal behaviour”, illustrated by resistance and susceptibility measurements and quantum theoretical calculations.

  6. The Quest for Metal-Metal Quadruple and Quintuple Bonds in Metal Carbonyl Derivatives: Nb2(CO)9 and Nb2(CO)8.

    Science.gov (United States)

    Tang, Lihong; Luo, Qiong; Li, Qian-Shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2012-03-13

    The synthesis by Power and co-workers of the first metal-metal quintuple bond (Science2005, 310, 844) is a landmark in inorganic chemistry. The 18-electron rule suggests that Nb2(CO)9 and Nb2(CO)8 are candidates for binary metal carbonyls containing metal-metal quadruple and quintuple bonds, respectively. Density functional theory (MPW1PW91 and BP86) indeed predicts structures having very short Nb-Nb distances of ∼2.5 Å for Nb2(CO)9 and ∼2.4 Å for Nb2(CO)8 as well as relatively large Nb-Nb Wiberg bond indices supporting these high formal Nb-Nb bond orders. However, analysis of the frontier molecular orbitals of these unbridged structures suggests formal Nb≡Nb triple bonds and 16-electron metal configurations. This contrasts with an analysis of the frontier orbitals in a model chromium(I) alkyl linear CH3CrCrCH3, which confirms the generally accepted presence of chromium-chromium quintuple bonds in such molecules. The presence of Nb≡Nb triple bonds rather than quadruple or quintuple bonds in the Nb2(CO)n (n = 9, 8) structures frees up d(xy) and d(x(2)-y(2)) orbitals for dπ→pπ* back-bonding to the carbonyl groups. The lowest energy Nb2(CO)n structures (n = 9, 8) are not these unbridged structures but structures having bridging carbonyl groups of various types and formal Nb-Nb orders no higher than three. Thus, the two lowest energy Nb2(CO)9 structures have Nb≡Nb triple bond distances of ∼2.8 Å and three semibridging carbonyl groups, leading to a 16-electron configuration rather than an 18-electron configuration for one of the niobium atoms. The lowest energy structure of the highly unsaturated Nb2(CO)8 is unusual since it has a formal single Nb-Nb bond of length ∼3.1 Å and two four-electron donor η(2)-μ-CO groups, thereby giving each niobium atom only a 16-electron configuration.

  7. Effect of metal primers and tarnish treatment on bonding between dental alloys and veneer resin

    Science.gov (United States)

    Choo, Seung-Sik; Huh, Yoon-Hyuk; Cho, Lee-Ra

    2015-01-01

    PURPOSE The aim of this study was to evaluate the effect of metal primers on the bonding of dental alloys and veneer resin. Polyvinylpyrrolidone solution's tarnish effect on bonding strength was also investigated. MATERIALS AND METHODS Disk-shape metal specimens (diameter 8 mm, thickness 1.5 mm) were made from 3 kinds of alloy (Co-Cr, Ti and Au-Ag-Pd alloy) and divided into 4 groups per each alloy. Half specimens (n=12 per group) in tarnished group were immersed into polyvinylpyrrolidone solution for 24 hours. In Co-Cr and Ti-alloy, Alloy Primer (MDP + VBATDT) and MAC-Bond II (MAC-10) were applied, while Alloy Primer and V-Primer (VBATDT) were applied to Au-Ag-Pd alloys. After surface treatment, veneering composite resin were applied and shear bond strength test were conducted. RESULTS Alloy Primer showed higher shear bond strength than MAC-Bond II in Co-Cr alloys and Au-Ag-Pd alloy (Pveneer resin to Co-Cr and Au-Ag-Pd alloys. PMID:26576256

  8. [Clinical analysis of laser welding on porcelain bonded metal surface].

    Science.gov (United States)

    Weng, Jia-wei; Dai, Wen-an; Wu, Xue-ying

    2011-02-01

    To evaluate the clinical effect of laser-welded crowns and bridges. Two hundred defective crowns and bridges were welded by using Heraplus laser welding machine, and then restored by porcelain. After being welded ,those defective crowns and bridges of different materials fit well and their marginal areas were also satisfactory. During the follow up period of one year, no fractured porcelain and crack were found at welding spots. The technology of laser welding has no direct effect on welding spots between metal and porcelain and could be used to deal with the usual problems of the crowns and bridges.

  9. Effect of alloy type and surface conditioning on roughness and bond strength of metal brackets

    NARCIS (Netherlands)

    Nergiz, I.; Schmage, P.; Herrmann, W.; Ozcan, M.; Nergiz, [No Value

    2004-01-01

    The effect of 5 different surface conditioning methods on bonding of metal brackets to cast dental alloys was examined. The surface conditioning methods were fine (30-µm) or rough (125-µm) diamond bur, sandblasting (50-µm or 110-µm aluminum oxide [Al2O3]), and silica coating (30-µm silica). Fifty

  10. Formation of metal-F bonds during frictional sliding : Influence of water and applied load

    NARCIS (Netherlands)

    Shen, J. T.; Pei, Y. T.; De Hosson, J. Th. M.

    2016-01-01

    Effects of water lubrication and applied load on the formation of PTFE transfer films and metal-F bonds during sliding when PTFE filled composites sliding against steel and Al2O3 are investigated. In water lubricated conditions, XPS analysis reveals that a thin layer of water molecules at the slidin

  11. Temperature effect on the static behaviour of adhesively-bonded metal skin to composite stiffener

    NARCIS (Netherlands)

    Teixeira De Freitas, S.; Sinke, J.

    2015-01-01

    The purpose of this research is to study the effect of temperature on the static behavior of an hybrid structure consisting of adhesively bonded Fiber Metal Laminate skin to a composite stiffener. This hybrid structure was tested using stiffener pull-off tests, which is a typical set-up used to simu

  12. Using amino acids for the chromatofocusing of metal ions on silica with bonded tetraethylenepentamine groups

    Science.gov (United States)

    Ivanov, A. V.

    2014-09-01

    Amino acid-based eluents are used for the chromatofocusing of metal ions on Tetren-SiO2 chelating sorbent (silica with bonded tetraethylenepentamine groups) for the first time. The smoothest quasilinear pH gradients form for eluents based on glutamic and aspartic acids. The separation of Mn2+, Cr3+, Co2+, Ni2+, and Cu2+ is achieved.

  13. Effect of alloy type and surface conditioning on roughness and bond strength of metal brackets

    NARCIS (Netherlands)

    Nergiz, I.; Schmage, P.; Herrmann, W.; Ozcan, M.; Nergiz, [No Value

    2004-01-01

    The effect of 5 different surface conditioning methods on bonding of metal brackets to cast dental alloys was examined. The surface conditioning methods were fine (30-µm) or rough (125-µm) diamond bur, sandblasting (50-µm or 110-µm aluminum oxide [Al2O3]), and silica coating (30-µm silica). Fifty di

  14. Bonding Form Analysis of Metals and Sulfur Fractionation in Methanol-Grown Anaerobic Granular Sludge

    NARCIS (Netherlands)

    Veen, van der A.; Gonzalez Fermoso, F.; Lens, P.N.L.

    2007-01-01

    This study investigates the metal and sulfur bonding form distribution in mesophilic (30 °C, pH 7) methanol-grown anaerobic granular sludge from upflow anaerobic sludge bed reactors operating at an organic loading rate of 3.8 g CH3OH-COD/L d. This was achieved by applying a modified Tessier sequenti

  15. Comparative study of ceramometal tensile bonding strength in two base metal alloys

    Directory of Open Access Journals (Sweden)

    Comparative study of ceramometal tensile bonding strength in two base metal alloys

    2005-06-01

    Full Text Available Statement of Problem: One of the greatest problems in metal –ceramic restorations is debonding of porcelain from dental alloys. Production of dental alloys by Iranian companies necessitates the evaluation of physical and handling properties of these products. Purpose: In this study the bond strength between porcelain and two types of base metal alloys, Supercast (with beryllium and Minalux (without beryllium was investigated. Materials and Methods: In this experimental study 10 cylindric bars from each base metal alloy were prepared. The bars were degassed and porcelain was applied around them in a disc form (8 mm diameter and 2 mm thickness. The bond strength of porcelain to metal bars was tested with the shear strength test by Instron. Data were analyzed with student t-test and P<0.05 was considered as the limit of significance. Results: The mean failure load was 71.58±6.4 KgF for Supercast and 67.34±5.48 for Minalux alloy. The bond strength of Supercast and Minalux were 55.85±4.99 MPa and 52.54±4.27 MPa respectively. The difference was statistically significant (P0.001. Conclusions: This study showed that nickel-chromium-beryllium alloy (Supercast produced significantly better ceramometal bonding than nickel chromium alloy without beryllium (Minalux.

  16. Bonding Form Analysis of Metals and Sulfur Fractionation in Methanol-Grown Anaerobic Granular Sludge

    NARCIS (Netherlands)

    Veen, van der A.; Gonzalez Fermoso, F.; Lens, P.N.L.

    2007-01-01

    This study investigates the metal and sulfur bonding form distribution in mesophilic (30 °C, pH 7) methanol-grown anaerobic granular sludge from upflow anaerobic sludge bed reactors operating at an organic loading rate of 3.8 g CH3OH-COD/L d. This was achieved by applying a modified Tessier

  17. Formation of metal-F bonds during frictional sliding : Influence of water and applied load

    NARCIS (Netherlands)

    Shen, J. T.; Pei, Y. T.; De Hosson, J. Th. M.

    2016-01-01

    Effects of water lubrication and applied load on the formation of PTFE transfer films and metal-F bonds during sliding when PTFE filled composites sliding against steel and Al2O3 are investigated. In water lubricated conditions, XPS analysis reveals that a thin layer of water molecules at the

  18. C-H bond activation by metal-superoxo species: what drives high reactivity?

    Science.gov (United States)

    Ansari, Azaj; Jayapal, Prabha; Rajaraman, Gopalan

    2015-01-01

    Metal-superoxo species are ubiquitous in metalloenzymes and bioinorganic chemistry and are known for their high reactivity and their ability to activate inert C-H bonds. The comparative oxidative abilities of M-O2(.-) species (M = Cr(III), Mn(III), Fe(III), and Cu(II)) towards C-H bond activation reaction are presented. These superoxo species generated by oxygen activation are found to be aggressive oxidants compared to their high-valent metal-oxo counterparts generated by O⋅⋅⋅O bond cleavage. Our calculations illustrate the superior oxidative abilities of Fe(III)- and Mn(III)-superoxo species compared to the others and suggest that the reactivity may be correlated to the magnetic exchange parameter.

  19. Effects of soldering and laser welding on bond strength of ceramic to metal.

    Science.gov (United States)

    Aladağ, Akin; Cömlekoğlu, M Erhan; Dündar, Mine; Güngör, M Ali; Artunç, Celal

    2011-01-01

    Welding or soldering of metal frameworks negatively affects the overall bond strength between the veneering ceramic and metal. The purpose of this study was to evaluate the effect of soldering and laser-welding procedures on the bond strength between ceramic and metal. Thirty Ni-based metal specimens (Wiron 99) (8 × 4 × 4 mm) were fabricated and divided into 3 groups; soldered (S), laser welded (L), and control (untreated cast alloy) (n=10). In S and L specimens, a notch (1 × 1.5 mm) was prepared longitudinally on the surface of each specimen and filled with compatible alloy (Wiron soldering rods and Wiroweld NC, respectively). Vickers hardness measurements were made after polishing the surfaces with a metallographic polishing kit. A veneering ceramic (VITA VMK 95) was vibrated, condensed in a mold, and fired on the metal frameworks. The specimens were sectioned in 2 axes to obtain nontrimmed bar specimens with a bonding area of approximately 1 mm². Forty bars per block were obtained. Each bar was subjected to microtensile bond strength (μTBS) testing with a crosshead speed of 1 mm/min. The μTBS data (MPa) were recorded, and SEM was used for failure analysis of the tested bars. The measurements were statistically analyzed using a 1-way ANOVA and Tamhane tests (α=.05). The mean differences in μTBS of veneering ceramic to soldered (10.4 ±2.4 MPa) and laser-welded (11.7 ±1.3 MPa) metal surfaces were not significantly different and were significantly lower than that of the cast alloy (25.4 ±3.6 MPa) (Plaser-welded groups (129 ±11 HV) (Plaser welding significantly decreased the μTBS of a veneering ceramic to a base metal alloy. Copyright © 2011 The Editorial Council of the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.

  20. Binding of hydrocarbons and other extremely weak ligands to transition metal complexes that coordinate hydrogen: Investigation of cis-interactions and delocalized bonding involving sigma bonds

    Energy Technology Data Exchange (ETDEWEB)

    Kubas, G.J.; Eckert, J.; Luo, X.L. [and others

    1997-07-01

    This is the final report of a three-year Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). At the forefront of chemistry are efforts to catalytically transform the inert C-H bonds in alkanes to more useful products using metal compounds. The goal is to observe binding and cleavage of alkane C-H bonds on metals or to use related silane Si-H bonding as models, analogous to the discovery of hydrogen (H{sub 2}) binding to metals. Studies of these unique sigma complexes (M{hor_ellipsis}H-Y; Y{double_bond}H, Si, C) will aid in developing new catalysts or technologies relevant to DOE interest, e.g., new methods for tritium isotope separation. Several transition metals (Mo, W, Mn, and Pt) were found to reversibly bind and cleave H{sub 2}, silanes, and halocarbons. The first metal-SiH{sub 4} complexes, thus serving as a model for methane reactions. A second goal is to study the dynamics and energetics of H-Y bonds on metals by neutron scattering, and evidence for interactions between bound H-Y and nearby H atoms on metal complexes has been found.

  1. Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex

    DEFF Research Database (Denmark)

    Hao, Xian; Zhu, Nan; Gschneidtner, Tina

    2013-01-01

    Coordination chemistry has been a consistently active branch of chemistry since Werner's seminal theory of coordination compounds inaugurated in 1893, with the central focus on transition metal complexes. However, control and measurement of metal-ligand interactions at the single-molecule level...... remain a daunting challenge. Here we demonstrate an interdisciplinary and systematic approach that enables measurement and modulation of the coordinative bonding forces in a transition metal complex. Terpyridine is derived with a thiol linker, facilitating covalent attachment of this ligand on both gold...

  2. Bonding of Metal Orthodontic Attachments to Sandblasted Porcelain and Zirconia Surfaces

    Science.gov (United States)

    2016-01-01

    This study evaluates tensile bond strength (TBS) of metal orthodontic attachments to sandblasted feldspathic porcelain and zirconia with various bonding protocols. Thirty-six (36) feldspathic and 36 zirconia disc samples were prepared, glazed, embedded in acrylic blocks and sandblasted, and divided into three groups according to one or more of the following treatments: hydrofluoric acid 4% (HF), Porcelain Conditioner silane primer, Reliance Assure® primer, Reliance Assure plus® primer, and Z Prime™ plus zirconia primer. A round traction hook was bonded to each sample. Static tensile bond strength tests were performed in a universal testing machine and adhesive remnant index (ARI) scoring was done using a digital camera. One-way ANOVA and Pearson chi-square tests were used to analyze TBS (MPa) and ARI scores. No statistically significant mean differences were found in TBS among the different bonding protocols for feldspathic and zirconia, p values = 0.369 and 0.944, respectively. No statistically significant distribution of ARI scores was found among the levels of feldspathic, p value = 0.569. However, statistically significant distribution of ARI scores was found among the levels of zirconia, p value = 0.026. The study concluded that silanization following sandblasting resulted in tensile bond strengths comparable to other bonding protocols for feldspathic and zirconia surface.

  3. In vitro analysis of shear bond strength and adhesive remnant index of different metal brackets

    Directory of Open Access Journals (Sweden)

    Fernanda de Souza Henkin

    Full Text Available ABSTRACT Introduction: There is a great variety of orthodontic brackets in the Brazilian market, and constantly evaluating them is critical for professionals to know their properties, so as to be able to choose which product best suits their clinical practice. Objectives: To evaluate the bond strength and the adhesive remnant index (ARI of different brands of metal brackets. Material and Methods: A total of 105 bovine incisors were used, and brackets of different brands were bonded to teeth. Seven different bracket brands were tested (MorelliTM, American OrthodonticsTM, TP OrthodonticsTM, Abzil-3MTM, OrthometricTM, TecnidentTM and UNIDENTM. Twenty-four hours after bonding, shear bond strength test was performed; and after debonding, the ARI was determined by using an optical microscope at a 10-fold increase. Results: Mean shear bond strength values ranged from 3.845 ± 3.997 (MorelliTM to 9.871 ± 5.106 MPa (TecnidentTM. The majority of the ARI index scores was 0 and 1. Conclusion: Among the evaluated brackets, the one with the lowest mean shear bond strength values was MorelliTM. General evaluation of groups indicated that a greater number of bond failure occurred at the enamel/adhesive interface.

  4. In vitro analysis of shear bond strength and adhesive remnant index of different metal brackets

    Science.gov (United States)

    Henkin, Fernanda de Souza; de Macêdo, Érika de Oliveira Dias; Santos, Karoline da Silva; Schwarzbach, Marília; Samuel, Susana Maria Werner; Mundstock, Karina Santos

    2016-01-01

    ABSTRACT Introduction: There is a great variety of orthodontic brackets in the Brazilian market, and constantly evaluating them is critical for professionals to know their properties, so as to be able to choose which product best suits their clinical practice. Objectives: To evaluate the bond strength and the adhesive remnant index (ARI) of different brands of metal brackets. Material and Methods: A total of 105 bovine incisors were used, and brackets of different brands were bonded to teeth. Seven different bracket brands were tested (MorelliTM, American OrthodonticsTM, TP OrthodonticsTM, Abzil-3MTM, OrthometricTM, TecnidentTM and UNIDENTM). Twenty-four hours after bonding, shear bond strength test was performed; and after debonding, the ARI was determined by using an optical microscope at a 10-fold increase. Results: Mean shear bond strength values ranged from 3.845 ± 3.997 (MorelliTM) to 9.871 ± 5.106 MPa (TecnidentTM). The majority of the ARI index scores was 0 and 1. Conclusion: Among the evaluated brackets, the one with the lowest mean shear bond strength values was MorelliTM. General evaluation of groups indicated that a greater number of bond failure occurred at the enamel/adhesive interface. PMID:28125142

  5. Bonding of Metal Orthodontic Attachments to Sandblasted Porcelain and Zirconia Surfaces

    Directory of Open Access Journals (Sweden)

    Amitoj S. Mehta

    2016-01-01

    Full Text Available This study evaluates tensile bond strength (TBS of metal orthodontic attachments to sandblasted feldspathic porcelain and zirconia with various bonding protocols. Thirty-six (36 feldspathic and 36 zirconia disc samples were prepared, glazed, embedded in acrylic blocks and sandblasted, and divided into three groups according to one or more of the following treatments: hydrofluoric acid 4% (HF, Porcelain Conditioner silane primer, Reliance Assure® primer, Reliance Assure plus® primer, and Z Prime™ plus zirconia primer. A round traction hook was bonded to each sample. Static tensile bond strength tests were performed in a universal testing machine and adhesive remnant index (ARI scoring was done using a digital camera. One-way ANOVA and Pearson chi-square tests were used to analyze TBS (MPa and ARI scores. No statistically significant mean differences were found in TBS among the different bonding protocols for feldspathic and zirconia, p values = 0.369 and 0.944, respectively. No statistically significant distribution of ARI scores was found among the levels of feldspathic, p value = 0.569. However, statistically significant distribution of ARI scores was found among the levels of zirconia, p value = 0.026. The study concluded that silanization following sandblasting resulted in tensile bond strengths comparable to other bonding protocols for feldspathic and zirconia surface.

  6. Chemical bonding and aromaticity in trinuclear transition-metal halide clusters.

    Science.gov (United States)

    Weck, Philippe F; Sergeeva, Alina P; Kim, Eunja; Boldyrev, Alexander I; Czerwinski, Kenneth R

    2011-02-07

    Trinuclear transition-metal complexes such as Re(3)X(9) (X = Cl, Br, I), with their uniquely featured structure among metal halides, have posed intriguing questions related to multicenter electron delocalization for several decades. Here we report a comprehensive study of the technetium halide clusters [Tc(3)(μ-X)(3)X(6)](0/1-/2-) (X = F, Cl, Br, I), isomorphous with their rhenium congeners, predicted from density functional theory calculations. The chemical bonding and aromaticity in these clusters are analyzed using the recently developed adaptive natural density partitioning method, which indicates that only [Tc(3)X(9)](2-) clusters exhibit aromatic character, stemming from a d-orbital-based π bond delocalized over the three metal centers. We also show that standard methods founded on the nucleus-independent chemical shift concept incorrectly predict the neutral Tc(3)X(9) clusters to be aromatic.

  7. Computational study of alkynes insertion into metal-hydride bonds catalyzed by bimetallic complexes.

    Science.gov (United States)

    Di Tommaso, Stefania; Tognetti, Vincent; Sicilia, Emilia; Adamo, Carlo; Russo, Nino

    2010-11-01

    Density Functional Theory investigations on the insertion mechanism of phenylacetylene into metal-hydride bonds in bimetallic (Pt,Os) catalysts have been carried out. The results obtained have been also compared with the non-reactive monometallic (Os-based) system, to elucidate the cooperative effects and to explain the observed absence of reactivity. The identified reaction path involves phenylacetylene coordination followed by the insertion into the metal-hydride bond, leading to the formation of the experimentally observed products. Both steps do not require large energies compatible with the experimental conditions. The comparison with the reaction path for the monometallic species gives some hints on the cooperative effects due to the presence of the second metal which is related to its role in the CO release for creating a coordination site for phenylacetylene and not in the insertion energetics. The calculations provide a detailed analysis of the reaction complexity and provide a rationale for the efficiency of the process.

  8. Adsorbate-metal bond effect on empirical determination of surface plasmon penetration depth.

    Science.gov (United States)

    Kegel, Laurel L; Menegazzo, Nicola; Booksh, Karl S

    2013-05-21

    The penetration depth of surface plasmons is commonly determined empirically from the observed response for adsorbate loading on gold surface plasmon resonance (SPR) substrates. However, changes in the SPR spectrum may originate from both changes in the effective refractive index near the metal surface and changes in the metal permittivity following covalent binding of the adsorbate layer. Herein, the significance of incorporating an additional adsorbate-metal bonding effect in the calculation is demonstrated in theory and in practice. The bonding effect is determined from the nonzero intercept of a SPR shift versus adsorbate thickness calibration and incorporated into the calculation of penetration depth at various excitation wavelengths. Determinations of plasmon penetration depth with and without the bonding response for alkanethiolate-gold are compared and are shown to be significantly different for a thiol monolayer adsorbate system. Additionally, plasmon penetration depth evaluated with bonding effect compensation shows greater consistency over different adsorbate thicknesses and better agreement with theory derived from Maxwell's equation, particularly for adsorbate thicknesses that are much smaller (<5%) than the plasmon penetration depth. The method is also extended to a more practically applicable polyelectrolyte multilayer adsorbate system.

  9. Comparison of Bond Strength of Metal and Ceramic Brackets Bonded with Conventional and High-Power LED Light Curing Units

    Science.gov (United States)

    Chalipa, Javad; Jalali, Yasamin Farajzadeh; Gorjizadeh, Fatemeh; Baghaeian, Pedram; Hoseini, Mohammad Hashem

    2016-01-01

    Objectives: The aim of this study was to evaluate the effect of conventional and high-power light emitting diode (LED) light curing units on shear bond strength (SBS) of metal and ceramic brackets to tooth surface. Materials and Methods: Forty sound bovine maxillary central incisors were used for the study. The teeth were divided into four groups (n=10). Teeth surfaces were etched with 37% phosphoric acid for 20 seconds. After applying a uniform layer of adhesive primer on the etched enamel, composite was placed on the base of brackets. The samples were light cured according to the manufacturer’s instructions and thermocycled. The SBS was measured. The failure mode was scored using the adhesive remnant index (ARI). Results: The mean SBS of samples in groups A (high-power LED, metal bracket), B (high-power LED, ceramic bracket), C (conventional LED, metal bracket) and D (conventional LED, ceramic bracket) was 23.1±3.69, 10.7±2.06, 24.92±6.37 and 10.74±3.18MPa, respectively. The interaction effect of type of LED unit (high-power/conventional) and bracket type on SBS was not statistically significant (P=0.483). In general, type of LED unit did not affect SBS. Type of bracket significantly affected SBS (P<0.001). The ARI score was not significantly influenced by the interaction between the type of LED unit and bracket. Conclusions: The obtained SBS is the same for both bracket types by use of high-power and conventional LED light curing units. Regardless of the type of LED unit, SBS of ceramic brackets was significantly lower than that of metal brackets.

  10. Environmental Exposure and Accelerated Testing of Rubber-to-Metal Vulcanized-Bonded Assemblies

    Science.gov (United States)

    1975-08-01

    53 percent for the unstressed and 66 percent for the stressed specimens. 4 A Z! - ~ - The attempt to improve the hydroltyic stability of vulcanized...vulcanized bonds show no loss in bond strength after two years otdoors at Rock Island * or after 14 days in the hydrolytic stability test in which...METAL Part b Weit COMPOUNDNG INGREDIENTS E57 MU__ N200 Nordel i04o0 ( EPDm ) 100 Stereon 700 (SBR) 100 Neoprene WD (CR) 100 Paracril AJ (NBR) 85 Paracril B

  11. Determination of bond energies by mass spectrometry. Some transition metal carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Michels, G.D.

    1979-01-01

    Two groups of transition metal carbonyls have been studied, M(CO)/sub 6/ and M(CO)/sub 5/CS complexes of the Group VIB metals and M/sub 2/(CO)/sub 10/ complexes of the Group VIIB metals. Results for the hexacarbonyl complexes indicate that the measured fragmentation energies are in error by 0.25 +- 0.02 eV per CO produced. This is attributed to excitation of CO to the first vibrational state. Least-squares dissociation energies calculated from corrected data for M(CO)/sub 5/CS complexes indicate that the M--CS bond is 3 to 4 times stronger than the M--CO bonds. Substitution of CS for CO in going from M(CO)/sub 6/ to M(CO)/sub 5/CS weakens the remaining M--CO bonds by an average of 0.2 eV. Previously unreported MnTc(CO)/sub 10/ and TcRe(CO)/sub 10/ are prepared by halide substitution of Tc(CO)/sub 5/Br and Re(CO)/sub 5/Br with Mn(CO)/sub 5//sup -/ and Tc(CO)/sub 5//sup -/, respectively. In the positive ion, metal and mixed-metal decacarbonyls are considered as (CO)/sub 5/M/sup +/--M(CO)/sub 5/ complexes possessing five strong and five weak M--CO bonds. For Mn/sub 2/(CO)/sub 10/ and Re/sub 2/(CO)/sub 10/, M/sup +/--M dissociation energies are 3.0 +- 0.1 and 4.0 +- 0.3 eV, respectively. These energies are 2.5 times greater than those reported for homolytic cleavage to M(CO)/sub 5//sup +/ and M(CO)/sub 5/.

  12. Shear bond strength and debonding characteristics of metal and ceramic brackets bonded with conventional acid-etch and self-etch primer systems: An in-vivo study.

    Science.gov (United States)

    Mirzakouchaki, Behnam; Shirazi, Sajjad; Sharghi, Reza; Shirazi, Samaneh; Moghimi, Mahsan; Shahrbaf, Shirin

    2016-02-01

    Different in-vitro studies have reported various results regarding shear bond strength (SBS) of orthodontic brackets when SEP technique is compared to conventional system. This in-vivo study was designed to compare the effect of conventional acid-etching and self-etching primer adhesive (SEP) systems on SBS and debonding characteristics of metal and ceramic orthodontic brackets. 120 intact first maxillary and mandibular premolars of 30 orthodontic patients were selected and bonded with metal and ceramic brackets using conventional acid-etch or self-etch primer system. The bonded brackets were incorporated into the wire during the study period to simulate the real orthodontic treatment condition. The teeth were extracted and debonded after 30 days. The SBS, debonding characteristics and adhesive remnant indices (ARI) were determined in all groups. The mean SBS of metal brackets was 10.63±1.42 MPa in conventional and 9.38±1.53 MPa in SEP system, (P=0.004). No statistically significant difference was noted between conventional and SEP systems in ceramic brackets. The frequency of 1, 2 and 3 ARI scores and debonding within the adhesive were the most common among all groups. No statistically significant difference was observed regarding ARI or failure mode of debonded specimens in different brackets or bonding systems. The SBS of metal brackets bonded using conventional system was significantly higher than SEP system, although the SBS of SEP system was clinically acceptable. No significant difference was found between conventional and SEP systems used with ceramic brackets. Total SBS of metal brackets was significantly higher than ceramic brackets. Due to adequate SBS of SEP system in bonding the metal brackets, it can be used as an alternative for conventional system. Shear bond strength, Orthodontic brackets, Adhesive remnant index, self-etch.

  13. Shear bond strength and debonding characteristics of metal and ceramic brackets bonded with conventional acid-etch and self-etch primer systems: An in-vivo study

    Science.gov (United States)

    Mirzakouchaki, Behnam; Sharghi, Reza; Shirazi, Samaneh; Moghimi, Mahsan; Shahrbaf, Shirin

    2016-01-01

    Background Different in-vitro studies have reported various results regarding shear bond strength (SBS) of orthodontic brackets when SEP technique is compared to conventional system. This in-vivo study was designed to compare the effect of conventional acid-etching and self-etching primer adhesive (SEP) systems on SBS and debonding characteristics of metal and ceramic orthodontic brackets. Material and Methods 120 intact first maxillary and mandibular premolars of 30 orthodontic patients were selected and bonded with metal and ceramic brackets using conventional acid-etch or self-etch primer system. The bonded brackets were incorporated into the wire during the study period to simulate the real orthodontic treatment condition. The teeth were extracted and debonded after 30 days. The SBS, debonding characteristics and adhesive remnant indices (ARI) were determined in all groups. Results The mean SBS of metal brackets was 10.63±1.42 MPa in conventional and 9.38±1.53 MPa in SEP system, (P=0.004). No statistically significant difference was noted between conventional and SEP systems in ceramic brackets. The frequency of 1, 2 and 3 ARI scores and debonding within the adhesive were the most common among all groups. No statistically significant difference was observed regarding ARI or failure mode of debonded specimens in different brackets or bonding systems. Conclusions The SBS of metal brackets bonded using conventional system was significantly higher than SEP system, although the SBS of SEP system was clinically acceptable. No significant difference was found between conventional and SEP systems used with ceramic brackets. Total SBS of metal brackets was significantly higher than ceramic brackets. Due to adequate SBS of SEP system in bonding the metal brackets, it can be used as an alternative for conventional system. Key words:Shear bond strength, Orthodontic brackets, Adhesive remnant index, self-etch. PMID:26855704

  14. Damascene patterned metal/adhesive wafer bonding for three-dimensional integration

    Science.gov (United States)

    McMahon, J. Jay

    Wafer bonding of damascene patterned metal/adhesive surfaces is explored for a new three-dimensional (3D) integration technology platform. By bonding a pair of damascene patterned metal/adhesive layers, high density micron-sized vias can be formed for interconnection of fully fabricated integrated circuit (IC) dies at the wafer-level. Such via dimensions increase the areal interconnect density by at least two orders of magnitude over current package and die-stacking approaches to 3D integration. The adhesive field-dielectric produces a high critical adhesion energy bond and has the potential to produce void-free bonded interfaces. This new technology platform has been demonstrated by fabricating and characterizing inter-wafer via-chains on 200 mm diameter Si wafers. Copper and partially cured divinylsiloxane bis-benzocyclobutene (BCB) are selected as the metal and adhesive, respectively, and unit processes for this demonstration are described. Typical alignment tolerance is ˜2 mum, and baseline bonding conditions include vacuum of 5x10-4 mbar, bonding force of 10 kN, and two step bonding temperature of 250°C for 60 min followed by 350°C for 60 min. Integration issues associated with the damascene patterning and the wafer bonding processes are discussed, particularly the resulting topography of damascene patterned Cu/BCB. Cross-sectional investigation of bonded and annealed inter-wafer interconnections provides insight into the Cu-Cu and BCB-BCB bonding interfaces. Inter-wafer specific contact resistance is measured to be on the order of 10-7 O-cm 2 for these via-chains. Several material characterization techniques have been explored to evaluate partially cured BCB as an adhesive field-dielectric. To investigate the critical adhesion energy, Gc, four-point bending is utilized to compare surfaces bonded after chemical-mechanical planarization (CMP) and various post-CMP treatments. The Gc of bonded 50% partially cured BCB is measured to be in the range of 32--44 J

  15. Joining of dissimilar metals by diffusion bonding. Titanium alloy with aluminum

    Energy Technology Data Exchange (ETDEWEB)

    Akca, Enes [International Univ. of Sarajevo (Bosnia and Herzegovina). Research and Development Center; International Univ. of Sarajevo (Bosnia and Herzegovina). Dept. of Mechanical Engineering; Gursel, Ali [International Univ. of Sarajevo (Bosnia and Herzegovina). Dept. of Mechanical Engineering

    2017-05-01

    This paper presents a novel diffusion bonding process of commercially pure aluminum to Ti-6Al-4V alloy at 520, 560, 600 and 640 C for 30, 45 and 60 minutes under argon gas shielding without the use of interlayer. The approach is to overcome the difficulties in fusion welding of dissimilar alloys. Diffusion bonding is a dissimilar metal welding process which can be applied to the materials without causing any physical deformations. Processed samples were metallographically prepared, optically examined followed by Vickers microhardness test and subjected to tensile test in order to determine joint strength. Scanning electron microscopy and energy dispersive spectroscopy were used in this work to investigate the compositional changes across the joint region. Elemental composition of the region has been successfully defined between titanium alloy and aluminum. The maximum tensile strength was obtained from the samples bonded at the highest temperatures of 600 and 640 C.

  16. In vitro tensile bond strength of denture repair acrylic resins to primed base metal alloys using two different processing techniques.

    Science.gov (United States)

    Banerjee, Sarmistha; Engelmeier, Robert L; O'Keefe, Kathy L; Powers, John M

    2009-12-01

    Approximately 38% of removable partial denture (RPD) failures involve fracture at the alloy/acrylic interface. Autopolymerizing resin is commonly used to repair RPDs. Poor chemical bonding of repair acrylic to base metal alloys can lead to microleakage and failure of the bond. Therefore, ideal repair techniques should provide a strong, adhesive bond. This investigation compared the tensile bond strength between cobalt-chromium (Super Cast, Pentron Laboratory Technologies, Llc., Wallingford, CT) and nickel-chromium (Rexalloy, Pentron Laboratory Technologies, Llc.) alloys and autopolymerized acrylic resin (Dentsply Repair Material, Dentsply Int, Inc, York, Pa) using three primers containing different functional monomers [UBar (UB), Sun Medical Co., Ltd., Shiga, Japan: Alloy Primer (AP) Kuraray Medical Inc., Okayama, Japan; and MR Bond (MRB) Tokyuyama Dental Corp., Tokyo, Japan] and two processing techniques (bench cure and pressure-pot cure). One hundred and twenty eight base metal alloy ingots were polished, air abraded, and ultrasonically cleaned. The control group was not primed. Specimens in the test groups were primed with one of the three metal primers. Autopolymerized acrylic resin material was bonded to the metal surfaces. Half the specimens were bench cured, and the other half were cured in a pressure pot. All specimens were stored in distilled water for 24 hours at 37 degrees C. The specimens were debonded under tension at a crosshead speed of 0.05 cm/min. The forces at which the bond failed were noted. Data were analyzed using ANOVA. Fisher's PLSD post hoc test was used to determine significant differences (p effect on bond strength of all specimens except Co-Cr alloy primed with UB. The highest bond strength was observed for both Co-Cr and Ni-Cr alloys that were sandblasted, primed with MRB, and pressure-pot cured. Co-Cr alloys primed with UB had the lowest bond strength whether bench cured or pressure-pot cured. Primed specimens generally experienced

  17. Optimum metallic-bond scheme: Theoretical study ofgeometric structures for ground-state sodium clusters

    Institute of Scientific and Technical Information of China (English)

    苏长荣; 李家明

    2002-01-01

    We present an optimum metallic-bond scheme to study the geometric structures of sodium clusters Nan (n≤15) systematically by combining the characteristics of metallic bonds and the first principle molecular dynamics simulation. The scheme provides an optimum way to examine almost all stable structures of sodium clusters and to determine their ground state structures. It is interesting to note that for the larger sodium clusters (13≤n≤15), there are some plane-like substructures on their surfaces, which resemble the fragments of the (110) plane with the highest atomic area density in the bulk bcc sodium crystal. We also propose a possible way to understand the formation of large icosahedral sodium clusters (1500<n<22000).

  18. The thermochemistry of C 2 hydrocarbons on transition metal surfaces: The bond-order-conservation approach

    Science.gov (United States)

    Shustorovich, Evgeny; Bell, Alexis T.

    1988-11-01

    The bond-order-conservation morse-potential (BOC-MP) approach has been used to calculate the total energy of C 2H x species in the adsorbed state, the relative stability of C 2H x adsorption in a dieoordinated versus a monocoordinated configuration, and the effects of metal composition and the structure of C 2H x species on the activation energy for OH and CC bond cleavage. The influence of metal composition on the thermal decomposition of C 2H 4 and C 2H 2, the hydrogenation of C 2H 4 and C 2H 2, and the hydrogenolysis of C 2H 6 are discussed in the light of these calculations. We find that most of the BOC-MP projections are in good agreement with experiment; however, some inconsistencies are noted and these are discussed.

  19. Interfacial effects on the behavior of partially bonded metal matrix composite properties

    Science.gov (United States)

    Caruso, J. J.; Chamis, C. C.

    1990-01-01

    A novel computational method developed at NASA-Lewis in order to predict the behavior of unidirectional composites has been used to explore the effects of partial debonding and fiber fracture on the behavior of room temperature and high temperature metal-matrix composites. Attention is presently given to the influence of disbonding, which occurs with fractured fibers, on the ply properties of metal-matrix composites with orthotropic fibers, in the case of a graphite fiber-reinforced copper-matrix composite. It is shown that, for small amounts of partial bonding on fractured fibers, composite material properties are not significantly affected.

  20. Amide bond cleavage initiated by coordination with transition metal ions and tuned by an auxiliary ligand.

    Science.gov (United States)

    Yang, Yongpo; Lu, Chunxin; Wang, Hailong; Liu, Xiaoming

    2016-06-21

    The reaction of ligand , N,N-bis(pyridin-2-ylmethyl)acetamide, with five transition metal salts, FeCl3·6H2O, CuCl2·2H2O, Cu(ClO4)2·6H2O, ZnCl2 and K2PtCl4/KI, produced five metal complexes, [(μ-O)(FeClL')(FeCl3)] (), [CuLCl2] (), [CuBPA(ClO4)(CHCN)] ClO4 (), [ZnLCl2] () and [PtLI2] (), where = 1-(2,4,5-tri(pyridin-2-yl)-3-(pyridin-2-ylmethyl)imidazolidin-1-yl)ethanone which formed in situ, and BPA = bis(pyridin-2-ylmethyl)amine. The ligand and complexes were characterized by a variety of spectroscopic techniques including X-ray single crystal diffraction where applicable. Depending on the metal ion and auxiliary ligand of the complex, the acetyl group of the ligand could be either intact or cleaved. When ferric chloride hexahydrate was used, the deacetylation proceeded even further and a novel heterocyclic compound () was formed in situ. A possible mechanism was proposed for the formation of the heterocyclic compound found in complex . Our results indicate that to cleave effectively an amide bond, it is essential for a metal centre to bind to the amide bond and the metal centre is of sufficient Lewis acidity.

  1. Metal-Ligand Interactions and Salt Bridges as Sacrificial Bonds in Mussel Byssus-Derived Materials.

    Science.gov (United States)

    Byette, Frédéric; Laventure, Audrey; Marcotte, Isabelle; Pellerin, Christian

    2016-10-10

    The byssus that anchors mussels to solid surfaces is a protein-based material combining strength and toughness as well as a self-healing ability. These exceptional mechanical properties are explained in part by the presence of metal ions forming sacrificial bonds with amino acids. In this study, we show that the properties of hydrogel films prepared from a byssus protein hydrolyzate (BPH) can also be improved following the biomimetic formation of sacrificial bonds. Strengthening and toughening of the materials are both observed when treating films with multivalent ions (Ca(2+) or Fe(3+)) or at the BPH isoelectric point (pI) as a result of the formation of metal-ligand bonds and salt bridges, respectively. These treatments also provide a self-healing behavior to the films during recovery time following a deformation. While pI and Ca(2+) treatments have a similar but limited pH-dependent effect, the modulus, strength, and toughness of the films increase largely with Fe(3+) concentration and reach much higher values. The affinity of Fe(3+) with multiple amino acid ligands, as shown by vibrational spectroscopy, and the more covalent nature of this interaction can explain these observations. Thus, a judicious choice of treatments on polyampholyte protein-based materials enables control of their mechanical performance and self-healing behavior through the strategic exploitation of reversible sacrificial bonds.

  2. Coulombic amino group-metal bonding: adsorption of adenine on Cu110.

    Science.gov (United States)

    Preuss, M; Schmidt, W G; Bechstedt, F

    2005-06-17

    The interaction between molecular amino groups and metal surfaces is analyzed from first-principles calculations using the adsorption of adenine on Cu110 as a model case. The amino group nitrogens are found to adsorb on top of the surface copper atoms. However, the bonding clearly cannot be explained in terms of covalent interactions. Instead, we find it to be largely determined by mutual polarization and Coulomb interaction between substrate and adsorbate.

  3. Dichlorostannylene complexes of group 10 metals, a unique bonding mode stabilized by bridging 2-pyridyldiphenylphosphine ligands

    NARCIS (Netherlands)

    Cabon, Y.; Kleijn, H.; Siegler, M. A.; Spek, A.L.; Klein Gebbink, R.J.M.; Deelman, B.J.

    2010-01-01

    The reaction of tin dichloride with catalytically-relevant group 10 metal precursors [M(Cl)(X)(2-PyPPh2)2] (M = Ni, Pd, Pt; 2-PyPPh2 = 2-pyridyldiphenylphosphine; X = Cl, Me) provides easy access to unprecedented cationic dichlorostannylene complexes [M(X)(2-PyPPh2)2(SnCl2)]+ where the M–Sn bond is

  4. Optimum Metallic-Bond Scheme: A Quantitative Analysis of Mass Spectra of Sodium Clusters

    Institute of Scientific and Technical Information of China (English)

    苏长荣; 李家明

    2001-01-01

    Based on the results of the optimum metallic-bond scheme for sodium clusters, we present a quantitative analysis of the detailed features of the mass spectra of sodium clusters. We find that, in the generation of sodium clusters with various abundances, the quasi-steady processes through adding or losing a sodium atom dominate. The quasi-steady processes through adding or losing a sodium dimer are also important to understand the detailed features of mass spectra for small clusters.

  5. Fracture analysis of cracked metallic plate repaired with adhesive bonding composite patch

    Institute of Scientific and Technical Information of China (English)

    Su Weiguo; Mu Zhitao

    2014-01-01

    Fatigue crack growth test of cracked metallic plate repaired with adhesive bonding composite patch was conducted to study the fracture behavior of crack patching. The failure mode was that crack grows along with adhesive debonding. The crack length and debonding area were measured at different numbers of cycles. The nonlinear three-dimensional(3D)finite element(FE)model considering adhesive debonding and crack growth simultaneously was developed. The experimental and analytical results were in good agreement with each other.

  6. In situ metalation of free base phthalocyanine covalently bonded to silicon surfaces

    Science.gov (United States)

    Lupo, Fabio; Tudisco, Cristina; Bertani, Federico; Dalcanale, Enrico

    2014-01-01

    Summary Free 4-undecenoxyphthalocyanine molecules were covalently bonded to Si(100) and porous silicon through thermic hydrosilylation of the terminal double bonds of the undecenyl chains. The success of the anchoring strategy on both surfaces was demonstrated by the combination of X-ray photoelectron spectroscopy with control experiments performed adopting the commercially available 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine, which is not suited for silicon anchoring. Moreover, the study of the shape of the XPS N 1s band gave relevant information on the interactions occurring between the anchored molecules and the substrates. The spectra suggest that the phthalocyanine ring interacts significantly with the flat Si surface, whilst ring–surface interactions are less relevant on porous Si. The surface-bonded molecules were then metalated in situ with Co by using wet chemistry. The efficiency of the metalation process was evaluated by XPS measurements and, in particular, on porous silicon, the complexation of cobalt was confirmed by the disappearance in the FTIR spectra of the band at 3290 cm−1 due to –NH stretches. Finally, XPS results revealed that the different surface–phthalocyanine interactions observed for flat and porous substrates affect the efficiency of the in situ metalation process. PMID:25551050

  7. In situ metalation of free base phthalocyanine covalently bonded to silicon surfaces

    Directory of Open Access Journals (Sweden)

    Fabio Lupo

    2014-11-01

    Full Text Available Free 4-undecenoxyphthalocyanine molecules were covalently bonded to Si(100 and porous silicon through thermic hydrosilylation of the terminal double bonds of the undecenyl chains. The success of the anchoring strategy on both surfaces was demonstrated by the combination of X-ray photoelectron spectroscopy with control experiments performed adopting the commercially available 2,3,9,10,16,17,23,24-octakis(octyloxy-29H,31H-phthalocyanine, which is not suited for silicon anchoring. Moreover, the study of the shape of the XPS N 1s band gave relevant information on the interactions occurring between the anchored molecules and the substrates. The spectra suggest that the phthalocyanine ring interacts significantly with the flat Si surface, whilst ring–surface interactions are less relevant on porous Si. The surface-bonded molecules were then metalated in situ with Co by using wet chemistry. The efficiency of the metalation process was evaluated by XPS measurements and, in particular, on porous silicon, the complexation of cobalt was confirmed by the disappearance in the FTIR spectra of the band at 3290 cm−1 due to –NH stretches. Finally, XPS results revealed that the different surface–phthalocyanine interactions observed for flat and porous substrates affect the efficiency of the in situ metalation process.

  8. Hydrogen bond-promoted metallic state in a purely organic single-component conductor under pressure.

    Science.gov (United States)

    Isono, Takayuki; Kamo, Hiromichi; Ueda, Akira; Takahashi, Kazuyuki; Nakao, Akiko; Kumai, Reiji; Nakao, Hironori; Kobayashi, Kensuke; Murakami, Youichi; Mori, Hatsumi

    2013-01-01

    Purely organic materials are generally insulating. Some charge-carrier generation, however, can provide them with electrical conductivity. In multi-component organic systems, carrier generation by intermolecular charge transfer has given many molecular metals. By contrast, in purely organic single-component systems, metallic states have rarely been realized although some neutral-radical semiconductors have been reported. Here we uncover a new type of purely organic single-component molecular conductor by utilizing strong hydrogen-bonding interactions between tetrathiafulvalene-based electron-donor molecules. These conductors are composed of highly symmetric molecular units constructed by the strong intra-unit hydrogen bond. Moreover, we demonstrate that, in this system, charge carriers are produced by the partial oxidation of the donor molecules and delocalized through the formation of the symmetric intra-unit hydrogen bonds. As a result, our conductors show the highest room-temperature electrical conductivity and the metallic state under the lowest physical pressure among the purely organic single-component systems, to our knowledge.

  9. Non-destructive Evaluation of Bonds Between Fiberglass Composite and Metal

    Science.gov (United States)

    Zhao, Selina; Sonta, Kestutis; Perey, Daniel F.; Cramer, K. E.; Berger, Libby

    2015-01-01

    To assess the integrity and reliability of an adhesive joint in an automotive composite component, several non-destructive evaluation (NDE) methodologies are correlated to lap shear bond strengths. A glass-fabric-reinforced composite structure was bonded to a metallic structure with a two-part epoxy adhesive. Samples were subsequently cut and tested in shear, and flaws were found in some areas. This study aims to develop a reliable and portable NDE system for service-level adhesive inspection in the automotive industry. The results of the experimental investigation using several NDE methods are presented and discussed. Fiberglass-to-metal bonding is the ideal configuration for NDE via thermography using excitation with induction heating, due to the conductive metal and non-conductive glass-fiber-reinforced composites. Excitation can be either by a research-grade induction heater of highly defined frequency and intensity, or by a service-level heater, such as would be used for sealing windshields in a body shop. The thermographs thus produced can be captured via a high-resolution infrared camera, with principal component analysis and 2D spatial Laplacian processing. Alternatively, the thermographs can be captured by low resolution thermochromic microencapsulated liquid crystal film imaging, which needs no post-processing and can be very inexpensive. These samples were also examined with phased-array ultrasound. The NDE methods are compared to the lap shear values and to each other for approximate cost, accuracy, and time and level of expertise needed.

  10. Ionic versus metallic bonding in AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters

    Science.gov (United States)

    Grover, Cameron J.; Reber, Arthur C.; Khanna, Shiv N.

    2017-06-01

    First principles electronic structure studies on the ground state geometries, stability, and the electronic structure of AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters have been carried out to examine the nature of bonding between Na or Mg and Al. Identifying whether the bonding is ionic or metallic in bulk materials is typically straightforward; however, in small clusters where quantum confinement is important, the nature of bonding may become unclear. We have performed a critical analysis of the bonding in these bimetallic clusters using charge analysis, electrical dipole moments, hybridization of the atomic orbitals, the Laplacian of the charge density at the bond critical points, and the change in the bonding energy between neutral and anionic forms of the cluster. For NanAlm clusters, we find that the Na binding is primarily ionic, while the bonding in AlnMgm is primarily metallic. We find that the Mulliken population of the 3p orbital of Na and Mg can provide a rapid assessment of the nature of bonding. We also find that the Hirshfeld charge and dipole moments are effective indicators, when placed in context. We found that the Laplacian of the charge density at the bond critical points can be misleading in identifying whether the bonding is ionic or metallic in small clusters.

  11. Fast pulsed operation of a small non-radioactive electron source with continuous emission current control.

    Science.gov (United States)

    Cochems, P; Kirk, A T; Bunert, E; Runge, M; Goncalves, P; Zimmermann, S

    2015-06-01

    Non-radioactive electron sources are of great interest in any application requiring the emission of electrons at atmospheric pressure, as they offer better control over emission parameters than radioactive electron sources and are not subject to legal restrictions. Recently, we published a simple electron source consisting only of a vacuum housing, a filament, and a single control grid. In this paper, we present improved control electronics that utilize this control grid in order to focus and defocus the electron beam, thus pulsing the electron emission at atmospheric pressure. This allows short emission pulses and excellent stability of the emitted electron current due to continuous control, both during pulsed and continuous operations. As an application example, this electron source is coupled to an ion mobility spectrometer. Here, the pulsed electron source allows experiments on gas phase ion chemistry (e.g., ion generation and recombination kinetics) and can even remove the need for a traditional ion shutter.

  12. Polarographic immunoassay coupled with catalysis of non-radioactive multiple iodine label

    Institute of Scientific and Technical Information of China (English)

    宋俊峰; 白亚丽; 过玮; 贾晓琳

    1997-01-01

    A now polarographic immunoassay was developed In this assay,human serum albumin (HSA) as the model antigen was covalently labeled with organic compound erythrosin B(EB) containing four non-radioactive iodides through Ⅰ step chemical reaction The labeling procedure is simple and the conditions needed are moderate.The molar labeling ratio of KB HSA was 12 Ⅰ The content of iodine in the conjugate obtained by the proposed procedure is ninth higher than that by the other existing methods.A heterogeneous competitive immunoassay was established by compling the catalysis of the conjugate to substrate As(Ⅲ)-Ce(Ⅳ) reaction with the linear-sweep polarographic detec-tion of As(Ⅲ) amount HSA can be determined in the HSA concentration range from 1 to 200μg/mL,with the de-tection hum of 0 66μg/ml.

  13. Surface analysis applied to metal-ceramic and bioceramic interfacial bonding

    Energy Technology Data Exchange (ETDEWEB)

    Smart, R.St.C.; Arora, P.S.; Steveson, M.; Kawashima, N.; Cavallaro, G.P.; Ming, H.; Skinner, W.M. [University of South Australia, Mawson Lakes, Adelaide, SA (Australia). Ian Wark Research Institute

    1999-12-01

    Full text: Low temperature plasma reactions, combined with sol-gel coatings, have been used to produce a variety of ceramic surface layers on metal substrates and interfacial layers between metals and oxides or other ceramics. These layers can be designed to be compositionally and functionally graded from the metal to bulk ceramic material, eg. silica, alumina, hydroxyapatite. The graded layers are generally <50nm thick, continuous, fully bonded to the substrate and deformable without disbonding. The objectives in design of these layers have been to produce: metal surfaces protected from oxidation, corrosion and acid attack; improved metal-ceramic bonding; and bioceramic titanium-based interfaces to bioactive hydroxyapatite for improved dental and medical implants. Modified Auger parameter studies for Si in XPS spectra show that the structure on the metal surfaces grades from amorphous, dehydroxylated silica on the outer surface through layer silicates, chain silicates, pyrosilicates to orthosilicates close to the metal interface. At the metal interface, detached grains of the metal are imaged with interpenetration of the oxide and silicate species linking the layer to the oxidised metal surface. The {approx}30nm layer has a substantially increased frictional load compared with the untreated oxidised metal, i.e. behaviour consistent with either stronger adhesion of the coating to the substrate or a harder surface. The composition, structure and thickness of these layers can be controlled by the duration of each plasma reaction and the choice of the final reagent. The mechanisms of reaction in each process step have been elucidated with a combination of XPS, TOF-SIMS, TEM, SEM and FTIR. Similar, graded titanium/oxide/silicate/silica ceramic surface layers have been shown to form using the low temperature plasma reactions on titanium alloys used in medical and dental implants. Thicker (i.e. {mu}m) overlayers of ceramic materials can be added to the graded surface

  14. Experimental study about the influence of adhesive stiffness to the bonding strengths of adhesives for ceramic/metal targets

    Directory of Open Access Journals (Sweden)

    W. Seifert

    2016-04-01

    The experimental results indicate that the damage behavior of the ceramic/metal composites depends on the absolute elongation of the adhesive layer. This can be controlled either by the thickness or the stiffness of the bonding layer.

  15. Probing the bonding and structures of metal-organic radicals with zero energy electrons

    Institute of Scientific and Technical Information of China (English)

    YANG DongSheng

    2012-01-01

    Metal-organic radicals are reactive and transient because of the existence of unpaired valence electrons,and thus the characterization of these open-shell systems is challenging.In our work,the radicals are synthesized by the reaction of bare metal atoms and organic ligands in a laser-vaporization supersonic molecular beam source and characterized with pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy.The molecular beam ZEKE technique routinely yields sub-meV spectral resolution and is a powerful means to study the molecular bonding and structures.This account presents several examples of single-photon ZEKE spectroscopic applications in determining metal binding modes and molecular conformations.

  16. Ultra-long metal nanowire arrays on solid substrate with strong bonding

    Directory of Open Access Journals (Sweden)

    Chen Lan

    2011-01-01

    Full Text Available Abstract Ultra-long metal nanowire arrays with large circular area up to 25 mm in diameter were obtained by direct electrodeposition on metalized Si and glass substrates via a template-based method. Nanowires with uniform length up to 30 μm were obtained. Combining this deposition process with lithography technology, micrometre-sized patterned metal nanowire array pads were successfully fabricated on a glass substrate. Good adhesion between the patterned nanowire array pads and the substrate was confirmed using scanning acoustic microscopy characterization. A pull-off tensile test showed strong bonding between the nanowires and the substrate. Conducting atomic force microscopy (C-AFM measurements showed that approximately 95% of the nanowires were electrically connected with the substrate, demonstrating its viability to use as high-density interconnect.

  17. Influence of various surface-conditioning methods on the bond strength of metal brackets to ceramic surfaces

    NARCIS (Netherlands)

    Schmage, P; Nergiz, [No Value; Herrmann, W; Ozcan, M; Nergiz, Ibrahim; �zcan, Mutlu

    2003-01-01

    With the increase in adult orthodontic treatment comes the need to find a reliable method for bonding orthodontic brackets onto metal or ceramic crowns and fixed partial dentures. In this study, shear bond strength and surface roughness tests were used to examine the effect of 4 different surface co

  18. Chiral nonracemic late-transition-metal organometallics with a metal-bonded stereogenic carbon atom: development of new tools for asymmetric organic synthesis.

    Science.gov (United States)

    Malinakova, Helena C

    2004-06-07

    Transition-metal-catalyzed cross-coupling reactions and the Heck reaction have evolved into powerful tools for the construction of carbon-carbon bonds. In most cases, the reactive organometallic intermediates feature a carbon-transition-metal sigma bond between a sp(2)-hybridized carbon atom and the transition metal (Csp(2)--TM). New, and potentially more powerful approach to transition-metal-catalyzed asymmetric organic synthesis would arise if catalytic chiral nonracemic organometallic intermediates with a stereogenic sp(3)-hybridized carbon atoms directly bonded to the transition metal (C*sp(3)--TM bond) could be formed from racemic or achiral organic substrates, and subsequently participate in the formation of a new carbon-carbon bond (C*sp(3)-C) with retention of the stereochemical information. To date, only a few catalytic processes that are based on this concept, have been developed. In this account, both "classical" and recent studies on preparation and reactivity of stable chiral nonracemic organometallics with a metal-bonded stereogenic carbon, which provide the foundation for the future design of new synthetic transformations exploiting the outlined concept, are discussed, along with examples of relevant catalytic processes.

  19. The influence of polymerization shrinkage of resin cements on bonding to metal.

    Science.gov (United States)

    Verzijden, C W; Feilzer, A J; Creugers, N H; Davidson, C L

    1992-02-01

    During the setting of a resin composite cement (RCC) used as an adhesive between a resin-bonded bridge and tooth structure, the adhesion may be disrupted by the development of shrinkage stress. The aim of this study was to investigate the influence of the shrinkage stress of three different RCCs on their adhesive and cohesive qualities when bonded to metal surfaces in a rigid set-up. Two opposing parallel NiCr discs (Wiron 77) were mounted in a tensilometer at a mutual distance of 200 microns and cemented with Panavia Ex, Clearfil F2, or Microfill Pontic C. The alloy surfaces were treated by either electrolytic etching, sand-blasting, silane-coating, or tin-plating. During setting, the discs were kept at their original mutual distance to simulate the extreme clinical situation of "complete" rigidity, where the casting and the tooth cannot move toward each other. The developing shrinkage stress was recorded continuously. During setting, the adhesive strength of the RCCs to silane-coated surfaces was always higher than their early cohesive strength. Electrolytically-etched surfaces as well as sand-blasted surfaces showed, in almost all cases, adhesive failure. The tin-plated samples showed mainly adhesive failure at the metal/resin interface. The highest bond strength values were found for silane-coated surfaces in combination with Clearfil F2.

  20. Nature of the bonding in metal-silane sigma-complexes.

    Science.gov (United States)

    McGrady, G Sean; Sirsch, Peter; Chatterton, Nicholas P; Ostermann, Andreas; Gatti, Carlo; Altmannshofer, Sandra; Herz, Verena; Eickerling, Georg; Scherer, Wolfgang

    2009-02-16

    The nature of metal silane sigma-bond interaction has been investigated in several key systems by a range of experimental and computational techniques. The structure of [Cp'Mn(CO)(2)(eta(2)-HSiHPh(2))] 1 has been determined by single crystal neutron diffraction, and the geometry at the Si atom is shown to approximate a trigonal bipyramid; salient bond distances and angles are Mn-H(1) 1.575(14), Si-H(1) 1.806(14), Si-H(2) 1.501(13) A, and H(1)-Si-H(2) 148.5(8) degrees. This complex is similar to [Cp'Mn(CO)(2)(eta(2)-HSiFPh(2))] 2, whose structure and bonding characteristics have recently been determined by charge density studies based on high-resolution X-ray and neutron diffraction data. The geometry at the Si atom in these sigma-bond complexes is compared with that in other systems containing hypercoordinate silicon. The Mn-H distances for 1 and 2 in solution have been estimated using NMR T(1) relaxation measurements, giving a value of 1.56(3) A in each case, in excellent agreement with the distances deduced from neutron diffraction. Density functional theory calculations have been employed to explore the bonding in the Mn-H-Si unit in 1 and 2 and in the related system [Cp'Mn(CO)(2)(eta(2)-HSiCl(3))] 3. These studies support the idea that the oxidative addition of a silane ligand to a transition metal center may be described as an asymmetric process in which the Mn-H bond is formed at an early stage, while both the establishment of the Mn-Si bond and also the activation of the eta(2)-coordinated Si-H moiety are controlled by the extent of Mn --> sigma*(X-Si-H) back-donation, which increases with increasing electron-withdrawing character of the X substituent trans to the metal-coordinated Si-H bond. This delocalized molecular orbital (MO) approach is complemented and supported by combined experimental and theoretical charge density studies: the source function S(r,Omega), which provides a measure of the relative importance of each atom's contribution to the density

  1. Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds.

    Science.gov (United States)

    Tian, Hua; Yang, Haijun; Zhu, Changjin; Fu, Hua

    2016-01-29

    Cross-dehydrogenative couplings of two different C-H bonds have emerged as an attractive goal in organic synthesis. However, achieving regioselective C-H activation is a great challenge because C-H bonds are ubiquitous in organic compounds. Actually, the regioselective couplings promoted by enzymes are a common occurrence in nature. Herein, we have developed simple, efficient and general transition metal-free intramolecular couplings of alphatic and aromatic C-H bonds. The protocol uses readily available aryl triazene as the radical initiator, cheap K2S2O8 as the oxidant, and the couplings were performed well with excellent tolerance of functional groups. Interestingly, α-carbon configuration of some amino acid residues in the substrates was kept after the reactions, and the couplings for substrates with substituted phenylalanine residues exhibited complete β-carbon diastereoselectivity for induction of the chiral α-carbon. Therefore, the present study should provide a novel strategy for regioselective cross-dehydrogenative couplings of two different C-H bonds.

  2. High-temperature, high-pressure bonding of nested tubular metallic components

    Science.gov (United States)

    Quinby, T.C.

    A tool is described for effecting high-temperature, high-compression bonding between the confronting faces of nested, tubular, metallic components. In a typical application, the tool is used to produce tubular target assemblies for irradiation in nuclear reactors or particle accelerators. The target assembly comprising a uranum foil and an aluninum-alloy substrate. The tool is composed of graphite. It comprises a tubular restraining member in which a mechanically expandable tubular core is mounted to form an annulus. The components to be bonded are mounted in nested relation in the annulus. The expandable core is formed of individually movable, axially elongated segments whose outer faces cooperatively define a cylindrical pressing surface and whose inner faces cooperatively define two opposed, inwardly tapered, axial bores. Tapered rams extend into the bores. The loaded tool is mounted in a conventional hot-press provided with evacuation means, heaters for maintaining its interior at bonding temperature, and hydraulic cylinders for maintaining a selected inwardly directed pressure on the tapered rams. With the hot-press evacuated and the loaded tool at the desired temperature, the cylinders are actuated to apply the selected pressure to the rams. The rams in turn expand the segmented core to maintain the nested components in compression against the restraining member. These conditions are maintained until the confronting faces of the nested components are joined in a continuous, uniform bond characterized by high thermal conductivity.

  3. Rare-earth transition-metal intermetallics: Structure-bonding-property relationships

    Energy Technology Data Exchange (ETDEWEB)

    Han, M. K. [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    The explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding property relationships. The work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe13-xSix system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn{sub 13}-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides Re2-xFe4Si14-y and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi2: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb3Zn3.6Al7.4: Partially ordered structure of Tb3Zn3.6Al7.4 compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn39(CrxAl1-x)81

  4. Rare-Earth Transition-Metal Intermetallics: Structure-bonding-Property Relationships

    Energy Technology Data Exchange (ETDEWEB)

    Han, Mi-Kyung [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    Our explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding-property relationships. Our work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe13-xSix system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn13-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides RE2-xFe4Si14-y and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi2: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb3Zn3.6Al7.4: Partially ordered structure of Tb3.6Zn13-xAl7.4 compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn39(CrxAl1-x

  5. Role of the metal in the bonding and properties of bimetallic complexes involving manganese, iron, and cobalt.

    Science.gov (United States)

    Tereniak, Stephen J; Carlson, Rebecca K; Clouston, Laura J; Young, Victor G; Bill, Eckhard; Maurice, Rémi; Chen, Yu-Sheng; Kim, Hyun Jung; Gagliardi, Laura; Lu, Connie C

    2014-02-05

    A multidentate ligand platform is introduced that enables the isolation of both homo- and heterobimetallic complexes of divalent first-row transition metal ions such as Mn(II), Fe(II), and Co(II). By means of a two-step metalation strategy, five bimetallic coordination complexes were synthesized with the general formula M1M2Cl(py3tren), where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. The metal-metal pairings include dicobalt (1), cobalt-iron (2), cobalt-manganese (3), diiron (4), and iron-manganese (5). The bimetallic complexes have been investigated by X-ray diffraction and X-ray anomalous scattering studies, cyclic voltammetry, magnetometry, Mössbauer spectroscopy, UV-vis-NIR spectroscopy, NMR spectroscopy, combustion analyses, inductively coupled plasma optical emission spectrometry, and ab initio quantum chemical methods. Only the diiron chloride complex in this series contains a metal-metal single bond (2.29 Å). The others show weak metal-metal interactions (2.49 to 2.53 Å). The diiron complex is also distinct with a septet ground state, while the other bimetallic species have much lower spin states from S = 0 to S = 1. We propose that the diiron system has delocalized metal-metal bonding electrons, which seems to correlate with a short metal-metal bond and a higher spin state. Multiconfigurational wave function calculations revealed that, indeed, the metal-metal bonding orbitals in the diiron complex are much more delocalized than those of the dicobalt analogue.

  6. From hydrogen bonding to metal coordination and back: Porphyrin-based networks on Ag(111)

    Energy Technology Data Exchange (ETDEWEB)

    Studener, F., E-mail: f.studener@rug.nl; Müller, K.; Stöhr, M., E-mail: m.a.stohr@rug.nl [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747AG Groningen (Netherlands); Marets, N.; Bulach, V., E-mail: bulach@unistra.fr; Hosseini, M. W., E-mail: hosseini@unistra.fr [Laboratoire de Tectonique Moléculaire, UMR UDS-CNRS 7140, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg (France)

    2015-03-14

    The self-assembly of a metal-free porphyrin bearing two pyridyl coordinating sites and two pentyl chains at trans meso positions was investigated under ultrahigh vacuum on a Ag(111) surface by scanning tunneling microscopy (STM). The STM measurements revealed a well-ordered close-packed structure with a rhombic unit cell for coverages ≤1 monolayer with their molecular plane parallel to the surface. The growth direction of the molecular islands is aligned along the step edges, which are restructured due to molecule-substrate interactions. The shorter unit cell vector of the molecular superstructure follows the 〈1-10〉 direction of the Ag(111) substrate. Hydrogen bonds between pyridyl and pyrrole groups of neighboring molecules as well as weak van der Waals forces between the pentyl chains stabilize the superstructure. Deposition of cobalt atoms onto the close-packed structure at room temperature leads to the formation of a hexagonal porous network stabilized by metal-ligand bonding between the pyridyl ligands and the cobalt atoms. Thermal annealing of the Co-coordination network at temperatures >450 K results in the transformation of the hexagonal network into a second close-packed structure. Changes in the molecule-substrate interactions due to metalation of the porphyrin core with Co as well as intermolecular interactions can explain the observed structural transformations.

  7. Analytic bond-order potentials for the bcc refractory metals Nb, Ta, Mo and W.

    Science.gov (United States)

    Čák, M; Hammerschmidt, T; Rogal, J; Vitek, V; Drautz, R

    2014-05-14

    Bond-order potentials (BOPs) are based on the tight-binding approximation for determining the energy of a system of interacting atoms. The bond energy and forces are computed analytically within the formalism of the analytic BOPs. Here we present parametrizations of the analytic BOPs for the bcc refractory metals Nb, Ta, Mo and W. The parametrizations are optimized for the equilibrium bcc structure and tested for atomic environments far from equilibrium that had not been included in the fitting procedure. These tests include structural energy differences for competing crystal structures; tetragonal, trigonal, hexagonal and orthorhombic deformation paths; formation energies of point defects as well as phonon dispersion relations. Our tests show good agreement with available experimental and theoretical data. In practice, we obtain the energetic ordering of vacancy, [1 1 1], [1 1 0], and [1 0 0] self-interstitial atom in agreement with density functional theory calculations.

  8. Transition metal impurities on the bond-centered site in Ge

    CERN Document Server

    Decoster, S; De Vries, B; Emmerich, H; Wahl, U; Correia, J G; Vantomme, A

    2009-01-01

    We report on the lattice location of ion implanted Fe, Cu, and Ag impurities in germanium from a combined approach of emission channeling experiments and ab initio total energy calculations. Following common expectation, a fraction of these transition metals (TMs) was found on the substitutional Ge position. Less expected is the observation of a second fraction on the sixfold coordinated bond-centered site. Ab initio calculated heats of formation suggest this is the result of the trapping of a vacancy by a substitutional TM impurity, spontaneously forming an impurity-vacancy complex in the split-vacancy configuration. We also present an approach to displace the TM impurities from the electrically active substitutional site to the bond-centered site.

  9. Oxygen-assisted cleavage of OH, NH, and CH bonds on transition metal surfaces: bond-order-conservation-Morse-potential analysis

    Science.gov (United States)

    Shustorovich, Evgeny; Bell, Alexis T.

    The energetics of OH, NH, and CH bond cleavage on clean and (low-coverage) oxygen-preadsorbed metal surfaces has been analyzed using the BOCMP (bond-order-conservation-Morse-potential) method. The molecules in question included CH 3OH, HCOOH, and NH 3, adsorbed on Ag(111), Cu(111), Ni(111), W(110), and CH 4 adsorbed on Ni(111) and Ni(100). The reaction enthalphies, ΔH, and the activation energies, ΔE ∗, have been calculated for a variety of elementary steps corresponding to the direct and oxygen-assisted cleavage of XH bonds (X = O, N, C). For the OH and NH bonds, the presence of preadsorbed oxygen always decreases the values of ΔH and ΔE ∗ for Ag(111), but increases them for W(110). For Cu(111) and Ni(111), the changes in ΔH and ΔE ∗ are less uniform but, as a whole, Cu(111) resembles Ag(111), whereas Ni(111) is closer to W(110). In other words, the effect of preadsorbed oxygen at low coverages on the OH and NH bond cleavage is projected to be reversed along the series Ag, Cu, Ni, W, from facilitating XH bond cleavage on the least active metals such as Ag (or Au), to inhibiting this process on the most active metals, such as W (or Mo). The presence of preadsorbed oxygen on Ni(111) and Ni(100) is detrimental to the cleavage of CH bonds in CH 4. The BOCMP model projections are in broad agreement with experimental observation.

  10. Imidazolin-2-iminato complexes of rare earth metals with very short metal-nitrogen bonds: experimental and theoretical studies.

    Science.gov (United States)

    Panda, Tarun K; Trambitas, Alexandra G; Bannenberg, Thomas; Hrib, Cristian G; Randoll, Sören; Jones, Peter G; Tamm, Matthias

    2009-06-15

    The reactions of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH, 1-H) with trimethylsilylmethyl lithium (LiCH(2)SiMe(3)) and anhydrous rare earth metal trichlorides MCl(3) afforded the imidazolin-2-iminato complexes [(1)MCl(2)(THF)(3)] (2a, M = Sc; 2b, M = Y; 2c, M = Lu) and [(1)GdCl(2)(THF)(2)] x [LiCl(THF)(2)] (2d). Treatment of complexes 2 with dipotassium cyclooctatetradienide, K(2)(C(8)H(8)) resulted in the formation of two- or three-legged piano-stool complexes of the type [(eta(8)-C(8)H(8))M(1)(THF)(n)] (3a, M = Sc, n = 1; 3b, M = Y, n = 2; 3c, M = Lu, n = 2; 3d, M = Gd, n = 2). X-ray diffraction analyses of all eight complexes 2 and 3 revealed the presence of very short metal-nitrogen bonds, which are among the shortest ever observed for these elements. [(eta(8)-C(8)H(8))Sc(1)(THF)] (3a) reacted with 2,6-dimethylphenyl isothiocyanate (Xy-NCS) to form the [2 + 2]-cycloaddition product 4, which contains a thioureato-N,N' moiety. The related COT-titanium complex [(eta(8)-C(8)H(8))TiCl(1)] (6) could be obtained from [(1)TiCl(3)] (5) by reaction with K(2)(C(8)H(8)) and was structurally characterized. As a theoretical analysis of the nature of the metal-nitrogen bond, density functional theory (DFT) calculations have been carried out for complexes 3a and 6 and also for the model complexes [(eta(8)-C(8)H(8))Sc(NIm(Me))] (7), [(eta(8)-C(8)H(8))Ti(NIm(Me))](+) (8), and [(eta(8)-C(8)H(8))Ti(NXy)] (9), revealing a marked similarity of the bonding in imidazolin-2-iminato and conventional imido metal complexes.

  11. Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

    Science.gov (United States)

    Toutov, Anton A.; Liu, Wen-Bo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.

    2015-02-01

    Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.

  12. Outcome of bonded vs all-ceramic and metal- ceramic fixed prostheses for single tooth replacement.

    Science.gov (United States)

    Karl, Matthias

    2016-01-01

    The conventional treatment of a single missing tooth is most frequently based on the provision of a fixed dental prosthesis (FDPs). A variety of designs and restorative materials are available which have an impact on the treatment outcome. Consequently, it was the aim of this review to compare resin-bonded, all-ceramic and metal-ceramic FDPs based on existing evidence. An electronic literature search using "metal-ceramic" AND "fixed dental prosthesis" AND "clinical, all-ceramic" AND "fixed dental prosthesis" AND "clinical, resin-bonded" AND "fixed dental prosthesis" AND "clinical, fiber reinforced composite" AND "clinical, monolithic" AND "zirconia" AND "clinical" was conducted and supplemented by the manual searching of bibliographies from articles already included. A total of 258 relevant articles were identified. Metal-ceramic FDPs still show the highest survival rates of all tooth-supported restorations. Depending on the ceramic system used, all-ceramic restorations may reach comparable survival rates while the technical complications, i.e. chipping fractures of veneering materials in particular, are more frequent. Resin-bonded FDPs can be seen as long-term provisional restorations with the survival rate being higher in anterior locations and when a cantilever design is applied. Inlay-retained FDPs and the use of fiber-reinforced composites overall results in a compromised long-term prognosis. Recently advocated monolithic zirconia restorations bear the risk of low temperature degradation. Several variables affect treatment planning for a given patient situation, with survival and success rates of different restorative options representing only one factor. The broad variety of designs and materials available for conventional tooth-supported restorations should still be considered as a viable treatment option for single tooth replacement.

  13. Energy decomposition analysis of cation-π, metal ion-lone pair, hydrogen bonded, charge-assisted hydrogen bonded, and π-π interactions.

    Science.gov (United States)

    Sharma, Bhaskar; Srivastava, Hemant Kumar; Gayatri, Gaddamanugu; Sastry, Garikapati Narahari

    2015-03-30

    This study probes the nature of noncovalent interactions, such as cation-π, metal ion-lone pair (M-LP), hydrogen bonding (HB), charge-assisted hydrogen bonding (CAHB), and π-π interactions, using energy decomposition schemes-density functional theory (DFT)-symmetry-adapted perturbation theory and reduced variational space. Among cation-π complexes, the polarization and electrostatic components are the major contributors to the interaction energy (IE) for metal ion-π complexes, while for onium ion-π complexes (NH4+, PH4+, OH3+, and SH3+) the dispersion component is prominent. For M-LP complexes, the electrostatic component contributes more to the IE except the dicationic metal ion complexes with H2 S and PH3 where the polarization component dominates. Although electrostatic component dominates for the HB and CAHB complexes, dispersion is predominant in π-π complexes.

  14. Shear Bond Strength of Porcelain to a Base-Metal Compared to Zirconia Core

    Directory of Open Access Journals (Sweden)

    Abrisham SM

    2017-03-01

    Full Text Available Statement of Problem: Recent clinical results for Zirconia all-ceramic restorations have revealed that the fracture rate 6-15% of the Zirconia framework is so low and the core of Zirconia has high stability. However, chipping-off fractures of porcelain are the most common reason for failures of Zirconia in the fixed partial dentures. Objectives: The purpose of this study was to compare the shear bond strength (SBS of porcelain in the porcelain fused to metal and all-ceramic crowns with Zirconia core. Materials and Methods: Two groups were selected: porcelain fused to metal (PFM and porcelain fused to Zirconia (PFZ (n = 30.In the PFM group, a wax model (10 × 10 × 10mmwas used to cast metal base (Ni_Cr alloy. In the PFZ group, an acrylic cubic model (10 × 10 × 10mm was made as Zirconia model for scanning.15 cubic Zirconia samples were milled by CAD-CAM. The procedure of porcelain veneering was conducted by the conventional layering technique up to 2 mm thickness (2.5 × 2.5 × 2 mm. All specimens were stored in water for 48 hrs. Thermal cycling was conducted for 20000 cycles between 55°C and 5ºC alternatively for 30s.All samples were mounted in acrylic resin and the SBS test was performed, using a universal testing machine. The analysis of data was performed at a significance level of 0.05 using Kolmogorov-Smirnov and Mann-Whitney U-test. Results: Mean of SBS in PFM and PFZ was 24.57 and 20.88, respectively. The results of Mann-Whitney test showed that there was no statistically significant difference between the two groups of porcelain fused to metal and Zirconia in item shear bond strength (p = 0.455. Conclusions: There was no significant difference between the two groups of PFM and PFZ in the item SBS.

  15. Shear Bond Strength of Porcelain to a Base-Metal Compared to Zirconia Core.

    Science.gov (United States)

    Abrisham, S M; Fallah Tafti, A; Kheirkhah, S; Tavakkoli, M A

    2017-03-01

    Recent clinical results for Zirconia all-ceramic restorations have revealed that the fracture rate 6-15% of the Zirconia framework is so low and the core of Zirconia has high stability. However, chipping-off fractures of porcelain are the most common reason for failures of Zirconia in the fixed partial dentures. The purpose of this study was to compare the shear bond strength (SBS) of porcelain in the porcelain fused to metal and all-ceramic crowns with Zirconia core. Two groups were selected: porcelain fused to metal (PFM) and porcelain fused to Zirconia (PFZ) (n = 30).In the PFM group, a wax model (10 × 10 × 10mm)was used to cast metal base (Ni_Cr alloy). In the PFZ group, an acrylic cubic model (10 × 10 × 10mm) was made as Zirconia model for scanning.15 cubic Zirconia samples were milled by CAD-CAM. The procedure of porcelain veneering was conducted by the conventional layering technique up to 2 mm thickness (2.5 × 2.5 × 2 mm). All specimens were stored in water for 48 hrs. Thermal cycling was conducted for 20000 cycles between 55°C and 5ºC alternatively for 30s.All samples were mounted in acrylic resin and the SBS test was performed, using a universal testing machine. The analysis of data was performed at a significance level of 0.05 using Kolmogorov-Smirnov and Mann-Whitney U-test. Mean of SBS in PFM and PFZ was 24.57 and 20.88, respectively. The results of Mann-Whitney test showed that there was no statistically significant difference between the two groups of porcelain fused to metal and Zirconia in item shear bond strength (p = 0.455). There was no significant difference between the two groups of PFM and PFZ in the item SBS.

  16. Energetics and bonding in aluminosilicate rings with alkali metal and alkaline-earth metal charge-compensating cations.

    Science.gov (United States)

    Gatti, Carlo; Ottonello, Giulio; Richet, Pascal

    2012-08-23

    The stabilizing effect of alkali and alkaline-earth metal ions on the oxygen donors of four- and six-membered faujausite-like rings has been calculated in terms of Kohn-Sham core-level (O1s) energy shifts with respect to these same complexes without cations. The results confirm and complement earlier investigations by Vayssilov and co-workers where Na(+) and K(+) were the only complexing cations. The oxygen donor centers in six-membered rings are stabilized by -3.6 ± 0.4, -3.9 ± 0.5, -7.3 ± 0.1, and -7.6 ± 0.2 eV by K(+), Na(+), Ca(2+), and Mg(2+) adions, respectively. The energy shifts are even greater for four-membered rings where the stabilization effects attain -3.7 ± 0.1, -4.1 ± 0.1, -8.1 ± 0.1, and -9.0 ± 0.1 eV, respectively. These effects are also observed on the low-lying σ-bonding and antibonding molecular orbitals (MOs) of the oxygen framework, but in a less systematic fashion. Clear relationships with the core-level shifts are found when the effects of alkali metal complexation are evaluated through electron localization/delocalization indices, which are defined in terms of the whole wave function and not just of the individual orbitals. Complexation with cations not only involves a small but significant electron sharing of the cation with the oxygen atoms in the ring but also enhances electron exchange among oxygen atoms while reducing that between the O atoms and the Si or Al atoms bonded to them. Such changes slightly increase from Na to K and from Mg to Ca, whereas they are significantly enhanced for alkaline-earth metals relative to alkali metals. With respect to Al-free complexes, Si/Al substitution and cation charge compensation generally enhance electron delocalization among the O atoms, except between those that are linked through an Al atom, and cause either an increased or a decreased Si-O ionicity (smaller/higher electron exchange) depending on the position of O in the chain relative to the Al atom(s). The generally increased

  17. CHEMICAL ACTIVATION OF MOLECULES BY METALS: EXPERIMENTAL STUDIES OF ELECTRON DISTRIBUTIONS AND BONDING

    Energy Technology Data Exchange (ETDEWEB)

    LICHTENBERGER, DENNIS L.

    2002-03-26

    This research program is directed at obtaining detailed experimental information on the electronic interactions between metals and organic molecules. These interactions provide low energy pathways for many important chemical and catalytic processes. A major feature of the program is the continued development and application of our special high-resolution valence photoelectron spectroscopy (UPS), and high-precision X-ray core photoelectron spectroscopy (XPS) instrumentation for study of organometallic molecules in the gas phase. The study involves a systematic approach towards understanding the interactions and activation of bound carbonyls, C-H bonds, methylenes, vinylidenes, acetylides, alkenes, alkynes, carbenes, carbynes, alkylidenes, alkylidynes, and others with various monometal, dimetal, and cluster metal species. Supporting ligands include -aryls, alkoxides, oxides, and phosphines. We are expanding our studies of both early and late transition metal species and electron-rich and electron-poor environments in order to more completely understand the electronic factors that serve to stabilize particular organic fragments and intermediates on metals. Additional new directions for this program are being taken in ultra-high vacuum surface UPS, XPS, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) experiments on both physisorbed and chemisorbed organometallic thin films. The combination of these methods provides additional electronic structure information on surface-molecule and molecule-molecule interactions. A very important general result emerging from this program is the identification of a close relationship between the ionization energies of the species and the thermodynamics of the chemical and catalytic reactions of these systems.

  18. Heavy metal and proximate composition associated with the ...

    African Journals Online (AJOL)

    User

    2014-05-08

    May 8, 2014 ... inorganic products, generating heat as a metabolic waste product. Heavy metal ..... Potencial Bioremediation Agent in Compost Material Contaminated with Heavy .... Toxicity of non-radioactive heavy metals and their salts in ...

  19. In-process electrical discharge dressing of arc-shaped metal bonded diamond wheels

    Science.gov (United States)

    Wang, Kai; Fan, Fei; Tian, Guoyu; Zhang, Feihu; Liu, Zhongde

    2016-10-01

    Due to the high hardness of SiC ceramics, the wear of the arc-shaped metal bonded diamond wheels is very serious during the grinding process of large-aperture aspheric SiC mirrors. The surface accuracy and surface/sub-surface quality of the aspheric mirror will be affected seriously if the grinding wheel is not timely dressed. Therefore, this paper focus on the in-process dressing of the arc-shaped metal bonded diamond wheels. In this paper, the application of the asymmetric arc profile grinding wheel in the grinding of aspheric mirrors is discussed first. Then a rotating cup-shaped electrode in-process electro discharge dressing device for the arc-shaped wheels is developed based on the analysis. The dressing experiments are carried out with the device. The experimental results show that the in-process dressing device can did the dressing for the asymmetric and symmetric arc-shaped wheel. The profile error of the arc can reach to 3μm with the in-process dressing device.

  20. Correlation between metal-ceramic bond strength and coefficient of linear thermal expansion difference

    Directory of Open Access Journals (Sweden)

    Stella Crosara Lopes

    2009-04-01

    Full Text Available The purpose of this study was to evaluate the metal-ceramic bond strength (MCBS of 6 metal-ceramic pairs (2 Ni-Cr alloys and 1 Pd-Ag alloy with 2 dental ceramics and correlate the MCBS values with the differences between the coefficients of linear thermal expansion (CTEs of the metals and ceramics. Verabond (VB Ni-Cr-Be alloy, Verabond II (VB2, Ni-Cr alloy, Pors-on 4 (P, Pd-Ag alloy, and IPS (I and Duceram (D ceramics were used for the MCBS test and dilatometric test. Forty-eight ceramic rings were built around metallic rods (3.0 mm in diameter and 70.0 mm in length made from the evaluated alloys. The rods were subsequently embedded in gypsum cast in order to perform a tensile load test, which enabled calculating the CMBS. Five specimens (2.0 mm in diameter and 12.0 mm in length of each material were made for the dilatometric test. The chromel-alumel thermocouple required for the test was welded into the metal test specimens and inserted into the ceramics. ANOVA and Tukey's test revealed significant differences (p=0.01 for the MCBS test results (MPa, with PI showing higher MCBS (67.72 than the other pairs, which did not present any significant differences. The CTE (10-6 oC-1 differences were: VBI (0.54, VBD (1.33, VB2I (-0.14, VB2D (0.63, PI (1.84 and PD (2.62. Pearson's correlation test (r=0.17 was performed to evaluate of correlation between MCBS and CTE differences. Within the limitations of this study and based on the obtained results, there was no correlation between MCBS and CTE differences for the evaluated metal-ceramic pairs.

  1. On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Vlaisavljevich, Bess; Miro, P.; Cramer, C. J.; Gagliardi, Laura; Infante, I.; Liddle, S. T.

    2011-06-28

    Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [(η⁵-C₅H₅)₂(THF)LuRu(η⁵-C₅H₅) (CO)₂], [(η⁵-C₅Me₅)₂(I)ThRu(η⁵-C₅H₅) (CO)₂], [(η⁵-C₅H₅)₂YRe(η⁵-C₅H₅)₂], [{N(CH₂CH₂NSiMe₃)₃}URe(η⁵-C₅H₅)₂], [Y{Ga(NArCh)₂}{C(PPh₂NSiH₃)₂}(CH₃OCH₃)₂], [{N(CH₂CH₂NSiMe₃)₃}U{Ga(NArCH)₂}(THF)], [(η⁵-C₅H₅)₃UGa(η⁵-C₅Me₅)], [Yb(η⁵-C₅H₅){Si(SiMe₃)₃(THF)₂}], [(η⁵-C₅H₅)₃U(SnPh₃)], [(η⁵-C₅H₅)₃U(SiPh₃)], and (Ph[Me]N)₃USi(SiMe₃)₃. Geometries in good agreement with experiment were obtained at the density functional level of theory. The multiconfigurational complete active space self-consistent field method (CASSCF) and subsequent corrections with second order perturbation theory (CASPT2) were applied to further understand the electronic structure of the lanthanide/actinide–metal (or metal–metalloid) bonds. Fragment calculations and energy-decomposition analyses were also performed and indicate that charge transfer occurs from one supported metal fragment to the other, while the bonding itself is always dominated by ionic character.

  2. Ligand dependence of metal-metal bonding in the d(3)d(3) dimers M(2)X(9)(n-) (M(III) = Cr, Mo, W; M(IV) = Mn, Tc, Re; X = F, Cl, Br, I).

    Science.gov (United States)

    Stranger, R; Turner, A; Delfs, C D

    2001-08-13

    The ligand dependence of metal-metal bonding in the d(3)d(3) face-shared M(2)X(9)(n-) (M(III) = Cr, Mo, W; M(IV) = Mn, Tc, Re; X = F, Cl, Br, I) dimers has been investigated using density functional theory. In general, significant differences in metal-metal bonding are observed between the fluoride and chloride complexes involving the same metal ion, whereas less dramatic changes occur between the bromide and iodide complexes and minimal differences between the chloride and bromide complexes. For M = Mo, Tc, and Re, change in the halide from F to I results in weaker metal-metal bonding corresponding to a shift from either the triple metal-metal bonded to single bonded case or from the latter to a nonbonded structure. A fragment analysis performed on M(2)X(9)(3-) (M = Mo, W) allowed determination of the metal-metal and metal-bridge contributions to the total bonding energy in the dimer. As the halide changes from F to I, there is a systematic reduction in the total interaction energy of the fragments which can be traced to a progressive destabilization of the metal-bridge interaction because of weaker M-X(bridge) bonding as fluoride is replaced by its heavier congeners. In contrast, the metal-metal interaction remains essentially constant with change in the halide.

  3. Identification of five novel FBN1 mutations by non-radioactive single-strand conformation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Liu, W.; Qian, C.; Comeau, K.; Francke, U. [Stanford Univ. Medical Center, Stanford, CA (United States)

    1994-09-01

    Marfan syndrome (MFS), one of the most common genetic disorders of connective tissue, is characterized by variable manifestations in skeletal, cardiovascular and ocular systems. Mutations in the fibrillin gene on chromosome 15 (FBN1) have been shown to cause MFS. To examine the relationship between FBN1 gene mutations, fibrillin protein function and MFS phenotypes, we screened for alternations in the fibrillin coding sequence in fibroblast derived cDNA from MFS patients. To date, abnormally migrating bands in more than 20 unrelated MFS patients have been identified by using non-radioactive single-strand conformation analysis and silver staining. Five altered bands have been directly sequenced. Two missense mutations and three splice site mutations have been identified. Both missense mutations substitute another amino acid for a cysteine residue (C1402W and C1672R) in EGF-like motifs of the fibrillin polypeptide chain. The two splice site mutations are at nucleotide positions 6994+1 (G{yields}A), and 7205-2 (A{yields}G) and result in in-frame skipping of exon 56 and 58, respectively. Skipping of exon 56 occurs in 50% of mutant transcripts. Use of a cryptic splice site 51 bp upstream of the normal donor site results in half of the mutant transcripts containing part of exon 56. Both products contain in-frame deletions. Another splice site mutation, identified by exon screening from patient genomic DNA using intron primers, is at nucleotide position 2293+2 (T{yields}A), but the predicted exon skipping has not been detected at the RT-PCR level. This may be due to instability of the mutant transcript. Including the mutations reported here, a total of 8 out of 36 published FBN1 gene mutations involve exon skipping. It may be inferred that FBN1 exon skipping plays an important pathogenic role in MFS.

  4. A new non-radioactive deoxyhypusine synthase assay adaptable to high throughput screening.

    Science.gov (United States)

    Park, Myung Hee; Mandal, Ajeet; Mandal, Swati; Wolff, Edith C

    2017-08-17

    Deoxyhypusine synthase (DHS) catalyzes the post-translational modification of eukaryotic translation factor 5A (eIF5A) by the polyamine, spermidine, that converts one specific lysine residue to deoxyhypusine [N (ε) -4-aminobutyl(lysine)], which is subsequently hydroxylated to hypusine [N (ε) -4-amino-2-hydroxybutyl(lysine)]. Hypusine synthesis represents the most critical function of polyamine. As eIF5A has been implicated in various human diseases, identification of specific inhibitors of hypusine modification is of vital importance. DHS catalyzes a complex reaction that occurs in two stages, first, the NAD-dependent cleavage of spermidine to form an enzyme-butylimine intermediate and enzyme-bound NADH, and second, the transfer of the butylimine moiety from the enzyme intermediate to the eIF5A precursor and subsequent reduction of the eIF5A-butylimine intermediate by enzyme-bound NADH to form deoxyhypusine [N (ε) -4-aminobutyl(lysine)]. Our data demonstrate that there is a measurable release of enzyme-bound NADH in the absence of eIF5A precursor and that the DHS activity can be determined by coupling the first phase reaction with the NADH-Glo assay in which the generation of luminescence is dependent on NADH derived from the DHS partial reaction. The conventional DHS assay that measures the incorporation of radioactivity from [1,8-(3)H]spermidine into the eIF5A precursor in the complete reaction cannot be readily adapted for high throughput screening (HTS). In contrast, the non-radioactive DHS/NADH-Glo coupled assay is highly specific, sensitive and reproducible and could be configured for HTS of small molecule libraries for the identification of new inhibitors of DHS. Furthermore, the coupled assay provides new insights into the dynamics of the DHS reaction especially regarding the fate of NADH.

  5. Atomic volume, atomic distances and chemical bonding in solid metallic elements; Atomvolumen, Atomabstaende und chemische Bindung in festen metallischen Elementen

    Energy Technology Data Exchange (ETDEWEB)

    Troemel, M.; Huebner, S. [Frankfurt Univ. (Germany). Inst. fuer Anorganische Chemie

    2001-05-01

    Relationships between bond lengths and bond numbers and also between atomic volumes and valencies are derived and parameters for their calculation are given for the s-block, p-block, and d-block metals. From the atomic volumes under pressure, the valencies of three solid lanthanoids have been confirmed or redetermined: La 3; Ce 2, 3, and 4; Yb 2 and 3. (orig.)

  6. Electron Density Distributions for Millerite, Vaesite , Heazlewoodite and Ni metal: A Case for the Importance of NiNi Bond Paths for Electron Transport

    Science.gov (United States)

    Ross, N. L.; Gibbs, G. V.; Downs, R. T.; Prewitt, C. T.; Rosso, K. M.; Cox, D. F.

    2006-12-01

    Bond paths and the bond critical point properties have been calculated for the bonded interactions comprising the Ni sulfide minerals millerite, vaesite and heazlewoodite and Ni metal. The experimental NiS bond lengths decrease linearly as the magnitudes of the properties each increases in value. Bond paths exist between the Ni atoms in heazlewoodite and millerite for NiNi separations that match the shortest separation in Ni metal, an indicator that the Ni atoms are bonded. Bond paths also exist between the Ni atoms in bulk Ni metal. In addition, the bcp properties of the bonded interactions in Ni metal are virtually the same as those in heazlewoodite and millerite. In contrast, NiNi bond paths are absent in vaesite where the NiNi separations are 60% greater than those in Ni metal. The bcp properties for the NiNi bonded interactions scatter along protractions of the NiS bond length-bcp property trends, suggesting that the two bonded interactions have similar characteristics. NiNi bond paths radiate throughout Ni metal and the metallic heazlewoodite structures as continuous networks whereas the NiNi paths in millerite are restricted to isolated Ni3 rings. Electron transport in Ni metal and heazlewoodite is pictured as occurring along the bond paths, which behave as networks of atomic size wires that radiate in a contiguous circuit throughout the two structures. Unlike heazlewoodite, the electron transport in millerite is pictured as involving a cooperative hopping of the d orbital electrons from the Ni3 rings comprising Ni3S9 clusters to Ni3 rings in adjacent clusters via the p orbitals on the interconnecting S atoms. Vaesite, an insulator at low temperatures and a doped semiconductor at higher temperatures, lacks NiNi bond paths.

  7. Bond formation effects on the metal-insulator transition in the half-filled kagome Hubbard model

    Science.gov (United States)

    Higa, Ryota; Asano, Kenichi

    2016-06-01

    We study the metal-insulator transition in the half-filled Hubbard model on a Kagome lattice using the variational cluster approximation. The strong coupling limit of the model corresponds to the S =1 /2 Kagome Heisenberg antiferromagnet, which is known to have a singlet ground state, although its detail is still debated. As the results of the cluster methods generally depend much on the choice of the unit cluster, we have chosen the clusters that are compatible with these singlet ground states in the strong coupling case found so far, which basically consist of even number of sites. It is found that the correlated electrons on the Kagome lattice have a strong tendency to form valence-bond structures, which are the resonation of electrons on a single bond or several bonds forming loops. The zero-temperature metal-insulator transition at some interaction strength is possibly driven by the formation of such short range valence bonds and shows a second order character, which is distinctive from the Brinkman-Rice scenario. The electrons on these valence bonds further localizes onto each site as the interaction increases, and the valence bonds of electrons finally turn into magnetic singlet bonds between localized S =1 /2 spins, which are consistent with the ground states of the Kagome antiferromagnet.

  8. Electrically Pumped Room-Temperature Pulsed InGaAsP-Si Hybrid Lasers Based on Metal Bonding

    Institute of Scientific and Technical Information of China (English)

    CHEN Ting; RAN Guang-Zhao; WANG Wei; QIN Guo-Gang; HONG Tao; PAN Jiao-Qing; CHEN Wei-Xi; CHENG Yuan-Bing; WANG Yang; MA Xiao-Bo; LIU Wei-Li; ZHAO Ling-Juan

    2009-01-01

    A pulsed InGaAsP-Si hybrid laser is fabricated using metal bonding.A novel structure in which the optical coupling and metal bonding areas are transversely separated is employed to integrate the silicon waveguide with an InGaAsP multi-quantum well distributed feedback structure.When electrically pumped at room temperature,the laser operates with a threshold current density of 2.9 kA/cm2 and a slope efficiency of 0.02 W/A.The 1542nm laser output exits mainly from the Si waveguide.

  9. Comparison of porcelain bond strength of different metal frameworks prepared by using conventional and recently introduced fabrication methods.

    Science.gov (United States)

    Kaleli, Necati; Saraç, Duygu

    2017-07-01

    Most studies evaluating dental laser sintering systems have focused on the marginal accuracy of the restorations. However, the bond strength at the metal-ceramic interface is another important factor that affects the survival of restorations, and currently, few studies focus on this aspect. The purpose of this in vitro study was to compare the porcelain bond strength of cobalt-chromium (Co-Cr) metal frameworks prepared by using the conventional lost-wax technique, milling, direct metal laser sintering (DMLS), and laser cusing, a direct process powder-bed system. A total of 96 metal frameworks (n=24 in each group) were prepared by using conventional lost-wax (group C), milling (group M), DMLS (group LS), and direct process powder-bed (group LC) methods according to International Organization for Standardization standard ISO 9693-1. After porcelain application, a 3-point bend test was applied to each specimen by using a universal testing machine. Data were statistically analyzed using 1-way ANOVA and Tukey honest significant difference tests (α=.05). Failure types at the metal-ceramic interfaces were examined using stereomicroscopy. Additionally, 1 specimen from each group was prepared for scanning electron microscopy analysis to evaluate the surface topography of metal frameworks. The mean bond strength was 38.08 ±3.82 MPa for group C, 39.29 ±3.51 MPa for group M, 40.73 ±3.58 MPa for group LS, and 41.24 ±3.75 MPa for group LC. Statistically significant differences were observed among the 4 groups (P=.016). All groups, except for LS, exhibited adhesive and mixed type bond failure. Both of the laser sintering methods were found to be successful in terms of metal-ceramic bond strength. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  10. Metallic-like bonding in plasma-born silicon nanocrystals for nanoscale bandgap engineering.

    Science.gov (United States)

    Vach, Holger; Ivanova, Lena V; Timerghazin, Qadir K; Jardali, Fatme; Le, Ha-Linh Thi

    2016-10-27

    Based on ab initio molecular dynamics simulations, we show that small nanoclusters of about 1 nm size spontaneously generated in a low-temperature silane plasma do not possess tetrahedral structures, but are ultrastable. Apparently small differences in the cluster structure result in substantial modifications in their electric, magnetic, and optical properties, without the need for any dopants. Their non-tetrahedral geometries notably lead to electron deficient bonds that introduce efficient electron delocalization that strongly resembles the one of a homogeneous electron gas leading to metallic-like bonding within a semiconductor nanocrystal. As a result, pure hydrogenated silicon clusters that form by self-assembly in a plasma reactor possess optical gaps covering most of the solar spectrum from 1.0 eV to 5.2 eV depending simply on their structure and, in turn, on their degree of electron delocalization. This feature makes them ideal candidates for future bandgap engineering not only for photovoltaics, but also for many nano-electronic devices employing nothing else but silicon and hydrogen atoms.

  11. Development of ultrasonic testing method of dissimilar metal transition joints by hot roll bonding

    Energy Technology Data Exchange (ETDEWEB)

    Hoshino, Ikuji; Fujisawa, Kazuo; Yamaguchi, Hisao [Sumitomo Metal Industries Ltd., Osaka (Japan); Nagai, Takayuki; Takeda, Seiichiro

    1996-03-01

    An ultrasonic inspection method for detection of debonding in a clad pipe was investigated. The clad pipe is composed of outer side stainless steel (SUS), inner side titanium alloy (Ti) and intermediate tantalum foil (Ta) 0.05 to 0.2mm in thickness. The clad pipe is machined to dissimilar metal transition tubular joints which are used in a nuclear fuel reprocessing plant. The ultrasonic echoes from sound bonding and debonding areas were calculated by combining echoes from SUS-Ta and Ti-Ta interfaces, and multiple reflection echoes in Ta foil, considering the reflection coefficient at each interface. The influence of multiple reflection echoes in Ta foil was also evaluated. The effects of center frequency and band width of ultrasonic pulse and inspection direction were analysed from the calculation results. The effect of inspection direction considering the pipe shift was also evaluated from the experiment. The determinations showed that inspection from the inner side of a pipe with a broad frequency band probe of 12 to 20 MHz is optimum. A test specimen with artificial defects 1 mm in diameter and specimens with a debonding area made by rolling oxidized material were inspected by the determined test condition. Findings allowed discrimination of the echoes from debonding boundaries from those from sound bonding boundaries. (author).

  12. B-H bond activation using an electrophilic metal complex: insights into the reaction pathway.

    Science.gov (United States)

    Kumar, Rahul; Jagirdar, Balaji R

    2013-01-07

    A highly electrophilic ruthenium center in the [RuCl(dppe)(2)][OTf] complex brings about the activation of the B-H bond in ammonia borane (H(3)N·BH(3), AB) and dimethylamine borane (Me(2)HN·BH(3), DMAB). At room temperature, the reaction between [RuCl(dppe)(2)][OTf] and AB or DMAB results in trans-[RuH(η(2)-H(2))(dppe)(2)][OTf], trans-[RuCl(η(2)-H(2))(dppe)(2)][OTf], and trans-[RuH(Cl)(dppe)(2)], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B-H bond activation were obtained. In both cases, the reaction proceeds via an η(1)-B-H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.

  13. C-H Bond Activation by Early Transition Metal Carbide Cluster Anion MoC3 (-).

    Science.gov (United States)

    Li, Zi-Yu; Hu, Lianrui; Liu, Qing-Yu; Ning, Chuan-Gang; Chen, Hui; He, Sheng-Gui; Yao, Jiannian

    2015-12-01

    Although early transition metal (ETM) carbides can activate CH bonds in condensed-phase systems, the electronic-level mechanism is unclear. Atomic clusters are ideal model systems for understanding the mechanisms of bond activation. For the first time, CH activation of a simple alkane (ethane) by an ETM carbide cluster anion (MoC3 (-) ) under thermal-collision conditions has been identified by using high-resolution mass spectrometry, photoelectron imaging spectroscopy, and high-level quantum chemical calculations. Dehydrogenation and ethene elimination were observed in the reaction of MoC3 (-) with C2 H6 . The CH activation follows a mechanism of oxidative addition that is much more favorable in the carbon-stabilized low-spin ground electronic state than in the high-spin excited state. The reaction efficiency between the MoC3 (-) anion and C2 H6 is low (0.23±0.05) %. A comparison between the anionic and a highly efficient cationic reaction system (Pt(+) +C2 H6 ) was made. It turned out that the potential-energy surfaces for the entrance channels of the anionic and cationic reaction systems can be very different. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Physical and adhesive properties of dental enamel after radiotherapy and bonding of metal and ceramic brackets.

    Science.gov (United States)

    Santin, Gabriela Cristina; Palma-Dibb, Regina Guenka; Romano, Fábio Lourenço; de Oliveira, Harley Francisco; Nelson Filho, Paulo; de Queiroz, Alexandra Mussolino

    2015-08-01

    The increasing success rates for cancer patients treated with radiotherapy and the frequent occurrence of tooth loss during treatment have led to an increased demand for orthodontic treatment after radiotherapy. The aim of this study was to evaluate tooth enamel of irradiated teeth after the bonding and debonding of metal and ceramic brackets. Ten permanent molars were cut into enamel fragments measuring 1 mm(2) and divided into an irradiated group (total dose of 60 Gy) and a nonirradiated group. The fragments were subjected to microshear testing to evaluate whether radiotherapy altered the strength of the enamel. Furthermore, 90 prepared premolars were divided into 6 groups and subgroups (n = 15): group 1, nonirradiated and nonaged; group 2, nonirradiated and aged (thermal cycled); group 3, irradiated and aged; each group was divided into 2 subgroups: metallic and ceramic brackets. After thermal cycling and radiotherapy, the brackets were bonded onto the specimens with Transbond XT (3M Unitek, Monrovia, Calif). After 24 hours, the specimens were subjected to the shear tests. Images of the enamel surfaces were classified using the adhesive remnant index. The composite resin-enamel interface was also evaluated. Enamel fragments subjected to radiation had lower strength than did the nonirradiated samples (P enamel interface, resin tags were more extensive on irradiated tooth enamel. Radiation decreased tooth enamel strength, and the specimens treated with radiotherapy had higher frequencies of adhesive failure between the bracket and the composite resin as well as more extensive tags. Copyright © 2015 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.

  15. Cupriphication of gold to sensitize d(10)-d(10) metal-metal bonds and near-unity phosphorescence quantum yields.

    Science.gov (United States)

    Galassi, Rossana; Ghimire, Mukunda M; Otten, Brooke M; Ricci, Simone; McDougald, Roy N; Almotawa, Ruaa M; Alhmoud, Dieaa; Ivy, Joshua F; Rawashdeh, Abdel-Monem M; Nesterov, Vladimir N; Reinheimer, Eric W; Daniels, Lee M; Burini, Alfredo; Omary, Mohammad A

    2017-06-27

    Outer-shell s(0)/p(0) orbital mixing with d(10) orbitals and symmetry reduction upon cupriphication of cyclic trinuclear trigonal-planar gold(I) complexes are found to sensitize ground-state Cu(I)-Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au4Cu2 {[Au4(μ-C(2),N(3)-EtIm)4Cu2(µ-3,5-(CF3)2Pz)2], (4a)}, Au2Cu {[Au2(μ-C(2),N(3)-BzIm)2Cu(µ-3,5-(CF3)2Pz)], (1) and [Au2(μ-C(2),N(3)-MeIm)2Cu(µ-3,5-(CF3)2Pz)], (3a)}, AuCu2 {[Au(μ-C(2),N(3)-MeIm)Cu2(µ-3,5-(CF3)2Pz)2], (3b) and [Au(μ-C(2),N(3)-EtIm)Cu2(µ-3,5-(CF3)2Pz)2], (4b)} and stacked Au3/Cu3 {[Au(μ-C(2),N(3)-BzIm)]3[Cu(µ-3,5-(CF3)2Pz)]3, (2)} form upon reacting Au3 {[Au(μ-C(2),N(3)-(N-R)Im)]3 ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu3 {[Cu(μ-3,5-(CF3)2Pz)]3 (3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via two Au(I)⋯Cu(I) metallophilic interactions, whereas 4a exhibits a hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d(10)-d(10) polar-covalent bond with ligand-unassisted Cu(I)-Au(I) distances of 2.8750(8) Å each-the shortest such an intermolecular distance ever reported between any two d(10) centers so as to deem it a "metal-metal bond" vis-à-vis "metallophilic interaction." Density-functional calculations estimate 35-43 kcal/mol binding energy, akin to typical M-M single-bond energies. Congruently, FTIR spectra of 4a show multiple far-IR bands within 65-200 cm(-1), assignable to vCu-Au as validated by both the Harvey-Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in

  16. Structure, bonding and energetics of N-heterocyclic carbene (NHC) stabilized low oxidation state group 2 (Be, Mg, Ca, Sr and Ba) metal complexes: A theoretical study

    Indian Academy of Sciences (India)

    Ashim Baishya; V Rao Mundlapati; Sharanappa Nembenna; Himansu S Biswal

    2014-11-01

    A series of N-heterocyclic carbene stabilized low oxidation state group 2 metal halide and hydrides with metal-metal bonds ([L(X) M-M(X) L]; L = NHC ((CHNH)2C:), M = Be, Mg, Ca, Sr and Ba, and X = Cl or H) has been studied by computational methods. The main objective of this study is to predict whether it is possible to stabilize neutral ligated low oxidation state alkaline-earth metal complexes with metal-metal bonds. The homolytic metal-metal Bond Dissociation Energy (BDE) calculation, Natural Bond Orbital (NBO) and Energy Decomposition Analyses (EDA) on density functional theory (DFT) optimized [L(X)M-M(X)L] complexes revealed that they are as stable as their -diketiminate, guanidinate and -diimine counterparts. The optimized structures of the complexes are in trans-linear geometries. The bond order analyses such as Wiberg Bond Indices (WBI) and Fuzzi Bond Order (FBO) confirm the existence of single bond between two metal atoms, and it is covalent in nature.

  17. Metal-metal bonding and aromaticity in [M2(NHCHNH)3]2 (μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh).

    Science.gov (United States)

    Yan, Xiuli; Meng, Lingpeng; Sun, Zheng; Li, Xiaoyan

    2016-02-01

    The nature of M-M bonding and aromaticity of [M2(NHCHNH)3]2(μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh) was investigated using atoms in molecules (AIM) theory, electron localization function (ELF), natural bond orbital (NBO) and molecular orbital analysis. These analyses led to the following main conclusions: in [M2(NHCHNH)3]2(μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh), the Nb-Nb, Ru-Ru, and Rh-Rh bonds belong to "metallic" bonds, whereas Mo-Mo and Tc-Tc drifted toward the "dative" side; all these bonds are partially covalent in character. The Nb-Nb, Mo-Mo, and Tc-Tc bonds are stronger than Ru-Ru and Rh-Rh bonds. The M-M bonds in [M2(NHCHNH)3]2(μ-S)2 are stronger than those in [M2(NHCHNH)3]2(μ-O)2 for M = Nb, Mo, Tc, and Ru. The NICS(1)ZZ values show that all of the studied molecules, except [Ru2(NHCHNH)3]2(μ-O)2, are aromaticity molecules. O-bridged compounds have more aromaticity than S-bridged compounds. Graphical Abstract Left Molecular graph, and right electron localization function (ELF) isosurface of [M2(NHCHNH)3]2(μ-E)2(E = O, S; M = Nb, Mo, Tc, Ru, Rh).

  18. Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table.

    Science.gov (United States)

    Craciun, Smaranda; Donald, Kelling J

    2009-07-06

    We examine the bonding possibilities of the bis(phenalenyl) MP(2) sandwich complexes of the divalent metals M = Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, at the B3LYP level of theory. The outcome is an extraordinarily diverse class of low symmetry bis(phenalenyl)metal complexes in which bonding preferences and binding enthalpies differ dramatically. The lowest energy group 2 metal MP(2) complexes include an intriguing eta(1),eta(3) BeP(2) structure, and bent eta(6),eta(6) systems for M = Ca, Sr, and Ba. The group 12 bis(phenalenyl) complexes are thermodynamically unstable eta(1),eta(1) slip-sandwich structures. To better understand changes in the structural preferences going from the (eta(6),eta(6)) group 2 to the (eta(1),eta(1)) group 12 complexes, we explored the bonding in the bis(phenalenyl) complexes of transition metals with stable +2 oxidations states between Ca and Zn in period 4. The computed binding enthalpies are large and negative for nearly all of the minimum energy bis(phenalenyl) complexes of the group 2 and the transition metals; they are tiny for MgP(2), and are quite positive for the group 12 systems. The structural preferences and stability of the complexes is a subtle negotiation of several influences: the (un)availability of (n - 1)d and np, orbitals for bonding, the cost of the rehybridization at carbon sites in the phenalenyl rings in preparation for bonding to the metals, and the (P---P) interaction between the phenalenyl radicals.

  19. Effect of femtosecond laser treatment on the shear bond strength of a metal bracket to prepared porcelain surface.

    Science.gov (United States)

    Akpinar, Yusuf Ziya; Irgin, Celal; Yavuz, Tevfik; Aslan, Muhammed Ali; Kilic, Hamdi Sukur; Usumez, Aslihan

    2015-04-01

    The aim of this study was to investigate the effects of femtosecond laser treatment (Group FS) on the shear bond strength (SBS) of a metal bracket to prepared porcelain surface, and to compare it with other surface treatment techniques [50 μm Al2O3 sandblasting (Group SB), 9.6% hydrofluoric acid gel (Group HF), and neodymium-doped yttrium aluminium garnet (Nd:YAG laser) (Group NY)]. Because of the increasing number of adult patients in current orthodontic practice, achieving sufficient bond strength of composite resin to porcelain restorations without bond failure during the treatment is a challenge for orthodontists. In total, 80 glazed feldspathic porcelain samples were prepared and randomly assigned to four groups of 20. Treated surfaces were treated with a silane agent. Brackets were bonded to porcelain samples. The specimens were stored in distilled water for 24 h and then thermocycled for 500 cycles between 5° and 55°C. The SBS of the brackets was tested with a universal testing machine at a crosshead speed of 1 mm/min, until bonding failure occurred. The data were analyzed statistically using analysis of variance (ANOVA) and Tamhane multiple comparisons tests. The results of ANOVA indicated that the SBS values varied according to the surface treatment method (ptreatment produced high SBS of the processes assessed; therefore, it appears to be an effective method for bonding orthodontic metal brackets to prepared porcelain surfaces.

  20. Search for a metallic dangling-bond wire on n-doped H-passivated semiconductor surfaces

    DEFF Research Database (Denmark)

    Engelund, Mads; Papior, Nick Rübner; Brandimarte, Pedro

    2016-01-01

    We have theoretically investigated the electronic properties of neutral and n-doped dangling bond (DB) quasi-one-dimensional structures (lines) in the Si(001):H and Ge(001):H substrates with the aim of identifying atomic-scale interconnects exhibiting metallic conduction for use in on-surface cir...

  1. Active Metal Brazing and Adhesive Bonding of Titanium to C/C Composites for Heat Rejection System

    Science.gov (United States)

    Singh, M.; Shpargel, Tarah; Cerny, Jennifer

    2006-01-01

    Robust assembly and integration technologies are critically needed for the manufacturing of heat rejection system (HRS) components for current and future space exploration missions. Active metal brazing and adhesive bonding technologies are being assessed for the bonding of titanium to high conductivity Carbon-Carbon composite sub components in various shapes and sizes. Currently a number of different silver and copper based active metal brazes and adhesive compositions are being evaluated. The joint microstructures were examined using optical microscopy, and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS). Several mechanical tests have been employed to ascertain the effectiveness of different brazing and adhesive approaches in tension and in shear that are both simple and representative of the actual system and relatively straightforward in analysis. The results of these mechanical tests along with the fractographic analysis will be discussed. In addition, advantages, technical issues and concerns in using different bonding approaches will also be presented.

  2. Infrared spectra of metal complexes with -x,5-dimethylpyrazole and 1,2,4-triazole in frequency range of valent vibrations of metal-ligand bond

    Energy Technology Data Exchange (ETDEWEB)

    Oglezneva, I.M.; Lavrenova, L.G.; Larionov, S.V. (AN SSSR, Novosibirsk. Inst. Neorganicheskoj Khimii)

    1984-06-01

    In the range 200-600 cm/sup -1/ IR absorption spectra of complexes of halides and nitrates of Cu/sup 2/, Ni/sup 2/, Co/sup 2/, Zn/sup 2/, Cd/sup 2/ with two heterocyclic nitrogen-containing ligands: 3,5-dimethylpyrazole and 1,2,4-triazole, have been investigated. Taking into account the structure of coordination polyhedron (according to the data of electron spectroscopy and magnetic measurements), the interpretation of frequencies of valent vibrations of metal-nitrogen and metal-helide bonds is made. Regularities of ..nu.. (MN) change depending on metal and ligand are pointed out.

  3. Assessment of Bond Strength between Metal Brackets and Non-Glazed Ceramic in Different Surface Treatment Methods

    Directory of Open Access Journals (Sweden)

    I. Harririan

    2010-06-01

    Full Text Available Objective: The aim of this study was to evaluate the bond strength between metal brackets and non-glazed ceramic with three different surface treatment methods.Materials and Methods: Forty-two non-glazed ceramic disks were assigned into three groups. Group I and II specimens were etched with 9.5% hydrofluoric acid. Subsequently in group I, silane and adhesive were applied and in group II, bonding agent was used only.In group III, specimens were treated with 35% phosphoric acid and then silane and adhesive were applied. Brackets were bonded with light-cured composites. The specimens were stored in water in room temperature for 24 hours and then thermocycled 500 times between 5°C and 55°C.Results: The difference of tensile bond strength between groups I and III was not significant(P=0.999. However, the tensile bond strength of group II was significantly lower than groups I, and III (P<0.001. The adhesive remnant index scores between the threegroups had statistically significant differences (P<0.001.Conclusion: With the application of scotch bond multi-purpose plus adhesive, we can use phosphoric acid instead of hydrofluoric acid for bonding brackets to non-glazed ceramic restorations.

  4. Covalency in Metal-Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

    Energy Technology Data Exchange (ETDEWEB)

    Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Bradley, Joseph A.; Daly, Scott R.; Kozimor, Stosh A.; Lukens, Wayne W.; Martin, Richard L.; Nordlund, Dennis; Seidler, Gerald T.; Shuh, David K.; Sokaras, Dimosthenis; Tyliszczak, Tolek; Wagner, Gregory L.; Weng, Tsu-Chein; Yang, Ping

    2014-01-01

    Advancing theories of how metal oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal peroxyanions, MO4x-, have formed the basis for new M O bonding theories. Herein, relative changes in M O orbital mixing in MO42- (M = Cr, Mo, W) and MO41- (M = Mn, Tc, Re) are evaluated for the first time by non-resonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and linear-response density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M O e () mixing. Meanwhile, t2 mixing ( + ) remains relatively constant within the same Group. These unexpected changes in frontier orbital energy and composition are evaluated in terms of periodic trends in d orbital energy and radial extension.

  5. Thermal Condensation of Glycine and Alanine on Metal Ferrite Surface: Primitive Peptide Bond Formation Scenario

    Science.gov (United States)

    Iqubal, Md. Asif; Sharma, Rachana; Jheeta, Sohan; Kamaluddin

    2017-01-01

    The amino acid condensation reaction on a heterogeneous mineral surface has been regarded as one of the important pathways for peptide bond formation. Keeping this in view, we have studied the oligomerization of the simple amino acids, glycine and alanine, on nickel ferrite (NiFe2O4), cobalt ferrite (CoFe2O4), copper ferrite (CuFe2O4), zinc ferrite (ZnFe2O4), and manganese ferrite (MnFe2O4) nanoparticles surfaces, in the temperature range from 50–120 °C for 1–35 days, without applying any wetting/drying cycles. Among the metal ferrites tested for their catalytic activity, NiFe2O4 produced the highest yield of products by oligomerizing glycine to the trimer level and alanine to the dimer level, whereas MnFe2O4 was the least efficient catalyst, producing the lowest yield of products, as well as shorter oligomers of amino acids under the same set of experimental conditions. It produced primarily diketopiperazine (Ala) with a trace amount of alanine dimer from alanine condensation, while glycine was oligomerized to the dimer level. The trend in product formation is in accordance with the surface area of the minerals used. A temperature as low as 50 °C can even favor peptide bond formation in the present study, which is important in the sense that the condensation process is highly feasible without any sort of localized heat that may originate from volcanoes or hydrothermal vents. However, at a high temperature of 120 °C, anhydrides of glycine and alanine formation are favored, while the optimum temperature for the highest yield of product formation was found to be 90 °C. PMID:28346388

  6. Environmental Exposure and Accelerated Testing of Rubber-to-Metal Vulcanized Bonded Assemblies

    Science.gov (United States)

    1974-11-01

    subjected to the hydrolytic stability test or when exposed to the severe climatic conditions at Panama. EPDM and nitrile vulcanized bonded-specimens...butadiene acrylonitrile rubber bonded Sassembliesshowed a severe loes of 100 percent in bond strength; the EPDM bond.ed assemblies shcwed a 40 percent lose...02 ~ 4 -0 04 0: 00 V 4 o ~no 󈧄 0 80 EPDM Spgcimens aged up to 450°F are .shown .in Table 7. At 3000F, all - bonding agents provided good retention

  7. Features of microstructure and fracture in the transient liquid phase bonded aluminium-based metal matrix composite joints

    Institute of Scientific and Technical Information of China (English)

    孙大谦; 刘卫红; 吴建红; 贾树盛; 邱小明

    2002-01-01

    Transient liquid phase (TLP) bonded aluminium-based metal matrix composite (MMC) joints can be classified into three distinct regions, i.e. the particulate segregation region, the denuded particulate region and the base material region. The microstructure of the particulate segregation region consists of alumina particulate and Al alloy matrix with the Al2Cu and MgAl2O4. It contains more and smaller alumina particulates compared with the base material region. The TLP bonded joints have the tensile strength of 150MPa~200MPa and the shear strength of 70MPa~100MPa. With increasing tensile stress, cracks initiate in the particulate segregation region, especially in the particulate/particulate interface and the particulate/matrix interface, and propagate along particulate/matrix interface, througth thin matrix metal and by linking up the close cracks. The particulate segregation region is the weakest during tensile testing and shear testing due to obviously increased proportion of weak bonds (particulate-particulate bond and particulate-matrix bond).

  8. Control of the Chemoselectivity of Metal N-Aryl Nitrene Reactivity: C-H Bond Amination versus Electrocyclization.

    Science.gov (United States)

    Kong, Chen; Jana, Navendu; Jones, Crystalann; Driver, Tom G

    2016-10-04

    A mechanism study to identify the elements that control the chemoselectivity of metal-catalyzed N-atom transfer reactions of styryl azides is presented. Our studies show that the proclivity of the metal N-aryl nitrene to participate in sp(3)-C-H bond amination or electrocyclization reactions can be controlled by either the substrate or the catalyst. Electrocyclization is favored for mono-β-substituted and sterically noncongested styryl azides, whereas sp(3)-C-H bond amination through an H-atom abstraction-radical recombination mechanism is preferred when a tertiary allylic reaction center is present. Even when a weakened allylic C-H bond is present, our data suggest that the indole is still formed through an electrocyclization instead of a common allyl radical intermediate. The site selectivity of metal N-aryl nitrenes was found to be controlled by the choice of catalyst: Ir(I)-alkene complexes trigger electrocyclization processes while Fe(III) porphyrin complexes catalyze sp(3)-C-H bond amination in substrates where Rh2(II) carboxylate catalysts provide both products.

  9. Shear Bond Strength of Al2O3 Sandblasted Y-TZP Ceramic to the Orthodontic Metal Bracket

    Directory of Open Access Journals (Sweden)

    Seon Mi Byeon

    2017-02-01

    Full Text Available As the proportion of adult orthodontic treatment increases, mainly for aesthetic reasons, orthodontic brackets are directly attached to yttria-stabilized tetragonal zirconia polycrystal (Y-TZP restorations. This, study analyzed the shear bond strength (SBS between various surface treated Y-TZP and orthodontic metal brackets. The Y-TZP specimens were conditioned by 110 μm Al2O3 sandblasting, or sandblasting followed by coating with one of the primers (silane, MDP, or an MDP-containing silane primer. After surface treatment, the orthodontic metal bracket was bonded to the specimen using a resin cement, and then 24 h storage in water and thermal cycling (5000 cycles, 5–55 °C, SBS was measured. Surface roughness was analyzed for surface morphology, and X-ray photoelectron spectroscopy (XPS was employed for characterization of the chemical bond between the Y-TZP and the MDP-based primers (MDP, MDP containing silane primer. It was found that after surface treatment, the surface roughness of all groups increased. The groups treated with 110 μm Al2O3 sandblasting and MDP, or MDP-containing silane primer showed the highest SBS values, at 11.92 ± 1.51 MPa and 13.36 ± 2.31 MPa, respectively. The SBS values significantly decreased in all the groups after thermal cycling. Results from XPS analysis demonstrated the presence of chemical bonds between Y-TZP and MDP. Thus, the application of MDP-based primers after Al2O3 sandblasting enhances the resin bond strength between Y-TZP and the orthodontic metal bracket. However, bonding durability of all the surface-treated groups decreased after thermal cycling.

  10. Silylations of Arenes with Hydrosilanes: From Transition-Metal-Catalyzed C¢X Bond Cleavage to Environmentally Benign Transition-Metal-Free C¢H Bond Activation.

    Science.gov (United States)

    Xu, Zheng; Xu, Li-Wen

    2015-07-08

    The construction of carbon-silicon bonds is highlighted as an exciting achievement in the field of organosilicon chemistry and green chemistry. Recent developments in this area will enable the sustainable chemical conversion of silicon resources into synthetically useful compounds. Especially, the catalytic silylation through C¢H bond activation without directing groups and hydrogen acceptors is one of the most challenging topics in organic chemistry and green chemistry. These remarkable findings on catalytic silylation can pave the way to a more environmentally benign utilization of earth-abundant silicon-based resources in synthetic chemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Metal-ligand cooperation by aromatization-dearomatization as a tool in single bond activation

    National Research Council Canada - National Science Library

    Milstein, David

    2015-01-01

    .... A recent new mode of activation of chemical bonds involves ligand aromatization-dearomatization processes in pyridine-based pincer complexes in which chemical bonds are broken reversibly across...

  12. The estimation of CO bond length changes in the excited states of transition metal carbonyls

    Science.gov (United States)

    Morrison, Sara L.; Turner, James J.

    1994-01-01

    Advances in vibrational spectroscopy have led to increased knowledge of shortlived excited states. In the case of transition metal carbonyl compounds, time-resolved infrared spectra can be measured directly. The CO energy factored force constants are used to estimate the CO bond length distortions upon excitation. The new empirical relationship rCO = 1.674 - 0.184 ln kCO allows excited states CO bond lenghts to be calculated with a standard deviation of ±0.005 Å. For energy factored systems it is deemed unnecessary to calculate pseudodiatomic frequencies ( vPD) from the potential energy distribution.

  13. Influence of various surface-conditioning methods on the bond strength of metal brackets to ceramic surfaces.

    Science.gov (United States)

    Schmage, Petra; Nergiz, Ibrahim; Herrmann, Wolfram; Ozcan, Mutlu

    2003-05-01

    With the increase in adult orthodontic treatment comes the need to find a reliable method for bonding orthodontic brackets onto metal or ceramic crowns and fixed partial dentures. In this study, shear bond strength and surface roughness tests were used to examine the effect of 4 different surface conditioning methods: fine diamond bur, sandblasting, 5% hydrofluoric acid, and silica coating for bonding metal brackets to ceramic surfaces of feldspathic porcelain. Sandblasting and hydrofluoric acid were further tested after silane application. A total of 120 ceramic disc samples were produced, and 50 were used for surface roughness measurements. The glazed ceramic surfaces were used as controls. Metal brackets were bonded to the ceramic substrates with a self-curing composite. The samples were stored in 0.9% NaCl solution for 24 hours and then thermocycled (5000 times, 5 degrees C to 55 degrees C, 30 seconds). Shear bond tests were performed with a universal testing device, and the results were statistically analyzed. Chemical surface conditioning with either hydrofluoric acid (4.3 microm) or silicatization (4.4 microm) resulted in significantly lower surface roughness than mechanical conditioning (9.3 microm, diamond bur; 9.7 microm, sandblasting) (P <.001). The surface roughness values reflect the mean peak-and-valley distances. The bond strengths of the brackets bonded to the ceramic surfaces treated by hydrofluoric acid with and without silane (12.2 and 14.7 MPa, respectively), silicatization (14.9 MPa), and sandblasting with silane (15.8 MPa) were significantly higher (P <.001) than those treated by mechanical roughening with fine diamond burs (1.6 MPa) or sandblasting (2.8 MPa). The highest bond strength values were obtained with sandblasting and silicatization with silane or hydrofluoric acid without silane; these fulfilled the required threshold. The use of silane after hydrofluoric acid etching did not increase the bond strength. Diamond roughening and

  14. Cu-(B4Cp metal matrix composites processed by accumulative roll-bonding

    Directory of Open Access Journals (Sweden)

    S. Mansourzadeh

    2016-12-01

    Full Text Available In this study, Cu/B4C metal matrix composites were prepared by accumulative roll-bonding (ARB. The microstructure of the processed samples was characterized by TEM, SEM and optical microscopy. The microhardness, uniaxial tensile and four-point probe tests were carried out to evaluate the mechanical properties and electrical resistivity of the ARBed monolithic and composite samples. The results showed that the reinforcement distribution was improved by increasing ARB cycles, which was quantitatively confirmed by some models. Based on TEM observations, the formation of an ultrafine grained structure in the composite matrix was also approved. It was shown that with increasing ARB cycles, the microhardness and tensile strength of the monolithic Cu samples were enhanced up to the 3rd cycle and then saturated, but the microhardness and tensile strength of the composites showed an increasing trend to the last cycle. Apart from a substantial improvement in the mechanical properties of the Cu/B4C composites, a minor decrement in electrical conductivity was detected after six ARB cycles.

  15. Synthesis and decomposition of ammonia on transition metal surfaces: bond-order-conservation-Morse-potential analysis

    Science.gov (United States)

    Shustorovich, Evgeny; Bell, Alexis T.

    1991-12-01

    The mechanism of ammonia synthesis and decomposition on transition metal surfaces has been analyzed using the BOC-MP (bond-order-conservation-Morse-potential) method. The analysis is based on calculations of the heats of chemisorption, Q, for all adsorbed species and activation barriers, Δ E∗, for all elementary reactions believed to be involved in the reaction N 2 + H 2 NH 3 over Pt(111), Ru(001), Fe(110), Re(001). The relevant experimental values of Q and Δ E∗ agree well with the BOC-MP estimates. It is shown that along the periodic series Pt, Ru, Fe, Re, the dissociation activation barriers decrease but the recombination and desorption barriers increase. In particular, we find that on all the surfaces the largest activation barrier corresponds to the recombinative desorption 2N s → N 2. This step is projected to be the rate-determining process for ammonia decomposition, and Pt is projected to be the most efficient catalyst. For the dissociation N 2 → 2N s, we find that the activation barrier sharply increases in the order Re ⩽ Fe ≪ Pt, which makes Pt surfaces incapable of catalyzing ammonia synthesis. These and other BOC-MP projections are in agreement with the results of mechanistic studies on Pt(111), Ru(001) and Fe(110).

  16. Consequences of metal-oxide interconversion for C-H bond activation during CH4 reactions on Pd catalysts.

    Science.gov (United States)

    Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-10-16

    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH4 react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to H-abstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cation-lattice oxygen pairs (Pd(2+)-O(2-)) in PdO. The charges in the CH3 and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*-covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd(2+)-O(2-) pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H3C···Pd···H)(‡) transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3(•)···*OH)(‡) that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd(2+) and vicinal O(2-), Pd(ox)-O(ox), cleave C-H bonds heterolytically via σ-bond metathesis, with Pd(2+) adding to the C-H bond, while O(2-) abstracts the H-atom to form a four-center (H3C(δ-)···Pd(ox)···H(δ+)···O(ox))(‡) transition state without detectable Pd(ox) reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH4 oxidation turnover rates at oxygen chemical potentials leading to Pd to PdO transitions. These distinct mechanistic pathways for C-H bond activation, inferred from theory

  17. Bonding strength of Al/Mg/Al alloy tri-metallic laminates fabricated by hot rolling

    Indian Academy of Sciences (India)

    X P Zhang; M J Tan; T H Yang; X J Xu; J T Wang

    2011-07-01

    One of major drawbacks of magnesium alloy is its low corrosion resistance, which can be improved by using an aluminized coating. In this paper, 7075 Al/Mg–12Gd–3Y–0.5Zr/7075 Al laminated composites were produced by a hot roll bonding method. The rolling temperature was determined based on the flow stresses of Mg–12Gd–3Y–0.5Zr magnesium alloy and 7075 Al alloy at elevated temperature. The bonding strength of the laminate composites and their mechanism were studied. The effects of the reduction ratio (single pass), the rolling temperature, and the subsequent annealing on the bonding strength were also investigated. It was observed that the bonding strength increased rapidly with the reduction ratio and slightly with the rolling temperature. The bonding strength increases with the annealing time until the annealing time reaches 2 h and then decreases. The mechanical bond plays a major role in the bonding strength.

  18. Nanoscale metals and semiconductors for the storage of solar energy in chemical bonds

    Science.gov (United States)

    Manthiram, Karthish

    The transduction of electrical energy into chemical bonds represents one potential strategy for storing energy derived from intermittent sources such as solar and wind. Driving the electrochemical reduction of carbon dioxide using light requires (1) developing light absorbers which convert photons into electron-hole pairs and (2) catalysts which utilize these electrons and holes to reduce carbon dioxide and oxidize water, respectively. For both the light absorbers and catalysts, the use of nanoscale particles is advantageous, as charge transport length scales are minimized in the case of nanoscale light absorbers and catalytic surface-area-to-volume ratio is maximized for nanoscale catalysts. In many cases, although semiconductors and metals in the form of thin films and foils are increasingly well-characterized as photoabsorbers and electrocatalysts for carbon dioxide reduction, respectively, the properties of their nanoscale counterparts remain poorly understood. This dissertation explores the nature of the light absorption mode of non-stoichiometric semiconductors which are utilized as light absorbers and the development of catalysts with enhanced stability, activity, and selectivity for carbon dioxide reduction. Chapter 1 provides an overview of the state of development of methods of transducing the energy of photons into chemical bonds. Chapters 2 and 3 investigate the development of stable, active, and selective catalysts for the electrochemical reduction of carbon dioxide. Chapter 2 examines how copper nanoparticles have enhanced activities and selectivities for methanation compared to copper foils. Chapter 3 focuses on the development of strategies to stabilize high-surface-area catalysts to prevent surface area loss during electrochemical carbon dioxide reduction. Chapters 4 and 5 entail a fundamental understanding of the light absorption mode of nanoscale photoabsorbers used in both photoelectrochemical cells and in photovoltaics. Chapter 4 focuses on the

  19. Bond making and breaking on transition-metal surfaces: Theoretical projections based on bond-order conservation

    Science.gov (United States)

    Shustorovich, Evgeny

    1986-11-01

    Our analytic Morse-potential model of chemisorption based on bond-order conservation [Surface Sci. 150 (1985) L115; 163 (1985) L645, L730] has been used to calculate the heats of chemisorption of various diatomic AB and polyatomic AB x species (coordinated via A) and to estimate the activation barriers for their dissociation and transformations. Examples include adspecies such as CH x, NH x, OH x, and possible intermediates and elementary steps of reactions such as CO + O → CO 2, NO + N → N 2 + O, N 2 + H 2 → NH 3, H 2 + O 2 → H 2O, and CO + H 2 → CH 4. Both the qualitative projections and numerical estimates are in good agreement with experiment. In particular, it is shown that (1) the most reactive adspecies should be the most weakly bound, and (2) the recombination activation barrier should primarily depend on (and may even be close to) the heat of chemisorption of the weaker bound partner.

  20. Reliability Tests of Aluminium Wedge Wire Bonding on Auto-catalytic Silver Immersion Gold (ASIG) PCB Metallization

    CERN Document Server

    Drozd, A; Kaufmann, S; Manolescu, F; McGill, I

    2011-01-01

    The Auto-catalytic Silver Immersion Gold (ASIG) PCB metallization is a new process that has clear advantages for PCB assembly especially with regard to lead-free soldering. As it may become a popular process in the future for electronics used in physics experiments, the quality of this metallization for aluminium wire bonding has been studied. Aluminium wedge wire bonding continues to be the interconnection method of choice for many physics detector sensors, for high density signal routing and for unpackaged die. Although advertised as having good quality for aluminium wire bonding, this study was performed to verify this claim as well as to test the longer term reliability of the wire bonds taking into consideration the environmental conditions and life-expectancy of devices, in particular for high energy physics detector applications. The tests were performed on PCBs made with the ASIG and ENIG (Electro-less Nickel Immersion Gold) processes at the same time in order to make a comparison with the current ind...

  1. Structure and property of metal melt Ⅰ:The number of residual bonds after solid-liquid phase changes

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Based on the mechanism of metal solid-liquid phase change and the theory of liquid metal’s micro-inhomogeneity,a physical model is established between latent heats of fusion and vaporization and the numbers of residual bonds and short-range ordered atoms at the melting point inside a metal melt.Meanwhile,the mathematical derivation and proof are also offered.This model produces the numbers of residual bonds and short-range ordered atoms after the solid-liquid phase change only by using basic parameters and thermophysical properties of the crystal structure.Therefore,it presents a more effective way to analyze the melt’s structural information.By using this model,this study calculates the numbers of residual bonds and short-range ordered atoms in Al and Ni melts.The calculated results are consistent with the experimental results.Simultaneously,this study discusses the atomic number’s influence on the numbers of residual bonds and short-range ordered atoms in the melts within the first(ⅠA) and second main group(ⅡA) elements.

  2. Sudy of the conditions of the formation of a strong bond during the explosive welding of powders with metals

    Energy Technology Data Exchange (ETDEWEB)

    Kaunov, A.M.

    1987-08-01

    The energy conditions for the formation of a strong bond between the coating and the substrate during the explosive welding of powders with metals are examined with reference to experimental results obtained for Cu, Ni, Mo, and Ti powders and iron substrates. A generalized energy criterion is proposed. Recommendations are given concerning welding process control and prediction of the properties of explosively welded coatings. 14 references.

  3. Influence of Temporary Cements on the Bond Strength of Self-Adhesive Cement to the Metal Coronal Substrate.

    Science.gov (United States)

    Peixoto, Raniel Fernandes; De Aguiar, Caio Rocha; Jacob, Eduardo Santana; Macedo, Ana Paula; De Mattos, Maria da Gloria Chiarello; Antunes, Rossana Pereira de Almeida

    2015-01-01

    This research evaluated the influence of temporary cements (eugenol-containing [EC] or eugenol-free [EF]) on the tensile strength of Ni-Cr copings fixed with self-adhesive resin cement to the metal coronal substrate. Thirty-six temporary crowns were divided into 4 groups (n=9) according to the temporary cements: Provy, Dentsply (eugenol-containing), Temp Cem, Vigodent (eugenol-containing), RelyX Temp NE, 3M ESPE (eugenol-free) and Temp Bond NE, Kerr Corp (eugenol-free). After 24 h of temporary cementation, tensile strength tests were performed in a universal testing machine at a crosshead speed of 0.5 mm/min and 1 kN (100 kgf) load cell. Afterwards, the cast metal cores were cleaned by scraping with curettes and air jet. Thirty-six Ni-Cr copings were cemented to the cast metal cores with self-adhesive resin cement (RelyX U200, 3M ESPE). Tensile strength tests were performed again. In the temporary cementation, Temp Bond NE (12.91 ± 2.54) and Temp Cem (12.22 ± 2.96) presented the highest values of tensile strength and were statistically similar to each other (p>0.05). Statistically significant difference (pcementation of Ni-Cr copings with self-adhesive resin cement. In addition, Temp Cem (120.68 ± 48.27) and RelyX Temp NE (103.04 ± 26.09) showed intermediate tensile strength values. In conclusion, the Provy eugenol-containing temporary cement was associated with the highest bond strength among the resin cements when Ni-Cr copings were cemented to cast metal cores. However, the eugenol cannot be considered a determining factor in increased bond strength, since the other tested cements (1 eugenol-containing and 2 eugenol-free) were similar.

  4. Improved stability of a metallic state in benzothienobenzothiophene-based molecular conductors: an effective increase of dimensionality with hydrogen bonds.

    Science.gov (United States)

    Higashino, Toshiki; Ueda, Akira; Yoshida, Junya; Mori, Hatsumi

    2017-02-27

    A dihydroxy-substituted benzothienobenzothiophene, BTBT(OH)2, was synthesized, and its charge-transfer (CT) salt, β-[BTBT(OH)2]2ClO4, was successfully obtained. Thanks to the introduced hydroxy groups, a hydrogen-bonded chain structure connecting the BTBT molecules and counter anions was formed in the CT salt, which effectively increases the dimensionality of the electronic structure and consequently leads to a stable metallic state.

  5. DFT modeling and spectroscopic study of metal ligand bonding in La(III) complex of coumarin-3-carboxylic acid

    Science.gov (United States)

    Mihaylov, Tz.; Trendafilova, N.; Kostova, I.; Georgieva, I.; Bauer, G.

    2006-09-01

    The binding mode of coumarin-3-carboxylic acid (HCCA) to La(III) is elucidated at experimental and theoretical level. The complexation ability of the deprotonated ligand (CCA -) to La(III) is studied using elemental analysis, DTA and TGA data as well as FTIR, 1H NMR and 13C NMR spectra. The experimental data suggest the complex formula La(CCA) 2(NO 3)(H 2O) 2. B3LYP, BHLYP, B3P86, B3PW91, PW91P86 and MPW1PW91 functionals are tested for geometry and frequency calculations of the neutral ligand and all of them show bond length deviations bellow 1%. B3LYP/6-31G(d) level combined with large quasi-relativistic effective core potential for lanthanum is selected to describe the molecular, electronic and vibrational structures as well as the conformational behavior of HCCA, CCA - and La-CCA complex. The metal-ligand binding mode is predicted through molecular modeling and energy estimation of different La-CCA structures. The calculated atomic charges and the bonding orbital polarizations point to strong ionic metal-ligand bonding in La-CCA complex and insignificant donor acceptor interaction. Detailed vibrational analysis of HCCA, CCA - and La(CCA) 2(NO 3)(H 2O) 2 systems based on both calculated and experimental frequencies confirms the suggested metal-ligand binding mode.

  6. Mechanical properties of a metal-organic framework containing hydrogen-bonded bifluoride linkers.

    Science.gov (United States)

    Li, Wei; Kiran, M S R N; Manson, Jamie L; Schlueter, John A; Thirumurugan, A; Ramamurty, U; Cheetham, Anthony K

    2013-05-18

    We report the mechanical properties of a framework structure, [Cu2F(HF)(HF2)(pyz)4][(SbF6)2]n (pyz = pyrazine), in which [Cu(pyz)2](2+) layers are pillared by HF2(-) anions containing the exceptionally strong F-H···F hydrogen bonds. Nanoindentation studies on single-crystals clearly demonstrate that such bonds are extremely robust and mechanically comparable with coordination bonds in this system.

  7. Hydrogen-bond and solvent dynamics in transition metal complexes: a combined simulation and NMR-investigation.

    Science.gov (United States)

    Huang, Jing; Häussinger, Daniel; Gellrich, Urs; Seiche, Wolfgang; Breit, Bernhard; Meuwly, Markus

    2012-12-13

    Self-assembling ligands through complementary hydrogen-bonding in the coordination sphere of a transition metal provides catalysts with unique properties for carbon-carbon and carbon-heteroatom formation. Their most distinguishing chemical bonding pattern is a double-hydrogen-bonded motif, which determines much of the chemical functionality. Here, we discuss the possibility of double proton transfer (DPT) along this motif using computational and experimental methods. The infrared and NMR spectral signatures for the double-hydrogen-bonded motif are analyzed. Atomistic simulations and experiments suggest that the dynamics of the catalyst is surprisingly complex and displays at least three different dynamical regimes which can be distinguished with NMR spectroscopy and analyzed from computation. The two hydrogen bonds are kept intact and in rapid tautomeric exchange down to 125 K, which provides an estimate of 5 kcal/mol for the barrier for DPT. This is confirmed by the simulations which predict 5.8 kcal/mol for double proton transfer. A mechanistic interpretation is provided and the distribution of the solvent shell surrounding the catalyst is characterized from extensive simulations.

  8. Preliminary assessment of metal-porcelain bonding strength of CoCrW alloy after 3 wt.% Cu addition

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Yanjin; Zhao, Chaoqian [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155Yangqiao Road West, Fuzhou (China); Ren, Ling [Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang (China); Guo, Sai; Gan, Yiliang [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155Yangqiao Road West, Fuzhou (China); Yang, Chunguang [Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang (China); Wu, Songquan; Lin, Junjie; Huang, Tingting [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155Yangqiao Road West, Fuzhou (China); Yang, Ke, E-mail: kyang@imr.ac.cn [Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang (China); Lin, Jinxin, E-mail: franklin@fjirsm.ac.cn [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155Yangqiao Road West, Fuzhou (China)

    2016-06-01

    In this work, a novel Cu-bearing CoCrW alloy fabricated by selective laser melting for dental application has been studied. For its successful application, the bonding strength of metal-porcelain is essential to be systematically investigated. Therefore, the aim of this study was to evaluate the metal-porcelain bonding strength of CoCrWCu alloy by three-point bending test, meanwhile the Ni-free CoCrW alloy was used as control. The oxygen content was investigated by an elemental analyzer; X-ray photoelectron spectroscopy (XPS) was used to analyze the surface chemical composition of CoCrW based alloy after preoxidation treatment; the fracture mode was investigated by X-ray energy spectrum analysis (EDS) and scanning electron microscope (SEM). Result from the oxygen content analysis showed that the content of oxygen dramatically increased after the Cu addition. And the XPS suggested that Co-oxidation, Cr{sub 2}O{sub 3}, CrO{sub 2}, WO{sub 3}, Cu{sub 2}O and CuO existed on the preoxidated surface of the CoCrWCu alloy; the three-point bending test showed that the bonding strength of the CoCrWCu alloy was 43.32 MPa, which was lower than that of the CoCrW group of 47.65 MPa. However, the average metal-porcelain bonding strength is significantly higher than the minimum value in the ISO 9693 standard. Results from the SEM images and EDS indicated that the fracture mode of CoCrWCu-porcelain was mixed between cohesive and adhesive. Based on the results obtained in this study, it can be indicated that the Cu-bearing CoCrW alloy fabricated by the selective laser melting is a promising candidate for use in dental application. - Highlights: • The bonding strength of metal-porcelain was slightly decreased with Cu addition; • Cu not only led to promote the diffusion of O and W element but also inhibited the diffusivity of Co in the outward direction; • The changed oxidation behavior resulted in lowering the bonding strength;.

  9. Evaluation and comparison of the effect of different surface preparations on bond strength of glass ionomer cement with nickel-chrome metal-ceramic alloy: a laboratory study.

    Science.gov (United States)

    Hasti, Kalpana; Jagadeesh, H G; Patil, Narendra P

    2011-03-01

    Retention of fixed partial dentures is mostly dependent upon the bond between metal and cement as well as cement and tooth structure. However, most of the time clinical failure of bond has been observed at metal and cement interface. The treatment of metal surface, prior to luting, plays a crucial role in bonding cement with the metal. This study is conducted to evaluate and compare the effect of different surface preparations on the bond strength of resin-modified glass ionomer cement with nickel-chromium metal ceramic alloy. Fifty caries-free extracted molar teeth were made flat until the dentin of the occlusal surface was exposed. After fabrication of the wax patterns and subsequent castings, the castings were subjected to porcelain firing cycles. The nickel-chromium metal ceramic alloy discs were also divided into five groups and subjected to various surface treatments: (1) Unsandblasted (U), (2) sandblasted (S), (3) sandblasted and treated with 10% aqueous solution of KMnO4 (SK), (4) unsandblasted and roughened with diamond abrasive points (UD) and (5) unsandblasted and roughened with diamond abrasive points and treated with 10% aqueous solution of KMnO(4) (UDK). After surface treatments, the castings were cemented using Fuji PLUS encapsulated resin-modified glass ionomer cement. The obtained values of all the groups were subjected to statistical analysis for Tensile and Shear bond strength. Different surface treatments of the metal affects the bond strength values of resin-modified glass ionomer cement when used as luting agent.

  10. Preliminary assessment of metal-porcelain bonding strength of CoCrW alloy after 3wt.% Cu addition.

    Science.gov (United States)

    Lu, Yanjin; Zhao, Chaoqian; Ren, Ling; Guo, Sai; Gan, Yiliang; Yang, Chunguang; Wu, Songquan; Lin, Junjie; Huang, Tingting; Yang, Ke; Lin, Jinxin

    2016-06-01

    In this work, a novel Cu-bearing CoCrW alloy fabricated by selective laser melting for dental application has been studied. For its successful application, the bonding strength of metal-porcelain is essential to be systematically investigated. Therefore, the aim of this study was to evaluate the metal-porcelain bonding strength of CoCrWCu alloy by three-point bending test, meanwhile the Ni-free CoCrW alloy was used as control. The oxygen content was investigated by an elemental analyzer; X-ray photoelectron spectroscopy (XPS) was used to analyze the surface chemical composition of CoCrW based alloy after preoxidation treatment; the fracture mode was investigated by X-ray energy spectrum analysis (EDS) and scanning electron microscope (SEM). Result from the oxygen content analysis showed that the content of oxygen dramatically increased after the Cu addition. And the XPS suggested that Co-oxidation, Cr2O3, CrO2, WO3, Cu2O and CuO existed on the preoxidated surface of the CoCrWCu alloy; the three-point bending test showed that the bonding strength of the CoCrWCu alloy was 43.32 MPa, which was lower than that of the CoCrW group of 47.65 MPa. However, the average metal-porcelain bonding strength is significantly higher than the minimum value in the ISO 9693 standard. Results from the SEM images and EDS indicated that the fracture mode of CoCrWCu-porcelain was mixed between cohesive and adhesive. Based on the results obtained in this study, it can be indicated that the Cu-bearing CoCrW alloy fabricated by the selective laser melting is a promising candidate for use in dental application.

  11. Effects of silica coating and silane surface conditioning on the bond strength of rebonded metal and ceramic brackets

    Directory of Open Access Journals (Sweden)

    Saadet Atsü

    2011-06-01

    Full Text Available OBJECTIVE: The aim of this study was to evaluate the effects of tribochemical silica coating and silane surface conditioning on the bond strength of rebonded metal and ceramic brackets. MATERIAL AND METHODS: Twenty debonded metal and 20 debonded ceramic brackets were randomly assigned to receive one of the following surface treatments (n=10 for each group: (1 sandblasting (control; (2 tribochemical silica coating combined with silane. Brackets were rebonded to the enamel surface on the labial and lingual sides of premolars with a light-polymerized resin composite. All specimens were stored in distilled water for 1 week and then thermocycled (5,000 cycles between 5-55ºC. Shear bond strength values were measured using a universal testing machine. Student's t-test was used to compare the data (α=0.05. Failure mode was assessed using a stereomicroscope, and the treated and non-treated bracket surfaces were observed by scanning electron microscopy. RESULTS: Rebonded ceramic brackets treated with silica coating followed by silanization had significantly greater bond strength values (17.7±4.4 MPa than the sandblasting group (2.4±0.8 MPa, P<0.001. No significant difference was observed between the rebonded metal brackets treated with silica coating with silanization (15±3.9 MPa and the sandblasted brackets (13.6±3.9 MPa. Treated rebonded ceramic specimens primarily exhibited cohesive failure in resin and adhesive failure at the enamel-adhesive interface. CONCLUSIONS: In comparison to sandblasting, silica coating with aluminum trioxide particles followed by silanization resulted in higher bond strengths of rebonded ceramic brackets.

  12. New bonding configuration on Si(111) and Ge(111) surfaces induced by the adsorption of alkali metals

    DEFF Research Database (Denmark)

    Lottermoser, L.; Landemark, E.; Smilgies, D.M.;

    1998-01-01

    The structure of the (3×1) reconstructions of the Si(111) and Ge(111) surfaces induced by adsorption of alkali metals has been determined on the basis of surface x-ray diffraction and low-energy electron diffraction measurements and density functional theory. The (3×1) surface results primarily f...... from the substrate reconstruction and shows a new bonding configuration consisting of consecutive fivefold and sixfold Si (Ge) rings in 〈11̅ 0〉 projection separated by channels containing the alkali metal atoms. © 1998 The American Physical Society......The structure of the (3×1) reconstructions of the Si(111) and Ge(111) surfaces induced by adsorption of alkali metals has been determined on the basis of surface x-ray diffraction and low-energy electron diffraction measurements and density functional theory. The (3×1) surface results primarily...

  13. Evaluation of Low Hazardous Air Pollutant Thermoset Adhesives for the Application of Rubber-to-Metal Bonding on Army Tank Pads and Road Wheels

    Science.gov (United States)

    2011-09-01

    rubber substrate during peel test (left) and after peel (right). ...............22  Figure 17. Asymetrical peel...crescent-shaped bond line is visible. All efforts were made to 23 Rubber to metal interface Figure 17. Asymetrical peel. maintain a straight bond

  14. Reusable ionic liquid-catalyzed oxidative coupling of azoles and benzylic compounds via sp(3) C-N bond formation under metal-free conditions.

    Science.gov (United States)

    Liu, Wenbo; Liu, Chenjiang; Zhang, Yonghong; Sun, Yadong; Abdukadera, Ablimit; Wang, Bin; Li, He; Ma, Xuecheng; Zhang, Zengpeng

    2015-07-14

    The heterocyclic ionic liquid-catalyzed direct oxidative amination of benzylic sp(3) C-H bonds via intermolecular sp(3) C-N bond formation for the synthesis of N-alkylated azoles under metal-free conditions is reported for the first time. The catalyst 1-butylpyridinium iodide can be recycled and reused with similar efficacies for at least eight cycles.

  15. Detection of Sleeping Beauty transposition in the genome of host cells by non-radioactive Southern blot analysis.

    Science.gov (United States)

    Aravalli, Rajagopal N; Park, Chang W; Steer, Clifford J

    2016-08-26

    The Sleeping Beauty transposon (SB-Tn) system is being used widely as a DNA vector for the delivery of therapeutic transgenes, as well as a tool for the insertional mutagenesis in animal models. In order to accurately assess the insertional potential and properties related to the integration of SB it is essential to determine the copy number of SB-Tn in the host genome. Recently developed SB100X transposase has demonstrated an integration rate that was much higher than the original SB10 and that of other versions of hyperactive SB transposases, such as HSB3 or HSB17. In this study, we have constructed a series of SB vectors carrying either a DsRed or a human β-globin transgene that was encompassed by cHS4 insulator elements, and containing the SB100X transposase gene outside the SB-Tn unit within the same vector in cis configuration. These SB-Tn constructs were introduced into the K-562 erythroid cell line, and their presence in the genomes of host cells was analyzed by Southern blot analysis using non-radioactive probes. Many copies of SB-Tn insertions were detected in host cells regardless of transgene sequences or the presence of cHS4 insulator elements. Interestingly, the size difference of 2.4 kb between insulated SB and non-insulated controls did not reflect the proportional difference in copy numbers of inserted SB-Tns. We then attempted methylation-sensitive Southern blots to assess the potential influence of cHS4 insulator elements on the epigenetic modification of SB-Tn. Our results indicated that SB100X was able to integrate at multiple sites with the number of SB-Tn copies larger than 6 kb in size. In addition, the non-radioactive Southern blot protocols developed here will be useful to detect integrated SB-Tn copies in any mammalian cell type.

  16. Detection of Sleeping Beauty transposition in the genome of host cells by non-radioactive Southern blot analysis

    Energy Technology Data Exchange (ETDEWEB)

    Aravalli, Rajagopal N., E-mail: aravalli@umn.edu [Department of Radiology, University of Minnesota Medical School, MMC 292, 420 Delaware Street SE, Minneapolis, MN 55455 (United States); Park, Chang W. [Department of Medicine, University of Minnesota Medical School, MMC 36, 420 Delaware Street SE, Minneapolis, MN 55455 (United States); Steer, Clifford J., E-mail: steer001@umn.edu [Department of Medicine, University of Minnesota Medical School, MMC 36, 420 Delaware Street SE, Minneapolis, MN 55455 (United States); Department of Genetics, Cell Biology and Development, University of Minnesota, Minneapolis, MN 55455 (United States)

    2016-08-26

    The Sleeping Beauty transposon (SB-Tn) system is being used widely as a DNA vector for the delivery of therapeutic transgenes, as well as a tool for the insertional mutagenesis in animal models. In order to accurately assess the insertional potential and properties related to the integration of SB it is essential to determine the copy number of SB-Tn in the host genome. Recently developed SB100X transposase has demonstrated an integration rate that was much higher than the original SB10 and that of other versions of hyperactive SB transposases, such as HSB3 or HSB17. In this study, we have constructed a series of SB vectors carrying either a DsRed or a human β-globin transgene that was encompassed by cHS4 insulator elements, and containing the SB100X transposase gene outside the SB-Tn unit within the same vector in cis configuration. These SB-Tn constructs were introduced into the K-562 erythroid cell line, and their presence in the genomes of host cells was analyzed by Southern blot analysis using non-radioactive probes. Many copies of SB-Tn insertions were detected in host cells regardless of transgene sequences or the presence of cHS4 insulator elements. Interestingly, the size difference of 2.4 kb between insulated SB and non-insulated controls did not reflect the proportional difference in copy numbers of inserted SB-Tns. We then attempted methylation-sensitive Southern blots to assess the potential influence of cHS4 insulator elements on the epigenetic modification of SB-Tn. Our results indicated that SB100X was able to integrate at multiple sites with the number of SB-Tn copies larger than 6 kb in size. In addition, the non-radioactive Southern blot protocols developed here will be useful to detect integrated SB-Tn copies in any mammalian cell type.

  17. Effects of two soft drinks on shear bond strength and adhesive remnant index of orthodontic metal brackets.

    Directory of Open Access Journals (Sweden)

    Soodabeh Sadat Sajadi

    2014-08-01

    Full Text Available Bond failure of brackets during orthodontic treatment is a common problem; which results in treatment interference, increased treatment time and prolonged clinical time for rebonding of failed brackets. The purpose of this study was to evaluate the effects of Coca-Cola and a non-alcoholic beer on the shear bond strength and adhesive remnant index (ARI of orthodontic metal brackets in vitro.Eighty intact human premolars were divided into two experimental groups of Coca-Cola and non-alcoholic beer (Istak, and a control group of artificial saliva. Over a period of thirty days, the test groups were immersed in the respective soft drinks for 5 minutes, twice a day. For the remainder of the time, they were kept in artificial saliva at 37°C. The control group was stored in artificial saliva during the experiment. All samples were subjected to shearing forces using Universal Testing Machine. ARI was determined with a stereomicroscope at ×12 magnification. The data of shear bond strength were statistically analyzed by one-way ANOVA and Tukey's Post-Hoc test and the data of ARI scores were analyzed by Kruskal-Wallis test.No significant difference was observed in ARIs of the three groups (P≤ 0.552. The shear bond strength of Coke group was significantly lower than that of the two other groups (P≤ 0.035; but there was no significant difference between the shear bond strength of Istak and the control group (P≤ 0.999.Coca-Cola decreased the shear bond strength of orthodontic brackets.

  18. Effects of two soft drinks on shear bond strength and adhesive remnant index of orthodontic metal brackets.

    Science.gov (United States)

    Sajadi, Soodabeh Sadat; Eslami Amirabadi, Gholamreza; Sajadi, Sepideh

    2014-07-01

    Bond failure of brackets during orthodontic treatment is a common problem; which results in treatment interference, increased treatment time and prolonged clinical time for rebonding of failed brackets. The purpose of this study was to evaluate the effects of Coca-Cola and a non-alcoholic beer on the shear bond strength and adhesive remnant index (ARI) of orthodontic metal brackets in vitro. Eighty intact human premolars were divided into two experimental groups of Coca-Cola and non-alcoholic beer (Istak), and a control group of artificial saliva. Over a period of thirty days, the test groups were immersed in the respective soft drinks for 5 minutes, twice a day. For the remainder of the time, they were kept in artificial saliva at 37°C. The control group was stored in artificial saliva during the experiment. All samples were subjected to shearing forces using Universal Testing Machine. ARI was determined with a stereomicroscope at ×12 magnification. The data of shear bond strength were statistically analyzed by one-way ANOVA and Tukey's Post-Hoc test and the data of ARI scores were analyzed by Kruskal-Wallis test. No significant difference was observed in ARIs of the three groups (P≤ 0.552). The shear bond strength of Coke group was significantly lower than that of the two other groups (P≤ 0.035); but there was no significant difference between the shear bond strength of Istak and the control group (P≤ 0.999). Coca-Cola decreased the shear bond strength of orthodontic brackets.

  19. Synergizing Noncovalent Bonding Interactions in the Self-Assembly of Organic Charge-Transfer Ferroelectrics and Metal-Organic Frameworks

    Science.gov (United States)

    Cao, Dennis

    Contemporary supramolecular chemistry---chemistry beyond the molecule---seeks to leverage noncovalent bonding interactions to generate emergent properties and complexity. These aims extend beyond the solution phase and into the solid state, where crystalline organic materials have attracted much attention for their ability to imitate the physical properties of inorganic crystals. This Thesis outlines my efforts to understand the properties of the solid-state materials that are self-assembled with noncovalent bonding motifs which I have helped to realize. In the first five Chapters, I chronicle the development of the lock-arm supramolecular ordering (LASO) paradigm, which is a general molecular design strategy for amplifying the crystallization of charge transfer complexes that revolves around the synergistic action of hydrogen bonding and charge transfer interactions. In an effort to expand upon the LASO paradigm, I identify a two-point halogen-bonding motif which appears to operate orthogonally from the hydrogen bonding and charge transfer interactions. Since some of these single crystalline materials are ferroelectric at room temperature, I discuss the implications of these experimental observations and reconcile them with the centrosymmetric space groups assigned after X-ray crystallographic refinements. I conclude in the final two Chapters by recording my endeavors to control the assembly of metal-organic frameworks (MOFs) with noncovalent bonding interactions between [2]catenane-bearing struts. First of all, I describe the formation of syndiotactic pi-stacked 2D MOF layers before highlighting a two-component MOF that assembles with a magic number ratio of components that is independent of the molar proportions present in the crystallization medium.

  20. Formation process,microstructure and mechanical property of transient liquid phase bonded aluminium-based metal matrix composite joint

    Institute of Scientific and Technical Information of China (English)

    孙大谦; 刘卫红; 贾树盛; 邱小明

    2004-01-01

    The formation process, microstructure and mechanical properties of transient liquid phase (TLP) bonded aluminium-based metal matrix composite (MMC) joint with copper interlayer were investigated. The formation process of the TLP joint comprises a number of stages: plastic deformation and solid diffusion (stage 1), dissolution of interlayer and base metal (stage 2), isothermal solidification (stage 3) and homogenization (stage 4). The microstructure of the joint depends on the joint formation process (distinct stages). The plastic deformation and solid diffusion in stage 1 favoure the intimate contact at interfaces and liquid layer formation. The microstructure of joint consists of aluminium solid solution, alumina particle, Al2Cu and MgAl2O4 compounds in stage 2. The most pronounced feature of joint microstructure in stage 3 is the alumina particle segregation in the center of the joint. The increase of joint shear strength with increasing bonding temperature is mainly attributed to improving the fluidity and wettability of liquid phase and decreasing the amount of Al2Cu brittle phase in the joint. The principal reason of higher bonding temperature (>600 ℃) resulting in lowering obviously the joint shear strength is the widening of alumina particle segregation region that acts as a preferential site for failure. The increase of joint shear strength with increasing holding time is mainly associated with decreasing the amount of Al2 Cu brittle phase and promoting homogenization of joint.

  1. Decomposition and reduction of NO on transition metal surfaces: bond order conservation Morse potential analysis

    Science.gov (United States)

    Shustorovich, Evgeny; Bell, Alexis T.

    1993-05-01

    Periodic trends in the decomposition of NO and its reduction to N 2 and NH 3 by CO and H 2 on transition metal surfaces have been analyzed theoretically using the bond order conservation Morse potential (BOCMP) method. The analysis is based on calculations of the energetics, the reaction enthalpies ΔH and activation barriers ΔH ∗, of elementary steps thought to comprise the mechanisms of the NO transformations. As the periodic series, the close-packed surfaces Pt(111), Rh(111), Ru(001), and Re(001) were chosen. The calculated heats of chemisorption Q of NH 3, NH 2, NH, NO, H 2O and OH are in good agreement with experiment. The activation barriers for dissociation of NO from a chemisorbed state, ΔE NOs∗ were found to decrease in the order Pt > Rh > Ru > Re. For reasonable values of QN and QO, in the zero-coverage extreme these activation barriers were calculated to be much smaller than the relevant heats of chemisorption QNO, so that dissociation of No upon heating is projected for all the surfaces studied with the possible exception of Pt(111). The presence of adsorbed N S and O S atoms may dramatically increase the values of ΔE NOS∗, for example, from 7-9 to 24-27 kcal/mol for Rh(100) and Rh(100)c(2 × 2)O,N, respectively. This sensitiv the values of ΔE NOs∗ to NO S coverage may explain the diversity of experimental results obtained for different coverages (exposu and temperatures even for the same single crystal face. The anisotropy of the values of QX(X = NO, N, O) for different surfaces and possible reconstructions of these surfaces also contribute to the balance between dissociation and desorption of NO. Of the two channels for recombinative desorption of N 2, 2N S→ N 2,g and N S + NO S→ N 2,g + O S, the latter has the smaller activati barrier. Because the N 2 formation barriers rapidly increase in the order Pt ˜ Rh ≪ Ru ≪ Re, Rh or Rh-Pt surfaces are projected to be the most efficient catalysts for NO reduction by CO (to N 2 and CO 2

  2. Synthesis of metal-hydrazone complexes and vapochromic behavior of their hydrogen-bonded proton-transfer assemblies.

    Science.gov (United States)

    Kobayashi, Atsushi; Dosen, Masa-aki; Chang, Mee; Nakajima, Kiyohiko; Noro, Shin-ichiro; Kato, Masako

    2010-11-03

    We synthesized and investigated a new series of metal-hydrazone complexes, including deprotonated [MX(mtbhp)] and protonated forms [MX(Hmtbhp)](ClO(4)) (M = Pd(2+), Pt(2+); X = Cl(-), Br(-); Hmtbhp = 2-(2-(2-(methylthio)benzylidene)hydrazinyl)pyridine) and hydrogen-bonded proton-transfer (HBPT) assemblies containing [PdBr(mtbhp)] and bromanilic acid (H(2)BA). The mtbhp hydrazone ligand acts as a tridentate SNN ligand and provides a high proton affinity. UV-vis spectroscopy revealed that these metal-hydrazone complexes follow a reversible protonation-deprotonation reaction ([MX(mtbhp)] + H(+) ⇋ [MX(Hmtbhp)](+)), resulting in a remarkable color change from red to yellow. Reactions between proton acceptor [PdBr(mtbhp)] (A) and proton donor H(2)BA (D) afforded four types of HBPT assemblies with different D/A ratios: for D/A = 1:1, {[PdBr(Hmtbhp)](HBA)·Acetone} and {[PdBr(Hmtbhp)](HBA)·2(1,4-dioxane)}; for D/A = 1:2, [PdBr(Hmtbhp)](2)(BA); and for D/A = 3:2, {[PdBr(Hmtbhp)](2)(HBA)(2)(H(2)BA)·2Acetonitrile}. The proton donor gave at least one proton to the acceptor to form the hydrogen bonded A···D pair of [PdBr(Hmtbhp)](+)···HBA(-). The strength of the hydrogen bond in the pair depends on the kind of molecule bound to the free monoanionic bromanilate OH group. Low-temperature IR spectra (T < 150 K) showed that the hydrogen bond distance between [PdBr(Hmtbhp)](+) and bromanilate was short enough (ca. 2.58 Å) to induce proton migration in the [PdBr(Hmtbhp)](2)(BA) assembly in the solid state. The hydrogen bonds formed not only between [PdBr(Hmtbhp)](+) and HBA(-) but also between HBA(-) and neutral H(2)BA molecules in the {[PdBr(Hmtbhp)](2)(HBA)(2)(H(2)BA)·2Acetonitrile} assembly. The H(2)BA-based flexible hydrogen bond network and strong acidic host structure result in an interesting vapor adsorption ability and vapochromic behavior in this assembly because the vapor-induced rearrangement of the hydrogen bond network, accompanied by changes in

  3. Investigation of Interface Bonding Mechanism of an Explosively Welded Tri-Metal Titanium/Aluminum/Magnesium Plate by Nanoindentation

    Science.gov (United States)

    Zhang, T. T.; Wang, W. X.; Zhou, J.; Cao, X. Q.; Yan, Z. F.; Wei, Y.; Zhang, W.

    2017-08-01

    A tri-metal titanium/aluminum/magnesium (Ti/Al/Mg) cladding plate, with an aluminum alloy interlayer plate, was fabricated for the first time by explosive welding. Nanoindentation tests and associated microstructure analysis were conducted to investigate the interface bonding mechanisms of the Ti/Al/Mg cladding plate. A periodic wavy bonding interface (with an amplitude of approximately 30 μm and a wavelength of approximately 160 μm) without a molten zone was formed between the Ti and Al plates. The bonding interface between the Al and the Mg demonstrated a similar wavy shape, but the wave at this location was much larger with an amplitude of approximately 390 μm and a wavelength of approximately 1580 μm, and some localized melted zones also existed at this location. The formation of the wavy interface was found to result from a severe deformation at the interface, which was caused by the strong impact or collision. The nanoindentation tests showed that the material hardness decreased with increasing distance from the bonding interface. Material hardness at a location was found to be correlated with the degree of plastic deformation at that site. A larger plastic deformation was correlated with an increase in hardness.

  4. Double hydrogen bond mediating self-assembly structure of cyanides on metal surface

    Science.gov (United States)

    Wang, Zhongping; Xiang, Feifei; Lu, Yan; Wei, Sheng; Li, Chao; Liu, Xiaoqing; Liu, Lacheng; Wang, Li

    2016-10-01

    Cyanides with different numbers of -C≡N, 1,2,4,5-Tetracyanobenzene (TCNB) and 2,3-Dicyanonaphthalene (2,3-DCN) deposited on Ag(111) and Ag(110) surfaces, have been investigated by room temperature scanning tunneling microscopy (RTSTM), respectively. High resolution STM images show double hydrogen bond is the main driving force to form variety of self-assembly structures, indicating the double hydrogen bond affects the electron distribution of cyanides and leads to a more stable structure with lower energy. In addition, the difference between Ag(111) and Ag(110) surfaces in their lattice structure induces a bigger assembly structural change of 2,3-DCN than that of 1,2,4,5-TCNB, which confirms the fact that the opposite double hydrogen bond formation formed by 1,2,4,5-TCNB is more stable than the neighboring double hydrogen bond formation formed by molecule 2,3-DCN.

  5. Towards bond selective chemistry from first principles: methane on metal surfaces.

    Science.gov (United States)

    Shen, X J; Lozano, A; Dong, W; Busnengo, H F; Yan, X H

    2014-01-31

    Controlling bond-selective chemical reactivity is of great importance and has a broad range of applications. Here, we present a molecular dynamics study of bond selective reactivity of methane and its deuterated isotopologues (i.e., CH(4-x)D(x), x=0,1,2,3,4) on Ni(111) and Pt(111) from first principles calculations. Our simulations allow for reproducing the full C-H bond selectivity recently achieved experimentally via mode-specific vibrational excitation and explain its origin. Moreover, we also predict the hitherto unexplored influence of the molecular translational energy on such a selectivity as well as the conditions under which the full selectivity can be realized for the a priori less active C-D bond.

  6. An Experimental Investigation of Silicone-to-Metal Bond Strength in Composite Space Docking System Seals

    Science.gov (United States)

    Gaier, James R.; Siamidis, John; Larkin, Elizabeth M. G.

    2010-01-01

    The National Aeronautics and Space Administration (NASA) is currently developing a new universal docking mechanism for future space exploration missions called the Low Impact Docking System (LIDS). A candidate LIDS main interface seal design is a composite assembly of silicone elastomer seals vacuum molded into grooves in an electroless nickel plated aluminum retainer. The strength of the silicone-tometal bond is a critical consideration for the new system, especially due to the presence of small areas of disbond created during the molding process. In the work presented herein, seal-to-retainer bonds of subscale seal specimens with different sizes of intentional disbond were destructively tensile tested. Nominal specimens without intentional disbonds were also tested. Tension was applied either uniformly on the entire seal circumference or locally in one short circumferential length. Bond failure due to uniform tension produced a wide scatter of observable failure modes and measured load-displacement behaviors. Although the preferable failure mode for the seal-to-retainer bond is cohesive failure of the elastomer material, the dominant observed failure mode under the uniform loading condition was found to be the less desirable adhesive failure of the bond in question. The uniform tension case results did not show a correlation between disbond size and bond strength. Localized tension was found to produce failure either as immediate tearing of the elastomer material outside the bond region or as complete peel-out of the seal in one piece. The obtained results represent a valuable benchmark for comparison in the future between adhesion loads under various separation conditions and composite seal bond strength.

  7. Accurate structure and dynamics of the metal-site of paramagnetic metalloproteins from NMR parameters using natural bond orbitals.

    Science.gov (United States)

    Hansen, D Flemming; Westler, William M; Kunze, Micha B A; Markley, John L; Weinhold, Frank; Led, Jens J

    2012-03-14

    A natural bond orbital (NBO) analysis of unpaired electron spin density in metalloproteins is presented, which allows a fast and robust calculation of paramagnetic NMR parameters. Approximately 90% of the unpaired electron spin density occupies metal-ligand NBOs, allowing the majority of the density to be modeled by only a few NBOs that reflect the chemical bonding environment. We show that the paramagnetic relaxation rate of protons can be calculated accurately using only the metal-ligand NBOs and that these rates are in good agreement with corresponding rates measured experimentally. This holds, in particular, for protons of ligand residues where the point-dipole approximation breaks down. To describe the paramagnetic relaxation of heavy nuclei, also the electron spin density in the local orbitals must be taken into account. Geometric distance restraints for (15)N can be derived from the paramagnetic relaxation enhancement and the Fermi contact shift when local NBOs are included in the analysis. Thus, the NBO approach allows us to include experimental paramagnetic NMR parameters of (15)N nuclei as restraints in a structure optimization protocol. We performed a molecular dynamics simulation and structure determination of oxidized rubredoxin using the experimentally obtained paramagnetic NMR parameters of (15)N. The corresponding structures obtained are in good agreement with the crystal structure of rubredoxin. Thus, the NBO approach allows an accurate description of the geometric structure and the dynamics of metalloproteins, when NMR parameters are available of nuclei in the immediate vicinity of the metal-site.

  8. Carbon-Carbon Bond Formation in a Weak Ligand Field: Leveraging Open Shell First Row Transition Metal Catalysts.

    Science.gov (United States)

    Chirik, Paul James

    2017-01-12

    Unique features of Earth abundant transition metal catalysts are reviewed in the context of catalytic carbon-carbon bond forming reactions. Aryl-substituted bis(imino)pyridine iron and cobalt dihalide compounds, when activated with alkyl aluminum reagents, form highly active catalysts for the polymerization of ethylene. Open shell iron and cobalt alkyl complexes have been synthesized that serve as single component olefin polymerization catalysts. Reduced bis(imino)pyridine iron- and cobalt dinitrogen compounds have also been discovered that promote the unique [2+2] cycloaddition of unactivated terminal alkenes. Electronic structure studies support open shell intermediates, a deviation from traditional strong field organometallic compounds that promote catalytic C-C bond formation.

  9. Explicit treatment of hydrogen bonds in the universal force field: Validation and application for metal-organic frameworks, hydrates, and host-guest complexes

    Science.gov (United States)

    Coupry, Damien E.; Addicoat, Matthew A.; Heine, Thomas

    2017-10-01

    A straightforward means to include explicit hydrogen bonds within the Universal Force Field (UFF) is presented. Instead of treating hydrogen bonds as non-bonded interaction subjected to electrostatic and Lennard-Jones potentials, we introduce an explicit bond with a negligible bond order, thus maintaining the structural integrity of the H-bonded complexes and avoiding the necessity to assign arbitrary charges to the system. The explicit hydrogen bond changes the coordination number of the acceptor site and the approach is thus most suitable for systems with under-coordinated atoms, such as many metal-organic frameworks; however, it also shows an excellent performance for other systems involving a hydrogen-bonded framework. In particular, it is an excellent means for creating starting structures for molecular dynamics and for investigations employing more sophisticated methods. The approach is validated for the hydrogen bonded complexes in the S22 dataset and then employed for a set of metal-organic frameworks from the Computation-Ready Experimental database and several hydrogen bonded crystals including water ice and clathrates. We show that the direct inclusion of hydrogen bonds reduces the maximum error in predicted cell parameters from 66% to only 14%, and the mean unsigned error is similarly reduced from 14% to only 4%. We posit that with the inclusion of hydrogen bonding, the solvent-mediated breathing of frameworks such as MIL-53 is now accessible to rapid UFF calculations, which will further the aim of rapid computational scanning of metal-organic frameworks while providing better starting points for electronic structure calculations.

  10. Chemical bonding in metal sandwich molecules M nR 2 with R = pyrene C 16H 10 and tetracene C 18H 12

    Science.gov (United States)

    Philpott, Michael R.; Kawazoe, Yoshiyuki

    2007-08-01

    The structures and properties of neutral molecular complexes of palladium transition metal atoms sandwiched between pyrene C 16H 10 and tetracene C 18H 12 molecules have been studied using plane wave based density functional theory. Changes in symmetry and variations in the number of metal atom ( n = 4, 8 for pyrene and n = 4-9 for tetracene) were considered. The metal atoms prefer edge sites with low coordination to ring carbon atoms over "interior" sites with the high coordination as found in bis(benzene) palladium. This appears as a general motif for small polyacene molecules. All compounds examined had stable singlet ( S = 0) ground states relative to separate hydrocarbon and metal cluster, and a lowest triplet state ( S = 1) with spin on the metal atoms. When restricted to D2 h symmetry the sandwich Pd 4(C 16H 10) 2 with pyrene had palladium atoms that were isolated from each other in η 2- and η 3-coordinated sites. The valence electron density was provided mainly by overlap of metal d xy- and d yz-functions with carbon p y ( y-axis ⊥ sandwich plane). The total charge density isometric surfaces showed that η 3-coordination involved higher charge density than η 2-coordination, and that both were weaker than C-C bond charge by an order of magnitude. In the pyrene n = 8 complex, weak metal-metal bonding was apparent around the molecular perimeter together with some metal bonding to the lone interior Pd atom. In sandwiches with tetracene the metal atoms had η 2- and η 3-coordination with ring edge carbon atoms. There were no metal atoms on interior sites. The n = 5 compound with a lopsided Pd distribution had a bonding pattern consistent with experimental work of Murahashi et al. [T. Murahashi, M. Fujimoto, M. Oka, Y. Hashimoto, T. Uemura, Y. Tatsumi, Y. Nakao, A. Ikeda, S. Sakaki, H. Kurosawa, Science 313 (2006) 1104]. Based on geometry (separation ⩽275 pm), total charge density and partial charge density components, we found evidence for metal-metal

  11. Metal-ligand cooperation by aromatization-dearomatization: a new paradigm in bond activation and "green" catalysis.

    Science.gov (United States)

    Gunanathan, Chidambaram; Milstein, David

    2011-08-16

    In view of global concerns regarding the environment and sustainable energy resources, there is a strong need for the discovery of new, green catalytic reactions. For this purpose, fresh approaches to catalytic design are desirable. In recent years, complexes based on "cooperating" ligands have exhibited remarkable catalytic activity. These ligands cooperate with the metal center by undergoing reversible structural changes in the processes of substrate activation and product formation. We have discovered a new mode of metal-ligand cooperation, involving aromatization-dearomatization of ligands. Pincer-type ligands based on pyridine or acridine exhibit such cooperation, leading to unusual bond activation processes and to novel, environmentally benign catalysis. Bond activation takes place with no formal change in the metal oxidation state, and so far the activation of H-H, C-H (sp(2) and sp(3)), O-H, and N-H bonds has been demonstrated. Using this approach, we have demonstrated a unique water splitting process, which involves consecutive thermal liberation of H(2) and light-induced liberation of O(2), using no sacrificial reagents, promoted by a pyridine-based pincer ruthenium complex. An acridine pincer complex displays unique "long-range" metal-ligand cooperation in the activation of H(2) and in reaction with ammonia. In this Account, we begin by providing an overview of the metal-ligand cooperation based on aromatization-dearomatization processes. We then describe a range of novel catalytic reactions that we developed guided by these new modes of metal-ligand cooperation. These reactions include the following: (1) acceptorless dehydrogenation of secondary alcohols to ketones, (2) acceptorless dehydrogenative coupling of alcohols to esters, (3) acylation of secondary alcohols by esters with dihydrogen liberation, (4) direct coupling of alcohols and amines to form amides and polyamides with liberation of dihydrogen, (5) coupling of esters and amines to form amides

  12. DFT modeling and spectroscopic study of metal-ligand bonding in La(III) complex of coumarin-3-carboxylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Mihaylov, Tz. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Trendafilova, N. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)], E-mail: ntrend@svr.igic.bas.bg; Kostova, I. [Department of Chemistry, Faculty of Pharmacy, Medical University, Sofia 1000 (Bulgaria); Georgieva, I. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Bauer, G. [Institute of Chemical Technologies and Analytics, Technical University of Vienna, Vienna A-1060 (Austria)

    2006-09-11

    The binding mode of coumarin-3-carboxylic acid (HCCA) to La(III) is elucidated at experimental and theoretical level. The complexation ability of the deprotonated ligand (CCA{sup -}) to La(III) is studied using elemental analysis, DTA and TGA data as well as FTIR, {sup 1}H NMR and {sup 13}C NMR spectra. The experimental data suggest the complex formula La(CCA){sub 2}(NO{sub 3})(H{sub 2}O){sub 2}. B3LYP, BHLYP, B3P86, B3PW91, PW91P86 and MPW1PW91 functionals are tested for geometry and frequency calculations of the neutral ligand and all of them show bond length deviations bellow 1%. B3LYP/6-31G(d) level combined with large quasi-relativistic effective core potential for lanthanum is selected to describe the molecular, electronic and vibrational structures as well as the conformational behavior of HCCA, CCA{sup -} and La-CCA complex. The metal-ligand binding mode is predicted through molecular modeling and energy estimation of different La-CCA structures. The calculated atomic charges and the bonding orbital polarizations point to strong ionic metal-ligand bonding in La-CCA complex and insignificant donor acceptor interaction. Detailed vibrational analysis of HCCA, CCA{sup -} and La(CCA){sub 2}(NO{sub 3})(H{sub 2}O){sub 2} systems based on both calculated and experimental frequencies confirms the suggested metal-ligand binding mode.

  13. Shear bond strength of metal brackets to feldspathic porcelain treated by Nd:YAG laser and hydrofluoric acid.

    Science.gov (United States)

    Hosseini, Mohammad Hashem; Sobouti, Farhad; Etemadi, Ardavan; Chiniforush, Nasim; Shariati, Mahsa

    2015-02-01

    Adult orthodontic treatment requires bonding orthodontic attachment to dental restorations. Ceramics are commonly used as esthetic restorative materials for the crowns and bridges. The present study evaluated the shear bond strength of metal orthodontic brackets to the feldspathic porcelain surfaces following conditioning by different powers of neodymium-doped yttrium aluminum garnet (Nd:YAG) laser and hydrofluoric acid as a conventional method. Seventy-two glazed porcelain samples were prepared and randomly attributed to six equal groups of 12. In the conventional hydrofluoric (HF) group, the specimens were etched by 9.6% hydrofluoric acid for 4 min. In laser groups, samples were conditioned by 0.75-, 1-, 1.25-, 1.5-, and 2-W Nd:YAG laser for 10 s. Metal brackets were bonded to porcelain samples and after being stored in distilled water for 24 h, they were subjected to thermocycling for 500 cycles. The debonding was carried out by a Zwick testing machine. The data were statistically analyzed by ANOVA and Tamhane multiple comparisons tests. The mean ± SD of the shear bond strength in the laser group 0.75, 1, 1.25, 1.5, and 2 W and HF group was 2.2 ± 0.9, 4.2 ± 1.1, 4.9 ± 2.4, 7 ± 1.7, 9.6 ± 2.7, and 9.4 ± 2.5, respectively. Together with the increased power of laser, the mean shear bond strength was increased continuously and no significant differences were found between the HF group and the laser groups with power of 1.5 or 2 W. Also, there was no significant difference between all test groups in ARI scores. There was no significant difference between bond strength of laser groups with power of 1.5 and 2 W and HF-etched group. So, Nd:YAG laser with appropriate parameters can be used as an alternative method for porcelain etching.

  14. Ultrastructural localisation of intramuscular expression of BDNF mRNA by silver-gold intensified non-radioactive in situ hybridisation

    NARCIS (Netherlands)

    Liem, RSB; Brouwer, N; Copray, JCVM

    2001-01-01

    A non-radioactive in situ hybridisation method is described for the detection of low intramuscular levels of brain-derived neurotrophic factor (BDNF) mRNA at the electron microscope level. Application of high-grade silver-gold intensification of the diaminobenzidine end product of in situ hybridisat

  15. Onset of Bonding Plasmon Hybridization Preceded by Gap Modes in Dielectric Splitting of Metal Disks

    DEFF Research Database (Denmark)

    Frederiksen, Maj; Bochenkov, Vladimir; Ogaki, Ryosuke;

    2013-01-01

    Dielectric splitting of nanoscale disks was studied experimentally and via finite-difference time-domain (FDTD) simulations through systematic introduction of multiple ultrathin dielectric layers. Tunable, hybridized dark bonding modes were seen with first-order gap modes preceding the appearance...... of bonding dipole−dipole disk modes. The observed bright dipolar mode did not show the energy shift expected from plasmon hybridization but activated dark higher order gap modes. Introducing lateral asymmetry was shown to remodel the field distribution resulting in 3D asymmetry that reoriented the dipole...

  16. Metal ion hydrocarbon bidentate bonding in alkyl acetates, methyl alkanoates, alcohols and 1-alkenes: a comparative study.

    Science.gov (United States)

    Burgers, Peter C; Holmes, John L; Terlouwc, Johan K

    2016-01-01

    The relative affinity of the monovalent metal ions Li(+), Na(+), Cu(+) and Ag(+) towards a series of aliphatic alkyl acetates and some selected 1-alkenes (P) was examined using the kinetic method. A detailed analysis of the dissociation characteristics of a series of mixed metal-bound dimer ions of the type P1-M(+)-P2 and the evaluated proton affinities (PAs) of the monomers shows that the affinity of the cation towards long-chain alkyl acetates and alkenes (having a chain length ≤ C4) is markedly enhanced. In line with recent studies of nitriles, alcohols and methyl alkanoates, this is attributed to a bidentate interaction of the metal ion with the functional group or double bond and the aliphatic chain. In particular, the longer chain alkyl acetates, methyl alkanoates and alcohols show a remarkably similar behaviour with respect to silver ion hydrocarbon bonding. The Ag(+) adducts of the alkyl acetates dissociate by loss of CH3COOH. This reaction becomes more pronounced at longer chain lengths, which points to metal ion bidentate formation in [Ag(+)···1-alkene] product ions having a long hydrocarbon chain. In the same vein, the heterodimers [1- hexene···Ag(+)···1-heptene] and [1- heptene···Ag(+)···1-octene] dissociate primarily into [Ag(+)···1-heptene] and [Ag(+)···1-octene] ions, respectively. Hydrocarbon bidentate formation in [Ag(+)···1-octene] also reveals itself by the reluctance of this ion to react with water in an ion trap, as opposed to [Ag(+)···1-hexene] which readily undergoes hydration.

  17. Microstructure and properies of hot roll bonding layer of dissimilar metals. Part 2. Bonding interface microstrcuture of Zr/stainless steel by hot roll bonding and its controlling; Ishu kinzoku no atsuen setsugo kaimen soshiki to shotokusei ni kansuru kenkyu. 2. Jirukoniumu to sutenresu ko no netsukan atsuen kaimen to sono seigyo

    Energy Technology Data Exchange (ETDEWEB)

    Yasuyama, M.; Ogawa, K.; Taka, T.; Nasuji, K. [Sumitomo Metal Industries Ltd., Osaka (Japan); Nakao, Y.; Nishimoto, K. [Osaka Univ., Osaka (Japan)

    1996-07-25

    When using melt welding for bonding of Zr and stainless teel, it is well known that Zr, Fe, Cr and Ni reacts to form intermetallic compound and high bonding strength can not be obtained. And, on diffusion bonding of joint used as transition joint, it is reported that growth of the intermetallic compound is controlled and characteristics of the bonding is improved by inserting pure tantalum foil as a diffusion prevention wall, on foreign materials bonding of Zr and stainless steel due to metal systematic investigation. In this study, rolling bonding interface using three axes tilt type special rolling mill (rotary mill) was investigated metal-systematically. As a result, it was found that on executing bonding under optimum condition using rotary rolling method, and bonding interface of the foreign materials bonding such as Zr/Ta and Ta/SUS304L, sound foreign materials bonding without hardened layer due to deposition of intermetallic compound and solid solution and with sufficient bonding strength could be obtained. 7 refs., 17 figs., 2 tabs.

  18. Interfacial and near interfacial crack growth phenomena in metal bonded alumina

    Energy Technology Data Exchange (ETDEWEB)

    Kruzic, Jamie Joseph [Univ. of California, Berkeley, CA (United States)

    2001-01-01

    Metal/ceramic interfaces can be found in many engineering applications including microelectronic packaging, multi-layered films, coatings, joints, and composite materials. In order to design reliable engineering systems that contain metal/ceramic interfaces, a comprehensive understanding of interfacial and near interfacial failure mechanisms is necessary.

  19. Interfacial and near interfacial crack growth phenomena in metal bonded alumina

    Energy Technology Data Exchange (ETDEWEB)

    Kruzic, Jamie Joseph

    2002-03-01

    Metal/ceramic interfaces can be found in many engineering applications including microelectronic packaging, multi-layered films, coatings, joints, and composite materials. In order to design reliable engineering systems that contain metal/ceramic interfaces, a comprehensive understanding of interfacial and near interfacial failure mechanisms is necessary.

  20. [Application of gypsum-bonded investment containing niobium carbide on casting of alloy for metal-ceramic restoration].

    Science.gov (United States)

    Tsuruta, S; Ban, S; Hasegawa, J; Hayashi, S; Iiyama, K; Yamamura, Y

    1990-07-01

    Experimental gypsum-bonded investments containing 0.5-5.0 wt% NbC were prepared by mechanical mixing of each powder. Setting and thermal expansion measurement, compressive strength and casting accuracy for Ni-Cr alloy for metal-ceramic restoration were investigated. Analysis of NbC during heating was carried out by X-ray diffraction, TG-DTA and SEM. NbC was oxidized to Nb2O5 with a volume change between 300-600 degrees C, as in the following equation: 2NbC + 4 1/2O2----Nb2O5 + 2CO2 The theoretical volume of 1/2Nb2O5 calculated from the lattice constants according to JCPDS file was approximately 4 times larger than that of NbC. The experimental investments of 70 wt% cristobalite and 30 wt% gypsum containing 2.0, 3.0 and 5.0 wt% NbC showed large thermal expansion of 7.0, 10.0 and 13.0% respectively. The investment containing 2.0 wt% NbC showed nearly the same casting accuracy for Ni-Cr alloys for metal-ceramic restoration as the commercial phosphate-bonded investment.

  1. Covalency in Metal-Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

    Energy Technology Data Exchange (ETDEWEB)

    Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Bradley, Joseph A; Daly, Scott R; Kozimor, Stosh A; Lukens, Wayne W; Martin, Richard L; Nordlund, Dennis; Seidler, Gerald T; Shuh, David K; Sokaras, Dimosthenis; Tyliszczak, Tolek; Wagner, Gregory L; Weng, Tsu-Chein; Yang, Ping [SLAC; (PNNL); (UWASH); (LLNL); (LBNL); (LANL)

    2013-03-12

    Advancing theories of how metal–oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal MO4x– anions have formed the basis for new M–O bonding theories. Herein, relative changes in M–O orbital mixing in MO42– (M = Cr, Mo, W) and MO4 (M = Mn, Tc, Re) are evaluated for the first time by nonresonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and time-dependent density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M–O e* (π*) mixing; for example, it more than doubles in ReO4 relative to CrO42–. Mixing in the t2* orbitals (σ* + π*) remains relatively constant within the same Group, but increases on moving from Group 6 to Group 7. These unexpected changes in orbital energy and composition for formally isoelectronic tetraoxometalates are evaluated in terms of periodic trends in d orbital energy and radial extension.

  2. Metal-metal and metal-ligand bonding at a QTAIM catastrophe: a combined experimental and theoretical charge density study on the alkylidyne cluster Fe3(μ-H)(μ-COMe)(CO)10.

    Science.gov (United States)

    Farrugia, Louis J; Senn, Hans Martin

    2010-12-30

    The charge density in the tri-iron methoxymethylidyne cluster Fe(3)(μ-H)(μ-COMe)(CO)(10) (1) has been studied experimentally at 100 K and by DFT calculations on the isolated molecule using the Quantum Theory of Atoms in Molecules (QTAIM). The COMe ligand acts as a nearly symmetric bridge toward two of the Fe atoms (Fe-C = 1.8554(4), 1.8608(4) Å) but with a much longer interaction to the third Fe atom, Fe-C = 2.6762(4) Å. Complex 1 provides a classic example where topological QTAIM catastrophes render an exact structure description ambiguous. While all experimental and theoretical studies agree in finding no direct metal-metal interaction for the doubly bridged Fe-Fe vector, the chemical bonding between the Fe(CO)(4) unit and the Fe(2)(μ-H)(μ-COMe)(CO)(6) moiety in terms of conventional QTAIM descriptors is much less clear. Bond paths implying direct Fe-Fe interactions and a weak interaction between the COMe ligand and the Fe(CO)(4) center are observed, depending on the experimental or theoretical density model examined. Theoretical studies using the Electron Localizability Indicator (ELI-D) suggest the metal-metal bonding is more significant, while the delocalization indices imply that both Fe-Fe bonding and Fe···C(alkylidyne) bonding are equally important. The source functions at various interfragment reference points are similar and highly delocalized. The potential-energy surface (PES) for the migration of the alkylidyne group from a μ(2) to a semi-μ(3) coordination mode has been explored by DFT calculations on 1 and the model complexes M(3)(μ-H)(μ-CH)(CO)(10) (M = Fe, 2; Ru, 3; and Os, 4). These calculations confirm a semi-μ(3) bridging mode for the alkylidyne ligand as the minimum-energy geometry for compounds 2-4 and demonstrate that, for 1, both Fe-Fe and Fe···C(alkylidyne) interactions are important in the cluster bonding. The PES between μ(2) and semi-μ(3) alkylidyne coordination for 1 is extremely soft, and the interconversion between

  3. Direct observation of structurally encoded metal discrimination and ether bond formation in a heterodinuclear metalloprotein.

    Science.gov (United States)

    Griese, Julia J; Roos, Katarina; Cox, Nicholas; Shafaat, Hannah S; Branca, Rui M M; Lehtiö, Janne; Gräslund, Astrid; Lubitz, Wolfgang; Siegbahn, Per E M; Högbom, Martin

    2013-10-22

    Although metallocofactors are ubiquitous in enzyme catalysis, how metal binding specificity arises remains poorly understood, especially in the case of metals with similar primary ligand preferences such as manganese and iron. The biochemical selection of manganese over iron presents a particularly intricate problem because manganese is generally present in cells at a lower concentration than iron, while also having a lower predicted complex stability according to the Irving-Williams series (Mn(II) Zn(II)). Here we show that a heterodinuclear Mn/Fe cofactor with the same primary protein ligands in both metal sites self-assembles from Mn(II) and Fe(II) in vitro, thus diverging from the Irving-Williams series without requiring auxiliary factors such as metallochaperones. Crystallographic, spectroscopic, and computational data demonstrate that one of the two metal sites preferentially binds Fe(II) over Mn(II) as expected, whereas the other site is nonspecific, binding equal amounts of both metals in the absence of oxygen. Oxygen exposure results in further accumulation of the Mn/Fe cofactor, indicating that cofactor assembly is at least a two-step process governed by both the intrinsic metal specificity of the protein scaffold and additional effects exerted during oxygen binding or activation. We further show that the mixed-metal cofactor catalyzes a two-electron oxidation of the protein scaffold, yielding a tyrosine-valine ether cross-link. Theoretical modeling of the reaction by density functional theory suggests a multistep mechanism including a valyl radical intermediate.

  4. Weakly coordinating anions: crystallographic and NQR studies of halogen-metal bonding in silver, thallium, sodium, and potassium halomethanesulfonates.

    Science.gov (United States)

    Wulfsberg, Gary; Parks, Katherine D; Rutherford, Richard; Jackson, Debra Jones; Jones, Frank E; Derrick, Dana; Ilsley, William; Strauss, Steven H; Miller, Susie M; Anderson, Oren P; Babushkina, T A; Gushchin, S I; Kravchenko, E A; Morgunov, V G

    2002-04-22

    35Cl, (79,81)Br, and (127)I NQR (nuclear quadrupole resonance) spectroscopy in conjunction with X-ray crystallography is potentially one of the best ways of characterizing secondary bonding of metal cations such as Ag(+) to halogen donor atoms on the surfaces of very weakly coordinating anions. We have determined the X-ray crystal structure of Ag(O(3)SCH(2)Cl) (a = 13.241(3) A; b = 7.544(2) A; c = 4.925(2) A; orthorhombic; space group Pnma; Z = 4) and compared it with the known structure of Ag(O(3)SCH(2)Br) (Charbonnier, F.; Faure, R.; Loiseleur, H. Acta Crystallogr., Sect. B 1978, 34, 3598-3601). The halogen atom in each is apical (three-coordinate), being weakly coordinated to two silver ions. (127)I NQR studies on Ag(O(3)SCH(2)I) show the expected NQR consequences of three-coordination of iodine: substantially reduced NQR frequencies nu(1) and nu(2) and a fairly small NQR asymmetry parameter eta. The reduction of the halogen NQR frequency of the coordinating halogen atom in Ag(O(3)SCH(2)X) becomes more substantial in the series X = Cl < Br < I, indicating that the coordination to Ag(+) strengthens in this series, as expected from hard-soft acid-base principles. The numbers of electrons donated by the organic iodine atom to Ag(+) have been estimated; these indicate that the bonding to the cation is weak but not insignificant. We have not found any evidence for the bonding of these organohalogen atoms to another soft-acid metal ion, thallium. A scheme for recycling of thallium halide wastes is included.

  5. Development of a Low-Cost Process for Manufacturing of Ti-Metal Matrix Composite by Roll-Diffusion Bonding

    Science.gov (United States)

    Testani, C.; Ferraro, F.

    2010-06-01

    Composite materials with titanium-alloy matrix are currently the class of material with the highest specific resistance at temperatures up to 800 °C. The main hurdle to their application is their final cost. Even if it is clear that the costs of constituent materials are decreasing due to volume production effects, the production processing costs remain high due to the batch production approach. Centro Sviluppo Materiali’s (CSM) efforts have focused on the manufacturing process in order to obtain an innovative solution to reduce the manufacturing costs with respect to the hot isostatic pressing (HIP) process that represents the standard production process for this class of materials. The new approach can allow a cost reduction of about 40%; this result was obtained by developing an experimental “diffusion bonding” plant for co-rolling at high temperature in a superplastic rolling regime, sheets of titanium alloy and monofilament silicon carbide fabrics. The experimental pilot plant was proposed for patent with RM2006A000261 in May 2006. This paper describes the manufacturing phases and process results. Moreover, has been shown that the diffusion in the solid state was obtained in a process window that was at least 100 times faster than that of HIP. High-temperature tensile tests were carried out on specimens machined from metallic matrix composite materials produced with the roll-diffusion bonding (RDB) process. The samples produced were also submitted to electrochemical dissolution tests of the metallic matrix in order to verify the geometric integrity of the fibers inside the matrix after the bonding phase. The results achieved as well as the process knowledge acquired with the CSM pilot plant are the base for further development of industrial application of the titanium roll-diffusion bonding.

  6. Development of rapid, sensitive and non-radioactive tissue-blot diagnostic method for the detection of citrus greening.

    Science.gov (United States)

    Nageswara-Rao, Madhugiri; Miyata, Shin-Ichi; Ghosh, Dilip; Irey, Mike; Garnsey, Stephen M; Gowda, Siddarame

    2013-01-01

    Citrus huanglongbing (HLB or citrus greening) is one of the most devastating diseases of citrus worldwide. The disease is caused by Gram-negative, phloem-limited α-proteobacterium, 'Candidatus Liberibacter asiaticus', vectored by the psyllid, Diaphorina citri Kuwayama. Citrus plants infected by the HLB bacterium may not show visible symptoms sometimes for years following infection and non-uniform distribution within the tree makes the detection of the pathogen very difficult. Efficient management of HLB disease requires rapid and sensitive detection early in the infection followed by eradication of the source of pathogen and the vector. The polymerase chain reaction (PCR) based method is most commonly employed for screening the infected/suspected HLB plants and psyllids. This is time consuming, cumbersome and not practical for screening large number of samples in the field. To overcome this, we developed a simple, sensitive, non-radioactive, tissue-blot diagnostic method for early detection and screening of HLB disease. Digoxigenin labeled molecular probes specific to 'Ca. L. asiaticus' nucleotide sequences have been developed and used for the detection of the pathogen of the HLB disease. The copy number of the target genes was also assessed using real-time PCR experiments and the optimized real-time PCR protocol allowed positive 'Ca. L. asiaticus' detection in citrus samples infected with 'Ca. L. asiaticus' bacterium.

  7. PET/CT alignment calibration with a non-radioactive phantom and the intrinsic 176Lu radiation of PET detector

    Science.gov (United States)

    Wei, Qingyang; Ma, Tianyu; Wang, Shi; Liu, Yaqiang; Gu, Yu; Dai, Tiantian

    2016-11-01

    Positron emission tomography/computed tomography (PET/CT) is an important tool for clinical studies and pre-clinical researches which provides both functional and anatomical images. To achieve high quality co-registered PET/CT images, alignment calibration of PET and CT scanner is a critical procedure. The existing methods reported use positron source phantoms imaged both by PET and CT scanner and then derive the transformation matrix from the reconstructed images of the two modalities. In this paper, a novel PET/CT alignment calibration method with a non-radioactive phantom and the intrinsic 176Lu radiation of the PET detector was developed. Firstly, a multi-tungsten-alloy-sphere phantom without positron source was designed and imaged by CT and the PET scanner using intrinsic 176Lu radiation included in LYSO. Secondly, the centroids of the spheres were derived and matched by an automatic program. Lastly, the rotation matrix and the translation vector were calculated by least-square fitting of the centroid data. The proposed method was employed in an animal PET/CT system (InliView-3000) developed in our lab. Experimental results showed that the proposed method achieves high accuracy and is feasible to replace the conventional positron source based methods.

  8. Properties and reactions of manganese methylene complexes in the gas phase. The importance of strong metal: carbene bonds for effective olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, A.E.; Beauchamp, J.L.

    1979-10-10

    In this communication the formation, properties and reactions of the gas phase carbenes MnCH/sub 2//sup +/, (CO)/sub 5/MnCH/sub 2//sup +/, and (CO)/sub 4/MnCH/sub 2//sup +/ are described. Reported results include observation of metathesis and abstraction reactions of the methylene ligand with olefins and the first experimental determination of metal-carbene bond dissociation energies. Important points are that: (a) metal-methylene bond energies are extremely strong; and (b) the Mn/sup +/-methylene bond energy is decreased substantially on addition of five carbonyls to the metal center. If the metal-carbene bond energy exceeds 100 kcal/mol, then transfer of the carbene to an olefin to give a cyclopropane or new olefin will be endothermic and thus will not compete with the metathesis reaction. In order to avoid low turnover numbers resulting from consumption of carbene intermediates, strong metal-carbene bonds are a desirable feature of practical metathesis catalysts. (DP)

  9. Microstructure and properties of hot roll bonding layer of dissimilar metals. 1. Effect of oxide layer on titanium surface on bonding strength of titanium clad steel by hot roll bonding; Ishu kinzoku no atsuen setsugo kaimen soshiki to shotokusei ni kansuru kenkyu. 1. Atsuen chitan clad ko no kaimen kyodo ni oyobosu chitan hyomen sankabutsuso no eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, K.; Komizo, Y.; Yasuyama, M. [Sumitomo Metal Industries, Ltd., Osaka (Japan); Ikezaki, H.; Murayama, J.

    1996-01-25

    The effect of surface oxide layer on the titanium before bonding on the bonding strength of titanium clad steel by hot roll bonding was investigated from a view point of microstructure of the bonding interface. The bonding test of iron and titanium by hot roll bonding at 850{degree}C was conducted under the various surface conditions of titanium plate such as as-relieved, oxidized or machined. The mechanical properties of clad steel was evaluated in terms of tensile test in the rectangular direction to the bonding interface and observation of micro structures of bonding layer. As results, the bonding strength deteriorated remarkably in the clad steel produced using the titanium having oxide layer on the surface comparing with that using the machined surface of titanium. In the clad steel produced using the titanium with surface oxide, uncontinuous intermetallic compound was observed at the interface of {beta}-Ti and Fe, while in the clad steel produced by the titanium without surface oxide, no remarkable intermetallic compound was observed. Oxide layer on the titanium surface promotes the formation of inter metallic compound of titanium and iron at the bonding interface and deterioration of bonding strength. Such oxide layer, however, was found to be not an obstacle to the accomplishment of metallurgical bonding. 6 refs., 13 figs.

  10. [Influence of different bonding agents on traction resistance of metal alloys to dentin].

    Science.gov (United States)

    Adabo, G L; da Silva Filho, F P; de Sá, D N; Rettondini, W C; dos Santos Cruz, C A

    1990-01-01

    They were casted pieces using three kinds of alloy (Ni-Cr, Ag-Sn and Cu-Al) with circular and smooth surface. They were cemented to human teeth, on occlusal surface, grounded at dentin level, through three different materials kind (zinc polycarboxylate cement, glassionomer cement and composite). After 24 hours storing, the samples were subjected to the tensile test. The results showed that the samples cemented with composite and the casts made with Ag-Sn alloy had higher bond strength.

  11. Visualization and Measurement of the Deflagration of JA2 Bonded to Various Metal Foils

    Science.gov (United States)

    2016-01-01

    nitrate ester -based propellants embedded with thermally conductive components. JA2 propellant was employed for the experiments. Strands were bonded...yielded measured values for 1) the JA2 stock’s normal, linear-burning rate, 2) test- article burning rates relative to an axis parallel to their side...foil-bounded sections was slightly less than that of foil-less sections. Because the test articles had a relatively simple geometry, the results

  12. A Discovery of Strong Metal-Support Bonding in Nanoengineered Au-Fe3O4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy.

    Science.gov (United States)

    Han, Chang Wan; Choksi, Tej; Milligan, Cory; Majumdar, Paulami; Manto, Michael; Cui, Yanran; Sang, Xiahan; Unocic, Raymond R; Zemlyanov, Dmitry; Wang, Chao; Ribeiro, Fabio H; Greeley, Jeffrey; Ortalan, Volkan

    2017-08-09

    The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous "strong metal-support bonding" between gold nanoparticles and "nano-engineered" Fe3O4 substrates by in situ microscopy. During in situ vacuum annealing of Au-Fe3O4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe3O4 on Au nanoparticles, the gold nanoparticles transform into the gold thin films and wet the surface of nano-Fe3O4, as the surface reduction of nano-Fe3O4 proceeds. This phenomenon results from a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe3O4 and the extremely strong adhesion between Au and the reduced Fe3O4. This strong metal-support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and ultimately for the development of improved catalysts and functional nanostructures.

  13. CO2 laser conditioning of porcelain surfaces for bonding metal orthodontic brackets.

    Science.gov (United States)

    Ahrari, Farzaneh; Heravi, Farzin; Hosseini, Mohsen

    2013-07-01

    Bonding to porcelain remains to be a challenge in orthodontic treatments. The objective of this study was to evaluate the effect of CO2 laser conditioning of porcelain surfaces on shear bond strength (SBS) of orthodontic brackets. Eighty feldspathic porcelain specimens were divided into four groups of 20. In each group, half of the porcelain surfaces were deglazed, while the others remained glazed. The specimens in groups 1 to 3 were treated with a fractional CO2 laser for 10 s using 10 mJ of energy, frequency of 200 Hz and powers of 10 W (group 1), 15 W (group 2) and 20 W (group 3). In group 4, a 9.6 % hydrofluoric (HF) acid gel was used for 2 min. A silane coupling agent was applied before bracket bonding, and the SBS was measured with a universal testing machine after 24 h. Deglazing caused significant increase in SBS of laser treated porcelain surfaces (p porcelain.

  14. A computational study on structure, stability and bonding in Noble Gas bound metal Nitrates, Sulfates and Carbonates (Metal = Cu, Ag, Au)

    Indian Academy of Sciences (India)

    MANAS GHARA; SUDIP PAN; JYOTIRMOY DEB; ANAND KUMAR; UTPAL SARKAR; PRATIM KUMAR CHATTARAJ

    2016-10-01

    A density functional theory based study is performed to investigate the noble gas (Ng = Ar-Rn) binding ability of nitrates, sulfates and carbonates of noble metal (M). Their ability to bind Ng atoms is assessed through bond dissociation energy and thermochemical parameters like dissociation enthalpy and dissociation free energy change corresponding to the dissociation of Ng bound compound producing Ngand the respective salt. The zero-point energy corrected dissociation energy values per Ng atom for the dissociation process producing Ng atom(s) and the corresponding salts range within 6.0–13.1 kcal/mol in NgCuNO₃, 3.1–9.8 kcal/mol in NgAgNO₃, 6.0–13.2 kcal/mol in NgCuSO₄, 3.2–10.1 kcal/mol in NgAgSO₄, 5.1–11.7 kcal/mol in Ng₂Cu₂SO₄, 2.5–8.6 kcal/mol in Ng₂Ag₂SO₂, 8.1–19.9 kcal/mol in Ng₂Au2SO₂, 5.7–12.4 kcal/mol in NgCuCO₃, 2.3–8.0 kcal/mol in Ng₂Ag₂CO₃ and 7.3–18.2 kcal/mol in Ng₂Au₂CO₃, with a gradual increase in moving from Ar to Rn. For a given type of system, the stability of Ng bound analogues follows the order as Au > Cu > Ag. All dissociation processes are endothermic in nature whereas they become endergonic as well in most of the cases of Kr-Rn bound analogues at 298 K. Natural population analysis along with the computation of Wiberg bond indices, and electron density analyses provide insights into the nature of the Ng-M bonds. The Ng-M bonds can be represented as partial covalent bonds as supported by the different electron density descriptors.

  15. Inverted-sandwich-type and open-lantern-type dinuclear transition metal complexes: theoretical study of chemical bonds by electronic stress tensor

    CERN Document Server

    Ichikawa, Kazuhide; Kurokawa, Yusaku I; Sakaki, Shigeyoshi; Tachibana, Akitomo

    2011-01-01

    We study the electronic structure of two types of transition metal complexes, the inverted-sandwich-type and open-lantern-type, by the electronic stress tensor. In particular, the bond order b_e measured by the energy density which is defined from the electronic stress tensor is studied and compared with the conventional MO based bond order. We also examine the patterns found in the largest eigenvalue of the stress tensor and corresponding eigenvector field, the "spindle structure" and "pseudo-spindle structure". As for the inverted-sandwich-type complex, our bond order b_e calculation shows that relative strength of the metal-benzene bond among V, Cr and Mn complexes is V > Cr > Mn which is consistent with the MO based bond order. As for the open-lantern-type complex, we find that our energy density based bond order can properly describe the relative strength of Cr--Cr and Mo--Mo bonds by the surface integration of the energy density over the "Lagrange surface" which can take into account the spatial extent ...

  16. Transition-metal dopants in tetrahedrally bonded semiconductors: Symmetry and exchange interactions from tight-binding models

    Science.gov (United States)

    Kortan, Victoria Ramaker

    It has become increasingly apparent that the future of electronic devices can and will rely on the functionality provided by single or few dopant atoms. The most scalable physical system for quantum technologies, i.e. sensing, communication and computation, are spins in crystal lattices. Diamond is an excellent host crystal offering long room temperature spin coherence times and there has been exceptional experimental work done with the nitrogen vacancy center in diamond demonstrating many forms of spin control. Transition metal dopants have additional advantages, large spin-orbit interaction and internal core levels, that are not present in the nitrogen vacancy center. This work explores the implications of the internal degrees of freedom associated with the core d levels using a tight-binding model and the Koster-Slater technique. The core d levels split into two separate symmetry states in tetrahedral bonding environments and result in two levels with different wavefunction spatial extents. For 4 d semiconductors, e.g. GaAs, this is reproduced in the tight-binding model by adding a set of d orbitals on the location of the transition metal impurity and modifying the hopping parameters from impurity to its nearest neighbors. This model does not work in the case of 3d semiconductors, e.g. diamond, where there is no physical reason to drastically alter the hopping from 3 d dopant to host and the difference in wavefunction extent is not as pronounced. In the case of iron dopants in gallium arsenide the split symmetry levels in the band gap are responsible for a decrease in tunneling current when measured with a scanning tunneling microscope due to interference between two elastic tunneling paths and comparison between wavefunction measurements and tight-binding calculations provides information regarding material parameters. In the case of transition metal dopants in diamond there is less distinction between the symmetry split d levels. When considering pairs of

  17. Metal-Organic Frameworks with d-f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

    NARCIS (Netherlands)

    Ferbinteanu, M.; Cimpoesu, F.; Tanase, S.; Cheng, P.

    2015-01-01

    We present a selection of metal-organic frameworks based on d-f and f-f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the

  18. Metal-Organic Frameworks with d-f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

    NARCIS (Netherlands)

    M. Ferbinteanu; F. Cimpoesu; S. Tanase

    2015-01-01

    We present a selection of metal-organic frameworks based on d-f and f-f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the interdisciplinar

  19. A single-dose toxicity study on non-radioactive iodinated hypericin for a targeted anticancer therapy in mice

    Institute of Scientific and Technical Information of China (English)

    Jun-jie LI; Yi-cheng NI; Marlein Miranda CONA; Yuan-bo FENG; Feng CHEN; Guo-zhi ZHANG; Xue-bin FU; Uwe HIMMELREICH; Raymond OYEN; Alfons VERBRUGGEN

    2012-01-01

    Aim: Hypericin (Hyp) and its radio-derivatives have been investigated in animal models with ischemic heart diseases and malignancies for diagnostic and therapeutic purposes.Before radioiodinated Hyp (123I-Hyp or 131I-Hyp) can be considered as a clinically useful drug,vigorous evaluations on its chemotoxicity are necessary.In the present study,we examined the toxicity of a single dose of non-radioactive 127I-Hyp in normal mice for 24 h and 14 d.Methods: Studies were performed on 132 normal mice.127I-Hyp at a clinically relevant dose of 0.1 mg/kg body weight and a 100-times higher dose of 10 mg/kg was intravenously injected into 40 mice.The safety aspects of clinical manifestations,serological biochemistry,and histopathology were assessed.In another 72 mice,127I-Hyp was administered intravenously at assumed values to bracket the value of LD50.The rest 20 mice were used in the control groups.Results: At 24 h and 14 d following the injection of 127I-Hyp at either 0.1 or 10 mg/kg,all mice tolerated well without mortality or any observable treatment-related symptoms.No significant differences were found in blood biochemical parameters between the test and control groups.All organs presented normal appearances upon histopathological inspection.The value of LD50 of 127I-Hyp in mice through intravenous injection was 20.26 mg/kg,with the 95% confidence interval between 18.90 and 21.55 mg/kg.Conclusion: The current study reveals a broad safety range of 127I-Hyp,which not only supports the use of 123I-Hyp or 131I-Hyp in the necrosis targeting theragnostic strategy,but also serves as a valuable reference for exploring other possible applications for iodinated Hyp.

  20. Orthodontic Metallic Lingual Brackets: The Dark Side of the Moon of Bond Failures?

    Directory of Open Access Journals (Sweden)

    Maria Francesca Sfondrini

    2017-07-01

    Full Text Available Lingual orthodontics, among both young and adult patients, increased in popularity during last years. The purposes of the present investigation were to evaluate the shear bond strength (SBS values and Adhesive Remnant Index (ARI scores of different lingual brackets compared with a vestibular control bracket. One hundred bovine teeth were extracted and embedded in resin blocks. Four different lingual brackets (Idea, Leone; STB, Ormco; TTR, RMO; 2D, Forestadent and a vestibular control bracket (Victory, 3M were bonded to the bovine enamel surfaces and subsequently shear tested to failure utilizing a Universal Testing Machine. SBS values were measured. A microscopic evaluation was performed to obtain ARI scores. Statistical analysis was performed at a statistically significant level of p < 0.05 to determine significant differences in SBS values and ARI Scores. No statistically significant variations in SBS were reported among the different groups. Conversely, significant differences were shown in ARI scores among the various groups. Clinical relevance of the present study is that orthodontists can expect similar resistance to debonding forces from lingual appliances as with vestibular brackets.

  1. Covalent Metal-Metal-Bonded Mn4 Tetrahedron Inscribed within a Four-Coordinate Manganese Cubane Cluster, As Evidenced by Unexpected Temperature-Independent Diamagnetism.

    Science.gov (United States)

    Vaddypally, Shivaiah; Jovinelli, Daniel J; McKendry, Ian G; Zdilla, Michael J

    2017-04-03

    The electronic structures of the manganese(IV) cubane cluster Mn(μ3-N(t)Bu)4(N(t)Bu)4 (1) and its one-electron-oxidized analogue, the 3:1 Mn(IV)/Mn(V) cluster [Mn(μ3-N(t)Bu)4(N(t)Bu)4](+)[PF6](-) (1(+)[PF6]), are described. The S = 0 spin quantum number of 1 is explained by a diamagnetic electronic structure where all metal-based d electrons are paired in Mn-Mn bonding orbitals. Temperature- and power-dependent studies of the S = (1)/2 electron paramagnetic resonance signal of 1(+) are consistent with an electronic structure described as a delocalized one-electron radical.

  2. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Ji, Pengfei; McIsaac, Alexandra R.; Lin, Zekai; Abney, Carter W.; Lin, Wenbin [UC

    2016-02-01

    We have designed the first chiral diene-based metal–organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

  3. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, X. J.; Xue, X. L.; Jia, Yu [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Guo, Z. X. [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Department of Chemistry and London Centre for Nanotechnology, University College London, London WC1H (United Kingdom); Li, S. F., E-mail: sflizzu@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Zhang, Zhenyu, E-mail: zhangzy@ustc.edu.cn [ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Gao, Y. F., E-mail: ygao7@utk.edu [Department of Materials Science and Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States); Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-11-07

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt{sub N} nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt{sub N}, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D{sub 6h} symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). However, the magic number of Pt{sub N} clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt{sub 57} motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d{sup 9}6s{sup 1}) of Pt, which result in a delicate balance between the enhanced Pt–Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. These findings about Pt{sub N} clusters are also applicable to Ir{sub N} clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. The findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.

  4. Bonding characteristics of the Al2O3-metal composite coating fabricated onto carbon steel by combustion synthesis

    Institute of Scientific and Technical Information of China (English)

    Xiao-feng Xue; Ze-hua Wang; Ze-hua Zhou; Shao-qun Jiang; Jiang-bo Cheng; Chang-hao Wang; Jia Shao

    2014-01-01

    The fabrication of an alumina-metal composite coating onto a carbon steel substrate by using a self-propagating high-temperature synthesis technique was demonstrated. The effects of the type and thickness of the pre-coated layer on the binding structure and surface qual-ity of the coating were systematically investigated. The macrostructure, phase composition, and bonding interface between the coating and the substrate were investigated by scanning electronic microscopy (SEM), X-ray diffraction (XRD), and energy-dispersive X-ray spectrome-try (EDS). The diffraction patterns indicated that the coating essentially consisted ofα-Al2O3, Fe(Cr), and FeO⋅Al2O3. With an increase in the thickness of the pre-coated working layer, the coating became more smooth and compact. The transition layer played an important role in enhancing the binding between the coating and the substrate. When the pre-coated working layer was 10 mm and the pre-coated transition layer was 1 mm, a compact structure and metallurgical bonding with the substrate were obtained. Thermal shock test results indicated that the ceramic coating exhibited good thermal shock resistance when the sample was rapidly quenched from 800°C to room temperature by plung-ing into water.

  5. Chemical bonding of water to metal surfaces studied with core-level spectroscopies

    DEFF Research Database (Denmark)

    Schiros, T.; Andersson, Klas Jerker; Pettersson, L.G.M.;

    2010-01-01

    and the interaction between the water monolayer and the surface. By combining synchrotron radiation-based X-ray photoelectron spectroscopy (XPS). X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) techniques with density functional theory (DFT) computational methods we obtain element......-specific information on the partial local density of states, local atomic structure, geometrical parameters and molecular orientation, allowing general principles for water-metal interaction to be derived....

  6. Application of Ceramic Bond Coating for Reusable Melting Crucible of Metallic Fuel Slugs

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ki-Hwan; Song, Hoon; Ko, Young-Mo; Park, Jeong-Yong; Lee, Chan-Bock [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Hong, Ki-Won [Chungnam National University, Daejeon (Korea, Republic of)

    2016-10-15

    Metal fuel slugs of the driver fuel assembly have been fabricated by injection casting of the fuel alloys under a vacuum state or an inert atmosphere. Traditionally, metal fuel such as a U-Zr alloy system for SFR has been melted in slurry-coated graphite crucibles and cast in slurry-coated quartz tube molds to prevent melt/material interactions. Reactive coatings and porous coatings can be a source of melt contaminations, and fuel losses, respectively. Ceramic Y{sub 2}O{sub 3}, TiC, and TaC coating materials showed no penetration in the protective layer after a melt dipping test. However, the ceramic coating materials showed separations in the coating interface between the substrate and coating layer, or between the coating layer and fuel melt after the dipping test. All plasma-spray coated methods maintained a sound coating state after a dipping test with U-10wt.%Zr melt. A single coating Y{sub 2}O{sub 3}(150) layer and double coating layer of TaC(50)-Y{sub 2}O{sub 3}(100), showed a sound state or little penetration in the protective layer after a dipping test with U-10wt.%Zr-5wt.%RE melt. Injection casting experiments of U-10wt.%Zr and U-10wt.%Zr-5wt.%RE fuel slugs have been performed to investigate the feasibility of a reusable crucible of the metal fuel slugs. U–10wt.%Zr and U–10wt.%Zr–5wt.%RE fuel slugs have been soundly fabricated without significant interactions of the graphite crucibles. Thus, the ceramic plasma-spray coatings are thought to be promising candidate coating methods for a reusable graphite crucible to fabricate metal fuel slugs.

  7. Dependence of bonding interactions in Layered Double Hydroxides on metal cation chemistry

    Science.gov (United States)

    Shamim, Mostofa; Dana, Kausik

    2016-12-01

    The evolution of various Infrared bands of Layered Double Hydroxides (LDH) with variable Zn:Al ratio was analyzed to correlate it with the changes in octahedral metal cation chemistry, interlayer carbonate anion and hydroxyl content of LDH. The synthesized phase-pure LDHs were crystallized as hexagonal 2H polytype with a Manasseite structure. The broad and asymmetric hydroxyl stretching region (2400-4000 cm-1) can be deconvoluted into four different bands. With increase in Zn2+:Al3+ metal ratio, the peak position of stretching frequencies of Al3+sbnd OH and carbonate-bridged hydroxyl (water) decrease almost linearly. Individual band's peak position and area under the curve have been successfully correlated with the carbonate and hydroxyl content of LDH. Due to lowering of symmetry of the carbonate anion, the IR-inactive peak νCsbnd O, symm at 1064 cm-1 becomes IR active. The peak position of metal-oxygen bands and carbonate bending modes are practically unaffected by the Zn2+:Al3+ ratio but the area under the individual M-O bands shows a direct correlation.

  8. Comparison between alkalimetal and group 11 transition metal halide and hydride tetramers: molecular structure and bonding.

    Science.gov (United States)

    El-Hamdi, Majid; Solà, Miquel; Frenking, Gernot; Poater, Jordi

    2013-08-22

    A comparison between alkalimetal (M = Li, Na, K, and Rb) and group 11 transition metal (M = Cu, Ag, and Au) (MX)4 tetramers with X = H, F, Cl, Br, and I has been carried out by means of the Amsterdam Density Functional software using density functional theory at the BP86/QZ4P level of theory and including relativistic effects through the ZORA approximation. We have obtained that, in the case of alkalimetals, the cubic isomer of Td geometry is more stable than the ring structure with D4h symmetry, whereas in the case of group 11 transition metal tetramers, the isomer with D4h symmetry (or D2d symmetry) is more stable than the Td form. To better understand the results obtained we have made energy decomposition analyses of the tetramerization energies. The results show that in alkalimetal halide and hydride tetramers, the cubic geometry is the most stable because the larger Pauli repulsion energies are compensated by the attractive electrostatic and orbital interaction terms. In the case of group 11 transition metal tetramers, the D4h/D2d geometry is more stable than the Td one due to the reduction of electrostatic stabilization and the dominant effect of the Pauli repulsion.

  9. Thin film metal sensors in fusion bonded glass chips for high-pressure microfluidics

    Science.gov (United States)

    Andersson, Martin; Ek, Johan; Hedman, Ludvig; Johansson, Fredrik; Sehlstedt, Viktor; Stocklassa, Jesper; Snögren, Pär; Pettersson, Victor; Larsson, Jonas; Vizuete, Olivier; Hjort, Klas; Klintberg, Lena

    2017-01-01

    High-pressure microfluidics offers fast analyses of thermodynamic parameters for compressed process solvents. However, microfluidic platforms handling highly compressible supercritical CO2 are difficult to control, and on-chip sensing would offer added control of the devices. Therefore, there is a need to integrate sensors into highly pressure tolerant glass chips. In this paper, thin film Pt sensors were embedded in shallow etched trenches in a glass wafer that was bonded with another glass wafer having microfluidic channels. The devices having sensors integrated into the flow channels sustained pressures up to 220 bar, typical for the operation of supercritical CO2. No leakage from the devices could be found. Integrated temperature sensors were capable of measuring local decompression cooling effects and integrated calorimetric sensors measured flow velocities over the range 0.5-13.8 mm s-1. By this, a better control of high-pressure microfluidic platforms has been achieved.

  10. Standard test method for ambient temperature fatigue life of metallic bonded resistance strain gages

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2003-01-01

    1.1 This test method covers a uniform procedure for the determination of strain gage fatigue life at ambient temperature. A suggested testing equipment design is included. 1.2 This test method does not apply to force transducers or extensometers that use bonded resistance strain gages as sensing elements. 1.3 Strain gages are part of a complex system that includes structure, adhesive, gage, leadwires, instrumentation, and (often) environmental protection. As a result, many things affect the performance of strain gages, including user technique. A further complication is that strain gages, once installed, normally cannot be reinstalled in another location. Therefore, it is not possible to calibrate individual strain gages; performance characteristics are normally presented on a statistical basis. 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices ...

  11. Electron density distributions calculated for the nickel sulfides millerite, vaesite, and heazlewoodite and nickel metal: a case for the importance of ni-ni bond paths for electron transport.

    Science.gov (United States)

    Gibbs, G V; Downs, R T; Prewitt, C T; Rosso, K M; Ross, N L; Cox, D F

    2005-11-24

    Bond paths and the bond critical point properties (the electron density (rho) and the Hessian of rho at the bond critical points (bcp's)) have been calculated for the bonded interactions comprising the nickel sulfide minerals millerite, NiS, vaesite, NiS(2), and heazlewoodite, Ni(3)S(2), and Ni metal. The experimental Ni-S bond lengths decrease linearly as the magnitudes of the properties each increases in value. Bond paths exist between the Ni atoms in heazlewoodite and millerite for the Ni-Ni separations that match the shortest separation in Ni metal, an indicator that the Ni atoms are bonded. The bcp properties of the bonded interactions in Ni metal are virtually the same as those in heazlewoodite and millerite. Ni-Ni bond paths are absent in vaesite where the Ni-Ni separations are 60% greater than those in Ni metal. The bcp properties for the Ni-Ni bonded interactions scatter along protractions of the Ni-S bond length-bcp property trends, suggesting that the two bonded interactions have similar characteristics. Ni-Ni bond paths radiate throughout Ni metal and the metallic heazlewoodite structures as continuous networks whereas the Ni-Ni paths in millerite, a p,d-metal displaying ionic and covalent features, are restricted to isolated Ni(3) rings. Electron transport in Ni metal and heazlewoodite is pictured as occurring along the bond paths, which behave as networks of atomic size wires that radiate in a contiguous circuit throughout the two structures. Unlike heazlewoodite, the electron transport in millerite is pictured as involving a cooperative hopping of the d-orbital electrons from the Ni(3) rings comprising Ni(3)S(9) clusters to Ni(3) rings in adjacent clusters via the p-orbitals on the interconnecting S atoms. Vaesite, an insulator at low temperatures and a doped semiconductor at higher temperatures, lacks Ni-Ni bond paths. The net charges conferred on the Ni and S atoms are about a quarter of their nominal charges for the atoms in millerite and vaesite

  12. Improvement of Joint Strength of SiCp/Al Metal Matrix Composite in Transient Liquid Phase Bonding Using Cu/Ni/Cu Film Interlayer

    Institute of Scientific and Technical Information of China (English)

    Rongfa CHEN; Dunwen ZUO; Min WANG

    2006-01-01

    The compact oxide on the surface of SiCp/Al metal matrix composite (SiCp/Al MMC) greatly depends on the property of the joint. Inlaid sputtering target was applied to etch the oxide completely on the bonding surface of SiCp/Al MMC by plasma erosion. Cu/Ni/Cu film of 5 μm in thickness was prepared by magnetron sputtering method on the clean bonding surface in the same vacuum chamber, which was acted as an interlayer in transient liquid phase (TLP) bonding process. Compared with the same thickness of single Cu foil and Ni foil interlayer,the shear strength of 200 MPa was obtained using Cu/Ni/Cu film interlayer during TLP bonding, which was 89.7% that of base metal. In addition, homogenization of the bonding region and no particle segregation in interfacial region were found by analysis of the joint microstructure. Scanning electron microscopy (SEM) was used to observe the micrograph of the joint interface. The result shows that a homogenous microstructure of joint was achieved, which is similar with that of based metal.

  13. Continuous One-Step Synthesis of Porous M-XF6 -Based Metal-Organic and Hydrogen-Bonded Frameworks.

    Science.gov (United States)

    Guillerm, Vincent; Garzón-Tovar, Luis; Yazdi, Amirali; Imaz, Inhar; Juanhuix, Jordi; Maspoch, Daniel

    2017-05-17

    Metal-organic frameworks (MOFs) built up from connecting M-XF6 pillars through N-donor ligands are among the most attractive adsorbents and separating agents for CO2 and hydrocarbons today. The continuous, one-step spray-drying synthesis of several members of this isoreticular MOF family varying the anionic pillar (XF6 =[SiF6 ](2-) and [TiF6 ](2-) ), the N-donor organic ligand (pyrazine and 4,4'-bipyridine) and the metal ion (M=Co, Cu and Zn) is demonstrated here. This synthetic method allows them to be obtained in the form of spherical superstructures assembled from nanosized crystals. As confirmed by CO2 and N2 sorption studies, most of the M-XF6 -based MOFs synthesised through spray-drying can be considered "ready-to-use" sorbents as they do not need additional purification and time consuming solvent exchange steps to show comparable porosity and sorption properties with the bulk/single-crystal analogues. Stability tests of nanosized M-SiF6 -based MOFs confirm their low stability in most solvents, including water and DMF, highlighting the importance of protecting them once synthesised. Finally, for the first time it was shown that the spray-drying method can also be used to assemble hydrogen-bonded open networks, as evidenced by the synthesis of MPM-1-TIFSIX. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Ultra-stable Molecule-Surface Architectures at Metal Oxides: Structure, Bonding, and Electron-transfer Processes

    Energy Technology Data Exchange (ETDEWEB)

    Hamers, Robert John

    2013-12-07

    Research funded by this project focused on the development of improved strategies for functionalization of metal oxides to enhance charge-transfer processes relevant to solar energy conversion. Initial studies included Fe2O3, WO3, TiO2, SnO2, and ZnO as model oxide systems; these systems were chosen due to differences in metal oxidation state and chemical bonding types in these oxides. Later studies focused largely on SnO2 and ZnO, as these materials show particularly promising surface chemistry, have high electron mobility, and can be readily grown in both spherical nanoparticles and as elongated nanorods. New molecules were synthesized that allowed the direct chemical assembly of novel nanoparticle ?dyadic? structures in which two different oxide materials are chemically joined, leading to an interface that enhances the separation of of charge upon illumination. We demonstrated that such junctions enhance photocatalytic efficiency using model organic compounds. A separate effort focused on novel approaches to linking dye molecules to SnO2 and ZnO as a way to enhance solar conversion efficiency. A novel type of surface binding through

  15. The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs)

    Science.gov (United States)

    Hogan, Greg Anthony

    The process of molecular transport and intercalation has been widely studied for many years, resulting in the discovery of molecular frameworks that are capable of hosting guest molecules or ions. Layered and porous metal-organic frameworks (MOFs) have been found to have applications in the field of catalysis, storage, separations, and ion-exchange. More recently, molecular components with peripheral hydrogen-bonding moieties have been used to affect the synthesis of hydrogen-bonded metal-organic frameworks (HMOFs) as an alternative to MOFs, which are interconnected via coordinate-covalent bonds. While MOFs are perhaps stronger materials, HMOFs have the advantage of being easily modifiable and more flexible. Because HMOFs have not been extensively studied for their ability to host molecules, and because their ability to withstand guest loss and guest exchange is essentially unknown, here we report the synthesis and molecular transport properties of both close-packed and porous HMOFs. Layered materials can mimic the behavior of naturally occurring clays, where guest molecules are absorbed and the layer will expand to accommodate the entering guest molecule. We have created a clay mimic composed of a metal pyridine-dicarboxylates and ammonium counterions (a layered HMOF), which is suitable for studying the ability of such materials to absorb guest molecules. We can control the distance of the interlayer region, as well as the chemical nature (hydrophobic or hydrophilic) by varying the organic amine. The metal complex contains axial water ligands that are replaceable, and such ligand exchange has precedence in coordination polymer (MOF) systems, and has been termed "coordinative intercalation". Using the synthesized layered material we examined the process of intercalation, having chosen a variety of guest molecules ranging from alkyl to aryl molecules, each of which have substituents varying in size, shape and electronics. The first set of guest molecules are non

  16. Experimental study about the influence of adhesive stiffness to the bonding strengths of adhesives for ceramic/metal targets

    Institute of Scientific and Technical Information of China (English)

    W. SEIFERT; E. STRASSBURGER; S. GREFEN; S. SCHAARE

    2016-01-01

    The aim of the investigations presented here was to understand how the stiffness of the adhesive affects the failure of ceramic tiles adhered to metallic backings. The working hypothesis was that varying the adhesive stiffness could have the same effect on the ballistic performance as a variation of the adhesive thickness. Two different projectile/target combinations were utilized for ballistic tests in order to generate extremely different loading conditions. With targets consisting of 6 mm aluminum oxide ceramic and 6 mm aluminum backing, complete penetration occurred in each test with 7.62 mm tungsten carbide core AP ammunition at an impact velocity of 940 m/s. In contrast, with ceramic tiles of 20 mm thickness on 13 mm steel backing, no penetration of the ceramic occurred at the impact of a 7.62 mm ball round at 840 m/s. Four different types of adhesive (high-strength till high-flexible) were tested in both configurations. The elongation of the adhesive layer, the deformation of the metallic backing and the failure of the ceramics were observed by means of a high-speed camera during the projectile/target interaction. The results of the ballistic tests showed that a higher fracture strain caused a larger deformation of the backing compared to adhesives, which exhibit a high tensile strength and low fracture strains. The experimental results indicate that the damage behavior of the ceramic/metal composites depends on the absolute elongation of the adhesive layer. This can be controlled either by the thickness or the stiffness of the bonding layer.

  17. Sensitive non-radioactive determination of aminotransferase stereospecificity for C-4' hydrogen transfer on the coenzyme

    Energy Technology Data Exchange (ETDEWEB)

    Jomrit, Juntratip [Department of Biotechnology, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 (Thailand); Center of Excellence for Agricultural Biotechnology: (AG-BIO/PERDO-CHE), Bangkok (Thailand); Summpunn, Pijug [Department of Biotechnology, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 (Thailand); Meevootisom, Vithaya [Department of Microbiology, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 (Thailand); Center of Excellence for Agricultural Biotechnology: (AG-BIO/PERDO-CHE), Bangkok (Thailand); Wiyakrutta, Suthep, E-mail: scsvy@mahidol.ac.th [Department of Microbiology, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 (Thailand); Center of Excellence for Agricultural Biotechnology: (AG-BIO/PERDO-CHE), Bangkok (Thailand)

    2011-02-25

    Research highlights: {yields} Stereochemical mechanism of PLP enzymes is important but difficult to determine. {yields} This new method is significantly less complicated than the previous ones. {yields} This assay is as sensitive as the radioactive based method. {yields} LC-MS/MS positively identify the analyte coenzyme. {yields} The method can be used with enzyme whose apo form is unstable. -- Abstract: A sensitive non-radioactive method for determination of the stereospecificity of the C-4' hydrogen transfer on the coenzymes (pyridoxal phosphate, PLP; and pyridoxamine phosphate, PMP) of aminotransferases has been developed. Aminotransferase of unknown stereospecificity in its PLP form was incubated in {sup 2}H{sub 2}O with a substrate amino acid resulted in PMP labeled with deuterium at C-4' in the pro-S or pro-R configuration according to the stereospecificity of the aminotransferase tested. The [4'-{sup 2}H]PMP was isolated from the enzyme protein and divided into two portions. The first portion was incubated in aqueous buffer with apo-aspartate aminotransferase (a reference si-face specific enzyme), and the other was incubated with apo-branched-chain amino acid aminotransferase (a reference re-face specific enzyme) in the presence of a substrate 2-oxo acid. The {sup 2}H at C-4' is retained with the PLP if the aminotransferase in question transfers C-4' hydrogen on the opposite face of the coenzyme compared with the reference aminotransferase, but the {sup 2}H is removed if the test and reference aminotransferases catalyze hydrogen transfer on the same face. PLP formed in the final reactions was analyzed by LC-MS/MS for the presence or absence of {sup 2}H. The method was highly sensitive that for the aminotransferase with ca. 50 kDa subunit molecular weight, only 2 mg of the enzyme was sufficient for the whole test. With this method, the use of radioactive substances could be avoided without compromising the sensitivity of the assay.

  18. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

    Science.gov (United States)

    Yik, Edwin Shyn-Lo

    convergence to a single phase is expected and predictable from thermodynamics at a given temperature and sulfur chemical potential, metastability of two phases can exist. We demonstrate, through extensive characterization and kinetic evidence, such behaviors exist in Re, where structural disparities between its phases lead to kinetic hurdles that prevent interconversions between layered ReSx nanostructures and sulfur-covered Re metal clusters. Such features allowed, for the first time, direct comparisons of reaction rates at identical conditions on two disparate phases of the same transition metal identity. Rigorous assessments of kinetic and selectivity data indicated that more universal mechanistic features persist across all catalysts studied, suggesting that differences in their catalytic activity were the result of different densities of HDS sites, which appeared to correlate with their respective metal-sulfur bond energies. Kinetic responses and product distributions indicated that the consumption of thiophene proceeds by the formation of a partially-hydrogenated surface intermediate, which subsequently produces tetrahydrothiophene (THT) and butene/butane (C4) via primary routes on similar types of sites. These sites are formed from desorption of weakly-bound sulfur adatoms on sulfur-covered metal surfaces, which can occur when the heat of sulfur adsorption is sufficiently low at high sulfur coverage as a result of increased sulfur-sulfur repulsive interactions. Relative stabilities and differences in the molecularity of the respective transition states that form THT and C4 dictate product distributions. THT desulfurization to form C4 occurs via readsorption and subsequent dehydrogenation, evidenced by secondary rates that exhibited negative H2 dependences. These behaviors suggest that C-S bond activation occurs on a partially (un)saturated intermediate, analogous to behaviors observed in C-C bond scission reactions of linear and cycloalkanes on hydrogen-covered metal

  19. Chemical Bonding of Transition-Metal Co13 Clusters with Graphene.

    Science.gov (United States)

    Alonso-Lanza, Tomás; Ayuela, Andrés; Aguilera-Granja, Faustino

    2015-12-01

    We carried out density functional calculations to study the adsorption of Co13 clusters on graphene. Several free isomers were deposited at different positions with respect to the hexagonal lattice nodes, allowing us to study even the hcp 2d isomer, which was recently obtained as the most stable one. Surprisingly, the Co13 clusters attached to graphene prefer icosahedron-like structures in which the low-lying isomer is much distorted; in such structures, they are linked with more bonds than those reported in previous works. For any isomer, the most stable position binds to graphene by the Co atoms that can lose electrons. We find that the charge transfer between graphene and the clusters is small enough to conclude that the Co-graphene binding is not ionic-like but chemical. Besides, the same order of stability among the different isomers on doped graphene is kept. These findings could also be of interest for magnetic clusters on graphenic nanostructures such as ribbons and nanotubes.

  20. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

    Science.gov (United States)

    Jia, Hong-Peng; Quadrelli, Elsje Alessandra

    2014-01-21

    Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

  1. K{sub 6} carbon: A metallic carbon allotrope in sp{sup 3} bonding networks

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Chun-Yao; Wang, Xin-Quan; Wang, Jian-Tao, E-mail: wjt@aphy.iphy.ac.cn [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China)

    2014-02-07

    We identify by first-principles calculations a new cubic carbon phase in I4{sub 1}32 (O{sup 8}) symmetry, named K{sub 6} carbon, which has a six atom primitive cell comprising sp{sup 3} hybridized C{sub 3} triangle rings. The structural stability is verified by phonon mode analysis. The calculated elastic constants show that the K{sub 6} carbon is a high ductile material with a density even lower than graphite. Electronic band and density of states calculations reveal that it is a metallic carbon allotrope with a high electronic density of states of ∼0.10 states/eV per atom at the Fermi level. These results broaden our understanding of the structural and electronic properties of carbon allotropes.

  2. K6 carbon: A metallic carbon allotrope in sp3 bonding networks

    Science.gov (United States)

    Niu, Chun-Yao; Wang, Xin-Quan; Wang, Jian-Tao

    2014-02-01

    We identify by first-principles calculations a new cubic carbon phase in I4132 (O8) symmetry, named K6 carbon, which has a six atom primitive cell comprising sp3 hybridized C3 triangle rings. The structural stability is verified by phonon mode analysis. The calculated elastic constants show that the K6 carbon is a high ductile material with a density even lower than graphite. Electronic band and density of states calculations reveal that it is a metallic carbon allotrope with a high electronic density of states of ˜0.10 states/eV per atom at the Fermi level. These results broaden our understanding of the structural and electronic properties of carbon allotropes.

  3. Pressure-induced Transformations of Dense Carbonyl Sulfide to Singly Bonded Amorphous Metallic Solid

    Science.gov (United States)

    Kim, Minseob; Dias, Ranga; Ohishi, Yasuo; Matsuoka, Takehiro; Chen, Jing-Yin; Yoo, Choong-Shik

    2016-08-01

    The application of pressure, internal or external, transforms molecular solids into non-molecular extended network solids with diverse crystal structures and electronic properties. These transformations can be understood in terms of pressure-induced electron delocalization; however, the governing mechanisms are complex because of strong lattice strains, phase metastability and path dependent phase behaviors. Here, we present the pressure-induced transformations of linear OCS (R3m, Phase I) to bent OCS (Cm, Phase II) at 9 GPa an amorphous, one-dimensional (1D) polymer at 20 GPa (Phase III); and an extended 3D network above ~35 GPa (Phase IV) that metallizes at ~105 GPa. These results underscore the significance of long-range dipole interactions in dense OCS, leading to an extended molecular alloy that can be considered a chemical intermediate of its two end members, CO2 and CS2.

  4. Prediction of inhomogeneous texture in clad sheet metals by hot roll bond method

    Science.gov (United States)

    Choi, Shi-Hoon; Kwon, Jae Wook; Oh, Kyu Hwan

    1996-06-01

    A finite element analysis was applied to analyze the evolution of an inhomogeneity of rolling texture in hot rolled clad metal with Taylor-Bishop-Hill model and Renourd-Winterberger method. The shear texture has been developed in the surface layer of the aluminum and plane strain texture has been developed in the center layer. The calculated texture variations through thickness direction could simulate experimental texture using deformation gradient from FEM. The ratio of shear strain to rolling strain, x, which represents the degree of rotation about transverse direction could give the degree of development of shear texture. The larger value of x gives the larger crystal rotation about transverse direction and subsequently the development of shear texture. The calculated (111) pole figures were in good agreement with experimentally measured pole figures.

  5. Structural and spectroscopic characterization of iron(II), cobalt(II), and nickel(II) ortho-dihalophenolate complexes: insights into metal-halogen secondary bonding.

    Science.gov (United States)

    Machonkin, Timothy E; Boshart, Monica D; Schofield, Jeremy A; Rodriguez, Meghan M; Grubel, Katarzyna; Rokhsana, Dalia; Brennessel, William W; Holland, Patrick L

    2014-09-15

    Metal complexes incorporating the tris(3,5-diphenylpyrazolyl)borate ligand (Tp(Ph2)) and ortho-dihalophenolates were synthesized and characterized in order to explore metal-halogen secondary bonding in biorelevant model complexes. The complexes Tp(Ph2)ML were synthesized and structurally characterized, where M was Fe(II), Co(II), or Ni(II) and L was either 2,6-dichloro- or 2,6-dibromophenolate. All six complexes exhibited metal-halogen secondary bonds in the solid state, with distances ranging from 2.56 Å for the Tp(Ph2)Ni(2,6-dichlorophenolate) complex to 2.88 Å for the Tp(Ph2)Fe(2,6-dibromophenolate) complex. Variable temperature NMR spectra of the Tp(Ph2)Co(2,6-dichlorophenolate) and Tp(Ph2)Ni(2,6-dichlorophenolate) complexes showed that rotation of the phenolate, which requires loss of the secondary bond, has an activation barrier of ~30 and ~37 kJ/mol, respectively. Density functional theory calculations support the presence of a barrier for disruption of the metal-halogen interaction during rotation of the phenolate. On the other hand, calculations using the spectroscopically calibrated angular overlap method suggest essentially no contribution of the halogen to the ligand-field splitting. Overall, these results provide the first quantitative measure of the strength of a metal-halogen secondary bond and demonstrate that it is a weak noncovalent interaction comparable in strength to a hydrogen bond. These results provide insight into the origin of the specificity of the enzyme 2,6-dichlorohydroquinone 1,2-dioxygenase (PcpA), which is specific for ortho-dihalohydroquinone substrates and phenol inhibitors.

  6. Effects of surface treatments and storage times on the tensile bond strength of adhesive cements to noble and base metal alloys.

    Science.gov (United States)

    Burmann, Paulo Afonso; Santos, Jose Fortunato Ferreira; May, Liliana Gressler; Pereira, Joao Eduardo da Silva; Cardoso, Paulo Eduardo Capel

    2008-01-01

    This work evaluated two resin cements and a glass-ionomer cement and their bond strength to gold-palladium (Au-Pd), silver-palladium (Ag-Pd), and nickel-chromium-beryllium (Ni-Cr-Be) alloys, utilizing three surface treatments over a period of six months. Eight hundred ten pieces were cast (in a button shape flat surfaces) in one of three alloys. Each alloy group was assigned to three other groups, based on the surface treatment utilized. Specimens were fabricated by bonding similar buttons in using one of three adhesive cements. The 405 pairs were thermocycled and stored in saline solution (0.9% NaCl) at 37 degrees C. The tensile bond strengths were measured in a universal testing machine after storage times of 2, 90, or 180 days. The highest mean bond strength value was obtained with the base metal alloy (10.9 +/- 8.6 MPa). In terms of surface treatment, oxidation resulted in the highest mean bond strength (13.7 +/- 7.3 MPa), followed by sandblasting (10.3 +/- 5.5 MPa) and polishing (3.0 +/- 6.4 MPa). Panavia Ex (13.2 +/- 9.3 MPa) showed significantly higher bond strengths than the other two cements, although the storage time reduced all bond strengths significantly.

  7. Chip-package nano-structured copper and nickel interconnections with metallic and polymeric bonding interfaces

    Science.gov (United States)

    Aggarwal, Ankur

    With the semiconductor industry racing toward a historic transition, nano chips with less than 45 nm features demand I/Os in excess of 20,000 that support computing speed in terabits per second, with multi-core processors aggregately providing highest bandwidth at lowest power. On the other hand, emerging mixed signal systems are driving the need for 3D packaging with embedded active components and ultra-short interconnections. Decreasing I/O pitch together with low cost, high electrical performance and high reliability are the key technological challenges identified by the 2005 International Technology Roadmap for Semiconductors (ITRS). Being able to provide several fold increase in the chip-to-package vertical interconnect density is essential for garnering the true benefits of nanotechnology that will utilize nano-scale devices. Electrical interconnections are multi-functional materials that must also be able to withstand complex, sustained and cyclic thermo-mechanical loads. In addition, the materials must be environmentally-friendly, corrosion resistant, thermally stable over a long time, and resistant to electro-migration. A major challenge is also to develop economic processes that can be integrated into back end of the wafer foundry, i.e. with wafer level packaging. Device-to-system board interconnections are typically accomplished today with either wire bonding or solders. Both of these are incremental and run into either electrical or mechanical barriers as they are extended to higher density of interconnections. Downscaling traditional solder bump interconnect will not satisfy the thermo-mechanical reliability requirements at very fine pitches of the order of 30 microns and less. Alternate interconnection approaches such as compliant interconnects typically require lengthy connections and are therefore limited in terms of electrical properties, although expected to meet the mechanical requirements. A novel chip-package interconnection technology is

  8. Promotional effects of chemisorbed oxygen and hydroxide in the activation of C-H and O-H bonds over transition metal surfaces

    Science.gov (United States)

    Hibbitts, David; Neurock, Matthew

    2016-08-01

    Electronegative coadsorbates such as atomic oxygen (O*) and hydroxide (OH*) can act as Brønsted bases when bound to Group 11 as well as particular Group 8-10 metal surfaces and aid in the activation of X-H bonds. First-principle density functional theory calculations were carried out to systematically explore the reactivity of the C-H bonds of methane and surface methyl intermediates as well as the O-H bond of methanol directly and with the assistance of coadsorbed O* and OH* intermediates over Group 11 (Cu, Ag, and Au) and Group 8-10 transition metal (Ru, Rh, Pd, Os, Ir, and Pt) surfaces. C-H as well as O-H bond activation over the metal proceeds via a classic oxidative addition type mechanism involving the insertion of the metal center into the C-H or O-H bond. O* and OH* assist C-H and O-H activation over particular Group 11 and Group 8-10 metal surfaces via a σ-bond metathesis type mechanism involving the oxidative addition of the C-H or O-H bond to the metal along with a reductive deprotonation of the acidic C-H and O-H bond over the M-O* or M-OH* site pair. The O*- and OH*-assisted C-H activation paths are energetically preferred over the direct metal catalyzed C-H scission for all Group 11 metals (Cu, Ag, and Au) with barriers that are 0.4-1.5 eV lower than those for the unassisted routes. The barriers for O*- and OH*-assisted C-H activation of CH4 on the Group 8-10 transition metals, however, are higher than those over the bare transition metal surfaces by as much as 1.4 eV. The C-H activation of adsorbed methyl species show very similar trends to those for CH4 despite the differences in structure between the weakly bound methane and the covalently adsorbed methyl intermediates. The activation of the O-H bond of methanol is significantly promoted by O* as well as OH* intermediates over both the Group 11 metals (Cu, Ag, and Au) as well as on all Group 8-10 metals studied (Ru, Rh, Pd, Os, Ir, and Pt). The O*- and OH*-assisted CH3O-H barriers are 0.6 to 2

  9. Extremely bulky amido first row transition metal(II) halide complexes: potential precursors to low coordinate metal-metal bonded systems.

    Science.gov (United States)

    Hicks, Jamie; Jones, Cameron

    2013-04-01

    Reactions of the extremely bulky potassium amide complexes, [KL'(η(6)-toluene)] or [KL"] (L'/L" = N(Ar*)(SiR3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4; R = Me (L') or Ph (L")), with a series of first row transition metal(II) halides have yielded 10 rare examples of monodentate amido first row transition metal(II) halide complexes, all of which were crystallographically characterized. They encompass the dimeric, square-planar chromium complexes, [{CrL'(THF)(μ-Cl)}2] and [{CrL"(μ-Cl)}2], the latter of which displays intramolecular η(2)-Ph···Cr interactions; the dimeric tetrahedral complexes, [{ML'(THF)(μ-Br)}2] (M = Mn or Fe), [{ML"(THF)(μ-X)}2] (M = Mn, Fe or Co; X = Cl or Br) and [{CoL"(μ-Cl)}2] (which displays intramolecular η(2)-Ph···Co interactions); and the monomeric zinc amides, [L'ZnBr(THF)] (three-coordinate) and [L"ZnBr] (two-coordinate). Solution state magnetic moment determinations on all but one of the paramagnetic compounds show them to be high-spin systems. Throughout, comparisons are made with related bulky terphenyl transition metal(II) halide complexes, and the potential for the use of the prepared complexes as precursors to low-valent transition metal systems is discussed.

  10. Adhesive bonding of resin composite to various titanium surfaces using different metal conditioners and a surface modification system

    Directory of Open Access Journals (Sweden)

    Hercules Jorge ALMILHATTI

    2013-12-01

    Full Text Available Objective: This study evaluated the effect of three metal conditioners on the shear bond strength (SBS of a prosthetic composite material to cpTi grade I having three surface treatments. Material and Methods: One hundred sixty eight rivet-shaped specimens (8.0x2.0 mm were cast and subjected to polishing (P or sandblasting with either 50 mm (50SB or 250 mm (250SB Al2O3. The metal conditioners Metal Photo Primer (MPP, Cesead II Opaque Primer (OP, Targis Link (TL, and one surface modification system Siloc (S, were applied to the specimen surfaces, which were covered with four 1-mm thick layers of resin composite. The resin layers were exposed to curing light for 90 s separately. Seven specimens from each experimental group were stored in water at 37ºC for 24 h while the other 7 specimens were subjected to 5,000 thermal cycles consisting of water baths at 4ºC and 60ºC (n=7. All specimens were subjected to SBS test (0.5 mm/min until failure occurred, and further 28 specimens were analyzed using scanning electron microscope (SEM and X-ray energy-dispersive spectroscopy (EDS. Data were analyzed by 3-way ANOVA followed by post-hoc Tukey's test (α=0.05. Results: On 50SB surfaces, OP groups showed higher SBS means than MPP (P<0.05, while no significant difference was found among OP, S, and TL groups. On 250SB surfaces, OP and TL groups exhibited higher SBS than MPP and S (P<0.05. No significant difference in SBS was found between OP and TL groups nor between MPP and S groups. The use of conditioners on 250SB surfaces resulted in higher SBS means than the use of the same products on 50SB surfaces (P<0.05. Conclusion: Sandblasting associated with the use of metal conditioners improves SBS of resin composites to cpTi.

  11. Research Update: Mechanical properties of metal-organic frameworks – Influence of structure and chemical bonding

    Directory of Open Access Journals (Sweden)

    Wei Li

    2014-12-01

    Full Text Available Metal-organic frameworks (MOFs, a young family of functional materials, have been attracting considerable attention from the chemistry, materials science, and physics communities. In the light of their potential applications in industry and technology, the fundamental mechanical properties of MOFs, which are of critical importance for manufacturing, processing, and performance, need to be addressed and understood. It has been widely accepted that the framework topology, which describes the overall connectivity pattern of the MOF building units, is of vital importance for the mechanical properties. However, recent advances in the area of MOF mechanics reveal that chemistry plays a major role as well. From the viewpoint of materials science, a deep understanding of the influence of chemical effects on MOF mechanics is not only highly desirable for the development of novel functional materials with targeted mechanical response, but also for a better understanding of important properties such as structural flexibility and framework breathing. The present work discusses the intrinsic connection between chemical effects and the mechanical behavior of MOFs through a number of prototypical examples.

  12. Study of van der Waals bonding and interactions in metal organic framework materials.

    Science.gov (United States)

    Zuluaga, Sebastian; Canepa, Pieremanuele; Tan, Kui; Chabal, Yves J; Thonhauser, Timo

    2014-04-02

    Metal organic framework (MOF) materials have attracted a lot of attention due to their numerous applications in fields such as hydrogen storage, carbon capture and gas sequestration. In all these applications, van der Waals forces dominate the interaction between the small guest molecules and the walls of the MOFs. In this review article, we describe how a combined theoretical and experimental approach can successfully be used to study those weak interactions and elucidate the adsorption mechanisms important for various applications. On the theory side, we show that, while standard density functional theory is not capable of correctly describing van der Waals interactions, functionals especially designed to include van der Waals forces exist, yielding results in remarkable agreement with experiment. From the experimental point of view, we show examples in which IR adsorption and Raman spectroscopy are essential to study molecule/MOF interactions. Importantly, we emphasize throughout this review that a combination of theory and experiment is crucial to effectively gain further understanding. In particular, we review such combined studies for the adsorption mechanism of small molecules in MOFs, the chemical stability of MOFs under humid conditions, water cluster formation inside MOFs, and the diffusion of small molecules into MOFs. The understanding of these phenomena is critical for the rational design of new MOFs with desired properties.

  13. Vibrational progressions in the valence ionizations of transition metal hydrides: evaluation of metal-hydride bonding and vibrations in (eta(5)-C(5)R(5))Re(NO)(CO)H [R = H, CH(3)].

    Science.gov (United States)

    Lichtenberger, Dennis L; Gruhn, Nadine E; Rai-Chaudhuri, Anjana; Renshaw, Sharon K; Gladysz, John A; Jiao, Haijun; Seyler, Jeff; Igau, Alain

    2002-02-20

    The first examples of vibrational structure in metal-ligand sigma-bond ionizations are observed in the gas-phase photoelectron spectra of CpRe(NO)(CO)H and CpRe(NO)(CO)H [Cp = eta(5)-C(5)H(5), Cp = eta(5)-C(5)(CH(3))(5)]. The vibrational progressions are due to the Re-H stretch in the ion states formed by removal of an electron from the predominantly Re-H sigma-bonding orbitals. A vibrational progression is also observed in the corresponding ionization of the deuterium analogue, CpRe(NO)(CO)D, but with lower vibrational energy spacing as expected from the reduced mass effect. The vibrational progressions in these valence ionizations are directly informative about the nature of the metal-hydride bonding and electronic structure in these molecules. Franck-Condon analysis shows that for these molecules the Re-H or Re-D bond lengthens by 0.25(1) A when an electron is removed from the Re-H or Re-D sigma-bond orbital. This bond lengthening is comparable to that of H(2) upon ionization. Removal of an electron from the Re-H or Re-D bonds leads to a quantum-mechanical inner sphere reorganization energy (lambda(QM)) of 0.34(1) eV. These observations suggest that even in these low symmetry molecules the orbital corresponding to the Re-H sigma bond and the Re-H vibrational mode is very localized. Theoretical calculations of the electronic structure and normal vibrational modes of CpRe(NO)(CO)H support a localized two-electron valence bond description of the Re-H interaction.

  14. Bond deformation paths and electronic instabilities of ultraincompressible transition metal diborides: Case study of OsB2 and IrB2

    Science.gov (United States)

    Zhang, R. F.; Legut, D.; Wen, X. D.; Veprek, S.; Rajan, K.; Lookman, T.; Mao, H. K.; Zhao, Y. S.

    2014-09-01

    The energetically most stable orthorhombic structure of OsB2 and IrB2 is dynamically stable for OsB2 but unstable for IrB2. Both diborides have substantially lower shear strength in their easy slip systems than their metal counterparts. This is attributed to an easy sliding facilitated by out-of-plane weakening of metallic Os-Os bonds in OsB2 and by an in-plane bond splitting instability in IrB2. A much higher shear resistance of Os-B and B-B bonds than Os-Os ones is found, suggesting that the strengthened Os-B and B-B bonds are responsible for hardness enhancement in OsB2. In contrast, an in-plane electronic instability in IrB2 limits its strength. The electronic structure of deformed diborides suggests that the electronic instabilities of 5d orbitals are their origin of different bond deformation paths. Neither IrB2 nor OsB2 can be intrinsically superhard.

  15. Metal-catalyzed C-C bond cleavage in alkanes: effects of methyl substitution on transition-state structures and stability.

    Science.gov (United States)

    Flaherty, David W; Hibbitts, David D; Iglesia, Enrique

    2014-07-01

    Methyl substituents at C-C bonds influence hydrogenolysis rates and selectivities of acyclic and cyclic C2-C8 alkanes on Ir, Rh, Ru, and Pt catalysts. C-C cleavage transition states form via equilibrated dehydrogenation steps that replace several C-H bonds with C-metal bonds, desorb H atoms (H*) from saturated surfaces, and form λ H2(g) molecules. Activation enthalpies (ΔH(‡)) and entropies (ΔS(‡)) and λ values for (3)C-(x)C cleavage are larger than for (2)C-(2)C or (2)C-(1)C bonds, irrespective of the composition of metal clusters or the cyclic/acyclic structure of the reactants. (3)C-(x)C bonds cleave through α,β,γ- or α,β,γ,δ-bound transition states, as indicated by the agreement between measured activation entropies and those estimated for such structures using statistical mechanics. In contrast, less substituted C-C bonds involve α,β-bound species with each C atom bound to several surface atoms. These α,β configurations weaken C-C bonds through back-donation to antibonding orbitals, but such configurations cannot form with (3)C atoms, which have one C-H bond and thus can form only one C-M bond. (3)C-(x)C cleavage involves attachment of other C atoms, which requires endothermic C-H activation and H* desorption steps that lead to larger ΔH(‡) values but also larger ΔS(‡) values (by forming more H2(g)) than for (2)C-(2)C and (2)C-(1)C bonds, irrespective of alkane size (C2-C8) or cyclic/acyclic structure. These data and their mechanistic interpretation indicate that low temperatures and high H2 pressures favor cleavage of less substituted C-C bonds and form more highly branched products from cyclic and acyclic alkanes. Such interpretations and catalytic consequences of substitution seem also relevant to C-X cleavage (X = S, N, O) in desulfurization, denitrogenation, and deoxygenation reactions.

  16. Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O, and Co-O bonded interactions for tephroite, Mn2SiO4, fayalite, Fe2SiO4, and Co2SiO4 olivine and selected organic metal complexes: comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides.

    Science.gov (United States)

    Gibbs, G V; Downs, R T; Cox, D F; Rosso, K M; Ross, N L; Kirfel, A; Lippmann, T; Morgenroth, W; Crawford, T D

    2008-09-18

    Bond critical point (bcp) and local energy density properties for the electron density (ED) distributions, calculated with first-principle quantum mechanical methods for divalent transition metal Mn-, Co-, and Fe-containing silicates and oxides are compared with experimental model ED properties for tephroite, Mn 2SiO 4, fayalite, Fe 2SiO 4, and Co 2SiO 4 olivine, each determined with high-energy synchrotron single-crystal X-ray diffraction data. Trends between the experimental bond lengths, R(M-O), (M = Mn, Fe, Co), and the calculated bcp properties are comparable with those observed for non-transition M-O bonded interactions. The bcp properties, local total energy density, H( r c), and bond length trends determined for the Mn-O, Co-O, and Fe-O interactions are also comparable. A comparison is also made with model experimental bcp properties determined for several Mn-O, Fe-O, and Co-O bonded interactions for selected organometallic complexes and several oxides. Despite the complexities of the structures of the organometallic complexes, the agreement between the calculated and model experimental bcp properties is fair to good in several cases. The G( r c)/rho( r c) versus R(M-O) trends established for non-transition metal M-O bonded interactions hold for the transition metal M-O bonded interactions with G( r c)/rho( r c) increasing in value as H( r c) becomes progressively more negative in value, indicating an increasing shared character of the interaction as G( r c)/rho( r c) increases in value. As observed for the non-transition metal M-O bonded interactions, the Laplacian, nabla (2)rho( r c), increases in value as rho( r c) increases and as H( r c) decreases and becomes progressive more negative in value. The Mn-O, Fe-O, and Co-O bonded interactions are indicated to be of intermediate character with a substantial component of closed-shell character compared with Fe-S and Ni-S bonded interactions, which show greater shared character based on the | V( r c)|/ G( r c

  17. Molecular Orbital, Generalized Valence Bond, and Complete Active Space Calculations on Transition Metal Compounds with Agostic Hydrogen and Bridging Carbonyls: New Basis Sets, Geometry of Trichloromethyltitanium, and Bonding of bis

    Science.gov (United States)

    Williamson, Rodney Lowell

    Total geometry optimizations are reported for Cr(CO)_6, HMn(CO)_5 , Fe(CO)_5, Ni(CO) _4, Cr(C_6H _6)_2, Fe(C_5H _5)_2, Ni(C_4 H_4)_2, Cr(NO) _4, (C_5H _5)Mn(CO)_3, and (C _6H_6)Cr(CO) _3. A variety of basis sets were examined, and, based on the results, a relatively compact and accurate basis set is proposed. Addition of electron correlation at the perfect pairing GVB level reduced the average difference in the metal-cyclopentadienyl bond length of 0.08 A. Optimization of the geometry of TiCl_4 and TiCl_3CH_3 at the self-consistent-field (SCF) level results in Ti-Cl bond lengths longer than the experimental values, even when d- and f-type polarization functions are added to the basis set. The bond lengths remain too long even as the Hartree-Fock limit is approached because the SCF level of theory over-estimates the noble-gas-like Cl cdotsCl repulsions, which hinder close Ti -Cl approach. The Ti-C-H angle of TiCl_3 CH_3 is calculated to be close to tetrahedral geometry with little flattening of the hydrogen atoms, which apparently was observed in the electron diffraction. These same calculations do predict the anomalously low methyl-rocking frequency for the titanium complex in agreement with the experimental IR. The large positive geminal hydrogen coupling constant observed in the NMR experiment is due primarily to the sigma -donor and pi-acceptor character of the TiCl_3 moiety and not to any flattening of the methyl group. The structure and bonding of (Cr(Cp)(CO) _2) _2 was examined by optimizing the geometry of the dimer, fragment moiety, and analogous stable monomers. The optimized structure of Cr(Cp)(CO)_2N has a "piano stool" geometry with a fragment moiety geometry nearly identical to the geometry of the fragment moiety in the dimer. Examination of x-ray and theoretical geometries of monomers with the fragment moiety bonded to single ligand show that the geometry of the fragment moiety is insensitive to the ligands bonded to it. Van der Waals calculations

  18. Intermolecular hydrogen bonding between neutral transition metal hydrides (eta(5)-C5H5)M(CO)3H (M = Mo, W) and bases.

    Science.gov (United States)

    Belkova, Natalia V; Gutsul, Evgenii I; Filippov, Oleg A; Levina, Vladislava A; Valyaev, Dmitriy A; Epstein, Lina M; Lledos, Agusti; Shubina, Elena S

    2006-03-22

    The interaction of CpM(CO)3H (M = Mo, W) hydrides as proton donors with different bases (B = pyridine, (n-Oc)3PO, ((CH3)2N)3PO, H3BNEt3) was studied by variable temperature IR spectroscopy and theoretically by DFT/B3LYP calculations. The data obtained show for the first time the formation of intermolecular hydrogen bonds between the neutral transition metal hydrides and bases in solutions of low polarity. These M-H...B hydrogen bonds are shown to precede the hydrides' deprotonation.

  19. Photochemical route to actinide-transition metal bonds: synthesis, characterization and reactivity of a series of thorium and uranium heterobimetallic complexes.

    Science.gov (United States)

    Ward, Ashleigh L; Lukens, Wayne W; Lu, Connie C; Arnold, John

    2014-03-01

    A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium, and cobalt. Complexes incorporating the binucleating ligand N[ο-(NHCH2P(i)Pr2)C6H4]3 with either Th(IV) (4) or U(IV) (5) and a carbonyl bridged [Co(CO)4](-) unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)4]. Irradiation of the resulting isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively unusual class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl and formation of the metal-metal bond is accompanied by coordination of a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) Å and 3.0319(7) Å for the thorium and uranium complexes, respectively, were observed. The solution-state behavior of the thorium complexes was evaluated using (1)H, (1)H-(1)H COSY, (31)P, and variable-temperature NMR spectroscopy. IR, UV-vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.

  20. Electro-Discharge Fine Truing of Metal-Bonded Fine-Grain Diamond Wheel Based on Real-Time Monitoring

    Institute of Scientific and Technical Information of China (English)

    JIN Weidong; REN Chengzu; HUA Jinhai; WANG Taiyong

    2005-01-01

    A data acquisition system based on LabVIEW is designed and implemented, and electro-discharge(ED) fine truing of metal-bonded fine-grain diamond wheel based on real-time monitoring is researched. Real-time monitoring not only makes efficient impulse specification of ED truing easily obtained, but also is good for timely identifying no-load, avoiding short circuit and arc discharge phenomena and then for obtaining normal machining state. ED fine truing of the fine-grain wheel includes two steps: rough truing for high efficiency and fine truing for high precision. Final ED truing precision and efficiency not only depend on electric process specification, but also is concerned with electrode shape, insulated performance of operating fluid and vertical feed quantity value and frequency. Experiments indicate that ED fine truing based on real-time monitoring can improve the truing precision and efficiency. Average machining efficiency of W10 wheel is about 0.95 μm/min; the final run-out by ED truing is less than 2 μm.

  1. Microstructure and Mechanical Properties of Accumulative Roll-Bonded AA1050A/AA5005 Laminated Metal Composites

    Directory of Open Access Journals (Sweden)

    Frank Kümmel

    2016-03-01

    Full Text Available Laminated metal composites (LMCs with alternating layers of commercial pure aluminum AA1050A and aluminum alloy AA5005 were produced by accumulative roll-bonding (ARB. In order to vary the layer thickness and the number of layer interfaces, different numbers of ARB cycles (4, 8, 10, 12, 14 and 16 were performed. The microstructure and mechanical properties were characterized in detail. Up to 8 ARB cycles, the ultrafine-grained (UFG microstructure of the layers in the LMC evolves almost equally to those in AA1050A and AA5005 mono-material sheets. However, the grain size in the composites tends to have smaller values. Nevertheless, the local mechanical properties of the individual layers in the LMCs are very similar to those of the mono-material sheets, and the macroscopic static mechanical properties of the LMCs can be calculated as the mean value of the mono-material sheets applying a linear rule of mixture. In contrast, for more than 12 ARB cycles, a homogenous microstructure was obtained where the individual layers within the composite cannot be visually separated any longer; thus, the hardness is at one constant and a high level across the whole sheet thickness. This results also in a significant higher strength in tensile testing. It was revealed that, with decreasing layer thickness, the layer interfaces become more and more dominating.

  2. Influence of metal bonding layer on strain sensing performance of FBG%金属化粘接层对FBG应变传感性能的影响

    Institute of Scientific and Technical Information of China (English)

    刘浩; 陈伟民; 章鹏; 刘立; 舒岳阶; 吴俊

    2013-01-01

    Metal bonding layer seriously affects the strain transfer performance of fiber Bragg grating (FBG). Based on the model of strain transfer of FBG,the effects of the length,the thickness,Poisson's ratio, elasticity modulus of bonding layer on the strain transfer coefficient of FBG are analyzed by numerical simulatioa The results show that the metal bonding layer has a larger advantage than the epoxy glue layer in strain transfer performance. The strain transfer coefficient increases with the length of metal bonding layer,decreases with the thickness of metal bonding layer and the influence of Poisson's ratio can be ignored. The FBG is packaged to steel wire using the metal bonding technology. The tensile tests under different bonding lengths and elasticity moduluses are carried out. The results indicate that the strain transfer coefficients of FBGs are 0. 948,0. 962 and the average strain sensitivities are 1. 076 pm/ με,l. 099 pm/με when the metal bonding layer is zinc,whose length is 15 mm,20 mm,respectively. The strain transfer coefficient of the FBG packaged by metal bonding layer is enhanced by 8. 9 % compared with the epoxy glue packaged one. The experiment result is general agreement with the analysis and provides guidance for metal package of FBG.%根据光纤布拉格光栅(FBG)应变传递模型,仿真分析了粘接层弹性模量、长度、厚度和泊松比对FBG应变传递效率的影响.分析结果表明,金属化粘接层应变传递特性优于环氧胶粘接层;金属化粘接层越长,FBG应变灵敏度越高,稳定性越好;厚度越小,应变传递效率越高,泊松比的影响可以忽略.采用新研制的FBG金属化连接技术将FBG封装到钢丝上,对不同粘接长度、粘接材料的FBG进行了拉力试验.实验结果表明,当Zn粘接层长为15 mm、20 mm时,FBG平均应变灵敏度为1.076 pm/με、1.099 pm/με,平均应变传递效率分别为0.948、0.962;金属化连接的FBG应变传递系数相比环

  3. Chemistry of sulfur oxides on transition metal surfaces: a bond order conservation-Morse potential modeling perspective

    Science.gov (United States)

    Sellers, Harrell; Shustorovich, Evgeny

    1996-06-01

    We have employed the bond order conservation-Morse potential (BOC-MP) method to analyze the chemistry of sulfur oxides on the copper and nickel group metals. Specifically, we have calculated the reaction energetics (heats of adsorption, reaction enthalpies and intrinsic activation barriers) of the decomposition and oxidation of sulfur dioxide at low coverages on fcc (111) surfaces of Cu, Ag, Au, Ni, Pd and Pt. The accuracy of the BOC-MP heats of adsorption has been corroborated by high quality ab initio calculations of the heats of SO2 adsorption on Ag and Pd surfaces. We have addressed the following issues: (1) the dissociation of SO2; (2) the stability of adsorbed SO and its likelihood of being a product of SO2 decomposition; (3) the oxidation of SO2; and, (4) the nature of adsorbed SO3 and SO4. The major model projections (obtained for low coverages and without considering diffusional effects) are: (1) the dissociation of SO2→SO + O is unfavorable on all the metals considered, but, the dissociation of SO2→S + O + O, showing distinct periodic trends, is feasible on Cu and particularly on Ni; in the presence of carbon monoxide the dissociation, SO2 + CO→S + O + CO2, may occur on all the metals examined; (2) on the Pt, Pd, Ni and Cu surfaces, SO is unstable; (3) the oxidation of SO2 to SO3 may be achieved with O, O2, H2O2 and NO as oxygen sources on Ag, Au, Pd and Pt surfaces. Although adsorbed SO3 may be readily obtained, it may be impossible to desorb SO3 intact at low coverages because SO3 will decompose to SO2 + O before desorption. (4) The most stable oxygen sulfur specie that withstands elevated temperatures should be dianion sulfate. The relevant experimental data have been discussed. Most of the model projections are in agreement with experiment, but, some suggest reconsideration of the reported experimental data or represent predictions to be verified.

  4. Comparison of Ultrasonic Welding and Thermal Bonding for the Integration of Thin Film Metal Electrodes in Injection Molded Polymeric Lab-on-Chip Systems for Electrochemistry

    Directory of Open Access Journals (Sweden)

    Marco Matteucci

    2016-10-01

    Full Text Available We compare ultrasonic welding (UW and thermal bonding (TB for the integration of embedded thin-film gold electrodes for electrochemical applications in injection molded (IM microfluidic chips. The UW bonded chips showed a significantly superior electrochemical performance compared to the ones obtained using TB. Parameters such as metal thickness of electrodes, depth of electrode embedding, delivered power, and height of energy directors (for UW, as well as pressure and temperature (for TB, were systematically studied to evaluate the two bonding methods and requirements for optimal electrochemical performance. The presented technology is intended for easy and effective integration of polymeric Lab-on-Chip systems to encourage their use in research, commercialization and education.

  5. Comparison of Ultrasonic Welding and Thermal Bonding for the Integration of Thin Film Metal Electrodes in Injection Molded Polymeric Lab-on-Chip Systems for Electrochemistry.

    Science.gov (United States)

    Matteucci, Marco; Heiskanen, Arto; Zór, Kinga; Emnéus, Jenny; Taboryski, Rafael

    2016-10-27

    We compare ultrasonic welding (UW) and thermal bonding (TB) for the integration of embedded thin-film gold electrodes for electrochemical applications in injection molded (IM) microfluidic chips. The UW bonded chips showed a significantly superior electrochemical performance compared to the ones obtained using TB. Parameters such as metal thickness of electrodes, depth of electrode embedding, delivered power, and height of energy directors (for UW), as well as pressure and temperature (for TB), were systematically studied to evaluate the two bonding methods and requirements for optimal electrochemical performance. The presented technology is intended for easy and effective integration of polymeric Lab-on-Chip systems to encourage their use in research, commercialization and education.

  6. Hydrogen bonding and proton transfer to ruthenium hydride complex CpRuH(dppe): metal and hydride dichotomy.

    Science.gov (United States)

    Silantyev, Gleb A; Filippov, Oleg A; Tolstoy, Peter M; Belkova, Natalia V; Epstein, Lina M; Weisz, Klaus; Shubina, Elena S

    2013-02-18

    The combination of variable temperature (190-297 K) IR and NMR spectroscopy studies with quantum-chemical calculations at the DFT/B3PW91 and AIM level had the aim to determine the mechanism of proton transfer to CpRuH(dppe) (1, dppe = Ph(2)P(CH(2))(2)PPh(2)) and the structures of intermediates. Dihydrogen bond (DHB) formation was established in the case of interaction with weak proton donors like CF(3)CH(2)OH. Low-temperature protonation (at about 200 K) by stronger proton donors leads via DHB complex to the cationic nonclassical complex [CpRu(η(2)-H(2))(dppe)](+) (2). Thermodynamic parameters of DHB formation (for CF(3)CH(2)OH: ΔH°(HB) = -4.9 ± 0.2 kcal·mol(-1), ΔS°(HB) = -17.8 ± 0.7 cal·mol(-1)·K(-1)) and proton transfer (for (CF(3))(2)CHOH: ΔH°(PT) = -5.2 ± 0.3 kcal·mol(-1), ΔS°(PT) = -23 ± 1 cal·mol(-1)·K(-1)) were determined. Above 240 K 2 transforms into trans-[CpRu(H)(2)(dppe)](+) (3) yielding a mixture of 2 and 3 in 1:2 ratio. Kinetic analysis and activation parameters for the "[Ru(η(2)-H(2))](+) → trans-[Ru(H)(2)](+)" transformation indicate reversibility of this process in contrast to irreversible intramolecular isomerization of the Cp* analogue. Calculations show that the driving force of this process is greater stability (by 1.5 kcal·mol(-1) in ΔE scale) of the dihydride cation in comparison with the dihydrogen complex. The calculations of the potential energy profile indicate the low barrier for deprotonation of 2 suggesting that the formation of trans-[CpRu(H)(2)(dppe)](+) proceeds via deprotonation of [Ru(η(2)-H(2))](+) to DHB complex, formation of hydrogen bond with Ru atom and subsequent proton transfer to the metal site.

  7. Carboxylic acid functionalized ortho-linked oxacalix[2]benzene[2]pyrazine: synthesis, structure, hydrogen bond and metal directed self-assembly.

    Science.gov (United States)

    Kong, Ling-Wei; Ma, Ming-Liang; Wu, Liang-Chun; Zhao, Xiao-Li; Guo, Fang; Jiang, Biao; Wen, Ke

    2012-05-14

    Cyclooligomerization of 2,6-dichloropyrazine 4 and benzyl 2,3-dihydroxybenzoate 5 under microwave irradiation resulted in a racemic pair of ester functionalized ortho-linked oxacalix[2]benzene[2]pyrazine 6, which was further transformed to the corresponding racemic carboxylic acid functionalized ortho-linked oxacalix[2]benzene[2]pyrazine 3. Both enantiomers of 3 adopt 1,3-alternate conformations with their two carboxylic acid groups pointing to opposite directions in the solid state. Enantiomers of 3 form a step-like one-dimensional supramolecular polymer via intermolecular hydrogen bond interactions between the carboxylic acids for crystals obtained in methanol. No hydrogen bonds were formed between the carboxylic acids for crystals of 3 obtained in pyridine and aqueous guanidine solutions; instead, intermolecular hydrogen bonds between the carboxylic acid groups of 3 and pyridine, as well as guanidinium ions were formed. Under metal-mediated self-assembly conditions, the pyrazinyl nitrogen atoms in 3 interacted with transition metal ions, such as Ag(I), Cu(II) and Zn(II), and resulted in the formation of four new metal-containing supramolecular complexes. Metallomacrocycles 7, 8 and 9 were formed by reactions of 3 with Ag(I) or Cu(II) ions by bridging two ligands 3 in the equatorial region via M-N coordination bonds. A one-dimensional coordination polymer 10 was generated by reaction between ligand 3 and Zn(II) ions, and a cage-based structure is presented in 10 by bridging of the cyclophane units by Zn(2+) ions via Zn-N and Zn-O bonds.

  8. Oxidation and aging in U and Pu probed by spin-orbit sum rule analysis: indications for covalent metal-oxide bonds

    Energy Technology Data Exchange (ETDEWEB)

    Moore, K; der Laan, G v; Haire, R; Wall, M; Schwartz, A

    2005-10-07

    Transmission electron microscopy is used to acquire electron energy-loss spectra from phase-specific regions of Pu and U metal, PuO{sub 2} and UO{sub 2}, and aged, self-irradiated Pu metal. The N{sub 4,5} (4d {yields} 5f) spectra are analyzed using the spin-orbit sum rule. Our results show that the technique is sensitive enough to detect changes in the branching ratio of the white-line peaks between the metal and dioxide of both U and Pu. There is a small change in the branching ratio between different Pu metals, and the data trends as would be expected for varying f electron localization, i.e., {alpha}-Pu, {delta}-Pu, aged {delta}-Pu. Moreover, our results suggest that the metal-oxide bonds in UO{sub 2} and PuO{sub 2} are strongly covalent in nature and do not exhibit an integer valence change as would be expected from purely ionic bonding.

  9. Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

    Energy Technology Data Exchange (ETDEWEB)

    T. Brent Gunnoe

    2011-02-17

    Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials. A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt

  10. Bond making and breaking on transition-metal surfaces revisited; when the bond-order-conservation criteria may not be sufficient

    Science.gov (United States)

    Shustorovich, Evgeny

    1987-08-01

    Our bond-order-conservation (BOC) estimates for the activation barriers Δ E* for recombination of chemisorbed species [Surface Sci. 176 (1986) L863] have been compared with the enthalpy differences Δ H of the products and reactants for a variety of surface reactions. Typically, Δ Es*≥Δ H, which makes physical sense. In a few cases, however, we found Δ E*<Δ H, which makes the BOC criteria insufficient. These cases are discussed.

  11. A comparison of fracture resistance of endodontically treated teeth restored with bonded partial restorations and full-coverage porcelain-fused-to-metal crowns.

    Science.gov (United States)

    Gupta, Abhishek; Musani, Smita; Dugal, Ramandeep; Jain, Nikhil; Railkar, Bhargavi; Mootha, Ajay

    2014-01-01

    The aim of this study was to evaluate the use of bonded partial restorations compared with full-coverage porcelain-fused-to-metal (PFM) crowns as a viable treatment option for endodontically treated posterior teeth. Forty-five recently extracted maxillary first premolars were collected, endodontically treated, and mounted in acrylic blocks. The specimens were randomly divided into three groups and prepared to receive their respective restorations. The teeth in group 1 received full-coverage porcelain-fused-to-metal crowns. The teeth in group 2 received bonded partial restorations made from pressed ceramics (lithium disilicate) involving a functional cusp (palatal). Finally, group 3 received bonded partial restorations made from pressed ceramics involving the buccal cusp and keeping a functional cusp (palatal) intact. All group 1 restorations were cemented using glass ionomer cement. Restorations in groups 2 and 3 were bonded using a dual-cured resin cement. All specimens were subjected to an aging process and tested for shear bond strength using a universal loading machine. The mean force applied in Newtons to cause failure for group I was 674.90 ± 94.16 N, for group 2, 463.46 ± 61.11 N, and for group 3, 849.33 ± 68.92 N. P values obtained using one-way analysis of variance showed a highly significant difference between groups 2 and 3 (P = .001), groups 1 and 2 (P = .001), and groups 1 and 3 (P = .001). The fracture modes observed in all groups involved restorations and tooth fracture. This in vitro study suggests that endodontically treated posterior teeth with intact functional cusps can be restored with bonded partial porcelain restorations. However, if the loss of tooth structure involves the functional cusp, full-coverage PFM crowns are the treatment of choice.

  12. Periodic regularities in bonding, coordination modes and reactivity of sulfur oxides on transition metal surfaces: Combined BOC-MP and ab initio results

    Energy Technology Data Exchange (ETDEWEB)

    Shustorovich, E. [Blue Planet Technologies Co., New York, NY (United States); Sellers, H. [South Dakota State Univ., Brookings, SD (United States)

    1995-12-01

    A combination of theoretical methods (BOC-MP and high quality ab initio calculations) has been employed to understand the nature of bonding, coordination modes and reactivity of sulfur oxides on metal fcc (111), (100), (110) surfaces along the periodic series Cu, Pt, Pd and Ni. The emphasis was on the molecular chemisorption of SO{sub 2} and its dissociative pathways: S + 20 <--- SO + O <--- SO{sub 2} --- > SO{sub 3} --- > SO{sub 4}. M

  13. Letter report: Pre-conceptual design study for a pilot-scale Non-Radioactive Low-Level Waste Vitrification Facility

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, R.A.; Morrissey, M.F.

    1996-03-01

    This report presents a pre-conceptual design study for a Non-Radioactive Low-Level Waste, Pilot-Scale Vitrification System. This pilot plant would support the development of a full-scale LLW Vitrification Facility and would ensure that the full-scale facility can meet its programmatic objectives. Use of the pilot facility will allow verification of process flowsheets, provide data for ensuring product quality, assist in scaling to full scale, and support full-scale start-up. The facility will vitrify simulated non-radioactive LLW in a manner functionally prototypic to the full-scale facility. This pre-conceptual design study does not fully define the LLW Pilot-Scale Vitrification System; rather, it estimates the funding required to build such a facility. This study includes identifying all equipment necessary. to prepare feed, deliver it into the melter, convert the feed to glass, prepare emissions for atmospheric release, and discharge and handle the glass. The conceived pilot facility includes support services and a structure to contain process equipment.

  14. Rapid detection of medium chain acyl-CoA dehydrogenase gene mutations by non-radioactive, single strand conformation polymorphism minigels.

    Science.gov (United States)

    Iolascon, A; Parrella, T; Perrotta, S; Guardamagna, O; Coates, P M; Sartore, M; Surrey, S; Fortina, P

    1994-07-01

    Medium chain acyl-CoA dehydrogenase (MCAD) deficiency is a common inherited metabolic disorder affecting fatty acid beta oxidation. Identification of carriers is important since the disease can be fatal and is readily treatable once diagnosed. Twelve molecular defects have been identified in the MCAD gene; however, a single highly prevalent mutation, A985G, accounts for > 90% of mutant alleles in the white population. In order to facilitate the molecular diagnosis of MCAD deficiency, oligonucleotide primers were designed to amplify the exon regions encompassing the 12 mutations enzymatically, and PCR products were then screened with a single strand conformation polymorphism (SSCP) based method. Minigels were used allowing much faster run times, and silver staining was used after gel electrophoresis to eliminate the need for radioisotopic labelling strategies. Our non-radioactive, minigel SSCP approach showed that normals can be readily distinguished from heterozygotes and homozygotes for all three of the 12 known MCAD mutations which were detected in our sampling of 48 persons. In addition, each band pattern is characteristic for a specific mutation, including those mapping in the same PCR product like A985G and T1124C. When necessary, the molecular defect was confirmed using either restriction enzyme digestion of PCR products or by direct DNA sequence analysis or both. This rapid, non-radioactive approach can become routine for molecular diagnosis of MCAD deficiency and other genetic disorders.

  15. B═B and B≡E (E = N and o) multiple bonds in the coordination sphere of late transition metals.

    Science.gov (United States)

    Brand, Johannes; Braunschweig, Holger; Sen, Sakya S

    2014-01-21

    Because of their unusual structural and bonding motifs, multiply bonded boron compounds are fundamentally important to chemists, leading to enormous research interest. To access these compounds, researchers have introduced sterically demanding ligands that provide kinetic as well as electronic stability. A conceptually different approach to the synthesis of such compounds involves the use of an electron-rich, coordinatively unsaturated transition metal fragment. To isolate the plethora of borane, boryl, and borylene complexes, chemists have also used the coordination sphere of transition metals to stabilize reactive motifs in these molecules. In this Account, we summarize our results showing that increasingly synthetically challenging targets such as iminoboryl (B≡N), oxoboryl (B≡O), and diborene (B═B) fragments can be stabilized in the coordination sphere of late transition metals. This journey began with the isolation of two new iminoboryl ligands trans-[(Cy3P)2(Br)M(B≡N(SiMe3))] (M = Pd, Pt) attached to palladium and platinum fragments. The synthesis involved oxidative addition of the B-Br bond in (Me3Si)2N═BBr2 to [M(PCy3)2] (M = Pt, Pd) and the subsequent elimination of Me3SiBr at room temperature. Variation of the metal, the metal-bound coligands, and the substituent at the nitrogen atom afforded a series of analogous iminoboryl complexes. Following the same synthetic strategy, we also synthesized the first oxoboryl complex trans-[(Cy3P)2BrPt(BO)]. The labile bromide ligand adjacent to platinum makes the complex a viable candidate for further substitution reactions, which led to a number of new oxoboryl complexes. In addition to allowing us to isolate these fundamental compounds, the synthetic strategy is very convenient and minimizes byproducts. We also discuss the reaction chemistry of these types of compounds. In addition to facilitating the isolation of compounds with B≡E (E = N, O) triple bonds, the platinum fragment can also stabilize a

  16. Mixed chloride/phosphine complexes of the dirhenium core. 10. Redox reactions of an edge-sharing dirhenium(III) non-metal-metal-bonded complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4).

    Science.gov (United States)

    Cotton, F A; Dikarev, E V; Petrukhina, M A

    2001-12-17

    Reduction and oxidation reactions of the dirhenium(III) non-metal-metal-bonded edge-sharing complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4) (1), have been studied. Several new mono- and dinuclear rhenium compounds have been isolated and structurally characterized in the course of this study. Reductions of 1 with 1 and 2 equiv of KC(8) result in an unusual face-sharing complex having an Re(2)(5+) core, Re(2)(mu-Cl)(3)Cl(2)(PMe(3))(4) (2), and a triply bonded Re(II) compound, 1,2,7,8-Re(2)Cl(4)(PMe(3))(4) (3), respectively. Two-electron reduction of 1 in the presence of tetrabutylammonium chloride affords a new triply bonded complex of the Re(2)(4+) core, [Bu(n)()(4)N][1,2,7-Re(2)Cl(5)(PMe(3))(3)] (4). Oxidation of 1 with NOBF(4) yields a Re(IV) mononuclear compound, trans-ReCl(4)(PMe(3))(2) (5). Two isomers of the monomeric Re(III) anion, [ReCl(4)(PMe(3))(2)](-) (6, 7), have been isolated as side products. The crystal structures of compounds 2 and 4-7 have been determined by X-ray crystallography. The Re-Re distance in the face-sharing complex 2 of 2.686(1) A is relatively short. The metal-metal bond length in anion 4 of 2.2354(7) A is consistent with the usual values for the triply bonded Re(2)(4+) core compounds. In addition, a cis arrangement of trimethylphosphine ligands in the starting material 1 is retained upon reduction in the dinuclear products 2-4.

  17. The solid phase extraction of some metal ions using palladium nanoparticles attached to silica gel chemically bonded by silica-bonded N-propylmorpholine as new sorbent prior to their determination by flame atomic absorption spectroscopy.

    Science.gov (United States)

    Ghaedi, M; Rezakhani, M; Khodadoust, S; Niknam, K; Soylak, M

    2012-01-01

    In this research at first palladium nanoparticle attached to a new chemically bonded silica gel has been synthesized and has been characterized with different techniques such as X-ray diffraction (XRD), fourier transform infrared (FT-IR), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Then, this new sorbent (chemically modified silica gel with N-propylmorpholine (PNP-SBNPM)) was efficiently used for preconcentration of some metal ions in various food samples. The influence of effective variables including mass of sorbent, flow rate, pH of sample solutions and condition of eluent such as volume, type and concentration on the recoveries of understudy metal ions were investigated. Following the optimization of variables, the interfering effects of some foreign ions on the preconcentration and determination of the investigated metal ions described. At optimum values of variables, all investigated metal ions were efficiently recovered with efficiency more than 95%, relative standard deviation (RSD) between 2.4 and 2.8, and detection limit in the range of 1.4-2.7 ng mL⁻¹. The present method is simple and rapidly applicable for the determination of the understudied metal ions (ng mL⁻¹) in different natural food samples.

  18. The Solid Phase Extraction of Some Metal Ions Using Palladium Nanoparticles Attached to Silica Gel Chemically Bonded by Silica-Bonded N-Propylmorpholine as New Sorbent prior to Their Determination by Flame Atomic Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    M. Ghaedi

    2012-01-01

    Full Text Available In this research at first palladium nanoparticle attached to a new chemically bonded silica gel has been synthesized and has been characterized with different techniques such as X-ray diffraction (XRD, fourier transform infrared (FT-IR, transmission electron microscopy (TEM, and scanning electron microscopy (SEM. Then, this new sorbent (chemically modified silica gel with N-propylmorpholine (PNP-SBNPM was efficiently used for preconcentration of some metal ions in various food samples. The influence of effective variables including mass of sorbent, flow rate, pH of sample solutions and condition of eluent such as volume, type and concentration on the recoveries of understudy metal ions were investigated. Following the optimization of variables, the interfering effects of some foreign ions on the preconcentration and determination of the investigated metal ions described. At optimum values of variables, all investigated metal ions were efficiently recovered with efficiency more than 95%, relative standard deviation (RSD between 2.4 and 2.8, and detection limit in the range of 1.4–2.7 ng mL−1. The present method is simple and rapidly applicable for the determination of the understudied metal ions (ng mL−1 in different natural food samples.

  19. Construction of metal-organic frameworks through coordination and hydrogen bonding interactions: Syntheses, structures and photoluminescent properties of metal complexes with macrocyclic ligand

    Science.gov (United States)

    Ouyang, Xing-Mei; Li, Zhen-Wu; Okamura, Taka-aki; Li, Yi-Zhi; Sun, Wei-Yin; Tang, Wen-Xia; Ueyama, Norikazu

    2004-01-01

    A macrocyclic ligand L with two diethylenetriamine units linked by two rigid biphenylene spacers was used as building block for construction of metal-organic frameworks. A silver(I) complex with macrocyclic and open-chain mix-type ligands [Ag 2( L)( L')](ClO 4) 2 ( 1) [ L'=1,6-bis(4-imidazol-1'-ylmethylphenyl)-2,5-diazahexane] was obtained by reaction of L and L' together with AgClO 4·H 2O. It is interesting that the open-chain tetradentate ligand L' only served as a bidentate ligand to bridge the Ag 2L units into an infinite one-dimensional (1D) cationic chain. Neutral 1D chain coordination polymer [Cu 2( L)( μ-SO 4) 2]·3H 2O·3MeOH ( 2) is formed by sulfate bridges between the neighboring Cu 2L units. When L reacted with nickel(II) sulfate instead of copper(II) sulfate, a monomacrocycle molecular complex [Ni 2( L)(H 2O) 4(SO 4) 2] ( 3) was obtained in which the sulfate anion acts as monodentate ligands rather than as bridges. When Cd(II) salts were used for the reactions with L, another two neutral 1D coordination polymers, [Cd 2( L)( μ-Cl) 2Cl 2]·2H 2O ( 4) and [Cd 2( L)( μ-Br) 2Br 2] ( 5), with the same structure were isolated. All the synthesized complexes exhibit three-dimensional framework structures linked by various hydrogen bonds. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature, and the Ag(I) and Cd(II) complexes were found to show strong blue luminescence.

  20. Key role of intramolecular metal chelation and hydrogen bonding in the cobalt-mediated radical polymerization of N-vinyl amides.

    Science.gov (United States)

    Debuigne, Antoine; Morin, Aurélie N; Kermagoret, Anthony; Piette, Yasmine; Detrembleur, Christophe; Jérôme, Christine; Poli, Rinaldo

    2012-10-01

    This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex bis(acetylacetonato)cobalt(II). The cobalt-mediated radical polymerization (CMRP) of a series of N-vinyl amides was considered with the aim of studying the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt-polymer bond in the order N-vinylpyrrolidonepolymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, through a covalent bond and a dative bond, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. Possible hydrogen bond formation is also taken into account in the case of N-vinyl acetamide and N-vinyl formamide. These results are essential for understanding the factors influencing Co-C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N-vinyl amide) materials, which are an important class of polymers that sustain numerous applications today.

  1. Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol.

    Science.gov (United States)

    Liu, Cuibo; Zhang, Bin

    2016-04-01

    The creation of new bonds via C-F bond cleavage of polyfluoroarenes has proven to be an important and powerful tool in synthetic chemistry. Using such a strategy, a myriad of valuable partially fluoroaromatic molecules and building blocks can be obtained. The transition-metal-free nucleophilic aromatic substitution (SN Ar) strategy has aroused the continuing interest of researchers due to its simple, mild, economical, and environmentally benign characteristics, which have been successfully applied to C-F bond functionalizations. In this account, we present a summary of the recent investigations of polyfluoroarenes involving SN Ar reactions and discuss some of our recent endeavors in the construction of partially fluoroaromatic molecules. Through this strategy, many new bonds including C-C, C-N, C-O, C-S, and C-H bonds can be created. Additionally, brief discussions on the transformation mechanisms are also provided. Finally, we discuss the existing limitations of the SN Ar reactions of polyfluoroarenes as well as our perspective on the future development of this chemistry. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Crystal structures and hydrogen bonding in the isotypic series of hydrated alkali metal (K, Rb and Cs complexes with 4-aminophenylarsonic acid

    Directory of Open Access Journals (Sweden)

    Graham Smith

    2017-02-01

    Full Text Available The structures of the alkali metal (K, Rb and Cs complex salts with 4-aminophenylarsonic acid (p-arsanilic acid manifest an isotypic series with the general formula [M2(C6H7AsNO32(H2O3], with M = K {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dipotassium], [K2(C6H7AsNO32(H2O3], (I}, Rb {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dirubidium], [Rb2(C6H7AsNO32(H2O3], (II}, and Cs {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dirubidium], [Cs2(C6H7AsNO32(H2O3], (III}, in which the repeating structural units lie across crystallographic mirror planes containing two independent and different metal cations and a bridging water molecule, with the two hydrogen p-arsanilate ligands and the second water molecule lying outside the mirror plane. The bonding about the two metal cations in all complexes is similar, one five-coordinate, the other progressing from five-coordinate in (I to eight-coordinate in both (II and (III, with overall M—O bond-length ranges of 2.694 (5–3.009 (7 (K, 2.818 (4–3.246 (4 (Rb and 2.961 (9–3.400 (10 Å (Cs. The additional three bonds in (II and (III are the result of inter-metal bridging through the water ligands. Two-dimensional coordination polymeric structures with the layers lying parallel to (100 are generated through a number of bridging bonds involving the water molecules (including hydrogen-bonding interactions, as well as through the arsanilate O atoms. These layers are linked across [100] through amine N—H...O hydrogen bonds to arsonate and water O-atom acceptors, giving overall three-dimensional network structures.

  3. Bond making and breaking on transition-metal surfaces revisited; when the bond-order-conversation criteria may not be sufficient

    Science.gov (United States)

    Shustorovich, Evgeny

    Our bond-order-conservation (BOC) estimates for the activation barriers ΔE ∗ for recombination of chemisorbed species [Surface Sci. 176 (1986) L863] have been compared with the enthalpy differences ΔH of the products and reactants for a variety of surface reactions. Typically, ΔE ∗ ⩾ ΔH , which makes physical sense. In a few cases, however, we found ΔE ∗ < ΔH , which makes the BOC criteria insufficient. These cases are discussed.

  4. Electronic bonding analyses and mechanical strengths of incompressible tetragonal transition metal dinitrides TMN2 (TM = Ti, Zr, and Hf)

    Science.gov (United States)

    Zhang, Meiguang; Cheng, Ke; Yan, Haiyan; Wei, Qun; Zheng, Baobing

    2016-11-01

    Motivated by recent successful synthesis of transition metal dinitride TiN2, the electronic structure and mechanical properties of the discovered TiN2 and other two family members (ZrN2 and HfN2) have been thus fully investigated by using first-principles calculations to explore the possibilities and provide guidance for future experimental efforts. The incompressible nature of these tetragonal TMN2 (TM = Ti, Zr, and Hf) compounds has been demonstrated by the calculated elastic moduli, originating from the strong N-N covalent bonds that connect the TMN8 units. However, as compared with traditional fcc transition metal mononitride (TMN), the TMN2 possess a larger elastic anisotropy may impose certain limitations on possible applications. Further mechanical strength calculations show that tetragonal TMN2 exhibits a strong resistance against (100)[010] shear deformation prevents the indenter from making a deep imprint, whereas the peak stress values (below 12 GPa) of TMN2 along shear directions are much lower than those of TMN, showing their lower shear resistances than these known hard wear-resistant materials. The shear deformation of TMN2 at the atomic level during shear deformation can be attributed to the collapse of TMN8 units with breaking of TM-N bonds through the bonding evolution and electronic localization analyses.

  5. Coordination modes and bonding of sulfur oxides on transition metal surfaces: combined ab initio and BOC-MP results

    Science.gov (United States)

    Seller, Harrell; Shustorovich, Evgeny

    1996-02-01

    Binding energies for sulfur oxides, SO x, x = 1-3, have been determined for several coordination modes on silver, gold and palladium surfaces employing ab initio quantum chemical methods and the bond order conservation Morse potential (BOC-MP) method. SO 2 coordination was studied in the most detail. In general the agreement between the BOC-MP and ab initio binding energies is good for the (111) surfaces of silver and palladium with both methods predicting that, in the zero coverage limit, di-coordination via S,O and O,O will be more favorable energetically than mono-coordination via S. In the case of chemisorption on the Pd (110) surface the two methods agree well for the cases in which there are formulas for the BOC-MP binding energies. In going from the (111) surfaces to the (110) surfaces of silver and palladium the ab initio calculations predict that the preferred chemisorption site shifts from the bridge site to the hollow site. On the silver surfaces the net charge transferred to the adsorbate as judged from the Mulliken populations correlates roughly with the binding energy. No significant charge transfer was found on the palladium surfaces. Our SO 2 chemisorption calculations indicate that the work functions of the metal surfaces examined should increase upon mono-S adsorption, increase to a lesser extent upon di S,O adsorption and may even decrease upon di O,O adsorption. Ab initio calculations provide evidence of the existence of SO 2 surface dimers. The binding energy predicted by the BOC-MP model for SO 3 in the bridging site agrees well with the ab initio result for SO 3 di-coordinated in the long bridge of the Ag(110) surface. The methods yield similar predictions for the case of SO on silver. Our modeling provides a coherent picture consistent with many aspects of the experimental literature. We present some model predictions, particularly the di O,O coordination mode for SO 2, that require verification experimentally.

  6. Carbon-carbon bond formation involving reactions of alkynes with group 9 metals (Ir, Rh, Co): preparation of conjugated olefins.

    Science.gov (United States)

    Chin, Chong Shik; Won, Gyongshik; Chong, Daesung; Kim, Mieock; Lee, Hyungeui

    2002-04-01

    Stable alkynyl complexes of iridium(III) (L(n)Ir-triple bond-R) that are prepared from the reactions of terminal alkynes readily undergo the intramolecular C-C bond-forming reactions between the alkynyl and adjacent hydrocarbyl ligands to yield conjugated olefins. These reactions are initiated by electrophiles (H(+), Me(+)) that attack the beta carbon of the alkynyl ligand to increase the electrophilicity of the alpha carbon of the alkynyl ligand. The C-C bond is then formed between the alpha carbons of the alkynyl and adjacent hydrocarbyl ligands.

  7. A comparison on the marginal gap of two base metal alloys (Minalux, VeraBond2 during firing cycles of porcelain

    Directory of Open Access Journals (Sweden)

    Monzavi A.

    2004-06-01

    Full Text Available Statement of Problem: Nowadays economical issues on high gold alloys have changed the practice of metal-ceramic restorations toward base-metal alloys. Minalux is one of the base-metal alloys produced in Iran. Marginal fitness is of high importance to be evaluated in dental alloys."nPurpose: The aim of the present study was to compare the marginal adaptation of two base-metal alloys, Minalux (Mavadkaran Co. Iran and VeraBond2 (Aibadent Co. USA during firing cycles of porcelain. Materials and Methods: In an experimental study 24 standard brass dies, with 135° chamfer finishing line were fabricated by Computer Numeric Controlled (CNC milling machine. The samples were randomly divided in two groups, A and B, 12 in each. Following wax-up, the samples were equally cast with two mentioned alloys. In each group, there were 4 controlled samples, which proceeded to firing cycle without veneering porcelain. Scanning electron microscope (SEM measurements of marginal gap from buccal and lingual aspects were performed after 4 stages of casting, degassing, porcelain application and glazing. The data were analyzed using Four-way ANOVA and multiple comparative test based on Tukey criteria. Results: The findings of this study revealed that there was no significant difference in the marginal gap of Minalux (31.10±7.8u.m and VeraBond2 (30.27±6.96u.m with confidence level at 0.95 (P=0.43. For both alloys the greatest gap was observed after degassing stage (P<0.05. Porcelain and porcelain veneering proximity caused significant changes in the marginal gap of Minalux castings (P<0.05, however, such changes did not occur in VeraBond2 (PO.05."nConclusion: Based on the findings of this study, the marginal gaps of two base metal alloys, Minalux and VeraBond2, were proved to be identical and that of the Minalux alloy existed in the range of acceptable clinical application. It was also concluded that Minalux dental alloys could provide proper marginal adaptation.

  8. Microstructure and strength of TiAl/40Cr joint diffusion bonded with vanadium-copper filler metal

    Institute of Scientific and Technical Information of China (English)

    何鹏; 冯吉才; 钱乙余; 张炳刚

    2002-01-01

    Intermetallics TiAl was diffusion-bonded to steel 40Cr in vacuum furnace with interlayer V/Cu. The results show that infinite sosoloid that made for bond performance is formed at the interface of V/Cu and Cu/40Cr, and three acting layers are formed at the interface of TiAl/V including Ti3Al layer at TiAl side, intermittent V5Al8 layer in the middle and Ti-V sosoloid at V side. Fragile reactors V5Al8 arising at the interface lead to bad performance of joints, and the strength of the joint is 200MPa, while it was still higher than the strength of the joint intermetallics TiAl to 40Cr steel diffusion-bonded directly. Intermetallic TiAl and 40Cr steel are diffusion-bonded successfully by using a composite isolation layer V/Cu.

  9. Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide

    Science.gov (United States)

    Scott, Carl D.; Smalley, Richard E.

    2003-01-01

    The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

  10. Solid-state Photochemical [2+2] Cycloaddition Reaction of Hydrogen-Bonded Zn(II) Metal Complex Containing Several Parallel C=C Bonds

    Indian Academy of Sciences (India)

    ABDUL MALIK P PEEDIKAKKAL

    2017-02-01

    A 2D hydrogen-bonded dinuclear Zn(II) complex, [{Zn(H₂O) ₃ (bpe) ₂} ₂ (bpe)](NO₃) ₄・3bpe・14H₂O,1 (bpe = 4,4_-bipyridylethylene) containing coordination complex cations, [{Zn(H₂O) ₃ (bpe) ₂} ₂ (μ-bpe)] ⁴⁺and free bpe and lattice water molecules shows face-to-face, π ・ ・ ・ π stacking of two of the four free bpemolecules with coordinated bpe ligands. Out of eight bpe molecules, six are aligned in parallel fashion withshort C・ ・ ・ C distances of 3.663–3.814Å and they undergo photochemical [2+2] cycloaddition reaction. The photoreaction conducted on ground sample of 1 in the solid-state affords rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) product in 75% yield. The molecular movement of free bpe molecules was tested by conducting thephotoreaction in ground sample and heated sample of single crystals. The photoreactivity study of 1 indicates that the free bpe molecules are locked between the cationic [{Zn(H₂O) ₃ (bpe) ₂} ₂ (bpe)] ⁴⁺ layers.

  11. Actinide metals with multiple bonds to carbon: synthesis, characterization, and reactivity of U(IV) and Th(IV) bis(iminophosphorano)methandiide pincer carbene complexes.

    Science.gov (United States)

    Ma, Guibin; Ferguson, Michael J; McDonald, Robert; Cavell, Ronald G

    2011-07-18

    Treatment of ThCl(4)(DME)(2) or UCl(4) with 1 equiv of dilithiumbis(iminophosphorano) methandiide, [Li(2)C(Ph(2)P═NSiMe(3))(2)] (1), afforded the chloro actinide carbene complexes [Cl(2)M(C(Ph(2)P═NSiMe(3))(2))] (2 (M = Th) and 3 (M = U)) in situ. Stable PCP metal-carbene complexes [Cp(2)Th(C(Ph(2)P═NSiMe(3))(2))] (4), [Cp(2)U(C(Ph(2)P═NSiMe(3))(2))] (5), [TpTh(C(Ph(2)P═NSiMe(3))(2))Cl] (6), and [TpU(C(Ph(2)P═NSiMe(3))(2))Cl] (7) were generated from 2 or 3 by further reaction with 2 equiv of thallium(I) cyclopentadienide (CpTl) in THF to yield 4 or 5 or with 1 equiv of potassium hydrotris(pyrazol-1-yl) borate (TpK) also in THF to give 6 or 7, respectively. The derivative complexes were isolated, and their crystal structures were determined by X-ray diffraction. All of these U (or Th)-carbene complexes (4-7) possess a very short M (Th or U)═carbene bond with evidence for multiple bond character. Gaussian 03 DFT calculations indicate that the M═C double bond is constructed by interaction of the 5f and 6d orbitals of the actinide metal with carbene 2p orbitals of both π and σ character. Complex 3 reacted with acetonitrile or benzonitrile to cyclo-add C≡N to the U═carbon double bond, thereby forming a new C-C bond in a new chelated quadridentate ligand in the bridged dimetallic complexes (9 and 10). A single carbon-U bond is retained. The newly coordinated uranium complex dimerizes with one equivalent of unconverted 3 using two chlorides and the newly formed imine derived from the nitrile as three connecting bridges. In addition, a new crystal structure of [CpUCl(3)(THF)(2)] (8) was determined by X-ray diffraction.

  12. Synthesis of 2-oxindoles via 'transition-metal-free' intramolecular dehydrogenative coupling (IDC) of sp2 C–H and sp3 C–H bonds

    Science.gov (United States)

    Bhunia, Subhajit

    2016-01-01

    Summary The synthesis of a variety of 2-oxindoles bearing an all-carbon quaternary center at the pseudo benzylic position has been achieved via a ‘transition-metal-free’ intramolecular dehydrogenative coupling (IDC). The construction of 2-oxindole moieties was carried out through formation of carbon–carbon bonds using KOt-Bu-catalyzed one pot C-alkylation of β-N-arylamido esters with alkyl halides followed by a dehydrogenative coupling. Experimental evidences indicated toward a radical-mediated path for this reaction. PMID:27559367

  13. Inserting CO2 into Aryl C-H Bonds of Metal-Organic Frameworks: CO2 Utilization for Direct Heterogeneous C-H Activation.

    Science.gov (United States)

    Gao, Wen-Yang; Wu, Haifan; Leng, Kunyue; Sun, Yinyong; Ma, Shengqian

    2016-04-25

    Described for the first time is that carbon dioxide (CO2 ) can be successfully inserted into aryl C-H bonds of the backbone of a metal-organic framework (MOF) to generate free carboxylate groups, which serve as Brønsted acid sites for efficiently catalyzing the methanolysis of epoxides. The work delineates the very first example of utilizing CO2 for heterogeneous C-H activation and carboxylation reactions on MOFs, and opens a new avenue for CO2 chemical transformations under mild reaction conditions.

  14. Synthesis, structure, and reactivity of iridium perfluorocarbene complexes: regio- and stereo-specific addition of HCl across a metal carbon double bond.

    Science.gov (United States)

    Yuan, Jian; Bourgeois, Cheryl J; Rheingold, Arnold L; Hughes, Russell P

    2015-12-07

    Reductive activation of an α-fluorine in the perfluoroalkyl complexes Cp*(L)(i)Ir-CF2RF using Mg/graphite leads to perfluorocarbene complexes Cp*(L)Ir[double bond, length as m-dash]CFRF (L = CO, PMe3; RF = CF3, C2F5, C6F5). New complexes E-Cp*(PMe3)Ir[double bond, length as m-dash]CFC2F5 and E-Cp*(CO)Ir[double bond, length as m-dash]CFC6F5 have been characterized by single crystal X-ray diffraction studies, and a comparison of metric parameters with previously reported analogues is reported. Experimental NMR and computational DFT (B3LYP/LACV3P**++) studies agree that for Ir[double bond, length as m-dash]CFRF complexes (RF = CF3, CF2CF3) the thermodynamic preference for the E or Z isomer depends on the steric requirements of ligand L; when L = CO the Z-isomer (F cis to Cp*) is preferred and for L = PMe3 the E-isomer is preferred. When reduction of the precursors is carried out in the dark the reaction is completely selective to produce E- or Z-isomers. Exposure of solutions of these compounds to ambient light results in slow conversion to a photostationary non-equilibrium mixture of E and Z isomers. In the dark, these E/Z mixtures convert thermally to their preferred E or Z equilibrium geometries in an even slower reaction. A study of the temperature dependent kinetics of this dark transformation allows ΔG(‡)298 for rotation about the Ir[double bond, length as m-dash]CFCF3 double bond to be experimentally determined as 25 kcal mol(-1); a DFT/B3LYP/LACV3P**++ calculation of this rotation barrier is in excellent agreement (27 kcal mol(-1)) with the experimental value. Reaction of HCl with toluene solutions of Cp*(L)Ir[double bond, length as m-dash]CFRF (L = CO, PMe3) or Cp*(CO)Ir[double bond, length as m-dash]C(CF3)2 at low temperature resulted in regiospecific addition of HCl across the metal carbon double bond, ultimately yielding Cp*(L)Ir(CHFRF)Cl and Cp*(CO)Ir[CH(CF3)2]Cl. Reaction of HCl with single E or Z diastereomers of Cp*(L)Ir[double bond, length as m

  15. Multicenter bond index analysis of influence of metal cations on the aromaticity of aromatic amino acids: Phenylalanine and tyrosine

    Science.gov (United States)

    Pakiari, A. H.; Farrokhnia, M.; Azami, S. M.

    2008-05-01

    In order to provide insight into the influence of metal cations on the aromaticity of amino acids, evaluation of six-center delocalization indices is accomplished in the context of quantum theory of atoms in molecules (QTAIM). Aromaticity of two amino acids, phenylalanine and tyrosine, is investigated as typical amino acids containing aromatic ring in their isolated state and complexed by some metal cations. The results showed that the metal cations affect the most important three connectivities differently. Also, it is shown that the existence of metal cations can increase two-center delocalization in certain parts of the aromatic rings.

  16. Adsorptive Removal of Pharmaceuticals and Personal Care Products from Water with Functionalized Metal-organic Frameworks: Remarkable Adsorbents with Hydrogen-bonding Abilities

    Science.gov (United States)

    Seo, Pill Won; Bhadra, Biswa Nath; Ahmed, Imteaz; Khan, Nazmul Abedin; Jhung, Sung Hwa

    2016-10-01

    Adsorption of typical pharmaceuticals and personal care products (PPCPs) (such as naproxen, ibuprofen and oxybenzone) from aqueous solutions was studied by using the highly porous metal-organic framework (MOF) MIL-101 with and without functionalization. Adsorption results showed that MIL-101s with H-donor functional groups such as -OH and -NH2 were very effective for naproxen adsorption, despite a decrease in porosity, probably because of H-bonding between O atoms on naproxen and H atoms on the adsorbent. For this reason, MIL-101 with two functional groups capable of H-bonding (MIL-101-(OH)2) exhibited remarkable adsorption capacity based on adsorbent surface area. The favorable contributions of -OH and -(OH)2 on MIL-101 in the increased adsorption of ibuprofen and oxybenzone (especially based on porosity) confirmed again the importance of H-bonding mechanism. The adsorbent with the highest adsorption capacity, MIL-101-OH, was very competitive when compared with carbonaceous materials, mesoporous materials, and pristine MIL-101. Moreover, the MIL-101-OH could be recycled several times by simply washing with ethanol, suggesting potential application in the adsorptive removal of PPCPs from water.

  17. Snapshots of the ``breaking” of the H-H bond in the oxidative addition of H2 to a metal centre

    Indian Academy of Sciences (India)

    Saikat Dutta; Balaji R Jagirdar

    2006-11-01

    Three new monocationic molecular hydrogen complexes of ruthenium of the type trans-[RuCl(2-H2)(PP)2][BF4] (PP = bis-1,2(diarylphosphino)ethane, aryl = -fluorobenzyl, benzyl, -methylbenzyl) have been prepared by protonating the precursor hydride complexes trans-[RuCl(H)(PP)2] using HBF4.Et2O. These three dihydrogen complexes are quite stable and have been isolated in the solid state. The intact nature of the H-H bond in these derivatives has been established from the short spin-lattice relaxation times (1, ) and the observation of substantial H, D couplings in the HD isotopomers. The H-H bond distances (HH, Å) increase from 0.97 to 1.01 Å as the electron donor ability of the diphosphine ligand increases from the -fluorobenzyl to the benzyl to the -methylbenzyl moiety. These dihydrogen complexes constitute the initial stages of elongation of the H-H bond enroute to its cleavage along the reaction coordinate for the oxidative addition of H2 to a metal centre.

  18. Adsorptive Removal of Pharmaceuticals and Personal Care Products from Water with Functionalized Metal-organic Frameworks: Remarkable Adsorbents with Hydrogen-bonding Abilities

    Science.gov (United States)

    Seo, Pill Won; Bhadra, Biswa Nath; Ahmed, Imteaz; Khan, Nazmul Abedin; Jhung, Sung Hwa

    2016-01-01

    Adsorption of typical pharmaceuticals and personal care products (PPCPs) (such as naproxen, ibuprofen and oxybenzone) from aqueous solutions was studied by using the highly porous metal-organic framework (MOF) MIL-101 with and without functionalization. Adsorption results showed that MIL-101s with H-donor functional groups such as –OH and –NH2 were very effective for naproxen adsorption, despite a decrease in porosity, probably because of H-bonding between O atoms on naproxen and H atoms on the adsorbent. For this reason, MIL-101 with two functional groups capable of H-bonding (MIL-101-(OH)2) exhibited remarkable adsorption capacity based on adsorbent surface area. The favorable contributions of –OH and –(OH)2 on MIL-101 in the increased adsorption of ibuprofen and oxybenzone (especially based on porosity) confirmed again the importance of H-bonding mechanism. The adsorbent with the highest adsorption capacity, MIL-101-OH, was very competitive when compared with carbonaceous materials, mesoporous materials, and pristine MIL-101. Moreover, the MIL-101-OH could be recycled several times by simply washing with ethanol, suggesting potential application in the adsorptive removal of PPCPs from water. PMID:27695005

  19. Transition metal-catalyzed oxidative double bond cleavage of simple and bio-derived alkenes and unsaturated fatty acids

    NARCIS (Netherlands)

    Spannring, Peter; Bruijnincx, Pieter C. A.; Weckhuysen, Bert. M.; Klein Gebbink, Bert

    2014-01-01

    The oxidative cleavage of the C=C double bond in unsaturated fatty acids into aldehydes or carboxylic acids is a reaction of current interest in biomass valorization. The products of this reaction, which is currently being performed on an industrial scale by means of ozonolysis, can be applied for t

  20. Structures, bonding and reactivity of iron and manganese high-valent metal-oxo complexes: A computational investigation

    Indian Academy of Sciences (India)

    Bhawana Pandey; Azaj Ansari; Nidhi Vyas; Gopalan Rajaraman

    2015-02-01

    Iron and manganese ions with terminal oxo and hydroxo ligands are discovered as key intermediates in several synthetic and biochemical catalytic cycles. Since many of these species possess vigorous catalytic abilities, they are extremely transient in nature and experiments which probe the structure and bonding on such elusive species are still rare. We present here comprehensive computational studies on eight iron and manganese oxo and hydroxo (FeIII/IV/V-O, FeIII-OH and MnIII/IV/V-O, MnIII-OH) species using dispersion corrected (B3LYP-D2) density functional method. By computing all the possible spin states for these eight species, we set out to determine the ground state S value of these species; and later on employing MO analysis, we have analysed the bonding aspects which contribute to the high reactivity of these species. Direct structural comparison to iron and manganese-oxo species are made and the observed similarity and differences among them are attributed to the intricate metal–oxygen bonding. By thoroughly probing the bonding in all these species, their reactivity towards common chemical reactions such as C–H activation and oxygen atom transfer are discussed.

  1. Photochemical route to actinide-transition metal bonds: synthesis, characterization and reactivity of a series of thorium and uranium heterobimetallic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Ward, Ashleigh; Lukens, Wayne; Lu, Connie; Arnold, John

    2014-04-01

    A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium and cobalt. Complexes incorporating the binucleating ligand N[-(NHCH2PiPr2)C6H4]3 and Th(IV) (4) or U(IV) (5) with a carbonyl bridged [Co(CO)4]- unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)4]. Irradiation of the isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively rare class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl is accompanied by coordination of a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) and 3.0319(7) for the thorium and uranium complexes, respectively, were observed. The solution state behavior of the thorium complexes was evaluated using 1H, 1H-1H COSY, 31P and variable-temperature NMR spectroscopy. IR, UV-Vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.

  2. Pressure-induced structural transition and thermodynamic properties of RhN2 and the effect of metallic bonding on its hardness

    Institute of Scientific and Technical Information of China (English)

    Liu Jun; Kuang Xiao-Yu; Wang Zhen-Hua; Huang Xiao-Fen

    2012-01-01

    The elastic constant,structural phase transition,and effect of metallic bonding on the hardness of RhN2 under high pressure are investigated through the first-principles calculation by means of the pseudopotential plane-wave method.Three structures are chosen to investigate for RhN2,namely,simple hexagonal P6/mmm (denoted as SH),orthorhombic Pnnm (marcasite),and simple tetragonal P4/mbm (denoted as ST).Our calculations show that the SH phase is energetically more stable than the other two phases at zero pressure.On the basis of the third-order BirchMurnaghan equation of states,we find that the phase transition pressures from an SH to a marcasite structure and from a marcasite to an ST structure are 1.09 GPa and 354.57 GPa,respectively.Elastic constants,formation enthalpies,shear modulus,Young's modulus,and Debye temperature of RhN2 are derived.The calculated values are,generally speaking,in good agreement with the previous theoretical results.Meanwhile,it is found that the pressure has an important influence on physical properties.Moreover,the effect of metallic bonding on the hardness of RhN2 is investigated.This is a quantitative investigation on the structural properties of RhN2,and it still awaits experimental confirmation.

  3. NMR J-Coupling Constants of Tl-Pt Bonded Metal Complexes in Aqueous Solution: Ab Initio Molecular Dynamics and Localized Orbital Analysis.

    Science.gov (United States)

    Ducati, Lucas C; Marchenko, Alex; Autschbach, Jochen

    2016-11-21

    The influence of solvent (water) coordination and dynamics on the electronic structure and nuclear magnetic resonance (NMR) indirect spin-spin coupling (J-coupling) constants in a series of Tl-Pt bonded complexes is investigated using Kohn-Sham (KS) Car-Parrinello molecular dynamics (CPMD) and relativistic hybrid KS NMR calculations with and without coordination to water. Coordination of the Tl center by water molecules has a dramatic impact on (1)J(Tl-Pt) and other J-coupling constants. It is shown that a previous computational study of the same complexes using static optimized structures and nonhybrid functionals was correct about the important role of the solvent but obtained reasonable agreement with experimental NMR data because of a cancellation of substantial errors. For example, the CPMD trajectories show that on average the inner coordination shell of Tl is not saturated, as previously assumed, which leads to poor agreement with experiment when the J-coupling constants are averaged over the CPMD trajectories using NMR calculations with nonhybrid functionals. The combination of CPMD with hybrid KS NMR calculations provides a much more realistic computational model that reproduces the large magnitudes of (1)J(Tl-Pt) and the correct trends for other coupling constants. An analysis of (1)J(Tl-Pt) in terms of localized orbitals shows that the presence of coordinating water molecules increases the capacity for covalent interactions between Tl and Pt. There is pronounced multicenter bonding along the metal-metal axis of the complexes.

  4. Pressure-induced structural transition and thermodynamic properties of RhN2 and the effect of metallic bonding on its hardness

    Science.gov (United States)

    Liu, Jun; Kuang, Xiao-Yu; Wang, Zhen-Hua; Huang, Xiao-Fen

    2012-08-01

    The elastic constant, structural phase transition, and effect of metallic bonding on the hardness of RhN2 under high pressure are investigated through the first-principles calculation by means of the pseudopotential plane-wave method. Three structures are chosen to investigate for RhN2, namely, simple hexagonal P6/mmm (denoted as SH), orthorhombic Pnnm (marcasite), and simple tetragonal P4/mbm (denoted as ST). Our calculations show that the SH phase is energetically more stable than the other two phases at zero pressure. On the basis of the third-order Birch—Murnaghan equation of states, we find that the phase transition pressures from an SH to a marcasite structure and from a marcasite to an ST structure are 1.09 GPa and 354.57 GPa, respectively. Elastic constants, formation enthalpies, shear modulus, Young's modulus, and Debye temperature of RhN2 are derived. The calculated values are, generally speaking, in good agreement with the previous theoretical results. Meanwhile, it is found that the pressure has an important influence on physical properties. Moreover, the effect of metallic bonding on the hardness of RhN2 is investigated. This is a quantitative investigation on the structural properties of RhN2, and it still awaits experimental confirmation.

  5. Effects of enamel sealing on shear bond strength and the adhesive remnant index : Study of three fluoride-releasing adhesives in combination with metal and ceramic brackets.

    Science.gov (United States)

    Hofmann, Elisabeth; Elsner, Laura; Hirschfelder, Ursula; Ebert, Thomas; Hanke, Sebastian

    2017-01-01

    Selected combinations of materials were used to create tooth-adhesive-bracket complexes to evaluate shear bond strength (SBS) and the adhesive remnant index (ARI) with regard to enamel sealing. Four adhesive systems also appropriate for use as enamel sealants were combined with four bracket types, resulting in 16 adhesive-bracket combinations, each of which was tested on 15 permanent bovine incisors. Sealant-adhesives included two recently introduced fluoride-releasing systems (Riva bond LC(®) and go!(®)), one established primer (Opal(®) Seal™), and one commonly used adhesive as control (Transbond™ XT). Brackets included two metal (discovery(®) by Dentaurum and Sprint(®)) and two ceramic (discovery(®) pearl and GLAM(®)) systems. After embedding the bovine teeth, bonding the brackets to their surface, and storing the resultant samples as per DIN 13990-2 with modifications, an SBS test was performed by applying the shear force directly at the bracket base in an incisocervical direction. Then the ARI scores were determined. Discovery(®) + Transbond™ XT yielded the highest (47.2 MPa) and GLAM(®) + go!(®) the lowest (17.0 MPa) mean SBS values. Significant differences (p < 0.0001) were found between metal and ceramic brackets of the same manufacturers (Dentaurum and Forestadent). Our ratings of the failure modes upon debonding predominantly yielded ARI 0 or 1. The high SBS values and low ARI scores observed with discovery(®) + Transbond XT™ were reflected in a high rate of enamel fracture, which occurred on 11 of the 15 tooth specimens in this group. All sealant-bracket combinations were found to yield levels of SBS adequate for clinical application. SBS values and ARI scores varied significantly depending on which sealant-brackets were used.

  6. Residual Stress and Bonding Strength in the ElectricalSialon Ceramics Joint Made by Using the Brazing Metal Layer

    OpenAIRE

    Kimura, Mitsuhiko; Asari, Koichi; GOTO, Shoji; Aso, Setsuo

    2002-01-01

    Electrical Sialons which have some TiN contents were joined with Ag-Cu-Ti active brazing metal layer having a thickness from 30μm to 400μm at a temperature from 1113 K to 1213 K in a vacuum. Residual stress in the brazed joint specimens was not observed when the thickness of brazing metal layer was 30 μ m. However, the residual stress of 80 MPa was detected when the thickness of brazing metal layer increased up to 400μm. When the brazing temperature was 1113 K, four-point bending strengths of...

  7. On the Dehydrocoupling of Alkenylacetylenes Mediated by Various Samarocene Complexes: A Charming Story of Metal Cooperativity Revealing a Novel Dual Metal σ-Bond Metathesis Type of Mechanism (DM|σ-BM

    Directory of Open Access Journals (Sweden)

    Christos E. Kefalidis

    2015-12-01

    Full Text Available The prevailing reductive chemistry of Sm(II has been accessed and explored mostly by the use of samarocene precursors. The highly reducing character of these congeners, along with their Lewis acidity and predominantly ionic bonding, allows for the relatively facile activation of C–H bonds, as well as peculiar transformations of unsaturated substrates (e.g., C–C couplings. Among other important C–C coupling reactions, the reaction of phenylacetylene with different mono- or bimetallic samarocene complexes affords trienediyl complexes of the type {[(C5Me52Sm]2(µ-η2:η2-PhC4Ph}. In contrast, when t-butylacetylene is used, uncoupled monomers of the type (C5Me52Sm(C≡C–tBu were obtained. Although this type of reactivity may appear to be simple, the mechanism underlying these transformations is complex. This conclusion is drawn from the density functional theory (DFT mechanistic studies presented herein. The operating mechanistic paths consist of: (i the oxidation of each samarium center and the concomitant double reduction of the alkyne to afford a binuclear intermediate; (ii the C–H scission of the acetylinic bond that lies in between the two metals; (iii a dual metal σ-bond metathesis (DM|σ-SBM process that releases H2; and eventually (iv the C–C coupling of the two bridged μ-alkynides to give the final bimetallic trienediyl complexes. For the latter mechanistic route, the experimentally used phenylacetylene was considered first as well as the aliphatic hex-1-yne. More interestingly, we shed light into the formation of the mono(alkynide complex, being the final experimental product of the reaction with t-butylacetylene.

  8. Structure and Bonding in Some Gd(Ⅲ) Metal Complexes Studied by Three-Dimensional X-Ray Analysis and 155Gd M(o)ssbauer Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique.The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, 155Gd, and 237Np M(o)ssbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds.In this article, the crystal structures of two novel Gd(Ⅲ) acetylacetonato complexes, Gd(pta)3·2H2O (pta=1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione) and Gd(bfa)3·2H2O (bfa=1, 1, 1-trifluoro-4-phenyl-2-4-butanedione) were reported.Though both of them were dihydrate and had distorted square antiprismatical structure, Gd(pta)3·2H2O crystallizes in the P 21/ n (#14) monoclinic space group and its lattice parameters are a =1.4141(6) nm, b =1.0708(3) nm, c =2.2344(4) nm, β=95.24(2)°, and Gd(bfa)3·2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a=1.322(1) nm, b =2.295(1) nm, c =1.0786(8) nm.In the meantime, the authors had finished a systematic investigation on the 155Gd M(o)ssbauer isomer shift (δ) of various Gd(Ⅲ) metal complexes having a different coordination number (C.N.) and different ratios coordinating oxygen to nitrogen.A tendency for the δ value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed.This indicated that the Gd-O and/or Gd-N bond in the investigated Gd(Ⅲ) metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the ligands donating electrons to 6s, 5d, and 4f orbitals of Gd.

  9. Bonding property of Cu/Mo/Cu cladding metal materials by hot rolling%Cu/Mo/Cu轧制复合界面的结合特性

    Institute of Scientific and Technical Information of China (English)

    张兵; 王快社; 孙院军; 王莎

    2011-01-01

    The Cu/Mo/Cu cladding metal materials were made by hot rolling. The interface structure, fracture characteristic and the effect of rolling process parameters on bond strength were studied by optical microscope, scanning electron microscope and electron-tensile tester. The results show that the bonding interface of composite materials is tight when deformation rate is 55% for a pass with heat-treatment at 750 ℃ for 8 min, the maximum value of shearing strength is 77 Mpa. The micro-structure of Mo layer is compressed fibrous and uniform distribution. The micro-structure of Cu layer is isometric crystal. The grain size is increased from the interface to the surface, and unevenly distributed. The mechanism of bonding is typically split bonding and mechanical interlocking.%采用轧制方法制备Cu/Mo/Cu复合材料,利用金相显微镜、扫描电镜和电子拉伸机等研究Cu/Mo/Cu复合材料的界面结构、断裂特点和工艺参数对结合强度的影响.结果表明:轧制前经(750℃,8 min)热处理,道次变形量为55%,复合材料的界面结合紧密,最大剪切强度为77 MPa;钼层金属显微组织呈扁平纤维状,组织较为均匀,铜层金属的晶粒呈等轴状,由界面至表面晶粒逐渐增大,且分布很不均匀;复合机制为典型的裂口结合和机械啮合.

  10. Laser-Direct Writing of Silver Metal Electrodes on Transparent Flexible Substrates with High-Bonding Strength.

    Science.gov (United States)

    Zhou, Weiping; Bai, Shi; Ma, Ying; Ma, Delong; Hou, Tingxiu; Shi, Xiaomin; Hu, Anming

    2016-09-21

    We demonstrate a novel approach to rapidly fabricate conductive silver electrodes on transparent flexible substrates with high-bonding strength by laser-direct writing. A new type of silver ink composed of silver nitrate, sodium citrate, and polyvinylpyrrolidone (PVP) was prepared in this work. The role of PVP was elucidated for improving the quality of silver electrodes. Silver nanoparticles and sintered microstructures were simultaneously synthesized and patterned on a substrate using a focused 405 nm continuous wave laser. The writing was completed through the transparent flexible substrate with a programmed 2D scanning sample stage. Silver electrodes fabricated by this approach exhibit a remarkable bonding strength, which can withstand an adhesive tape test at least 50 times. After a 1500 time bending test, the resistance only increased 5.2%. With laser-induced in-situ synthesis, sintering, and simultaneous patterning of silver nanoparticles, this technology is promising for the facile fabrication of conducting electronic devices on flexible substrates.

  11. A New Activation Method for Electroless Metal Plating: Palladium Laden via Bonding with Self-Assembly Monolayers

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition. A closely packed electroless copper film with strong adhesion is successfully fonned by AFM observation. XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs.

  12. Neutral transition metal hydrides as acids in hydrogen bonding and proton transfer: media polarity and specific solvation effects.

    Science.gov (United States)

    Levina, Vladislava A; Filippov, Oleg A; Gutsul, Evgenii I; Belkova, Natalia V; Epstein, Lina M; Lledos, Agusti; Shubina, Elena S

    2010-08-18

    Structural, spectroscopic, and electronic features of weak hydrogen-bonded complexes of CpM(CO)(3)H (M = Mo (1a), W (1b)) hydrides with organic bases (phosphine oxides R(3)PO (R = n-C(8)H(17), NMe(2)), amines NMe(3), NEt(3), and pyridine) are determined experimentally (variable temperature IR) and computationally (DFT/M05). The intermediacy of these complexes in reversible proton transfer is shown, and the thermodynamic parameters (DeltaH degrees , DeltaS degrees ) of each reaction step are determined in hexane. Assignment of the product ion pair structure is made with the help of the frequency calculations. The solvent effects were studied experimentally using IR spectroscopy in CH(2)Cl(2), THF, and CH(3)CN and computationally using conductor-like polarizable continuum model (CPCM) calculations. This complementary approach reveals the particular importance of specific solvation for the hydrogen-bond formation step. The strength of the hydrogen bond between hydrides 1 and the model bases is similar to that of the M-H...X hydrogen bond between 1 and THF (X = O) or CH(3)CN (X = N) or between CH(2)Cl(2) and the same bases. The latter competitive weak interactions lower the activities of both the hydrides and the bases in the proton transfer reaction. In this way, these secondary effects shift the proton transfer equilibrium and lead to the counterintuitive hampering of proton transfer upon solvent change from hexane to moderately polar CH(2)Cl(2) or THF.

  13. The cryogenic bonding evaluation at the metallic-composite interface of a composite overwrapped pressure vessel with additional impact investigation

    Science.gov (United States)

    Clark, Eric A.

    A bonding evaluation that investigated the cryogenic tensile strength of several different adhesives/resins was performed. The test materials consisted of 606 aluminum test pieces adhered to a wet-wound graphite laminate in order to simulate the bond created at the liner-composite interface of an aluminum-lined composite overwrapped pressure vessel. It was found that for cryogenic applications, a flexible, low modulus resin system must be used. Additionally, the samples prepared with a thin layer of cured resin -- or prebond -- performed significantly better than those without. It was found that it is critical that the prebond surface must have sufficient surface roughness prior to the bonding application. Also, the aluminum test pieces that were prepared using a surface etchant slightly outperformed those that were prepared with a grit blast surface finish and performed significantly better than those that had been scored using sand paper to achieve the desired surface finish. An additional impact investigation studied the post impact tensile strength of composite rings in a cryogenic environment. The composite rings were filament wound with several combinations of graphite and aramid fibers and were prepared with different resin systems. The rings were subjected to varying levels of Charpy impact damage and then pulled to failure in tension. It was found that the addition of elastic aramid fibers with the carbon fibers mitigates the overall impact damage and drastically improves the post-impact strength of the structure in a cryogenic environment.

  14. Establishment and Validation of a Non-Radioactive Method for In Vitro Transcription Assay Using Primer Extension and Quantitative Real Time PCR.

    Science.gov (United States)

    Wang, Juan; Zhao, Shasha; Zhou, Ying; Wei, Yun; Deng, Wensheng

    2015-01-01

    Primer extension-dependent in vitro transcription assay is one of the most important approaches in the research field of gene transcription. However, conventional in vitro transcription assays incorporates radioactive isotopes that cause environmental and health concerns and restricts its scope of application. Here we report a novel non-radioactive method for in vitro transcription analysis by combining primer extension with quantitative real time PCR (qPCR). We show that the DNA template within the transcription system can be effectively eliminated to a very low level by our specially designed approach, and that the primers uniquely designed for primer extension and qPCR can specifically recognize the RNA transcripts. Quantitative PCR data demonstrate that the novel method has successfully been applied to in vitro transcription analyses using the adenovirus E4 and major late promoters. Furthermore, we show that the TFIIB recognition element inhibits transcription of TATA-less promoters using both conventional and nonradioactive in vitro transcription assays. Our method will benefit the laboratories that need to perform in vitro transcription but either lack of or choose to avoid radioactive facilities.

  15. Use of a non-radioactive hybridisation assay for direct detection of gram-negative bacteria carrying TEM beta-lactamase genes in infected urine.

    Science.gov (United States)

    Carter, G I; Towner, K J; Pearson, N J; Slack, R C

    1989-02-01

    DNA in infected urines from 81 patients with urinary tract infection was hybridised directly with a non-radioactive DNA probe specific for bacterial genes coding for TEM-type beta-lactamase. The results were assessed by means of a computerised image analysis system and compared with those obtained following isolation of the infecting organism, conventional sensitivity testing and isoelectric focusing (IEF) procedures for the detection of TEM-type beta-lactamase. Of the 27 ampicillin-resistant gram-negative organisms isolated in pure culture from the urines, 14 were shown by both hybridisation and IEF to carry a gene for TEM beta-lactamase production. Only four discordant results were obtained: three "false positive" direct hybridisation results, one due to urine pigmentation, and one, possibly, to a TEM beta-lactamase gene which was not being expressed, and one "false negative" result due to insufficient cell numbers in the urine. The system is capable of screening large numbers of samples and is applicable to any gene for which a suitable DNA probe is available.

  16. Novel, Non-Radioactive, Simple and Multiplex PCR-cRFLP Methods for Genotyping Human SP-A and SP-D Marker Alleles

    Directory of Open Access Journals (Sweden)

    Susan DiAngelo

    1999-01-01

    Full Text Available We have previously identified an allele of the human SP-A2 gene that occurs with greater frequency in an RDS population [12]. Because of the importance of SP-A in normal lung function and its newly emerging role in innate host defense and regu-lation of inflammatory processes, we wish to better characterize genotypes of both SP-A1 and SP-A2 genes. It has been determined that SP-D shares similar roles in immune response. Therefore, in this report we 1 describe a novel, non radioactive PCR based-cRFLP method for genotyping both SP-A and SP-D; 2 describe two previously unpublished biallelic polymorphisms within the SP-D gene; 3 present the partial sequence of one new SP-A1 allele (6A14 and describe other new SP-A1 and SP-A2 alleles; and 4 describe additional methodologies for SP-A genotype assessment. The ability to more accurately and efficiently genotype samples from individuals with various pulmonary diseases will facilitate population and family based association studies. Genetic poly-morphisms may be identified that partially explain individual disease susceptibility and/or treatment effectiveness.

  17. Discovery of novel inhibitors of human S-adenosylmethionine decarboxylase based on in silico high-throughput screening and a non-radioactive enzymatic assay.

    Science.gov (United States)

    Liao, Chenzeng; Wang, Yanlin; Tan, Xiao; Sun, Lidan; Liu, Sen

    2015-06-01

    Natural polyamines are small polycationic molecules essential for cell growth and development, and elevated level of polyamines is positively correlated with various cancers. As a rate-limiting enzyme of the polyamine biosynthetic pathway, S-adenosylmethionine decarboxylase (AdoMetDC) has been an attractive drug target. In this report, we present the discovery of novel human AdoMetDC (hAdoMetDC) inhibitors by coupling computational and experimental tools. We constructed a reasonable computational structure model of hAdoMetDC that is compatible with general protocols for high-throughput drug screening, and used this model in in silico screening of hAdoMetDC inhibitors against a large compound library using a battery of computational tools. We also established and validated a simple, economic, and non-radioactive enzymatic assay, which can be adapted for experimental high-throughput screening of hAdoMetDC inhibitors. Finally, we obtained an hAdoMetDC inhibitor lead with a novel scaffold. This study provides both new tools and a new lead for the developing of novel hAdoMetDC inhibitors.

  18. Interrelationships among biological activity, disulfide bonds, secondary structure, and metal ion binding for a chemically synthesized 34-amino-acid peptide derived from alpha-fetoprotein.

    Science.gov (United States)

    MacColl, R; Eisele, L E; Stack, R F; Hauer, C; Vakharia, D D; Benno, A; Kelly, W C; Mizejewski, G J

    2001-10-01

    A 34-amino-acid peptide has been chemically synthesized based on a sequence from human alpha-fetoprotein. The purified peptide is active in anti-growth assays when freshly prepared in pH 7.4 buffer at 0.20 g/l, but this peptide slowly becomes inactive. This functional change is proven by mass spectrometry to be triggered by the formation of an intrapeptide disulfide bond between the two cysteine residues on the peptide. Interpeptide cross-linking does not occur. The active and inactive forms of the peptide have almost identical secondary structures as shown by circular dichroism (CD). Zinc ions bind to the active peptide and completely prevents formation of the inactive form. Cobalt(II) ions also bind to the peptide, and the UV-Vis absorption spectrum of the cobalt-peptide complex shows that: (1) a near-UV sulfur-to-metal-ion charge-transfer band had a molar extinction coefficient consistent with two thiolate bonds to Co(II); (2) the lowest-energy visible d-d transition maximum at 659 nm, also, demonstrated that the two cysteine residues are ligands for the metal ion; (3) the d-d molar extinction coefficient showed that the metal ion-ligand complex was in a distorted tetrahedral symmetry. The peptide has two cysteines, and it is speculated that the other two metal ion ligands might be the two histidines. The Zn(II)- and Co(II)-peptide complexes had similar peptide conformations as indicated by their ultraviolet CD spectra, which differed very slightly from that of the free peptide. Surprisingly, the cobalt ions acted in the reverse of the zinc ions in that, instead of stabilizing anti-growth form of the peptide, they catalyzed its loss. Metal ion control of peptide function is a saliently interesting concept. Calcium ions, in the conditions studied, apparently do not bind to the peptide. Trifluoroethanol and temperature (60 degrees C) affected the secondary structure of the peptide, and the peptide was found capable of assuming various conformations in solution

  19. Theoretical investigation of paramagnetic NMR shifts in transition metal acetylacetonato complexes: analysis of signs, magnitudes, and the role of the covalency of ligand-metal bonding.

    Science.gov (United States)

    Pritchard, Ben; Autschbach, Jochen

    2012-08-06

    Ligand chemical shifts are calculated and analyzed for three paramagnetic transition metal tris-acetylacetonato (acac) complexes, namely high-spin Fe(III) and Cr(III), and low-spin Ru(III), using scalar relativistic density functional theory (DFT). The signs and magnitudes of the paramagnetic NMR ligand chemical shifts are directly related to the extent of covalent acac oxygen-to-metal σ donation involving unoccupied metal valence d(σ) acceptor orbitals. The role of delocalization of metal-centered spin density over the ligand atoms plays a minor secondary role. Of particular interest is the origin of the sign and magnitude of the methyl carbon chemical shift in the acac ligands, and the role played by the DFT delocalization error when calculating such shifts. It is found that the α versus β spin balance of oxygen σ donation to metal valence d acceptor orbitals is responsible for the sign and the magnitude of the ligand methyl carbon chemical shift. A problematic case is the methyl carbon shift of Fe(acac)(3). Most functionals produce shifts in excess of 1400 ppm, whereas the experimental shift is approximately 279 ppm. Range-separated hybrid functionals that are optimally tuned for Fe(acac)(3) based on DFT energetic criteria predict a lower limit of about 2000 ppm for the methyl carbon shift of the high-spin electronic configuration. Since the experimental value is based on a very strongly broadened signal it is possibly unreliable.

  20. Comparative study on the tensile bond strength and marginal fit of complete veneer cast metal crowns using various luting agents: An in vitro study

    Directory of Open Access Journals (Sweden)

    B Devi Parameswari

    2016-01-01

    Full Text Available Introduction: Several commercially available luting agents are used to cement the dental restorations such as intra-coronal, extra-coronal, and fixed partial dentures. Tensile bond strength (TBS and accurate marginal fit are the essential factors to determine the good clinical results in fixed prosthesis. The retentivity of the luting cements is assessed by their adhesive capacity over the tooth surface and metal surface. Generally, the adhesive ability has been evaluated with in vitro testing, with tensile bond tests. The failure of fixed prosthesis may be happened as a result of incomplete seating during cementation. Most research on cementation of crowns relates seating failure to the thickness of the cement film. Materials and Methods: The study is divided into four groups with 10 samples for each of the luting cement taken up for testing TBS and four groups with 5 samples for each luting agent chosen for assessing marginal fit. The results were tabulated and statistically analyzed. Results: In this in vitro study, the TBS of luting cements, and marginal fit in relation to luting cements were tested by using appropriate testing devices. The TBS of cement is measured using universal testing machine, and the results are tabulated. The marginal gap that exists between the margin of the cast metal crown, and the finish line is measured using travelling microscope before and after cementation. The difference between these two values gives the discrepancy that is due to the film thickness of cement used for luting the restoration. Summary and Conclusion: The TBS value of zinc phosphate cement and glass ionomer cement were found to be almost same. The chemical adhesiveness of the glass ionomer with calcium ions of enamel and dentin may be the attributed reason (ionic bonding. In this study, the polycarboxylate is the one that showed low TBS, and it may be attributed to the weakness of the cement due to reduced film thickness, though this cement has

  1. All-metal electride molecules CuAg@Ca7M (M = Be, Mg, and Ca) with multi-excess electrons and all-metal polyanions: molecular structures and bonding modes as well as large infrared nonlinear optical responses.

    Science.gov (United States)

    He, Hui-Min; Li, Ying; Sun, Wei-Ming; Wang, Jia-Jun; Wu, Di; Zhong, Rong-Lin; Zhou, Zhong-Jun; Li, Zhi-Ru

    2016-02-14

    All-metal electride molecules, CuAg@Ca7M (M = Be, Mg and Ca), have been designed and researched in theory for the first time. In these molecules, a pull-push electron relay occurs. Unusually, the all-metal polyanions of fourfold negatively charged [Cu-Ag-Be/Mg](4-) and [Cu-Ag](4-) with 4 extra electrons gained from Ca atoms push the remaining valence electrons of the Ca atoms forming the multi-excess electrons (Ne = 10/12). Therefore, these molecules can be described as salt-like [(Ca(2+))7(CuAgM)(4-)] + 10e(-) (M = Be and Mg) and [(Ca(2+))8(CuAg)(4-)] + 12e(-). In these salt-like molecules, there are extraordinary covalent bonding modes, which include 2c-2e/3c-2e σ-bonding in the polyanions and the Ca(2+) cations sharing the diffuse multi-excess electrons. For an intriguing nonlinear optical (NLO) response, these all-metal electride molecules display large electronic first hyperpolarizabilities (β0), thus a new class of NLO molecules, all-metal electride NLO molecules, emerge. Moreover, it is also found that manipulating the atomic number and position of M is a new strategy to enhance β0. As a result, CuAg@Ca7Mg(1) exhibits a considerable β0 (1.43 × 10(4) au), which is 16 times the β0 sum of two isolated CuAg and Ca7Mg(1) subunits, and this deeply reveals the fundamental origin of the considerable β0, namely, the multi-excess electrons generated by the subunit interaction. These all-metal electride molecules have the infrared (IR) transparent region of 1.3-6 μm, and hence are new IR NLO molecules. In addition the electronic contribution, β0, the large effects of vibrations on the static first hyperpolarizabilities of these all-metal electride molecules are also estimated. Thus, this study opens the new research field of all-metal electride IR NLO molecules.

  2. Silica chemically bonded N-propyl kriptofix 21 and 22 with immobilized palladium nanoparticles for solid phase extraction and preconcentration of some metal ions.

    Science.gov (United States)

    Ghaedi, Mehrorang; Niknam, Khodabakhsh; Zamani, Saeed; Larki, Habib Abasi; Roosta, Mostafa; Soylak, Mustafa

    2013-08-01

    Silica gel chemically bonded N-propyl kriptofix 21 (SBNPK 21) and N-propyl kriptofix 22 (SBNPK 22) and subsequently immobilized with palladium nanoparticles (PNP-SBNPK 21 and PNP-SBNPK 22) to produce two new complexing lipophilic materials. Then these novel sorbents were applied for the enrichment of some metal ions and their subsequent determination by flame atomic absorption spectroscopy (FAAS). The influences of the variables including pH, amount of solid phase, sample flow rate, eluent conditions and sample volume on the metal ion recoveries were investigated. The detection limit of proposed method was in the interval 2.1-2.3 and 1.7-2.8 ng mL(-1) for PNP-SBNPK 21 and PNP-SBNPK 22 respectively, while the preconcentration factor was 80 for two sorbents. The relative standard deviations of recoveries were between 1.23-1.31 and 1.28-1.49 for PNP-SBNPK 21 and PNP-SBNPK 22 respectively. The method has high sorption-preconcentration efficiency even in the presence of various interfering ions. Due to the reasonable selectivity of proposed method, the relative standard deviation of recoveries of all understudied metal ions in some complicated matrices was less than 3.0%.

  3. Design and synthesis of multidentate ligands via metal promoted C-N bond formation processes and their coordination chemistry

    Indian Academy of Sciences (India)

    Kunal K Kamar; Amrita Saha; Sreebrata Goswami

    2002-08-01

    This presentation reports some novel examples of organic ring amination reactions via metal mediation. The organic transformations are highly regioselective and can be controlled by the proper selection of the mediator complex. The two isomeric organic ligands viz. HL1 and HL2 were isolated in their pure states by the removal of the metal ions. These were fully characterized. The ligand HL1 has low , 8.5. Upon deprotonation, it behaves as a potential bis chelating N,N,N-donors. The coordination chemistry of the HL1 ligand involving some 3-metal ions is described. Two unusual low-spin complexes of manganese(II) and iron(III) are reported. The ferric complex displayed a rhombic EPR while, the corresponding manganese compound showed a complex pattern due to hyperfine coupling. All the complexes displayed large number of redox responses. A brief mention about the future projection of this work is noted.

  4. Chemistry of glass-ceramic to metal bonding for header applications. I. Effect of treatments on Inconel 718 and Hastelloy C-276 metallic surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Kramer, D P; Craven, S M; Schneider, R E; Moddeman, W E; Brohard, D W

    1984-02-02

    Auger electron spectroscopy and depth Auger profiling were used to study the surfaces of Inconel 718 and Hastelloy C-276. The metal surfaces were processed in the same manner as is presently being used in the manufacturing of glass-ceramic headers. At each step in the process, samples were studied with Auger spectroscopy to determine their resultant elemental surface composition and film thickness. In addition, the effect of a final plasma cleaning operation on the metal surface was examined. The results show that the type and concentration of surface species and the thickness of the surface oxides are dependent on the processing technique.

  5. IRMPD spectroscopy of metalated flavins: structure and bonding of Mq+-lumichrome complexes (Mq+ = Li+-Cs+, Ag+, Mg2+)

    NARCIS (Netherlands)

    Günther, A.; Nieto, P.; Berden, G.; Oomens, J.; Dopfer, O.

    2014-01-01

    Infrared multiphoton dissociation (IRMPD) spectra of mass selected isolated metal-lumichrome ionic complexes, Mq+LCn with Mq+ = Li+, Na+, K+, Rb+, Cs+, Ag+ (n = 1), and Mg2+ (n = 2), are recorded in the fingerprint range. The complexes are generated in an electrospray ionization source coupled to an

  6. Ligand field splittings in core level transitions for transition metal (TM) oxides: Tanabe-Sugano diagrams and (TM) dangling bonds in vacated O-atom defects

    Science.gov (United States)

    Lucovsky, Gerry; Wu, Kun; Pappas, Brian; Whitten, Jerry

    2013-04-01

    Defect states in the forbidden band-gap below the conduction band edge are active as electron traps in nano-grain high-) transition metal (TM) oxides with thickness >0.3 nm, e.g., ZrO2 and HfO2. These oxides have received considerable attention as gate-dielectrics in complementary metal oxide semiconductor (CMOS) devices, and more recently are emerging as candidates for charge storage and memory devices. To provide a theoretical basis for device functionality, ab-initio many-electron theory is combined with X-ray absorption spectroscopy (XAS) to study O K edge and TM core level transitions. These studies identify ligand field splittings (ΔLF) for defect state features,. When compared with those obtained from O-atom and TM-atom core spectroscopic transitions, this provides direct information about defect state sun-nm bonding arrangements. comparisons are made for (i) elemental TiO2 and Ti2O3 with different formal ionic charges, Ti4+ and Ti3+ and for (ii) Magneli Phase alloys, TinO2n-1, n is an integer 9>=n>3, and (TiO2)x(HfO2)1-x alloys. The alloys display multi-valent behavior from (i) different ionic-charge states, (ii} local bond-strain, and (iii) metallic hopping transport. The intrinsic bonding defects in TM oxides are identified as pairs of singly occupied dangling bonds. For 6-fold coordinated Ti-oxides defect excited states in 2nd derivative O K pre-edge spectra are essentially the same as single Ti-atom d2 transitions in Tanabe-Sugano (T-S) diagrams. O-vacated site defects in 8-fold coordinated ZrO2 and HfO2 are described by d8 T-S diagrams. T-S defect state ordering and splittings are functions of the coordination and symmetry of vacated site bordering TM atoms. ΔLF values from the analysis of T-S diagrams indicate medium range order (MRO) extending to 3rd and 4th nearest-neighbor (NN) TM-atoms. Values are different for 6-fold Ti, and 8-fold ZrO2 and HfO2, and scale inversely with differences in respective formal ionic radii. O-vacated site bonding

  7. An empirical method for the estimation of yield strength on bonds and strands of expanded metal meshes

    Directory of Open Access Journals (Sweden)

    Dimas José Smith-López

    2015-01-01

    Full Text Available El proceso de fabricación de mallas de metal expandido se basa en la expansión en línea de láminas de metal parcialmente cortadas, creando un patrón formado por venas y nodos. Después de este proceso las propiedades mecánicas del metal base cambian, especialmente en los nodos. Debido al tamaño de las venas y los nodos es difícil cuantificar la cantidad de trabajo en frío que estos experimentan, en consecuencia las propiedades mecánicas en las mallas finales son difíciles de predecir. Este trabajo presenta un método empírico para la estimación del esfuerzo de fluencia de mallas de metal expandido estándar y aplanado, correlacionando la microdureza Vickers con el esfuerzo de fluencia mediante la relación de Tabor. Adicionalmente, se evalúa el efecto de diferentes tratamientos térmicos sobre el esfuerzo de fluencia del metal expandido. Los resultados muestran que los esfuerzos de fluencia estimados a través de la ecuación de Tabor concuerdan con los obtenidos a través de ensayos mecánicos para diferentes niveles de trabajo en frío. Adicionalmente, se obtuvo que el proceso de manufactura introduce en el material cierto nivel de heterogeneidad y anisotropía, y que se requieren tratamientos térmicos con largos tiempos de exposición para reducir los efectos del trabajo en frío.

  8. Silica chemically bonded N-propyl kriptofix 21 and 22 with immobilized palladium nanoparticles for solid phase extraction and preconcentration of some metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Ghaedi, Mehrorang, E-mail: m_ghaedi@mail.yu.ac.ir [Chemistry Department, Yasouj University, Yasouj, 75914-353 (Iran, Islamic Republic of); Niknam, Khodabakhsh, E-mail: niknam@pgu.ac.ir [Chemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr, 75169 (Iran, Islamic Republic of); Zamani, Saeed; Abasi Larki, Habib [Chemistry Department, Islamic Azad University, Omidiyeh Branch, Omidiyeh (Iran, Islamic Republic of); Roosta, Mostafa [Chemistry Department, Yasouj University, Yasouj, 75914-353 (Iran, Islamic Republic of); Soylak, Mustafa [Chemistry Department, University of Erciyes, 38039 Kayseri (Turkey)

    2013-08-01

    Silica gel chemically bonded N-propyl kriptofix 21 (SBNPK 21) and N-propyl kriptofix 22 (SBNPK 22) and subsequently immobilized with palladium nanoparticles (PNP-SBNPK 21 and PNP-SBNPK 22) to produce two new complexing lipophilic materials. Then these novel sorbents were applied for the enrichment of some metal ions and their subsequent determination by flame atomic absorption spectroscopy (FAAS). The influences of the variables including pH, amount of solid phase, sample flow rate, eluent conditions and sample volume on the metal ion recoveries were investigated. The detection limit of proposed method was in the interval 2.1–2.3 and 1.7–2.8 ng mL{sup −1} for PNP-SBNPK 21 and PNP-SBNPK 22 respectively, while the preconcentration factor was 80 for two sorbents. The relative standard deviations of recoveries were between 1.23–1.31 and 1.28–1.49 for PNP-SBNPK 21 and PNP-SBNPK 22 respectively. The method has high sorption-preconcentration efficiency even in the presence of various interfering ions. Due to the reasonable selectivity of proposed method, the relative standard deviation of recoveries of all understudied metal ions in some complicated matrices was less than 3.0%. Highlights: • Highly selective sorbents for solid phase extraction were synthesized. • The method has been successfully applied for the determination of trace metals ions. • Excellent properties of the sorbent have been illustrated in detail.

  9. A new consideration on reinforcement distribution in the different planes of nanostructured metal matrix composite sheets prepared by accumulative roll bonding (ARB)

    Energy Technology Data Exchange (ETDEWEB)

    Yazdani, Ali [Department of Materials Science and Engineering, School of Engineering, Shiraz University, Zand Blvd., 7134851154 Shiraz (Iran, Islamic Republic of); Salahinejad, E., E-mail: erfan.salahinejad@gmail.com [Department of Materials Science and Engineering, School of Engineering, Shiraz University, Zand Blvd., 7134851154 Shiraz (Iran, Islamic Republic of); Moradgholi, J.; Hosseini, M. [Department of Materials Science and Engineering, School of Engineering, Shiraz University, Zand Blvd., 7134851154 Shiraz (Iran, Islamic Republic of)

    2011-09-29

    Highlights: > Al-B{sub 4}C composites can be successfully prepared by accumulative roll bonding (ARB). > TEM reveals the development of nanostructures in Al-B{sub 4}C composites processed by ARB. > The reinforcement distribution in the RD-ND planes is more uniform than the TD-ND planes. - Abstract: Recently, a number of novel methods based on accumulative roll bonding (ARB) have been introduced to produce particulate metal matrix composites. Nonetheless, the microstructure uniformity from the reinforcement distribution viewpoint in the different planes of ARBed composite sheets has not been focused up to date. This paper aims to compare the evolution of the B{sub 4}C particles distribution in nanostructured Al-10 vol.% B{sub 4}C composites prepared by ARB in the rolling direction-normal direction (RD-ND) and transverse direction-normal direction (TD-ND) planes. From optical microscopic evaluations quantified by the radial distribution function analysis, it is realized that the homogeneity in the RD-ND planes is in excess of the TD-ND planes. In addition, transmission electron microscopy reveals the development of nanostructures in the Al matrix after seven ARB passes.

  10. High-performance resin-bonded magnets produced from zinc metal-coated Sm2(Fe0.9Co0.1)17Nx fine powders

    Science.gov (United States)

    Noguchi, K.; Machida, K.; Yamamoto, K.; Nishimura, M.; Adachi, G.

    1999-09-01

    Fine powders of Sm2(Fe0.9Co0.1)17Nx (x=˜3) with particle sizes (d) around 1 μm as coated with zinc metal produced via the photodecomposition of diethylzinc [Zn(C2H5)2], which still provided high remanence (Br) and coercivity (Hcj) values of ˜1.43 T and ˜0.85 MAm-1, were molded to compression-type resin bonded Zn/Sm2(Fe0.9Co0.1)17Nx magnets with density values of ˜6.33 g cm-3. By optimizing the preparation conditions such as grinding, surface coating, and molding for them, the highest maximum energy product of (BH)max=186 kJm-3 for Hcj=0.73 MAm-1 was recorded among all kinds of the Sm-Fe-N based magnets reported to date. Furthermore, the excellent aging behavior of the bonded Zn/Sm2(Fe0.9Co0.1)17Nx magnets was observed after standing in air at ˜393 K and the thermal coefficient for permanent magnet was evaluated to be α(Br)=-0.04% K-1.

  11. Brain uptake of a non-radioactive pseudo-carrier and its effect on the biodistribution of [(18)F]AV-133 in mouse brain.

    Science.gov (United States)

    Wu, Xianying; Zhou, Xue; Zhang, Shuxian; Zhang, Yan; Deng, Aifang; Han, Jie; Zhu, Lin; Kung, Hank F; Qiao, Jinping

    2015-07-01

    9-[(18)F]Fluoropropyl-(+)-dihydrotetrabenazine ([(18)F]AV-133) is a new PET imaging agent targeting vesicular monoamine transporter type II (VMAT2). To shorten the preparation of [(18)F]AV-133 and to make it more widely available, a simple and rapid purification method using solid-phase extraction (SPE) instead of high-pressure liquid chromatography (HPLC) was developed. The SPE method produced doses containing the non-radioactive pseudo-carrier 9-hydroxypropyl-(+)-dihydrotetrabenazine (AV-149). The objectives of this study were to evaluate the brain uptake of AV-149 by UPLC-MS/MS and its effect on the biodistribution of [(18)F]AV-133 in the brains of mice. The mice were injected with a bolus including [(18)F]AV-133 and different doses of AV-149. Brain tissue and blood samples were harvested. The effect of different amounts of AV-149 on [(18)F]AV-133 was evaluated by quantifying the brain distribution of radiolabelled tracer [(18)F]AV-133. The concentrations of AV-149 in the brain and plasma were analyzed using a UPLC-MS/MS method. The concentrations of AV-149 in the brain and plasma exhibited a good linear relationship with the doses. The receptor occupancy curve was fit, and the calculated ED50 value was 8.165mg/kg. The brain biodistribution and regional selectivity of [(18)F]AV-133 had no obvious differences at AV-149 doses lower than 0.1mg/kg. With increasing doses of AV-149, the brain biodistribution of [(18)F]AV-133 changed significantly. The results are important to further support that the improved radiolabelling procedure of [(18)F]AV-133 using an SPE method may be suitable for routine clinical application. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. The Variety of Carbon-Metal Bonds inside Cu-ZSM-5 Zeolites: A Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Takashi Yumura

    2010-04-01

    Full Text Available Large-scale density functional theory calculations (DFT found various types of binding of an unsaturated hydrocarbon (C2H2 and C2H4 to a ZSM-5 zeolite extraframework copper cation. We employed the DFT calculations based on the B3LYP functional to obtain local minima of an unsaturated hydrocarbon adsorbed on one or two copper cations embedded inside ZSM-5, and then compared their stabilization energies. The DFT results show that the stabilization energies are strongly dependent on the copper coordination environment as well as configurations of two copper cations. Consequently, the inner copper-carbon bonds are influenced substantially by a nanometer-scale cavity of ZSM-5.

  13. An analysis of formic acid decomposition on metal surfaces by the bond-order-conservation-Morse-potential approach

    Science.gov (United States)

    Shustorovich, Evgeny; Bell, Alexis T.

    1989-11-01

    The bond-order-conservation-Morse-potential method, extended to treat the heat of chemisorption of bidentate species and of molecular radicals, has been used to analyze the energetics of formic acid decomposition at low coverages on Ag(111), Ni(111), and Fe/W(110) surfaces. These calculations project that on all three surfaces formate species are produced, with a parallel formation of formyl plus hydroxyl species on Ni and Fe/W. Bidentate coordination of formate species is preferred over monodentate coordination, the energy difference increasing in the order Ag < Ni < Fe/W. The decomposition of formate species leads to atomic hydrogen and CO 2 on Ag, whereas on Ni and especially on Fe/W formate decomposition leads mainly to atomic oxygen and formyl species, the latter of which decomposes practically without activation to CO and atomic hydrogen. The findings of this study are in general agreement with experimental observation.

  14. A formal high oxidation state inverse-sandwich diuranium complex. A new route to f-block-metal bonds

    Energy Technology Data Exchange (ETDEWEB)

    Patel, Dipti; Moro, Fabrizio; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry

    2011-10-24

    Reduction of [U(Ts{sup Xy})(Cl)(thf)] [Ts{sup Xy}=HC(SiMe{sub 2}NAr){sub 3}; Ar=3,5-Me{sub 2}C{sub 6}H{sub 3}] with KC{sub 8} in toluene afforded the new arene-bridged diuranium complex 2, whereas reduction of 1 in aliphatic hydrocarbons resulted in C-N bond activation and formation of an imido-aryl complex, which exhibits an unusual ferromagnetic interaction between the two uranium centers. The synthetic utility of 2 was demonstrated by the first synthesis of a U-Co complex, [U(Ts{sup Xy})Co(CO){sub 3}(PPh{sub 3})].

  15. ScRe 2O 6: A new ternary oxide with metallic Re-Re-bonds and a ferromagnetic component above room temperature

    Science.gov (United States)

    Mikhailova, D.; Ehrenberg, H.; Miehe, G.; Trots, D.; Hess, C.; Schneider, R.; Fuess, H.

    2008-01-01

    AbstactA new phase in the system Sc-Re-O, ScRe 2O 6, was synthesized for the first time in sealed silica tubes and its crystal structure was solved by single crystal X-ray diffraction. ScRe 2O 6 (space group P2 1/ a, a=5.6176(9) Å, b=4.7970(9) Å, c=7.5143(16) Å, β=97.49(2)°, Z=2) crystallizes in a new rutile-type structure, derived from three formula units by splitting the cation site in ratio 1:2. Re 2O 10 clusters can be considered as structural units, in which the rhenium ions form pairs by metallic bonds with a Re-Re distance of 2.523(3) Å. No phase transition was observed in the temperature range of 295-930 K. The compound has a metallic character of conductivity in the temperature range of at least 4-950 K and displays a ferromagnetic ordering above room temperature ("unconventional Re-magnetism").

  16. Structural, spectroscopic, and multiconfigurational quantum chemical investigations of the electron-rich metal-metal triple-bonded Tc(2)X(4)(PMe(3))(4) (X = Cl, Br) complexes.

    Science.gov (United States)

    Poineau, Frederic; Forster, Paul M; Todorova, Tanya K; Gagliardi, Laura; Sattelberger, Alfred P; Czerwinski, Kenneth R

    2010-07-19

    The compounds Tc(2)Cl(4)(PMe(3))(4) and Tc(2)Br(4)(PMe(3))(4) were formed from the reaction between (n-Bu(4)N)(2)Tc(2)X(8) (X = Cl, Br) and trimethylphosphine. The Tc(II) dinuclear species were characterized by single-crystal XRD, UV-visible spectroscopy, and cyclic voltammetry techniques, and the results are compared to those obtained from density functional theory and multiconfigurational (CASSCF/CASPT2) quantum chemical studies. The compound Tc(2)Cl(4)(PMe(3))(4) crystallizes in the monoclinic space group C2/c [a = 17.9995(9) A, b = 9.1821(5) A, c = 17.0090(9) A, beta = 115.4530(10) degrees ] and is isostructural to M(2)Cl(4)(PMe(3))(4) (M = Re, Mo, W) and to Tc(2)Br(4)(PMe(3))(4). The metal-metal distance (2.1318(2) A) is similar to the one found in Tc(2)Br(4)(PMe(3))(4) (2.1316(5) A). The calculated molecular structures of the ground states are in excellent agreement with the structures determined experimentally. Calculations of effective bond orders for Tc(2)X(8)(2-) and Tc(2)X(4)(PMe(3))(4) (X = Cl, Br) indicate stronger pi bonds in the Tc(2)(4+) core than in Tc(2)(6+) core. The electronic spectra were recorded in benzene and show a series of low intensity bands in the range 10 000-26 000 cm(-1). Assignment of the bands as well as computing their excitation energies and intensities were performed at both TD-DFT and CASSCF/CASPT2 levels of theory. Calculations predict that the lowest energy band corresponds to the delta* --> sigma* transition, the difference between calculated and experimental values being 228 cm(-1) for X = Cl and 866 cm(-1) for X = Br. The next bands are attributed to delta* --> pi*, delta --> sigma*, and delta --> pi* transitions. The cyclic voltammograms exhibit two reversible waves and indicate that Tc(2)Br(4)(PMe(3))(4) exhibits more positive oxidation potentials than Tc(2)Cl(4)(PMe(3))(4.) This phenomenon is discussed and ascribed to stronger metal (d) to halide (d) back bonding in the bromo complex. Further analysis indicates that Tc

  17. Oxidative cross-coupling of pyridine N-oxides and ethers between C(sp(2))-H/C(sp(3))-H bonds under transition-metal-free conditions.

    Science.gov (United States)

    Sun, Wei; Xie, Zuguang; Liu, Jie; Wang, Lei

    2015-04-21

    A novel and efficient method based on the cross-coupling reactions of pyridine N-oxides with ethers between C(sp(2))-H/C(sp(3))-H bonds in the presence of TBHP was developed. The strategy provides an alternative approach to the pyridine moiety under transition-metal-free conditions.

  18. C(sp₃)-H bond activation with triel metals: indium and gallium zwitterions through internal hydride abstraction in rigid salan ligands.

    Science.gov (United States)

    Maudoux, Nicolas; Fang, Jian; Roisnel, Thierry; Dorcet, Vincent; Maron, Laurent; Carpentier, Jean-François; Sarazin, Yann

    2014-06-16

    The hydropyrimidine salan (salan=N,N'-dimethyl-N,N'-bis[(2-hydroxyphenyl)methylene]-1,2-diaminoethane) proteo-ligands with a rigid backbone {ON^(CH2)^NO}H2 react with M(CH2SiMe3)3 (M=Ga, In) to yield the zwitterions {ON^(CH(+))^NO}M(-)(CH2SiMe3)2 (M=Ga, 2; In, 3) by abstraction of a hydride from the ligand backbone followed by elimination of dihydrogen. By contrast, with Al2Me6, the neutral-at-metal bimetallic complex [{ON^(CH2)^NO}AlMe]2 ([1]2) is obtained quantitatively. The formation of indium zwitterions is also observed with sterically more encumbered ligands containing o-Me substituents on the phenolic rings, or an N (CHPh) N moiety in the heterocyclic core. Overall, the ease of C(sp3)-H bond activation follows the order Al≪Gametal-hydride species. DFT calculations indicate that the systems {ON^(CH2)^NO}H2+M(CH2SiMe3)3 (M=Al, Ga, In) all initially lead to the formation of the neutral monophenolate dihydrocarbyl species through a single protonolysis. From here, the thermodynamic product, the model neutral-at-metal complex 1, is formed in the case of aluminum after a second protonolysis. On the other hand, lower activation energy pathways lead to the generation of zwitterionic complexes 2 and 3 in the cases of gallium and indium, and the formation of these zwitterions obeys a strict kinetic control; the computations suggest that, as inferred from the experimental data, the reaction proceeds through an instable metal-hydride species, which could not be isolated synthetically.

  19. SLC30A3 (ZnT3 oligomerization by dityrosine bonds regulates its subcellular localization and metal transport capacity.

    Directory of Open Access Journals (Sweden)

    Gloria Salazar

    Full Text Available Non-covalent and covalent homo-oligomerization of membrane proteins regulates their subcellular localization and function. Here, we described a novel oligomerization mechanism affecting solute carrier family 30 member 3/zinc transporter 3 (SLC30A3/ZnT3. Oligomerization was mediated by intermolecular covalent dityrosine bonds. Using mutagenized ZnT3 expressed in PC12 cells, we identified two critical tyrosine residues necessary for dityrosine-mediated ZnT3 oligomerization. ZnT3 carrying the Y372F mutation prevented ZnT3 oligomerization, decreased ZnT3 targeting to synaptic-like microvesicles (SLMVs, and decreased resistance to zinc toxicity. Strikingly, ZnT3 harboring the Y357F mutation behaved as a "gain-of-function" mutant as it displayed increased ZnT3 oligomerization, targeting to SLMVs, and increased resistance to zinc toxicity. Single and double tyrosine ZnT3 mutants indicate that the predominant dimeric species is formed between tyrosine 357 and 372. ZnT3 tyrosine dimerization was detected under normal conditions and it was enhanced by oxidative stress. Covalent species were also detected in other SLC30A zinc transporters localized in different subcellular compartments. These results indicate that covalent tyrosine dimerization of a SLC30A family member modulates its subcellular localization and zinc transport capacity. We propose that dityrosine-dependent membrane protein oligomerization may regulate the function of diverse membrane protein in normal and disease states.

  20. Cooperative catalysis of metal and O-H···O/sp3-C-H···O two-point hydrogen bonds in alcoholic solvents: Cu-catalyzed enantioselective direct alkynylation of aldehydes with terminal alkynes.

    Science.gov (United States)

    Ishii, Takaoki; Watanabe, Ryo; Moriya, Toshimitsu; Ohmiya, Hirohisa; Mori, Seiji; Sawamura, Masaya

    2013-09-27

    Catalyst-substrate hydrogen bonds in artificial catalysts usually occur in aprotic solvents, but not in protic solvents, in contrast to enzymatic catalysis. We report a case in which ligand-substrate hydrogen-bonding interactions cooperate with a transition-metal center in alcoholic solvents for enantioselective catalysis. Copper(I) complexes with prolinol-based hydroxy amino phosphane chiral ligands catalytically promoted the direct alkynylation of aldehydes with terminal alkynes in alcoholic solvents to afford nonracemic secondary propargylic alcohols with high enantioselectivities. Quantum-mechanical calculations of enantiodiscriminating transition states show the occurrence of a nonclassical sp(3)-C-H···O hydrogen bond as a secondary interaction between the ligand and substrate, which results in highly directional catalyst-substrate two-point hydrogen bonding.

  1. Bonding of SiC and Ti by means of aluminum alloy (6063) insert metal; Aluminium gokin (6063) wo insert zai to shita SiC to Ti no setsugo

    Energy Technology Data Exchange (ETDEWEB)

    Tsuchitori, I. [Hiroshima Industrial Research Institute, Hiroshima (Japan); Kikuchi, Y.; Ozawa, M. [Osaka University, Osaka (Japan). Joining and Welding Research Institute; Haji, A. [Seishin Tetrpack, Co., Kobe (Japan)

    1998-03-20

    The high bonding strength was obtained when SiC ceramic was joined with Titanium under vacuum by using the insert metal of 6063 alloy. The ultimate tensile strength of the bonded specimen of SiC to Ti by 6063 insert alloy showed up to 125 MPa. It was bonded under the conditions of 813K-60 min by diffusion bonding method in vacuum. Pure aluminum was used to as the stress relieving of joint interface. The fractured surfaces between SiC and 6063 alloy was observed and analyzed by SEM-EDX, Mg was enriched on the surface. The enriched regions were near the boundary between 6063 alloy and SiC. Then Oxygen is enriched in any place. It was found by TEM-EDX investigation that the region of the oxide of aluminum existed at the interface. 18 refs., 10 figs., 3 tabs.

  2. Ruthenate-ferrites AMRu{sub 5}O{sub 11} (A = Sr, Ba; M = Ni, Zn). Distortion of kagome nets via metal-metal bonding

    Energy Technology Data Exchange (ETDEWEB)

    Shlyk, Larysa; Strobel, Sabine; Niewa, Rainer [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie; Schleid, Thomas

    2012-11-01

    Crystals of the three novel oxorhutenates SrNiRu{sub 5}O{sub 11} (a = 11.7374(2) Aa, c = 13.2088(4) Aa), SrZnRu{sub 5}O{sub 11} (a = 11.7271(2) Aa, c = 13.4246(4) Aa), and Sr{sub 0.63(1)}Ba{sub 0.37}ZnRu{sub 5}O{sub 11} (a = 11.7245(4) Aa, 13.5268(4)) were obtained applying a flux-growth technique. A superstructure of the R-type ferrite crystal structure with doubled hexagonal a-axis (space group P6{sub 3}/m, Z = 8) originates from Ru-Ru pair formation within the kagome nets extending in (001). No indication for an intermixing of 3d metals at the Ru sites was observed. (orig.)

  3. Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

    KAUST Repository

    Minenkov, Yury

    2015-08-27

    The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.

  4. Synthesis and structural characterization of some compounds involving metal-metal bonding of tellurium, bismuth, and zirconium. [Complex with hexaoxadiazabicyclohexacosane potassium

    Energy Technology Data Exchange (ETDEWEB)

    Cisar, A.

    1978-08-01

    Salts of the tritelluride(2-) and tetrabismuthide(2-) ions with the complex cation (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo(8.8.8)hexacosane potassium) (abbreviated crypt K/sup +/) were synthesized and their structures determined. The dark red (crypt K/sup +/)/sub 2/ Te/sub 3//sup 2 -/.en was produced by oxidation of K/sub 2/Te with an excess of tellurium and the very dark green (crypt K/sup +/)/sub 2/Bi/sub 4//sup 2 -/ was produced by the reaction of either K/sub 3/Bi, K/sub 3/Bi/sub 2/, K/sub 5/Bi/sub 4/, or KBi/sub 2/ with solvent. (Crypt K/sup +/)/sub 2/Te/sub 3//sup 2 -/.en crystallizes in the trigonal space group P3/sub 2/ with a = 12.229(1)A and c = 31.242(4)A and three formula units per cell. The Te/sub 3//sup 2 -/ ion has bond lengths of 2.692(5) and 2.720(4)A, an angle of 113.1(2)/sup 0/, and a hydrogen bond to an en molecule with d/sub Te-N/ = 3.46(6)A. (Crypt K/sup +/)/sub 2/Bi/sub 4//sup 2 -/ crystallizes in the triclinic space group P anti 1 with a = 11.604(4)A, b = 11.796(4)A, c = 11.096(3)A, ..cap alpha.. = 98.12(3)/sup 0/, ..beta.. = 98.02(3)/sup 0/, and ..gamma.. = 61.37(3)/sup 0/ and one formula per cell. The structure of the more common form of stoichiometric ZrCl/sub 2/, which is isostructural with 3R-MoS/sub 2/, (R3m, with a = 3.3819(3) and c = 19.378(3)A) was refined from single crystal data. A cluster form which is isostructural with Zr/sub 6/I/sub 12/ was found and its structure determined from powder data. 6T-Zr/sub 1+x/Cl/sub 2/ was determined from an intergrown ''single'' crystal containing 3R-ZrCl/sub 2/, to be a 6-slab superstructure based on a 2H/sub b/-MoS/sub 2/ type subcell with a = 3.3791(4) and c = 38.713(7)A. Another, 18T-Zr/sub 1+y/Cl/sub 2/, found in both single crystals and powder, has an 18 slab repeat sequence with a = 3.3820(2) and c = 116.21(2)A. The third is of unknown composition and exhibits ordering along a.

  5. Probing the presence of multiple metal-metal bonds in technetium chlorides by X-ray absorption spectroscopy: implications for synthetic chemistry.

    Science.gov (United States)

    Poineau, Frederic; Johnstone, Erik V; Forster, Paul M; Ma, Longzou; Sattelberger, Alfred P; Czerwinski, Kenneth R

    2012-09-03

    The cesium salts of [Tc(2)X(8)](3-) (X = Cl, Br), the reduction product of (n-Bu(4)N)[TcOCl(4)] with (n-Bu(4)N)BH(4) in THF, and the product obtained from reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C have been characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. For the [Tc(2)X(8)](3-) anions, the Tc-Tc separations found by EXAFS spectroscopy (2.12(2) Å for both X = Cl and Br) are in excellent agreement with those found by single-crystal X-ray diffraction (SCXRD) measurements (2.117[4] Å for X = Cl and 2.1265(1) Å for X = Br). The Tc-Tc separation found by EXAFS in these anions is slightly shorter than those found in the [Tc(2)X(8)](2-) anions (2.16(2) Å for X = Cl and Br). Spectroscopic and SCXRD characterization of the reduction product of (n-Bu(4)N)[TcOCl(4)] with (n-Bu(4)N)BH(4) are consistent with the presence of dinuclear species that are related to the [Tc(2)Cl(8)](n-) (n = 2, 3) anions. From these results, a new preparation of (n-Bu(4)N)(2)[Tc(2)Cl(8)] was developed. Finally, EXAFS characterization of the product obtained from reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C indicates the presence of amorphous α-TcCl(3). The Tc-Tc separation (i.e., 2.46(2) Å) measured in this compound is consistent with the presence of Tc═Tc double bonds in the [Tc(3)](9+) core.

  6. Finding high-temperature superconductors by metallizing theσ-bonding electrons%通过金属化s电子寻找高温超导体

    Institute of Scientific and Technical Information of China (English)

    高淼; 卢仲毅; 向涛

    2015-01-01

    Raising superconducting transition temperature (Tc) is an important task of fun-damental research on superconductivity. It is also a prerequisite for the large scale application of superconductors. Since the microscopic mechanism of high-Tc superconductivity is unknown, the conventional approach for increasing Tc is either to apply high pressure to a material which has the potential to become superconducting, or to push it close to an antiferromagnetic or some other quantum instability point by chemical doping. In this article, the authors point out that another general approach for raising Tc is to lift theσ-bonding bands to the Fermi level, or to metalize theσ-bonding elections. This approach can increase the probability of finding a novel high-Tc super-conductor because the coupling ofσ-bonding electrons with phonons is generally strong and the superconducting transition induced by this interaction can occur at relatively high temperatures. After elucidating the underlying mechanism, the authors discuss a number of schemes to metalizeσ-bonding electrons, and present their recent prediction for the crystalline and electronic struc-tures of two potential high-Tc superconductors, Li2B3C and Li3B4C2, with Tc higher than 50 K.%提高超导相变温度是超导基础研究的一个重要目标,也是超导广泛应用的一个前提。在高温超导微观机理尚不清楚的情况下,寻找高温超导体一般是通过对材料施加高压或通过掺杂使材料尽可能地接近反铁磁或其他量子不稳定点来实现。这篇文章介绍的是一种通过金属化σ电子能带来提高超导相变温度的方法。这种方法之所以有效,能够提高发现新的高温超导体的概率,是因为σ电子与声子之间通常存在很强的相互作用,可以显著增强电子的超导配对能,从而提升超导相变温度。作者以具体材料为例介绍了金属化σ能带的几种可行途径,并介绍了他们

  7. Adhesive performance of silver-palladium-copper-gold alloy and component metals bonded with organic sulfur-based priming agents and a tri-n-butylborane initiated luting material.

    Science.gov (United States)

    Yamashita, Miyuki; Koizumi, Hiroyasu; Ishii, Takaya; Nakayama, Daisuke; Oba, Yusuke; Matsumura, Hideo

    2013-01-01

    The purpose of the current study was to evaluate the effect of thione-based metal priming agents on the adhesive behavior of a Ag-Pd-Cu-Au alloy and component metals bonded with an acrylic resin. Disk specimens (10 mm in diameter by 3 mm thick) were prepared from a silver-palladium-copper-gold (Ag-Pd-Cu-Au) alloy (Castwell M.C.12), high-purity silver, palladium, copper and gold. Four single-liquid priming agents containing organic sulfur compound (Alloy Primer, Metaltite, M.L. Primer and V-Primer) and three acidic priming agents (All Bond II Primer B, Estenia Opaque Primer and Super-Bond Liquid) were assessed. The metal specimens were flat-ground with abrasive papers, primed with one of the agents and bonded with a tri-n-butylborane initiated resin. The shear bond strengths were determined both before and after repeated thermocycling (5°C and 55°C, 1 min each, 20,000 cycles). The results were statistically analyzed with a non-parametric procedure (p = 0.05 level). The post-thermocycling bond strengths in MPa (median; n = 11) associated with the Alloy Primer, Metaltite, M.L. Primer and V-Primer materials were, respectively, 20.8, 22.8, 17.8 and 18.4 for the Ag-Pd-Cu-Au alloy; 19.6, 21.9, 14.4 and 20.1 for silver; 5.4, 4.5, 12.8 and 5.3 for palladium; 17.1, 19.2, 0.7 and 6.6 for copper; and 18.5, 17.7, 22.8 and 15.4 for gold. It can be concluded that the use of the four priming agents, which are based on organic sulfur compounds, effectively enhanced bonding to the Ag-Pd-Cu-Au alloy and the component metals, although the bonding performance varied among the priming agents and metal elements. The priming agents appeared to have more of an effect on the alloy, silver and gold than on the palladium and copper.

  8. Resistência ao cisalhamento de braquetes metálicos utilizando sistema adesivo autocondicionante Shear bond strength evaluation of metallic brackets using self-etching system

    Directory of Open Access Journals (Sweden)

    Camilo Aquino Melgaço

    2011-08-01

    Full Text Available OBJETIVO: avaliar a resistência ao cisalhamento de braquetes metálicos colados com sistema autocondicionante utilizado imediatamente e após 2, 5 e 9 dias depois da ativação e armazenagem. MÉTODOS: utilizaram-se 64 dentes bovinos divididos igualmente em quatro grupos e devidamente preparados para receber a colagem dos braquetes. Em T1, realizou-se a ativação de 7 blisters de adesivos autocondicionantes (de acordo com as normas do fabricante e procedeu-se à colagem imediata apenas dos braquetes do grupo I. Os adesivos ativados foram, então, armazenados à temperatura de 4ºC e reutilizados em períodos de 2 dias (T2, 5 dias (T3 e 9 dias (T4 para a colagem dos braquetes dos grupos II, III e IV, respectivamente. RESULTADOS: não se observou diferença estatística quando comparados os valores médios de tensão para resistência ao cisalhamento entre os grupos I, II e III. Entretanto, diferença estatística foi encontrada quando esses valores foram comparados aos do grupo IV. CONCLUSÃO: o armazenamento do adesivo autocondicionante depois de ativado, à temperatura média de 4ºC, por até 5 dias, parece não afetar os resultados quanto às tensões de resistência ao cisalhamento; novos estudos são necessários para avaliação das demais características do material quando de sua utilização por período de tempo prolongado após sua ativação.OBJECTIVE: To evaluate the shear bond strength of metallic brackets using the self-etching system after its activation and storage for 2, 5 and 9 day periods. METHODS: A total of 64 bovine teeth were divided in four groups and prepared to receive the brackets. Initially, seven self-etching primer blisters were activated and used to bond the brackets of group I. The blisters were store at a constant temperature of 4ºC for 2, 5 and 9 days and used to bond the brackets of groups II, III and IV, respectively. RESULTS: No statistic difference was found in shear bond strength comparing groups I, II

  9. 不同金属处理剂对钴铬合金与基托树脂粘结强度的影响%Shear bond strength of polymethyl methacrylate to cobalt-chromium treated with different metal primers

    Institute of Scientific and Technical Information of China (English)

    朱海连; 何升腾; 杨斌

    2013-01-01

    Objective:This study was undertaken to evaluate the shear bond strength of a denture base resin to cobalt-chromium alloy treated with three different adhesive primers.Methods:40 Co-Cr alloy disk (6.0mm diameter,2.5mm thick) were divided into four groups randomly.The surfaces of the disks were sandblasted and laser-induced thermal etching,followed by treatment with 3 different primers (Metal Primer Ⅱ,Estenia Opaque Primer,Metal Base M).A denture base resin was then applied on the disks with hole-punched sticky tape and a Teflon ring.Specimens without primer served as controls.Bonded specimens were stored in 37℃ distilled water for 24 hours,then all the specimens were subjected to shear force in a universal testing machine at a crosshead speed of 0.5mm/min.Results:All of the primers significantly(P<0.05) improved shear bond strengths of denture base resin to the Co-Cr alloy.Specimens treated with Metal Primer Ⅱ and Estenia Opaque Primer showed higher bond strength than treated with Metal Base M (P<0.05).And there was no significant difference between the Metal Primer Ⅱ and Estenia Opaque Primer (P>0.05).Conclusion:These three metal primers could increase the shear bond strength of a denture base resin to the Co-Cr alloy.Metal Primer Ⅱ and Estenia Opaque Primers exhibited greater bond strength improvement than Metal Base M.%目的:研究三种金属处理剂对钴铬合金与基托树脂粘接强度的影响.方法:制备40个钴铬合金试件随机分为4组,采用喷砂和激光对各个试件表面进行处理后,除对照组外,其它组试件分别采用Metal Primer Ⅱ,Estenia Opaque Primer,Metal Base M三种金属处理剂对试件表面进行处理,后将基托树脂与金属试件进行粘接.经37℃恒温水浴24h后,测定金属试件与基托树脂间的剪切粘接强度,并进行统计分析.结果:三种金属处理剂组所获得的钴铬合金与基托树脂间的剪切粘接强度均显著高于对照组(P<0.05).Metal Primer

  10. Self-assembly of amino acids on noble metal surfaces: universality of the amino acid bonding scheme

    Energy Technology Data Exchange (ETDEWEB)

    Reichert, Joachim; Auwaerter, Willi; Marschall, Matthias; Barth, Johannes V. [Physik Department, TU Muenchen (Germany); Schiffrin, Agustin [Physik Department, TU Muenchen (Germany); Chemistry Department, University of British Columbia, Vancouver (Canada); Pennec, Yan; Weber-Bargioni, Alexander [Chemistry Department, University of British Columbia, Vancouver (Canada); Cvetko, Dean; Cossaro, Albano; Morgante, Alberto [INFM/TASC, Trieste (Italy)

    2009-07-01

    We investigated the molecular self-assemblies of L-methionine on Cu(111) and L-tyrosine on Ag(111) by means of STM, HAS, XPS and NEXAFS in UHV. The self-assembly of L-methionine on Cu(111) is strongly influenced by the substrate reactivity and reveals a temperature dependent structural transformation involving a chiral orientational switch and the emergence of an ordered 1D high temperature phase. XPS data show that this transformation is triggered by a thermally activated deprotonation of the NH{sub 3}{sup +} group. The ordered phase shows noncovalent molecular dimerization and alignment into chains which are commensurate with the underlying substrate. L-tyrosine on Ag(111) self-assembles into linear nanoribbons primarily following the substrate crystalline symmetry. A zwitterionic noncovalent molecular dimerization is observed, and NEXAFS data provide evidence of a non-flat adsorption of the phenol ring. This dimerization scheme is reminiscent of methionine on Cu(111) and Ag(111), and supports a universal self-assembling trend for amino acids on close-packed noble metal surfaces.

  11. Shear bond strength of recycled metal brackets%金属托槽重复利用的抗剪切强度

    Institute of Scientific and Technical Information of China (English)

    刘新强; 李正明; 马长柏; 张丁; 孙志辉

    2008-01-01

    BACKGROUND: Bracket dropping is often seen in clinic. Can these shed brackets be used again; what should be done to treat these brackets; is the bond strength of these recycled brackets different from those new ones, these questions are often concerned by orthodontists in their clinic and are the purpose of our study as well.OBJECTIVE: To evaluate the shear bond strength and compare two base-cure methods of recycled brackets. DESIGN: Grouping control study. SITTING: Department of Orthodontics, the Affiliated Hospital of Medical College, Qingdao University; Department of Materials, Dental School, Beijing University. MATERIALS: The teeth were collected from Oral Surgery, the Affiliated Hospital of Medical College, Qingdao University. The age was from 11 to 19 years. The gender was half male and half female. Intact enamel of the crown was required, but decayed, fracture, tetracycline pigmentation teeth or fluorosis teeth were excluded. Patients provided the confirmed consent for this experiment.METHODS: The experiment was carried out in Stomatology College of Peaking University in December 2005. Thirty ex vivo teeth were selected randomly from those prepared enamel surfaces, used as sample for rebounding. The edgewise brackets of swallow-tailed brackets were bonded on each tooth and rebonded after 24 hours. The teeth were cleaned and divided randomly into 3 groups. There were 10 teeth in each group. Group 1 was bonded with new brackets; group 2 with recycled brackets whose adhesive remnant were burned and got rid of; group 3 with recycled brackets whose adhesive remnant in the groove of the base were stored. Bracket was provided by Standard edgewise, Orsu Company, Hangzhou, China. After 24 hours, the shear bond strength was tested with material testing machine (Autogragh, Shimadzu, Japan). Adhesive remnant index (ARI) was added up. MAIN OUTCOME MEASURES: Shear strength of old metal bracket after rebonding and adhesive remnant.RESULTS: ① Shear bond strength: The

  12. Rational Design of Emissive NIR-Absorbing Chromophores: Rh(III) Porphyrin-Aza-BODIPY Conjugates with Orthogonal Metal-Carbon Bonds.

    Science.gov (United States)

    Zhou, Jinfeng; Gai, Lizhi; Zhou, Zhikuan; Yang, Wu; Mack, John; Xu, Kejing; Zhao, Jianzhang; Zhao, Yue; Qiu, Hailin; Chan, Kin Shing; Shen, Zhen

    2016-09-01

    The facile synthesis of Group 9 Rh(III) porphyrin-aza-BODIPY conjugates that are linked through an orthogonal Rh-C(aryl) bond is reported. The conjugates combine the advantages of the near-IR (NIR) absorption and intense fluorescence of aza-BODIPY dyes with the long-lived triplet states of transition metal rhodium porphyrins. Only one emission peak centered at about 720 nm is observed, irrespective of the excitation wavelength, demonstrating that the conjugates act as unique molecules rather than as dyads. The generation of a locally excited (LE) state with intramolecular charge-transfer (ICT) character has been demonstrated by solvatochromic effects in the photophysical properties, singlet oxygen quantum yields in polar solvents, and by the results of density functional theory (DFT) calculations. In nonpolar solvents, the Rh(III) conjugates exhibit strong aza-BODIPY-centered fluorescence at around 720 nm (ΦF =17-34 %), and negligible singlet oxygen generation. In polar solvents, enhancements of the singlet-oxygen quantum yield (ΦΔ =19-27 %, λex =690 nm) have been observed. Nanosecond pulsed time-resolved absorption spectroscopy confirms that relatively long-lived triplet excited states are formed. The synthetic methodology outlined herein provides a useful strategy for the assembly of functional materials that are highly desirable for a wide range of applications in material science and biomedical fields.

  13. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  14. Cupriphication of gold to sensitize d10–d10 metal–metal bonds and near-unity phosphorescence quantum yields

    Science.gov (United States)

    Galassi, Rossana; Ghimire, Mukunda M.; Otten, Brooke M.; Ricci, Simone; McDougald, Roy N.; Almotawa, Ruaa M.; Alhmoud, Dieaa; Ivy, Joshua F.; Rawashdeh, Abdel-Monem M.; Nesterov, Vladimir N.; Reinheimer, Eric W.; Daniels, Lee M.; Burini, Alfredo; Omary, Mohammad A.

    2017-01-01

    Outer-shell s0/p0 orbital mixing with d10 orbitals and symmetry reduction upon cupriphication of cyclic trinuclear trigonal-planar gold(I) complexes are found to sensitize ground-state Cu(I)–Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au4Cu2 {[Au4(μ-C2,N3-EtIm)4Cu2(µ-3,5-(CF3)2Pz)2], (4a)}, Au2Cu {[Au2(μ-C2,N3-BzIm)2Cu(µ-3,5-(CF3)2Pz)], (1) and [Au2(μ-C2,N3-MeIm)2Cu(µ-3,5-(CF3)2Pz)], (3a)}, AuCu2 {[Au(μ-C2,N3-MeIm)Cu2(µ-3,5-(CF3)2Pz)2], (3b) and [Au(μ-C2,N3-EtIm)Cu2(µ-3,5-(CF3)2Pz)2], (4b)} and stacked Au3/Cu3 {[Au(μ-C2,N3-BzIm)]3[Cu(µ-3,5-(CF3)2Pz)]3, (2)} form upon reacting Au3 {[Au(μ-C2,N3-(N-R)Im)]3 ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu3 {[Cu(μ-3,5-(CF3)2Pz)]3 (3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via two Au(I)⋯Cu(I) metallophilic interactions, whereas 4a exhibits a hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d10–d10 polar-covalent bond with ligand-unassisted Cu(I)–Au(I) distances of 2.8750(8) Å each—the shortest such an intermolecular distance ever reported between any two d10 centers so as to deem it a “metal–metal bond” vis-à-vis “metallophilic interaction.” Density-functional calculations estimate 35–43 kcal/mol binding energy, akin to typical M–M single-bond energies. Congruently, FTIR spectra of 4a show multiple far-IR bands within 65–200 cm−1, assignable to vCu-Au as validated by both the Harvey–Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilic

  15. Investigation into the bond strength of metal brackets to ceramic restoration%瓷修复体与金属托槽粘接强度的实验研究

    Institute of Scientific and Technical Information of China (English)

    王春晔; 邵玶; 赵媛; 徐实谦; 宋冰

    2012-01-01

    Objective To investigate the influence of different bracket base surfaces ( swallow-tail-backed and mesh-backed ) on the bond strength of metal brackets to porcelain. Methods Methods 80 ceramics specimen were randomly and equally divided into 4 groups according to different conditioning techniques: (A)deglazing by grinding and bonding swallow-tail-backed metal brackets, (B)deglazing by grinding and bonding mesh-backed metal brackets.(C) etching with 9.6% hydrofluoric acid(HF) and bonding swallow-tail-backed metal brackets, (D) etching with 9.6% HF and bonding mesh-backed metal brackets. Each group was further divided into 2 groups randomly and equally: (1) all specimens were stored in artificial saliva at 37t: for 24 hours, (2) untreated. Silane coupling agents and Durafill BondTM adhesive were utilized to bond the bracket onto each sample. The shear bond strength and the Adhesive remnant index (ARI) were determined. Results After artificial saliva bath.the swallow-tail-backed groups resulted in a statistically significant higher bond strength. Deglazing specimens,mesh-backed group in which has a statistically significant higher adhesive remnant index (ARI). Conclusion The swallow-tail-backed groups resulted in a higher bond strength (SBS). The deglazing group had a higher SBS than the group of etching with 9.6% hydrofluoric acid(HF) for 3 min.%目的:研究两种不同形状的底板(燕尾状、网状)对正畸金属托槽与瓷修复体粘接强度的影响.方法:根据瓷面处理方式及所粘接托槽的不同,将80个瓷修复体随机平均分为4组:金刚砂车针打磨+燕尾状底板托槽;金刚砂车针打磨+网状底板托槽;9.6%氢氟酸(hydrofluoric acid,HF)酸蚀+燕尾状底板托槽;9.6% HF酸蚀+网状底板托槽.将粘接后的每组瓷修复体随机平均分为2组:组1用37℃人工唾液水浴24h;组2不予处理.用硅烷偶联剂、杜拉菲勒光固化复合树脂充填材料进行粘接.检测抗剪

  16. Carbon K-edge X-ray absorption spectroscopy and time-dependent density functional theory examination of metal-carbon bonding in metallocene dichlorides.

    Science.gov (United States)

    Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Kozimor, Stosh A; Martin, Richard L; Shuh, David K; Tyliszczak, Tolek; Vernon, Louis J

    2013-10-01

    Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.

  17. A non-radioactive DAPI-based high-throughput in vitro assay to assess Plasmodium falciparum responsiveness to antimalarials--increased sensitivity of P. falciparum to chloroquine in Senegal.

    Science.gov (United States)

    Ndiaye, Daouda; Patel, Vishal; Demas, Allison; LeRoux, Michele; Ndir, Omar; Mboup, Souleymane; Clardy, Jon; Lakshmanan, Viswanathan; Daily, Johanna P; Wirth, Dyann F

    2010-02-01

    The spread of Plasmodium falciparum drug resistance is outpacing new antimalarial development and compromising effective malaria treatment. Combination therapy is widely implemented to prolong the effectiveness of currently approved antimalarials. To maximize utility of available drugs, periodic monitoring of drug efficacy and gathering of accurate information regarding parasite-sensitivity changes are essential. We describe a high-throughput, non-radioactive, field-based assay to evaluate in vitro antimalarial drug sensitivity of P. falciparum isolates from 40 Senegalese patients. Compared with earlier years, we found a significant decrease in chloroquine in vitro and in genotypic resistances (> 50% and > 65%, respectively, in previous studies) with only 23% of isolates showing resistance. This is possibly caused by a withdrawal of chloroquine from Senegal in 2002. We also found a range of artemisinin responses. Prevalence of drug resistance is dynamic and varies by region. Therefore, the implementation of non-radioactive, robust, high-throughput antimalarial sensitivity assays is critical for defining region-specific prophylaxis and treatment guidelines.

  18. A Non-Radioactive DAPI-based High-Throughput In Vitro Assay to Assess Plasmodium falciparum Responsiveness to Antimalarials—Increased Sensitivity of P. falciparum to Chloroquine in Senegal

    Science.gov (United States)

    Ndiaye, Daouda; Patel, Vishal; Demas, Allison; LeRoux, Michele; Ndir, Omar; Mboup, Souleymane; Clardy, Jon; Lakshmanan, Viswanathan; Daily, Johanna P.; Wirth, Dyann F.

    2010-01-01

    The spread of Plasmodium falciparum drug resistance is outpacing new antimalarial development and compromising effective malaria treatment. Combination therapy is widely implemented to prolong the effectiveness of currently approved antimalarials. To maximize utility of available drugs, periodic monitoring of drug efficacy and gathering of accurate information regarding parasite-sensitivity changes are essential. We describe a high-throughput, non-radioactive, field-based assay to evaluate in vitro antimalarial drug sensitivity of P. falciparum isolates from 40 Senegalese patients. Compared with earlier years, we found a significant decrease in chloroquine in vitro and in genotypic resistances (> 50% and > 65%, respectively, in previous studies) with only 23% of isolates showing resistance. This is possibly caused by a withdrawal of chloroquine from Senegal in 2002. We also found a range of artemisinin responses. Prevalence of drug resistance is dynamic and varies by region. Therefore, the implementation of non-radioactive, robust, high-throughput antimalarial sensitivity assays is critical for defining region-specific prophylaxis and treatment guidelines. PMID:20133997

  19. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  20. Comparison of Ultrasonic Welding and Thermal Bonding for the Integration of Thin Film Metal Electrodes in Injection Molded Polymeric Lab-on-Chip Systems for Electrochemistry

    DEFF Research Database (Denmark)

    Matteucci, Marco; Heiskanen, Arto; Zor, Kinga

    2016-01-01

    We compare ultrasonic welding (UW) and thermal bonding (TB) for the integration of embedded thin-film gold electrodes for electrochemical applications in injection molded (IM) microfluidic chips. The UW bonded chips showed a significantly superior electrochemical performance compared to the ones ...

  1. Recent Progress in the Research of Transition-Metal-Catalyzed C-CN Bond Cleavage%过渡金属催化的C—CN键断裂的研究进展

    Institute of Scientific and Technical Information of China (English)

    寇学振; 范佳骏; 童晓峰; 沈增明

    2013-01-01

    有机氰化物是一种重要的合成中间体,在药物、农药、染料和活性物质中都有应用.使用廉价、简单、低毒的氰基化合物在过渡金属的催化下通过C-CN键断裂生成复杂的氰化物是合成有机氰化物的重要手段之一.综述了不同过渡金属(如Ni,Pd,Rh,Cu,Ru,Fe,Mo,Co等)催化不同种类的氰基化合物C-CN键断裂的最新研究进展,如含C(sp1)-CN键化合物、C(sp2)-CN键化合物以及C(sp3)-CN键化合物,并对有关的反应机理及C-CN键断裂机理的进展进行了探讨.%Nitriles are an important class of organic compounds which can be found in pharmaceuticals,agrochemicals,dyes,and bioactive compounds.Transition-metal-catalyzed C-CN bond cleavage using inexpensive,simple and less toxic nitriles is one of the most attractive modem methods for the synthesis of complicated organic cyanides.Research progress of transition-metal-catalyzed (Ni,Pd,Rh,Cu,Ru,Fe,Mo,Co) different types of C-CN bond cleavage is reviewed,which includes some organic cyanides containing C(sp1)—CN bond,C(sp2)—CN bond and C(sp3)—CN bond.The C-CN cleavage mechanisms are also discussed in this review.

  2. Morphology-controlled self-assembled nanostructures of 5,15-di[4-(5-acetylsulfanylpentyloxy)phenyl]porphyrin derivatives. Effect of metal-ligand coordination bonding on tuning the intermolecular interaction.

    Science.gov (United States)

    Gao, Yingning; Zhang, Xiaomei; Ma, Changqin; Li, Xiyou; Jiang, Jianzhuang

    2008-12-17

    Novel metal-free 5,15-di[4-(5-acetylsulfanylpentyloxy)phenyl]porphyrin H2[DP(CH3COSC5H10O)2P] (1) and its zinc congener Zn[DP(CH3COSC5H10O)2P] (2) were designed and synthesized. Single-crystal X-ray diffraction (XRD) analysis confirmed the tetrapyrrole nature of these two compounds, revealing the existence of metal-ligand coordination bond between the carbonyl oxygen in the aryloxy side chain of meso-attached phenyl group in the porphyrin molecule with the zinc center of neighboring porphyrin molecule in the crystal structure of 2. This intermolecular Zn-O coordination bond induces the formation of a supramolecular chain structure in which the porphyrinato zinc moieties are arranged in a "head-to-tail" mode (J-aggregate), which is in contrast to a "face-to-face" stacking mode (H-aggregate) in the supramolecular structure formed depending on the C-H...pi interaction in the crystal of 1. Their self-assembling properties in MeOH and n-hexane were comparatively investigated by scanning electronic microscopy and XRD technique. Intermolecular pi-pi interaction of metal-free porphyrin 1 leads to the formation of hollow nanospheres and nanoribbons in MeOH and n-hexane, respectively. In contrast, introduction of additional Zn-O coordination bond for porphyrinato zinc complex 2 induces competition with intermolecular pi-pi interaction, resulting in nanostructures with nanorod and hollow nanosphere morphology in MeOH and n-hexane. The IR and XRD results clearly reveal the presence and absence of such metal-ligand coordination bond in the nanostructures formed from porphyrinato zinc complex 2 and metal-free porphyrin 1, respectively, which is further unambiguously confirmed by the single-crystal XRD analysis result for both compounds. Electronic absorption spectroscopic data on the self-assembled nanostructures reveal the H-aggregate nature in the hollow nanospheres and nanoribbons formed from metal-free porphyrin 1 due to the pi-pi intermolecular interaction between porphyrin

  3. Effect of Bonding Temperature on Phase Transformation of Diffusion-Bonded Joints of Duplex Stainless Steel and Ti-6Al-4V Using Nickel and Copper as Composite Intermediate Metals

    Science.gov (United States)

    Kundu, Sukumar; Thirunavukarasu, Gopinath; Chatterjee, Subrata; Mishra, Brajendra

    2015-12-01

    In the present study, the effect of bonding temperature on phase transformation of diffusion-bonded joints of duplex stainless steel (DSS) and Ti-6Al-4V (Ti64) using simultaneously both nickel (Ni) and copper (Cu) interlayers was investigated in the temperature range of 1148 K to 1223 K (875 °C to 950 °C) insteps of 25 K (25 °C) for 60 minutes under 4 MPa uniaxial pressure in vacuum. Interfaces were characterized by scanning electron microscopy and interdiffusion of the chemical species across the diffusion interfaces were witnessed by electron probe microanalysis. At 1148 K (875 °C), layer-wise Cu4Ti, Cu2Ti, Cu4Ti3, CuTi, and CuTi2 phases were observed at the Cu-Ti64 interface; however, DSS-Ni and Ni-Cu interfaces were free from any intermetallic. At 1173 K and 1198 K (900 °C and 925 °C), Cu interlayer could not restrict the diffusion of atoms from Ti64 to Ni, and vice versa; and Ni-Ti-based intermetallics were formed at the Ni-Cu interface and throughout the Cu zone as well; however, at 1223 K (950 °C), both Ni and Cu interlayers could not inhibit the diffusion of atoms from Ti64 to DSS, and vice versa. The maximum shear strength of ~377 MPa was obtained for the diffusion couple processed at 1148 K (875 °C) and strength of the bonded joints gradually decreased with the increasing bonding temperature due to the widening of brittle intermetallics at the diffusion zone. Fracture path indicated that failure took place through the Cu4Ti intermetallic at the Cu-Ti64 interface when bonding was processed at 1148 K (875 °C). When bonding was processed at 1173 K and 1198 K (900 °C and 925 °C), fracture took place through the Ni3Ti intermetallic at the Ni-(Ni + Cu + Ti64 diffusion reaction) interface; however, at 1223 K (950 °C), fracture morphology indicated the brittle nature and the fracture took place apparently through the σ phase at the DSS-(DSS + Ni + Cu + Ti64 diffusion reaction) interface.

  4. Facile fabrication of magnetically recyclable metal-organic framework nanocomposites for highly efficient and selective catalytic oxidation of benzylic C-H bonds.

    Science.gov (United States)

    Chen, Yifa; Huang, Xianqiang; Feng, Xiao; Li, Jikun; Huang, Yingyu; Zhao, Jingshu; Guo, Yuexin; Dong, Xinmei; Han, Ruodan; Qi, Pengfei; Han, Yuzhen; Li, Haiwei; Hu, Changwen; Wang, Bo

    2014-08-07

    HKUST-1@Fe3O4 chemically bonded core-shell nanoparticles have been prepared by growing HKUST-1 thin layers joined by carboxyl groups onto Fe3O4 nanospheres. These magnetic core-shell MOF nanostructures show exceptional catalytic activity for the oxidation of benzylic C-H bonds and they can be recovered by magnetic separation and reused without losing any activity.

  5. Exchange interaction between TCNQ and transition metal ion mediated by hydrogen bonds in [Mn(phen)3](TCNQ)2·H2O and [Co(phen)3](TCNQ)2·H2O

    Science.gov (United States)

    Šoltésová, D.; Vasylets, G.; Čižmár, E.; Botko, M.; Cheranovskii, V.; Starodub, V.; Feher, A.

    2016-12-01

    The magnetic properties, specific heat and EPR spectra of anion-radical salts [Mn(phen)3](TCNQ)2·H2O and [Co(phen)3](TCNQ)2·H2O, in which TCNQ molecules and transition metal ions are not connected by covalent bonds and magnetic interactions are mediated via hydrogen bonds, were investigated. Measurements of the magnetic response were performed down to 1.8 K in magnetic fields up to 7 T. The heat capacity of investigated compounds was measured in temperature range from 0.38 K to 35 K in magnetic fields up to 9 T for [Mn(phen)3](TCNQ)2·H2O and up to 3 T for [Co(phen)3](TCNQ)2·H2O. The EPR spectra of studied samples were investigated for both samples in the temperature range from 2 K to 300 K. Theoretical model of weakly-coupled magnetic units composed of four TCNQ anion radicals and of two transition metal ions was proposed for interpretation of obtained data. The energy of exchange interactions between TCNQ molecules and transition metal ion is important for the description of low-temperature behavior of studied anion-radical salts and was estimated to be in the range of 1.3-1.5 K.

  6. Binding to Redox-Inactive Alkali and Alkaline Earth Metal Ions Strongly Deactivates the C-H Bonds of Tertiary Amides toward Hydrogen Atom Transfer to Reactive Oxygen Centered Radicals.

    Science.gov (United States)

    Salamone, Michela; Carboni, Giulia; Mangiacapra, Livia; Bietti, Massimo

    2015-09-18

    The effect of alkali and alkaline earth metal ions on the reactions of the cumyloxyl radical (CumO(•)) with N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) was studied by laser flash photolysis. In acetonitrile, a >2 order of magnitude decrease in the rate constant for hydrogen atom transfer (HAT) from the C-H bonds of these substrates (kH) was measured after addition of Li(+). This behavior was explained in terms of a strong interaction between Li(+) and the oxygen atom of both DMF and DMA that increases the extent of positive charge on the amide, leading to C-H bond deactivation toward HAT to the electrophilic radical CumO(•). Similar effects were observed after addition of Ca(2+), which was shown to strongly bind up to four equivalents of the amide substrates. With Mg(2+), weak C-H deactivation was observed for the first two substrate equivalents followed by stronger deactivation for two additional equivalents. No C-H deactivation was observed in DMSO after addition of Li(+) and Mg(2+). These results point toward the important role played by metal ion Lewis acidity and solvent Lewis basicity, indicating that C-H deactivation can be modulated by varying the nature of the metal cation and solvent and allowing for careful control over the HAT reactivity of amide substrates.

  7. Reactivity of the metal-->BX3 dative sigma-bond: 1,2-addition reactions of the Fe-->BX3 moiety of the ferraboratrane complex [kappa4-B(mimBu t)3]Fe(CO)2.

    Science.gov (United States)

    Figueroa, Joshua S; Melnick, Jonathan G; Parkin, Gerard

    2006-09-04

    The ferraboratrane [kappa4-B(mim(Bu)t)3]Fe(CO)2 (mim(Bu)t = 2-mercapto-1-tert-butylimidazolyl), the first example of a complex which possesses a retrodative (i.e., metal-to-ligand) Fe-->B bond, is obtained via reaction of the tris(2-mercapto-1-tert-butylimidazolyl)hydroborato complex [Tm(Bu)t]FeCl with LiCH2SiMe3 followed by treatment with CO. Significantly, [kappa4-B(mim(Bu)t)3]Fe(CO)2 exhibits novel reactivity towards a variety of reagents that results in eradication of the Fe-->B bond via a formal 1,2-addition process and the formation of B-functionalized tris(mercaptoimidazolyl)borate derivatives, [XTm(Bu)t]FeY.

  8. Cascade C═O/C═C/C-N Bond Formation: Metal-Free Reactions of 1,4-Diynes and 1-En-4-yn-3-ones with Isoquinoline and Quinoline N-Oxides.

    Science.gov (United States)

    Zhang, Bing; Huang, Long; Yin, Shiwei; Li, Xuetong; Xu, Tao; Zhuang, Biyang; Wang, Tao; Zhang, Zunting; Hashmi, A Stephen K

    2017-08-18

    The metal-free reactions of 1,4-diynes and 1-en-4-yn-3-ones with isoquinoline and quinoline N-oxides are developed, resulting in the formation of 3,4-dihydro-2H-pyrido[2,1-a]isoquinolines and 2,3-dihydro-1H-pyrido[1,2-a]quinolines via cascade C═O/C═C/C-N bond formation. It is the first report in which in the alkyne oxidation by N-oxides both the oxygen atom of N-oxides and the nitrogen atom are involved in a second C-heteroatom bond formation. The reactions showed a broad substrate scope and functional group tolerance. Furthermore, the products were found to display green-blue fluorescence in DMSO with fluorescence quantum yields up to 0.59.

  9. Comparative evaluation of effect of metal primer and sandblasting on the shear bond strength between heat cured acrylic denture base resin and cobalt-chromium alloy: An in vitrostudy

    Directory of Open Access Journals (Sweden)

    Sandeep Kalra

    2015-01-01

    Full Text Available Aims: The aim of this study was to evaluate the effect of metal primers and sandblasting on the shear bond strength (SBS of heat cured acrylic denture base resin to cobalt-chromium (Co-Cr alloy. Materials and Methods: A total number of 40 disk shaped wax patterns (10 mm in diameter and 2 mm in thickness were cast in Co-Cr alloy. Samples were divided into 4 groups depending on the surface treatment received. Group 1: No surface treatment was done and acts as control group. Group 2: Only sandblasting was done. Group 3: Only metal primer was applied. Group 4: Both metal primer and sandblasting were done. After surface treatment samples had been tested in Universal Testing Machine at crosshead speed of 0.5 mm/min in shear mode and scanning, electron microscope evaluation was done to observe the mode of failure. Statistical Analysis: All the observations obtained were analyzed statistically using software SPSS version 17; one-way analysis of variance (ANOVA and post-hoc Tukey test were applied. Results: The one-way ANOVA indicated that SBS values varied according to type of surface treatment done. The SBS was highest (18.70 ± 1.2 MPa when both sandblasting and metal primer was done when compared with no surface treatment (2.59 ± 0.32 MPa. Conclusions: It could be concluded that the use of metal primers along with sandblasting significantly improves the bonding of heat cured acrylic denture base resin with the Co-Cr alloy.

  10. Comprehensive thermochemistry of W-H bonding in the metal hydrides CpW(CO)2(IMes)H, [CpW(CO)2(IMes)H](•+), and [CpW(CO)2(IMes)(H)2]+. Influence of an N-heterocyclic carbene ligand on metal hydride bond energies.

    Science.gov (United States)

    Roberts, John A S; Appel, Aaron M; DuBois, Daniel L; Bullock, R Morris

    2011-09-21

    The free energies interconnecting nine tungsten complexes have been determined from chemical equilibria and electrochemical data in MeCN solution (T = 22 °C). Homolytic W-H bond dissociation free energies are 59.3(3) kcal mol(-1) for CpW(CO)(2)(IMes)H and 59(1) kcal mol(-1) for the dihydride [CpW(CO)(2)(IMes)(H)(2)](+) (where IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), indicating that the bonds are the same within experimental uncertainty for the neutral hydride and the cationic dihydride. For the radical cation, [CpW(CO)(2)(IMes)H](•+), W-H bond homolysis to generate the 16-electron cation [CpW(CO)(2)(IMes)](+) is followed by MeCN uptake, with free energies for these steps being 51(1) and -16.9(5) kcal mol(-1), respectively. Based on these two steps, the free energy change for the net conversion of [CpW(CO)(2)(IMes)H](•+) to [CpW(CO)(2)(IMes)(MeCN)](+) in MeCN is 34(1) kcal mol(-1), indicating a much lower bond strength for the 17-electron radical cation of the metal hydride compared to the 18-electron hydride or dihydride. The pK(a) of CpW(CO)(2)(IMes)H in MeCN was determined to be 31.9(1), significantly higher than the 26.6 reported for the related phosphine complex, CpW(CO)(2)(PMe(3))H. This difference is attributed to the electron donor strength of IMes greatly exceeding that of PMe(3). The pK(a) values for [CpW(CO)(2)(IMes)H](•+) and [CpW(CO)(2)(IMes)(H)(2)](+) were determined to be 6.3(5) and 6.3(8), much closer to the pK(a) values reported for the PMe(3) analogues. The free energy of hydride abstraction from CpW(CO)(2)(IMes)H is 74(1) kcal mol(-1), and the resultant [CpW(CO)(2)(IMes)](+) cation is significantly stabilized by binding MeCN to form [CpW(CO)(2)(IMes)(MeCN)](+), giving an effective hydride donor ability of 57(1) kcal mol(-1) in MeCN. Electrochemical oxidation of [CpW(CO)(2)(IMes)](-) is fully reversible at all observed scan rates in cyclic voltammetry experiments (E° = -1.65 V vs Cp(2)Fe(+/0) in MeCN), whereas CpW(CO)(2

  11. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  12. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  13. Do Practical Standard Coupled Cluster Calculations Agree Better than Kohn-Sham Calculations with Currently Available Functionals When Compared to the Best Available Experimental Data for Dissociation Energies of Bonds to 3d Transition Metals?

    Science.gov (United States)

    Xu, Xuefei; Zhang, Wenjing; Tang, Mingsheng; Truhlar, Donald G

    2015-05-12

    Coupled-cluster (CC) methods have been extensively used as the high-level approach in quantum electronic structure theory to predict various properties of molecules when experimental results are unavailable. It is often assumed that CC methods, if they include at least up to connected-triple-excitation quasiperturbative corrections to a full treatment of single and double excitations (in particular, CCSD(T)), and a very large basis set, are more accurate than Kohn-Sham (KS) density functional theory (DFT). In the present work, we tested and compared the performance of standard CC and KS methods on bond energy calculations of 20 3d transition metal-containing diatomic molecules against the most reliable experimental data available, as collected in a database called 3dMLBE20. It is found that, although the CCSD(T) and higher levels CC methods have mean unsigned deviations from experiment that are smaller than most exchange-correlation functionals for metal-ligand bond energies of transition metals, the improvement is less than one standard deviation of the mean unsigned deviation. Furthermore, on average, almost half of the 42 exchange-correlation functionals that we tested are closer to experiment than CCSD(T) with the same extended basis set for the same molecule. The results show that, when both relativistic and core-valence correlation effects are considered, even the very high-level (expensive) CC method with single, double, triple, and perturbative quadruple cluster operators, namely, CCSDT(2)Q, averaged over 20 bond energies, gives a mean unsigned deviation (MUD(20) = 4.7 kcal/mol when one correlates only valence, 3p, and 3s electrons of transition metals and only valence electrons of ligands, or 4.6 kcal/mol when one correlates all core electrons except for 1s shells of transition metals, S, and Cl); and that is similar to some good xc functionals (e.g., B97-1 (MUD(20) = 4.5 kcal/mol) and PW6B95 (MUD(20) = 4.9 kcal/mol)) when the same basis set is used. We

  14. Computational Study of Metal-Dinitrogen Keggin-Type Polyoxometalate Complexes [PW11O39M(II)N2)](5-) (M = Ru, Os, Re, Ir): Bonding Nature and Dinitrogen Splitting.

    Science.gov (United States)

    Liu, Chun-Guang; Liu, Shuang; Zheng, Ting

    2015-08-17

    Molecular geometry, electronic structure, and metal-dinitrogen bonding nature of a series of metal-dinitrogen derivatives of Keggin-type polyoxometalates (POMs) [PW11O39M(II)N2)](5-) (M = Ru, Os, Re, Ir) have been studied by using a density functional theory (DFT) method with the M06L functional. Among these Keggin-type POM complexes, Os- and Re-substituted POM complexes are the most active for N2 adsorption with considerable adsorption energy. The electronic structure analysis shows that Os(II) and Re(II) centers in their metal-dinitrogen POM complexes possess π(2)xzπ(2)yzπ(2)xy and π(2)xzπ(2)yzπ(1)xy configurations, respectively. DFT-M06L calculations show that the possible synthesis routes proposed in this work for the Ru-, Os-, and Re-dinitrogen POM complexes are thermodynamically feasible under various solvent environments. Meanwhile, the Re-dinitrogen POM complex was assessed for the direct cleavage of dinitrogen molecule. In the reaction mechanism, a dimeric Keggin-type POM derivative of rhenium could represent the intermediate which undergoes N-N bond scission. The calculated free energy barrier (ΔG(⧧)) for a transition state with a zigzag conformation is 16.05 kcal mol(-1) in tetrahydrofuran, which is a moderate barrier for the cleavage of the N-N bond when compared with the literature values. In conclusion, regarding the direct cleavage of the dinitrogen molecule, the findings would be very useful to guide the search for a potential N2 cleavage compound into totally inorganic POM fields.

  15. Electrically pumped 1.3 microm room-temperature InAs/GaAs quantum dot lasers on Si substrates by metal-mediated wafer bonding and layer transfer.

    Science.gov (United States)

    Tanabe, Katsuaki; Guimard, Denis; Bordel, Damien; Iwamoto, Satoshi; Arakawa, Yasuhiko

    2010-05-10

    An electrically pumped InAs/GaAs quantum dot laser on a Si substrate has been demonstrated. The double-hetero laser structure was grown on a GaAs substrate by metal-organic chemical vapor deposition and layer-transferred onto a Si substrate by GaAs/Si wafer bonding mediated by a 380-nm-thick Au-Ge-Ni alloy layer. This broad-area Fabry-Perot laser exhibits InAs quantum dot ground state lasing at 1.31 microm at room temperature with a threshold current density of 600 A/cm(2).

  16. Effects of two erbium-doped yttrium aluminum garnet lasers and conventional treatments as composite surface abrasives on the shear bond strength of metal brackets bonded to composite resins

    Science.gov (United States)

    Sobouti, Farhad; Dadgar, Sepideh; Sanikhaatam, Zahra; Nateghian, Nazanin; Saravi, Mahdi Gholamrezaei

    2016-01-01

    Background: Bonding brackets to dental surfaces restored with composites are increasing. No studies to date have assessed the efficacy of laser irradiation in roughening of composite and the resulted shear bond strength (SBS) of the bonded bracket. We assessed, for the 1st time, the efficacy of two laser beams compared with conventional methods. Materials and Methods: Sixty-five discs of light-cured composite resin were stored in deionized distilled water for 7 days. They were divided into five groups of 12 plus a group of five for scanning electron microscopy (SEM): Bur-abrasion followed by phosphoric acid etching (bur-PA), hydrofluoric acid conditioning (HF), sandblasting, 3 W and 2 W erbium-doped yttrium aluminum garnet laser irradiation for 12 s. After bracket bonding, specimens were water-stored (24 h) and thermocycled (500 cycles), respectively. SBS was tested at 0.5 mm/min crosshead speed. The adhesive remnant index (ARI) was scored under ×10 magnification. SEM was carried out as well. Data were analyzed using analysis of variance (ANOVA), Kruskal–Wallis, Tukey, Dunn, one-sample t-test/Wilcoxon tests, and Weibull analysis (α =0.05). Results: The SBS values (megapascal) were bur-PA (11.07 ± 1.95), HF (19.70 ± 1.91), sandblasting (7.75 ± 1.10), laser 2 W (15.38 ± 1.38), and laser 3 W (20.74 ± 1.73) (compared to SBS = 6, all P = 0.000). These differed significantly (ANOVA P = 0.000) except HF versus 3 W laser (Tukey P > 0.05). ARI scores differed significantly (Kruskal–Wallis P = 0.000), with sandblasting and 2 W lasers having scores inclined to the higher end (safest debonding). Weibull analysis implied successful clinical outcome for all groups, except for sandblasting with borderline results. Conclusion: Considering its high efficacy and the lack of adverse effects bound with other methods, the 3 W laser irradiation is recommended for clinical usage. PMID:26998473

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

    Science.gov (United States)

    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.

  18. Supramolecular Chemistry of 4,4'-Bipyridine-N,N'-dioxide in Transition Metal Complexes: A Rich Diversity of Co-ordinate, Hydrogen-Bond and Aromatic Stacking Interactions

    Science.gov (United States)

    Jia, Junhua; Hubberstey, Peter; Champness, Neil R.; Schröder, Martin

    4,4'-Bipyridine-N,N'-dioxide (L1) has enormous flexibility as a supramolecular linker since it can be involved not only in co-ordinate and hydrogen bonds via its N,N'-dioxide oxygen centres, but the pyridine-N-oxide rings can also form aromatic π-π stacking interactions. Thus, L1 can bridge between, or act as a pendant ligand to metal centres and can support hydrogen-bonds within a lattice in a site remote from the metal centre. Of the structurally characterised transition metal complexes abstracted from the literature for this review, 26 form molecular compounds, 14 form 1D chains, 9 form 2D sheets of either 36, 44 or 63 topology, while 5 form 3D networks with either 41263 (α-Po type) or 48668 topology. To target multidimensional architectures it has been found to be necessary to avoid aqueous solutions and strongly co-ordinating anions, and consequently the synthesis of multidimensional L1-bridged transition metal co-ordination polymers has usually involved reaction of L1 with metal salts of weakly co-ordinating anions in low molecular weight alcohols. Of the 98 distinct molecules of L1 reported for complexes in the literature, 42 are bridging, 36 pendant and 20 are non-co-ordinated hydrogen-bonded molecules. Approximately 75% of the bridging L1 molecules adopt an anti-conformation, while the remainder adopt a syn-conformation. This prevalence of the anti-conformation contrasts markedly with the situation observed for lanthanide compounds, for which approximately 75% adopt a syn-conformation. A number of trends in the co-ordination behaviour of L1 with transition metals can be identified. Co-ordination to metal centres is based on sp 2 hybridised oxygen donors, but the π-interaction between the oxygen p z orbital and the aromatic ring is sufficiently weak that the oxygen lone pairs are normally twisted out of the plane of the pyridine-N-oxide by a steric clash between the metal centre and the α-hydrogen of the pyridine ring. As a result of this steric

  19. Bonding PMMA microfluidics using commercial microwave ovens

    Science.gov (United States)

    Toossi, A.; Moghadas, H.; Daneshmand, M.; Sameoto, D.

    2015-08-01

    In this paper, a novel low-cost, rapid substrate-bonding technique is successfully applied to polymethyl methacrylate (PMMA) microfluidics bonding for the first time. This technique uses a thin intermediate metallic microwave susceptor layer at the interface of the bonding site (microchannels) which produces localized heating required for bonding during microwave irradiation. The metallic susceptor pattern is designed using a multiphysics simulation model developed in ANSYS Multiphysics software (high-frequency structural simulation (HFSS) coupled with ANSYS-Thermal). In our experiments, the required microwave energy for bonding is delivered using a relatively inexpensive, widely accessible commercial microwave oven. Using this technique, simple PMMA microfluidics prototypes are successfully bonded and sealed in less than 35 seconds with a minimum measured bond strength of 1.375 MPa.

  20. Predicting Bond Dissociation Energies of Transition-Metal Compounds by Multiconfiguration Pair-Density Functional Theory and Second-Order Perturbation Theory Based on Correlated Participating Orbitals and Separated Pairs.

    Science.gov (United States)

    Bao, Junwei Lucas; Odoh, Samuel O; Gagliardi, Laura; Truhlar, Donald G

    2017-02-14

    We study the performance of multiconfiguration pair-density functional theory (MC-PDFT) and multireference perturbation theory for the computation of the bond dissociation energies in 12 transition-metal-containing diatomic molecules and three small transition-metal-containing polyatomic molecules and in two transition-metal dimers. The first step is a multiconfiguration self-consistent-field calculation, for which two choices must be made: (i) the active space and (ii) its partition into subspaces, if the generalized active space formulation is used. In the present work, the active space is chosen systematically by using three correlated-participating-orbitals (CPO) schemes, and the partition is chosen by using the separated-pair (SP) approximation. Our calculations show that MC-PDFT generally has similar accuracy to CASPT2, and the active-space dependence of MC-PDFT is not very great for transition-metal-ligand bond dissociation energies. We also find that the SP approximation works very well, and in particular SP with the fully translated BLYP functional SP-ftBLYP is more accurate than CASPT2. SP greatly reduces the number of configuration state functions relative to CASSCF. For the cases of FeO and NiO with extended-CPO active space, for which complete active space calculations are unaffordable, SP calculations are not only affordable but also of satisfactory accuracy. All of the MC-PDFT results are significantly better than the corresponding results with broken-symmetry spin-unrestricted Kohn-Sham density functional theory. Finally we test a perturbation theory method based on the SP reference and find that it performs slightly worse than CASPT2 calculations, and for most cases of the nominal-CPO active space, the approximate SP perturbation theory calculations are less accurate than the much less expensive SP-PDFT calculations.

  1. The Effect of Post-Bond Heat Treatment on Tensile Property of Diffusion Bonded Austenitic Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Sunghoon; Kim, Sung Kwan; Jang, Changheui [KAIST, Daejeon (Korea, Republic of); Sah, Injin [KAERI, Daejeon (Korea, Republic of)

    2015-12-15

    Diffusion bonding is the key manufacturing process for the micro-channel type heat exchangers. In this study, austenitic alloys such as Alloy 800HT, Alloy 690, and Alloy 600, were diffusion bonded at various temperatures and the tensile properties were measured up to 650 ℃. Tensile ductility of diffusion bonded Alloy 800HT was significantly lower than that of base metal at all test temperatures. While, for Alloy 690 and Alloy 600, tensile ductility of diffusion bonded specimens was comparable to that of base metals up to 500 ℃, above which the ductility became lower. The poor ductility of diffusion bonded specimen could have caused by the incomplete grain boundary migration and precipitates along the bond-line. Application of post-bond heat treatment (PBHT) improved the ductility close to that of base metals up to 550 ℃. Changes in tensile properties were discussed in view of the microstructure in the diffusionbonded area.

  2. Influence of bonding time on bond strength of metallic orthodontic bracket with etching base.%粘结时间对微蚀刻底托槽粘结强度的影响

    Institute of Scientific and Technical Information of China (English)

    杨瑞; 魏志民; 杨凯云; 张栋; 赵婧; 孙佩佩; 潘淑勤

    2012-01-01

    目的:对比微蚀刻底托槽粘结后不同时间的粘结强度,寻找合适的力的加载时机.方法:随机挑选对称性拔除上下颌第一前磨牙正畸患者30例,分为A、B、C三组进行全口微蚀刻底托槽粘结,分别在粘结后5 min,30 min,60min进行弓丝结扎,统计患者第一次复诊时托槽脱落率.将30例患者拔除的上颌第一前磨牙60颗,随机分成1~6组,每组10颗.1~6组离体牙粘结微蚀刻底直丝托槽,分别在粘结后5 min,10 min,15 min,30 min,60 min,24h进行抗剪切强度(SBS)测定,并统计粘结剂残留指数(ARI),扫描电镜观察托槽粘结前后底板形貌.结果:微蚀刻底托槽在体外粘结后24 h抗剪切强度达到最大.结论:微蚀刻底托槽的粘结强度能够满足临床需要,临床医师可在托槽粘结后5 min进行力的加载.%Objective: To measure the SBS of bracket with etching base at different time after bond and to find the appropriate time to load the bracket. Method: A total of 30 patients were randomly divided into 3 groups (10 per group) .480 bracket were bonded for them. They were loaded at 5 min,30 min,60 min seperately,and were observed for the first return visit.The failure of debond were recorded .Sixty youth maxillary first premolars extracted from the 30 patients above were randomly divided into 6 groups(10 per group). The shear bond test of group 1~6 was performed at different debond time of 5 min, 10 min, 15 min, 30 min, and 60 min and 24 hours. The chisquared test was used to determine signi? Cant differences for the ARI scores among the groups Ip < 0.05). Result: Highest shear bond strength was obtained with a debond time of 24 hours and the SBS was signi? Cantly different (P <0.001). Conclusion: Bracket with etching base is to meet the clinical requirement.lt is reliable to load the bracket 5 minutes after it is bonded.

  3. Diffusion bonding of copper to niobium

    Science.gov (United States)

    Wagner, Adrian R.

    Processes used to join metal to ceramic at low temperatures have proven to be inefficient because multiple brazing cycles with different brazing temperatures and braze filler metals are required. Even though this is reproducible and robust, it is not ideal due to the manufacturing time and cost associated with multiple brazing cycles. A more efficient and cost effective process is to utilize the diffusion bonding technique to join different metallic layers prior to joining the entire ceramic assembly in one brazing cycle. In this study, the diffusion bonding of copper to niobium was examined. To the author's knowledge, the diffusion bonding of Cu to Nb has not been researched, and the diffusion of Cu into Nb or Nb into Cu has not been observed. A series of diffusion bonding experiments were conducted to determine the optimal bonding time, temperature, and pressure for the Cu-Nb system. The diffusion bonded samples were evaluated using mechanical testing and microscopy. Results from characterization indicate that diffusion of Nb into Cu occurs, and a robust bond with no interfacial voids is formed using different combinations of bonding parameters. The diffusion of Nb into Cu and with failure occurring outside the diffusion bonded region during all mechanical testing indicate that Cu can be bonded to Nb via the diffusion bonding technique.

  4. Kinetics and mechanism for reversible chloride transfer between mercury(II) and square-planar platinum(II) chloro ammine, aqua, and sulfoxide complexes. Stabilities, spectra, and reactivities of transient metal-metal bonded platinum-mercury adducts.

    Science.gov (United States)

    Gröning, O; Sargeson, A M; Deeth, R J; Elding, L I

    2000-09-18

    The Hg2+aq- and HgCl+aq-assisted aquations of [PtCl4]2- (1), [PtCl3(H2O)]- (2), cis-[PtCl2(H2O)2] (3), trans-[PtCl2(H2O)2] (4), [PtCl(H2O)3]+ (5), [PtCl3Me2SO]- (6), trans-[PtCl2(H2O)Me2SO] (7), cis-[PtCl(H2O)2Me2SO]+ (8), trans-[PtCl(H2O)2M32SO]+ (9), trans-[PtCl2(NH3)2] (10), and cis-[PtCl2(NH3)2] (11) have been studied at 25.0 degrees C in a 1.00 M HClO4 medium buffered with chloride, using stopped-flow and conventional spectrophotometry. Saturation kinetics and instantaneous, large UV/vis spectral changes on mixing solutions of platinum complex and mercury are ascribed to formation of transient adducts between Hg2+ and several of the platinum complexes. Depending on the limiting rate constants, these adducts are observed for a few milliseconds to a few minutes. Thermodynamic and kinetics data together with the UV/vis spectral changes and DFT calculations indicate that their structures are characterized by axial coordination of Hg to Pt with remarkably short metal-metal bonds. Stability constants for the Hg2+ adducts with complexes 1-6, 10, and 11 are (2.1 +/- 0.4) x 10(4), (8 +/- 1) x 10(2), 94 +/- 6, 13 +/- 2, 5 +/- 2, 60 +/- 6, 387 +/- 2, and 190 +/- 3 M-1, respectively, whereas adduct formation with the sulfoxide complexes 7-9 is too weak to be observed. For analogous platinum(II) complexes, the stabilities of the Pt-Hg adducts increase in the order sulfoxide < aqua < ammine complex, reflecting a sensitivity to the pi-acid strength of the Pt ligands. Rate constants for chloride transfer from HgCl+ and HgCl2 to complexes 1-11 have been determined. Second-order rate constants for activation by Hg2+ are practically the same as those for activation by HgCl+ for each of the platinum complexes studied, yet resolved contributions for Hg2+ and HgCl+ reveal that the latter does not form dinuclear adducts of any significant stability. The overall experimental evidence is consistent with a mechanism in which the accumulated Pt(II)-Hg2+ adducts are not reactive

  5. Covalent Bonding of Metal-Organic Framework-5/Graphene Oxide Hybrid Composite to Stainless Steel Fiber for Solid-Phase Microextraction of Triazole Fungicides from Fruit and Vegetable Samples.

    Science.gov (United States)

    Zhang, Shuaihua; Yang, Qian; Wang, Wenchang; Wang, Chun; Wang, Zhi

    2016-04-06

    A hybrid material of the zinc-based metal-organic framework-5 and graphene oxide (metal-organic framework-5/graphene oxide) was prepared as a novel fiber coating material for solid-phase microextraction (SPME). The SPME fibers were fabricated by covalent bonding via chemical cross-linking between the coating material metal-organic framework-5/graphene oxide and stainless steel wire. The prepared fiber was used for the extraction of five triazole fungicides from fruit and vegetable samples. Gas chromatography coupled with microelectron capture detector (GC-μECD) was used for quantification. The developed method gave a low limit of detection (0.05-1.58 ng g(-1)) and good linearity (0.17-100 ng g(-1)) for the determination of the triazole fungicides in fruit and vegetable samples. The relative standard deviations (RSDs) for five replicate extractions of the triazole fungicides ranged from 3.7 to 8.9%. The method recoveries for spiked fungicides (5, 20, and 50 ng g(-1)) in grape, apple, cucumber, celery cabbage, pear, cabbage, and tomato samples were in the range of 85.6-105.8% with the RSDs ranging from 3.6 to 11.4%, respectively, depending on both the analytes and samples. The metal-organic framework-5/graphene oxide coated fiber was stable enough for 120 extraction cycles without a significant loss of extraction efficiency. The method was suitable for the determination of triazole fungicides in fruit and vegetable samples.

  6. Shear Bond Strength of Orthodontic Brackets Bonded to Zirconium Crowns

    Science.gov (United States)

    Mehmeti, Blerim; Azizi, Bleron; Kelmendi, Jeta; Iljazi-Shahiqi, Donika; Alar, Željko

    2017-01-01

    Background An increasing demand for esthetic restorations has resulted in an increased use of all-ceramic restorations, such as zirconium. However, one of the challenges the orthodontist must be willing to face is how to increase bond strength between the brackets and various ceramic restorations.Bond strength can beaffected bybracket type, by the material that bracketsaremade of, and their base surface design or retention mode. ​ Aim: of this study was to perform a comparative analysis of the shear bond strength (SBS) of metallic and ceramic orthodontic brackets bonded to all-zirconium ceramic surfaces used for prosthetic restorations, and also to evaluate the fracture mode of these two types of orthodontic brackets. Material and methods Twenty samples/semi-crowns of all-zirconium ceramic, on which orthodontic brackets were bonded, 10 metallic and 10 ceramic polycrystalline brackets, were prepared for this research. SBS has been testedby Universal Testing Machine, with a load applied using a knife edged rod moving at a fixed rate of 1 mm/min, until failure occurred. The force required to debond the brackets was recorded in Newton, then SBS was calculated to MPa. In addition, the samples were analyzed using a digital camera magnifier to determine Adhesive Remnant Index (ARI). Statistical data were processed using t-test, and the level of significance was set at α = 0.05. Results Higher shear bond strength values were observed in metallic brackets bonded to zirconium crowns compared tothoseof ceramic brackets, with a significant difference. During the test, two of the ceramic brackets were partially or totally damaged. Conclusion Metallic brackets, compared to ceramic polycrystalline brackets, seemed tocreate stronger adhesion with all-zirconium surfaces due to their better retention mode. Also, ceramic brackets showed higher fragility during debonding. PMID:28827846

  7. Preresonance Raman studies of metal-to-ligand charge transfer in (NH sub 3 ) sub 4 Ru(2,2 prime -bpy) sup 2+. In situ bond length changes, force constants, and reorganization energies

    Energy Technology Data Exchange (ETDEWEB)

    Doorn, S.K.; Hupp, J.T. (Northwestern Univ., Evanston, IL (USA))

    1989-06-21

    As a prototype for charge-transfer reactions in general, the intense metal-to-ligand charge-transfer transition occurring in Ru(NH{sub 3}){sub 4}(bpy){sup 2+} (bpy = 2,2{prime}-bipyridine) has been examined experimentally by resonance and preresonance Raman spectroscopy and analytically by time-dependent scattering theory. To their knowledge, the present example represents the first application of the theory to charge-transfer problems. From the experiments and corresponding theory, the normal-coordinate changes accompanying the transition have been calculated. Both metal-ligand and intraligand bonds are found to distort significantly. When the distortion data are combined with the observed vibrational frequencies, a mode-by-mode assessment of the inner-shell reorganization energy is possible. Further experiments, in which the nature of the solvent is systematically varied, show that selected force constants (and therefore selected components of the internal reorganization energy) are modulated significantly (ca. 6-11 %) by ligand-solvent hydrogen bonding. Finally, variations in the nature of the solvent are found to shift ground- and/or excited-state energies in such a way as to either enhance or attenuate the occurrence of net photochemistry.

  8. Chemical bonding in transition metal complexes with beryllium ligands [(PMe(3))(2)M-BeCl(2)], [(PMe(3))(2)M-BeClMe], and [(PMe(3))(2)M-BeMe(2)] (M = Ni, Pd, Pt).

    Science.gov (United States)

    Parameswaran, Pattiyil; Frenking, Gernot

    2010-08-26

    The equilibrium geometries and bond dissociation energies of the 14 valence electron (VE) complexes [(PMe(3))(2)M-BeCl(2)], [(PMe(3))(2)M-BeClMe], and [(PMe(3))(2)M-BeMe(2)] with M = Ni, Pd, and Pt have been calculated using density functional theory at the BP86/TZ2P level. The nature of the M-Be bond was analyzed with the NBO charge decomposition analysis and the EDA energy decomposition analysis. The theoretical results predict the equilibrium structures with a T-shaped geometry at the transition metal where the PMe(3) ligands are in the axial positions. The calculated bond dissociation energies show that the M-E bond strengths are in the range of donor-acceptor complexes of divalent beryllium compounds with ammonia. The bond strength decreases when the substituent at beryllium changes from Cl to CH(3). The NBO analysis shows a negative charge at the BeX(2) fragment, which indicates a net charge flow from the transition metal fragment to the beryllium fragment. The energy decomposition analysis of the M-Be bonds suggests two donor-acceptor bonds with sigma and pi symmetry where the transition metal fragment is a double donor with respect to the beryllium ligand. The pi component of the [Ni]-->BeXX' donation is much smaller than the sigma component.

  9. Influence of different silane coupling agents on shear bond strength of metal brackets to porcelain surface%不同偶联剂对烤瓷瓷面与金属托槽抗剪切力的影响

    Institute of Scientific and Technical Information of China (English)

    丁宏

    2015-01-01

    Objective To investigate the influence of different silane coupling agents to the shear bond strength of metal brackets bonded to porcelain surface. Methods 30 porcelain specimens were deglazed by water sandpaper and etched,rinsed with distilled water and dried before applying the silane primer.All specimens were divided randomly into 3 groups according to different silane coupling agents application,every group had 10 porcelain facets.30 metal brackets were bonded to ceramic specimens.All specimens were stored in artificial saliva bath at 37℃ for 24 hours.after brackets bonded for 60min,then the specimens were underwent shear testing with Instron universal testing machine. Results The shear bond strength of the groups treated with silane primer were higher than that without silane primer(P0.05).The groups treated without silane coupling agent showed lower porcelain fracture than the groups treated with silane coupling agent. Conclusions Silane coupling agent can improve the shear bond strength between metal brackets and porcelain surface.There was not any statistically significant in the shear bond strength between the group of one-mix silane coupling agent and the group of two-mix silane coupling agent.%目的:研究不同类型硅烷偶联剂对烤瓷瓷面与金属托槽之间抗剪切力的影响。方法:将30个烤瓷瓷面行水砂纸打磨去釉,HF酸蚀处理,根据硅烷偶联剂的不同随机分3组,将30个金属托槽粘结于烤瓷瓷面,托槽粘结60min后经37℃恒温人工唾液水浴孵化24h,使用Instron万能材料力学试验机测定样本抗剪切力。结果:使用硅烷偶联剂组抗剪切力比未使用硅烷偶联剂组大,差异有统计学意义(P<0.05);单组份和双组份硅烷偶联剂组之间抗剪切力比较,差异无统计学意义(P>0.05);未使用硅烷偶联剂组瓷面破损指数明显小于使用硅烷偶联剂组,差异有统计学意义(P<0.05)。结论:硅烷偶联剂能有

  10. Applications of Bis(1-R-imidazol-2-yl)disulfides and Diselenides as Ligands for Main Group and Transition Metals: κ2-[N,N] Coordination, S-S Bond Cleavage and S-S/E-E (E = S, Se) Bond Metathesis Reactions

    Science.gov (United States)

    Figueroa, Joshua S.; Yurkerwich, Kevin; Melnick, Jonathan; Buccella, Daniela; Parkin, Gerard

    2008-01-01

    Bis(1-R-imidazol-2-yl)disulfides, (mimR)2 (R = Ph, But), and diselenides, (seimMes)2, serve as bidentate [N,N]-donor ligands for main group and transition metals. For example, [κ2-(mimBut)2]MCl2 (M = Fe, Co, Ni, Zn), [κ2-(mimPh)2]MCl2 (M = Co, Zn), [κ2-(mimBut)2]CuX (X = Cl, I) and [κ2-(seimMes)2]MCl2 (M = Fe, Co, Ni) are obtained by treatment of (mimBut)2 or (seimMes)2 with the respective metal halide, and have been structurally characterized by X-ray diffraction. On the other hand, the zerovalent nickel complex Ni(PMe3)4 effects cleavage of the disulfide bond of (mimBut)2 to give square planar trans-Ni(PMe3)2(mimBut)2 in which the (mimBut) ligands coordinate via nitrogen rather than sulfur, a most uncommon coordination mode for this class of ligands. Although [κ2-(mimR)2]MCl2 (M = Fe, Co, Ni, Zn) are not subject to homolytic cleavage of the S-S bond because the tetravalent state is not readily accessible, the observation that [κ2-(mimPh)2]CoCl2 and [κ2-(mimBut)2]CoCl2 form an equilibrium mixture with the asymmetric disulfide [κ2-(mimPh)(mimBut)]CoCl2 indicates that S-S bond cleavage via another mechanism is possible. Likewise, metathesis between disulfide and diselenide ligands is observed in the formation of [κ2-(mimBut)(seimMes)]CoCl2 upon treatment of [κ2-(mimBut)2]CoCl2 with [κ2-(seimMes)2]CoCl2. PMID:17900186

  11. 异核金属多重键配合物Cp2 MM'(μ-C8 H8)的理论研究%Theoretical Study on the Heteronuclear Metal-metal Multiple Bond Complexes Cp2 MM'(μ-C8 H8)

    Institute of Scientific and Technical Information of China (English)

    刘楠楠; 丁益宏; 刘树萍

    2014-01-01

    The structure and bonding of the heteronuclear metal-metal multiple bond complexes Cp2 MM’(μ-C8 H8 ) ( MM’=ScMn, TiCr, ScCo, TiFe, VMn) were theoretically studied. The calculated results shows that: ( 1 ) for the 28 ve systems, the ground-state of Cp2 V2 (μ-C8 H8 ) is triplet state with V-V triple bond, the isoelectronic Cp2 TiCr (μ-C8 H8 ) is singlet state with Ti-Cr quadruple bond, and the isoelectronic species Cp2 ScMn(μ-C8 H8 ) is singlet state with Sc-Mn triple bond. (2) For the 30 valence electron systems, the ground-states of Cp2 Cr2 (μ-C8 H8 ) is singlet state with Cr-Cr triple bond, the isoelectronic species Cp2 VMn(μ-C8 H8 ) is triplet state with V-Mn single bond, while the isoelectronic species Cp2 ScCo(μ-C8 H8 ) and Cp2 TiFe (μ-C8 H8 ) are singlet states with double metal-metal bond. In the triplet state of Cp2 MM’(μ-C8 H8 ) , the two metal atoms are generally 17-electron configuration, while in the singlet state, the two metal atoms are generally respectively 16-and 18-electron configuration.%研究了双核金属多重键配合物Cp2 MM'(μ-C8 H8)( MM'=ScMn, TiCr, ScCo, TiFe, VMn, VV, CrCr)的结构和成键模式。计算结果表明,对于28价电子体系, Cp2 V2(μ-C8 H8)基态为含V-V三重键的三态构型,其等电子体Cp2 TiCr(μ-C8 H8)为Ti-Cr四重键的单态,等电子体Cp2 ScMn(μ-C8 H8)为Sc-Mn三重键的单态。对于30价电子体系, Cp2 Cr2(μ-C8 H8)基态为含Cr-Cr三重键的单态,等电子体Cp2 VMn(μ-C8 H8)为含V-Mn单键的三态,等电子体Cp2 ScCo(μ-C8 H8)和Cp2 TiFe(μ-C8 H8)为含Sc-Co和Ti-Fe双键的单态。在三态Cp2 MM'(μ-C8 H8)中,两个金属原子多为17电子构型,而单态结构中两种金属原子多分别为16和18电子构型。

  12. Inter-layer charge disproportionation in the dual-layer organic metal (tTTF-I)2ClO4 with unsymmetrical I···O halogen bond interactions.

    Science.gov (United States)

    Shin, Kyoung-Soon; Jeannin, Olivier; Brezgunova, Mariya; Dahaoui, Slimane; Aubert, Emmanuel; Espinosa, Enrique; Auban-Senzier, Pascale; Świetlik, Roman; Frąckowiak, Arkadiusz; Fourmigué, Marc

    2014-04-14

    A mixed-valence salt of tTTF-I with ClO4(-), formulated as (tTTF-I)2ClO4, is characterized by the presence of two crystallographically independent donor molecules, segregated in different layers and linked together through I···O interactions with the ClO4(-) anion disordered at room temperature. The tTTF-I donor molecule was prepared by metallation of tTTF (trimethylene tetrathiafulvalene) followed by reaction with iodine to afford the mono and diiodo derivatives tTTF-I and tTTFI2, respectively. The crystal structure of the latter neutral tTTFI2 shows the occurrence of strong type II, II halogen bond interactions. Band structure calculations of the dual-layer structure of the 2 : 1 salt (tTTF-I)2ClO4 show co-existence of both 1D open and 2D closed Fermi surfaces. The salt undergoes a metal-insulator phase transition at T(MI) = 90 K, associated with an electronic dimensionality decrease, since already at 100 K, the 2D part of the Fermi surface transforms into 1D corrugated planes. High resolution X-ray investigations performed at 100 K, combined with multipolar refinements, indicate an approximately equivalent +0.5e charge in both donor molecules, as also deduced from the intramolecular bond distances. On the other hand, Raman spectroscopic investigations show that at ambient temperature the charge is actually distributed non-uniformly in conducting layers of tTTF-I molecules, with the identification of molecules with charges +1, +0.5, 0e, while at low temperature the charge distribution becomes essentially uniform (+0.5e), as confirmed from the X-ray high resolution data. These apparently contradictory behaviors are actually a consequence of a partial electron transfer between the two independent slabs to reach a common Fermi level in the metallic phase.

  13. Evidence of covalent bond formation at the silane-metal interface during plasma polymerization of bis-1,2-(triethoxysilyl)ethane (BTSE) on aluminium

    Science.gov (United States)

    Batan, A.; Mine, N.; Douhard, B.; Brusciotti, F.; De Graeve, I.; Vereecken, J.; Wenkin, M.; Piens, M.; Terryn, H.; Pireaux, J. J.; Reniers, F.

    2010-06-01

    Silane and silane-like films were deposited from bis-1,2-(triethoxysilyl)ethane by vacuum and atmospheric plasma onto aluminium. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used for probing the aluminium/plasma polymer film interface. An AlOSi + fragment was identified at nominal mass m/ z = 70.9539 amu, indicating a strong chemical interaction (formation of a covalent bond) at the substrate/film interface. Until now, this strong silane-aluminium interaction has never been observed in plasma polymer BTSE films. Ageing tests in an ultrasonic water bath combined with X-ray photoelectron spectroscopy measurements allowed to indirectly confirm good adhesion, and therefore the formation of a chemical bond at the interface.

  14. Aqueous-Medium Carbon-Carbon Bond-Forming Radical Reactions Catalyzed by Excited Rhodamine B as a Metal-Free Organic Dye under Visible Light Irradiation.

    Science.gov (United States)

    Yoshioka, Eito; Kohtani, Shigeru; Jichu, Takahisa; Fukazawa, Takuya; Nagai, Toyokazu; Kawashima, Akira; Takemoto, Yoshiji; Miyabe, Hideto

    2016-08-19

    The utility of rhodamine B as a water-soluble organic photocatalyst was studied in the cascade radical addition-cyclization-trapping reactions under visible light irradiation. In the presence of (i-Pr)2NEt, the electron transfer from the excited rhodamine B to perfluoroalkyl iodides proceeded smoothly to promote the carbon-carbon bond-forming radical reactions in aqueous media. When i-C3F7I was employed as a radical precursor, the aqueous-medium radical reactions proceeded even in the absence of (i-Pr)2NEt. In these reactions, the direct electron transfer from the excited singlet state of rhodamine B would take place. Furthermore, the cleavage of the C-I bond in less reactive i-PrI could be achieved by the reductive electron transfer from the excited rhodamine B, which was confirmed by the fluorescence quenching of rhodamine B with the addition of i-PrI.

  15. TBAI-Catalyzed/Water-Assisted Double C-S Bond Formations: An Efficient Approach to Sulfides through Metal-Free Three-Component Reactions.

    Science.gov (United States)

    Chu, Xue-Qiang; Xu, Xiao-Ping; Ji, Shun-Jun

    2016-09-26

    An aqueous catalytic method for double C-S bond formations that involves alcohol derivatives, organic halides, and sodium thiosulfate has been developed. A diverse range of functionalized sulfides, including pharmaceutical and biological derivatives, can be obtained in an efficient and eco-friendly manner under air. The mechanistic studies revealed that this tetrabutylammonium-iodide-catalyzed/water-assisted reaction generated a mercaptan species as the key intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Transition metal-promoted synthesis of 2-aryl/heteroaryl-thioquinazoline: C-S Bond formation by “Chan-Lam Cross-Coupling” Reaction

    Indian Academy of Sciences (India)

    SATYA KARUNA PULAKHANDAM; NARESH KUMAR KATARI; RAVI PRAKASH REDDY MANDA

    2017-02-01

    An efficient method for the synthesis of S-aryl/heteroaryl-quinazoline has been developed through the cross-coupling of 1,4-dihydroquinazoline with a variety of aryl and heteroaryl boronic acids assisted by [Cu(OAc)₂] as the catalyst for the formation of carbon-sulfur bonds. This newly developed method demonstratesthat the conditions of the traditional copper-catalyzed Chan-Lam reaction can be improved. Optimized reaction involves base, solvent and catalyst.

  17. Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals: Co, Rh, Ir.

    Science.gov (United States)

    Glezakou, Vassiliki-Alexandra; Rousseau, Roger; Elbert, Stephen T; Franz, James A

    2017-03-09

    The homolytic bond dissociation energies of a series of five- and six-coordinate mono- and dihydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2](+) (where M = Co, Rh, and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2](+) species. For M = Ir the bond energies of the five- and six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties compared with experimentally available data that are difficult to obtain.

  18. Terahertz spectroscopy of 25MgH (X2Σ+) and (67)ZnH (X2Σ+): bonding in simple metal hydrides.

    Science.gov (United States)

    Bucchino, Matthew P; Ziurys, Lucy M

    2013-10-03

    Pure rotational spectra of (25)MgH (X(2)Σ(+)) and (67)ZnH (X(2)Σ(+)) were recorded using direct absorption techniques. These free radicals were synthesized by the reaction of metal vapor, generated in a Broida-type oven, with H2 in a dc discharge. The N = 0 → 1 and N = 1 → 2 transitions were recorded for both species in the frequency range 342-789 GHz. Spin-rotation and metal and proton hyperfine interactions were resolved in the spectra. From these data, rotational, fine structure, and hyperfine constants were determined, including the Fermi contact, dipolar, and electric quadrupole parameters of the (25)Mg and (67)Zn nuclei. Comparison of the metal and proton hyperfine terms suggests that the unpaired electron resides in a σ molecular orbital that has significant s contributions from both the metal and the hydrogen atoms. The dipolar terms for both metals are relatively large, in contrast to those of the proton, and indicate spσ and possibly sdσ (zinc only) orbital hybridization. The quadrupole constants arise principally from the p/d orbital character of the unpaired electron, although there is a non-negligible polarization contribution. These results suggest significant covalent character in both MgH and ZnH, in contrast to their fluoride analogs.

  19. Metal- and ligand-assisted CO2 insertion into Ru-C, Ru-N, and Ru-O bonds of ruthenium(II) phosphine complexes: a density functional theory study.

    Science.gov (United States)

    Vadivelu, Prabha; Suresh, Cherumuttathu H

    2015-01-20

    The CO2 insertion reactions of [L4Ru(η(2)-CH2C6H4)] (1), [L4Ru(η(2)-OC6H3Me)] (2), and [L4Ru(η(2)-NHC6H4)] (3), where L = PH3 and PMe3, are modeled using density functional theory methods. In 1 and 2, the metal-assisted CO2 insertion occurs because of the favorable initial axial phosphine dissociation mechanism, whereas in 3, the ligand (NHC6H4)-assisted mechanism operates (ΔG(⧧) = +19.0 kcal/mol), wherein the nucleophilic affinity of the -NHC6H4 moiety aids the CO2 insertion process. The modeled mechanisms are consistent with the experimental findings by Hartwig et al. (J. Am. Chem. Soc, 1991, 113, 6499), in which the rate of the reactions of 1 and 2 depends on the added phosphine concentration, whereas the rate of the reaction of 3 is independent of the added phosphine concentration. In 1 and 2, CO2 is preferably inserted into the Ru-Caryl bond rather than the competitive Ru-CH2 and Ru-O bonds, respectively. In 1, the π-type orbital interaction of the aryl ring with the metal center is found to stabilize the transition state for Ru-Caryl bond insertion (ΔG(⧧) = +25.7 kcal/mol). In 2, the Ru-Caryl insertion (ΔG(⧧) = +23.0 kcal/mol) is thermodynamically preferred, while the kinetically preferred Ru-O bond insertion (ΔG(⧧) = +17.4 kcal/mol) is highly reversible. The more electron-donating and sterically bulky PMe3 facilitates the CO2 insertion of 1 and 2 because the initial dissociation of axial PMe3 is easier than that of PH3 by ca. +11.0 kcal/mol, whereas in the case of 3, the effect of PMe3 slightly increases the ΔG(⧧) value of 3. The increase in the nucleophilic affinity of amido nitrogen in 3 and the increase in the polarity of the solvent decrease the ΔG(⧧) value of 3 by 48%. The inclusion of the chelating dimethylphosphinoethane ligand in 3 along with the electron-donating substituent at the -NHC6H4 moiety and the polar solvent further reduces the ΔG(⧧) value of 3 by 62%, which demonstrates the role of the chelating ligand, electron

  20. 选区激光熔化钴铬合金金-瓷结合强度初探%Metal-ceramic bond strength of Co-Cr alloy processed by selective laser melting

    Institute of Scientific and Technical Information of China (English)

    刘洁; 刘洋; 孙荣; 战德松; 王彦岩

    2013-01-01

    Objective To eveluate the metal-ceramic bond strength of a selective laser melting Co-Cr alloy.Methods Twelve Co-Cr metal bars were prepared according to the ISO 9693 standard with Vita porcelain fused onto the centre of each bar.Then the sample bars were devided into two groups of six each.The control group was made by traditional cast process(cast group),and the experimental group was processed by selective laser melting (SLM) technology (SLM group).Metal-ceramic bonding strength and fracture mode were assessed using three-point bending test.Fracture mode analysis was determined by scanning electronic microscope/energy dispersive spectroscopy.Student's t-test was used to analyze the data in SPSS 13.0.Results The metal-ceramic bond strength value of the cast group was (33.45 ±2.34) MPa,and that of the SLM group was (31.62 ± 2.34) MPa (t =0.79,P > 0.05).A mixed fracture mode on the debonding interface of all specimens was observed,while little porcelain was reserved.Conclusions The metal-ceramic system processed by SLM exhibited a bonding strength that satisfies the requirement of clinical application.%目的 采用三点弯曲法评价选区激光熔化钴铬合金金-瓷结合强度,以期为修复临床提供参考.方法 依据ISO 9693标准,分别用铸造法(铸造组)和选区激光熔化法(选区激光熔化组)制作钴铬合金试件,每组6个,试件中间区域熔附瓷粉.三点弯曲法测试金-瓷结合强度,采用SPSS 13.0软件进行t检验,分析两组金-瓷结合强度差异;扫描电镜和能谱仪进行金-瓷结合界面分析.结果 铸造组和选区激光熔化组金-瓷结合强度分别为(33.45 ±2.34)和(31.62 ±2.34) MPa,两组差异无统计学意义(t =0.79,P>0.05).两组试件断裂类型均为混合断裂,仅微量瓷残余.结论 选区激光熔化钴铬合金修复体可满足临床对金-瓷结合强度的要求.

  1. Non-bonded ultrasonic transducer

    Science.gov (United States)

    Eoff, J.M.

    1984-07-06

    A mechanically assembled non-bonded ultrasonic transducer includes a substrate, a piezoelectric film, a wetting agent, a thin metal electrode, and a lens held in intimate contact by a mechanical clamp. No epoxy or glue is used in the assembly of this device.

  2. Bonding to a porcelain surface: Factors affecting the shear bond strength

    Directory of Open Access Journals (Sweden)

    Shishir Singh

    2013-01-01

    Full Text Available Objectives: Bonding to porcelain veneers, crowns or restorations is a major challenge for an orthodontist. A study was undertaken wherein, the shear bond strengths of metal and ceramic brackets on porcelain were compared and the effects of debonding on the debonded surfaces were evaluated. Materials and Methods: A total of 50 acrylic duplicate samples were fabricated from a therapeutically extracted maxillary first premolar, duly prepared for metal crown with porcelain facing. The samples were divided into two equal groups for bonding of metal and ceramic brackets. The shear bond strength of the samples was measured with a universal testing machine. Results: The metal brackets showed shear bond strengths with a mean of 12.21 ± 1.4 MPa, whereas the ceramic brackets displayed shear bond strengths with a mean of 17.45 ± 2.36 MPa. Visual and scanning electron microscope examination revealed multiple failure patterns with more of porcelain fractures in the ceramic brackets group. Conclusion: Bonding of metal and ceramic brackets to porcelain can be achieved with bond strengths comparable to that when bonded to enamel surface. Porcelain fractures are more commonly associated with debonding of ceramic brackets.

  3. Competition between Hydrogen Bonds and Coordination Bonds Steered by the Surface Molecular Coverage.

    Science.gov (United States)

    Cai, Liangliang; Sun, Qiang; Bao, Meiling; Ma, Honghong; Yuan, Chunxue; Xu, Wei

    2017-04-25

    In addition to the choices of metal atoms/molecular linkers and surfaces, several crucial parameters, including surface temperature, molecular stoichiometric ratio, electrical stimulation, concentration, and solvent effect for liquid/solid interfaces, have been demonstrated to play key roles in the formation of on-surface self-assembled supramolecular architectures. Moreover, self-assembled structural transformations frequently occur in response to a delicate control over those parameters, which, in most cases, involve either conversions from relatively weak interactions to stronger ones (e.g., hydrogen bonds to coordination bonds) or transformations between the comparable interactions (e.g., different coordination binding modes or hydrogen bonding configurations). However, intermolecular bond conversions from relatively strong coordination bonds to weak hydrogen bonds were rarely reported. Moreover, to our knowledge, a reversible conversion between hydrogen bonds and coordination bonds has not been demonstrated before. Herein, we have demonstrated a facile strategy for the regulation of stepwise intermolecular bond conversions from the metal-organic coordination bond (Cu-N) to the weak hydrogen bond (CH···N) by increasing the surface molecular coverage. From the DFT calculations we quantify that the loss in intermolecular interaction energy is compensated by the increased molecular