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Sample records for chemical bonding analysis

  1. Gradient Bundle Analysis: A Full Topological Approach to Chemical Bonding

    CERN Document Server

    Morgenstern, Amanda

    2016-01-01

    The "chemical bond" is a central concept in molecular sciences, but there is no consensus as to what a bond actually is. Therefore, a variety of bonding models have been developed, each defining the structure of molecules in a different manner with the goal of explaining and predicting chemical properties. This thesis describes the initial development of gradient bundle analysis (GBA), a chemical bonding model that creates a high resolution picture of chemical interactions within the charge density framework. GBA is based on concepts from the quantum theory of atoms in molecules (QTAIM), but uses a more complete picture of the topology and geometry of the electron charge density to understand and predict bonding interactions. Gradient bundles are defined as volumes bounded by zero-flux surfaces (ZFSs) in the gradient of the charge density with well-defined energies. The structure of gradient bundles provides an avenue for detecting the locations of valence electrons, which correspond to reactive regions in a ...

  2. Chemical Bond Analysis of Single Crystal Growth of Magnesium Oxide

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Starting from the crystallographic structure of magnesium oxide (MgO), both the chemical bond model of solids and Pauling's third rule (polyhedral sharing rule) were employed to quantitatively analyze the chemical bonding structure of constituent atoms and single crystal growth. Our analytical results show that MgO single crystals prefer to grow along the direction and the growth rate of the {100} plane is the slowest one. Therefore, the results show that the {100} plane of MgO crystals can be the ultimate morphology face, which is in a good agreement with our previous experimental results. The study indicate that the structure analysis is an effective tool to control the single-crystal growth.

  3. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot

    2014-01-01

    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  4. Density Functionals of Chemical Bonding

    Directory of Open Access Journals (Sweden)

    Mihai V. Putz

    2008-06-01

    Full Text Available The behavior of electrons in general many-electronic systems throughout the density functionals of energy is reviewed. The basic physico-chemical concepts of density functional theory are employed to highlight the energy role in chemical structure while its extended influence in electronic localization function helps in chemical bonding understanding. In this context the energy functionals accompanied by electronic localization functions may provide a comprehensive description of the global-local levels electronic structures in general and of chemical bonds in special. Becke-Edgecombe and author’s Markovian electronic localization functions are discussed at atomic, molecular and solid state levels. Then, the analytical survey of the main workable kinetic, exchange, and correlation density functionals within local and gradient density approximations is undertaken. The hierarchy of various energy functionals is formulated by employing both the parabolic and statistical correlation degree of them with the electronegativity and chemical hardness indices by means of quantitative structure-property relationship (QSPR analysis for basic atomic and molecular systems.

  5. Micro-chemical analysis of diffusion bonded W-SiC joint

    Energy Technology Data Exchange (ETDEWEB)

    Matsuo, Genichiro [Graduate Student, Graduate School of Engineering, Hokkaido University, Sapporo Hokkaido 060-8628 (Japan); Shibayama, Tamaki, E-mail: shiba@ufml.caret.hokudai.ac.jp [Center for Advanced Research of Energy Conversion Materials, Hokkaido University, Sapporo Hokkaido 060-8628 (Japan); Kishimoto, Hirotatsu [Department of Materials Science and Engineering, Muroran Institute of Technology, Muroran Hokkaido 050-8585 (Japan); Hamada, Kouichi; Watanabe, Seiichi [Center for Advanced Research of Energy Conversion Materials, Hokkaido University, Sapporo Hokkaido 060-8628 (Japan)

    2011-10-01

    W and SiC joining has an attractive feature for high-temperature energy conversion systems. However, it is unclear and that is necessary to study the microstructure of the reaction phase between W and SiC by using the thermal diffusion bonding method. This work demonstrates the strengthening mechanism of W and SiC joining through a microstructure analysis of the reaction phase by FE-TEM/EDS and the observation of the interface in W and SiC after the crack propagation in HVEM. The reaction phase was amorphous, with a gap from 500 to 600 nm between W and SiC. Fine precipitates with a diameter of several tens nanometer were formed in the reaction phase. The reaction phase and precipitates did not match the chemical composition of the equilibrium compound. It is conceivable that the reaction phase and precipitates exist as a non-equilibrium condition before they reach equilibrium condition.

  6. Anatomy of bond formation. Bond length dependence of the extent of electron sharing in chemical bonds from the analysis of domain-averaged Fermi holes.

    Science.gov (United States)

    Ponec, Robert; Cooper, David L

    2007-01-01

    We demonstrate that domain-average Fermi hole (DAFH) analysis, which has previously been used at the Hartree-Fock level, remains useful after the proper introduction of electron correlation. We perform a systematic investigation of the variation of the picture of bonding with increasing bond length in simple diatomic molecules such as N2 and LiH. Alongside values of a shared-electron distribution index (SEDI), this analysis provides further insight into the geometry dependence of the extent of electron sharing in polar and non-polar systems. We also use DAFH analysis, with correlated wave functions, to evaluate the (potential) multicentre bonding in the electron-deficient and electron-rich molecules CH2Li2 and CH2N2, respectively.

  7. Chemical bonding and charge density distribution analysis of undoped and lanthanum doped barium titanate ceramics

    Indian Academy of Sciences (India)

    J MANGAIYARKKARASI; R SARAVANAN; MUKHLIS M ISMAIL

    2016-12-01

    A-site deficient, Lanthanum substituted Ba1−xLa2x/3TiO3 (x=0.000, 0.005, 0.015, 0.020 and 0.025) ceramics have been synthesized by chemical route. The effects of lanthanum dopant on the BaTiO3 lattice and the electron density distributions in the unit cell of the samples were investigated. Structural studies suggested the reduction in cell parameters and shrinkage in cell volume with the increase in lanthanum content. Chemical bonding and electron density distributions were examined through high resolution maximum entropy method (MEM). The mid bond electron density values revealed the enhancement of covalent nature between titanium and oxygen ions and predominant ionic nature between barium and oxygen ions. Average grain sizes were estimated for the undoped and doped samples. SEM investigations showed the existence of smaller grains with large voids in between them.

  8. A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

    Energy Technology Data Exchange (ETDEWEB)

    Raupach, Marc; Tonner, Ralf, E-mail: tonner@chemie.uni-marburg.de [Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35032 Marburg (Germany)

    2015-05-21

    The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the addition of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H{sub 2} on M(001), M = Pd, Cu), and semiconducting (CO and C{sub 2}H{sub 2} on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.

  9. [Intramolecular hygrogen bonds in conformers of 2'-deoxycytidine: results of quantum-chemical analysis of electron density topology].

    Science.gov (United States)

    Zhurakivs'kyĭ, R O; Hovorun, D M

    2006-01-01

    As many as 13 types of intramolecular hygrogen bonds are determined in 89 conformers of 2'-deoxycytidine nucleoside by means of quantum-chemical analysis (at DFT B3LYP/6-31G(d,p) theory level) of electron density topology with Atoms-in-Molecules (AIM) theory. The total number of H-bonds is 168 and their types are C1'H...O2, C2'H2...O5', C2'H2...O2, C3'H...O2, C5'H1...O2, C5'H2...O2, C6H...O4', C6H...O5', C3'H...HC6, O3'H...O5', O5'H...O3', O5'H...O4' and O5'H...O2. Conformational, geometric and electron-topological properties of H-bonds are presented.

  10. Valence-Bond Theory and Chemical Structure.

    Science.gov (United States)

    Klein, Douglas J.; Trinajstic, Nenad

    1990-01-01

    Discussed is the importance of valence bond theory on the quantum-mechanical theory of chemical structure and the nature of the chemical bond. Described briefly are early VB theory, development of VB theory, modern versions, solid-state applications, models, treatment in textbooks, and flaws in criticisms of valence bond theory. (KR)

  11. The chemical bond in inorganic chemistry the bond valence model

    CERN Document Server

    Brown, I David

    2016-01-01

    The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

  12. Surface chemical-bonds analysis of silicon particles from diamond-wire cutting of crystalline silicon

    Science.gov (United States)

    Benayad, Anass; Hajjaji, Hamza; Coustier, Fabrice; Benmansour, Malek; Chabli, Amal

    2016-12-01

    The recycling of the Si powder resulting from the kerf loss during silicon ingot cutting into wafers for photovoltaic application shows both significant and achievable economic and environmental benefits. A combined x-ray photoelectron spectroscopy (XPS), attenuated total reflection (ATR)-Fourier transform infrared (FTIR) and micro-Raman spectral analyses were applied to kerf-loss Si powders reclaimed from the diamond wire cutting using different cutting fluids. These spectroscopies performed in suitable configurations for the analysis of particles, yield detailed insights on the surface chemical properties of the powders demonstrating the key role of the cutting fluid nature. A combined XPS core peak, plasmon loss, and valence band study allow assessing a qualitative and quantitative chemical, structural change of the kerf-loss Si powders. The relative contribution of the LO and TO stretching modes to the Si-O-Si absorption band in the ATR-FTIR spectra provide a consistent estimation of the effective oxidation level of the Si powders. The change in the cutting media from deionized water to city water, induces a different silicon oxide layer thickness at the surface of the final kerf-loss Si, depending on the powder reactivity to the media. The surfactant addition induces an enhanced carbon contamination in the form of grafted carbonated species on the surface of the particles. The thickness of the modified surface, depending on the cutting media, was estimated based on a simple model derived from the combined XPS core level and plasmon peak intensities. The effective nature of these carbonated species, sensitive to the water quality, was evidenced based on coupled XPS core peak and valence band study. The present work paves the way to a controlled process to reclaim the kerf-loss Si powder without heavy chemical etching steps.

  13. Coulombic Models in Chemical Bonding.

    Science.gov (United States)

    Sacks, Lawrence J.

    1986-01-01

    Compares the coulumbic point charge model for hydrogen chloride with the valence bond model. It is not possible to assign either a nonpolar or ionic canonical form of the valence bond model, while the covalent-ionic bond distribution does conform to the point charge model. (JM)

  14. 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.

  15. Surfactant free synthesis of CdS nanospheres, microstructural analysis, chemical bonding, optical properties and photocatalytic activities

    Science.gov (United States)

    Ganesh, R. Sankar; Sharma, Sanjeev K.; Durgadevi, E.; Navaneethan, M.; Binitha, H. S.; Ponnusamy, S.; Muthamizhchelvan, C.; Hayakawa, Y.; Kim, Deuk Young

    2017-04-01

    The surfactant free cadmium sulfide (CdS) nanospheres were synthesized by the chemical method in a single step. The uniform shape of CdS spheres was controlled by the variation of concentration of thioacetamide (C2H5NS). The cubic phase of CdS nanopowder was determined from XRD analysis, which closely matched to the standard card. The spherical grains of CdS powder were confirmed from the microstructural analysis. The concentration of thioacetamide (TAA) played a vital role in the formation of nanospheres. The bandgap of CdS nanospheres decreased from 2.44 to 2.22 eV as the mole concentration of C2H5NS increased from 0.05 M to 2.0 M. FTIR spectra confirmed the presence of the stretching bond of Cdsbnd S. The dominant PL peak of purely and uniformed CdS nanospheres was observed at 528 nm due to S vacancies or surface defects. The prepared photocatalyst demonstrated the superior visible light photocatalytic degradation of methylene blue (MB). The highest degradation (96%) of MB was achieved within 180 min. Therefore, CdS nanospheres grown in the single step by the chemical method has a remarkable enhancement in the degradation of pollutants under irradiation of visible light.

  16. Physio-chemical Investigation and Natural Bond Orbital Analysis of the Most Actives Ingredient of Fennel Plant

    Directory of Open Access Journals (Sweden)

    Mansoureh Pishehabadi

    2016-10-01

    Full Text Available In this study, physio-chemical properties of effective compounds of fennel plant were investigated through using computational chemistry. To do this, trans-anethole, estragole, 3'- hydroxyanethole and 4- methoxycinnamyl alcohol compounds that the most active ingredient combinations make up the fennel plant have been carried out at three different levels of HF, BLYP and B3LYP theories using 6-31G*, 6-311G*, 6-311G**, 6-311+G and 6-311++G basis sets. Additionally, ab initio calculation in the gas phase have been studied and physio-chemical parameters including Gibbs free energy, thermal energy, enthalpy, entropy, and thermal capacity in constant volume (CV of these compounds have been computed as well as Gibbs free energy in polar solvents such as ethanol and methanol and water. Based on these obtained data the structural stabilities of these flavorful compounds have been discussed. However, in these herbal effective compounds presented here the natural bond orbital (NBO analysis has been performed which seemed quite informative to show some important atomic and structural features. The result lead to the issue that all those compounds in polar solvents, particularly alcoholic solvents solved and the compounds can be used sufficiently to extract the active ingredients of herb fennel.

  17. Bond-length analysis of the omega structure in Ti,Zr,Hf and their alloys: experimental data, new correlations and implications for chemical bonding models

    Energy Technology Data Exchange (ETDEWEB)

    Grad, G.B.; Benites, G.M. [Comision Nacional de Energia Atomica, San Carlos de Bariloche (Argentina). Centro Atomico Bariloche; Aurelio, G. [Departamento de Fisica, Universidad del Comahue, 8300, Neuquen (Argentina); Fernandez Guillermet, A. [Centro Atomico Bariloche, 8400, San Carlos de Bariloche (Argentina)

    1999-12-15

    An analysis is performed of the experimental information on the key interatomic distances (IDs) of the AlB{sub 2} type structure, the so-called omega ({omega}) phase in Ti and Zr, as well as in Ti-V and Zr-Nb alloys. Various remarkable correlations are found between these IDs and standard measures of the atomic size, and with Pauling's bond-lengths. These observations are discussed in the light of the phenomenological bonding pictures of the {omega} structure, and with our recent ab initio calculations of the electronic structure of this phase. (orig.)

  18. The correlation theory of the chemical bond

    CERN Document Server

    Szalay, Szilárd; Szilvási, Tibor; Veis, Libor; Legeza, Örs

    2016-01-01

    The notion of chemical bond is a very useful concept in chemistry. It originated at the beginning of chemistry, it is expressive for the classically thinking mind, and the errors arising from the approximative nature of the concept can often be ignored. In the first half of the twentieth century, however, we learned that the proper description of the microworld is given by quantum mechanics. Quantum mechanics gives more accurate results for chemical systems than any preceding model, however, it is very inexpressive for the classically thinking mind. The quantum mechanical description of the chemical bond is given in terms of delocalized bonding orbitals, or, alternatively, in terms of correlations of occupations of localized orbitals. However, in the latter case, multiorbital correlations were treated only in terms of two-orbital correlations, although the structure of multiorbital correlations is far richer; and, in the case of bonds established by more than two electrons, multiorbital correlations represent...

  19. Chemical Bond Calculations of Crystal Growth of KDP and ADP

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A novel method was proposed to calculate the crystal morphology (or growth habit) on the basis of chemical bond analysis. All constituent chemical bonds were distinguished as relevant and independent bonds according to their variations during the crystallization process. By employing the current method, the influence of specific growth conditions on the crystal morphology can be considered in the structure analysis process. The ideal morphologies of both KDP (KH2PO4) and ADP (NH4H2PO4) crystals were calculated and compared with our obtained crystallites at room temperature, which validates the present calculation method very well.

  20. Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids.

    Science.gov (United States)

    Maintz, Stefan; Deringer, Volker L; Tchougréeff, Andrei L; Dronskowski, Richard

    2013-11-05

    Quantum-chemical computations of solids benefit enormously from numerically efficient plane-wave (PW) basis sets, and together with the projector augmented-wave (PAW) method, the latter have risen to one of the predominant standards in computational solid-state sciences. Despite their advantages, plane waves lack local information, which makes the interpretation of local densities-of-states (DOS) difficult and precludes the direct use of atom-resolved chemical bonding indicators such as the crystal orbital overlap population (COOP) and the crystal orbital Hamilton population (COHP) techniques. Recently, a number of methods have been proposed to overcome this fundamental issue, built around the concept of basis-set projection onto a local auxiliary basis. In this work, we propose a novel computational technique toward this goal by transferring the PW/PAW wavefunctions to a properly chosen local basis using analytically derived expressions. In particular, we describe a general approach to project both PW and PAW eigenstates onto given custom orbitals, which we then exemplify at the hand of contracted multiple-ζ Slater-type orbitals. The validity of the method presented here is illustrated by applications to chemical textbook examples-diamond, gallium arsenide, the transition-metal titanium-as well as nanoscale allotropes of carbon: a nanotube and the C60 fullerene. Remarkably, the analytical approach not only recovers the total and projected electronic DOS with a high degree of confidence, but it also yields a realistic chemical-bonding picture in the framework of the projected COHP method.

  1. The chemical bond of stibium. Technological aspects

    Directory of Open Access Journals (Sweden)

    Ashcheulov A. A.

    2011-08-01

    Full Text Available Thin structure of the chemical bond of the hexagonal and rhombohedral modifications of stibium was investigated. The boundaries of their polymorphism were identified, which opens new technological possibilities of creating optical, photoelectric, thermoelectric, and other materials for electronic equipment components.

  2. Chemical Bonding: The Orthogonal Valence-Bond View

    Directory of Open Access Journals (Sweden)

    Alexander F. Sax

    2015-04-01

    Full Text Available Chemical bonding is the stabilization of a molecular system by charge- and spin-reorganization processes in chemical reactions. These processes are said to be local, because the number of atoms involved is very small. With multi-configurational self-consistent field (MCSCF wave functions, these processes can be calculated, but the local information is hidden by the delocalized molecular orbitals (MO used to construct the wave functions. The transformation of such wave functions into valence bond (VB wave functions, which are based on localized orbitals, reveals the hidden information; this transformation is called a VB reading of MCSCF wave functions. The two-electron VB wave functions describing the Lewis electron pair that connects two atoms are frequently called covalent or neutral, suggesting that these wave functions describe an electronic situation where two electrons are never located at the same atom; such electronic situations and the wave functions describing them are called ionic. When the distance between two atoms decreases, however, every covalent VB wave function composed of non-orthogonal atomic orbitals changes its character from neutral to ionic. However, this change in the character of conventional VB wave functions is hidden by its mathematical form. Orthogonal VB wave functions composed of orthonormalized orbitals never change their character. When localized fragment orbitals are used instead of atomic orbitals, one can decide which local information is revealed and which remains hidden. In this paper, we analyze four chemical reactions by transforming the MCSCF wave functions into orthogonal VB wave functions; we show how the reactions are influenced by changing the atoms involved or by changing their local symmetry. Using orthogonal instead of non-orthogonal orbitals is not just a technical issue; it also changes the interpretation, revealing the properties of wave functions that remain otherwise undetected.

  3. The chemical bond structure and dynamics

    CERN Document Server

    Zewail, Ahmed

    1992-01-01

    This inspired book by some of the most influential scientists of our time--including six Nobel laureates--chronicles our emerging understanding of the chemical bond through the last nine decades and into the future. From Pauling's early structural work using x-ray and electron diffraction to Zewail's femtosecond lasers that probe molecular dynamics in real time; from Crick's molecular biology to Rich's molecular recognition, this book explores a rich tradition of scientific heritage and accomplishment. The perspectives given by Pauling, Perutz, Rich, Crick, Porter, Polanyi, Herschbach, Zewail,

  4. A Corpuscular Picture of Electrons in Chemical Bond

    CERN Document Server

    Ando, Koji

    2015-01-01

    We introduce a theory of chemical bond with a corpuscular picture of electrons. It employs a minimal set of localized electron wave packets with 'floating and breathing' degrees of freedom and the spin-coupling of non-orthogonal valence-bond theory. It accurately describes chemical bonds in ground and excited states of spin singlet and triplet, in a distinct manner from conventional theories, indicating potential for establishing a dynamical theory of electrons in chemical bonds.

  5. A periodic Energy Decomposition Analysis (pEDA) method for the Investigation of Chemical Bonding in Extended Systems

    CERN Document Server

    Raupach, Marc

    2015-01-01

    The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the binding energy between two fragments (e.g. the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic and dispersion interaction, Pauli repulsion and orbital relaxation energies. The pEDA presented here for an AO-based implementation can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy and k-space sampling. Four typical bonding scenarios for surface adsorbate complexes were chosen to highlight th...

  6. Emphasizing the Significance of Electrostatic Interactions in Chemical Bonding

    Science.gov (United States)

    Venkataraman, Bhawani

    2017-01-01

    This paper describes a pedagogical approach to help students understand chemical bonding by emphasizing the importance of electrostatic interactions between atoms. The approach draws on prior studies that have indicated many misconceptions among students in understanding the nature of the chemical bond and energetics associated with bond formation…

  7. Analysis of Hydrogen Bonds in Crystals

    Directory of Open Access Journals (Sweden)

    Sławomir J. Grabowski

    2016-05-01

    Full Text Available The determination of crystal structures provides important information on the geometry of species constituting crystals and on the symmetry relations between them. Additionally, the analysis of crystal structures is so conclusive that it allows us to understand the nature of various interactions. The hydrogen bond interaction plays a crucial role in crystal engineering and, in general, its important role in numerous chemical, physical and bio-chemical processes was the subject of various studies. That is why numerous important findings on the nature of hydrogen bonds concern crystal structures. This special issue presents studies on hydrogen bonds in crystals, and specific compounds and specific H-bonded patterns existing in crystals are analyzed. However, the characteristics of the H-bond interactions are not only analyzed theoretically; this interaction is compared with other ones that steer the arrangement of molecules in crystals, for example halogen, tetrel or pnicogen bonds. More general findings concerning the influence of the hydrogen bond on the physicochemical properties of matter are also presented.

  8. Concept of chemical bond and aromaticity based on quantum information theory

    CERN Document Server

    Szilvási, T; Legeza, Ö

    2015-01-01

    Quantum information theory (QIT) emerged in physics as standard technique to extract relevant information from quantum systems. It has already contributed to the development of novel fields like quantum computing, quantum cryptography, and quantum complexity. This arises the question what information is stored according to QIT in molecules which are inherently quantum systems as well. Rigorous analysis of the central quantities of QIT on systematic series of molecules offered the introduction of the concept of chemical bond and aromaticity directly from physical principles and notions. We identify covalent bond, donor-acceptor dative bond, multiple bond, charge-shift bond, and aromaticity indicating unified picture of fundamental chemical models from ab initio.

  9. The electronic structure and chemical bonding of vitamin B12

    Science.gov (United States)

    Kurmaev, E. Z.; Moewes, A.; Ouyang, L.; Randaccio, L.; Rulis, P.; Ching, W. Y.; Bach, M.; Neumann, M.

    2003-05-01

    The electronic structure and chemical bonding of vitamin B12 (cyanocobalamin) and B12-derivative (methylcobalamin) are studied by means of X-ray emission (XES) and photoelectron (XPS) spectroscopy. The obtained results are compared with ab initio electronic structure calculations using the orthogonalized linear combination of the atomic orbital method (OLCAO). We show that the chemical bonding in vitamin B12 is characterized by the strong Co-C bond and relatively weak axial Co-N bond. It is further confirmed that the Co-C bond in cyanocobalamin is stronger than that of methylcobalamin resulting in their different biological activity.

  10. Tracing the Fingerprint of Chemical Bonds within the Electron Densities of Hydrocarbons: A Comparative Analysis of the Optimized and the Promolecule Densities.

    Science.gov (United States)

    Keyvani, Zahra Alimohammadi; Shahbazian, Shant; Zahedi, Mansour

    2016-10-18

    The equivalence of the molecular graphs emerging from the comparative analysis of the optimized and the promolecule electron densities in two hundred and twenty five unsubstituted hydrocarbons was recently demonstrated [Keyvani et al. Chem. Eur. J. 2016, 22, 5003]. Thus, the molecular graph of an optimized molecular electron density is not shaped by the formation of the C-H and C-C bonds. In the present study, to trace the fingerprint of the C-H and C-C bonds in the electron densities of the same set of hydrocarbons, the amount of electron density and its Laplacian at the (3, -1) critical points associated with these bonds are derived from both optimized and promolecule densities, and compared in a newly proposed comparative analysis. The analysis not only conforms to the qualitative picture of the electron density build up between two atoms upon formation of a bond in between, but also quantifies the resulting accumulation of the electron density at the (3, -1) critical points. The comparative analysis also reveals a unified mode of density accumulation in the case of 2318 studied C-H bonds, but various modes of density accumulation are observed in the case of 1509 studied C-C bonds and they are classified into four groups. The four emerging groups do not always conform to the traditional classification based on the bond orders. Furthermore, four C-C bonds described as exotic bonds in previous studies, for example the inverted C-C bond in 1,1,1-propellane, are naturally distinguished from the analysis.

  11. Upper Secondary Teachers' Knowledge for Teaching Chemical Bonding Models

    Science.gov (United States)

    Bergqvist, Anna; Drechsler, Michal; Chang Rundgren, Shu-Nu

    2016-01-01

    Researchers have shown a growing interest in science teachers' professional knowledge in recent decades. The article focuses on how chemistry teachers impart chemical bonding, one of the most important topics covered in upper secondary school chemistry courses. Chemical bonding is primarily taught using models, which are key for understanding…

  12. Combined analysis of chemical bonding in a Cu(II) dimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches.

    Science.gov (United States)

    Vologzhanina, Anna V; Kats, Svitlana V; Penkova, Larisa V; Pavlenko, Vadim A; Efimov, Nikolay N; Minin, Vadim V; Eremenko, Igor L

    2015-10-01

    Interaction of 1-(1H-pyrazol-5-yl)ethanone oxime (H2PzOx) with copper(II) chloride in the presence of pyridine afforded a binuclear discrete [Cu2(HPzOx)2Cl2py2] complex, which was characterized by Fourier transform-IR and electron paramagnetic resonance (EPR) spectra, magnetochemistry and high-resolution X-ray diffraction experiments. Multipole refinement of X-ray diffraction data and density-functional theory (DFT) calculations of an isolated molecule allowed charge and spin distributions to be obtained for this compound. Magnetochemistry data, EPR spectra and DFT calculations of an isolated molecule show antiferromagnetic coupling between copper(II) ions. The spin distribution suggests an exchange pathway via the bridging pyrazole ring in the equatorial plane of the CuN4Cl coordination polyhedron, thus providing support for the classical superexchange mechanism; the calculated value of the magnetic coupling constant -2J is equal to 220 cm(-1), which compares well with the experimental value of 203 ± 2 cm(-1). Chemical connectivity was derived by Bader's 'quantum theory of atoms in molecules' and compared with Voronoi tessellation and Hirshfeld surface representations of crystal space. All methodologies gave a similar qualitative and semi-quantitative description of intra- and intermolecular connectivity.

  13. Closing in on chemical bonds by opening up relativity theory.

    Science.gov (United States)

    Whitney, Cynthia K

    2008-03-01

    This paper develops a connection between the phenomenology of chemical bonding and the theory of relativity. Empirical correlations between electron numbers in atoms and chemical bond stabilities in molecules are first reviewed and extended. Quantitative chemical bond strengths are then related to ionization potentials in elements. Striking patterns in ionization potentials are revealed when the data are viewed in an element-independent way, where element-specific details are removed via an appropriate scaling law. The scale factor involved is not explained by quantum mechanics; it is revealed only when one goes back further, to the development of Einstein's special relativity theory.

  14. Experimental charge density and neutron structural study of cis-HMn(CO){sub 4}PPh{sub 3}: Comprehensive analysis of chemical bonding and evidence for a C-H{hor_ellipsis}H-Mn hydrogen bond

    Energy Technology Data Exchange (ETDEWEB)

    Abramov, Y.A.; Brammer, L. [Univ. of Missouri, St. Louis, MO (United States). Dept. of Chemistry; Klooster, W.T.; Bullock, R.M. [Brookhaven National Lab., Upton, NY (United States). Chemistry Dept.

    1998-11-30

    The structure and bonding in cis-HMn(CO){sub 4}PPh{sub 3} have been studied by low-temperature neutron and high-resolution X-ray diffraction, the latter study using a charge-coupled device (CCD) area detector. A charge density analysis, including the deformation density, a full topological analysis of {minus}{del}{sup 2}{rho}, has been conducted. The electrostatic component of the H{sup {delta}+}{hor_ellipsis}H{sup {delta}{minus}} interaction energy is calculated to be 5.7 kcal/mol from the experimental data. This electrostatic evidence coupled with the geometry C-H{hor_ellipsis}H 129.0(2){degree} and H{hor_ellipsis}H-Mn 126.5(1){degree} and the identification of an H{hor_ellipsis}H bond path in the charge density distribution strongly supports the characterization of this interaction as an intramolecular C-H{hor_ellipsis}H-Mn hydrogen bond. Both the deformation density and the topological study clearly illustrate the {sigma}-donor nature of both the H-Mn and Ph{sub 3}P-Mn interactions and the {sigma}-donor/{pi}-acceptor nature of the manganese-carbonyl bonds. The topological study further confirms the decrease in C-O bond order upon coordination to the metal and demonstrates for the first time by this method that the metal-ligand bonds, although showing characteristics of a closed-shell interaction, do have a significant dative covalent component to the bond. The latter is reinforced by a study of the derived Mn d-orbital populations, in which populations of the d{sub z{sup 2}} and d{sub x{sup 2}{minus}y{sup 2}} orbitals are significantly higher than would be predicted by a simple crystal field theory model of metal-ligand bonding.

  15. Structure of adsorbed monolayers. The surface chemical bond

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, G.A.; Bent, B.E.

    1984-06-01

    This paper attempts to provide a summary of what has been learned about the structure of adsorbed monolayers and about the surface chemical bond from molecular surface science. While the surface chemical bond is less well understood than bonding of molecules in the gas phase or in the solid state, our knowledge of its properties is rapidly accumulating. The information obtained also has great impact on many surface science based technologies, including heterogeneous catalysis and electronic devices. It is hoped that much of the information obtained from studies at solid-gas interfaces can be correlated with molecular behavior at solid-liquid interfaces. 31 references, 42 figures, 1 table.

  16. Electronegativity, Bond Energy, and Chemical Reactivity.

    Science.gov (United States)

    Myers, R. Thomas

    1979-01-01

    Discusses the Pauling electronegativity concept which rationalizes several kinds of chemical reactions of covalent substances. Electronegativity differences applied to some reactions are demonstrated. (SA)

  17. The Bondons: The Quantum Particles of the Chemical Bond

    Directory of Open Access Journals (Sweden)

    Mihai V. Putz

    2010-10-01

    Full Text Available By employing the combined Bohmian quantum formalism with the U(1 and SU(2 gauge transformations of the non-relativistic wave-function and the relativistic spinor, within the Schrödinger and Dirac quantum pictures of electron motions, the existence of the chemical field is revealed along the associate bondon particle  characterized by its mass (mΒ, velocity (vΒ, charge (eΒ, and life-time (tΒ. This is quantized either in ground or excited states of the chemical bond in terms of reduced Planck constant ħ, the bond energy Ebond and length Xbond, respectively. The mass-velocity-charge-time quaternion properties of bondons’ particles were used in discussing various paradigmatic types of chemical bond towards assessing their covalent, multiple bonding, metallic and ionic features. The bondonic picture was completed by discussing the relativistic charge and life-time (the actual zitterbewegung problem, i.e., showing that the bondon equals the benchmark electronic charge through moving with almost light velocity. It carries negligible, although non-zero, mass in special bonding conditions and towards observable femtosecond life-time as the bonding length increases in the nanosystems and bonding energy decreases according with the bonding length-energy relationship Ebond[kcal/mol]*Xbond[A]=182019, providing this way the predictive framework in which the particle may be observed. Finally, its role in establishing the virtual states in Raman scattering was also established.

  18. Benchmarking Density Functionals for Chemical Bonds of Gold

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2017-01-01

    Gold plays a major role in nanochemistry, catalysis, and electrochemistry. Accordingly, hundreds of studies apply density functionals to study chemical bonding with gold, yet there is no systematic attempt to assess the accuracy of these methods applied to gold. This paper reports a benchmark...... against 51 experimental bond enthalpies of AuX systems and seven additional polyatomic and cationic molecules. Twelve density functionals were tested, covering meta functionals, hybrids with variable HF exchange, double-hybrid, dispersion-corrected, and nonhybrid GGA functionals. The defined benchmark...... bonds between gold and noble gases. Zero-point vibrational corrections are relatively small for Au-X bonds, ∼ 11-12 kJ/mol except for Au-H bonds. Dispersion typically provides ∼5 kJ/mol of the total bond enthalpy but grows with system size and is 10 kJ/mol for AuXe and AuKr. HF exchange and LYP...

  19. Chemical bonding structural analysis of nitrogen-doped ultrananocrystalline diamond/hydrogenated amorphous carbon composite films prepared by coaxial arc plasma deposition

    Science.gov (United States)

    Gima, Hiroki; Zkria, Abdelrahman; Katamune, Yūki; Ohtani, Ryota; Koizumi, Satoshi; Yoshitake, Tsuyoshi

    2017-01-01

    Nitrogen-doped ultra-nanocrystalline diamond/hydrogenated amorphous carbon composite films prepared in hydrogen and nitrogen mixed-gas atmospheres by coaxial arc plasma deposition with graphite targets were studied electrically and chemical-bonding-structurally. The electrical conductivity was increased by nitrogen doping, accompanied by the production of n-type conduction. From X-ray photoemission, near-edge X-ray absorption fine-structure, hydrogen forward-scattering, and Fourier transform infrared spectral results, it is expected that hydrogen atoms that terminate diamond grain boundaries will be partially replaced by nitrogen atoms and, consequently, π C–N and C=N bonds that easily generate free electrons will be formed at grain boundaries.

  20. Upper Secondary Teachers' Knowledge for Teaching Chemical Bonding Models

    Science.gov (United States)

    Bergqvist, Anna; Drechsler, Michal; Rundgren, Shu-Nu Chang

    2016-01-01

    Researchers have shown a growing interest in science teachers' professional knowledge in recent decades. The article focuses on how chemistry teachers impart chemical bonding, one of the most important topics covered in upper secondary school chemistry courses. Chemical bonding is primarily taught using models, which are key for understanding science. However, many studies have determined that the use of models in science education can contribute to students' difficulties understanding the topic, and that students generally find chemical bonding a challenging topic. The aim of this study is to investigate teachers' knowledge of teaching chemical bonding. The study focuses on three essential components of pedagogical content knowledge (PCK): (1) the students' understanding, (2) representations, and (3) instructional strategies. We analyzed lesson plans about chemical bonding generated by 10 chemistry teachers with whom we also conducted semi-structured interviews about their teaching. Our results revealed that the teachers were generally unaware of how the representations of models they used affected student comprehension. The teachers had trouble specifying students' difficulties in understanding. Moreover, most of the instructional strategies described were generic and insufficient for promoting student understanding. Additionally, the teachers' rationale for choosing a specific representation or activity was seldom directed at addressing students' understanding. Our results indicate that both PCK components require improvement, and suggest that the two components should be connected. Implications for the professional development of pre-service and in-service teachers are discussed.

  1. Synthesis, molecular structure, hydrogen-bonding, NBO and chemical reactivity analysis of a novel 1,9-bis(2-cyano-2-ethoxycarbonylvinyl)-5-(4-hydroxyphenyl)-dipyrromethane: a combined experimental and theoretical (DFT and QTAIM) approach.

    Science.gov (United States)

    Singh, R N; Kumar, Amit; Tiwari, R K; Rawat, Poonam

    2013-09-01

    The spectroscopic analysis of a newly synthesized 1,9-bis(2-cyano-2-ethoxycarbonylvinyl)-5-(4-hydroxyphenyl)-dipyrromethane (3) has been carried out using (1)H NMR, UV-Visible, FT-IR and Mass spectroscopic techniques. All the quantum chemical calculations have been carried out using DFT level of theory, B3LYP functional and 6-31G(d,p) as basis set. Thermodynamic parameters (H, G, S) of all the reactants and products have been used to determine the nature of the chemical reaction. The chemical shift of pyrrolic NH in (1)H NMR spectrum appears at 9.4 ppm due to intramolecular hydrogen bonding. TD-DFT calculation shows the nature of electronic transitions as π→π(*) within the molecule. A combined experimental and theoretical vibrational analysis designates the existence of H-bonding between pyrrole N-H as proton donor and nitrogen of cyanide as proton acceptor, therefore, lowering in stretching vibration of NH and CN. To investigate the strength and nature of H-bonding, topological parameters at bond critical points (BCPs) are analyzed by 'Quantum theory of Atoms in molecules' (QTAIMs). Natural bond orbitals (NBOs) analysis has been carried out to investigate the intramolecular conjugative and hyperconjugative interactions within molecule and their second order stabilization energy (E((2))). Global electrophilicity index (ω=4.528 eV) shows that title molecule (3) is a strong electrophile. The maximum values of local electrophilic reactivity descriptors (fk(+),sk(+),ωk(+)) at vinyl carbon (C6/C22) of (3) indicate that these sites are more prone to nucleophilic attacks. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Chemical cleaning agents and bonding to glass-fiber posts.

    Science.gov (United States)

    Gonçalves, Ana Paula Rodrigues; Ogliari, Aline de Oliveira; Jardim, Patrícia dos Santos; Moraes, Rafael Ratto de

    2013-01-01

    The influence of chemical cleaning agents on the bond strength between resin cement and glass-fiber posts was investigated. The treatments included 10% hydrofluoric acid, 35% phosphoric acid, 50% hydrogen peroxide, acetone, dichloromethane, ethanol, isopropanol, and tetrahydrofuran. Flat glass-fiber epoxy substrates were exposed to the cleaners for 60 s. Resin cement cylinders were formed on the surfaces and tested in shear. All treatments provided increased bond strength compared to untreated control specimens. All failures were interfacial. Although all agents improved the bond strength, dichloromethane and isopropanol were particularly effective.

  3. Chemical cleaning agents and bonding to glass-fiber posts

    Directory of Open Access Journals (Sweden)

    Ana Paula Rodrigues Gonçalves

    2013-02-01

    Full Text Available The influence of chemical cleaning agents on the bond strength between resin cement and glass-fiber posts was investigated. The treatments included 10% hydrofluoric acid, 35% phosphoric acid, 50% hydrogen peroxide, acetone, dichloromethane, ethanol, isopropanol, and tetrahydrofuran. Flat glass-fiber epoxy substrates were exposed to the cleaners for 60 s. Resin cement cylinders were formed on the surfaces and tested in shear. All treatments provided increased bond strength compared to untreated control specimens. All failures were interfacial. Although all agents improved the bond strength, dichloromethane and isopropanol were particularly effective.

  4. Developing and validating a chemical bonding instrument for Korean high school students

    Science.gov (United States)

    Jang, Nak Han

    The major purpose of this study was to develop a reliable and valid instrument designed to collect and investigate on Korean high school students' understanding about concepts regarding chemical bonding. The Chemical Bonding Diagnostic Test (CBDT) was developed by the procedure by previously relevant researches (Treagust, 1985; Peterson, 1986; Tan, 1994). The final instrument consisted of 15 two-tier items. The reliability coefficient (Cronbach alpha) for the whole test was 0.74. Also, the range of values for the discrimination index was from 0.38 to 0.90 and the overall average difficulty index was 0.38. The test was administered to 716 science declared students in Korean high school. The 37 common misconceptions on chemical bonding were identified through analysis of the items from the CBDT. The grade 11 students had slightly more misconceptions than the grade 12 students for ionic bonding, covalent bonding, and hydrogen bonding while the grade 12 students had more misconceptions about octet rule and hydrogen bonding than the grade 11 students. From the analysis of ANCOVA, there was no significant difference in grades, and between grade levels and gender on the mean score of CBDT. However, there was a significant difference in gender and a significant interaction between grade levels and chemistry preference. In conclusion, Korean high school students had the most common misconception about the electron configuration on ionic bonding and the water density on hydrogen bonding. Korean students' understanding about the chemical bonding was dependent on the interaction between grade levels and the chemistry preference. Consequently, grade 12 chemistry-preferred students had the highest mean scores among student groups concerned by this study.

  5. Chemical Security Analysis Center

    Data.gov (United States)

    Federal Laboratory Consortium — In 2006, by Presidential Directive, DHS established the Chemical Security Analysis Center (CSAC) to identify and assess chemical threats and vulnerabilities in the...

  6. Ligand size dependence of U-N and U-O bond character in a series of uranyl hexaphyrin complexes: quantum chemical simulation and density based analysis.

    Science.gov (United States)

    Di Pietro, Poppy; Kerridge, Andrew

    2017-03-02

    A series of uranyl complexes with hexaphyrin ligands are investigated at the density functional level of theory and analysed using a variety of density-based techniques. A relationship is identified between the size of the ligand and the stability of the complex, controlled by the presence of meso-carbon centres in the porphyrin ring. The complex with the smallest ligand, cyclo[6]pyrrole, is found to have enhanced covalent character in equatorial U-N bonds as defined by the quantum theory of atoms in molecules (QTAIM), as well as enhanced stability, compared to the larger complexes. QTAIM data are supported by electron density difference distributions, integrated electronic properties and analysis of the reduced density gradient (RDG), which all show unambiguous evidence of electron sharing in all U-N bonds. In all complexes, a weakening of the covalent axial U-Oyl interaction in comparison to free uranyl is found, with evidence for a separation of electronic charge resulting in a more ionic interaction. A relationship between covalent character in the U-N bonds and the magnitude of uranyl charge redistribution is identified, where the greater the covalent character of the U-N interaction, the more ionic the U-Oyl interaction appears. The complex with the largest ligand, hexaphyrin(1.1.1.1.1.1), is found to have additional interactions with the uranyl oxygen centres, perturbing the U-Oyl interaction.

  7. The genesis of the quantum theory of the chemical bond

    CERN Document Server

    Esposito, S

    2013-01-01

    An historical overview is given of the relevant steps that allowed the genesis of the quantum theory of the chemical bond, starting from the appearance of the new quantum mechanics and following later developments till approximately 1931. General ideas and some important details are discussed concerning molecular spectroscopy, as well as quantum computations for simple molecular systems performed within perturbative and variational approaches, for which the Born-Oppenheimer method provided a quantitative theory accounting for rotational, vibrational and electronic states. The novel concepts introduced by the Heitler-London theory, complemented by those underlying the method of the molecular orbitals, are critically analyzed along with some of their relevant applications. Further improvements in the understanding of the nature of the chemical bond are also considered, including the ideas of one-electron and three-electron bonds introduced by Pauling, as well as the generalizations of the Heitler-London theory ...

  8. Chemical strategies for die/wafer submicron alignment and bonding.

    Energy Technology Data Exchange (ETDEWEB)

    Martin, James Ellis; Baca, Alicia I.; Chu, Dahwey; Rohwer, Lauren Elizabeth Shea

    2010-09-01

    This late-start LDRD explores chemical strategies that will enable sub-micron alignment accuracy of dies and wafers by exploiting the interfacial energies of chemical ligands. We have micropatterned commensurate features, such as 2-d arrays of micron-sized gold lines on the die to be bonded. Each gold line is functionalized with alkanethiol ligands before the die are brought into contact. The ligand interfacial energy is minimized when the lines on the die are brought into registration, due to favorable interactions between the complementary ligand tails. After registration is achieved, standard bonding techniques are used to create precision permanent bonds. We have computed the alignment forces and torque between two surfaces patterned with arrays of lines or square pads to illustrate how best to maximize the tendency to align. We also discuss complex, aperiodic patterns such as rectilinear pad assemblies, concentric circles, and spirals that point the way towards extremely precise alignment.

  9. Characterizing and Representing Student's Conceptual Knowledge of Chemical Bonding

    Science.gov (United States)

    Yayon, Malka; Mamlok-Naaman, Rachel; Fortus, David

    2012-01-01

    Chemical bonding knowledge is fundamental and essential to the understanding of almost every topic in chemistry, but it is very difficult to learn. While many studies have characterized some of the central elements of knowledge of this topic, these elements of knowledge have not been systematically organized. We describe the development and…

  10. Genetic analysis of the Fourier-transform infrared spectra of bovine milk with emphasis on individual wavelengths related to specific chemical bonds.

    Science.gov (United States)

    Bittante, G; Cecchinato, A

    2013-09-01

    transmittance, and the heritability estimates of individual waves were generally very low (with some exceptions). The 3 other identified regions contained many transmittance peaks that represented important chemical bonds; these showed much lower phenotypic and genetic variability in terms of individual waves, but relatively higher and less variable heritability estimates. Among them, the SWIR region (near-infrared) showed a peculiar cyclic pattern of the heritability coefficients of transmittance, the MWIR-1 region was particularly important for the estimation of fat, and the MWIR-LWIR region (also known also as the "fingerprint region") had 3 areas of relatively high heritability. In summary, we found that the transmittance data from the FTIR spectra of milk have genetic variability that may prove useful for the direct genetic improvement of dairy species, rather than only through indirect phenotypic predictions of individual milk quality and technological traits.

  11. Representational Classroom Practices that Contribute to Students' Conceptual and Representational Understanding of Chemical Bonding

    Science.gov (United States)

    Hilton, Annette; Nichols, Kim

    2011-11-01

    Understanding bonding is fundamental to success in chemistry. A number of alternative conceptions related to chemical bonding have been reported in the literature. Research suggests that many alternative conceptions held by chemistry students result from previous teaching; if teachers are explicit in the use of representations and explain their content-specific forms and functions, this might be avoided. The development of an understanding of and ability to use multiple representations is crucial to students' understanding of chemical bonding. This paper draws on data from a larger study involving two Year 11 chemistry classes (n = 27, n = 22). It explores the contribution of explicit instruction about multiple representations to students' understanding and representation of chemical bonding. The instructional strategies were documented using audio-recordings and the teacher-researcher's reflection journal. Pre-test-post-test comparisons showed an improvement in conceptual understanding and representational competence. Analysis of the students' texts provided further evidence of the students' ability to use multiple representations to explain macroscopic phenomena on the molecular level. The findings suggest that explicit instruction about representational form and function contributes to the enhancement of representational competence and conceptual understanding of bonding in chemistry. However, the scaffolding strategies employed by the teacher play an important role in the learning process. This research has implications for professional development enhancing teachers' approaches to these aspects of instruction around chemical bonding.

  12. Fast and accurate predictions of covalent bonds in chemical space

    Science.gov (United States)

    Chang, K. Y. Samuel; Fias, Stijn; Ramakrishnan, Raghunathan; von Lilienfeld, O. Anatole

    2016-05-01

    We assess the predictive accuracy of perturbation theory based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated σ bonding to hydrogen, as well as σ and π bonding between main-group elements, occurring in small sets of iso-valence-electronic molecules with elements drawn from second to fourth rows in the p-block of the periodic table. Numerical evidence suggests that first order Taylor expansions of covalent bonding potentials can achieve high accuracy if (i) the alchemical interpolation is vertical (fixed geometry), (ii) it involves elements from the third and fourth rows of the periodic table, and (iii) an optimal reference geometry is used. This leads to near linear changes in the bonding potential, resulting in analytical predictions with chemical accuracy (˜1 kcal/mol). Second order estimates deteriorate the prediction. If initial and final molecules differ not only in composition but also in geometry, all estimates become substantially worse, with second order being slightly more accurate than first order. The independent particle approximation based second order perturbation theory performs poorly when compared to the coupled perturbed or finite difference approach. Taylor series expansions up to fourth order of the potential energy curve of highly symmetric systems indicate a finite radius of convergence, as illustrated for the alchemical stretching of H 2+ . Results are presented for (i) covalent bonds to hydrogen in 12 molecules with 8 valence electrons (CH4, NH3, H2O, HF, SiH4, PH3, H2S, HCl, GeH4, AsH3, H2Se, HBr); (ii) main-group single bonds in 9 molecules with 14 valence electrons (CH3F, CH3Cl, CH3Br, SiH3F, SiH3Cl, SiH3Br, GeH3F, GeH3Cl, GeH3Br); (iii) main-group double bonds in 9 molecules with 12 valence electrons (CH2O, CH2S, CH2Se, SiH2O, SiH2S, SiH2Se, GeH2O, GeH2S, GeH2Se); (iv) main-group triple bonds in 9 molecules with 10 valence electrons (HCN, HCP, HCAs, HSiN, HSi

  13. Vitrified chemically bonded phosphate ceramics for immobilization of radioisotopes

    Science.gov (United States)

    Wagh, Arun S.

    2016-04-05

    A method of immobilizing a radioisotope and vitrified chemically bonded phosphate ceramic (CBPC) articles formed by the method are described. The method comprises combining a radioisotope-containing material, MgO, a source of phosphate, and optionally, a reducing agent, in water at a temperature of less than 100.degree. C. to form a slurry; curing the slurry to form a solid intermediate CBPC article comprising the radioisotope therefrom; comminuting the intermediate CBPC article, mixing the comminuted material with glass frits, and heating the mixture at a temperature in the range of about 900 to about 1500.degree. C. to form a vitrified CBPC article comprising the radioisotope immobilized therein.

  14. Evidence for chemical bond formation at rubber-brass interface: Photoelectron spectroscopy study of bonding interaction between copper sulfide and model molecules of natural rubber

    Science.gov (United States)

    Ozawa, Kenichi; Mase, Kazuhiko

    2016-12-01

    Strong adhesion between rubber and brass has been considered to arise mainly from the mechanical interaction, which is characterized by dendritic interlocking at the interface. In order to examine a possible contribution of the chemical interaction, chemical state analysis was carried out for model molecules of natural rubber (2-methyl-2-butene and isoprene) adsorbed on Cu2S, a key chemical species for adhesion, by means of photoelectron spectroscopy (PES). Absence of a C 1s PES component associated with C=C bonds and the appearance of adsorption-induced components in the S 2p region indicate that the molecules interact with the Cu2S surface via the C=C bond to form C-S covalent bonds. This proves that the chemical interaction certainly plays a role in rubber-brass adhesion along with the mechanical interaction.

  15. Majorana, Pauling and the quantum theory of the chemical bond

    CERN Document Server

    Esposito, S

    2013-01-01

    We discuss in detail very little known results obtained by Majorana as early as 1931, regarding the quantum theory of the chemical bond in homopolar molecules, based on the key concept of exchange interaction. After a brief historical overview of the quantum homopolar valence theory, we address the intriguing issues of the formation of the helium molecular ion, He2+, and of the accurate description of the hydrogen molecule, H2. For the first case, the group theory-inspired approach used by Majorana is contrasted with that more known followed by Pauling (and published few months after that of Majorana), while for the second case we focus on his proposal concerning the possible existence of ionic structures in homopolar compounds, just as in the hydrogen molecule. The novelty and relevance of Majorana's results in the modern research on molecular and chemical physics is emphasized as well.

  16. Chemical bonding in TiSb(2) and VSb(2): a quantum chemical and experimental study.

    Science.gov (United States)

    Armbrüster, Marc; Schnelle, Walter; Schwarz, Ulrich; Grin, Yuri

    2007-08-06

    The chemical bonding in the isostructural intermetallic compounds TiSb2 and VSb2, crystallizing in the CuAl2 type, was investigated by means of quantum chemical calculations, particularly the electron localization function (ELF), as well as by Raman spectroscopy, Hall effect and conductivity measurements on oriented single crystals, and high-pressure X-ray powder diffraction. The homogeneity ranges of the compounds were determined by powder X-ray diffraction, WDXS, and DSC measurements. TiSb2 exhibits no significant homogeneity range, while VSb2 shows a small homogeneity range of approximately 0.3 at. %. According to the ELF calculations, the Sb atoms form dumbbells via a two-center two-electron bond, while the T atoms (T = Ti, V) build up chains along the crystallographic c-axis. Both building units are connected by covalent T-Sb-T three-center bonds, thus forming a three-dimensional network. The strength of the bonds involving Sb was determined by fitting a force constant model to the vibrational mode frequencies observed by polarized Raman measurements on oriented single crystals. The resulting bond order of the Sb2 dumbbells is 1, while the strength of the three-center bonds resembles a bond order of 1.5. The weak pressure dependence of the c/a ratio confirms the slightly different bonding picture in TiSb2 compared to that in CuAl2. Electrical transport measurements show the presence of free charge carriers, as well as a metal-like temperature dependence of the electrical resistivity.

  17. Multivariate Quantitative Chemical Analysis

    Science.gov (United States)

    Kinchen, David G.; Capezza, Mary

    1995-01-01

    Technique of multivariate quantitative chemical analysis devised for use in determining relative proportions of two components mixed and sprayed together onto object to form thermally insulating foam. Potentially adaptable to other materials, especially in process-monitoring applications in which necessary to know and control critical properties of products via quantitative chemical analyses of products. In addition to chemical composition, also used to determine such physical properties as densities and strengths.

  18. Multivariate Quantitative Chemical Analysis

    Science.gov (United States)

    Kinchen, David G.; Capezza, Mary

    1995-01-01

    Technique of multivariate quantitative chemical analysis devised for use in determining relative proportions of two components mixed and sprayed together onto object to form thermally insulating foam. Potentially adaptable to other materials, especially in process-monitoring applications in which necessary to know and control critical properties of products via quantitative chemical analyses of products. In addition to chemical composition, also used to determine such physical properties as densities and strengths.

  19. [Influence of primers ' chemical composition on shear bond strength of resin cement to zirconia ceramic].

    Science.gov (United States)

    Łagodzińska, Paulina; Bociong, Kinga; Dejak, Beata

    2014-01-01

    Resin cements establish a strong durable bond between zirconia ceramic and hard tissues of teeth. It is essential to use primers with proper chemical composition before cementation. The aim of this study was to assess the influence of primer's chemical composition on the shear bond strength of zirconia ceramic to resin cements. 132 zirconia specimens were randomly assigned to four groups. There were four resin systems used. They included resin cement and respective primer, dedicated to zirconia: Clearfil Ceramic Primer/Panavia F2.0, Monobond Plus/Multilink Automix, AZ - Primer/ResiCem, Z - Prime Plus/Duo-Link. In each group the protocol of cementation was as follows: application of primer to the zirconia surface and application of the respective resin cement in cylindric mold (dimensions: 3.0 mm height and 3.0 mm diameter). Then, the shear bond strength was evaluated and the failure type was assessed in lupes (×2.5 magnification), also random specimens under SEM. The Wilcoxon test was used to analyze the data, the level of significance was α = 0.05. Finally, the known chemical composition of each primer was analysed in reference to probable chemical bonds, which may occure between primers and zirconia. The mean shear bond strength between resin cements and zirconia was the highest for Z-Prime Plus/Duo-Link (8.24 ± 3,21 MPa) and lowest for Clearfil Ceramic Primer/Panavia F 2.0 (4.60 ± 2.21 MPa). The analysis revealed significant difference between all groups, except pair Clearfil Ceramic Primer/Panavia F 2.0 and AZ-Primer/ResiCem. The failure type in groups of Clearfil Ceramic Primer/Panavia F 2.0 and AZ-Primer/ResiCem was mainly adhesive, in groups Monobond Plus/ /Multilink Automix and Z-Prime Plus/Duo-Link mainly mixed. The chemical composition of primers affects different bond mechanisms between resin cements and zirconia. The highest shear bond strength of resin cement to zirconia can be obtained for the primer composed of 10-Methacryloyloxydecyl dihydrogen

  20. Chemical process hazards analysis

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-02-01

    The Office of Worker Health and Safety (EH-5) under the Assistant Secretary for the Environment, Safety and Health of the US Department (DOE) has published two handbooks for use by DOE contractors managing facilities and processes covered by the Occupational Safety and Health Administration (OSHA) Rule for Process Safety Management of Highly Hazardous Chemicals (29 CFR 1910.119), herein referred to as the PSM Rule. The PSM Rule contains an integrated set of chemical process safety management elements designed to prevent chemical releases that can lead to catastrophic fires, explosions, or toxic exposures. The purpose of the two handbooks, ``Process Safety Management for Highly Hazardous Chemicals`` and ``Chemical Process Hazards Analysis,`` is to facilitate implementation of the provisions of the PSM Rule within the DOE. The purpose of this handbook ``Chemical Process Hazards Analysis,`` is to facilitate, within the DOE, the performance of chemical process hazards analyses (PrHAs) as required under the PSM Rule. It provides basic information for the performance of PrHAs, and should not be considered a complete resource on PrHA methods. Likewise, to determine if a facility is covered by the PSM rule, the reader should refer to the handbook, ``Process Safety Management for Highly Hazardous Chemicals`` (DOE- HDBK-1101-96). Promulgation of the PSM Rule has heightened the awareness of chemical safety management issues within the DOE. This handbook is intended for use by DOE facilities and processes covered by the PSM rule to facilitate contractor implementation of the PrHA element of the PSM Rule. However, contractors whose facilities and processes not covered by the PSM Rule may also use this handbook as a basis for conducting process hazards analyses as part of their good management practices. This handbook explains the minimum requirements for PrHAs outlined in the PSM Rule. Nowhere have requirements been added beyond what is specifically required by the rule.

  1. Chemical Bond Parameters in Sr3MRhO6 (M=Rare earth)

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Chemical bond parameters, that is, bond covalency, bond valence, macroscopic linear susceptibility, and oxidation states of elements in Sr3MRhO6 (M=Sm, Eu, Tb, Dy, Ho, Er, Yb) have been calculated. The results indicate that the bond covalency of M-O decreases sharply with the decrease of ionic radius of M3+ from Sm to Yb, while no obvious trend has been found for Rh-O and Sr-O bonds. The global instability index indicates that the crystal structures of Sr3MrhO6 (M = Sm, Eu, Tb, Dy, Ho) have strained bonds.

  2. Method of waste stabilization with dewatered chemically bonded phosphate ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Wagh, Arun; Maloney, Martin D.

    2010-06-29

    A method of stabilizing a waste in a chemically bonded phosphate ceramic (CBPC). The method consists of preparing a slurry including the waste, water, an oxide binder, and a phosphate binder. The slurry is then allowed to cure to a solid, hydrated CBPC matrix. Next, bound water within the solid, hydrated CBPC matrix is removed. Typically, the bound water is removed by applying heat to the cured CBPC matrix. Preferably, the quantity of heat applied to the cured CBPC matrix is sufficient to drive off water bound within the hydrated CBPC matrix, but not to volatalize other non-water components of the matrix, such as metals and radioactive components. Typically, a temperature range of between 100.degree. C.-200.degree. C. will be sufficient. In another embodiment of the invention wherein the waste and water have been mixed prior to the preparation of the slurry, a select amount of water may be evaporated from the waste and water mixture prior to preparation of the slurry. Another aspect of the invention is a direct anyhydrous CBPC fabrication method wherein water is removed from the slurry by heating and mixing the slurry while allowing the slurry to cure. Additional aspects of the invention are ceramic matrix waste forms prepared by the methods disclosed above.

  3. Method of waste stabilization with dewatered chemically bonded phosphate ceramics

    Science.gov (United States)

    Wagh, Arun; Maloney, Martin D.

    2010-06-29

    A method of stabilizing a waste in a chemically bonded phosphate ceramic (CBPC). The method consists of preparing a slurry including the waste, water, an oxide binder, and a phosphate binder. The slurry is then allowed to cure to a solid, hydrated CBPC matrix. Next, bound water within the solid, hydrated CBPC matrix is removed. Typically, the bound water is removed by applying heat to the cured CBPC matrix. Preferably, the quantity of heat applied to the cured CBPC matrix is sufficient to drive off water bound within the hydrated CBPC matrix, but not to volatalize other non-water components of the matrix, such as metals and radioactive components. Typically, a temperature range of between 100.degree. C.-200.degree. C. will be sufficient. In another embodiment of the invention wherein the waste and water have been mixed prior to the preparation of the slurry, a select amount of water may be evaporated from the waste and water mixture prior to preparation of the slurry. Another aspect of the invention is a direct anyhydrous CBPC fabrication method wherein water is removed from the slurry by heating and mixing the slurry while allowing the slurry to cure. Additional aspects of the invention are ceramic matrix waste forms prepared by the methods disclosed above.

  4. Comprehensive analysis of individual pulp fiber bonds quantifies the mechanisms of fiber bonding in paper

    Science.gov (United States)

    Hirn, Ulrich; Schennach, Robert

    2015-05-01

    The process of papermaking requires substantial amounts of energy and wood consumption, which contributes to larger environmental costs. In order to optimize the production of papermaking to suit its many applications in material science and engineering, a quantitative understanding of bonding forces between the individual pulp fibers is of importance. Here we show the first approach to quantify the bonding energies contributed by the individual bonding mechanisms. We calculated the impact of the following mechanisms necessary for paper formation: mechanical interlocking, interdiffusion, capillary bridges, hydrogen bonding, Van der Waals forces, and Coulomb forces on the bonding energy. Experimental results quantify the area in molecular contact necessary for bonding. Atomic force microscopy experiments derive the impact of mechanical interlocking. Capillary bridges also contribute to the bond. A model based on the crystal structure of cellulose leads to values for the chemical bonds. In contrast to general believe which favors hydrogen bonding Van der Waals bonds play the most important role according to our model. Comparison with experimentally derived bond energies support the presented model. This study characterizes bond formation between pulp fibers leading to insight that could be potentially used to optimize the papermaking process, while reducing energy and wood consumption.

  5. A natural orbital analysis of the long range behavior of chemical bonding and van der Waals interaction in singlet H2: the issue of zero natural orbital occupation numbers.

    Science.gov (United States)

    Sheng, X W; Mentel, Ł M; Gritsenko, O V; Baerends, E J

    2013-04-28

    This paper gives a natural orbital (NO) based analysis of the van der Waals interaction in (singlet) H2 at long distance. The van der Waals interaction, even if not leading to a distinct van der Waals well, affects the shape of the interaction potential in the van der Waals distance range of 5-9 bohrs and can be clearly distinguished from chemical bonding effects. In the NO basis the van der Waals interaction can be quantitatively covered with, apart from the ground state configurations (1σ(g))(2) and (1σ(u))(2), just the 4 configurations (2σ(g))(2) and (2σ(u))(2), and (1π(u))(2) and (1π(g))(2). The physics of the dispersion interaction requires and explains the peculiar relatively large positive CI coefficients of the doubly excited electron configurations (2σ(u))(2) and (1π(g))(2) (the occupancy amplitudes of the 2σ(u) and 1π(gx, y) NOs) in the distance range 5-9 bohrs, which have been observed before by Cioslowski and Pernal [Chem. Phys. Lett. 430, 188 (2006)]. We show that such positive occupancy amplitudes do not necessarily lead to the existence of zero occupation numbers at some H-H distances.

  6. Intermolecular atom-atom bonds in crystals - a chemical perspective.

    Science.gov (United States)

    Thakur, Tejender S; Dubey, Ritesh; Desiraju, Gautam R

    2015-03-01

    Short atom-atom distances between molecules are almost always indicative of specific intermolecular bonding. These distances may be used to assess the significance of all hydrogen bonds, including the C-H⋯O and even weaker C-H⋯F varieties.

  7. YNi and its hydrides: Phase stabilities, electronic structures and chemical bonding properties from first principles

    Energy Technology Data Exchange (ETDEWEB)

    Matar, S.F., E-mail: matar@icmcb-bordeaux.cnrs.fr [CNRS, Universite de Bordeaux, ICMCB, 87 avenue du Docteur Albert Schweitzer, F-33608 Pessac (France); Nakhl, M. [Universite Libanaise, Laboratoire de Chimie-Physique des Materiaux LCPM, Fanar (Lebanon); Al Alam, A.F.; Ouaini, N. [Universite Saint-Esprit de Kaslik, Faculte des Sciences et de Genie Informatique, Jounieh (Lebanon); Chevalier, B. [CNRS, Universite de Bordeaux, ICMCB, 87 avenue du Docteur Albert Schweitzer, F-33608 Pessac (France)

    2010-11-25

    Graphical abstract: Base centered orthorhombic YNiH{sub X} structure. For x = 3, only H1 and H2 are present. Highest hydrogen content YNiH{sub 4} is obtained when H3 are added. - Abstract: Within density functional theory, establishing the equations of states of YNi in two different controversial structures in the literature, leads to determine the orthorhombic FeB-type as the ground state one with small energy difference. For YNiH{sub 3} and YNiH{sub 4} hydrides crystallizing in the orthorhombic CrB-type structure the geometry optimization and the ab initio determination of the H atomic positions show that the stability of hydrogen decreases from the tri- to the tetra- hydride. New states brought by hydrogen within the valence band lead to its broadening and to enhanced localization of metal density of states. The chemical bonding analysis shows a preferential Ni-H bonding versus Y-H.

  8. LOBSTER: A tool to extract chemical bonding from plane-wave based DFT.

    Science.gov (United States)

    Maintz, Stefan; Deringer, Volker L; Tchougréeff, Andrei L; Dronskowski, Richard

    2016-04-30

    The computer program LOBSTER (Local Orbital Basis Suite Towards Electronic-Structure Reconstruction) enables chemical-bonding analysis based on periodic plane-wave (PAW) density-functional theory (DFT) output and is applicable to a wide range of first-principles simulations in solid-state and materials chemistry. LOBSTER incorporates analytic projection routines described previously in this very journal [J. Comput. Chem. 2013, 34, 2557] and offers improved functionality. It calculates, among others, atom-projected densities of states (pDOS), projected crystal orbital Hamilton population (pCOHP) curves, and the recently introduced bond-weighted distribution function (BWDF). The software is offered free-of-charge for non-commercial research. © 2016 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.

  9. Hybrid density functional study on lattice vibration, thermodynamic properties, and chemical bonding of plutonium monocarbide

    Science.gov (United States)

    Rong, Yang; Bin, Tang; Tao, Gao; BingYun, Ao

    2016-06-01

    Hybrid density functional theory is employed to systematically investigate the structural, magnetic, vibrational, thermodynamic properties of plutonium monocarbide (PuC and PuC0.75). For comparison, the results obtained by DFT, DFT + U are also given. For PuC and PuC0.75, Fock-0.25 hybrid functional gives the best lattice constants and predicts the correct ground states of antiferromagnetic (AFM) structure. The calculated phonon spectra suggest that PuC and PuC0.75 are dynamically stable. Values of the Helmholtz free energy ΔF, internal energy ΔE, entropy S, and constant-volume specific heat C v of PuC and PuC0.75 are given. The results are in good agreement with available experimental or theoretical data. As for the chemical bonding nature, the difference charge densities, the partial densities of states and the Bader charge analysis suggest that the Pu-C bonds of PuC and PuC0.75 have a mixture of covalent character and ionic character. The effect of carbon vacancy on the chemical bonding is also discussed in detail. We expect that our study can provide some useful reference for further experimental research on the phonon density of states, thermodynamic properties of the plutonium monocarbide. Project supported by the National Natural Science Foundation of China (Grant Nos. 21371160 and 21401173).

  10. An alternative empirical model for the relationship between the bond valence and the thermal expansion rate of chemical bonds.

    Science.gov (United States)

    Sidey, Vasyl

    2015-08-01

    The relationship between the bond valence s and the thermal expansion rate of chemical bonds (dr/dT) has been closely approximated by using the alternative three-parameter empirical model (dr/dT) = (u + vs)(-1/w), where u, v and w are the refinable parameters. Unlike the s-(dr/dT) model developed by Brown et al. [(1997), Acta Cryst. B53, 750-761], this alternative model can be optimized for particular s-(dr/dT) datasets in the least-squares refinement procedure. For routine calculations of the thermal expansion rates of chemical bonds, the alternative model with the parameters u = -63.9, v = 2581.0 and w = 0.647 can be recommended.

  11. AIScore chemically diverse empirical scoring function employing quantum chemical binding energies of hydrogen-bonded complexes.

    Science.gov (United States)

    Raub, Stephan; Steffen, Andreas; Kämper, Andreas; Marian, Christel M

    2008-07-01

    In this work we report on a novel scoring function that is based on the LUDI model and focuses on the prediction of binding affinities. AIScore extends the original FlexX scoring function using a chemically diverse set of hydrogen-bonded interactions derived from extensive quantum chemical ab initio calculations. Furthermore, we introduce an algorithmic extension for the treatment of multifurcated hydrogen bonds (XFurcate). Charged and resonance-assisted hydrogen bond energies and hydrophobic interactions as well as a scaling factor for implicit solvation were fitted to experimental data. To this end, we assembled a set of 101 protein-ligand complexes with known experimental binding affinities. Tightly bound water molecules in the active site were considered to be an integral part of the binding pocket. Compared to the original FlexX scoring function, AIScore significantly improves the prediction of the binding free energies of the complexes in their native crystal structures. In combination with XFurcate, AIScore yields a Pearson correlation coefficient of R P = 0.87 on the training set. In a validation run on the PDBbind test set we achieved an R P value of 0.46 for 799 attractively scored complexes, compared to a value of R P = 0.17 and 739 bound complexes obtained with the FlexX original scoring function. The redocking capability of AIScore, on the other hand, does not fully reach the good performance of the original FlexX scoring function. This finding suggests that AIScore should rather be used for postscoring in combination with the standard FlexX incremental ligand construction scheme.

  12. Nature of the chemical bond and origin of the inverted dipole moment in boron fluoride: a generalized valence bond approach.

    Science.gov (United States)

    Fantuzzi, Felipe; Cardozo, Thiago Messias; Nascimento, Marco Antonio Chaer

    2015-05-28

    The generalized product function energy partitioning (GPF-EP) method has been applied to investigate the nature of the chemical bond and the origin of the inverted dipole moment of the BF molecule. The calculations were carried out with GPF wave functions treating all of the core electrons as a single Hartree-Fock group and the valence electrons at the generalized valence bond perfect-pairing (GVB-PP) or full GVB levels, with the cc-pVTZ basis set. The results show that the chemical structure of both X (1)Σ(+) and a (3)Π states is composed of a single bond. The lower dissociation energy of the excited state is attributed to a stabilizing intraatomic singlet coupling involving the B 2sp-like lobe orbitals after bond dissociation. An increase of electron density on the B atom caused by the reorientation of the boron 2sp-like lobe orbitals is identified as the main responsible effect for the electric dipole inversion in the ground state of BF. Finally, it is shown that π back-bonding from fluorine to boron plays a minor role in the electron density displacement to the bonding region in both states. Moreover, this effect is associated with changes in the quasi-classical component of the electron density only and does not contribute to covalency in either of the states. Therefore, at least for the case of the BF molecule, the term back-bonding is misleading, since it does not contribute to the bond formation.

  13. Energy-based analysis of biochemical cycles using bond graphs.

    Science.gov (United States)

    Gawthrop, Peter J; Crampin, Edmund J

    2014-11-08

    Thermodynamic aspects of chemical reactions have a long history in the physical chemistry literature. In particular, biochemical cycles require a source of energy to function. However, although fundamental, the role of chemical potential and Gibb's free energy in the analysis of biochemical systems is often overlooked leading to models which are physically impossible. The bond graph approach was developed for modelling engineering systems, where energy generation, storage and transmission are fundamental. The method focuses on how power flows between components and how energy is stored, transmitted or dissipated within components. Based on the early ideas of network thermodynamics, we have applied this approach to biochemical systems to generate models which automatically obey the laws of thermodynamics. We illustrate the method with examples of biochemical cycles. We have found that thermodynamically compliant models of simple biochemical cycles can easily be developed using this approach. In particular, both stoichiometric information and simulation models can be developed directly from the bond graph. Furthermore, model reduction and approximation while retaining structural and thermodynamic properties is facilitated. Because the bond graph approach is also modular and scaleable, we believe that it provides a secure foundation for building thermodynamically compliant models of large biochemical networks.

  14. Glutamic Acid Selective Chemical Cleavage of Peptide Bonds.

    Science.gov (United States)

    Nalbone, Joseph M; Lahankar, Neelam; Buissereth, Lyssa; Raj, Monika

    2016-03-04

    Site-specific hydrolysis of peptide bonds at glutamic acid under neutral aqueous conditions is reported. The method relies on the activation of the backbone amide chain at glutamic acid by the formation of a pyroglutamyl (pGlu) imide moiety. This activation increases the susceptibility of a peptide bond toward hydrolysis. The method is highly specific and demonstrates broad substrate scope including cleavage of various bioactive peptides with unnatural amino acid residues, which are unsuitable substrates for enzymatic hydrolysis.

  15. Quantum Chemical Strain Analysis For Mechanochemical Processes.

    Science.gov (United States)

    Stauch, Tim; Dreuw, Andreas

    2017-03-24

    The use of mechanical force to initiate a chemical reaction is an efficient alternative to the conventional sources of activation energy, i.e., heat, light, and electricity. Applications of mechanochemistry in academic and industrial laboratories are diverse, ranging from chemical syntheses in ball mills and ultrasound baths to direct activation of covalent bonds using an atomic force microscope. The vectorial nature of force is advantageous because specific covalent bonds can be preconditioned for rupture by selective stretching. However, the influence of mechanical force on single molecules is still not understood at a fundamental level, which limits the applicability of mechanochemistry. As a result, many chemists still resort to rules of thumb when it comes to conducting mechanochemical syntheses. In this Account, we show that comprehension of mechanochemistry at the molecular level can be tremendously advanced by quantum chemistry, in particular by using quantum chemical force analysis tools. One such tool is the JEDI (Judgement of Energy DIstribution) analysis, which provides a convenient approach to analyze the distribution of strain energy in a mechanically deformed molecule. Based on the harmonic approximation, the strain energy contribution is calculated for each bond length, bond angle and dihedral angle, thus providing a comprehensive picture of how force affects molecules. This Account examines the theoretical foundations of quantum chemical force analysis and provides a critical overview of the performance of the JEDI analysis in various mechanochemical applications. We explain in detail how this analysis tool is to be used to identify the "force-bearing scaffold" of a distorted molecule, which allows both the rationalization and the optimization of diverse mechanochemical processes. More precisely, we show that the inclusion of every bond, bending and torsion of a molecule allows a particularly insightful discussion of the distribution of mechanical

  16. Molecular structure, spectral investigation (1H NMR, 13C NMR, UV-Visible, FT-IR, FT-Raman), NBO, intramolecular hydrogen bonding, chemical reactivity and first hyperpolarizability analysis of formononetin [7-hydroxy-3(4-methoxyphenyl)chromone]: A quantum chemical study

    Science.gov (United States)

    Srivastava, Anubha; Mishra, Rashmi; Kumar, Sudhir; Dev, Kapil; Tandon, Poonam; Maurya, Rakesh

    2015-03-01

    Formononetin [7-hydroxy-3(4-methoxyphenyl)chromone or 4‧-methoxy daidzein] is a soy isoflavonoid that is found abundantly in traditional Chinese medicine Astragalus mongholicus (Bunge) and Trifolium pretense L. (red clover), and in an Indian medicinal plant, Butea (B.) monosperma. Crude extract of B.monosperma is used for rapid healing of fracture in Indian traditional medicine. In this study, a combined theoretical and experimental approach is used to study the properties of formononetin. The optimized geometry was calculated by B3LYP method using 6-311++G(d,p) as a large basis set. The FT-Raman and FT-IR spectra were recorded in the solid phase, and interpreted in terms of potential energy distribution (PED) analysis. Density functional theory (DFT) is applied to explore the nonlinear optical properties of the molecule. Good consistency is found between the calculated results and observed data for the electronic absorption, IR and Raman spectra. The solvent effects have been calculated using time-dependent density functional theory in combination with the integral equation formalism polarized continuum model, and the results are in good agreement with observed measurements. The double well potential energy curve of the molecule about the respective bonds, have been plotted, as obtained from DFT/6-31G basis set. The computational results diagnose the most stable conformer of formononetin. The HOMO-LUMO energy gap of possible conformers has been calculated for comparing their chemical activity. Chemical reactivity has been measured by reactivity descriptors and molecular electrostatic potential surface (MEP). The 1H and 13C NMR chemical shifts of the molecule were calculated by the Gauge including atomic orbital (GIAO) method. Furthermore, the role of CHsbnd O intramolecular hydrogen bond in the stability of molecule is investigated on the basis of the results of topological properties of AIM theory and NBO analysis. The calculated first hyperpolarizability shows

  17. Reliability Analysis of Adhesive Bonded Scarf Joints

    DEFF Research Database (Denmark)

    Kimiaeifar, Amin; Toft, Henrik Stensgaard; Lund, Erik;

    2012-01-01

    A probabilistic model for the reliability analysis of adhesive bonded scarfed lap joints subjected to static loading is developed. It is representative for the main laminate in a wind turbine blade subjected to flapwise bending. The structural analysis is based on a three dimensional (3D) finite...... the FEA model, and a sensitivity analysis on the influence of various geometrical parameters and material properties on the maximum stress is conducted. Because the yield behavior of many polymeric structural adhesives is dependent on both deviatoric and hydrostatic stress components, different ratios...... of the compressive to tensile adhesive yield stresses in the failure criterion are considered. It is shown that the chosen failure criterion, the scarf angle and the load are significant for the assessment of the probability of failure....

  18. Trigermanides AEGe{sub 3} (AE = Ca, Sr, Ba). Chemical bonding and superconductivity

    Energy Technology Data Exchange (ETDEWEB)

    Castillo, Rodrigo; Schnelle, Walter; Baranov, Alexey I.; Burkhardt, Ulrich; Bobnar, Matej; Cardoso-Gil, Raul; Schwarz, Ulrich; Grin, Yuri [Max-Planck-Institut fuer Chemische Physik Fester Stoffe, Dresden (Germany)

    2016-08-01

    The crystal structures of the trigermanides AEGe{sub 3}(tI32) (AE = Ca, Sr, Ba; space group I4/mmm, for SrGe{sub 3}: a = 7.7873(1), c = 12.0622(3) Aa) comprise Ge{sub 2} dumbbells forming layered Ge substructures which enclose embedded AE atoms. The chemical bonding analysis by application of the electron localizability approach reveals a substantial charge transfer from the AE atoms to the germanium substructure. The bonding within the dumbbells is of the covalent two-center type. A detailed analysis of SrGe{sub 3} reveals that the interaction on the bond-opposite side of the Ge{sub 2} groups is not lone pair-like - as it would be expected from the Zintl-like interpretation of the crystal structure with anionic Ge layers separated by alkaline-earth cations - but multi-center strongly polar between the Ge{sub 2} dumbbells and the adjacent metal atoms. Similar atomic interactions are present in CaGe{sub 3} and BaGe{sub 3}. The variation of the alkaline-earth metal has a merely insignificant influence on the superconducting transition temperatures in the s,p-electron compounds AEGe{sub 3}.

  19. Innovations in bonding to zirconia-based materials. Part II: focusing on chemical interactions

    NARCIS (Netherlands)

    M.N. Aboushelib; H. Mirmohamadi; J.P. Matinlinna; E. Kukk; H.F. Ounsi; Z. Salameh

    2009-01-01

    Objectives: The zirconia-resin bond strength was enhanced using novel engineered zirconia primers in combination with selective infiltration etching as a surface pre-treatment. The aim of this study was to evaluate the effect of artificial aging on the chemical stability of the established bond and

  20. EVALUATION OF CHEMICALLY BONDED PHOSPHATE CERAMICS FOR MERCURY STABILIZATION OF A MIXED SYNTHETIC WASTE

    Science.gov (United States)

    This experimental study was conducted to evaluate the stabilization and encapsulation technique developed by Argonne National Laboratory, called the Chemically Bonded Phosphate Ceramics technology for Hg- and HgCl2-contaminated synthetic waste materials. Leachability ...

  1. Quantum-Mechanical Definition of Atoms and Chemical Bonds in Molecules

    Science.gov (United States)

    2015-01-01

    AFRL-RQ-ED-TR-2014-0025 Quantum-Mechanical Definition of Atoms and Chemical Bonds in Molecules P.W. Langhoff J.D. Mills J.A...manufacture, use, or sell any patented invention that may relate to them. Qualified requestors may obtain copies of this report from the Defense...DATES COVERED (From - To) 15 Oct 2013 - 15 Oct 2014 4. TITLE AND SUBTITLE Quantum-Mechanical Definition of Atoms and Chemical Bonds in Molecules

  2. An analysis of hot die size fuel bonding

    Energy Technology Data Exchange (ETDEWEB)

    Gurwell, W.E.

    1967-08-01

    A critical analysis of the Al-Ni-U bond and the hot die size bonding technique is given as the result of a literature search. Metallurgical aspects of the bond and the technique of hot die sizing are commented upon in particular.

  3. The Chemical Bond and Solid-state Physics

    Science.gov (United States)

    Phillips, James C.

    1970-01-01

    Proposes a new scale of ionicity, with which the ionic character of bonding in crystals can be predicted and measured. This new scale of ionicity has led to improved understanding of such crystalline properties as lattice structure, heats of formation, elastic constants, and nonlinear optical properties. Bibliography. (LC)

  4. Effects of chemical bonding on heat transport across interfaces.

    Science.gov (United States)

    Losego, Mark D; Grady, Martha E; Sottos, Nancy R; Cahill, David G; Braun, Paul V

    2012-04-22

    Interfaces often dictate heat flow in micro- and nanostructured systems. However, despite the growing importance of thermal management in micro- and nanoscale devices, a unified understanding of the atomic-scale structural features contributing to interfacial heat transport does not exist. Herein, we experimentally demonstrate a link between interfacial bonding character and thermal conductance at the atomic level. Our experimental system consists of a gold film transfer-printed to a self-assembled monolayer (SAM) with systematically varied termination chemistries. Using a combination of ultrafast pump-probe techniques (time-domain thermoreflectance, TDTR, and picosecond acoustics) and laser spallation experiments, we independently measure and correlate changes in bonding strength and heat flow at the gold-SAM interface. For example, we experimentally demonstrate that varying the density of covalent bonds within this single bonding layer modulates both interfacial stiffness and interfacial thermal conductance. We believe that this experimental system will enable future quantification of other interfacial phenomena and will be a critical tool to stimulate and validate new theories describing the mechanisms of interfacial heat transport. Ultimately, these findings will impact applications, including thermoelectric energy harvesting, microelectronics cooling, and spatial targeting for hyperthermal therapeutics.

  5. A qualitative study of high school students' pre- and post instructional conceptions in chemical bonding

    Science.gov (United States)

    Wang, Renhong

    This study investigated high school students' understanding of chemical bonding prior to and after formal chemistry instruction. Two sets of clinical interviews were conducted prior to and after formal instructions on the topic of chemical bonding using a teacher-as-researcher protocol. Twenty-two students enrolled in a New York Regents Chemistry course were interviewed. Six students participated in the pilot study and the other sixteen were involved in the full study. Oral and pictorial data from the interviews were collected and analyzed in two parts; first, the students' conceptual understanding of chemical bonding including common themes, ideas and misconceptions were identified; second, profiles of each student were made to determine conceptual changes due to formal instruction. The findings showed that students were not familiar with the basic components and structure of atoms, especially the electrostatic properties of the sub-atomic particles. Inter-particle distance, rather than the electrostatic forces between particles, was believed to be the determining cause of the state of matter of a substance. The role of repulsive and attractive electrostatic forces in chemical bonding was not recognized. Students were unable to accurately describe the underlying scientific concepts for all types of chemical bonding and revealed a number of misconceptions, which were resistant to change by instruction. Specific areas of difficulty included the accurate descriptions of ionic bonding, covalent bonding and hydrogen bonding. Further, almost all the students could not use electrostatic forces to explain three states of water and phase changes and most students were unable to describe the energy that was released or absorbed due to bond formation or breaking. Student difficulties stemmed from a lack of understanding of some of the underlying, fundamental chemistry, such as the basic atomic structure, the particulate nature of mater and the role of electrostatic forces in

  6. The adsorption of acrolein on a Pt (1 1 1): A study of chemical bonding and electronic structure

    Science.gov (United States)

    Pirillo, S.; López-Corral, I.; Germán, E.; Juan, A.

    2012-12-01

    The adsorption of acrolein on a Pt (1 1 1) surface was studied using ab-initio and semiempirical calculations. Geometry optimization and densities of states (DOS) curves were carried out using the Vienna Ab-initio Simulation Package (VASP) code. We started our study with the preferential geometries corresponding to the different acrolein/Pt (1 1 1) adsorption modes previously reported. Then, we examined the evolution of the chemical bonding in these geometries, using the crystal orbital overlap population (COOP) and overlap population (OP) analysis of selected pairs of atoms. We analyzed the acrolein intramolecular bonds, Pt (1 1 1) superficial bonds and new moleculesbnd surface formed bonds after adsorption. We found that Ptsbnd Pt bonds interacting with the molecule and acrolein Cdbnd O and Cdbnd C bonds are weakened after adsorption; this last bond is significantly linked to the surface. The obtained Csbnd Pt and Osbnd Pt OP values suggest that the most stable adsorption modes are η3-cis and η4-trans, while the η1-trans is the less favored configuration. We also found that C pz orbital and Pt pz and d orbitals participate strongly in the adsorption process.

  7. Effects of Mechanical and Chemical Pretreatments of Zirconia or Fiber Posts on Resin Cement Bonding.

    Directory of Open Access Journals (Sweden)

    Rui Li

    Full Text Available The bonding strength between resin cement and posts is important for post and core restorations. An important method of improving the bonding strength is the use of various surface pretreatments of the post. In this study, the surfaces of zirconia (fiber posts were treated by mechanical and/or chemical methods such as sandblasting and silanization. The bonding strength between the zirconia (fiber post and the resin cement was measured by a push-out method after thermocycling based on the adhesion to Panavia F 2.0 resin cement. The zirconia and fiber posts exhibited different bonding strengths after sandblasting and/or silanization because of the different strengths and chemical structures. The zirconia post showed a high bonding strength of up to 17.1 MPa after a combined treatment of sandblasting and silanization because of the rough surface and covalent bonds at the interface. This effect was also enhanced by using 1,2-bis(trimethoxysilylethane for the formation of a flexible layer at the interface. In contrast, a high bonding strength of 13.9 MPa was obtained for the fiber post treated by silane agents because the sandblasting treatment resulted in damage to the fiber post, as observed by scanning electron microscopy. The results indicated that the improvement in the bonding strength between the post and the resin cement could be controlled by different chemical and/or mechanical treatments. Enhanced bonding strength depended on covalent bonding and the surface roughness. A zirconia post with high bonding strength could potentially be used for the restoration of teeth in the future.

  8. Isotope effects on chemical shifts in the study of intramolecular hydrogen bonds

    DEFF Research Database (Denmark)

    Hansen, Poul Erik

    2015-01-01

    The paper deals with the use of isotope effects on chemical shifts in characterizing intramolecular hydrogen bonds. Both so-called resonance-assisted (RAHB) and non-RAHB systems are treated. The importance of RAHB will be discussed. Another very important issue is the borderline between “static......” and tautomeric systems. Isotope effects on chemical shifts are particularly useful in such studies. All kinds of intramolecular hydrogen bonded systems will be treated, typical hydrogen bond donors: OH, NH, SH and NH+, typical acceptors C=O, C=N, C=S C=N−. The paper will be deal with both secondary and primary...... isotope effects on chemical shifts. These two types of isotope effects monitor the same hydrogen bond, but from different angles...

  9. Initiated chemical vapor deposited nanoadhesive for bonding National Ignition Facility's targets

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Tom [Univ. of California, Berkeley, CA (United States)

    2016-05-19

    Currently, the target fabrication scientists in National Ignition Facility Directorate at Lawrence Livermore National Laboratory (LLNL) is studying the propagation force resulted from laser impulses impacting a target. To best study this, they would like the adhesive used to glue the target substrates to be as thin as possible. The main objective of this research project is to create adhesive glue bonds for NIF’s targets that are ≤ 1 μm thick. Polyglycidylmethacrylate (PGMA) thin films were coated on various substrates using initiated chemical vapor deposition (iCVD). Film quality studies using white light interferometry reveal that the iCVD PGMA films were smooth. The coated substrates were bonded at 150 °C under vacuum, with low inflow of Nitrogen. Success in bonding most of NIF’s mock targets at thicknesses ≤ 1 μm indicates that our process is feasible in bonding the real targets. Key parameters that are required for successful bonding were concluded from the bonding results. They include inert bonding atmosphere, sufficient contact between the PGMA films, and smooth substrates. Average bond strength of 0.60 MPa was obtained from mechanical shearing tests. The bonding failure mode of the sheared interfaces was observed to be cohesive. Future work on this project will include reattempt to bond silica aerogel to iCVD PGMA coated substrates, stabilize carbon nanotube forests with iCVD PGMA coating, and kinetics study of PGMA thermal crosslinking.

  10. First-principles simulations on bonding pathways of chemical transformations under hydrostatic compression

    Science.gov (United States)

    Hu, Anguang; Zhang, Fan

    2012-02-01

    High pressure as a thermodynamic parameter provides a strong structural constraint to lead chemical transformations with selective ways. Thus, chemical transformations under pressure can create novel materials which may not be accessible by covalent synthesis. However, bonding evolution toward high pressure chemical transformations can be a complex process and may happen over widely different pressures. To understand bonding evolution pathways of high pressure chemical transformations, first-principles simulations were performed following hydrostatic compression enthalpy minimization paths to obtain experimentally and theoretically established phase transitions of carbon. The results showed that the chemical transformations from hydrostatic compression carbon to single-bonded phases were characterized by a sudden decrease in principal stress components, indicating the onset of chemical transformation. On this basis, a number of hydrostatic compression chemical transformations from molecular precursors to novel materials were predicted, such as hydrocarbon graphane, a hydrogenated carbon nitride sheet, and carbon nitrides. All predicted hydrostatic compression transformations are featured as a sudden change in principal stress components, representing chemical bonding destruction and formation reactions with a cell volume collapse.

  11. Layer-by-layer fabrication of chemical-bonded graphene coating for solid-phase microextraction.

    Science.gov (United States)

    Zhang, Suling; Du, Zhuo; Li, Gongke

    2011-10-01

    A new fabrication strategy of the graphene-coated solid-phase microextraction (SPME) fiber is developed. Graphite oxide was first used as starting coating material that covalently bonded to the fused-silica substrate using 3-aminopropyltriethoxysilane (APTES) as cross-linking agent and subsequently deoxidized by hydrazine to give the graphene coating in situ. The chemical bonding between graphene and the silica fiber improve its chemical stability, and the obtained fiber was stable enough for more than 150 replicate extraction cycles. The graphene coating was wrinkled and folded, like the morphology of the rough tree bark. Its performance is tested by headspace (HS) SPME of polycyclic aromatic hydrocarbons (PAHs) followed by GC/MS analysis. The results showed that the graphene-coated fiber exhibited higher enrichment factors (EFs) from 2-fold for naphthalene to 17-fold for B(b)FL as compared to the commercial polydimethylsioxane (PDMS) fiber, and the EFs increased with the number of condensed rings of PAHs. The strong adsorption affinity was believed to be mostly due to the dominant role of π-π stacking interaction and hydrophobic effect, according to the results of selectivity study for a variety of organic compounds including PAHs, the aromatic compounds with different substituent groups, and some aliphatic hydrocarbons. For PAHs analysis, the graphene-coated fiber showed good precision (<11%), low detection limits (1.52-2.72 ng/L), and wide linearity (5-500 ng/L) under the optimized conditions. The repeatability of fiber-to-fiber was 4.0-10.8%. The method was applied to simultaneous analysis of eight PAHs with satisfactory recoveries, which were 84-102% for water samples and 72-95% for soil samples, respectively.

  12. Relaxation of the chemical bond skin chemisorption size matter ZTP mechanics H2O myths

    CERN Document Server

    Sun, Chang Q

    2014-01-01

    The aim of this book is to explore the detectable properties of a material to the parameters of bond and non-bond involved and to clarify the interdependence of various properties. This book is composed of four parts; Part I deals with the formation and relaxation dynamics of bond and non-bond during chemisorptions with uncovering of the correlation among the chemical bond, energy band, and surface potential barrier (3B) during reactions; Part II is focused on the relaxation of bonds between atoms with fewer neighbors than the ideal in bulk with unraveling of the bond order-length-strength (BOLS) correlation mechanism, which clarifies the nature difference between nanostructures and bulk of the same substance; Part III deals with the relaxation dynamics of bond under heating and compressing with revealing of rules on the temperature-resolved elastic and plastic properties of low-dimensional materials; Part IV is focused on the asymmetric relaxation dynamics of the hydrogen bond (O:H-O) and the anomalous behav...

  13. Electronic parameters of Sr2Nb2O7 and chemical bonding

    DEFF Research Database (Denmark)

    Atuchin, V.V.; Grivel, Jean-Claude; Korotkov, A.S.

    2008-01-01

    /2)) and Delta(O-Sr) = BE(O 1s)-BE(Sr 3d(5/2)), were used to characterize the valence electron transfer on the formation of the Nb-O and Sr-O bonds. The chemical bonding effects were considered on the basis of our XPS results for Sr2Nb2O7 and earlier published structural and XPS data for other Sr- or Nb...

  14. Chemical bonding in aqueous hexacyano cobaltate from photon- and electron-detection perspectives

    Science.gov (United States)

    Lalithambika, Sreeju Sreekantan Nair; Atak, Kaan; Seidel, Robert; Neubauer, Antje; Brandenburg, Tim; Xiao, Jie; Winter, Bernd; Aziz, Emad F.

    2017-01-01

    The electronic structure of the [Co(CN)6]3- complex dissolved in water is studied using X-ray spectroscopy techniques. By combining electron and photon detection methods from the solutions ionized or excited by soft X-rays we experimentally identify chemical bonding between the metal center and the CN ligand. Non-resonant photoelectron spectroscopy provides solute electron binding energies, and nitrogen 1 s and cobalt 2p resonant core-level photoelectron spectroscopy identifies overlap between metal and ligand orbitals. By probing resonances we are able to qualitatively determine the ligand versus metal character of the respective occupied and non-occupied orbitals, purely by experiment. For the same excitations we also detect the emitted X-rays, yielding the complementary resonant inelastic X-ray scattering spectra. For a quantitative interpretation of the spectra, we perform theoretical electronic-structure calculations. The latter provide both orbital energies and orbital character which are found to be in good agreement with experimental energies and with experimentally inferred orbital mixing. We also report calculated X-ray absorption spectra, which in conjunction with our orbital-structure analysis, enables us to quantify various bonding interactions with a particular focus on the water-solvent - ligand interaction and the strength of π-backbonding between metal and ligand.

  15. Effective solidification/stabilisation of mercury-contaminated wastes using zeolites and chemically bonded phosphate ceramics.

    Science.gov (United States)

    Zhang, Shaoqing; Zhang, Xinyan; Xiong, Ya; Wang, Guoping; Zheng, Na

    2015-02-01

    In this study, two kinds of zeolites materials (natural zeolite and thiol-functionalised zeolite) were added to the chemically bonded phosphate ceramic processes to treat mercury-contaminated wastes. Strong promotion effects of zeolites (natural zeolite and thiol-functionalised zeolite) on the stability of mercury in the wastes were obtained and these technologies showed promising advantages toward the traditional Portland cement process, i.e. using Portland cement as a solidification agent and natural or thiol-functionalised zeolite as a stabilisation agent. Not only is a high stabilisation efficiency (lowered the Toxicity Characteristic Leaching Procedure Hg by above 10%) obtained, but also a lower dosage of solidification (for thiol-functionalised zeolite as stabilisation agent, 0.5 g g(-1) and 0.7 g g(-1) for chemically bonded phosphate ceramic and Portland cement, respectively) and stabilisation agents (for natural zeolite as stabilisation agent, 0.35 g g(-1) and 0.4 g g(-1) for chemically bonded phosphate ceramic and Portland cement, respectively) were used compared with the Portland cement process. Treated by thiol-functionalised zeolite and chemically bonded phosphate ceramic under optimum parameters, the waste containing 1500 mg Hg kg(-1) passed the Toxicity Characteristic Leaching Procedure test. Moreover, stabilisation/solidification technology using natural zeolite and chemically bonded phosphate ceramic also passed the Toxicity Characteristic Leaching Procedure test (the mercury waste containing 625 mg Hg kg(-1)). Moreover, the presence of chloride and phosphate did not have a negative effect on the chemically bonded phosphate ceramic/thiol-functionalised zeolite treatment process; thus, showing potential for future application in treatment of 'difficult-to-manage' mercury-contaminated wastes or landfill disposal with high phosphate and chloride content.

  16. Analysis of tensile bond strengths using Weibull statistics.

    Science.gov (United States)

    Burrow, Michael F; Thomas, David; Swain, Mike V; Tyas, Martin J

    2004-09-01

    Tensile strength tests of restorative resins bonded to dentin, and the resultant strengths of interfaces between the two, exhibit wide variability. Many variables can affect test results, including specimen preparation and storage, test rig design and experimental technique. However, the more fundamental source of variability, that associated with the brittle nature of the materials, has received little attention. This paper analyzes results from micro-tensile tests on unfilled resins and adhesive bonds between restorative resin composite and dentin in terms of reliability using the Weibull probability of failure method. Results for the tensile strengths of Scotchbond Multipurpose Adhesive (3M) and Clearfil LB Bond (Kuraray) bonding resins showed Weibull moduli (m) of 6.17 (95% confidence interval, 5.25-7.19) and 5.01 (95% confidence interval, 4.23-5.8). Analysis of results for micro-tensile tests on bond strengths to dentin gave moduli between 1.81 (Clearfil Liner Bond 2V) and 4.99 (Gluma One Bond, Kulzer). Material systems with m in this range do not have a well-defined strength. The Weibull approach also enables the size dependence of the strength to be estimated. An example where the bonding area was changed from 3.1 to 1.1 mm diameter is shown. Weibull analysis provides a method for determining the reliability of strength measurements in the analysis of data from bond strength and tensile tests on dental restorative materials.

  17. X-ray photoelectron spectra structure and chemical bonding in AmO2

    Directory of Open Access Journals (Sweden)

    Teterin Yury A.

    2015-01-01

    Full Text Available Quantitative analysis was done of the X-ray photoelectron spectra structure in the binding energy range of 0 eV to ~35 eV for americium dioxide (AmO2 valence electrons. The binding energies and structure of the core electronic shells (~35 eV-1250 eV, as well as the relativistic discrete variation calculation results for the Am63O216 and AmO8 (D4h cluster reflecting Am close environment in AmO2 were taken into account. The experimental data show that the many-body effects and the multiplet splitting contribute to the spectral structure much less than the effects of formation of the outer (0-~15 eV binding energy and the inner (~15 eV-~35 eV binding energy valence molecular orbitals. The filled Am 5f electronic states were shown to form in the AmO2 valence band. The Am 6p electrons participate in formation of both the inner and the outer valence molecular orbitals (bands. The filled Am 6p3/2 and the O 2s electronic shells were found to make the largest contributions to the formation of the inner valence molecular orbitals. Contributions of electrons from different molecular orbitals to the chemical bond in the AmO8 cluster were evaluated. Composition and sequence order of molecular orbitals in the binding energy range 0-~35 eV in AmO2 were established. The experimental and theoretical data allowed a quantitative scheme of molecular orbitals for AmO2, which is fundamental for both understanding the chemical bond nature in americium dioxide and the interpretation of other X-ray spectra of AmO2.

  18. Hydrogen Bonding in Thermoplastic Polyurethane Elastomers: IR Thermal Analysis

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The hydrogen bond percentage and its temperature dependence of the three TPU samples synthesized from polytetrahydrofuran, 4,4-diphenylmethane diisocyanate, N-methyl diethanol amine or 1,4-butane diol were studied by means of IR thermal analysis. The enthalpy and the entropy of the hydrogen bond dissociation were determined by the Vant Hoff plot.

  19. Chemical synthesis of La1 isolated from the venom of the scorpion Liocheles australasiae and determination of its disulfide bonding pattern.

    Science.gov (United States)

    Nagao, Junya; Miyashita, Masahiro; Nakagawa, Yoshiaki; Miyagawa, Hisashi

    2015-08-01

    La1 is a 73-residue cysteine-rich peptide isolated from the scorpion Liocheles australasiae venom. Although La1 is the most abundant peptide in the venom, its biological function remains unknown. Here, we describe a method for efficient chemical synthesis of La1 using the native chemical ligation (NCL) strategy, in which three peptide components of less than 40 residues were sequentially ligated. The peptide thioester necessary for NCL was synthesized using an aromatic N-acylurea approach with Fmoc-SPPS. After completion of sequential NCL, disulfide bond formation was carried out using a dialysis method, in which the linear peptide dissolved in an acidic solution was dialyzed against a slightly alkaline buffer to obtain correctly folded La1. Next, we determined the disulfide bonding pattern of La1. Enzymatic and chemical digests of La1 without reduction of disulfide bonds were analyzed by liquid chromatography/mass spectrometry (LC/MS), which revealed two of four disulfide bond linkages. The remaining two linkages were assigned based on MS/MS analysis of a peptide fragment containing two disulfide bonds. Consequently, the disulfide bonding pattern of La1 was found to be similar to that of a von Willebrand factor type C (VWC) domain. To our knowledge, this is the first report of the experimental determination of the disulfide bonding pattern of peptides having a single VWC domain as well as their chemical synthesis. La1 synthesized in this study will be useful for investigation of its biological role in the venom.

  20. Halogen bonded supramolecular capsules: a challenging test case for quantum chemical methods.

    Science.gov (United States)

    Sure, Rebecca; Grimme, Stefan

    2016-08-02

    Recently, Diederich et al. synthesized the first supramolecular capsule with a well-defined four-point halogen bonding interaction [Angew. Chem., Int. Ed., 2015, 54, 12339]. This interesting system comprising about 400 atoms represents a challenging test case for accurate quantum chemical methods. We investigate it with our new density functional based composite method for structures and noncovalent interactions (PBEh-3c) as well as our standard protocol for supramolecular thermochemistry and give predictions for chemical modifications to improve the binding strength.

  1. Effect of Microwave Radiation on Enzymatic and Chemical Peptide Bond Synthesis on Solid Phase

    Directory of Open Access Journals (Sweden)

    Alessandra Basso

    2009-01-01

    Full Text Available Peptide bond synthesis was performed on PEGA beads under microwave radiations. Classical chemical coupling as well as thermolysin catalyzed synthesis was studied, and the effect of microwave radiations on reaction kinetics, beads' integrity, and enzyme activity was assessed. Results demonstrate that microwave radiations can be profitably exploited to improve reaction kinetics in solid phase peptide synthesis when both chemical and biocatalytic strategies are used.

  2. The role of radial nodes of atomic orbitals for chemical bonding and the periodic table.

    Science.gov (United States)

    Kaupp, Martin

    2007-01-15

    The role of radial nodes, or of their absence, in valence orbitals for chemical bonding and periodic trends is discussed from a unified viewpoint. In particular, we emphasize the special role of the absence of a radial node whenever a shell with angular quantum number l is occupied for the first time (lack of "primogenic repulsion"), as with the 1s, 2p, 3d, and 4f shells. Although the consequences of the very compact 2p shell (e.g. good isovalent hybridization, multiple bonding, high electronegativity, lone-pair repulsion, octet rule) are relatively well known, it seems that some of the aspects of the very compact 3d shell in transition-metal chemistry are less well appreciated, e.g., the often weakened and stretched bonds at equilibrium structure, the frequently colored complexes, and the importance of nondynamical electron-correlation effects in bonding. Copyright (c) 2006 Wiley Periodicals, Inc.

  3. Generating giant and tunable nonlinearity in a macroscopic mechanical resonator from a single chemical bond

    Science.gov (United States)

    Huang, Pu; Zhou, Jingwei; Zhang, Liang; Hou, Dong; Lin, Shaochun; Deng, Wen; Meng, Chao; Duan, Changkui; Ju, Chenyong; Zheng, Xiao; Xue, Fei; Du, Jiangfeng

    2016-05-01

    Nonlinearity in macroscopic mechanical systems may lead to abundant phenomena for fundamental studies and potential applications. However, it is difficult to generate nonlinearity due to the fact that macroscopic mechanical systems follow Hooke's law and respond linearly to external force, unless strong drive is used. Here we propose and experimentally realize high cubic nonlinear response in a macroscopic mechanical system by exploring the anharmonicity in chemical bonding interactions. We demonstrate the high tunability of nonlinear response by precisely controlling the chemical bonding interaction, and realize, at the single-bond limit, a cubic elastic constant of 1 × 1020 N m-3. This enables us to observe the resonator's vibrational bi-states transitions driven by the weak Brownian thermal noise at 6 K. This method can be flexibly applied to a variety of mechanical systems to improve nonlinear responses, and can be used, with further improvements, to explore macroscopic quantum mechanics.

  4. Chemical substructure analysis in toxicology

    Energy Technology Data Exchange (ETDEWEB)

    Beauchamp, R.O. Jr. [Center for Information on Toxicology and Environment, Raleigh, NC (United States)

    1990-12-31

    A preliminary examination of chemical-substructure analysis (CSA) demonstrates the effective use of the Chemical Abstracts compound connectivity file in conjunction with the bibliographic file for relating chemical structures to biological activity. The importance of considering the role of metabolic intermediates under a variety of conditions is illustrated, suggesting structures that should be examined that may exhibit potential activity. This CSA technique, which utilizes existing large files accessible with online personal computers, is recommended for use as another tool in examining chemicals in drugs. 2 refs., 4 figs.

  5. The Collaboration of Cooperative Learning and Conceptual Change: Enhancing the Students' Understanding of Chemical Bonding Concepts

    Science.gov (United States)

    Eymur, Gülüzar; Geban, Ömer

    2017-01-01

    The main purpose of this study was to investigate the effects of cooperative learning based on conceptual change approach instruction on ninth-grade students' understanding in chemical bonding concepts compared to traditional instruction. Seventy-two ninth-grade students from two intact chemistry classes taught by the same teacher in a public high…

  6. Nuclear radiation as a probe of chemical bonding: the current interplay between theory and experiment

    Energy Technology Data Exchange (ETDEWEB)

    Newton, M D

    1978-01-01

    After a survey of appropriate theoretical formalisms, recent confrontations of theory and experiment in the areas of neutron scattering, Moessbauer spectroscopy, and positron chemistry are discussed, with major emphasis on the degree to which simple concepts of chemical bonding can be refined by complementary use of the above experimental probes and the powerful techniques of computational quantum chemistry.

  7. Characterization and intramolecular bonding patterns of busulfan: Experimental and quantum chemical approach

    Science.gov (United States)

    Karthick, T.; Tandon, Poonam; Singh, Swapnil; Agarwal, Parag; Srivastava, Anubha

    2017-02-01

    The investigations of structural conformers, molecular interactions and vibrational characterization of pharmaceutical drug are helpful to understand their behaviour. In the present work, the 2D potential energy surface (PES) scan has been performed on the dihedral angles C6sbnd O4sbnd S1sbnd C5 and C25sbnd S22sbnd O19sbnd C16 to find the stable conformers of busulfan. In order to show the effects of long range interactions, the structures on the global minima of PES scan have been further optimized by B3LYP/6-311 ++G(d,p) method with and without empirical dispersion functional in Gaussian 09W package. The presence of n → σ* and σ → σ* interactions which lead to stability of the molecule have been predicted by natural bond orbital analysis. The strong and weak hydrogen bonds between the functional groups of busulfan were analyzed using quantum topological atoms in molecules analysis. In order to study the long-range forces, such as van der Waals interactions, steric effect in busulfan, the reduced density gradient as well as isosurface defining these interactions has been plotted using Multiwfn software. The spectroscopic characterization on the solid phase of busulfan has been studied by experimental FT-IR and FT-Raman spectra. From the 13C and 1H NMR spectra, the chemical shifts of individual C and H atoms of busulfan have been predicted. The maximum absorption wavelengths corresponding to the electronic transitions between the highest occupied molecular orbital and the lowest unoccupied molecular orbital of busulfan have been found by UV-vis spectrum.

  8. Chemical Analysis Facility

    Data.gov (United States)

    Federal Laboratory Consortium — FUNCTION: Uses state-of-the-art instrumentation for qualitative and quantitative analysis of organic and inorganic compounds, and biomolecules from gas, liquid, and...

  9. Principles and applications of halogen bonding in medicinal chemistry and chemical biology.

    Science.gov (United States)

    Wilcken, Rainer; Zimmermann, Markus O; Lange, Andreas; Joerger, Andreas C; Boeckler, Frank M

    2013-02-28

    Halogen bonding has been known in material science for decades, but until recently, halogen bonds in protein-ligand interactions were largely the result of serendipitous discovery rather than rational design. In this Perspective, we provide insights into the phenomenon of halogen bonding, with special focus on its role in drug discovery. We summarize the theoretical background defining its strength and directionality, provide a systematic analysis of its occurrence and interaction geometries in protein-ligand complexes, and give recent examples where halogen bonding has been successfully harnessed for lead identification and optimization. In light of these data, we discuss the potential and limitations of exploiting halogen bonds for molecular recognition and rational drug design.

  10. Progressive Damage Analysis of Bonded Composite Joints

    Science.gov (United States)

    Leone, Frank A., Jr.; Girolamo, Donato; Davila, Carlos G.

    2012-01-01

    The present work is related to the development and application of progressive damage modeling techniques to bonded joint technology. The joint designs studied in this work include a conventional composite splice joint and a NASA-patented durable redundant joint. Both designs involve honeycomb sandwich structures with carbon/epoxy facesheets joined using adhesively bonded doublers.Progressive damage modeling allows for the prediction of the initiation and evolution of damage within a structure. For structures that include multiple material systems, such as the joint designs under consideration, the number of potential failure mechanisms that must be accounted for drastically increases the complexity of the analyses. Potential failure mechanisms include fiber fracture, intraply matrix cracking, delamination, core crushing, adhesive failure, and their interactions. The bonded joints were modeled using highly parametric, explicitly solved finite element models, with damage modeling implemented via custom user-written subroutines. Each ply was discretely meshed using three-dimensional solid elements. Layers of cohesive elements were included between each ply to account for the possibility of delaminations and were used to model the adhesive layers forming the joint. Good correlation with experimental results was achieved both in terms of load-displacement history and the predicted failure mechanism(s).

  11. Valence XPS structure and chemical bond in Cs2UO2Cl4

    Directory of Open Access Journals (Sweden)

    Teterin Yury A.

    2016-01-01

    Full Text Available Quantitative analysis was done of the valence electrons X-ray photoelectron spectra structure in the binding energy (BE range of 0 eV to ~35 eV for crystalline dicaesium tetrachloro-dioxouranium (VI (Cs2UO2Cl4. This compound contains the uranyl group UO2. The BE and structure of the core electronic shells (~35 eV-1250 eV, as well as the relativistic discrete variation calculation results for the UO2Cl4(D4h cluster reflecting U close environment in Cs2UO2Cl4 were taken into account. The experimental data show that many-body effects due to the presence of cesium and chlorine contribute to the outer valence (0-~15 eV BE spectral structure much less than to the inner valence (~15 eV-~35 eV BE one. The filled U5f electronic states were theoretically calculated and experimentally confirmed to be present in the valence band of Cs2UO2Cl4. It corroborates the suggestion on the direct participation of the U5f electrons in the chemical bond. Electrons of the U6p atomic orbitals participate in formation of both the inner (IVMO and the outer (OVMO valence molecular orbitals (bands. The filled U6p and the O2s, Cl3s electronic shells were found to make the largest contributions to the IVMO formation. The molecular orbitals composition and the sequence order in the binding energy range 0 eV-~35 eV in the UO2Cl4 cluster were established. The experimental and theoretical data allowed a quantitative molecular orbitals scheme for the UO2Cl4 cluster in the BE range 0-~35 eV, which is fundamental for both understanding the chemical bond nature in Cs2UO2Cl4 and the interpretation of other X-ray spectra of Cs2UO2Cl4. The contributions to the chemical binding for the UO2Cl4 cluster were evaluated to be: the OVMO contribution - 76%, and the IVMO contribution - 24 %.

  12. Electronic structure and chemical bond nature in Cs2PuO2Cl4

    Directory of Open Access Journals (Sweden)

    Teterin Yury A.

    2015-01-01

    Full Text Available X-ray photoelectron spectral analysis of dicaesiumtetrachlorodioxoplutonate (Cs2PuO2Cl4 single crystal was done in the binding energy range 0-~35 eV on the basis of binding energies and structure of the core electronic shells (~35 eV-1250 eV, as well as the relativistic discrete variation calculation results for the PuO2Cl4 (D4h. This cluster reflects Pu close environment in Cs2PuO2Cl4 containing the plutonyl group PuO2. The many-body effects due to the presence of cesium and chlorine were shown to contribute to the outer valence (0-~15 eV binding energy spectral structure much less than to the inner valence (~15 eV- ~35 eV binding energy one. The filled Pu 5f electronic states were theoretically calculated and experimentally con- firmed to present in the valence band of Cs2PuO2Cl4. It corroborates the suggestion on the direct participation of the Pu 5f electrons in the chemical bond. The Pu 6p atomic orbitals were shown to participate in formation of both the inner and the outer valence molecular orbitals (bands, while the filled Pu 6p and O 2s, Cl 3s electronic shells were found to take the largest part in formation of the inner valence molecular orbitals. The composition of molecular orbitals and the sequence order in the binding energy range 0-~35 eV in Cs2PuO2Cl4 were established. The quantitative scheme of molecular orbitals for Cs2PuO2Cl4 in the binding energy range 0-~15 eV was built on the basis of the experimental and theoretical data. It is fundamental for both understanding the chemical bond nature in Cs2PuO2Cl4 and the interpretation of other X-ray spectra of Cs2PuO2Cl4. The contributions to the chemical binding for the PuO2Cl4 cluster were evaluated to be: the contribution of the outer valence molecular orbitals -66 %, the contribution of the inner valence molecular orbitals -34 %.

  13. Students' Reasoning about Basic Chemical Thermodynamics and Chemical Bonding: What Changes Occur during a Context-based Post-16 Chemistry Course?

    Science.gov (United States)

    Barker, Vanessa; Millar, Robin

    2000-01-01

    A longitudinal study of students (n=250) following the Salters Advanced Chemistry course probed a range of chemical ideas including the exothermicity of bond formation and the development of thinking about covalent, ionic, and intermolecular bonds. At the start, many students demonstrated misunderstandings about these chemical ideas, but their…

  14. Electron-electron interactions in the chemical bond: ``1/3” Effect in the bond length of hydrogen molecule

    Indian Academy of Sciences (India)

    P Ganguly

    2001-10-01

    The prominent ``1/3” effect observed in the Hall effect plateaus of twodimensional electron gas (2DEG) systems has been postulated to indicating 1/3 fractional charge quasiparticle excitations arising from electron-electron interactions. Tunneling shot-noise experiments on 2DEF exhibiting fractional quantum Hall effect (FQHE) shows evidence for tunnelling of particles with and /3 charges for a constant band mass. A ``1/3” effect in the hydrogen molecule is seen in as much as its internuclear distance, - = - + +, with |+/-| = 1/3. This is examined in terms of electron-electron interactions involving electron- and hole quasiparticles, (-) and (ℎ+), equivalent to those observed in FQHE shot-noise experiments. The (/) ratio of the (-) and (ℎ+) quasiparticles is kept at 1: -3. Instead of a 2DEG, these particles are treated as being in flat Bohr orbits. A treatment in the language of charge-flux tube composites for the hydrogen atom as well as the hydrogen molecule is attempted. Such treatment gives important insights into changes in chemical potential and bond energy on crossing a phase boundary during the atom-bond transition as well as on models for FQHE itself.

  15. The Load and Time Dependence of Chemical Bonding-Induced Frictional Ageing of Silica at the Nanoscale

    Science.gov (United States)

    Tian, K.; Gosvami, N. N.; Goldsby, D. L.; Carpick, R. W.

    2015-12-01

    fitting ageing vs. load data which shows that the friction drop data points all fall on a master curve. The analysis yields physically reasonable values for the activation energy and activation volume of the chemical bonding process. Our study provides a basis to hypothesize that the kinetic processes in chemical bonding-induced ageing do not depend strongly on normal load.

  16. Electronic structure and chemical bonding of Li4Pt3Si

    Science.gov (United States)

    Matar, S. F.; Pöttgen, R.; Al Alam, A. F.; Ouaini, N.

    2012-07-01

    The electronic structure of rhombohedral Li4Pt3Si (space group R32) is examined from ab initio with an assessment of the properties of chemical bonding relating to the presence of different Li and Pt Wyckoff sites. The structure with totally de-intercalated Li keeps the characteristics of the pristine compound with a reduction of the volume albeit with less cohesive energy. The binding energies of Li point to different bonding intensities according to their different Wyckoff sites and indicate the possibility of delithiation.

  17. Novel microstructures and technologies applied in chemical analysis techniques

    NARCIS (Netherlands)

    Spiering, Vincent L.; Spiering, V.L.; van der Moolen, Johannes N.; Burger, Gert-Jan; Burger, G.J.; van den Berg, Albert

    1997-01-01

    Novel glass and silicon microstructures and their application in chemical analysis are presented. The micro technologies comprise (deep) dry etching, thin layer growth and anodic bonding. With this combination it is possible to create high resolution electrically isolating silicon dioxide structures

  18. Molecular structure, heteronuclear resonance assisted hydrogen bond analysis, chemical reactivity and first hyperpolarizability of a novel ethyl-4-{[(2,4-dinitrophenyl)-hydrazono]-ethyl}-3,5-dimethyl-1H-pyrrole-2-carboxylate: a combined DFT and AIM approach.

    Science.gov (United States)

    Singh, R N; Kumar, Amit; Tiwari, R K; Rawat, Poonam; Baboo, Vikas; Verma, Divya

    2012-06-15

    A new ethyl-4-{[(2,4-dinitrophenyl)-hydrazono]-ethyl}-3,5-dimethyl-1H-pyrrole-2-carboxylate (EDPHEDPC) has been synthesized and characterized by FT-IR, (1)H NMR, UV-vis, DART-Mass spectroscopy and elemental analysis. Quantum chemical calculations have been performed by DFT level of theory using B3LYP functional and 6-31G(d,p) as basis set. The (1)H NMR chemical shifts are calculated using gauge including atomic orbitals (GIAO) approach in DMSO as solvent. The time dependent density functional theory (TD-DFT) is used to find the various electronic transitions and their nature within molecule. A combined theoretical and experimental wavenumber analysis confirms the existence of dimer. Topological parameters such as electron density (ρ(BCP)), Laplacian of electron density (nabla(2)ρ(BCP)), kinetic electron energy density (G(BCP)), potential electron density (V(BCP)) and the total electron energy density (H(BCP)) at bond critical points (BCP) have been analyzed by Bader's 'Atoms in molecules' AIM theory in detail. The intermolecular hydrogen bond energy of dimer is calculated as -12.51 kcal/mol using AIM calculations. AIM ellipticity analysis is carried out to confirm the presence of resonance assisted intra and intermolecular hydrogen bonds in dimer. The calculated thermodynamic parameters show that reaction is exothermic and non-spontaneous at room temperature. The local reactivity descriptors such as Fukui functions (f(k)(+), f(k)(-)), local softnesses (s(k)(-), s(k)(+)) and electrophilicity indices (ω(k)(+), ω(k)(-)) analyses are performed to determine the reactive sites within molecule. Nonlinear optical (NLO) behavior of title compound is investigated by the computed value of first hyperpolarizability (β(0)). Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Mapping lipid and collagen by multispectral photoacoustic imaging of chemical bond vibration

    Science.gov (United States)

    Wang, Pu; Wang, Ping; Wang, Han-Wei; Cheng, Ji-Xin

    2012-09-01

    Photoacoustic microscopy using vibrational overtone absorption as a contrast mechanism allows bond-selective imaging of deep tissues. Due to the spectral similarity of molecules in the region of overtone vibration, it is difficult to interrogate chemical components using photoacoustic signal at single excitation wavelength. Here we demonstrate that lipids and collagen, two critical markers for many kinds of diseases, can be distinguished by multispectral photoacoustic imaging of the first overtone of C-H bond. A phantom consisting of rat-tail tendon and fat was constructed to demonstrate this technique. Wavelengths between 1650 and 1850 nm were scanned to excite both the first overtone and combination bands of C-H bonds. B-scan multispectral photoacoustic images, in which each pixel contains a spectrum, were analyzed by a multivariate curve resolution-alternating least squares algorithm to recover the spatial distribution of collagen and lipids in the phantom.

  20. Studying Chemical Reactions, One Bond at a Time, with Single Molecule AFM Techniques

    Science.gov (United States)

    Fernandez, Julio M.

    2008-03-01

    The mechanisms by which mechanical forces regulate the kinetics of a chemical reaction are unknown. In my lecture I will demonstrate how we use single molecule force-clamp spectroscopy and protein engineering to study the effect of force on the kinetics of thiol/disulfide exchange. Reduction of disulfide bond via the thiol/disulfide exchange chemical reaction is crucial in regulating protein function and is of common occurrence in mechanically stressed proteins. While reduction is thought to proceed through a substitution nucleophilic bimolecular (SN2) reaction, the role of a mechanical force in modulating this chemical reaction is unknown. We apply a constant stretching force to single engineered disulfide bonds and measure their rate of reduction by dithiothreitol (DTT). We find that while the reduction rate is linearly dependent on the concentration of DTT, it is exponentially dependent on the applied force, increasing 10-fold over a 300 pN range. This result predicts that the disulfide bond lengthens by 0.34 å at the transition state of the thiol/disulfide exchange reaction. In addition to DTT, we also study the reduction of the engineered disulfide bond by the E. coli enzyme thioredoxin (Trx). Thioredoxins are enzymes that catalyze disulfide bond reduction in all organisms. As before, we apply a mechanical force in the range of 25-450 pN to the engineered disulfide bond substrate and monitor the reduction of these bonds by individual enzymes. In sharp contrast with the data obtained with DTT, we now observe two alternative forms of the catalytic reaction, the first requiring a reorientation of the substrate disulfide bond, causing a shortening of the substrate polypeptide by 0.76±0.07 å, and the second elongating the substrate disulfide bond by 0.21±0.01 å. These results support the view that the Trx active site regulates the geometry of the participating sulfur atoms, with sub-ångström precision, in order to achieve efficient catalysis. Single molecule

  1. Microstructure and chemical bond evolution of diamond-like carbon films machined by femtosecond laser

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jing; Wang, Chunhui [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi’an 710072 (China); Liu, Yongsheng, E-mail: yongshengliu@nwpu.edu.cn [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi’an 710072 (China); Cheng, Laifei [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi’an 710072 (China); Li, Weinan [State Key Laboratory of Transient Optics and Photonics, Xi’an Institute of Optics and Precision Mechanics, Chinese Academy of Sciences, Xi’an 10068 (China); Zhang, Qing [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi’an 710072 (China); Yang, Xiaojun [State Key Laboratory of Transient Optics and Photonics, Xi’an Institute of Optics and Precision Mechanics, Chinese Academy of Sciences, Xi’an 10068 (China)

    2015-06-15

    Highlights: • The machining depth was essentially proportional to the laser power. • The well patterned microgrooves and ripple structures with nanoparticles were formed distinctly in the channels. And the number of nanoparticles increased with the processing power as well. • It revealed a conversion from amorphous carbon to nanocrystalline graphite after laser treated with increasing laser power. • It showed that a great decrease of sp{sup 3}/sp{sup 2} after laser treatment. - Abstract: Femtosecond laser is of great interest for machining high melting point and hardness materials such as diamond-like carbon, SiC ceramic, et al. In present work, the microstructural and chemical bond evolution of diamond-like carbon films were investigated using electron microscopy and spectroscopy techniques after machined by diverse femtosecond laser power in air. The results showed the machining depth was essentially proportional to the laser power. The well patterned microgrooves and ripple structures with nanoparticles were formed distinctly in the channels. Considering the D and G Raman band parameters on the laser irradiation, it revealed a conversion from amorphous carbon to nanocrystalline graphite after laser treated with increasing laser power. X-ray photoelectron spectroscopy analysis showed a great decrease of sp{sup 3}/sp{sup 2} after laser treatment.

  2. Investigation of Chemical Bond Properties and Mssbauer Spectroscopy in YBa2Cu3O7

    Institute of Scientific and Technical Information of China (English)

    高发明; 李东春; 张思远

    2003-01-01

    Chemical bond properties of YBa2Cu3O7 were studied by using the average band-gap model. The calculated results show that the covalency of Cu(1)-O bond is 0.406, and one of Cu(2)-O is 0.276. Mssbauer isomer shifts of 57Fe in Y-123 were calculated by the chemical surrounding factor hv defined by covalency and electronic polarizability. The charge-state and site of Fe were determined. The relation between the coupling constant of electron-phonon interaction and covalency is employed to explain that the Cu(2)-O plane is more important than the Cu(1)-O chain on the superconductivity in the Y-123 compounds.

  3. Detection of sub-GeV Dark Matter and Solar Neutrinos via Chemical-Bond Breaking

    CERN Document Server

    Essig, Rouven; Slone, Oren; Volansky, Tomer

    2016-01-01

    We explore a new low-threshold direct-detection concept for dark matter, based on the breaking of chemical bonds between atoms. This includes the dissociation of molecules and the creation of defects in a lattice. With thresholds of a few to 10's of eV, such an experiment could probe the nuclear couplings of dark matter particles as light as a few MeV. We calculate the expected rates for dark matter to break apart diatomic molecules, which we take as a case study for more general systems. We briefly mention ideas for how chemical-bond breaking might be detected in practice. We also discuss the possibility of detecting solar neutrinos, including pp neutrinos, with this experimental concept. With an event rate of $\\mathcal{O}$(0.1/kg-year), large exposures are required, but measuring low-energy solar neutrinos would provide a crucial test of the solar model.

  4. 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.

  5. Developing density functional theory for Bose-Einstein condensates. The case of chemical bonding

    Energy Technology Data Exchange (ETDEWEB)

    Putz, Mihai V., E-mail: mvputz@cbg.uvt.ro [Laboratory of Physical and Computational Chemistry, Chemistry Department, West University of Timisoara, Str. Pestalozzi No. 16, 300115 Timisoara, Romania and Theoretical Physics Institute, Free University Berlin, Arnimallee 14, 14195 Berlin (Germany)

    2015-01-22

    Since the nowadays growing interest in Bose-Einstein condensates due to the expanded experimental evidence on various atomic systems within optical lattices in weak and strong coupling regimes, the connection with Density Functional Theory is firstly advanced within the mean field framework at three levels of comprehension: the many-body normalization condition, Thomas-Fermi limit, and the chemical hardness closure with the inter-bosonic strength and universal Hohenberg-Kohn functional. As an application the traditional Heitler-London quantum mechanical description of the chemical bonding for homopolar atomic systems is reloaded within the non-linear Schrödinger (Gross-Pitaevsky) Hamiltonian; the results show that a two-fold energetic solution is registered either for bonding and antibonding states, with the bosonic contribution being driven by the square of the order parameter for the Bose-Einstein condensate density in free (gas) motion, while the associate wave functions remain as in classical molecular orbital model.

  6. The nature of resonance-assisted hydrogen bonds: a quantum chemical topology perspective.

    Science.gov (United States)

    Guevara-Vela, José Manuel; Romero-Montalvo, Eduardo; Costales, Aurora; Pendás, Ángel Martín; Rocha-Rinza, Tomás

    2016-10-14

    Resonance Assisted Hydrogen Bonds (RAHBs) are particularly strong H-Bonds (HBs) which are relevant in several fields of chemistry. The traditional explanation for the occurrence of these HBs is built on mesomeric structures evocative of electron delocalisation in the system. Nonetheless, there are several theoretical studies which have found no evidence of such electron delocalisation. We considered the origin of RAHBs by employing Quantum Chemical Topology tools, more specifically, the Quantum Theory of Atoms in Molecules (QTAIM) and the Interacting Quantum Atoms energy partition. Our results indicate that the π-conjugated bonds allow for a larger adjustment of electron density throughout the H-bonded system as compared with non-conjugated carbonyl molecules. This rearrangement of charge distribution is a response to the electric field due to the H atom involved in the hydrogen bonding of the considered compounds. As opposed to the usual description of RAHB interactions, these HBs lead to a larger electron localisation in the system, and concomitantly to larger QTAIM charges which in turn lead to stronger electrostatic, polarization and charge transfer components of the interaction. Overall, the results presented here offer a new perspective on the cause of strengthening of these important interactions.

  7. Chemical Reasoning Based on an Invariance Property: Bond and Lone Pair Pictures in Quantum Structural Formulas

    Directory of Open Access Journals (Sweden)

    Joseph Alia

    2010-07-01

    Full Text Available Chemists use one set of orbitals when comparing to a structural formula, hybridized AOs or NBOs for example, and another for reasoning in terms of frontier orbitals, MOs usually. Chemical arguments can frequently be made in terms of energy and/or electron density without the consideration of orbitals at all. All orbital representations, orthogonal or not, within a given function space are related by linear transformation. Chemical arguments based on orbitals are really energy or electron density arguments; orbitals are linked to these observables through the use of operators. The Valency Interaction Formula, VIF, offers a system of chemical reasoning based on the invariance of observables from one orbital representation to another. VIF pictures have been defined as one-electron density and Hamiltonian operators. These pictures are classified in a chemically meaningful way by use of linear transformations applied to them in the form of two pictorial rules and the invariance of the number of doubly, singly, and unoccupied orbitals or bonding, nonbonding, and antibonding orbitals under these transformations. The compatibility of the VIF method with the bond pair – lone pair language of Lewis is demonstrated. Different electron lone pair representations are related by the pictorial rules and have stability understood in terms of Walsh’s rules. Symmetries of conjugated ring systems are related to their electronic state by simple mathematical formulas. Description of lone pairs in conjugated systems is based on the strength and sign of orbital interactions around the ring. Simple models for bonding in copper clusters are tested, and the bonding of O2 to Fe(II in hemoglobin is described. Arguments made are supported by HF, B3LYP, and MP2 computations.

  8. Effect of raw material ratios on the compressive strength of magnesium potassium phosphate chemically bonded ceramics.

    Science.gov (United States)

    Wang, Ai-juan; Yuan, Zhi-long; Zhang, Jiao; Liu, Lin-tao; Li, Jun-ming; Liu, Zheng

    2013-12-01

    The compressive strength of magnesium potassium phosphate chemically bonded ceramics is important in biomedical field. In this work, the compressive strength of magnesium potassium phosphate chemically bonded ceramics was investigated with different liquid-to-solid and MgO-to-KH2PO4 ratios. X-ray diffractometer was applied to characterize its phase composition. The microstructure was imaged using a scanning electron microscope. The results showed that the compressive strength of the chemically bonded ceramics increased with the decrease of liquid-to-solid ratio due to the change of the packing density and the crystallinity of hydrated product. However, with the increase of MgO-to-KH2PO4 weight ratio, its compressive strength increased firstly and then decreased. The low compressive strength in lower MgO-to-KH2PO4 ratio might be explained by the existence of the weak phase KH2PO4. However, the low value of compressive strength with the higher MgO-to-KH2PO4 ratio might be caused by lack of the joined phase in the hydrated product. Besides, it has been found that the microstructures were different in these two cases by the scanning electron microscope. Colloidal structure appeared for the samples with lower liquid-to-solid and higher MgO-to-KH2PO4 ratios possibly because of the existence of amorphous hydrated products. The optimization of both liquid-to-solid and MgO-to-KH2PO4 ratios was important to improve the compressive strength of magnesium potassium phosphate chemically bonded ceramics.

  9. Chemically bonded phosphate ceramics for radioactive and mixed waste solidification and stabilization

    Energy Technology Data Exchange (ETDEWEB)

    Wagh, A.S.; Cunnane, J.C.; Singh, D.; Reed, D.T.; Armstrong, S.; Subhan, W.; Chawla, N.

    1993-01-01

    Results of an initial investigation of low temperature setting chemically bonded magnesium ammonium phosphate (MAP) ceramics as waste form materials, for solidification and stabilization of radioactive and mixed waste, are reported. The suitability of MAP for solidifying and encapsulating waste materials was tested by encapsulating zeolites at loadings up to [approximately]50 wt%. The resulting composites exhibited very good compressive strength characteristics. Microstructure studies show that zeolite grains remain unreacted in the matrix. Potential uses for solidifying and stab wastes are discussed.

  10. Chemically bonded phosphate ceramics for radioactive and mixed waste solidification and stabilization

    Energy Technology Data Exchange (ETDEWEB)

    Wagh, A.S.; Cunnane, J.C.; Singh, D.; Reed, D.T.; Armstrong, S.; Subhan, W.; Chawla, N.

    1993-01-01

    Results of an initial investigation of low temperature setting chemically bonded magnesium ammonium phosphate (MAP) ceramics as waste form materials, for solidification and stabilization of radioactive and mixed waste, are reported. The suitability of MAP for solidifying and encapsulating waste materials was tested by encapsulating zeolites at loadings up to {approximately}50 wt%. The resulting composites exhibited very good compressive strength characteristics. Microstructure studies show that zeolite grains remain unreacted in the matrix. Potential uses for solidifying and stab wastes are discussed.

  11. Multi-layered, chemically bonded lithium-ion and lithium/air batteries

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya Kumar; Nanda, Jagjit; Bischoff, Brian L; Bhave, Ramesh R

    2014-05-13

    Disclosed are multilayer, porous, thin-layered lithium-ion batteries that include an inorganic separator as a thin layer that is chemically bonded to surfaces of positive and negative electrode layers. Thus, in such disclosed lithium-ion batteries, the electrodes and separator are made to form non-discrete (i.e., integral) thin layers. Also disclosed are methods of fabricating integrally connected, thin, multilayer lithium batteries including lithium-ion and lithium/air batteries.

  12. Multi-layered, chemically bonded lithium-ion and lithium/air batteries

    Science.gov (United States)

    Narula, Chaitanya Kumar; Nanda, Jagjit; Bischoff, Brian L; Bhave, Ramesh R

    2014-05-13

    Disclosed are multilayer, porous, thin-layered lithium-ion batteries that include an inorganic separator as a thin layer that is chemically bonded to surfaces of positive and negative electrode layers. Thus, in such disclosed lithium-ion batteries, the electrodes and separator are made to form non-discrete (i.e., integral) thin layers. Also disclosed are methods of fabricating integrally connected, thin, multilayer lithium batteries including lithium-ion and lithium/air batteries.

  13. Electronic structure and chemical bonding in LaIrSi-type intermetallics

    Energy Technology Data Exchange (ETDEWEB)

    Matar, Samir F. [Bordeaux Univ., Pessac (France). CNRS; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Nakhl, Michel [Univ. Libanaise, Fanar (Lebanon). Ecole Doctorale Sciences et Technologies

    2017-05-01

    The cubic LaIrSi type has 23 representatives in aluminides, gallides, silicides, germanides, phosphides, and arsenides, all with a valence electron count of 16 or 17. The striking structural motif is a three-dimensional network of the transition metal (T) and p element (X) atoms with TX{sub 3/3} respectively XT{sub 3/3} coordination. Alkaline earth or rare earth atoms fill cavities within the polyanionic [TX]{sup δ-} networks. The present work presents a detailed theoretical study of chemical bonding in LaIrSi-type representatives, exemplarily for CaPtSi, BaIrP, BaAuGa, LaIrSi, CeRhSi, and CeIrSi. DFT-GGA-based electronic structure calculations show weakly metallic compounds with itinerant small magnitude DOSs at E{sub F} except for CeRhSi whose large Ce DOS at E{sub F} leads to a finite magnetization on Ce (0.73 μ{sub B}) and induced small moments of opposite sign on Rh and Si in a ferromagnetic ground state. The chemical bonding analyses show dominant bonding within the [TX]{sup δ-} polyanionic networks. Charge transfer magnitudes were found in accordance with the course of the electronegativites of the chemical constituents.

  14. Evidence for excited-state intramolecular proton transfer in 4-chlorosalicylic acid from combined experimental and computational studies: Quantum chemical treatment of the intramolecular hydrogen bonding interaction

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Bijan Kumar [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India); Guchhait, Nikhil, E-mail: nikhil.guchhait@rediffmail.com [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India)

    2012-07-25

    Highlights: Black-Right-Pointing-Pointer Experimental and computational studies on the photophysics of 4-chlorosalicylic acid. Black-Right-Pointing-Pointer Spectroscopically established ESIPT reaction substantiated by theoretical calculation. Black-Right-Pointing-Pointer Quantum chemical treatment of IMHB unveils strength, nature and directional nature. Black-Right-Pointing-Pointer Superiority of quantum chemical treatment of H-bond over geometric criteria. Black-Right-Pointing-Pointer Role of H-bond as a modulator of aromaticity. -- Abstract: The photophysical study of a pharmaceutically important chlorine substituted derivative of salicylic acid viz., 4-chlorosalicylic acid (4ClSA) has been carried out by steady-state absorption, emission and time-resolved emission spectroscopy. A large Stokes shifted emission band with negligible solvent polarity dependence marks the spectroscopic signature of excited-state intramolecular proton transfer (ESIPT) reaction in 4ClSA. Theoretical calculation by ab initio and Density Functional Theory methods yields results consistent with experimental findings. Theoretical potential energy surfaces predict the occurrence of proton transfer in S{sub 1}-state. Geometrical and energetic criteria, Atoms-In-Molecule topological parameters, Natural Bond Orbital population analysis have been exploited to evaluate the intramolecular hydrogen bond (IMHB) interaction and to explore its directional nature. The inter-correlation between aromaticity and resonance assisted H-bond is also discussed in this context. Our results unveil that the quantum chemical treatment is a more accurate tool to assess hydrogen bonding interaction in comparison to geometrical criteria.

  15. Non-standard tests for process control in chemically bonded sands

    Directory of Open Access Journals (Sweden)

    S. Ramrattan

    2016-01-01

    Full Text Available Chemically bonded sand cores and molds are more commonly referred to as precision sand systems in the high production automotive powertrain sector. Their behavior in contact with molten metal can lead to casting defects. Consequently, the interaction is of great interest and an important part of metal casting technology. The American Foundry Society (AFS sand testing is based on physical, mechanical, thermal and chemical properties of the sand system. Foundry engineers have long known that certain AFS sand tests provide limited information regarding control of molding and casting quality. The inadequacy is due to the fact that sand casting processes are inherently thermo-mechanical, thermo-chemical and thermo-physical. Non-standard foundry sand testing has proven useful for laboratory measurement of these characteristics in foundry sand using a disc-shaped specimen. Similarly, the equivalent disc-shaped specimens are used for casting trials. In order to accomplish near-net-shape casting with minimal defects, it is necessary to understand both the properties of the sand system, as well as the interface of molten metal when different binders, additives and/or refractory coatings are used. The methodology for the following non-standard chemically bonded sand tests is described: (1 disc transverse; (2 impact; (3 modified permeability; (4 abrasion; (5 thermal distortion; (6 quick loss on ignition. The data related to the non-standard sand tests were analyzed and interpreted. The test results indicate that there is relatively lower test-to-test variability with the disc-shaped specimens. The non-standard tests were able to discriminate between the chemically bonded polyurethane cold box sand specimens. Further studies should be conducted on various other sand and binder systems as well as on different specimen thicknesses.

  16. Non-standard tests for process control in chemically bonded sands

    Directory of Open Access Journals (Sweden)

    S. Ramrattan

    2016-01-01

    Full Text Available Chemically bonded sand cores and molds are more commonly referred to as precision sand systems in the high production automotive powertrain sector. Their behavior in contact with molten metal can lead to casting defects. Consequently, the interaction is of great interest and an important part of metal casting technology. The American Foundry Society (AFS sand testing is based on physical, mechanical, thermal and chemical properties of the sand system. Foundry engineers have long known that certain AFS sand tests provide limited information regarding control of molding and casting quality. The inadequacy is due to the fact that sand casting processes are inherently thermo-mechanical, thermo-chemical and thermo-physical. Non-standard foundry sand testing has proven useful for laboratory measurement of these characteristics in foundry sand using a disc-shaped specimen. Similarly, the equivalent disc-shaped specimens are used for casting trials. In order to accomplish near-net-shape casting with minimal defects, it is necessary to understand both the properties of the sand system, as well as the interface of molten metal when different binders, additives and/or refractory coatings are used. The methodology for the following non-standard chemically bonded sand tests is described: (1 disc transverse; (2 impact; (3 modified permeability; (4 abrasion; (5 thermal distortion; (6 quick loss on ignition. The data related to the non-standard sand tests were analyzed and interpreted. The test results indicate that there is relatively lower test-to-test variability with the disc-shaped specimens. The non-standard tests were able to discriminate between the chemically bonded polyurethane cold box sand specimens. Further studies should be conducted on various other sand and binder systems as well as on different specimen thicknesses.

  17. Structure and Chemical Bond of Thermoelectric Ce-Co-Sb Skutterudites

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The correlations among composition,structure,chemical bond and thermoelectric property of skutterudites CoSb3 and CeCo5Fe3Sb12 have been studied by using density function and discrete variation (DFT-DVM) method.Three models for this study were proposed and calculated by which the "rattling" pattern was described.Model 1 is with Ce in the center,model 2 is with Ce away the center and near to Sb,and model 3 is also with Ce away the center but near to Fe.The calculated results show that in model 3,the ionic bond is the strongest,but the covalent bond is the weakest.Due to the different changes between ionic and covalent bond,there is less difference in the stability among the models 1,2 and 3.Therefore,these different models can exist at the same time,or can translate from one to another more easily.In other words,the "rattling" pattern has taken place.Unfilled model of CoSb3,without Ce and Fe,is called model 4.The covalent bond of Co-Sb or Fe-Sb in models 1,2 and 3 is weaker than that of Co-Sb in model 4,as some electrical cloud of Sb takes part in the covalent bond of Ce-Sb in the filled models.The result is consistent with the experimental result that the thermal conductivity of CeCo5Fe3Sb12 is lower than that of CoSb3,and the thermoelectric property of CeCo5Fe3Sb12 is superior to that of CoSb3.

  18. Four chemical methods of porcelain conditioning and their influence over bond strength and surface integrity

    Science.gov (United States)

    Stella, João Paulo Fragomeni; Oliveira, Andrea Becker; Nojima, Lincoln Issamu; Marquezan, Mariana

    2015-01-01

    OBJECTIVE: To assess four different chemical surface conditioning methods for ceramic material before bracket bonding, and their impact on shear bond strength and surface integrity at debonding. METHODS: Four experimental groups (n = 13) were set up according to the ceramic conditioning method: G1 = 37% phosphoric acid etching followed by silane application; G2 = 37% liquid phosphoric acid etching, no rinsing, followed by silane application; G3 = 10% hydrofluoric acid etching alone; and G4 = 10% hydrofluoric acid etching followed by silane application. After surface conditioning, metal brackets were bonded to porcelain by means of the Transbond XP system (3M Unitek). Samples were submitted to shear bond strength tests in a universal testing machine and the surfaces were later assessed with a microscope under 8 X magnification. ANOVA/Tukey tests were performed to establish the difference between groups (α= 5%). RESULTS: The highest shear bond strength values were found in groups G3 and G4 (22.01 ± 2.15 MPa and 22.83 ± 3.32 Mpa, respectively), followed by G1 (16.42 ± 3.61 MPa) and G2 (9.29 ± 1.95 MPa). As regards surface evaluation after bracket debonding, the use of liquid phosphoric acid followed by silane application (G2) produced the least damage to porcelain. When hydrofluoric acid and silane were applied, the risk of ceramic fracture increased. CONCLUSIONS: Acceptable levels of bond strength for clinical use were reached by all methods tested; however, liquid phosphoric acid etching followed by silane application (G2) resulted in the least damage to the ceramic surface. PMID:26352845

  19. Four chemical methods of porcelain conditioning and their influence over bond strength and surface integrity

    Directory of Open Access Journals (Sweden)

    João Paulo Fragomeni Stella

    2015-08-01

    Full Text Available OBJECTIVE: To assess four different chemical surface conditioning methods for ceramic material before bracket bonding, and their impact on shear bond strength and surface integrity at debonding.METHODS: Four experimental groups (n = 13 were set up according to the ceramic conditioning method: G1 = 37% phosphoric acid etching followed by silane application; G2 = 37% liquid phosphoric acid etching, no rinsing, followed by silane application; G3 = 10% hydrofluoric acid etching alone; and G4 = 10% hydrofluoric acid etching followed by silane application. After surface conditioning, metal brackets were bonded to porcelain by means of the Transbond XP system (3M Unitek. Samples were submitted to shear bond strength tests in a universal testing machine and the surfaces were later assessed with a microscope under 8 X magnification. ANOVA/Tukey tests were performed to establish the difference between groups (α= 5%.RESULTS: The highest shear bond strength values were found in groups G3 and G4 (22.01 ± 2.15 MPa and 22.83 ± 3.32 Mpa, respectively, followed by G1 (16.42 ± 3.61 MPa and G2 (9.29 ± 1.95 MPa. As regards surface evaluation after bracket debonding, the use of liquid phosphoric acid followed by silane application (G2 produced the least damage to porcelain. When hydrofluoric acid and silane were applied, the risk of ceramic fracture increased.CONCLUSIONS: Acceptable levels of bond strength for clinical use were reached by all methods tested; however, liquid phosphoric acid etching followed by silane application (G2 resulted in the least damage to the ceramic surface.

  20. FONO: a difficult case for theory. The ELF and ELI-D topological studies on the chemical bonding using correlated wavefunctions.

    Science.gov (United States)

    Berski, Slawomir; Gordon, Agnieszka J; Latajka, Zdzislaw

    2013-04-01

    The complicated nature of the chemical bonding in cis and trans isomers of F-O-N=O is discussed based on the results obtained from the topological analysis of electron localization function (η) (ELF), electron localizability index (Y(D)(σ)), and electron density (ρ). The calculations have been performed for correlated wavefunctions using the CCSD and CASSCF methods. The F-O1 bond with non-bonding basins, V(F) and V(')(O1), belongs to the protocovalent type (η,Y(D)(σ)) and its total population ranges between 0.2 and 0.4e. The central N-O1 bond in the cis form is protocovalent (η, Y(D)(σ)) with two basins, V(N) and V(O1). The total population oscillates between 0.7 and 0.9e. In the trans isomer, topology of ELF depends on used method. At the CCSD level only one non-bonding basin, V(N), is observed (η). Its population is about 0.5e. According to the definition of a heteronuclear charge-shift (CS) bond, only N-O1 bond in trans-FONO belongs to the CS class. A relation between η- and ρ-topology and N-O1 bond length is discussed.

  1. Electronic Structure and Chemical Bond of Ti3SiC2 and Adding Al Element

    Institute of Scientific and Technical Information of China (English)

    MIN Xinmin; LU Ning; MEI Bingchu

    2006-01-01

    The relation among electronic structure, chemical bond and property of Ti3SiC2 and Al-doped was studied by density function and discrete variation (DFT-DVM) method. When Al element is added into Ti3SiC2, there is a less difference of ionic bond, which does not play a leading role to influent the properties. After adding Al, the covalent bond of Al and the near Ti becomes somewhat weaker, but the covalent bond of Al and the Si in the same layer is obviously stronger than that of Si and Si before adding. Therefore, in preparation of Ti3SiC2, adding a proper quantity of Al can promote the formation of Ti3SiC2. The density of state shows that there is a mixed conductor character in both of Ti3SiC2 and adding Al element. Ti3SiC2 is with more tendencies to form a semiconductor. The total density of state near Fermi lever after adding Al is larger than that before adding, so the electric conductivity may increase after adding Al.

  2. Weak Intermolecular Hydrogen Bonds with Fluorine: Detection and Implications for Enzymatic/Chemical Reactions, Chemical Properties, and Ligand/Protein Fluorine NMR Screening.

    Science.gov (United States)

    Dalvit, Claudio; Vulpetti, Anna

    2016-05-23

    It is known that strong hydrogen-bonding interactions play an important role in many chemical and biological systems. However, weak or very weak hydrogen bonds, which are often difficult to detect and characterize, may also be relevant in many recognition and reaction processes. Fluorine serving as a hydrogen-bond acceptor has been the subject of many controversial discussions and there are different opinions about it. It now appears that there is compelling experimental evidence for the involvement of fluorine in weak intramolecular or intermolecular hydrogen bonds. Using established NMR methods, we have previously characterized and measured the strengths of intermolecular hydrogen-bond complexes involving the fluorine moieties CH2 F, CHF2 , and CF3 , and have compared them with the well-known hydrogen-bond complex formed between acetophenone and the strong hydrogen-bond donor p-fluorophenol. We now report evidence for the formation of hydrogen bonds involving fluorine with significantly weaker donors, namely 5-fluoroindole and water. A simple NMR method is proposed for the simultaneous measurement of the strengths of hydrogen bonds between an acceptor and a donor or water. Important implications of these results for enzymatic/chemical reactions involving fluorine, for chemical and physical properties, and for ligand/protein (19) F NMR screening are analyzed through experiments and theoretical simulations.

  3. Analysis of Bonds as an Instrument for Financing Mining Investments

    Science.gov (United States)

    Ranosz, Robert

    2017-06-01

    The purpose of this article is to examine the structure of financing for mining enterprises in the years 2007-2013, with particular emphasis on bonds. The document pays special attention to Polish mining enterprises. The financing structure analysis was based on data collected from financial statements (cash flows) of the largest mining companies in Poland, and their comparison with the results of global mining enterprises pursuant to reports prepared by international advisory firms. The article takes into account capital sources such as: corporate bonds, bank loans and issue of shares. As indicated by the performed analysis, mining enterprises both around the world and in Poland are increasingly eager to take advantage of obtaining business financing from issue of corporate bonds. It should also be recognized that in the analyzed period, both global and Polish mining enterprises deviate from forms of financing such as issue of shares. This may be caused by the fact that the bonds market in Poland is becoming increasingly popular, mainly due to interest rate on bonds being lower in comparison with bank loans. Another reason may be that banks and potential buyers of shares are less eager to finance this type of investment due to a relatively substantial risk acceptable to bondholders.

  4. Synthesis of chemically bonded graphene/carbon nanotube composites and their application in large volumetric capacitance supercapacitors.

    Science.gov (United States)

    Jung, Naeyoung; Kwon, Soongeun; Lee, Dongwook; Yoon, Dong-Myung; Park, Young Min; Benayad, Anass; Choi, Jae-Young; Park, Jong Se

    2013-12-17

    Chemically bonded graphene/carbon nanotube composites as flexible supercapacitor electrode materials are synthesized by amide bonding. Carbon nanotubes attached along the edges and onto the surface of graphene act as spacers to increase the electrolyte-accessible surface area. Our lamellar structure electrodes demonstrate the largest volumetric capacitance (165 F cm(-3) ) ever shown by carbon-based electrodes.

  5. Electronic Structures and Chemical Bonds of Cobaltite and Ni-Doped

    Institute of Scientific and Technical Information of China (English)

    MIN Xinmin; XING Xueling; ZHU Lei

    2005-01-01

    The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co2 O6 and Ni-doped was studied by density function theory and discrete variation method(DFT-DVM). The results indicate that the highest valence band (HVB) and the lowest conduction band(LCB) are mainly attributed to Co3 d, Ni3 d and O2 p atomic orbitals. The property of a semiconductor is shown from the gap between HVB and LCB. The gap of Ni-doped one is less than that of Ca3 Co2 O6. The non-metal bond or ceramic characteristic of Ni-doped one is weaker than that of Ca3 Co2 O6, but the metal characteristics of Ni-doped one are stronger than those of Ca3 Co2O6. The thermoelectric property should be improved by adding Ni element into the system of Ca3 Co2 O6.

  6. Atom-specific look at the surface chemical bond using x-ray emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nilsson, A.; Wassdahl, N.; Weinelt, M. [Uppsala Univ. (Sweden)] [and others

    1997-04-01

    CO and N{sub 2} adsorbed on the late transition metals have become prototype systems regarding the general understanding of molecular adsorption. It is in general assumed that the bonding of molecules to transition metals can be explained in terms of the interaction of the frontier HOMO and LUMO molecular orbitals with the d-orbitals. In such a picture the other molecular orbitals should remain essentially the same as in the free molecule. For the adsorption of the isoelectronic molecules CO and N{sub 2} this has led to the so called Blyholder model i.e., a synergetic {sigma} (HOMO) donor and {pi} (LUMO) backdonation bond. The authors results at the ALS show that such a picture is oversimplified. The direct observation and identification of the states related to the surface chemical bond is an experimental challenge. For noble and transition metal surfaces, the adsorption induced states overlap with the metal d valence band. Their signature is therefore often obscured by bulk substrate states. This complication has made it difficult for techniques such as photoemission and inverse photoemission to provide reliable information on the energy of chemisorption induced states and has left questions unanswered regarding the validity of the frontier orbitals concept. Here the authors show how x-ray emission spectroscopy (XES), in spite of its inherent bulk sensitivity, can be used to investigate adsorbed molecules. Due to the localization of the core-excited intermediate state, XE spectroscopy allows an atomic specific separation of the valence electronic states. Thus the molecular contributions to the surface measurements make it possible to determine the symmetry of the molecular states, i.e., the separation of {pi} and {sigma} type states. In all the authors can obtain an atomic view of the electronic states involved in the formation of the chemical bond to the surface.

  7. Heteromolecular metal–organic interfaces: Electronic and structural fingerprints of chemical bonding

    Energy Technology Data Exchange (ETDEWEB)

    Stadtmüller, Benjamin; Schröder, Sonja [Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich GmbH, D-52425 Jülich (Germany); Jülich-Aachen Research Alliance (JARA) – Fundamentals of Future Information Technology, 52425 Jülich (Germany); Kumpf, Christian, E-mail: c.kumpf@fz-juelich.de [Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich GmbH, D-52425 Jülich (Germany); Jülich-Aachen Research Alliance (JARA) – Fundamentals of Future Information Technology, 52425 Jülich (Germany)

    2015-10-01

    Highlights: • We present a study of molecular donor–acceptor blends adsorbed on Ag(1 1 1). • Geometric and electronic structure of blends and pristine phases are compared. • The surface bonding of the acceptor is strengthened, that of the donor weakened. • But counter intuitively, the acceptor (donor) bond length becomes larger (smaller). • This contradiction is resolved by a model based on charge transfer via the surface. - Abstract: Beside the fact that they attract highest interest in the field of organic electronics, heteromolecular structures adsorbed on metal surfaces, in particular donor–acceptor blends, became a popular field in fundamental science, possibly since some surprising and unexpected behaviors were found for such systems. One is the apparent breaking of a rather fundamental rule in chemistry, namely that stronger chemical bonds go along with shorter bond lengths, as it is, e.g., well-known for the sequence from single to triple bonds. In this review we summarize the results of heteromolecular monolayer structures adsorbed on Ag(1 1 1), which – regarding this rule – behave in a counterintuitive way. The charge acceptor moves away from the substrate while its electronic structure indicates a stronger chemical interaction, indicated by a shift of the formerly lowest unoccupied molecular orbital toward higher binding energies. The donor behaves in the opposite way, it gives away charge, hence, electronically the bonding to the surface becomes weaker, but at the same time it also approaches the surface. It looks as if the concordant link between electronic and geometric structure was broken. But both effects can be explained by a substrate-mediated charge transfer from the donor to the acceptor. The charge reorganization going along with this transfer is responsible for both, the lifting-up of the acceptor molecule and the filling of its LUMO, and also for the reversed effects at the donor molecules. In the end, both molecules

  8. A constitutive model for bonded geomaterials subject to mechanical and/or chemical degradation

    Science.gov (United States)

    Nova, R.; Castellanza, R.; Tamagnini, C.

    2003-08-01

    The mechanical behaviour of bonded geomaterials is described by means of an elastoplastic strain-hardening model. The internal variables, taking into account the history of the material, depend on the plastic strains experienced and on a conveniently defined scalar measure of damage induced by weathering and/or chemical degradation.For the sake of simplicity, it is assumed that only internal variables are affected by mechanical and chemical history of the material. Despite this simplifying assumption, it can be shown that many interesting phenomena exhibited by weathered bonded geomaterials can be successfully described. For instance, (i) the transition from brittle to ductile behaviour with increasing pressure of a calcarenite with collapsing internal structure, (ii) the complex behaviour of chalk and other calcareous materials in oedometric tests, (iii) the chemically induced variation of the stress and strain state of such kind of materials, are all phenomena that can be qualitatively reproduced. Several comparisons with experimental data show that the model can capture the observed behaviour also quantitatively.

  9. An unexpected bridge between chemical bonding indicators and electrical conductivity through the localization tensor.

    Science.gov (United States)

    Pendás, Ángel Martín; Guevara-Vela, José Manuel; Crespo, Daniel Menéndez; Costales, Aurora; Francisco, Evelio

    2017-01-18

    While the modern theory of the insulating state shows that the conducting or insulating properties of a system can be extracted solely from the ground state properties via the so-called localization tensor (LT), no chemical reading of this important quantity has ever been offered. Here, a remarkable link between the LT and the bond orders as described by the delocalization indices (DIs) of chemical bonding theory is reported. This is achieved through a real space partition of the LT into intra- and interatomic contributions. We show that the convergence or divergence of the LT in the thermodynamic limit, which signals the insulating or conducting nature of an extended system, respectively, can be nailed down to DIs. This allows for the exploitation of traditional chemical intuition to identify essential and spectator atomic groups in determining electrical conductivity. The thermodynamic limit of the LT is controlled by the spatial decay rate of the interatomic DIs, exponential in insulators and power-law in conductors. Computational data of a few selected toy systems corroborate our results.

  10. Processing and quantitative analysis of biodegradable polymers (PLLA and PCL) thermal bonding

    Science.gov (United States)

    Boutry, C. M.; Kiran, R.; Umbrecht, F.; Hierold, C.

    2010-08-01

    A quantitative analysis of the bond strength and microstructure integrity achieved when bonding the biodegradable polymers poly(L-lactide) (PLLA) and poly(ɛ-caprolactone) (PCL) has been performed using the response surface methodology. The respective influence of the bonding parameters (temperature, pressure, duration) on the bond strength and microchannel integrity was investigated. PLLA and PCL were identified as suitable candidates for packaging materials for bioelectronic circuits of conductive biodegradable polymers. For a future packaging application, the bonding parameters were adapted to optimize the bond strength; the estimated values for the bond strength and channel integrity that were predicted by the surface plots were 2.32 ± 0.26 MPa and 33.7 ± 12.9% for PLLA, and 0.81 ± 0.11 MPa and 50.9 ± 5.7% for PCL. These values were in good agreement with the experimentally determined bond strength of 2.00 ± 1.10 MPa (PLLA) and 0.67 ± 0.22 MPa (PCL) and deformation of 31.4 ± 7.0% (PLLA) and 52.9 ± 4.1% (PCL). Microchannels with an aspect ratio of 1:12.5 were successfully fabricated. The impact of the fabrication process on the PLLA and PCL chemical properties was also investigated through differential scanning calorimetry and gel permeation chromatography measurements. It was observed that the weight average molecular weight Mw decreases after each fabrication step, as much as 68% for PLLA and 59% for PCL. The strongest reduction was observed after the compression molding (above the melting temperature) which should be kept as short as possible. An annealing step allowed increasing the crystallinity and improved the overall polymer stiffness.

  11. Evolution of chemical bonding and electron density rearrangements during D(3h) → D(3d) reaction in monolayered TiS2: a QTAIM and ELF study.

    Science.gov (United States)

    Ryzhikov, Maxim R; Slepkov, Vladimir A; Kozlova, Svetlana G; Gabuda, Svyatoslav P

    2014-08-15

    Monolayered titanium disulfide TiS2, a prospective nanoelectronic material, was previously shown to be subject to an exothermic solid-state D3h -D3d reaction that proceeds via a newly discovered transition state. Here, we study the reaction in detail using topological methods of quantum chemistry (quantum theory of atoms in molecules and electron localization function analysis) and show how electron density and chemical bonding between the atoms change in the course of the reaction. The reaction is shown to undergo a series of topological catastrophes, associated with elementary chemical events such as break and formation of bonds (including the unexpected formation of S-S bonding between sulfur layers), and rearrangement of electron density of outer valence and core shells.

  12. 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.

  13. The use of dialogic electronic journal writing to develop students' understanding of chemical bonding

    Science.gov (United States)

    English, Sarah Collard

    The intent of this study is to examine how the implementation of a dialogic electronic journal writing environment continues the development of students' understanding of chemistry, specifically chemical bonding, through written communication between the individual students and their chemistry teacher. This study is framed within a constructivist theoretical context where students' understanding is constructed through written discussions with the educator, the students' interaction with the classroom environment, and his/her interaction with the computer environment. The research design of collective case study was employed to allow multiple perspectives and processes conveyed by the participants to be examined in the context in which they occurred while considering multiple sources of information. Data sources included electronic journal entries, classroom artifacts, and semi-structured interviews. Data were analyzed using the constant comparative method, which involved coding, categorizing, and interpreting for patterns and relationships. Four cases were reported in detail. This study found that the dialogic electronic journal-writing environment was an effective venue in revealing previously undiscovered students' alternative conceptions of chemical bonding. Opportunities to actively confront and reconcile such conceptions were afforded through educator/student dialogic written interaction. The dialogic electronic journal-writing environment was also critical in the identification of gaps in students' conceptual understanding linked to improper sequencing of chemistry content. This study also found that the on-line environment provided the educator the opportunity to scaffold chemical bonding concepts to meet the needs of the students involved in the study. This study concluded that the dialogic electronic journal-writing environment positively contributed to the development of student understanding. These findings may have practical implications for teachers in

  14. Peptide Bond Synthesis by a Mechanism Involving an Enzymatic Reaction and a Subsequent Chemical Reaction.

    Science.gov (United States)

    Abe, Tomoko; Hashimoto, Yoshiteru; Zhuang, Ye; Ge, Yin; Kumano, Takuto; Kobayashi, Michihiko

    2016-01-22

    We recently reported that an amide bond is unexpectedly formed by an acyl-CoA synthetase (which catalyzes the formation of a carbon-sulfur bond) when a suitable acid and l-cysteine are used as substrates. DltA, which is homologous to the adenylation domain of nonribosomal peptide synthetase, belongs to the same superfamily of adenylate-forming enzymes, which includes many kinds of enzymes, including the acyl-CoA synthetases. Here, we demonstrate that DltA synthesizes not only N-(d-alanyl)-l-cysteine (a dipeptide) but also various oligopeptides. We propose that this enzyme catalyzes peptide synthesis by the following unprecedented mechanism: (i) the formation of S-acyl-l-cysteine as an intermediate via its "enzymatic activity" and (ii) subsequent "chemical" S → N acyl transfer in the intermediate, resulting in peptide formation. Step ii is identical to the corresponding reaction in native chemical ligation, a method of chemical peptide synthesis, whereas step i is not. To the best of our knowledge, our discovery of this peptide synthesis mechanism involving an enzymatic reaction and a subsequent chemical reaction is the first such one to be reported. This new process yields peptides without the use of a thioesterified fragment, which is required in native chemical ligation. Together with these findings, the same mechanism-dependent formation of N-acyl compounds by other members of the above-mentioned superfamily demonstrated that all members most likely form peptide/amide compounds by using this novel mechanism. Each member enzyme acts on a specific substrate; thus, not only the corresponding peptides but also new types of amide compounds can be formed.

  15. 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].

  16. Processing–structure–property relations of chemically bonded phosphate ceramic composites

    Indian Academy of Sciences (India)

    H A Colorado; C Hiel; H T Hahn

    2011-07-01

    Mechanical properties and microstructures of a chemically bonded phosphate ceramic (CBPC) and its composite with 1.0 wt% graphite nanoplatelets (GNPs) reinforcement have been investigated. Microstructure was identified by using optical and scanning electron microscopes, X-ray tomography, and X-ray diffraction. In addition, weight loss of the resin at room temperature was studied. The microstructure characterization shows that CBPC is itself a composite with several crystalline (wollastonite and brushite) and amorphous phases. SEM and micro tomography show a homogeneous distribution of crystalline phases. Bending and compression strength of the CBPC was improved by reducing bubbles via preparation in vacuum.

  17. Influence of chemical bonding on X-ray spectra of different aluminium compounds

    Energy Technology Data Exchange (ETDEWEB)

    Bonetto, Rita [Centro de Investigacion y Desarrollo en Ciencias Aplicadas Dr. Jorge Ronco, Calle 47 No. 257, CC 59, 1900 La Plata (Argentina) and Consejo Nacional de Investigaciones Cientificas y Tecnicas de la Republica Argentina (Argentina)]. E-mail: bonetto@quimica.unlp.edu.ar; Trincavelli, Jorge [Facultad de Matematica, Astronomia y Fisica, Universidad Nacional de Cordoba, Ciudad Universitaria, 5000, Cordoba (Argentina) and Consejo Nacional de Investigaciones Cientificas y Tecnicas de la Republica Argentina (Argentina)]. E-mail: jorge@quechua.fis.uncor.edu; Vasconcellos, Marcos [Instituto de Fisica, Universidade Federal de Rio Grande do Sul, Campus do Vale, Av. Bento Goncalves 9500, CEP: 91501-970, Porto Alegre (Brazil)]. E-mail: marcos@if.ufrgs.br

    2005-11-15

    Five minerals containing aluminium in different crystal configurations are studied. The different kinds of chemical bonding between aluminium and oxygen originate molecular orbitals with energy levels and transition probabilities varying from one compound to another. This effect appears as shifts and changes in relative intensities of K{alpha} emission lines and as modifications of the K{beta} characteristic spectrum. In the present work, the aluminium K characteristic spectra obtained by means of an electron microprobe with a wavelength dispersive system are compared for topaz, albite, spodumene, biotite and corundum.

  18. A tutorial for understanding chemical reactivity through the valence bond approach.

    Science.gov (United States)

    Usharani, Dandamudi; Lai, Wenzhen; Li, Chunsen; Chen, Hui; Danovich, David; Shaik, Sason

    2014-07-21

    This is a tutorial on the usage of valence bond (VB) diagrams for understanding chemical reactivity in general, and hydrogen atom transfer (HAT) reactivity in particular. The tutorial instructs the reader how to construct the VB diagrams and how to estimate HAT barriers from raw data, starting with the simplest reaction H + H2 and going all the way to HAT in the enzyme cytochrome P450. Other reactions are treated as well, and some unifying principles are outlined. The tutorial projects the unity of reactivity treatments, following Coulson's dictum "give me insight, not numbers", albeit with its modern twist: giving numbers and insight.

  19. Quantum chemical calculations of bond dissociation energies for COOH scission and electronic structure in some acids

    Institute of Scientific and Technical Information of China (English)

    Zeng Hui; Zhao Jun; Xiao Xun

    2013-01-01

    Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies (BDEs) for 15 acids.These compounds are studied by utilizing the hybrid density functional theory (DFT) (B3LYP,B3PW91,B3P86,PBE1PBE) and the complete basis set (CBS-Q) method in conjunction with the 6-31 lG** basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed.

  20. Chemically bonded phosphorus/graphene hybrid as a high performance anode for sodium-ion batteries.

    Science.gov (United States)

    Song, Jiangxuan; Yu, Zhaoxin; Gordin, Mikhail L; Hu, Shi; Yi, Ran; Tang, Duihai; Walter, Timothy; Regula, Michael; Choi, Daiwon; Li, Xiaolin; Manivannan, Ayyakkannu; Wang, Donghai

    2014-11-12

    Room temperature sodium-ion batteries are of great interest for high-energy-density energy storage systems because of low-cost and natural abundance of sodium. Here, we report a novel phosphorus/graphene nanosheet hybrid as a high performance anode for sodium-ion batteries through facile ball milling of red phosphorus and graphene stacks. The graphene stacks are mechanically exfoliated to nanosheets that chemically bond with the surfaces of phosphorus particles. This chemical bonding can facilitate robust and intimate contact between phosphorus and graphene nanosheets, and the graphene at the particle surfaces can help maintain electrical contact and stabilize the solid electrolyte interphase upon the large volume change of phosphorus during cycling. As a result, the phosphorus/graphene nanosheet hybrid nanostructured anode delivers a high reversible capacity of 2077 mAh/g with excellent cycling stability (1700 mAh/g after 60 cycles) and high Coulombic efficiency (>98%). This simple synthesis approach and unique nanostructure can potentially be applied to other phosphorus-based alloy anode materials for sodium-ion batteries.

  1. Chemical bonding and humidity sensing properties of amorphous carbon nitride (a-CNx) by acetylene gas

    Science.gov (United States)

    Aziz, Siti Aisyah Abd; Purhanudin, Noorain; Awang, Rozidawati

    2017-05-01

    Amorphous carbon nitride (a-CNx) thin films were deposited by radio frequency plasma enhance chemical vapor deposition (RF-PECVD) using a fixed mixture of acetylene (C2H2) at 20 sccm and nitrogen (N2) gases at 50 sccm. The films were deposited at different RF power of 60, 70, 80, 90 and 100 W. The deposition pressure, deposition time and substrate temperature were kept constant at 0.8 mbar, 30 minutes and 100°C, respectively. The chemical bonding of the a-CNx thin films was characterized using Fourier transform infrared spectroscopy (FTIR) and its sensing properties was determined using a home built humidity sensor system. The increase of RF powers leads to an increment of formation of double (C=N) and triple (C≡N) bonds as compared to a-CNx deposited using methane (CH4) or ethane (C2H6) gas. This is due to a higher ratio of C to H atoms in C2H2. The humidity sensing performance show the sensitivity of the films is the highest at low deposition power in changes of relative humidity (%RH). The a-CNx thin film show good repeatability and high sensitivity as a humidity sensing materials which prepared at low RF power.

  2. Experimental evidence of chemical components in the bonding of helium and neon with neutral molecules.

    Science.gov (United States)

    Cappelletti, David; Bartocci, Alessio; Grandinetti, Felice; Falcinelli, Stefano; Belpassi, Leonardo; Tarantelli, Francesco; Pirani, Fernando

    2015-04-13

    The complexes of helium and neon with gaseous neutral molecules are generally perceived to be van der Waals adducts held together by physical (non-covalent) forces, owing to the combination of size (exchange) repulsion with dispersion/induction attraction. Molecular beam experiments confirm that this is the case for He-CF4 , Ne-CF4 adducts, but revealed that the interaction of He and Ne with CCl4 features an appreciable contribution of chemical components that arise from the anisotropy of the electron density of CCl4 that enhances a charge transfer from Ng (Ng=He, Ne). These findings furnish a novel assay of the bonding capabilities of helium and neon, and invite to revisit the neutral complexes of these elements as systems of chemical relevance. The CCl4 -Ng are also peculiar examples of halogen bonds, a group of interactions of major current concern. Finally, this investigation is a prelude to the development of semi-empirical models for force fields aimed to the unified description of static and dynamical properties of systems of comparable or higher complexity.

  3. Load and Time Dependence of Interfacial Chemical Bond-Induced Friction at the Nanoscale

    Science.gov (United States)

    Tian, Kaiwen; Gosvami, Nitya N.; Goldsby, David L.; Liu, Yun; Szlufarska, Izabela; Carpick, Robert W.

    2017-02-01

    Rate and state friction (RSF) laws are widely used empirical relationships that describe the macroscale frictional behavior of a broad range of materials, including rocks found in the seismogenic zone of Earth's crust. A fundamental aspect of the RSF laws is frictional "aging," where friction increases with the time of stationary contact due to asperity creep and/or interfacial strengthening. Recent atomic force microscope (AFM) experiments and simulations found that nanoscale silica contacts exhibit aging due to the progressive formation of interfacial chemical bonds. The role of normal load (and, thus, normal stress) on this interfacial chemical bond-induced (ICBI) friction is predicted to be significant but has not been examined experimentally. Here, we show using AFM that, for nanoscale ICBI friction of silica-silica interfaces, aging (the difference between the maximum static friction and the kinetic friction) increases approximately linearly with the product of the normal load and the log of the hold time. This behavior is attributed to the approximately linear dependence of the contact area on the load in the positive load regime before significant wear occurs, as inferred from sliding friction measurements. This implies that the average pressure, and thus the average bond formation rate, is load independent within the accessible load range. We also consider a more accurate nonlinear model for the contact area, from which we extract the activation volume and the average stress-free energy barrier to the aging process. Our work provides an approach for studying the load and time dependence of contact aging at the nanoscale and further establishes RSF laws for nanoscale asperity contacts.

  4. Application of chemical structure and bonding of actinide oxide materials for forensic science

    Energy Technology Data Exchange (ETDEWEB)

    Wilkerson, Marianne Perry [Los Alamos National Laboratory

    2010-01-01

    We are interested in applying our understanding of actinide chemical structure and bonding to broaden the suite of analytical tools available for nuclear forensic analyses. Uranium- and plutonium-oxide systems form under a variety of conditions, and these chemical species exhibit some of the most complex behavior of metal oxide systems known. No less intriguing is the ability of AnO{sub 2} (An: U, Pu) to form non-stoichiometric species described as AnO{sub 2+x}. Environmental studies have shown the value of utilizing the chemical signatures of these actinide oxide materials to understand transport following release into the environment. Chemical speciation of actinide-oxide samples may also provide clues as to the age, source, or process history of the material. The scientific challenge is to identify, measure and understand those aspects of speciation of actinide analytes that carry information about material origin and history most relevant to forensics. Here, we will describe our efforts in material synthesis and analytical methods development that we will use to provide the fundamental science to characterize actinide oxide molecular structures for forensic science. Structural properties and initial results to measure structural variability of uranium oxide samples using synchrotron-based X-ray Absorption Fine Structure will be discussed.

  5. Gas phase chemical detection with an integrated chemical analysis system

    Energy Technology Data Exchange (ETDEWEB)

    CASALNUOVO,STEPHEN A.; FRYE-MASON,GREGORY CHARLES; KOTTENSTETTE,RICHARD; HELLER,EDWIN J.; MATZKE,CAROLYN M.; LEWIS,PATRICK R.; MANGINELL,RONALD P.; BACA,ALBERT G.; HIETALA,VINCENT M.

    2000-04-12

    Microfabrication technology has been applied to the development of a miniature, multi-channel gas phase chemical laboratory that provides fast response, small size, and enhanced versatility and chemical discrimination. Each analysis channel includes a sample preconcentrator followed by a gas chromatographic separator and a chemically selective surface acoustic wave detector array to achieve high sensitivity and selectivity. The performance of the components, individually and collectively, is described.

  6. [Laboratory chemical analysis in ascites].

    Science.gov (United States)

    Satz, N

    1991-04-13

    Chemical analysis of ascitic fluid may be helpful in determining the underlying disease. We discuss the diagnostic accuracy of the common and newer chemical parameters (protein, LDH, lactate, glucose, cholesterol, triglycerides, phospholipids, fibronectin, albumin gradient [value of serum minus value of ascites], ferritin, tumor markers, immunomodulators, leukocytes, bacterial and cytologic examinations). We also review the pathogenesis and clinical findings of the most frequent ascites forms (benign hepatic, infective, malignant ascites, ascites associated with liver metastases or hepatocellular carcinoma, cardiac and pancreatic ascites) and the most important diagnosis criteria. In the malignant ascites a high cholesterol, a narrow albumin gradient or a high ferritin value have high diagnostic accuracy, but diagnosis is by the finding of malignant cells. For the diagnosis of infective ascites, bacteriology is mandatory even though the results are negative in most cases, particularly in spontaneous bacterial peritonitis where diagnosis has to be established clinically, by a low pH or by a high leukocyte count. Benign hepatic ascites is diagnosed by demonstrating an underlying chronic liver disease and laboratory examinations of the peritoneal fluid to exclude other causes. The laboratory tests in ascites associated with liver metastases or with hepatocellular carcinoma were similar to those in benign hepatic ascites and the two ascites forms must be separated by other clinical and technical findings. Pancreatic ascites can easily be distinguished from the other forms by the high amylase and lipase content.

  7. First principles study of the alloying effect on chemical bonding characteristics of helium in La-Ni-M tritides

    Energy Technology Data Exchange (ETDEWEB)

    Hu, C.H. [Institute of Metal Research, Chinese Academy of Science, 72 Wenhua Road, Shenyang 110016 (China); Zhang, R.J. [Institute of Metal Research, Chinese Academy of Science, 72 Wenhua Road, Shenyang 110016 (China); Shi, L.Q. [Applied Ion Bean Physics Laboratory, Fudan University, Shanghai 200433 (China); Chen, D.M. [Institute of Metal Research, Chinese Academy of Science, 72 Wenhua Road, Shenyang 110016 (China); Wang, Y.M. [Institute of Metal Research, Chinese Academy of Science, 72 Wenhua Road, Shenyang 110016 (China)]. E-mail: ymwang@imr.ac.cn; Yang, K. [Institute of Metal Research, Chinese Academy of Science, 72 Wenhua Road, Shenyang 110016 (China)

    2005-11-15

    The alloying effect on the electronic structure of La-Ni-M tritides is investigated using the first principles discrete variational X{alpha}(DV-X{alpha}) method. The calculated results show that the covalent interaction between atoms will play a much more important role in studying the alloying effect on chemical bonding characteristics in La-Ni-M tritides than ionic interaction. It is also found that in La-Ni-M tritides helium forms stronger covalent bonds with the weaker hydride forming elements than La. By analyzing the relation between the binding energy difference and bond order, our study indicates that after some alloying elements substituting for Ni locating in 3g site in tritides, the helium retention capability becomes stronger, changes as the following sequence: Al > Cr > Mn > Fe > Co > Ni, and is also very distinct for Cu although the chemical bonding between Cu atom and Ni atom is degraded drastically.

  8. Influence of chemical bonding of chlorides with aluminates in cement hidratation process on corrosion steel bars in concrete

    OpenAIRE

    2010-01-01

    The presence of chlorides in concrete is a permanent subject of research because they cause corrosion of steel bars. Chlorides added to the concrete during preparation, as accelerators of the bonding of cement minerals process, enter into reaction with aluminates, creating a phase known as chloroaluminate hydrates. In everyday conditions the product of chemical bonding between chlorides and aluminates is usually monochloridealuminate C3A·CaCl2·Hx, better known as Friedel's salt. In this paper...

  9. Theoretical prediction of hydrogen-bond basicity pKBHX using quantum chemical topology descriptors.

    Science.gov (United States)

    Green, Anthony J; Popelier, Paul L A

    2014-02-24

    Hydrogen bonding plays an important role in the interaction of biological molecules and their local environment. Hydrogen-bond strengths have been described in terms of basicities by several different scales. The pKBHX scale has been developed with the interests of medicinal chemists in mind. The scale uses equilibrium constants of acid···base complexes to describe basicity and is therefore linked to Gibbs free energy. Site specific data for polyfunctional bases are also available. The pKBHX scale applies to all hydrogen-bond donors (HBDs) where the HBD functional group is either OH, NH, or NH+. It has been found that pKBHX can be described in terms of a descriptor defined by quantum chemical topology, ΔE(H), which is the change in atomic energy of the hydrogen atom upon complexation. Essentially the computed energy of the HBD hydrogen atom correlates with a set of 41 HBAs for five common HBDs, water (r2=0.96), methanol (r2=0.95), 4-fluorophenol (r2=0.91), serine (r2=0.93), and methylamine (r2=0.97). The connection between experiment and computation was strengthened with the finding that there is no relationship between ΔE(H) and pKBHX when hydrogen fluoride was used as the HBD. Using the methanol model, pKBHX predictions were made for an external set of bases yielding r2=0.90. Furthermore, the basicities of polyfunctional bases correlate with ΔE(H), giving r2=0.93. This model is promising for the future of computation in fragment-based drug design. Not only has a model been established that links computation to experiment, but the model may also be extrapolated to predict external experimental pKBHX values.

  10. Chemical bonding and electronic-structure in MAX phases as viewed by X-ray spectroscopy and density functional theory

    Science.gov (United States)

    Magnuson, Martin; Mattesini, Maurizio

    2017-01-01

    This is a critical review of MAX-phase carbides and nitrides from an electronic-structure and chemical bonding perspective. This large group of nanolaminated materials is of great scientific and technological interest and exhibit a combination of metallic and ceramic features. These properties are related to the special crystal structure and bonding characteristics with alternating strong M-C bonds in high-density MC slabs, and relatively weak M-A bonds between the slabs. Here, we review the trend and relationship between the chemical bonding, conductivity, elastic and magnetic properties of the MAX phases in comparison to the parent binary MX compounds with the underlying electronic structure probed by polarized X-ray spectroscopy. Spectroscopic studies constitute important tests of the results of state-of-the-art electronic structure density functional theory that is extensively discussed and are generally consistent. By replacing the elements on the M, A, or X-sites in the crystal structure, the corresponding changes in the conductivity, elasticity, magnetism and other materials properties makes it possible to tailor the characteristics of this class of materials by controlling the strengths of their chemical bonds.

  11. Fabrication of a molecular-level multilayer film on organic polymer surfaces via chemical bonding assembly.

    Science.gov (United States)

    Zhao, Hongchi; Yang, Peng; Deng, Jianping; Liu, Lianying; Zhu, Jianwu; Sui, Yuan; Lu, Jiaoming; Yang, Wantai

    2007-02-13

    A fresh multilayer film was fabricated on a molecular level and successfully tethered to the surface of a hydroxylated organic substrate via chemical bonding assembly (CBA). Sulfate anion groups (SO4-) were preintroduced onto the surface of biaxially oriented polypropylene (BOPP) films via a reference method. Upon hydrolysis of the SO4- groups, hydroxyl groups (--OH) were formed that subsequently acted as initial reagents for a series of alternate reactions with terephthalyl chloride (TPC) and bisphenol A (BPA). A stable and well-defined multilayer film was thus fabricated via the CBA method. As a result of the nanoscale multilayer fresh film being abundant with reactive groups, it is believed that the film and its fabrication method should provide a fundamental platform for further surface functionalization and direct the design of advanced materials with desired properties.

  12. Wollastonite based-Chemically Bonded Phosphate Ceramics with lead oxide contents under gamma irradiation

    Science.gov (United States)

    Colorado, H. A.; Pleitt, J.; Hiel, C.; Yang, J. M.; Hahn, H. T.; Castano, C. H.

    2012-06-01

    The shielding properties to gamma rays as well as the effect of lead concentration incorporated into Chemically Bonded Phosphate Ceramics (CBPCs) composites are presented. The Wollastonite-based CBPC was fabricated by mixing a patented aqueous phosphoric acid formulation with Wollastonite powder. CBPC has been proved to be good structural material, with excellent thermal resistant properties, and research already showed their potential for radiation shielding applications. Wollastonite-based CBPC is a composite material itself with several crystalline and amorphous phases. Irradiation experiments were conducted on different Wollastonite-based CBPCs with lead oxide. Radiation shielding potential, attenuation coefficients in a broad range of energies pertinent to engineering applications and density experiments showing the effect of the PbO additions (to improve gamma shielding capabilities) are also presented. Microstructure was identified by using scanning electron microscopy and X-ray diffraction.

  13. Method for Producing Chemically Bonded Phosphate Ceramics and for Stabilizing Contaminants Encapsulated therein Utilizing Reducing Agents

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Dileep; Wagh, Arun S.; Jeong, Seung-Young

    1999-05-05

    Known phosphate ceramic formulations are improved and the ability to produce iron-based phosphate ceramic systems is enabled by the addition of an oxidizing or reducing step during the acid-base reactions that form the phosphate ceramic products. The additives allow control of the rate of the acid-base reactions and concomitant heat generation. In an alternate embodiment, waste containing metal anions is stabilized in phosphate ceramic products by the addition of a reducing agent to the phosphate ceramic mixture. The reduced metal ions are more stable and/or reactive with the phosphate ions, resulting in the formation of insoluble metal species within the phosphate ceramic matrix, such that the resulting chemically bonded phosphate ceramic product has greater leach resistance.

  14. Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study

    CERN Document Server

    Engel, Nicholas; Suljoti, Edlira; Garcia-Diez, Raul; Lange, Kathrin M; Atak, Kaan; Golnak, Ronny; Kothe, Alexander; Dantz, Marcus; Kühn, Oliver; Aziz, Emad F

    2013-01-01

    Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge transfer bands and thereby evidence for strong {\\sigma}-donation and {\\pi}-back-donation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.

  15. Intramolecular hydrogen bonding in myricetin and myricitrin. Quantum chemical calculations and vibrational spectroscopy

    Science.gov (United States)

    Vojta, Danijela; Dominković, Katarina; Miljanić, Snežana; Spanget-Larsen, Jens

    2017-03-01

    The molecular structures of myricetin (3,3‧,4‧,5,5‧,7-hexahydroxyflavone; MCE) and myricitrin (myricetin 3-O-rhamnoside; MCI) are investigated by quantum chemical calculations (B3LYP/6-311G**). Two preferred molecular rotamers of MCI are predicted, corresponding to different conformations of the O-rhamnoside subunit. The rotamers are characterized by different hydrogen bonded cross-links between the hydroxy groups of the rhamnoside substituent and the parent MCE moiety. The predicted OH stretching frequencies are compared with vibrational spectra of MCE and MCI recorded for the sake of this investigation (IR and Raman). In addition, a reassignment of the Cdbnd O stretching bands is suggested.

  16. Novel Chemically-Bonded Phosphate Ceramic Borehole Sealants (Ceramicretes) for Arctic Environments

    Energy Technology Data Exchange (ETDEWEB)

    Shirish Patil; Godwin A. Chukwu; Gang Chen; Santanu Khataniar

    2008-12-31

    Novel chemically bonded phosphate ceramic borehole sealant, i.e. Ceramicrete, has many advantages over conventionally used permafrost cement at Alaska North Slope (ANS). However, in normal field practices when Ceramicrete is mixed with water in blenders, it has a chance of being contaminated with leftover Portland cement. In order to identify the effect of Portland cement contamination, recent tests have been conducted at BJ services in Tomball, TX as well as at the University of Alaska Fairbanks with Ceramicrete formulations proposed by the Argonne National Laboratory. The tests conducted at BJ Services with proposed Ceramicrete formulations and Portland cement contamination have shown significant drawbacks which has caused these formulations to be rejected. However, the newly developed Ceramicrete formulation at the University of Alaska Fairbanks has shown positive results with Portland cement contamination as well as without Portland cement contamination for its effective use in oil well cementing operations at ANS.

  17. Effect of cross-linking with riboflavin and ultraviolet A on the chemical bonds and ultrastructure of human sclera

    Science.gov (United States)

    Jung, Gyeong-Bok; Lee, Hui-Jae; Kim, Ji-Hye; Lim, Jin Ik; Choi, Samjin; Jin, Kyung-Hyun; Park, Hun-Kuk

    2011-12-01

    This study examined the effect of the cross-linking with riboflavin-ultraviolet A (UVA) irradiation on the chemical bonds and ultrastructural changes of human sclera tissues using Raman spectroscopy and atomic force microscopy (AFM). Raman spectroscopy of the normal and cross-linked human sclera tissue revealed different types of the riboflavin-UVA and collagen interactions, which could be identified from their unique peaks, intensity, and shape. Raman spectroscopy can prove to be a powerful tool for examining the chemical bond of collagenous tissues at the molecular level. After riboflavin-UVA treatment, unlike a regular parallel arrangement of normal collagen fibrils, the AFM image revealed interlocking arrangements of collagen fibrils. The observed changes in the surface topography of the collagen fibrils, as well as in their chemical bonds in the sclera tissue, support the formation of interfibrilar cross-links in sclera tissues.

  18. Mechanical properties of chemically bonded sand core materials dipped in sol-gel coating impregnated with filter

    DEFF Research Database (Denmark)

    Nwaogu, Ugochukwu Chibuzoh; Tiedje, Niels Skat

    2012-01-01

    -displacement curve from which the mechanical properties of the materials are deduced. The fracture surfaces were examined using a stereomicroscope and a scanning electron microscope. From the results, the strengths of the core materials were slightly reduced by the coating in tensile and flexural modes, while...... the strengths were increased under compression. The mode of fracture of the chemically bonded sand core materials was observed to be intergranular through the binder. The stiffness of the chemically bonded sand core materials was determined. For better understanding of the mechanical properties......A novel sol-gel coating impregnated with filter dust was applied on chemically bonded sand core materials by dipping. After curing, the strengths of the core materials were measured under uniaxial loading using a new strength testing machine (STM). The STM presents the loading history as a force...

  19. Hydrogen trapping in MAX phase Ti3SiC2: Insight from chemical bonding by density functional theory

    Science.gov (United States)

    Zhang, H. F.; Ren, X. L.; Zhang, J. Y.; Huang, J.; Xu, C. H.; Du, A. J.; Wang, Y. X.

    2017-05-01

    Understanding hydrogen (H) isotope trapping in materials is essential to optimize the material performance in a nuclear environment for the fabrication of nuclear devices. By using the density functional theory (DFT), herein we have systematically investigated the behaviour of hydrogen in the MAX phase Ti3SiC2 in the presence and absence of a vacancy (V). When a vacancy is generated in a favorable plane for hydrogen accumulating (Si plane), two distinct behavours of hydrogen in the Si plane have been identified by chemical bond analysis, i.e., the Ti-H and Si-H bonding, which synergistically results in VH2 complexes prevailing in the host matrix. Different from metals and other ceramics, the trapping mechanism of H in Ti3SiC2 essentially originates from the spatially inhomogeneous distribution of free-charge density and large discrepancy of electronegativity between the host atoms. Our theoretical results offer great insights into the rational design of new high-performance nuclear materials.

  20. The bonding picture in hypervalent XF3 (X = Cl, Br, I, At) fluorides revisited with quantum chemical topology.

    Science.gov (United States)

    Amaouch, Mohamed; Sergentu, Dumitru-Claudiu; Steinmetz, David; Maurice, Rémi; Galland, Nicolas; Pilmé, Julien

    2017-08-03

    Hypervalent XF3 (X = Cl, Br, I, At) fluorides exhibit T-shaped C2V equilibrium structures with the heavier of them, AtF3 , also revealing an almost isoenergetic planar D3h structure. Factors explaining this behavior based on simple "chemical intuition" are currently missing. In this work, we combine non-relativistic (ClF3 ), scalar-relativistic and two-component (X = Br - At) density functional theory calculations, and bonding analyses based on the electron localization function and the quantum theory of atoms in molecules. Typical signatures of charge-shift bonding have been identified at the bent T-shaped structures of ClF3 and BrF3 , while the bonds of the other structures exhibit a dominant ionic character. With the aim of explaining the D3h structure of AtF3 , we extend the multipole expansion analysis to the framework of two-component single-reference calculations. This methodological advance enables us to rationalize the relative stability of the T-shaped C2v and the planar D3h structures: the Coulomb repulsions between the two lone-pairs of the central atom and between each lone-pair and each fluorine ligand are found significantly larger at the D3h structures than at the C2v ones for X = Cl - I, but not with X = At. This comes with the increasing stabilization, along the XF3 series, of the planar D3h structure with respect to the global T-shaped C2v minima. Hence, we show that the careful use of principles that are at the heart of the valence shell electron pair repulsion model provides reasonable justifications for stable planar D3h structures in AX3 E2 systems. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  1. Electronic properties and chemical bonding in quaternary arsenide oxides LaZnAsO and YZnAsO

    Energy Technology Data Exchange (ETDEWEB)

    Bannikov, V.V.; Shein, I.R. [Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences, Pervomaiskaya, 91, 620041, Ekaterinburg (Russian Federation); Ivanovskii, A.L., E-mail: ivanovskii@ihim.uran.ru [Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences, Pervomaiskaya, 91, 620041, Ekaterinburg (Russian Federation)

    2009-07-15

    First principles FLAPW-GGA band structure calculations are employed to obtain the structural, electronic properties and chemical bonding picture for two related phases, namely, quaternary arsenide oxides LaZnAsO and YZnAsO. These compounds are found to be direct-transition type semiconductors with the GGA gaps of about 0.65-1.30 eV. The peculiarities of chemical bonding in these phases are investigated and discussed in comparison with quaternary arsenide oxide LaFeAsO-a basic phase for the newly discovered 26-55 K superconductors.

  2. Failure analysis of resin composite bonded to ceramic.

    Science.gov (United States)

    Della Bona, Alvaro; Anusavice, Kenneth J; Mecholsky, John J

    2003-12-01

    To use fractographic principles to classify the mode of failure of resin composite bonded to ceramic specimens after microtensile testing. A leucite-based ceramic (IPS Empress)-E1) and a lithia disilicate-based ceramic (IPS Empress2)-E2) were selected for the study. Fifteen blocks of E1 and E2 were polished through 1 microm alumina abrasive. The following ceramic surface treatments were applied to three blocks of each ceramic: (1) 9.5% hydrofluoric acid (HF) for 2 min; (2) 4% acidulated phosphate fluoride (APF) for 2 min; (3) Silane coating (S); (4) HF+S; (5) APF+S. An adhesive resin and a resin composite were applied to all treated surfaces and light cured. Twenty bar specimens for each group were prepared from the composite-ceramic blocks and stored in 37 degrees C distilled water for 30 days before loading to failure under tension in an Instron testing machine. Fracture surfaces were examined using scanning electron microscopy and X-ray dot mapping. Statistical analysis was performed using one-way ANOVA, Duncan's multiple range test, and Weibull analyses. Similar surface treatments were associated with significantly different bond strengths and modes of failures for E1 and E2. All fractures occurred within the adhesion zone. The microstructural difference between etched E1 and E2 ceramics was a major controlling factor on adhesion. The quality of the bond should not be assessed based on bond strength data alone. Mode of failure and fractographic analyses should provide important information leading to predictions of clinical performance limits.

  3. 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.

  4. Carbene→N⁺ Coordination Bonds in Drugs: A Quantum Chemical Study

    Indian Academy of Sciences (India)

    DEEPIKA KATHURIA; MINHAJUL ARFEEN; APOORVA A BANKAR; PRASAD V BHARATAM

    2016-10-01

    Coordination chemistry of bonds between main group elements and electron donating ligands as in L→E (where E is electron acceptor centre like C⁰, Si⁰, N¹, P¹, As¹, B¹ and L is an electron donating N-heterocyclic carbene) have been recently gaining attention. Many important drugs have nitrogen atom as an electron acceptor center and can be represented by two general formulae:(L→N←L)⊕ and L→N-R. Divalent N¹ compounds possess two lone pairs at central nitrogen and low nucleophilicity associated with them are found to be of importance. In this article, electronic structure analysis of drug molecules like picloxydine, chlorhexidine, and moroxydine were performed at B3LYP/6-311++G(d,p) level of theory. Evaluation of electron localization function (ELF), molecular orbitals, charge density, nucleophilicity, proton affinity and complexation energy estimation confirm the presence of coordination bonds (L→N←L)⊕ in the above mentioned drug molecules in their cationic state. Further, electronic structure analysis of drugs like clonidine, apraclonidine, brimonidine and xylazine indicated the presence of electronic structure similar to L→N-R systems.

  5. Chemical adhesion rather than mechanical retention enhances resin bond durability of a dental glass-ceramic with leucite crystallites

    Energy Technology Data Exchange (ETDEWEB)

    Meng, X F [Department of Prosthodontics, The Stomatological Hospital Affiliated Medical School, Nanjing University, Nanjing 210008 (China); Yoshida, K [Division of Applied Prosthodontics, Graduate School of Biomedical Sciences, Nagasaki University, Nagasaki 852-8588 (Japan); Gu, N, E-mail: mengsoar@nju.edu.c [Jiangsu Key Laboratory for Biomaterials and Devices, School of Biological Science and Medical Engineering, Southeast University, Nanjing 210096 (China)

    2010-08-01

    This study aims to evaluate the effect of chemical adhesion by a silane coupler and mechanical retention by hydrofluoric acid (HFA) etching on the bond durability of resin to a dental glass ceramic with leucite crystallites. Half of the ceramic plates were etched with 4.8% HFA (HFA group) for 60 s, and the other half were not treated (NoHFA group). The scale of their surface roughness and rough area was measured by a 3D laser scanning microscope. These plates then received one of the following two bond procedures to form four bond test groups: HFA/cement, NoHFA/cement, HFA/silane/cement and NoHFA/silane/cement. The associated micro-shear bond strength and bond failure modes were tested after 0 and 30 000 thermal water bath cycles. Four different silane/cement systems (Monobond S/Variolink II, GC Ceramic Primer/Linkmax HV, Clearfil Ceramic Primer/Clearfil Esthetic Cement and Porcelain Liner M/SuperBond C and B) were used. The data for each silane/cement system were analyzed by three-way ANOVA. HFA treatment significantly increased the surface R{sub a} and R{sub y} values and the rough area of the ceramic plates compared with NoHFA treatment. After 30 000 thermal water bath cycles, the bond strength of all the test groups except the HFA/Linkmax HV group was significantly reduced, while the HFA/Linkmax HV group showed only adhesive interface failure. The other HFA/cement groups and all NoHFA/cement groups lost bond strength completely, and all NoHFA/silane/cement groups with chemical adhesion had significantly higher bond strength and more ceramic cohesive failures than the respective HFA/cement groups with mechanical retention. The result of the HFA/silane/cement groups with both chemical adhesion and mechanical retention revealed that HFA treatment could enhance the bond durability of resin/silanized glass ceramics, which might result from the increase of the chemical adhesion area on the ceramic rough surface and subsequently reduced degradation speed of the silane

  6. Understanding boron through size-selected clusters: structure, chemical bonding, and fluxionality.

    Science.gov (United States)

    Sergeeva, Alina P; Popov, Ivan A; Piazza, Zachary A; Li, Wei-Li; Romanescu, Constantin; Wang, Lai-Sheng; Boldyrev, Alexander I

    2014-04-15

    Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center-two-electron (2c-2e) σ bonds on the periphery and delocalized multicenter-two-electron (nc-2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron's electron deficiency and leads to fluxional behavior, which has been observed in B13(+) and B19(-). A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiation has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B(-), formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B(-)/C analogy. It is

  7. Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality

    Energy Technology Data Exchange (ETDEWEB)

    Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A.; Li, Wei-Li; Romanescu, Constantin; Wang, Lai S.; Boldyrev, Alexander I.

    2014-04-15

    Conspectus Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center–two-electron (2c–2e) σ bonds on the periphery and delocalized multicenter–two-electron (nc–2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron’s electron deficiency and leads to fluxional behavior, which has been observed in B13+ and B19–. A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiation has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B–, formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B

  8. The electronic nature of the 1,4-β-glycosidic bond and its chemical environment: DFT insights into cellulose chemistry.

    Science.gov (United States)

    Loerbroks, Claudia; Rinaldi, Roberto; Thiel, Walter

    2013-11-25

    The molecular understanding of the chemistry of 1,4-β-glucans is essential for designing new approaches to the conversion of cellulose into platform chemicals and biofuels. In this endeavor, much attention has been paid to the role of hydrogen bonding occurring in the cellulose structure. So far, however, there has been little discussion about the implications of the electronic nature of the 1,4-β-glycosidic bond and its chemical environment for the activation of 1,4-β-glucans toward acid-catalyzed hydrolysis. This report sheds light on these central issues and addresses their influence on the acid hydrolysis of cellobiose and, by analogy, cellulose. The electronic structure of cellobiose was explored by DFT at the BB1 K/6-31++G(d,p) level. Natural bond orbital (NBO) analysis was performed to grasp the key bonding concepts. Conformations, protonation sites, and hydrolysis mechanisms were examined. The results for cellobiose indicate that cellulose is protected against hydrolysis not only by its supramolecular structure, as currently accepted, but also by its electronic structure, in which the anomeric effect plays a key role.

  9. Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements.

    Science.gov (United States)

    Huang, Wei; Jiang, Ning; Schwarz, W H Eugen; Yang, Ping; Li, Jun

    2017-08-04

    The geometric and electronic ground-state structures of 30 isomers of six MS4 molecules (M=Group 8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density functional theory and correlated wavefunction approaches. The MS4 species were compared to analogous MO4 species recently investigated (W. Huang, W.-H. Xu, W. H. E. Schwarz, J. Li, Inorg. Chem. 2016, 55, 4616). A metal oxidation state (MOS) with a high value of eight appeared in the low-spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4 , whereas a low MOS of two appeared in the high-spin septet D2d species Fe(S2 )2 and (slightly excited) metastable Fe(O2 )2 . The ground states of all other molecules had intermediate MOS values, with S(2-) , S2(2-) , S2(1-) (and O(2-) , O(1-) , O2(2-) , O2(1-) ) ligands bonded by ionic, covalent, and correlative contributions. The known tendencies toward lower MOS on going from oxides to sulfides, from Hs to Os to Ru, and from Pu to Sm, and the specific behavior of Fe, were found to arise from the different atomic orbital energies and radii of the (n-1)p core and (n-1)d and (n-2)f valence shells of the metal atoms in row n of the periodic table. The comparative results of the electronic and geometric structures of the MO4 and MS4 species provides insight into the periodicity of oxidation states and bonding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Organometallic Bonding in an Ullmann-Type On-Surface Chemical Reaction Studied by High-Resolution Atomic Force Microscopy.

    Science.gov (United States)

    Kawai, Shigeki; Sadeghi, Ali; Okamoto, Toshihiro; Mitsui, Chikahiko; Pawlak, Rémy; Meier, Tobias; Takeya, Jun; Goedecker, Stefan; Meyer, Ernst

    2016-10-01

    The on-surface Ullmann-type chemical reaction synthesizes polymers by linking carbons of adjacent molecules on solid surfaces. Although an organometallic compound is recently identified as the reaction intermediate, little is known about the detailed structure of the bonded organometallic species and its influence on the molecule and the reaction. Herein atomic force microscopy at low temperature is used to study the reaction with 3,9-diiododinaphtho[2,3-b:2',3'-d]thiophene (I-DNT-VW), which is polymerized on Ag(111) in vacuum. Thermally sublimated I-DNT-VW picks up a Ag surface atom, forming a CAg bond at one end after removing an iodine. The CAg bond is usually short-lived, and a CAgC organometallic bond immediately forms with an adjacent molecule. The existence of the bonded Ag atoms strongly affects the bending angle and adsorption height of the molecular unit. Density functional theory calculations reveal the bending mechanism, which reveals that charge from the terminus of the molecule is transferred via the Ag atom into the organometallic bond and strengths the local adsorption to the substrate. Such deformations vanish when the Ag atoms are removed by annealing and CC bonds are established.

  11. Correlation between topological band character and chemical bonding in a Bi14Rh3I9-based family of insulators

    Science.gov (United States)

    Rasche, Bertold; Isaeva, Anna; Ruck, Michael; Koepernik, Klaus; Richter, Manuel; van den Brink, Jeroen

    2016-02-01

    Recently the presence of topologically protected edge-states in Bi14Rh3I9 was confirmed by scanning tunnelling microscopy consolidating this compound as a weak 3D topological insulator (TI). Here, we present a density-functional-theory-based study on a family of TIs derived from the Bi14Rh3I9 parent structure via substitution of Ru, Pd, Os, Ir and Pt for Rh. Comparative analysis of the band-structures throughout the entire series is done by means of a unified minimalistic tight-binding model that evinces strong similarity between the quantum-spin-Hall (QSH) layer in Bi14Rh3I9 and graphene in terms of -molecular orbitals. Topologically non-trivial energy gaps are found for the Ir-, Rh-, Pt- and Pd-based systems, whereas the Os- and Ru-systems remain trivial. Furthermore, the energy position of the metal -band centre is identified as the parameter which governs the evolution of the topological character of the band structure through the whole family of TIs. The -band position is shown to correlate with the chemical bonding within the QSH layers, thus revealing how the chemical nature of the constituents affects the topological band character.

  12. Tensile bond strength of silicone-based soft denture liner to two chemically different denture base resins after various surface treatments.

    Science.gov (United States)

    Akin, Hakan; Tugut, Faik; Guney, Umit; Kirmali, Omer; Akar, Turker

    2013-01-01

    This study evaluated the effect of various surface treatments on the tensile bond strength of a silicone-based soft denture liner to two chemically different denture base resins, heat-cured polymethyl methacrylate (PMMA), and light-activated urethane dimethacrylate or Eclipse denture base resin. PMMA test specimens were fabricated and relined with a silicone-based soft denture liner (group AC). Eclipse test specimens were prepared according to the manufacturer's recommendation. Before they were relined with a silicone-based soft denture liner, each received one of three surface treatments: untreated (control, group EC), Eclipse bonding agent applied (group EB), and laser-irradiated (group EL). Tensile bond strength tests (crosshead speed = 5 mm/min) were performed for all specimens, and the results were analyzed using the analysis of variance followed by Tukey's test (p = 0.05). Eclipse denture base and PMMA resins presented similar bond strengths to the silicone-based soft denture liner. The highest mean force was observed in group EL specimens, and the tensile bond strengths in group EL were significantly different (p < 0.05) from those in the other groups.

  13. 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

  14. Solvent-free thermoplastic-poly(dimethylsiloxane) bonding mediated by UV irradiation followed by gas-phase chemical deposition of an adhesion linker

    Science.gov (United States)

    Ahn, S. Y.; Lee, N. Y.

    2015-07-01

    Here, we introduce a solvent-free strategy for bonding various thermoplastic substrates with poly(dimethylsiloxane) (PDMS) using ultraviolet (UV) irradiation followed by the gas-phase chemical deposition of aminosilane on the UV-irradiated thermoplastic substrates. The thermoplastic substrates were first irradiated with UV for surface hydrophilic treatment and were then grafted with vacuum-evaporated aminosilane, where the alkoxysilane side reacted with the oxidized surface of the thermoplastic substrate. Next, the amine-terminated thermoplastic substrates were treated with corona discharge to oxidize the surface and were bonded with PDMS, which was also oxidized via corona discharge. The two substrates were then hermetically sealed and pressed under atmospheric pressure for 30 min at 60 °C. This process enabled the formation of a robust siloxane bond (Si-O-Si) between the thermoplastic substrate and PDMS under relatively mild conditions using an inexpensive and commercially available UV lamp and Tesla coil. Various thermoplastic substrates were examined for bonding with PDMS, including poly(methylmethacrylate) (PMMA), polycarbonate (PC), poly(ethyleneterephthalate) (PET) and polystyrene (PS). Surface characterizations were performed by measuring the contact angle and performing x-ray photoelectron spectroscopy analysis, and the bond strength was analyzed by conducting various mechanical force measurements such as pull, delamination, leak and burst tests. The average bond strengths for the PMMA-PDMS, PC-PDMS, PET-PDMS and PS-PDMS assemblies were measured at 823.6, 379.3, 291.2 and 229.0 kPa, respectively, confirming the highly reliable performance of the introduced bonding strategy.

  15. Analysis of Adhesively Bonded Ceramics Using an Asymmetric Wedge Test

    Science.gov (United States)

    2008-12-01

    moisture durability of adhesive bonding of ceramics is dental applications (12–14). The adhesive bonding of ceramic orthodontic inserts presents unique...sample sets. Environmental exposure is often limited to mechanical testing on the millimeter scale of bonded ceramic blocks or extracted human...Dressler, K. B.; Grenadier, M. R. Direct Bonding of Orthodontic Brackets to Esthetic Restorative Materials Using a Silane. Am. J. Orthodontics and

  16. Chemical reactivity of C-F bonds attached to graphene with diamines depending on their nature and location.

    Science.gov (United States)

    Li, Baoyin; He, Taijun; Wang, Zaoming; Cheng, Zheng; Liu, Yang; Chen, Teng; Lai, Wenchuan; Wang, Xu; Liu, Xiangyang

    2016-06-29

    The attachment of fluorine to graphene is a facile means to activate the carbon bonds for subsequent covalent bonding to other molecules for the preparation of desired graphene derivatives. Therefore, an insight into the chemical reactivity of fluorinated graphene (FG) is very essential to enable precise control of the composition and structure of the final products. In this study, FG has been treated with various mass amounts of poly(oxypropylene)diamine (PEA) ranging from starvation to saturation to explore the dependence of a substitution reaction of diamines on the nature and location (attached onto the basal planes or along defects or edges) of C-F bonds. X-ray photoelectron spectroscopy directly tracked the atomic percentage of fluorine present and the carbon 1s bonding state, showing that the grafting ratio of diamines gradually increases with increased diamine mass ratio. The varying of the types and orientation of C-F bonds characterized by polarized attenuated total reflectance Fourier transform infrared spectroscopy indicates that "covalent" C-F bonds are more sensitive to the substitution reaction of diamines than ''semi-ionic'' C-F bonds, and the C-F bonds attached onto basal planes more preferably participate in the functionalization reaction of diamines than that of C-F bonded on non-coplanar regions (edges or defects). The one-dimensional expansion along the graphene c-axis shown by wide angle X-ray diffraction provides further evidence on the preferred functionalization reaction of C-F attached on the basal planes, resulting in a change of the average intersheet distance by various magnitudes.

  17. Photoelastic stress analysis in perforated (Rochette) resin bonded bridge design.

    Science.gov (United States)

    Ziada, H M; Orr, J F; Benington, I C

    2000-05-01

    Rochette described the perforated cast metal bonded design for splinting periodontally compromised teeth. The design was later used for replacing missing teeth. The main causes of failure of the perforated (Rochette) type design were attributed to inappropriate case selection and erosion of the composite from perforations. The aim of this study was to analyse the effect of stress magnitude and direction on failure of perforated resin bonded bridges (RBBs). The objective was to compare stress magnitudes in this design with those reported on the non-perforated RBBs. Photoelastic modelling materials were selected to represent the relative stiffnesses of a posterior mandibular and an anterior maxillary perforated (Rochette) type design. The sizes of the models were scaled to x 2.5 in order to enhance visual analysis of the stress patterns. Stress magnitudes were quantified from isochromatic fringes and stress directions were evaluated from stress trajectories. These revealed a high-stress concentration around the perforations, particularly for those at the proximo-lingual/palatal (connector) areas. This experimental study revealed that the main reason for failure of Rochette designs is deformation at the perforations.

  18. Influence of chemical bonding of chlorides with aluminates in cement hidratation process on corrosion steel bars in concrete

    Directory of Open Access Journals (Sweden)

    Bikić Farzet H.

    2010-01-01

    Full Text Available The presence of chlorides in concrete is a permanent subject of research because they cause corrosion of steel bars. Chlorides added to the concrete during preparation, as accelerators of the bonding of cement minerals process, enter into reaction with aluminates, creating a phase known as chloroaluminate hydrates. In everyday conditions the product of chemical bonding between chlorides and aluminates is usually monochloridealuminate C3A·CaCl2·Hx, better known as Friedel's salt. In this paper, the influence of chemical bonding of chlorides with aluminates during the process of cement hydration on corrosion of steel bars in concrete was investigated. The process of chlorides bonding with aluminates yielding monochloride aluminate is monitored by XRD analyses. It was found that the amount of chlorides bonding with aluminates increases with an increase of temperature, and as a result, reduces the amount of 'free' chlorides in concrete. Potentiodynamic measurements have shown that increase in temperature of the heat treatment of working electrodes by chlorides leads to a reduction of steel bars corrosion as a result of either the increase of the monochloride-aluminate content or the decrease of free chlorides amount. Chlorides bound in chloroaluminate hydrates do not cause activation of steel bars corrosion in concrete. It was also proven that the increase of free chlorides concentration in the concrete leads to intensification of steel bars corrosion. This additionally approves that free chlorides are only the activators of process of steel bars corrosion in the concrete.

  19. Poisson Analysis of Streptococcal Bond-strengthening on Saliva-coated Enamel

    NARCIS (Netherlands)

    Mei, L.; Ren, Y.; Busscher, H. J.; Chen, Y.; van der Mei, H. C.

    The forces responsible for bond-strengthening in initial oral bacterial adhesion are unknown. Since Lifshitz-Van der Waals and electrostatic forces work instantaneously upon approach, it is hypothesized that bond-strengthening is governed by hydrogen bonding. Poisson analysis of adhesion forces

  20. Poisson analysis of streptococcal bond strengthening on stainless steel with and without a salivary conditioning film

    NARCIS (Netherlands)

    Mei, Li; van der Mei, Henny C.; Ren, Yijin; Norde, Willem; Busscher, Henk J.

    2009-01-01

    Poisson analysis of retract force-distance curves in atomic force microscopy (AFM) has yielded a new dimension to the decoupling of individual bond forces into a hydrogen bonding and nonspecific force component. Accordingly, bacterial adhesion forces have been decoupled into a hydrogen bonding and

  1. Poisson analysis of streptococcal bond strengthening on stainless steel with and without salivary conditioning film

    NARCIS (Netherlands)

    Mei, Li; Mei, van der H.C.; Ren, Y.; Norde, W.; Busscher, H.J.

    2009-01-01

    Poisson analysis of retract force-distance curves in atomic force microscopy (AFM) has yielded a new dimension to the decoupling of individual bond forces into a hydrogen bonding and nonspecific force component. Accordingly, bacterial adhesion forces have been decoupled into a hydrogen bonding and

  2. Stabilization of Rocky Flats Pu-contaminated ash within chemically bonded phosphate ceramics

    Science.gov (United States)

    Wagh, A. S.; Strain, R.; Jeong, S. Y.; Reed, D.; Krause, T.; Singh, D.

    A feasibility study was conducted on the use of chemically bonded phosphate ceramics for stabilization of combustion residue of high transuranic (TRU) wastes. Using a matrix of magnesium potassium phosphate formed by the room-temperature reaction of MgO and KH 2PO 4 solution, we made waste forms that contained 5 wt% Pu to satisfy the requirements of the Waste Isolation Pilot Plant. The waste forms were ceramics whose compression strength was twice that of conventional cement grout and whose connected porosity was ≈50% that of cement grout. Both surrogate and actual waste forms displayed high leaching resistance for both hazardous metals and Pu. Hydrogen generation resulting from the radiolytic decomposition of water and organic compounds present in the waste form did not appear to be a significant issue. Pu was present as PuO 2 that was physically microencapsulated in the matrix. In the process, pyrophoricity was removed and leaching resistance was enhanced. The high leaching resistance was due to the very low solubility of PuO 2 coupled with superior microencapsulation. As a result, the waste forms satisfied the current Safeguard Termination Limit requirement for storage of TRU combustion residues.

  3. Chemical Bonding States of TiC Films before and after Hydrogen Ion Irradiation

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    TiC films deposited by rf magnetron sputtering followed by Ar+ ion bombardment were irradiated with a hydrogen ion beam. X-ray photoelectron spectroscopy (XPS) was used for characterization of the chemical bonding states of C and Ti elements of the TiC films before and after hydrogen ion irradiation, in order to understand the effect of hydrogen ion irradiation on the films and to study the mechanism of hydrogen resistance of TiC films. Conclusions can be drawn that ion bombardment at moderate energy can cause preferential physical sputtering of carbon atoms from the surface of low atomic number (Z) material. This means that ion beam bombardment leads to the formation of a non-stoichiometric composition of TiC on the surface.TiC films prepared by ion beam mixing have the more excellent characteristic of hydrogen resistance. One important cause, in addition to TiC itself, is that there are many vacant sites in TiC created by ion beam mixing.These defects can easily trap hydrogen and effectively enhance the effect of hydrogen resistance.

  4. 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.

  5. Role of the chemical bonding for the time-dependent electron transport through an interacting quantum dot

    KAUST Repository

    Goker, Ali

    2011-06-01

    A combination of ab initio and many-body calculations is utilized to determine the effects of the bonding in Au electrodes on the time dependent current through a quantum dot suddenly shifted into the Kondo regime by a gate voltage. For an asymmetrically coupled system the instantaneous conductance exhibits fluctuations. The frequencies of the fluctuations turn out to be proportional to the energetic separation between the dominating peaks in the density of states and the Fermi level. The chemical bonding in the electrodes, thus, drastically alters the transient current, which can be accessed by ultrafast pump-probe techniques. © 2011 Elsevier B.V. All rights reserved.

  6. Intermolecular CH···O/N H-bonds in the biologically important pairs of natural nucleobases: a thorough quantum-chemical study.

    Science.gov (United States)

    Brovarets', Ol'ha O; Yurenko, Yevgen P; Hovorun, Dmytro M

    2014-01-01

    This study aims to cast light on the physico-chemical nature and energetic of the non-conventional CH···O/N H-bonds in the biologically important natural nucleobase pairs using a comprehensive quantum-chemical approach. As a whole, the 36 biologically important pairs, involving canonical and rare tautomers of nucleobases, were studied by means of all available up-to-date state-of-the-art quantum-chemical techniques along with quantum theory "Atoms in molecules" (QTAIM), Natural Bond Orbital (NBO) analysis, Grunenberg's compliance constants theory, geometrical and vibrational analyses to identify the CH···O/N interactions, reveal their physico-chemical nature and estimate their strengths as well as contribution to the overall base-pairs stability. It was shown that all the 38 CH···O/N contacts (25 CH···O and 13 CH···N H-bonds) completely satisfy all classical geometrical, electron-topological, in particular Bader's and "two-molecule" Koch and Popelier's, and vibrational criteria of H-bonding. The positive values of Grunenberg's compliance constants prove that the CH···O/N contacts in nucleobase pairs are stabilizing interactions unlike electrostatic repulsion and anti-H-bonds. NBO analysis indicates the electron density transfer from the lone electron pair of the acceptor atom (O/N) to the antibonding orbital corresponding to the donor group σ(∗)(CH). Moreover, significant increase in the frequency of the out-of-plane deformation modes γ (CH) under the formation of the CH···O (by 17.2÷81.3/10.8÷84.7 cm(-1)) and CH···N (by 32.7÷85.9/9.0÷77.9 cm(-1)) H-bonds at the density functional theory (DFT)/second-order Møller-Plesset (MP2) levels of theory, respectively, and concomitant changes of their intensities can be considered as reliable indicators of H-bonding. The strengths of the CH···O/N interactions, evaluated by means of Espinosa-Molins-Lecomte formula, lie within the range 0.45÷3.89/0.62÷4.10 kcal/mol for the CH

  7. Adhesive Characterization and Progressive Damage Analysis of Bonded Composite Joints

    Science.gov (United States)

    Girolamo, Donato; Davila, Carlos G.; Leone, Frank A.; Lin, Shih-Yung

    2014-01-01

    The results of an experimental/numerical campaign aimed to develop progressive damage analysis (PDA) tools for predicting the strength of a composite bonded joint under tensile loads are presented. The PDA is based on continuum damage mechanics (CDM) to account for intralaminar damage, and cohesive laws to account for interlaminar and adhesive damage. The adhesive response is characterized using standard fracture specimens and digital image correlation (DIC). The displacement fields measured by DIC are used to calculate the J-integrals, from which the associated cohesive laws of the structural adhesive can be derived. A finite element model of a sandwich conventional splice joint (CSJ) under tensile loads was developed. The simulations indicate that the model is capable of predicting the interactions of damage modes that lead to the failure of the joint.

  8. Chemical origin of blue- and redshifted hydrogen bonds: intramolecular hyperconjugation and its coupling with intermolecular hyperconjugation.

    Science.gov (United States)

    Li, An Yong

    2007-04-21

    Upon formation of a H bond Y...H-XZ, intramolecular hyperconjugation n(Z)-->sigma*(X-H) of the proton donor plays a key role in red- and blueshift characters of H bonds and must be introduced in the concepts of hyperconjugation and rehybridization. Intermolecular hyperconjugation transfers electron density from Y to sigma*(X-H) and causes elongation and stretch frequency redshift of the X-H bond; intramolecular hyperconjugation couples with intermolecular hyperconjugation and can adjust electron density in sigma*(X-H); rehybridization causes contraction and stretch frequency blueshift of the X-H bond on complexation. The three factors--intra- and intermolecular hyperconjugations and rehybridization--determine commonly red- or blueshift of the formed H bond. A proton donor that has strong intramolecular hyperconjugation often forms blueshifted H bonds.

  9. Computed tomography analysis of wood-adhesive bonds

    Science.gov (United States)

    Modzel, Gunter Georg Rolf

    The importance of wood bonding increased in the last decades due to the increased usage of wood composites whose performance depends to a large extent on the adhesive penetration and subsequent bonding of the adherends. The presented research used XMT (x-ray microtomography) to perform a non-destructive, three-dimensional analysis of the adhesive bondline and wood-structure of Southern yellow pine, Douglas-fir and yellow-poplar samples. A phenol-formaldehyde adhesive was used. The sodium hydroxide catalyst was replaced with rubidium hydroxide during resin formulation. This was done to improve the image contrast. The reconstructions of the wood structure of Southern yellow pine showed tracheids, rays, fusiform rays, resin canals and pits. On the Douglas-fir sample tracheids, pits and rays were displayed clearly. The yellow-poplar images showed vessels, fibers, bordered pits, scalariform sieve plates and rays. The renderings of the adhesive-bondline of Southern yellow pine proved the dominant role of tracheids for the adhesive flow and showed rays as a secondary pathway of adhesive flow. The results revealed no adhesive flow occured through bordered pits, while simple pits permitted some adhesive flow through ray parenchyma. The results for Douglas-fir showed a similar result; the tracheids were the predominant path of adhesive penetration, while rays played a secondary role and no adhesive flow through the pit aperture was visible. The adhesive flow through the microstructure of yellow-poplar wood occured mainly through vessels and also through rays, but no adhesive flow through the pits was directly observed. The segmentation of the images in three phases: void space, cell wall substance and adhesive, enabled the calculation of the effective bondline thickness based on the adhesive, as well as the volumetric measurement of all three elements and their share on the sample volume. Subsequent experiments showed that the exposure of the Southern yellow pine and yellow

  10. Parental bonding and alexithymia: a meta-analysis.

    Science.gov (United States)

    Thorberg, F A; Young, R McD; Sullivan, K A; Lyvers, M

    2011-04-01

    The primary purpose of this meta-analysis was to explore, clarify and report the strength of the relationship between alexithymia, as measured by the Toronto Alexithymia Scale (TAS-20), and parenting style as measured by the Parental Bonding Instrument (PBI). Web of Science, PsycInfo, PubMed and ProQuest: Dissertations and Theses searches were undertaken, yielding nine samples with sufficient data to be included in the meta-analysis. Evidence indicated moderate to strong relationships between maternal care and alexithymia, and between maternal care and two of the three TAS-20 alexithymia facets (Difficulties Describing Feelings and Difficulties Identifying Feelings, but not Externally Oriented Thinking). Moderate relationships were observed for both maternal- and paternal-overprotection and alexithymia respectively, and for overprotection (both maternal and paternal) and Difficulties Describing Feelings. This study is the first meta-analysis of the relationship between parenting styles and alexithymia, and findings confirm an especially strong association between maternal care and key elements of alexithymia. This review highlights the issues that still remain to be addressed in exploring the link between parenting style and alexithymia. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

  11. Chemical bonding and the incorporation of potassium into the Earth's core

    Energy Technology Data Exchange (ETDEWEB)

    Sherman, D.M. (Geological Survey, Denver, CO (USA))

    1990-05-01

    It has been argued that most of the Earth's potassium was segregated into the outer core and that the radioactive decay of {sup 40}K provided the heat source for the geodynamo. This idea rests on the assumption that the affinity of potassium for sulfur or metallic iron is enhanced at high pressure. In this paper, the high pressure electronic structures of K in sulfide, iron sulfide and metallic iron coordination environments were determined from molecular orbital (SCF-X{alpha}-SW) calculations on (KS{sub 8}){sup 15{minus}}, (KS{sub 8}Fe{sub 6}){sup 3{minus}} and KFe{sub 14} clusters. It is shown that, even at high pressure, potassium cannot alloy with metallic iron. Although a high-pressure electronic transition may enhance the potassium-sulfur chemical bond, the electronic structure of the KS{sub 8}Fe{sub 6} cluster shows that this electronic transition cannot happen in an iron sulfide melt. Consequently, potassium will not have an enhanced affinity for sulfur in planetary interiors. If the lower mantle were more reducing, potassium might be excluded from the silicate phases by more strongly lithophile elements and segregated into a metal sulfide phase in the outer core (cf. the phase assemblages in enstatite chondrites). Given the oxidation state of the Earth, however, it is unlikely that significant quantities of potassium have been incorporated into the outer core. The Earth, like the moon and the eucrite parent body, is depleted in potassium. An alternative heat source (e.g., the radioactive decay of U and Th) must be invoked to explain the geodynamo.

  12. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    Science.gov (United States)

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  13. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    Science.gov (United States)

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  14. Optical MEMS for chemical analysis and biomedicine

    CERN Document Server

    Jiang, Hongrui

    2016-01-01

    This book describes the current state of optical MEMS in chemical and biomedical analysis and brings together current trends and highlights topics representing the most exciting progress in recent years in the field.

  15. Research on the Interaction of Hydrogen-Bond Acidic Polymer Sensitive Sensor Materials with Chemical Warfare Agents Simulants by Inverse Gas Chromatography

    OpenAIRE

    Liu Yang; Qiang Han; Shuya Cao; Feng Huang; Molin Qin; Chenghai Guo; Mingyu Ding

    2015-01-01

    Hydrogen-bond acidic polymers are important high affinity materials sensitive to organophosphates in the chemical warfare agent sensor detection process. Interactions between the sensor sensitive materials and chemical warfare agent simulants were studied by inverse gas chromatography. Hydrogen bonded acidic polymers, i.e., BSP3, were prepared for micro-packed columns to examine the interaction. DMMP (a nerve gas simulant) and 2-CEES (a blister agent simulant) were used as probes. Chemical an...

  16. Functional Analysis for Chemical Engineers.

    Science.gov (United States)

    Ramkrishna, D.

    1979-01-01

    Described is a graduate level engineering course on functional analysis offered at Purdue University. The course restricts itself to linear problems, specifically analysis of linear operators on vector spaces. Key applications in the course demonstrating the utility of abstract formulations are presented. (BT)

  17. Risk Analysis of the Bond Portfolio Price Sensitivity

    Institute of Scientific and Technical Information of China (English)

    LiZhou; JinlinLi

    2004-01-01

    The paper described three methods of scaling the bond portfolio price. They were duration, convexity and time value. From the principle of No-arbitrage, there was one and only one relationship of duration, convexity and time value. It chose three corporation bonds of China and analyzed the risk of two investment strategies.

  18. Chemical insight from density functional modeling of molecular adsorption: Tracking the bonding and diffusion of anthracene derivatives on Cu(111) with molecular orbitals

    Energy Technology Data Exchange (ETDEWEB)

    Wyrick, Jonathan; Bartels, Ludwig, E-mail: ludwig.bartels@ucr.edu [Pierce Hall, University of California-Riverside, Riverside, California 92521 (United States); Einstein, T. L. [Department of Physics and Condensed Matter Theory Center, University of Maryland, College Park, Maryland 20742-4111 (United States)

    2015-03-14

    We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species’ diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.

  19. Chemical insight from density functional modeling of molecular adsorption: Tracking the bonding and diffusion of anthracene derivatives on Cu(111) with molecular orbitals

    Science.gov (United States)

    Wyrick, Jonathan; Einstein, T. L.; Bartels, Ludwig

    2015-03-01

    We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species' diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.

  20. TOXICOLOGICAL ANALYSIS OF WHOLE-BLOOD SAMPLES BY MEANS OF BOND-ELUT CERTIFY COLUMNS AND GAS-CHROMATOGRAPHY WITH NITROGEN-PHOSPHORUS DETECTION

    NARCIS (Netherlands)

    ZWEIPFENNING, PGM; WILDERINK, AHCM; HORSTHUIS, P; FRANKE, JP; DEZEEUW, RA

    1994-01-01

    The application of Bond-Elut Certify solid-phase extraction columns to the systematic toxicological analysis of whole blood was evaluated. The reproducibility of the extraction was tested with thirteen drugs varying in physico-chemical properties. Analysis was performed with capillary gas chromatogr

  1. TOXICOLOGICAL ANALYSIS OF WHOLE-BLOOD SAMPLES BY MEANS OF BOND-ELUT CERTIFY COLUMNS AND GAS-CHROMATOGRAPHY WITH NITROGEN-PHOSPHORUS DETECTION

    NARCIS (Netherlands)

    ZWEIPFENNING, PGM; WILDERINK, AHCM; HORSTHUIS, P; FRANKE, JP; DEZEEUW, RA

    1994-01-01

    The application of Bond-Elut Certify solid-phase extraction columns to the systematic toxicological analysis of whole blood was evaluated. The reproducibility of the extraction was tested with thirteen drugs varying in physico-chemical properties. Analysis was performed with capillary gas

  2. Determining Chemical Reactivity Driving Biological Activity from SMILES Transformations: The Bonding Mechanism of Anti-HIV Pyrimidines

    Directory of Open Access Journals (Sweden)

    Mihai V. Putz

    2013-07-01

    Full Text Available Assessing the molecular mechanism of a chemical-biological interaction and bonding stands as the ultimate goal of any modern quantitative structure-activity relationship (QSAR study. To this end the present work employs the main chemical reactivity structural descriptors (electronegativity, chemical hardness, chemical power, electrophilicity to unfold the variational QSAR though their min-max correspondence principles as applied to the Simplified Molecular Input Line Entry System (SMILES transformation of selected uracil derivatives with anti-HIV potential with the aim of establishing the main stages whereby the given compounds may inhibit HIV infection. The bonding can be completely described by explicitly considering by means of basic indices and chemical reactivity principles two forms of SMILES structures of the pyrimidines, the Longest SMILES Molecular Chain (LoSMoC and the Branching SMILES (BraS, respectively, as the effective forms involved in the anti-HIV activity mechanism and according to the present work, also necessary intermediates in molecular pathways targeting/docking biological sites of interest.

  3. Determining chemical reactivity driving biological activity from SMILES transformations: the bonding mechanism of anti-HIV pyrimidines.

    Science.gov (United States)

    Putz, Mihai V; Dudaş, Nicoleta A

    2013-07-30

    Assessing the molecular mechanism of a chemical-biological interaction and bonding stands as the ultimate goal of any modern quantitative structure-activity relationship (QSAR) study. To this end the present work employs the main chemical reactivity structural descriptors (electronegativity, chemical hardness, chemical power, electrophilicity) to unfold the variational QSAR though their min-max correspondence principles as applied to the Simplified Molecular Input Line Entry System (SMILES) transformation of selected uracil derivatives with anti-HIV potential with the aim of establishing the main stages whereby the given compounds may inhibit HIV infection. The bonding can be completely described by explicitly considering by means of basic indices and chemical reactivity principles two forms of SMILES structures of the pyrimidines, the Longest SMILES Molecular Chain (LoSMoC) and the Branching SMILES (BraS), respectively, as the effective forms involved in the anti-HIV activity mechanism and according to the present work, also necessary intermediates in molecular pathways targeting/docking biological sites of interest.

  4. Spectroscopic Chemical Analysis Methods and Apparatus

    Science.gov (United States)

    Hug, William F. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor); Lane, Arthur L. (Inventor)

    2017-01-01

    Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

  5. Indications of chemical bond contrast in AFM images of a hydrogen-terminated silicon surface

    Science.gov (United States)

    Labidi, Hatem; Koleini, Mohammad; Huff, Taleana; Salomons, Mark; Cloutier, Martin; Pitters, Jason; Wolkow, Robert A.

    2017-02-01

    The origin of bond-resolved atomic force microscope images remains controversial. Moreover, most work to date has involved planar, conjugated hydrocarbon molecules on a metal substrate thereby limiting knowledge of the generality of findings made about the imaging mechanism. Here we report the study of a very different sample; a hydrogen-terminated silicon surface. A procedure to obtain a passivated hydrogen-functionalized tip is defined and evolution of atomic force microscopy images at different tip elevations are shown. At relatively large tip-sample distances, the topmost atoms appear as distinct protrusions. However, on decreasing the tip-sample distance, features consistent with the silicon covalent bonds of the surface emerge. Using a density functional tight-binding-based method to simulate atomic force microscopy images, we reproduce the experimental results. The role of the tip flexibility and the nature of bonds and false bond-like features are discussed.

  6. Bader’s Theory of Atoms in Molecules (AIM) and its Applications to Chemical Bonding

    Indian Academy of Sciences (India)

    P SHYAM VINOD KUMAR; V RAGHAVENDRA; V SUBRAMANIAN

    2016-10-01

    In this perspective article, the basic theory and applications of the “Quantum Theory of Atoms in Molecules” have been presented with examples from different categories of weak and hydrogen bonded molecular systems.

  7. Indications of chemical bond contrast in AFM images of a hydrogen-terminated silicon surface

    Science.gov (United States)

    Labidi, Hatem; Koleini, Mohammad; Huff, Taleana; Salomons, Mark; Cloutier, Martin; Pitters, Jason; Wolkow, Robert A.

    2017-01-01

    The origin of bond-resolved atomic force microscope images remains controversial. Moreover, most work to date has involved planar, conjugated hydrocarbon molecules on a metal substrate thereby limiting knowledge of the generality of findings made about the imaging mechanism. Here we report the study of a very different sample; a hydrogen-terminated silicon surface. A procedure to obtain a passivated hydrogen-functionalized tip is defined and evolution of atomic force microscopy images at different tip elevations are shown. At relatively large tip-sample distances, the topmost atoms appear as distinct protrusions. However, on decreasing the tip-sample distance, features consistent with the silicon covalent bonds of the surface emerge. Using a density functional tight-binding-based method to simulate atomic force microscopy images, we reproduce the experimental results. The role of the tip flexibility and the nature of bonds and false bond-like features are discussed. PMID:28194036

  8. Chemical-assisted bonding of thermoplastics/elastomer for fabricating microfluidic valves.

    Science.gov (United States)

    Gu, Pan; Liu, Ke; Chen, Hong; Nishida, Toshikazu; Fan, Z Hugh

    2011-01-01

    Thermoplastics such as cyclic olefin copolymer (COC) and polymethylmethacrylate (PMMA) have been increasingly used in fabricating microfluidic devices. However, the state-of-the-art microvalve technology is a polydimethylsiloxane (PDMS)-based three-layer structure. In order to integrate such a valve with a thermoplastics-based microfluidic device, a bonding method for thermoplastics/PDMS must be developed. We report here a method to bond COC with PDMS through surface activation by corona discharge, surface modification using 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), and thermal annealing. The method is also applicable to PMMA. The bonding strength between thermoplastics and PDMS was represented by the peeling force, which was measured using a method established by the International Organization for Standardization (ISO). The bonding strength measurement offered an objective and quantitative indicator for protocol optimization, as well as comparison with other PDMS-associated bonding methods. Using optimized bonding conditions, two valve arrays were fabricated in a COC/PDMS/COC device and cyclic operations of valve closing/opening were successfully demonstrated. The valve-containing devices withstood 100 psi (∼689 KPa) without delamination. Further, we integrated such valve arrays in a device for protein separation and demonstrated isoelectric focusing in the presence of valves.

  9. Chemical bonding and magnetic properties of gadolinium (Gd) substituted cobalt ferrite

    Energy Technology Data Exchange (ETDEWEB)

    Puli, Venkata Sreenivas, E-mail: vspuli@utep.edu [Department of Mechanical Engineering, University of Texas, El Paso, TX 79968 (United States); Adireddy, Shiva [Department of Physics and Engineering Physics, Tulane University, New Orleans, LA 70118 (United States); Ramana, C.V. [Department of Mechanical Engineering, University of Texas, El Paso, TX 79968 (United States)

    2015-09-25

    Graphical abstract: Room temperature Raman spectra of CoFe{sub 2−x}Gd{sub x}O{sub 4} (CFGO, x = 0.0–0.3) compounds as a function of wavenumber (cm{sup −1}). - Highlights: • Gd substituted ferrites were synthesized under controlled concentration. • Gd ion induced lattice dynamical changes are significant. • Enhanced magnetization is observed upon Gd-incorporation in cobalt ferrite. • A correlation between lattice dynamics and magnetic properties is established. - Abstract: Polycrystalline gadolinium (Gd) substituted cobalt ferrites (CoFe{sub 2−x}Gd{sub x}O{sub 4}; x = 0–0.3, referred to CFGO) ceramics have been synthesized by solid state reaction method. Chemical bonding, crystal structure and magnetic properties of CFGO compounds have been evaluated as a function of Gd-content. X-ray diffraction (XRD) and Raman spectroscopic analyses confirmed the formation of inverse spinel cubic structure. However, a secondary ortho-ferrite phase (GdFeO{sub 3}) nucleates for higher values of Gd-content. A considerable increase in the saturation magnetization has been observed upon the initial substitution of Gd (x = 0.1). The saturation magnetization drastically decreases at higher Gd content (x ⩾ 0.3). No contribution from ortho-ferrite GdFeO{sub 3} phase is noted to the magnetic properties. The increase in the magnetic saturation magnetization is attributed to the higher magnetic moment of Gd{sup 3+} (4f{sup 7}) residing in octahedral sites is higher when compared to that of Fe{sup 3+} (3d{sup 5}) and as well due to the migration of Co{sup 2+} (3d{sup 7}) ions from the octahedral to the tetrahedral sites with a magnetic moment aligned anti-parallel to those of rare earth (RE{sup 3+}) ions in the spinel lattice. Increase in coercivity with increase in Gd{sup 3+} is content is attributed to magnetic anisotropy in the ceramics.

  10. What a difference a bond makes: the structural, chemical, and physical properties of methyl-terminated Si(111) surfaces.

    Science.gov (United States)

    Wong, Keith T; Lewis, Nathan S

    2014-10-21

    The chemical, electronic, and structural properties of surfaces are affected by the chemical termination of the surface. Two-step halogenation/alkylation of silicon provides a scalable, wet-chemical method for grafting molecules onto the silicon surface. Unlike other commonly studied wet-chemical methods of surface modification, such as self-assembly of monolayers on metals or hydrosilylation on silicon, the two-step method enables attachment of small alkyl chains, even methyl groups, to a silicon surface with high surface coverage and homogeneity. The methyl-terminated Si(111) surface, by comparison to hydrogen-terminated Si(111), offers a unique opportunity to study the effects of the first surface bond connecting the overlayer to the surface. This Account describes studies of methyl-terminated Si(111), which have shown that the H-Si(111) and CH3-Si(111) surfaces are structurally nearly identical, yet impart significantly different chemical and electronic properties to the resulting Si surface. The structure of methyl-terminated Si(111) formed by a two-step halogenation/methylation process has been studied by a variety of spectroscopic methods. A covalent Si-C bond is oriented normal to the surface, with the methyl group situated directly atop a surface Si atom. Multiple spectroscopic methods have shown that methyl groups achieve essentially complete coverage of the surface atoms while maintaining the atomically flat, terraced structure of the original H-Si(111) surface. Thus, the H-Si(111) and CH3-Si(111) surface share essentially identical structures aside from the replacement of a Si-H bond with a Si-C bond. Despite their structural similarity, hydrogen and methyl termination exhibit markedly different chemical passivation. Specifically, CH3-Si(111) exhibits significantly greater oxidation resistance than H-Si(111) in air and in aqueous electrolyte under photoanodic current flow. Both surfaces exhibit similar thermal stability in vacuum, and the Si-H and Si

  11. Chemical sensing in process analysis.

    Science.gov (United States)

    Hirschfeld, T; Callis, J B; Kowalski, B R

    1984-10-19

    Improvements in process control, which determine production efficiency and product quality, are critically dependent upon on-line process analysis. The technology of the required instrumentation will be substantially expanded by advances in sensing devices. In the future, the hardware will consist of sensor arrays and miniaturized instruments fabricated by microlithography and silicon micromachining. Chemometrics will be extensively used in software to provide error detection, selfcalibration, and correction as well as multivariate data analysis for the determination of anticipated and unanticipated species. A number of examples of monolithically fabricated sensors now exist and more will be forthcoming as the new paradigms and new tools are widely adopted. A trend toward not only on-line but even in-product sensors is becoming discernible.

  12. 40 CFR 761.253 - Chemical analysis.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... analysis. (a) Extract PCBs from the standard wipe sample collection medium and clean-up the extracted...

  13. QTAIM analysis of the bonding in Mo-Mo bonded dimolybdenum complexes.

    Science.gov (United States)

    Van der Maelen, Juan F; Cabeza, Javier A

    2012-07-02

    A number of local and integral topological parameters of the electron density of relevant bonding interactions in the binuclear molybdenum complexes [Mo(2)Cl(8)](4-), [Mo(2)(μ-CH(3)CO(2))(4)], [Mo(2)(μ-CF(3)CO(2))(4)], [Mo(2)(μ-CH(3)CO(2))(4)Br(2)](2-), [Mo(2)(μ-CF(3)CO(2))(4)Br(2)](2-), [Mo(2)(μ-CH(3)CO(2))(2)Cl(4)](2-), [Mo(2)(μ-CH(3)CO(2))(2)(μ-Cl)(2)Cl(4)](2-), and [Mo(2)(μ-Cl)(3)Cl(6)](3-) have been calculated and interpreted under the perspective of the quantum theory of atoms in molecules (QTAIM). These data have allowed a comparison between related but different atom-atom interactions, such as different Mo-Mo formal bond orders, ligand-unbridged versus Cl-bridged, CH(3)CO(2)-bridged, and CF(3)CO(2)-bridged Mo-Mo interactions, and Mo-Cl(terminal) and Mo-Cl(bridge) versus Mo-Br and Mo-O interactions. Calculations carried out using nonrelativistic and relativistic approaches afforded similar results.

  14. Synthesis, vibrational and quantum chemical investigations of hydrogen bonded complex betaine dihydrogen selenite

    Science.gov (United States)

    Arjunan, V.; Marchewka, Mariusz K.; Kalaivani, M.

    2012-10-01

    The molecular complex of betaine with selenious acid namely, betaine dihydrogen selenite (C5H13NO5Se, BDHSe) was synthesised by the reaction of betaine and SeO2 in a 1:1:1 solution of isopropanol, methanol and water. Crystals were grown from this solution by cooling to 253 K for few days. The complex was formed without accompanying proton transfer from selenious acid molecule to betaine. The complete vibrational assignments and analysis of BDHSe have been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings was added from the quantum chemical studies performed with DFT (B3LYP) method using 6-311++G∗∗, 6-31G∗∗, cc-pVDZ and 3-21G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of BDHSe were determined by the DFT method. The 1H and 13C isotropic chemical shifts (δ ppm) of BDHSe with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. SHG experiment was carried out using Kurtz-Perry powder technique. The efficiency of second harmonic generation for BDHSe was estimated relatively to KDP: deff = 0.97 deff (KDP).

  15. Synthesis, vibrational and quantum chemical investigations of hydrogen bonded complex betaine dihydrogen selenite.

    Science.gov (United States)

    Arjunan, V; Marchewka, Mariusz K; Kalaivani, M

    2012-10-01

    The molecular complex of betaine with selenious acid namely, betaine dihydrogen selenite (C(5)H(13)NO(5)Se, BDHSe) was synthesised by the reaction of betaine and SeO(2) in a 1:1:1 solution of isopropanol, methanol and water. Crystals were grown from this solution by cooling to 253 K for few days. The complex was formed without accompanying proton transfer from selenious acid molecule to betaine. The complete vibrational assignments and analysis of BDHSe have been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings was added from the quantum chemical studies performed with DFT (B3LYP) method using 6-311++G(**), 6-31G(**), cc-pVDZ and 3-21G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of BDHSe were determined by the DFT method. The (1)H and (13)C isotropic chemical shifts (δ ppm) of BDHSe with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. SHG experiment was carried out using Kurtz-Perry powder technique. The efficiency of second harmonic generation for BDHSe was estimated relatively to KDP: d(eff)=0.97 d(eff) (KDP).

  16. CHEMICALLY BONDED CEMENTS FROM BOILER ASH AND SLUDGE WASTES. PHASE I REPORT AUGUST 1997 - JULY 1998

    Energy Technology Data Exchange (ETDEWEB)

    SUGAMA,T.; YAGER,K.A.

    2002-08-05

    In exploring methods to recycle boiler ash (BA) and waste water treatment sludge (WWTS), by-products generated from Keyspan's power plants, into commercially viable materials, we synthesized chemically bonded cements (CBC) offering the following three specific characteristics; (1) immobilization of hazardous heavy metals, such as Pb, Ni, and V, (2) rapid hardening and setting properties, and (3) development of high mechanical strength. The CBCs were prepared through an acid-base reaction between these by-products acting as the solid base reactants and the sodium polyphosphate solution as the cement-forming acid reactant, followed by a hydrating reaction. Furthermore, two additives, the calcium aluminate cements (CAC) and the calcium silicate cements (CSC) were incorporated into the CBC systems to improve their properties. Using a CBC formulation consisting of 53.8 wt% WWTS, 23.1 wt% CSC, and 23.1 wt% [40 wt% -(-NaPO{sub 3}-)-{sub n}]{sub 2} the Toxicity Characteristics Leaching Procedure (TCLP) tests showed that the concentrations of Pb, Ni, and V metals leached out from the specimens were minimal. This formulation originally contained {approx} 28800 mg/kg of Pb, {approx} 6300 mg/kg of Ni, and {approx} 11130 mg/kg of V; the amounts leaching into the acid extraction fluid were only 0.15 mg/L of Pb, 0.15 mg/L of Ni, and 4.63 mgiL of V. On the other hand, CBC specimens derived from a formulation consisting of 42 wt% BA, 18 wt% CAC and 40 wt% [40 wt% -(-NaPO{sub 3}-)-{sub n}] displayed an excellent compressive strength of 10.8 MPa at an early curing age of 2 hours after mixing at room temperature. The reason for its rapid hardening was due to a high exothermic energy evolved by the acid-base reaction. Furthermore, when these specimens were immersed for 28 days in water at 25 C, and exposed for 20 hours to steam at 80 C, a very high compressive strength of 3.32 MPa developed. Two physico-chemical factors played an important role in improving the mechanical strength

  17. Análise química e morfológica do esmalte dentário humano tratado com laser argônio durante a colagem ortodôntica Chemical and morphological analysis of the human dental enamel treated with argon laser during orthodontic bonding

    Directory of Open Access Journals (Sweden)

    Glaucio Serra Guimarães

    2011-04-01

    Full Text Available INTRODUÇÃO: as principais utilizações do laser argônio na Ortodontia são a redução do tempo de polimerização durante a colagem ortodôntica e o aumento da resistência à cárie do esmalte dentário. OBJETIVO: o objetivo deste trabalho foi avaliar as alterações químicas e morfológicas do esmalte dentário humano tratado com laser argônio nos parâmetros da colagem ortodôntica. MÉTODOS: quinze primeiros pré-molares hígidos, extraídos por indicação ortodôntica, foram selecionados e seccionados no sentido do longo eixo em dois segmentos iguais. Uma metade de cada elemento dentário foi tratada e a outra permaneceu sem tratamento. Um total de 30 amostras foi analisado, criando o grupo laser (n = 15 e o grupo controle (n = 15. O tratamento foi feito com laser argônio com 250mW de potência por 5 segundos, com densidade de energia de 8J/cm². RESULTADOS: a análise de difração de raios X demonstrou duas fases em ambos os grupos, as fases apatita e monetita. A redução da fase monetita foi significativa após o tratamento com laser, sugerindo maior cristalinidade. A análise de Espectroscopia de Energia Dispersiva (EDS indicou aumento na razão cálcio-fósforo no grupo laser, compatível com a diminuição da fase monetita. A morfologia superficial do esmalte dentário apresentou-se mais lisa após o tratamento com laser argônio. CONCLUSÕES: o aumento de cristalinidade e a lisura superficial do esmalte no grupo laser são fatores sugestivos de aumento de resistência à cárie no esmalte dentário.INTRODUCTION: The main utilities of the argon laser in orthodontics are the high speed curing process in orthodontic bonding and the caries resistance promotion of the tooth enamel. OBJECTIVE: The objective of this study was to evaluate the chemical and morphological changes in the tooth enamel treated with the argon laser in the orthodontic bonding parameters. METHODS: Fifteen sound human first premolars, removed for orthodontic

  18. Proton NMR Chemical Shift Behavior of Hydrogen-Bonded Amide Proton of Glycine-Containing Peptides and Polypeptides as Studied by ab initio MO Calculation

    Directory of Open Access Journals (Sweden)

    I. Ando

    2002-08-01

    Full Text Available Abstract: NMR chemical shifts of the amide proton of a supermolecule, an Nmethylacetamide hydrogen-bonded with a formamide, were calculated as functions of hydrogen-bond length RN…O and hydrogen-bond angles by FPT-GIAO method within the framework of HF/STO 6-31++G(d,p ab initio MO method. The calculations explained reasonably the experimental data reported previously that the isotropic proton chemical shifts move downfield with a decrease in RN…O. Further, the behavior of proton chemical shift tensor components depending on the hydrogen-bond length and hydrogen-bond angle was discussed.

  19. Chemical analysis of aquatic pheromones in fish.

    Science.gov (United States)

    Stewart, Michael; Baker, Cindy F; Sorensen, Peter W

    2013-01-01

    Pheromones are chemicals that pass between members of the same species that have inherent meaning. In the case of fish, pheromones are water-soluble and found in low concentrations. As such, sensitive and selective methods are needed to separate and analyze these pheromones from an environmental matrix that may contain many other chemicals. This chapter describes a generic method used to concentrate and identify these chemicals and two extremely sensitive and selective methods for analysis, namely, mass spectrometry and enzyme-linked immunosorbent assay.

  20. Halogen Bonding: An AIM Analysis of the Weak Interactions

    Institute of Scientific and Technical Information of China (English)

    ZOU, Jian-Wei; LU, Yun-Xiang; YU, Qing-Sen; ZHANG, Hua-Xin; JIANG, Yong-Jun

    2006-01-01

    A series of complexes formed between halogen-containing molecules and ammonia have been investigated by means of the atoms in molecules (AIM) approach to gain a deeper insight into halogen bonding. The existence of the halogen bond critical points (XBCP) and the values of the electron density (ρb) and Laplacian of electron density (▽2pb) at the XBCP reveal the closed-shell interactions in these complexes. Integrated atomic properties such as charge, energy, polarization moment, volume of the halogen bond donor atoms, and the corresponding changes (△) upon complexation have been calculated. The present calculations have demonstrated that the halogen bond represents different AIM properties as compared to the well-documented hydrogen bond. Both the electron density and the Laplacian of electron density at the XBCP have been shown to correlate well with the interaction energy, which indicates that the topological parameters at the XBCP can be treated as a good measure of the halogen bond strength.In addition, an excellent linear relationship between the interatomic distance d(X…N) and the logarithm of ρb has been established.

  1. Comparison of shear bond strength of resin reinforced chemical cure glass ionomer, conventional chemical cure glass ionomer and chemical cure composite resin in direct bonding systems: an in vitro study.

    Science.gov (United States)

    Rao, Kolasani Srinivasa; Reddy, T Praveen Kumar; Yugandhar, Garlapati; Kumar, B Sunil; Reddy, S N Chandrasekhar; Babu, Devatha Ashok

    2013-01-01

    The acid pretreatment and use of composite resins as the bonding medium has disadvantages like scratching and loss of surface enamel, decalcification, etc. To overcome disadvantages of composite resins, glass ionomers and its modifications are being used for bonding. The study was conducted to evaluate the efficiency of resin reinforced glass ionomer as a direct bonding system with conventional glass ionomer cement and composite resin. The study showed that shear bond strength of composite resin has the higher value than both resin reinforced glass ionomer and conventional glass ionomer cement in both 1 and 24 hours duration and it increased from 1 to 24 hours in all groups. The shear bond strength of resin reinforced glass ionomer cement was higher than the conventional glass ionomer cement in both 1 and 24 hours duration. Conditioning with polyacrylic acid improved the bond strength of resin reinforced glass ionomer cement significantly but not statistically significant in the case of conventional glass ionomer cement.

  2. Quantum chemical study on influence of intermolecular hydrogen bonding on the geometry, the atomic charges and the vibrational dynamics of 2,6-dichlorobenzonitrile.

    Science.gov (United States)

    Agarwal, Parag; Bee, Saba; Gupta, Archana; Tandon, Poonam; Rastogi, V K; Mishra, Soni; Rawat, Poonam

    2014-01-01

    FT-IR (4000-400 cm(-1)) and FT-Raman (4000-200 cm(-1)) spectral measurements on solid 2,6-dichlorobenzonitrile (2,6-DCBN) have been done. The molecular geometry, harmonic vibrational frequencies and bonding features in the ground state have been calculated by density functional theory at the B3LYP/6-311++G (d,p) level. A comparison between the calculated and the experimental results covering the molecular structure has been made. The assignments of the fundamental vibrational modes have been done on the basis of the potential energy distribution (PED). To investigate the influence of intermolecular hydrogen bonding on the geometry, the charge distribution and the vibrational spectrum of 2,6-DCBN; calculations have been done for the monomer as well as the tetramer. The intermolecular interaction energies corrected for basis set superposition error (BSSE) have been calculated using counterpoise method. Based on these results, the correlations between the vibrational modes and the structure of the tetramer have been discussed. Molecular electrostatic potential (MEP) contour map has been plotted in order to predict how different geometries could interact. The Natural Bond Orbital (NBO) analysis has been done for the chemical interpretation of hyperconjugative interactions and electron density transfer between occupied (bonding or lone pair) orbitals to unoccupied (antibonding or Rydberg) orbitals. UV spectrum was measured in methanol solution. The energies and oscillator strengths were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. TD-DFT method has also been used for theoretically studying the hydrogen bonding dynamics by monitoring the spectral shifts of some characteristic vibrational modes involved in the formation of hydrogen bonds in the ground and the first excited state. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge independent atomic orbital

  3. Information-Theoretical Complexity Analysis of Selected Elementary Chemical Reactions

    Science.gov (United States)

    Molina-Espíritu, M.; Esquivel, R. O.; Dehesa, J. S.

    We investigate the complexity of selected elementary chemical reactions (namely, the hydrogenic-abstraction reaction and the identity SN2 exchange reaction) by means of the following single and composite information-theoretic measures: disequilibrium (D), exponential entropy(L), Fisher information (I), power entropy (J), I-D, D-L and I-J planes and Fisher-Shannon (FS) and Lopez-Mancini-Calbet (LMC) shape complexities. These quantities, which are functionals of the one-particle density, are computed in both position (r) and momentum (p) spaces. The analysis revealed that the chemically significant regions of these reactions can be identified through most of the single information-theoretic measures and the two-component planes, not only the ones which are commonly revealed by the energy, such as the reactant/product (R/P) and the transition state (TS), but also those that are not present in the energy profile such as the bond cleavage energy region (BCER), the bond breaking/forming regions (B-B/F) and the charge transfer process (CT). The analysis of the complexities shows that the energy profile of the abstraction reaction bears the same information-theoretical features of the LMC and FS measures, however for the identity SN2 exchange reaction does not hold a simple behavior with respect to the LMC and FS measures. Most of the chemical features of interest (BCER, B-B/F and CT) are only revealed when particular information-theoretic aspects of localizability (L or J), uniformity (D) and disorder (I) are considered.

  4. Critical surface energy of composite cement containing MDP (10-methacryloyloxydecyl dihydrogen phosphate) and chemical bonding to hydroxyapatite.

    Science.gov (United States)

    Dabsie, Firas; Grégoire, Geneviève; Sharrock, Patrick

    2012-01-01

    Self-adhesive composite cements are increasingly used for cementing inlays/onlays, intraradicular posts, crowns and laminate veneers. Wider clinical acceptance is driven by simpler and faster handling procedures, much like observed for self-etching adhesives. 10-Methacryloyloxydecyl dihydrogen phosphate (MDP) is a bi-functional monomer incorporated as the reactive ingredient in a contemporary self-adhesive cement. We have examined the surface free energy parameters of this cement and studied the mode of action of the cement on dentine substrate by contact angle measurements to determine the critical surface energy of the cement. Retention of the infrared absorption bands characteristic of the acrylate moieties on the surface of hydroxyapatite particles suggests that MDP contributes to the overall bonding to dentine by forming ionic chemical bonds with surface calcium ions in dentine crystalites.

  5. Compression analysis of rectangular elastic layers bonded between rigid plates

    Energy Technology Data Exchange (ETDEWEB)

    Hsiang-Chuan Tsai [National Taiwan University of Science and Technology, Taipei (China). Dept. of Construction Engineering

    2005-06-01

    An elastic layer bonded between two rigid plates has higher compression stiffness than the elastic layer without bonding. While the finite element method can be applied to calculate the stiffness, the compression stiffness of bonded rectangular layers derived through a theoretical approach in this paper provides a convenient way for parametric study. Based on two kinematics assumptions, the governing equation for the mean pressure is derived from the equilibrium equations. Using the approximate shear boundary condition, the mean pressure is solved and the compression stiffness of the bonded rectangular layer is then established in an explicit single-series form. Through the solved pressure, the horizontal displacements are derived from the corresponding equilibrium equations, from which the shear stress on the bonding surface can be found. It is found that the effect of the rectangular aspect on the compression stiffness is significant only when Poisson's ratio is near 0.5. For the smaller Poisson's ratio, the compression stiffness of the rectangular layer can be approximated by the formula for the infinite-strip layer of the same shape factor. (author)

  6. Identification of the Chemical Bonding Prompting Adhesion of a-C:H Thin Films on Ferrous Alloy Intermediated by a SiCx:H Buffer Layer.

    Science.gov (United States)

    Cemin, F; Bim, L T; Leidens, L M; Morales, M; Baumvol, I J R; Alvarez, F; Figueroa, C A

    2015-07-29

    Amorphous carbon (a-C) and several related materials (DLCs) may have ultralow friction coefficients that can be used for saving-energy applications. However, poor chemical bonding of a-C/DLC films on metallic alloys is expected, due to the stability of carbon-carbon bonds. Silicon-based intermediate layers are employed to enhance the adherence of a-C:H films on ferrous alloys, although the role of such buffer layers is not yet fully understood in chemical terms. The chemical bonding of a-C:H thin films on ferrous alloy intermediated by a nanometric SiCx:H buffer layer was analyzed by X-ray photoelectron spectroscopy (XPS). The chemical profile was inspected by glow discharge optical emission spectroscopy (GDOES), and the chemical structure was evaluated by Raman and Fourier transform infrared spectroscopy techniques. The nature of adhesion is discussed by analyzing the chemical bonding at the interfaces of the a-C:H/SiCx:H/ferrous alloy sandwich structure. The adhesion phenomenon is ascribed to specifically chemical bonding character at the buffer layer. Whereas carbon-carbon (C-C) and carbon-silicon (C-Si) bonds are formed at the outermost interface, the innermost interface is constituted mainly by silicon-iron (Si-Fe) bonds. The oxygen presence degrades the adhesion up to totally delaminate the a-C:H thin films. The SiCx:H deposition temperature determines the type of chemical bonding and the amount of oxygen contained in the buffer layer.

  7. CHEMICALLY BONDED CEMENTS FROM BOILER ASH AND SLUDGE WASTES. PHASE II REPORT, SEPT.1998-JULY 1999.

    Energy Technology Data Exchange (ETDEWEB)

    SUGAMA,T.YAGER,K.A.BLANKENHORN,D.(KEYSPAN R AND D INITIATIVE)

    1999-08-01

    Based upon the previous Phase I research program aimed at looking for ways of recycling the KeySpan-generated wastes, such as waste water treatment sludge (WWTS) and bottom ash (BA), into the potentially useful cementitious materials called chemically bonded cement (CBC) materials, the emphasis of this Phase II program done at Brookhaven National Laboratory, in a period of September 1998 through July 1999, was directed towards the two major subjects: One was to assess the technical feasibility of WWTS-based CBC material for use as Pb-exchange adsorbent (PEA) which remediates Pb-contaminated soils in the field; and the other was related to the establishment of the optimum-packaging storage system of dry BA-based CBC components that make it a promising matrix material for the steam-cured concrete products containing sand and coarse aggregate. To achieve the goal of the first subject, a small-scale field demonstration test was carried out. Using the PEA material consisting of 30 wt% WWTS, 13 wt% Type I cement and 57 wt% water, the PES slurry was prepared using a rotary shear concrete mixer, and then poured on the Pb-contaminated soil. The PEA-to-soil ratio by weight was a factor of 2.0. The placed PEA slurry was blended with soil using hand mixing tools such as claws and shovels. The wettability of soils with the PEA was very good, thereby facilitating the soil-PEA mix procedures. A very promising result was obtained from this field test; in fact, the mount of Pb leached out from the 25-day-aged PEA-treated soil specimen was only 0.74 mg/l, meeting the requirement for EPA safe regulation of < 5 mg/l. In contrast, a large amount (26.4 mg/l) of Pb was detected from the untreated soil of the same age. Thus, this finding demonstrated that the WWTS-based CBC has a potential for use as PEA material. Regarding the second subject, the dry-packed storage system consisting of 68.7 wt% BA, 13.0 wt% calcium aluminate cement (CAC), 13.0 wt% Type I portland cement and 5.3 wt

  8. Automation Tools for Finite Element Analysis of Adhesively Bonded Joints

    Science.gov (United States)

    Tahmasebi, Farhad; Brodeur, Stephen J. (Technical Monitor)

    2002-01-01

    This article presents two new automation creation tools that obtain stresses and strains (Shear and peel) in adhesively bonded joints. For a given adhesively bonded joint Finite Element model, in which the adhesive is characterised using springs, these automation tools read the corresponding input and output files, use the spring forces and deformations to obtain the adhesive stresses and strains, sort the stresses and strains in descending order, and generate plot files for 3D visualisation of the stress and strain fields. Grids (nodes) and elements can be numbered in any order that is convenient for the user. Using the automation tools, trade-off studies, which are needed for design of adhesively bonded joints, can be performed very quickly.

  9. Covalent features in the hydrogen bond of a water dimer: molecular orbital analysis

    CERN Document Server

    Wang, Bo; Dai, Xing; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin

    2015-01-01

    The covalent-like characteristics of hydrogen bonds offer a new perspective on intermolecular interactions. Here, using density functional theory and post-Hartree-Fock methods, we reveal that there are two bonding molecular orbitals (MOs) crossing the O and H atoms of the hydrogen-bond in water dimer. Energy decomposition analysis also shows a non-negligible contribution of the induction term. These results illustrate the covalent-like character of the hydrogen bond between water molecules, which contributes to the essential understanding of ice, liquid water, related materials, and life sciences.

  10. The electron density distribution in the hydrogen bond. A quantum chemical and crystallographic study

    NARCIS (Netherlands)

    Feil, Dirk

    1990-01-01

    With the help of Hartree—Fock—Slater calculations in which very large basis sets are employed, the polarisation of the water molecule by an electric field is explored. The various features in the electron density distribution are encountered again in the long hydrogen bond in the water dimer, showin

  11. Physico-Chemical Factors Affecting Hydrothermal Resistance and Bonding of Polymeric Composites to Steel Surfaces

    Science.gov (United States)

    1985-11-01

    7 , I 71iil 7 7 771111011111111111171111 Type A consists of a strong ionic interaction associated with charge transfer bonding mechanisms which...the ionic interaction regions and the density of entangleicnt macromol- ecules at interfaces are not evident from the limited data. Nevertheless

  12. Application of Bonded Joints for Quantitative Analysis of Adhesion

    Directory of Open Access Journals (Sweden)

    Jarmila Trpčevská

    2016-01-01

    Full Text Available The performance of hot-dip coated steel sheets is associated with properties of the zinc coatings on steel substrate. For the characterization of the adhesion behaviour of zinc coating on steel various tests were employed. The study was focused on quantification assessment of galvanized coating adhesion to substrates. Methods for evaluation of the bonding strength of zinc coating by the shear strength and the T-peel tests applying four special types of adhesives were used. The experimental tests of bonded joints show that the adhesion of the zinc coating to the substrate was higher than that of the applied adhesive with the highest strength.

  13. Chemical and instrumental approaches to cheese analysis.

    Science.gov (United States)

    Subramanian, Anand; Rodriguez-Saona, Luis

    2010-01-01

    Overcoming the complexity of cheese matrix to reliably analyze cheese composition, flavor, and ripening changes has been a challenge. Several sample isolation or fractionation methods, chemical and enzymatic assays, and instrumental methods have been developed over the decades. While some of the methods are well established standard methods, some still need to be researched and improved. This chapter reviews the chemical and instrumental methods available to determine cheese composition and monitor biochemical events (e.g., glycolysis, lipolysis, and proteolysis) during cheese ripening that lead to the formation of cheese flavor. Chemical and enzymatic methods available for analysis of cheese composition (fat, protein, lactose, salt, nitrogen content, moisture, etc.) are presented. Electrophoretic, chromatographic, and spectroscopic techniques are also reviewed in the light of their application to monitor cheese ripening and flavor compounds. Novel instrumental methods based on Fourier-transform infrared spectroscopy that are currently being researched and applied to cheese analysis are introduced.

  14. Synthesis of advanced chemically bonded ceramics for solidification of radioactive wastes

    Energy Technology Data Exchange (ETDEWEB)

    Seneda, Jose A.; Dellamano, Jose C.; Queiroz, Carlos A.S.; Genova, Luis A.; Rocha, Soraya M.R. da; Vicente, Roberto, E-mail: jaseneda@ipen.b, E-mail: jcdellam@ipen.b, E-mail: cqueiroz@ipen.b, E-mail: lgenova@ipen.b, E-mail: smrrocha@ipen.b, E-mail: rvicente@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2011-07-01

    This paper presents the results of a preliminary study on the synthesis of advanced chemically bounded ceramics for use to immobilize radioactive wastes. A monolithic, crystalline, ceramic-like material, in the form of MgKPO{sub 4}.6H{sub 2}O, is obtained by reaction of magnesium oxide with potassium monophosphate, at room temperature. The thermodynamics of the reaction indicates the need of a previous treatment of the MgO above 1200 deg C to avoid the formation of magnesium phosphate salts, as revealed by thermogravimetric analysis and X-ray diffraction. The different crystalline phases and microstructure of reaction products are analyzed by X-ray diffraction and scanning electron microscopy, indicating that the material has the characteristics of a matrix for immobilization of radioactive waste. Results obtained thus far indicate the possibility of using this material to replace Portland cement in waste immobilization, offsetting the higher cost of raw material input with a larger fraction of waste in the waste form. More research on characterization of the waste form with mechanical strength tests of specimens incorporating varying waste compositions, and on the leaching potential of the material for a series of radioactive as well hazardous industrial wastes is being planned. (author)

  15. Improvement in reinforcing bond strength in reinforced concrete with self-repairing chemical adhesives

    Science.gov (United States)

    Dry, Carolyn M.

    1997-05-01

    Self-healing concretes have embedded adhesives which are released from hollow fibers inside the concrete when and where cracking of the matrix and the fibers occurs. It was found that the adhesive improves the strength of the cracked portions of the concrete and increases its ability to deflect under load. Structural materials subjected to dynamic events such as earthquakes and impacts can have improved response by the noise of adhesive type which can impart improved damping, lateral stiffness, or deflection. Testing also assessed the improvement of the bond strength in structures. In laboratory tests the internal adhesive repair system improved the bond between the reinforcing steel and the concrete to prevent pullout failure or debonding at the interface.

  16. Extraordinarily Long 2-Electron - 4-Center (2e-/4c) 2.9-Å Carbon-Carbon Bonds - What is a Chemical Bond?

    OpenAIRE

    Miller, Joel S.

    2014-01-01

    Carbon-carbon (CC) bonding is a key essence of organic and biochemistry. The length of a CC bond, i.e. 1.54 Å found in the diamond allotrope of carbon and ethane, is among the essential information learned by all chemistry students. This is the length of a single bond () between sp3-hybridized carbons and is the longest of all common CC bonds. Our studies of the [TCNE]22- (TCNE = tetracyanoethylene) dimers reveal that 2.89 ± 0.05 Å 2 electron/4 center (2e-/4c) CC bonds are present. Struc...

  17. First-Principles Calculations on Electronic, Chemical Bonding and Optical Properties of Cubic Hf3N4

    Institute of Scientific and Technical Information of China (English)

    FENG Li-Ping; WANG Zhi-Qiang; LIU Zheng-Tang

    2013-01-01

    Electronic,chemical bonding and optical properties of cubic Hf3N4(c-Hf3N4) are calculated using the firstprinciples based on the density functional theory (DFT).The optimized lattice parameter is in good agreement with the available experimental and calculational values.Band structure shows that c-Hf3N4 has direct band gap.Densities of states (DOS) and charge densities indicate that the bonding between Hf and N is ionic.The optical properties including complex dielectric function,refractive index,extinction coefficient,absorption coefficient,and reflectivity are predicted.From the theory of crystal-field and molecudar-orbital bonding,the optical transitions of c-Hf3N4 affected by the electronic structure and molecular orbital are studied.It is found that the absorptive transitions of c-Hf3N4 compound are predominantly composed of the transitions from N T22p valence bands to HfT2 (dxy,dxz,dyz) conduction bands.

  18. Evaluation of molecular assembly, spectroscopic interpretation, intra-/inter molecular hydrogen bonding and chemical reactivity of two pyrrole precursors

    Science.gov (United States)

    Rawat, Poonam; Singh, R. N.

    2014-10-01

    This paper describes the evaluation of conformational, spectroscopic, hydrogen bonding and chemical reactivity of pyrrole precursor: ethyl 3,5 dimethyl-1H-pyrrole-2-carboxylate (EDPC) and ethyl 3,4-dimethyl-4-acetyl-1H-pyrrole-2-carboxylate (EDAPC) for the convenient characterization, synthetic usefulness and comparative evaluations. All experimental spectral values of 1H NMR, UV-Vis and FT-IR spectra coincide well with calculated values by DFT. The orbital interactions in EDPC and EDAPC are found to lengthen their Nsbnd H and Cdbnd O bonds and lowers their vibrational frequencies (red shift) resulting to dimer formation. The QTAIM and NBO analyses provide the strength of interactions and charge transfer in the hydrogen bonding unit and stability of dimers. The binding energy of EDPC and EDPAC dimer are found to be 9.92, 10.22 kcal/mol, respectively. In EDPAC and EDPC dimer, hyperconjugative interactions between monomer units is due to n1(O) → σ*(Nsbnd H) that stabilize the molecule up to 9.7 and 9.3 kcal/mol, respectively. On evaluation of molecular electrostatic potential (MEP) and electronic descriptors for EDPC it has been found that it is a good precursor for synthesis of formyl and acetyl derivatives whereas EDAPC has been found to be a good precursor for synthesis of schiff base, hydrazones, hydrazide-hydrazones and chalcones.

  19. A comparative effect of various surface chemical treatments on the resin composite-composite repair bond strength

    Directory of Open Access Journals (Sweden)

    Shaloo Gupta

    2015-01-01

    Full Text Available Aim: The aim of this in vitro study was an attempt to investigate the effect of different surface treatments on the bond strength between pre-existing composite and repair composite resin. Materials and Methods: Forty acrylic blocks were prepared in a cuboidal mould. In each block, a well of 5 mm diameter and 5 mm depth was prepared to retain the composite resin (Filtek™ Z350, 3M/ESPE. Aging of the composite discs was achieved by storing them in water at 37°C for 1 week, and after that were divided into 5 groups (n = 8 according to surface treatment: Group I- 37% phosphoric acid, Group II-10% hydrofluoric acid, Group III-30% citric acid, Group IV-7% maleic acid and Group V- Adhesive (no etchant. The etched surfaces were rinsed and dried followed by application of bonding agent (Adper™ Single Bond 2. 3M/ESPE. The repair composite was placed on aged composite, light-cured for 40 seconds and stored in water at 37°C for 1 week. Shear bond strength between the aged and the new composite resin was determined with a universal testing machine (crosshead speed of 0.5 mm/min. Statistical Analysis: The compressive shear strengths were compared for differences using ANOVA test followed by Tamhane′s T2 post hoc analysis. Results: The surface treatment with 10% hydrofluoric acid showed the maximum bond strength followed by 30% citric acid, 7% maleic acid and 37% phosphoric acid in decreasing order. Conclusion: The use of 10% hydrofluoric acid can be a good alternative for surface treatment in repair of composite resin restoration as compared to commonly used 37% orthophosphoric acid.

  20. Geometrical criteria versus quantum chemical criteria for assessment of intramolecular hydrogen bond (IMHB) interaction: A computational comparison into the effect of chlorine substitution on IMHB of salicylic acid in its lowest energy ground state conformer

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Bijan Kumar [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Calcutta 700009 (India); Guchhait, Nikhil, E-mail: nikhil.guchhait@rediffmail.com [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Calcutta 700009 (India)

    2013-02-01

    Highlights: ► Intramolecular hydrogen bonding (IMHB) in salicylic acid and its chloro derivatives. ► A complex effect of +R and −I effect of chlorine substituents on IMHB energy. ► Interplay between IMHB energy and aromaticity. ► Directional nature of IMHB from quantum chemical assessment. ► Quantum chemical treatment vs. geometrical criteria to assess weak interaction. - Abstract: Density functional theory based computational study has been performed to characterize intramolecular hydrogen bonding (IMHB) interaction in a series of salicylic acid derivatives varying in chlorine substitution on the benzene ring. The molecular systems studied are salicylic acid, 5-chlorosalicylic acid, 3,5-dichlorosalicylic acid and 3,5,6-tricholorosalicylic acid. Major emphasis is rendered on the analysis of IMHB interaction by calculation of electron density ρ(r) and Laplacian ∇{sup 2}ρ(r) at the bond critical point using atoms-in-molecule theory. Topological features, energy densities based on ρ(r) through perturbing the intramolecular H-bond distances suggest that at equilibrium geometry the IMHB interaction develops certain characteristics typical of covalent interaction. The interplay between aromaticity and resonance-assisted hydrogen bonding (RAHB) is discussed using both geometrical and magnetic criteria as the descriptors of aromaticity. The optimized geometry features, molecular electrostatic potential map analysis are also found to produce a consensus view in relation with the formation of RAHB in these systems.

  1. Chemical abundance analysis of 19 barium stars

    CERN Document Server

    Yang, G C; Spite, M; Chen, Y Q; Zhao, G; Zhang, B; Liu, G Q; Liu, Y J; Liu, N; Deng, L C; Spite, F; Hill, V; Zhang, C X

    2016-01-01

    We aim at deriving accurate atmospheric parameters and chemical abundances of 19 barium (Ba) stars, including both strong and mild Ba stars, based on the high signal-to-noise ratio and high resolution Echelle spectra obtained from the 2.16 m telescope at Xinglong station of National Astronomical Observatories, Chinese Academy of Sciences. The chemical abundances of the sample stars were obtained from an LTE, plane-parallel and line-blanketed atmospheric model by inputting the atmospheric parameters (effective temperatures, surface gravities, metallicity and microturbulent velocity) and equivalent widths of stellar absorption lines. These samples of Ba stars are giants indicated by atmospheric parameters, metallicities and kinematic analysis about UVW velocity. Chemical abundances of 17 elements were obtained for these Ba stars. Their light elements (O, Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn and Ni) are similar to the solar abundances. Our samples of Ba stars show obvious overabundances of neutron-capture (n-ca...

  2. In search of low cost biological analysis: Wax or acrylic glue bonded paper microfluidic devices

    KAUST Repository

    Kodzius, Rimantas

    2011-11-04

    In this body of work we have been developing and characterizing paper based microfluidic fabrication technologies to produce low cost biological analysis. Specifically we investigated the performance of paper microfluidics that had been bonded using wax o

  3. Electrical Power Analysis Using the Scattering Bond Graph

    Directory of Open Access Journals (Sweden)

    Roberto Tapia-Sánchez

    2015-01-01

    Full Text Available The perspective of the well known concept of active and reactive power in electrical systems is addressed in this paper. This concept is presented from the point of view of the bond graph methodology. The scattering matrix concept is used in order to deal with these formulations. The concept of active and reactive power is presented with some examples derived from single-phase AC circuits. The formulations and simulations of these circuits are presented.

  4. Effect of applied dc bias voltage on composition, chemical bonding and mechanical properties of carbon nitride films prepared by PECVD

    Institute of Scientific and Technical Information of China (English)

    LI Hong-xuan; XU Tao; HAO Jun-ying; CHEN Jian-min; ZHOU Hui-di; XUE Qun-ji; LIU Hui-wen

    2004-01-01

    Carbon nitride films were deposited on Si (100) substrates using plasma-enhanced chemical vapor deposition (PECVD) technique from CH4 and N2 at different applied dc bias voltage. The microstructure, composition and chemical bonding of the resulting films were characterized by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The mechanical properties such as hardness and elastic modulus of the films were evaluated using nano-indentation. As the results, the Raman spectra, showing the G and D bands, indicate the amorphous structure of the films. XPS and FTIR measurements demonstrate the existence of various carbon-nitride bonds in the films and the hydrogenation of carbon nitride phase. The composition ratio of N to C, the nano-hardness and the elastic modulus of the carbon nitride films increase with increasing dc bias voltage and reach the maximums at a dc bias voltage of 300 V, then they decrease with further increase of the dc bias voltage. Moreover, the XRD analyses indicate that the carbon nitride film contains some polycrystalline C3N4 phase embedded in the amorphous matrix at optimized deposition condition of dc bias voltage of 300 V.

  5. A DFT and NBO Analysis of the Bonding in Titanocenyl Complexes ...

    African Journals Online (AJOL)

    NICO

    C-C bonds from the experimental values. Since comparisons of ..... Zhang, Z. Liu, G.Wang and D. Wu, Appl. Organomet. Chem., 2006, 20,. 117–124; (e) ... 13 W.J. Hehre, A Guide to Molecular Mechanics and Quantum Chemical. Calculations ...

  6. Structure-property relationships in cubic cuprous iodide: A novel view on stability, chemical bonding, and electronic properties

    Science.gov (United States)

    Pishtshev, A.; Karazhanov, S. Zh.

    2017-02-01

    Based on the combination of density functional theory and theory-group methods, we performed systematic modeling of γ-CuI structural design at the atomistic level. Being started from the metallic copper lattice, we treated a crystal assembly as a stepwise iodination process characterized in terms of a sequence of intermediate lattice geometries. These geometries were selected and validated via screening of possible structural transformations. The genesis of chemical bonding was studied for three structural transformations by analyzing the relevant changes in the topology of valence electron densities. We determined structural trends driven by metal-ligand coupling. This allowed us to suggest the improved scenario of chemical bonding in γ-CuI. In particular, the unconventional effect of spatial separation of metallic and covalent interactions was found to be very important with respect to the preferred arrangements of valence electrons in the iodination process. We rigorously showed that useful electronic and optical properties of γ-CuI originate from the combination of two separated bonding patterns—strong covalency established in I-Cu tetrahedral connections and noncovalent interactions of copper cores is caused by the 3d10 closed-shell electron configurations. The other finding of ours is that the self-consistency of the GW calculations is crucial for correctly determining the dynamic electronic correlations in γ-CuI. Detail reinvestigation of the quasi-particle energy structure by means of the self-consistent GW approach allowed us to explain how p-type electrical conductivity can be engineered in the material.

  7. Structure-property relationships in cubic cuprous iodide: A novel view on stability, chemical bonding, and electronic properties.

    Science.gov (United States)

    Pishtshev, A; Karazhanov, S Zh

    2017-02-14

    Based on the combination of density functional theory and theory-group methods, we performed systematic modeling of γ-CuI structural design at the atomistic level. Being started from the metallic copper lattice, we treated a crystal assembly as a stepwise iodination process characterized in terms of a sequence of intermediate lattice geometries. These geometries were selected and validated via screening of possible structural transformations. The genesis of chemical bonding was studied for three structural transformations by analyzing the relevant changes in the topology of valence electron densities. We determined structural trends driven by metal-ligand coupling. This allowed us to suggest the improved scenario of chemical bonding in γ-CuI. In particular, the unconventional effect of spatial separation of metallic and covalent interactions was found to be very important with respect to the preferred arrangements of valence electrons in the iodination process. We rigorously showed that useful electronic and optical properties of γ-CuI originate from the combination of two separated bonding patterns-strong covalency established in I-Cu tetrahedral connections and noncovalent interactions of copper cores is caused by the 3d(10) closed-shell electron configurations. The other finding of ours is that the self-consistency of the GW calculations is crucial for correctly determining the dynamic electronic correlations in γ-CuI. Detail reinvestigation of the quasi-particle energy structure by means of the self-consistent GW approach allowed us to explain how p-type electrical conductivity can be engineered in the material.

  8. Strong and weak hydrogen bonds in drug–DNA complexes: A statistical analysis

    Indian Academy of Sciences (India)

    Sunil K Panigrahi; Gautam R Desiraju

    2007-06-01

    A statistical analysis of strong and weak hydrogen bonds in the minor groove of DNA was carried out for a set of 70 drug–DNA complexes. The terms `strong’ and `weak’ pertain to the inherent strengths and weakness of the donor and acceptor fragments rather than to any energy considerations. The dataset was extracted from the protein data bank (PDB). The analysis was performed with an in-house software, hydrogen bond analysis tool (HBAT). In addition to strong hydrogen bonds such as O−H···O and N−H···O, the ubiquitous presence of weak hydrogen bonds such as C−H···O is implicated in molecular recognition. On an average, there are 1.4 weak hydrogen bonds for every strong hydrogen bond. For both categories of interaction, the N(3) of purine and the O(2) of pyrimidine are favoured acceptors. Donor multifurcation is common with the donors generally present in the drug molecules, and shared by hydrogen bond acceptors in the minor groove. Bifurcation and trifurcation are most commonly observed. The metrics for strong hydrogen bonds are consistent with established trends. The geometries are variable for weak hydrogen bonds. A database of recognition geometries for 26 literature amidinium-based inhibitors of Human African Trypanosomes (HAT) was generated with a docking study using seven inhibitors which occur in published crystal structures included in the list of 70 complexes mentioned above, and 19 inhibitors for which the drug–DNA complex crystal structures are unknown. The virtual geometries so generated correlate well with published activities for these 26 inhibitors, justifying our assumption that strong and weak hydrogen bonds are optimized in the active site.

  9. Ring Opening Reactions through C-O Bond Cleavage Uniquely Adding Chemical Functionality to Boron Subphthalocyanine

    Directory of Open Access Journals (Sweden)

    Catherine Bonnier

    2015-10-01

    Full Text Available We are reporting the unexpected reaction between bromo-boron subphthalocyanine (Br-BsubPc and THF, 1,4-dioxane or γ-butyrolactone that results in the ring opening of the solvent and its addition into the BsubPc moiety. Under heating, the endocyclic C-O bond of the solvent is cleaved and the corresponding bromoalkoxy-BsubPc derivative is obtained. These novel alkoxy-BsubPc derivatives have remaining alkyl-bromides suitable for further functionalization. The alkoxy-BsubPcs maintain the characteristic strongly absorption in visible spectrum and their fluorescence quantum yields.

  10. Research on the Interaction of Hydrogen-Bond Acidic Polymer Sensitive Sensor Materials with Chemical Warfare Agents Simulants by Inverse Gas Chromatography

    Directory of Open Access Journals (Sweden)

    Liu Yang

    2015-06-01

    Full Text Available Hydrogen-bond acidic polymers are important high affinity materials sensitive to organophosphates in the chemical warfare agent sensor detection process. Interactions between the sensor sensitive materials and chemical warfare agent simulants were studied by inverse gas chromatography. Hydrogen bonded acidic polymers, i.e., BSP3, were prepared for micro-packed columns to examine the interaction. DMMP (a nerve gas simulant and 2-CEES (a blister agent simulant were used as probes. Chemical and physical parameters such as heats of absorption and Henry constants of the polymers to DMMP and 2-CEES were determined by inverse gas chromatography. Details concerning absorption performance are also discussed in this paper.

  11. Research on the interaction of hydrogen-bond acidic polymer sensitive sensor materials with chemical warfare agents simulants by inverse gas chromatography.

    Science.gov (United States)

    Yang, Liu; Han, Qiang; Cao, Shuya; Huang, Feng; Qin, Molin; Guo, Chenghai; Ding, Mingyu

    2015-06-02

    Hydrogen-bond acidic polymers are important high affinity materials sensitive to organophosphates in the chemical warfare agent sensor detection process. Interactions between the sensor sensitive materials and chemical warfare agent simulants were studied by inverse gas chromatography. Hydrogen bonded acidic polymers, i.e., BSP3, were prepared for micro-packed columns to examine the interaction. DMMP (a nerve gas simulant) and 2-CEES (a blister agent simulant) were used as probes. Chemical and physical parameters such as heats of absorption and Henry constants of the polymers to DMMP and 2-CEES were determined by inverse gas chromatography. Details concerning absorption performance are also discussed in this paper.

  12. Chemically bonded hybrid systems from functionalized hydroxypyridine molecular bridge: characterization and photophysical properties.

    Science.gov (United States)

    Yan, Bing; Qian, Kai

    2009-01-01

    A series of novel photoactive hybrid materials with organic parts covalently linked to inorganic parts via the acylamino group have been assembled by sol-gel process. The organic parts as molecular bridge derive from alpha-hydroxypyridine (HP) functionalized by 3-(triethoxysilyl)-propyl isocyanate (TESPIC). Finally homogeneous, molecular-based hybrid materials with different microstructure (uniform spherical or clubbed) are obtained, in which no phase separation is observed. This may be ascribed as the different coordination behavior of metal ions (Eu3+ (Tb3+) or Zn2+). Red emission of Eu-HP-Si, green emission of Tb-HP-Si and violet-blue luminescence of Zn-HP-Si hybrids can be achieved within these molecular-based hybrid materials. Besides, both Eu(Tb) and Zn are introduced into the same hybrid systems (Eu(Zn)-HP-Si or Tb(Zn)-HP-Si) through the covalent Si-O bond, whose sphere particle size can be modified. Especially the photoluminescence behavior can be enhanced, suggesting that intramolecular energy transfer takes place between inert Zn2+ and Eu3+ (Tb3+) in the covalently bonded hybrid systems.

  13. Shear bond strength and fracture analysis of human vs. bovine teeth.

    Directory of Open Access Journals (Sweden)

    Stefan Rüttermann

    Full Text Available PURPOSE: To evaluate if bovine enamel and dentin are appropriate substitutes for the respective human hard tooth tissues to test shear bond strength (SBS and fracture analysis. MATERIALS AND METHODS: 80 sound and caries-free human erupted third molars and 80 freshly extracted bovine permanent central incisors (10 specimens for each group were used to investigate enamel and dentine adhesion of one 2-step self-etch (SE and one 3-step etch and rinse (E&R product. To test SBS the buccal or labial areas were ground plane to obtain appropriate enamel or dentine areas. SE and E&R were applied and SBS was measured prior to and after 500 thermocycles between +5 and +55°C. Fracture analysis was performed for all debonded areas. RESULTS: ANOVA revealed significant differences of enamel and dentin SBS prior to and after thermocycling for both of the adhesives. SBS- of E&R-bonded human enamel increased after thermocycling but SE-bonded did not. Bovine enamel SE-bonded showed higher SBS after TC but E&R-bonded had lower SBS. No differences were found for human dentin SE- or E&R-bonded prior to or after thermocycling but bovine dentin SE-bonded increased whereas bovine dentine E&R-bonded decreased. Considering the totalized and adhesive failures, fracture analysis did not show significances between the adhesives or the respective tooth tissues prior to or after thermocycling. CONCLUSION: Although SBS was different on human and bovine teeth, no differences were found for fracture analysis. This indicates that solely conducted SBS on bovine substrate are not sufficient to judge the perfomance of adhesives, thus bovine teeth are questionnable as a substrate for shear bond testing.

  14. System Response Analysis and Model Order Reduction, Using Conventional Method, Bond Graph Technique and Genetic Programming

    Directory of Open Access Journals (Sweden)

    Lubna Moin

    2009-04-01

    Full Text Available This research paper basically explores and compares the different modeling and analysis techniques and than it also explores the model order reduction approach and significance. The traditional modeling and simulation techniques for dynamic systems are generally adequate for single-domain systems only, but the Bond Graph technique provides new strategies for reliable solutions of multi-domain system. They are also used for analyzing linear and non linear dynamic production system, artificial intelligence, image processing, robotics and industrial automation. This paper describes a unique technique of generating the Genetic design from the tree structured transfer function obtained from Bond Graph. This research work combines bond graphs for model representation with Genetic programming for exploring different ideas on design space tree structured transfer function result from replacing typical bond graph element with their impedance equivalent specifying impedance lows for Bond Graph multiport. This tree structured form thus obtained from Bond Graph is applied for generating the Genetic Tree. Application studies will identify key issues and importance for advancing this approach towards becoming on effective and efficient design tool for synthesizing design for Electrical system. In the first phase, the system is modeled using Bond Graph technique. Its system response and transfer function with conventional and Bond Graph method is analyzed and then a approach towards model order reduction is observed. The suggested algorithm and other known modern model order reduction techniques are applied to a 11th order high pass filter [1], with different approach. The model order reduction technique developed in this paper has least reduction errors and secondly the final model retains structural information. The system response and the stability analysis of the system transfer function taken by conventional and by Bond Graph method is compared and

  15. System Response Analysis and Model Order Reduction, Using Conventional Method, Bond Graph Technique and Genetic Programming

    Directory of Open Access Journals (Sweden)

    Shahid Ali

    2009-04-01

    Full Text Available This research paper basically explores and compares the different modeling and analysis techniques and than it also explores the model order reduction approach and significance. The traditional modeling and simulation techniques for dynamic systems are generally adequate for single-domain systems only, but the Bond Graph technique provides new strategies for reliable solutions of multi-domain system. They are also used for analyzing linear and non linear dynamic production system, artificial intelligence, image processing, robotics and industrial automation. This paper describes a unique technique of generating the Genetic design from the tree structured transfer function obtained from Bond Graph. This research work combines bond graphs for model representation with Genetic programming for exploring different ideas on design space tree structured transfer function result from replacing typical bond graph element with their impedance equivalent specifying impedance lows for Bond Graph multiport. This tree structured form thus obtained from Bond Graph is applied for generating the Genetic Tree. Application studies will identify key issues and importance for advancing this approach towards becoming on effective and efficient design tool for synthesizing design for Electrical system. In the first phase, the system is modeled using Bond Graph technique. Its system response and transfer function with conventional and Bond Graph method is analyzed and then a approach towards model order reduction is observed. The suggested algorithm and other known modern model order reduction techniques are applied to a 11th order high pass filter [1], with different approach. The model order reduction technique developed in this paper has least reduction errors and secondly the final model retains structural information. The system response and the stability analysis of the system transfer function taken by conventional and by Bond Graph method is compared and

  16. Experimental Analysis of Bisbenzocyclobutene Bonded Capacitive Micromachined Ultrasonic Transducers

    OpenAIRE

    2016-01-01

    Experimental measurement results of a 1.75 mm × 1.75 mm footprint area Capacitive Micromachined Ultrasonic Transducer (CMUT) planar array fabricated using a bisbenzocyclobutene (BCB)-based adhesive wafer bonding technique has been presented. The array consists of 40 × 40 square diaphragm CMUT cells with a cavity thickness of 900 nm and supported by 10 µm wide dielectric spacers patterned on a thin layer of BCB. A 150 µm wide one µm thick gold strip has been used as the contact pad for gold wi...

  17. Bond population analysis on combination of favorable growth unit of Al(OH)3 crystals

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The quantum chemical calculation on four representative combination modes of the favorable growth unit Al6(OH)18(H2O)6of Al(OH)3 crystals and the single unit were calculated. On the base of the prior investigation, and from the point of view of bond population and net atomic charge, the relationships between the combination mode of the favorable growth unit and the relative intensity of chemical bond of the systems were discussed. The quantum chemistry calculations were performed at RB3LYP/6-31G and RHF/6-31G levels by ab initio and DFT methods respectively. From the point of view of bond population, it can be preliminarily presumed that the interatomic bond force of the system with side-face-combination-B mode is weaker to a certain extent. From the point of view of the net charge, when the combination mode is obverse-face-combination-D, the interatomic bond force will be enhanced.

  18. “Evaluation of shear bond strength of a composite resin to white mineral trioxide aggregate with three different bonding systems”-An in vitro analysis

    Science.gov (United States)

    Patil, Anand C.

    2016-01-01

    Background Mineral trioxide aggregate (MTA) is a biomaterial that has been investigated for endodontic applications. With the increased use of MTA in pulp capping, pulpotomy, perforation repair, apexification and obturation, the material that would be placed over MTA as a final restoration is an important matter. As composite resins are one of the most widely used final restorative materials, this study was conducted to evaluate the shear bond strength of a composite resin to white mineral trioxide aggregate (WMTA) using three different bonding systems namely the two-step etch and rinse adhesive, the self-etching primer and the All-in-one system. Material and Methods Forty five specimens of white MTA (Angelus) were prepared and randomly divided into three groups of 15 specimens each depending on the bonding systems used respectively. In Group A, a Two-step etch and rinse adhesive or ‘total-etch adhesive’, Adper Single Bond 2 (3M/ESPE) and Filtek Z350 (3M ESPE, St Paul, MN) were placed over WMTA. In group B, a Two-step self-etching primer system, Clearfil SE Bond (Kuraray, Medical Inc) and Filtek Z350 were used. In Group C, an All-in-one system, G Bond (GC corporation, Tokyo, Japan) and Filtek Z350 were used. The shear bond strength was measured for all the specimens. The data obtained was subjected to One way Analysis of Variance (ANOVA) and Scheffe’s post hoc test. Results The results suggested that the Two-step etch and rinse adhesive when used to bond a composite resin to white MTA gave better bond strength values and the All-in-one exhibited the least bond strength values. Conclusions The placement of composite used with a Two-step etch and rinse adhesive over WMTA as a final restoration may be appropriate. Key words:Composite resins, dentin bonding agents, mineral trioxide aggregate, shear bond strength. PMID:27398177

  19. Effects of Jigsaw Cooperative Learning and Animation Techniques on Students' Understanding of Chemical Bonding and Their Conceptions of the Particulate Nature of Matter

    Science.gov (United States)

    Karacop, Ataman; Doymus, Kemal

    2013-04-01

    The aim of this study was to determine the effect of jigsaw cooperative learning and computer animation techniques on academic achievements of first year university students attending classes in which the unit of chemical bonding is taught within the general chemistry course and these students' learning of the particulate nature of matter of this unit. The sample of this study consisted of 115 first-year science education students who attended the classes in which the unit of chemical bonding was taught in a university faculty of education during the 2009-2010 academic year. The data collection instruments used were the Test of Scientific Reasoning, the Purdue Spatial Visualization Test: Rotations, the Chemical Bonding Academic Achievement Test, and the Particulate Nature of Matter Test in Chemical Bonding (CbPNMT). The study was carried out in three different groups. One of the groups was randomly assigned to the jigsaw group, the second was assigned to the animation group (AG), and the third was assigned to the control group, in which the traditional teaching method was applied. The data obtained with the instruments were evaluated using descriptive statistics, one-way ANOVA, and MANCOVA. The results indicate that the teaching of chemical bonding via the animation and jigsaw techniques was more effective than the traditional teaching method in increasing academic achievement. In addition, according to findings from the CbPNMT, the students from the AG were more successful in terms of correct understanding of the particulate nature of matter.

  20. Bond Portfolio Analysis with Parallel Collections in Scala

    Directory of Open Access Journals (Sweden)

    Mark Logan

    2012-07-01

    Full Text Available In this paper, we report the results of new experiments that test the performance of Scala parallel collections to find the fair value of riskless bond portfolios using commodity multicore platforms. We developed four algorithms, each of two kinds in Scala and ran them for one to 1024 portfolios, each with a variable number of bonds with daily to yearly cash flows and 1 year to 30 year. We ran each algorithm 11 times at each workload size on three different multicore platforms. We systematically observed the differences and tested them for statistical significance. All the parallel algorithms exhibited super-linear speedup and super-efficiency consistent with maximum performance expectations for scientific computing workloads. The first-order effort or “naïve” parallel algorithms were easiest to write since they followed directly from the serial algorithms. We found we could improve upon the naïve approach with second-order efforts, namely, fine-grain parallel algorithms, which showed the overall best, statistically significant performance, followed by coarse-grain algorithms. To our knowledge these results have not been presented elsewhere.

  1. Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

    Science.gov (United States)

    González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

    2014-08-07

    In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

  2. Using Concept Mapping to Uncover Students' Knowledge Structures of Chemical Bonding Concepts

    Science.gov (United States)

    Burrows, Nikita L.; Mooring, Suazette Reid

    2015-01-01

    General chemistry is the first undergraduate course in which students further develop their understanding of fundamental chemical concepts. Many of these fundamental topics highlight the numerous conceptual interconnections present in chemistry. However, many students possess incoherent knowledge structures regarding these topics. Therefore,…

  3. Catalytic C-C Bond Cleavage for the Production of Chemicals from Lignin

    NARCIS (Netherlands)

    Jastrzebski, R.

    2016-01-01

    Lignin is a major component of lignocellulosic biomass and could be an important renewable feedstock in industry for the production of (aromatic) bulk and fine chemicals. To this end, the development of new catalytic processes is required; both to depolymerise the biopolymer into small aromatic buil

  4. Catalytic C-C Bond Cleavage for the Production of Chemicals from Lignin

    NARCIS (Netherlands)

    Jastrzebski, R.|info:eu-repo/dai/nl/338017747

    2016-01-01

    Lignin is a major component of lignocellulosic biomass and could be an important renewable feedstock in industry for the production of (aromatic) bulk and fine chemicals. To this end, the development of new catalytic processes is required; both to depolymerise the biopolymer into small aromatic

  5. The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

    Science.gov (United States)

    Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

    2011-01-07

    Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully

  6. The Synthesis, Structures, and Chemical Properties of Macrocyclic Ligands Covalently Bonded into Layered Arrays

    Energy Technology Data Exchange (ETDEWEB)

    Clearfield, Abraham [Texas A & M Univ., College Station, TX (United States)

    2014-11-01

    In this part of the proposal we have concentrated on the surface functionalization of α-zirconium phosphate of composition Zr(O3POH)2•H2O. It is a layered compound that can be prepared as particles as small as 30 nm to single crystals in the range of cm. This compound is an ion exchanger with a capacity of 6.64 meq per gram. It finds use as a catalyst, proton conductor, sensors, biosensors, in kidney dialysis and drug delivery. By functionalizing the surface additional uses are contemplated as will be described. The layers consist of the metal, with 4+ charge, that is positioned slightly above and below the mean layer plane and bridged by three of the four phosphate oxygens. The remaining POH groups point into the interlayer space creating double rows of POH groups but single arrays on the surface layers. The surface groups are reactive and we were able to bond silanes, isocyanates, epoxides, acrylates ` and phosphates to the surface POH groups. The layers are easily exfoliated or filled with ions by ion exchange or molecules by intercalation reactions. Highlights of our work include, in addition to direct functionalization of the surfaces, replacement of the protons on the surface with ions of different charge. This allows us to bond phosphates, biophosphates, phosphonic acids and alcohols to the surface. By variation of the ion charge of the ions that replace the surface protons, different surface structures are obtained. We have already shown that polymer fillers, catalysts and Janus particles may be prepared. The combination of surface functionalization with the ability to insert molecules and ions between the layers allow for a rich development of numerous useful other applications as well as nano-surface chemistry.

  7. The effect of working pressure on the chemical bond structure and hydrophobic properties of PET surface treated by N ion beams bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Ding Wanyu, E-mail: dwysd_2000@163.com [Engineering Research Center of Optoelectronic Materials and Devices Education Department of Liaoning Province, Dalian, 116028 (China) and School of Materials Science and Engineering, Dalian Jiaotong University, Dalian, 116028 (China) and Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Dalian University of Technology, Ministry of Education, Dalian, 116024 (China); Ju Dongying, E-mail: dyju@sit.ac.jp [Department of Material Science and Engineering, Saitama Institute of Technology Fukaya, 369-0293 (Japan); Chai Weiping, E-mail: wpchai@djtu.edu.cn [Engineering Research Center of Optoelectronic Materials and Devices Education Department of Liaoning Province, Dalian, 116028 (China); School of Materials Science and Engineering, Dalian Jiaotong University, Dalian, 116028 (China)

    2010-09-01

    Polyethylene terephthalate (PET) surface was bombarded by N ion beams at room temperature. Varying the working pressure of the ion beams, PET surfaces with different composition and properties were obtained. Characterization by X-ray photoelectron spectrometry showed that only on film surface, ester bonds, especially C-O bonds, were broken and N element chemical bonded with C. The influence depth was less than 5 nm because of the lower ion energy (about 10{sup 3} eV). Contact angle results revealed that with increasing the working pressure of ion beams, the contact angle of PET surface to pure water increased from 51 deg. to 130 deg.. With these results, one conclusion could be deduced that the hydrophilic and hydrophobic properties of PET surface could be influenced by N atom chemical bond with C, which in turn is controlled by the working pressure of N ion beams.

  8. Reduction reaction analysis of nanoparticle copper oxide for copper direct bonding using formic acid

    Science.gov (United States)

    Fujino, Masahisa; Akaike, Masatake; Matsuoka, Naoya; Suga, Tadatomo

    2017-04-01

    Copper direct bonding is required for electronics devices, especially power devices, and copper direct bonding using formic acid is expected to lower the bonding temperature. In this research, we analyzed the reduction reaction of copper oxide using formic acid with a Pt catalyst by electron spin resonance analysis and thermal gravimetry analysis. It was found that formic acid was decomposed and radicals were generated under 200 °C. The amount of radicals generated was increased by adding the Pt catalyst. Because of these radicals, both copper(I) oxide and copper(II) oxide start to be decomposed below 200 °C, and the reduction of copper oxide is accelerated by reactants such as H2 and CO from the decomposition of formic acid above 200 °C. The Pt catalyst also accelerates the reaction of copper oxide reduction. Herewith, it is considered that the copper surface can be controlled more precisely by using formic acid to induce direct bonding.

  9. Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

    Science.gov (United States)

    Wang, XinJie; Wu, YanQing; Huang, FengLei

    2017-01-05

    A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials.

  10. Electronic parameters of Sr2M2O7 (M = V, Nb, Ta) and Sr-O chemical bonding

    DEFF Research Database (Denmark)

    Atuchin, Victor V.; Grivel, Jean-Claude; Zhang, Zhaoming

    2010-01-01

    on the formation of the Sr-O bonds. The chemical bonding effects were considered on the basis of our XPS results for Sr2Nb2O7 and Sr2Ta2O7 and the previously published structural and XPS data for other Sr-oxide compounds. A new empirical relationship between Δ(O-Sr) and L(Sr-O) was obtained. Possible applications...

  11. Experimental Analysis of Bisbenzocyclobutene Bonded Capacitive Micromachined Ultrasonic Transducers

    Science.gov (United States)

    Manwar, Rayyan; Chowdhury, Sazzadur

    2016-01-01

    Experimental measurement results of a 1.75 mm × 1.75 mm footprint area Capacitive Micromachined Ultrasonic Transducer (CMUT) planar array fabricated using a bisbenzocyclobutene (BCB)-based adhesive wafer bonding technique has been presented. The array consists of 40 × 40 square diaphragm CMUT cells with a cavity thickness of 900 nm and supported by 10 µm wide dielectric spacers patterned on a thin layer of BCB. A 150 µm wide one µm thick gold strip has been used as the contact pad for gold wire bonding. The measured resonant frequency of 19.3 MHz using a Polytec™ laser Doppler vibrometer (Polytec™ MSA-500) is in excellent agreement with the 3-D FEA simulation result using IntelliSuite™. An Agilent ENA5061B vector network analyzer (VNA) has been used for impedance measurement and the resonance and anti-resonance values from the imaginary impedance curve were used to determine the electromechanical coupling co-efficient. The measured coupling coefficient of 0.294 at 20 V DC bias exhibits 40% higher transduction efficiency as compared to a measured value published elsewhere for a silicon nitride based CMUT. A white light interferometry method was used to measure the diaphragm deflection profiles at different DC bias. The diaphragm center velocity was measured for different sub-resonant frequencies using a Polytec™ laser Doppler vibrometer that confirms vibration of the diaphragm at different excitation frequencies and bias voltages. Transmit and receive operations of CMUT cells were characterized using a pitch-catch method and a −6 dB fractional bandwidth of 23% was extracted from the received signal in frequency domain. From the measurement, it appears that BCB-based CMUTs offer superior transduction efficiency as compared to silicon nitride or silicon dioxide insulator-based CMUTs, and provide a very uniform deflection profile thus making them a suitable candidate to fabricate highly energy efficient CMUTs. PMID:27347955

  12. Determining hydrogen-bond interactions in spider silk with 1H-13C HETCOR fast MAS solid-state NMR and DFT proton chemical shift calculations.

    Science.gov (United States)

    Holland, Gregory P; Mou, Qiushi; Yarger, Jeffery L

    2013-07-28

    Two-dimensional (2D) (1)H-(13)C heteronuclear correlation (HETCOR) solid-state NMR spectra collected with fast magic angle spinning (MAS) are used in conjunction with density functional theory (DFT) proton chemical shift calculations to determine the hydrogen-bonding strength for ordered β-sheet and disordered 310-helical structures in spider dragline silk. The hydrogen-bond strength is determined to be identical for both structures in spider silk with a 1.83-1.84 Å NH···OC hydrogen-bond distance.

  13. Magnetovolume and chemical bonding effects of Sn atom in the γ'-(Fe1-xSnx)4N compounds

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Combining x-ray diffraction and high pressure Mossbauer spectroscopy,the structure and the hyperfine parameters of Sn substituted for Fe in γ'-Fe4N were in-vestigated. The results of x-ray diffraction indicate that single phase γ'-(Fel-xSnx)4Ncompounds can be synthesized in the composition range 0≤ x ≤ 0.3, and the latticeparameter can be well fitted with two linear formulas α0(x) = 3.795 + 0.019 × x (0.0≤x ≤0.10) and α0(x) = 3.795+ 0.228 × (x- 0.1)(0.10 ≤ x ≤0.30) for different contentof Sn. Using high pressure Mossbauer spectra, the influences of the magnetovolunceffect and the chemical bonding effect of Sn atom on the hyperfine magnetic field andthe isomer shift were first distinguished. It is found that the magnetovolume and thechemical bonding have different influences on the properties of γ'-(Fe1-xSnx)4N, andthe latter plays a more important role.

  14. Mechanical control of the plasmon coupling with Au nanoparticle arrays fixed on the elastomeric film via chemical bond

    Science.gov (United States)

    Bedogni, Elena; Kaneko, Satoshi; Fujii, Shintaro; Kiguchi, Manabu

    2017-03-01

    We have fabricated Au nanoparticle arrays on the flexible poly(dimethylsiloxane) (PDMS) film. The nanoparticles were bound to the film via a covalent bond by a ligand exchange reaction. Thanks to the strong chemical bonding, highly stable and uniformly dispersed Au nanoparticle arrays were fixed on the PDMS film. The Au nanoparticle arrays were characterized by the UV–vis, scanning electron microscope (SEM) and surface enhanced Raman scattering (SERS). The UV–vis and SEM measurements showed the uniformity of the surface-dispersed Au nanoparticles, and SERS measurement confirmed the chemistry of the PDMS film. Reflecting the high stability and the uniformity of the Au nanoparticle arrays, the plasmon wavelength of the Au nanoparticles reversely changed with modulation of the interparticle distance, which was induced by the stretching of the PDMS film. The plasmon wavelength linearly decreased from 664 to 591 nm by stretching of 60%. The plasmon wavelength shift can be explained by the change in the strength of the plasmon coupling which is mechanically controlled by the mechanical strain.

  15. A Comparative Evaluation of Effect of Different Chemical Solvents on the Shear Bond Strength of Glass Fiber reinforced Post to Core Material.

    Science.gov (United States)

    Sharma, Ashish; Samadi, Firoza; Jaiswal, Jn; Saha, Sonali

    2014-01-01

    To compare the effect of different chemical solvents on glass fiber reinforced posts and to study the effect of these solvents on the shear bond strength of glass fiber reinforced post to core material. This study was conducted to evaluate the effect of three chemical solvents, i.e. silane coupling agent, 6% H2O2 and 37% phosphoric acid on the shear bond strength of glass fiber post to a composite resin restorative material. The changes in post surface characteristics after different treatments were also observed, using scanning electron microscopy (SEM) and shear bond strength was analyzed using universal testing machine (UTM). Surface treatment with hydrogen peroxide had greatest impact on the post surface followed by 37% phosphoric acid and silane. On evaluation of the shear bond strength, 6% H2O2 exhibited the maximum shear bond strength followed in descending order by 37% phosphoric acid and silane respectively. The surface treatment of glass fiber post enhances the adhesion between the post and composite resin which is used as core material. Failure of a fiber post and composite resin core often occurs at the junction between the two materials. This failure process requires better characterization. How to cite this article: Sharma A, Samadi F, Jaiswal JN, Saha S. A Comparative Evaluation of Effect of Different Chemical Solvents on the Shear Bond Strength of Glass Fiber Reinforced Post to Core Material. Int J Clin Pediatr Dent 2014;7(3):192-196.

  16. The Effect of Various Types of Mechanical and Chemical Preconditioning on the Shear Bond Strength of Orthodontic Brackets on Zirconia Restorations

    Directory of Open Access Journals (Sweden)

    Jihun Kim

    2017-01-01

    Full Text Available The purpose of this study was to investigate the combined effect of mechanical and chemical treatments on the shear bond strength (SBS of metal orthodontic brackets on zirconia restoration. The zirconia specimens were randomly divided into 12 groups (n=10 according to three factors: AL (Al2O3 and CO (CoJet™ by sandblasting material; SIL (silane, ZPP (Zirconia Prime Plus, and SBU (Single Bond Universal by primer; and N (not thermocycled and T (thermocycled. The specimens were evaluated for shear bond strength, and the fractured surfaces were observed using a stereomicroscope. Scanning electron microscopy images were also obtained. CO-SBU combination had the highest bond strength after thermocycling (26.2 MPa. CO-SIL showed significantly higher SBS than AL-SIL (p0.05. Modified Adhesive Remnant Index (ARI scoring and SEM figures were consistent with the results of the surface treatments. In conclusion, CO-SBU, which combines the effect of increased surface area and chemical bonding with both 10-MDP and silane, showed the highest SBS. Sandblasting with either material improved the mechanical bonding by increasing the surface area, and all primers showed clinically acceptable increase of shear bond strength for orthodontic treatment.

  17. A quantum-chemical validation about the formation of hydrogen bonds and secondary interactions in intermolecular heterocyclic systems

    Directory of Open Access Journals (Sweden)

    Boaz Galdino Oliveira

    2009-08-01

    Full Text Available We have performed a detailed theoretical study in order to understand the charge density topology of the C2H4O···C2H2 and C2H4S···C2H2 heterocyclic hydrogen-bonded complexes. Through the calculations derived from Quantum Theory of Atoms in Molecules (QTAIM, it was observed the formation of hydrogen bonds and secondary interactions. Such analysis was performed through the determination of optimized geometries at B3LYP/6-31G(d,p level of theory, by which is that QTAIM topological operators were computed, such as the electronic density ρ(r, Laplacian Ñ2ρ(r, and ellipticity ε. The examination of the hydrogen bonds has been performed through the measurement of ρ(r, Ñ2ρ(r and ε between (O···H—C and (S···H—C, whereas the secondary interaction between axial hydrogen atoms Hα and carbon of acetylene. In this insight, it was verified the existence of secondary interaction only in C2H4S···C2H2 complex because its structure is propitious to form multiple interactions.

  18. Robust C–C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas

    Directory of Open Access Journals (Sweden)

    Damien Thirion

    2016-10-01

    Full Text Available Effective carbon dioxide (CO2 capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon–carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile–aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m2/g and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C.

  19. Electronic structure, chemical bond and thermal stability of hydrogen absorber Li2MgN2H2

    Institute of Scientific and Technical Information of China (English)

    WANG Qiang; CHEN YunGui; WU ChaoLing; TAO MingDa; GAI JingGang

    2009-01-01

    The lowest total energy crystal structure of Li2MgN2H2 was identified by the first principle calculation with RPBE exchange-correlation function. Furthermore, the fine structure parameters of this crystal structure were calculated with PBE and PW91 exchange-correlation function. In a further step, the density of states, electron density, charge density difference on (0 0 1) plane and heat of formation of Li2MgN2H2 hydrogenation were computed with PW91 exchange-correlation function. Consequently, the electronic structures and chemical bonds in this compound were analyzed and discussed, and then the thermodynamic character of Li2MgN2H2 for hydrogen storage was evacuated.

  20. Evidence for porphyrins bound, via ester bonds, to the Messel oil shale kerogen by selective chemical degradation experiments

    Science.gov (United States)

    Huseby, B.; Ocampo, R.

    1997-09-01

    High amounts of nickel mono- and di-acid porphyrins were released from Messel oil shale kerogen (Eocene, Germany) by selective chemical degradation (acid and base hydrolysis). The released porphyrin fractions were quantified (UV-vis) and their constituents isolated and characterized at the molecular level (UV-vis, MS, NMR). The mono-acid porphyrin fraction released contained four compounds of similar abundance which arise from an obvious chlorophyll or bacteriochlorophyll precursor. The di-acid porphyrin fraction was, however, dominated by far by one compound, mesoporphyrin IX, which must have originated from heme-like precursors (heme, cytochromes, etc.). These results show unambigously that the released mono- and di-acid porphyrins were linked to the macromolecular kerogen network via ester bonds and suggest that precursor heme-like pigments could be selectively and/or more readily incorporated into the macromolecular kerogen network than precursor chlorophylls and bacteriochlorophylls.

  1. Sandwiched Thin-Film Anode of Chemically Bonded Black Phosphorus/Graphene Hybrid for Lithium-Ion Battery.

    Science.gov (United States)

    Liu, Hanwen; Zou, Yuqin; Tao, Li; Ma, Zhaoling; Liu, Dongdong; Zhou, Peng; Liu, Hongbo; Wang, Shuangyin

    2017-09-01

    A facile vacuum filtration method is applied for the first time to construct sandwich-structure anode. Two layers of graphene stacks sandwich a composite of black phosphorus (BP), which not only protect BP from quickly degenerating but also serve as current collector instead of copper foil. The BP composite, reduced graphene oxide coated on BP via chemical bonding, is simply synthesized by solvothermal reaction at 140 °C. The sandwiched film anode used for lithium-ion battery exhibits reversible capacities of 1401 mAh g(-1) during the 200th cycle at current density of 100 mA g(-1) indicating superior cycle performance. Besides, this facile vacuum filtration method may also be available for other anode material with well dispersion in N-methyl pyrrolidone (NMP). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Robust C-C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas.

    Science.gov (United States)

    Thirion, Damien; Lee, Joo S; Özdemir, Ercan; Yavuz, Cafer T

    2016-01-01

    Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon-carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile-aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m(2)/g) and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C.

  3. Robust C–C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas

    Science.gov (United States)

    Thirion, Damien; Lee, Joo S; Özdemir, Ercan

    2016-01-01

    Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon–carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile–aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m2/g) and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C. PMID:28144294

  4. Effects of lithium doping on microstructure, electrical properties, and chemical bonds of sol-gel derived NKN thin films

    Science.gov (United States)

    Lin, Chun-Cheng; Chen, Chan-Ching; Weng, Chung-Ming; Chu, Sheng-Yuan; Hong, Cheng-Shong; Tsai, Cheng-Che

    2015-02-01

    Highly (100/110) oriented lead-free Lix(Na0.5K0.5)1-xNbO3 (LNKN, x = 0, 0.02, 0.04, and 0.06) thin films are fabricated on Pt/Ti/SiO2/Si substrates via a sol-gel processing method. The lithium (Li) dopants modify the microstructure and chemical bonds of the LNKN films, and therefore improve their electrical properties. The optimal values of the remnant polarization (Pr = 14.3 μC/cm2), piezoelectric coefficient (d33 = 48.1 pm/V), and leakage current (Poole-Frenkel emission effect under high electric fields.

  5. VALIDATION GUIDELINES FOR LABORATORIES PERFORMING FORENSIC ANALYSIS OF CHEMICAL TERRORISM

    Science.gov (United States)

    The Scientific Working Group on Forensic Analysis of Chemical Terrorism (SWGFACT) has developed the following guidelines for laboratories engaged in the forensic analysis of chemical evidence associated with terrorism. This document provides a baseline framework and guidance for...

  6. VALIDATION GUIDELINES FOR LABORATORIES PERFORMING FORENSIC ANALYSIS OF CHEMICAL TERRORISM

    Science.gov (United States)

    The Scientific Working Group on Forensic Analysis of Chemical Terrorism (SWGFACT) has developed the following guidelines for laboratories engaged in the forensic analysis of chemical evidence associated with terrorism. This document provides a baseline framework and guidance for...

  7. Investigation of finite-size effects in chemical bonding of AuPd nanoalloys

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Beien [Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Oğuz, Ismail Can; Guesmi, Hazar, E-mail: hazar.guesmi@enscm.fr [CNRS-ICG UMR 5253, équipe MACS, 8 rue de l’Ecole Normale, 34296 Montpellier (France)

    2015-10-14

    In this paper, the size-dependent changes in energetic, vibrational, and electronic properties of C–O gas molecule interacting with surface Pd atom of a variety of AuPd nanoalloy structures are investigated by means of first principles calculations. The variation in C–O adsorption energies, C–O vibration frequencies (ν{sub C−O}), and Pd d-bond centers (ε{sub d}) on a series of non-supported Au{sub n−1}–Pd{sub 1} nanoparticles (with n varying from 13 to 147) and on two semi-finite surfaces are inspected with cluster size. We demonstrate for the first time that, with small AuPd bimetallic three-dimensional clusters as TOh{sub 38}, one can reach cluster size convergence even for such a sensitive observable as the adsorption energy on a metal surface. Indeed, the results show that the adsorbate-induced perturbation is extremely local and it only concerns the isolated Pd interacting with the reactive gas molecule. Except for 13 atom clusters, in which molecular behaviour is predominant, no finite-size effects are observed for surface Pd atom substituted in AuPd free nanoclusters above 38 atoms.

  8. Crystal structure and chemical bonding of the high-temperature phase of AgN3.

    Science.gov (United States)

    Schmidt, Carsten L; Dinnebier, Robert; Wedig, Ulrich; Jansen, Martin

    2007-02-05

    The crystal structure of silver azide (AgN3) in its high-temperature (HT) modification was determined from X-ray powder diffraction data, recorded at T = 170 degrees C and was further refined by the Rietveld method. The structure is monoclinic (P21/c (No. 14), a = 6.0756(2) A, b = 6.1663(2) A, c = 6.5729(2) A, beta = 114.19(0) degrees, V = 224.62(14) A3, Z = 4) and consists of two-dimensional Ag and N containing layers in which the silver atoms are coordinated by four nitrogen atoms exhibiting a distorted square coordination environment. These sheets are linked together by weaker perpendicular Ag-N contacts, thus forming a 4 + 2 coordination geometry around the silver atoms. The phase transition has been characterized by DTA, DSC, and measurement of the density, as well as of the ionic conductivity. Both, the room-temperature and the HT phase are electrically insulating. This fact is getting support by DFT band structure calculations within the generalized gradient approximation, using the PBE functional. On the basis of the DFT band structure, the bonding characteristics of both phases are essentially the same. Finally, the implication of the existence of a low-symmetry HT-phase in a crystalline explosive concerning decomposition mechanisms is discussed.

  9. Crystal Structure and Chemical Bonding of the High-Temperature Phase of AgN3

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt,C.; Dinnebier, R.; Wedig, U.; Jansen, M.

    2007-01-01

    The crystal structure of silver azide (AgN{sub 3}) in its high-temperature (HT) modification was determined from X-ray powder diffraction data, recorded at T = 170 {sup o}C and was further refined by the Rietveld method. The structure is monoclinic (P2{sub 1}lc (No. 14), a = 6.0756(2) {angstrom}, b = 6.1663(2) {angstrom}, c = 6.5729(2) {angstrom}, {beta} = 114.19(0){sup o}, V = 224.62(14) {angstrom}{sup 3}, Z = 4) and consists of two-dimensional Ag and N containing layers in which the silver atoms are coordinated by four nitrogen atoms exhibiting a distorted square coordination environment. These sheets are linked together by weaker perpendicular Ag-N contacts, thus forming a 4 + 2 coordination geometry around the silver atoms. The phase transition has been characterized by DTA, DSC, and measurement of the density, as well as of the ionic conductivity. Both, the room-temperature and the HT phase are electrically insulating. This fact is getting support by DFT band structure calculations within the generalized gradient approximation, using the PBE functional. On the basis of the DFT band structure, the bonding characteristics of both phases are essentially the same. Finally, the implication of the existence of a low-symmetry HT-phase in a crystalline explosive concerning decomposition mechanisms is discussed.

  10. Toxic hazard and chemical analysis of leachates from furfurylated wood

    NARCIS (Netherlands)

    Pilgard, A.; Treu, A.; Zeeland, van A.N.T.; Gosselink, R.J.A.; Westin, M.

    2010-01-01

    The furfurylation process is an extensively investigated wood modification process. Furfuryl alcohol molecules penetrate into the wood cell wall and polymerize in situ. This results in a permanent swelling of the wood cell walls. It is unclear whether or not chemical bonds exist between the furfuryl

  11. How do halogen bonds (S-O⋯I, N-O⋯I and C-O⋯I) and halogen-halogen contacts (C-I⋯I-C, C-F⋯F-C) subsist in crystal structures? A quantum chemical insight.

    Science.gov (United States)

    Pandiyan, B Vijaya; Deepa, P; Kolandaivel, P

    2017-01-01

    Thirteen X-ray crystal structures containing various non-covalent interactions such as halogen bonds, halogen-halogen contacts and hydrogen bonds (I⋯N, I⋯F, I⋯I, F⋯F, I⋯H and F⋯H) were considered and investigated using the DFT-D3 method (B97D/def2-QZVP). The interaction energies were calculated at MO62X/def2-QZVP and MP2/aug-cc-pvDZ level of theories. The higher interaction and dispersion energies (2nd crystal) of -9.58 kcal mol(-1) and -7.10 kcal mol(-1) observed for 1,4-di-iodotetrafluorobenzene bis [bis (2-phenylethyl) sulfoxide] structure indicates the most stable geometrical arrangement in the crystal packing. The electrostatic potential values calculated for all crystal structures have a positive σ-hole, which aids understanding of the nature of σ-hole bonds. The significance of the existence of halogen bonds in crystal packing environments was authenticated by replacing iodine atoms by bromine and chlorine atoms. Nucleus independent chemical shift analysis reported on the resonance contribution to the interaction energies of halogen bonds and halogen-halogen contacts. Hirshfeld surface analysis and topological analysis (atoms in molecules) were carried out to analyze the occurrence and strength of all non-covalent interactions. These analyses revealed that halogen bond interactions were more dominant than hydrogen bonding interactions in these crystal structures. Graphical Abstract Molecluar structure of 1,4-Di-iodotetrafluorobenzene bis(thianthrene 5-oxide) moelcule and its corresponding molecular electrostatic potential map for the view of σ-hole.

  12. 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.

  13. Finite Size Effects in Chemical Bonding: From Small Clusters to Solids

    DEFF Research Database (Denmark)

    Kleis, Jesper; Greeley, Jeffrey Philip; Romero, N. A.

    2011-01-01

    We address the fundamental question of which size a metallic nano-particle needs to have before its surface chemical properties can be considered to be those of a solid, rather than those of a large molecule. Calculations of adsorption energies for carbon monoxide and oxygen on a series of gold n......). Below that critical size, finite-size effects can be observed, and we show those to be related to variations in the local atomic structure augmented by quantum size effects for the smallest clusters.......We address the fundamental question of which size a metallic nano-particle needs to have before its surface chemical properties can be considered to be those of a solid, rather than those of a large molecule. Calculations of adsorption energies for carbon monoxide and oxygen on a series of gold...... nanoparticles ranging from 13 to 1,415 atoms, or 0.8–3.7 nm, have been made possible by exploiting massively parallel computing on up to 32,768 cores on the Blue Gene/P computer at Argonne National Laboratory. We show that bulk surface properties are obtained for clusters larger than ca. 560 atoms (2.7 nm...

  14. Bond strength of direct and indirect bonded brackets after thermocycling.

    Science.gov (United States)

    Daub, Jacob; Berzins, David W; Linn, Brandon James; Bradley, Thomas Gerard

    2006-03-01

    Thermocycling simulates the temperature dynamics in the oral environment. With direct bonding, thermocycling reduces the bond strength of orthodontic adhesives to tooth structure. The purpose of this study was to evaluate the shear bond strengths (SBS) of one direct and two indirect bonding methods/adhesives after thermocycling. Sixty human premolars were divided into three groups. Teeth in group 1 were bonded directly with Transbond XT. Teeth in group 2 were indirect bonded with Transbond XT/Sondhi Rapid Set, which is chemically cured. Teeth in group 3 were indirect bonded with Enlight LV/Orthosolo and light cured. Each sample was thermocycled between 5 degrees C and 55 degrees C for 500 cycles. Mean SBS in groups 1, 2, and 3 were not statistically significantly different (13.6 +/- 2.9, 12.3 +/- 3.0, and 11.6 +/- 3.2 MPa, respectively; P > .05). However, when these values were compared with the results of a previous study using the same protocol, but without thermocycling, the SBS was reduced significantly (P = .001). Weibull analysis further showed that group 3 had the lowest bonding survival rate at the minimum clinically acceptable bond-strength range. The Adhesive Remnant Index was also determined, and group 2 had a significantly (P bond failures at the resin/enamel interface.

  15. Mission-profile-based stress analysis of bond-wires in SiC power modules

    DEFF Research Database (Denmark)

    Bahman, Amir Sajjad; Iannuzzo, Francesco; Blaabjerg, Frede

    2016-01-01

    This paper proposes a novel mission-profile-based reliability analysis approach for stress on bond wires in Silicon Carbide (SiC) MOSFET power modules using statistics and thermo-mechanical FEM analysis. In the proposed approach, both the operational and environmental thermal stresses are taken i...

  16. Immobilization of TiO2 nanoparticles in polymeric substrates by chemical bonding for multi-cycle photodegradation of organic pollutants.

    Science.gov (United States)

    Lei, Ping; Wang, Feng; Gao, Xiaowei; Ding, Yanfen; Zhang, Shimin; Zhao, Jincai; Liu, Shaoren; Yang, Mingshu

    2012-08-15

    Nano titanium dioxide (TiO(2)) photocatalyst is generally immobilized onto the matrix through the physical absorption, hydrogen bonding or chemical bonding, which is utilized for the application of wastewater treatment. In this research, TiO(2) nanoparticles were immobilized in polyvinyl alcohol (PVA) matrix via solution-casting combined with heat-treatment method. Structure characterization indicated that Ti-O-C chemical bond formed via dehydration reaction between TiO(2) and PVA during the heat treatment process, and TiO(2) nanoparticles had been chemically immobilized in PVA matrix. Photodegradation results of methyl orange (MO) showed that the film with 10 wt% TiO(2) and treated at 140°C for 2h exhibited a remarkable ultraviolet (UV) photocatalytic activity, approximately close to the TiO(2) slurry system. This was mainly attributed to the fixation effect by Ti-O-C chemical bonds, which was indirectly confirmed by the slight loss of TiO(2) photocatalysts even after 25-cycle use. In addition, the good swelling ability of PVA matrix provided the MO molecules with more opportunities to fully contact with TiO(2), thus benefited the photocatalysis. This route to chemically immobilize TiO(2) nanoparticles is simple and cheap to prepare polymer/TiO(2) hybrid materials with high photocatalytic activity for multi-cycle use, which is of significance to the practical application of TiO(2) catalysts.

  17. Rationalizing structure, stability, and chemical bonding of pure and doped clusters, isolated and solvated multiply charged anions, and solid-state materials

    Science.gov (United States)

    Sergeeva, Alina P.

    Chemistry is the study of materials and the changes that materials undergo. One can tune the properties of the known materials and design the novel materials with desired properties knowing what is responsible for the chemical reactivity, structure, and stability of those materials. The unified chemical bonding theory could address all these questions, but we do not have one available yet. The most accepted general theory of chemical bonding was proposed by Lewis in 1916, though Lewis's theory fails to explain the bonding in materials with delocalized electron density such as sub-nano and nanoclusters, as well as aromatic organic and organometallic molecules. The dissertation presents a set of projects that can be considered the steps towards the development of the unified chemical bonding theory by extending the ideas of Lewis. The dissertation also presents the studies of the properties of multiply charged anions, which tend to undergo Coulomb explosion in the isolated state and release the excess energy stored in them. It is shown how the properties of multiply charged anions can be tuned upon changing the chemical identity of the species or interaction with solvent molecules. Our findings led to the discovery of a new long-lived triply charged anionic species, whose metastability was explained by the existence of a repulsive Coulomb barrier. We also proposed two ways to restore high symmetry of compounds by suppression of the pseudo Jahn-Teller effect, which could lead to the design of new materials with the restored symmetry and therefore the novel properties.

  18. Systems analysis of past, present, and future chemical terrorism scenarios.

    Energy Technology Data Exchange (ETDEWEB)

    Hoette, Trisha Marie

    2012-03-01

    Throughout history, as new chemical threats arose, strategies for the defense against chemical attacks have also evolved. As a part of an Early Career Laboratory Directed Research and Development project, a systems analysis of past, present, and future chemical terrorism scenarios was performed to understand how the chemical threats and attack strategies change over time. For the analysis, the difficulty in executing chemical attack was evaluated within a framework of three major scenario elements. First, historical examples of chemical terrorism were examined to determine how the use of chemical threats, versus other weapons, contributed to the successful execution of the attack. Using the same framework, the future of chemical terrorism was assessed with respect to the impact of globalization and new technologies. Finally, the efficacy of the current defenses against contemporary chemical terrorism was considered briefly. The results of this analysis justify the need for continued diligence in chemical defense.

  19. Microtensile bond strength test and failure analysis to assess bonding characteristics of different adhesion approaches to ground versus unground enamel.

    Science.gov (United States)

    Hipólito, Vinicius Di; Alonso, Roberta Caroline Bruschi; Carrilho, Marcela Rocha de Oliveira; Anauate Netto, Camillo; Sinhoreti, Mário Alexandre Coelho; Goes, Mario Fernando de

    2011-01-01

    This study evaluated the bonding characteristics to ground and unground enamel obtained with different strategies. For this purpose, 24 sound third-molars were bisected mesiodistally to obtain tooth halves. A flat enamel area was delimited in the tooth sections, which were randomly distributed into 8 groups (n=6), according to the enamel condition (ground and unground) and adhesive system (Adper Single Bond 2 - SB2; Adper Prompt L-Pop - PLP; Adper Prompt - AD; Clearfil SE Bond - SE). Each system was applied according manufacturers' instructions and a 6-mm-high resin composite "crown" was incrementally built up on bonded surfaces. Hourglass-shaped specimens with 0.8 mm(2) cross-section were produced. Microtensile bond strength (μTBS) was recorded and the failure patterns were classified. Results were analyzed by two-way ANOVA and Tukey's test (α=0.05). There were no statistically significant differences among the μTBS values of SB2, PLP and AD (p>0.05). SE values were significantly lower (p0.05). There was prevalence of cohesive failure within enamel, adhesive system and resin composite for SB2. The self-etch systems produced higher incidence of cohesive failures in the adhesive system. Enamel condition did not determine significant differences on bonding characteristics for the same bonding system. In conclusion, the bonding systems evaluated in this study resulted in specific μTBS and failure patterns due to the particular interaction with enamel.

  20. The Effects of Reasoning, Use of Models, Sex Type, and Their Interactions on Posttest Achievement in Chemical Bonding after Constant Instruction.

    Science.gov (United States)

    Staver, John R.; Halsted, Douglas A.

    1985-01-01

    Determined the effects of reasoning, use of models during testing, and sex type on posttest achievement in chemical bonding under controlled instruction. Indicates that chemistry students' (N=84) reasoning capabilities influenced performance; other variables were not significant. Other conclusions are noted and discussed. (DH)

  1. Survival of bonded lingual retainers with chemical or photo polymerization over a 2-year period: a single-center, randomized controlled clinical trial

    NARCIS (Netherlands)

    Pandis, N.; Fleming, P.S.; Kloukos, D.; Polychronopoulou, A.; Katsaros, C.; Eliades, T.

    2013-01-01

    INTRODUCTION: The objective of this trial was to compare the survival rates of mandibular lingual retainers bonded with either chemically cured or light-cured adhesive after orthodontic treatment. METHODS: Patients having undergone orthodontic treatment at a private orthodontic office were randomly

  2. Thermal-hydraulic modeling and analysis of hydraulic system by pseudo-bond graph

    Institute of Scientific and Technical Information of China (English)

    胡均平; 李科军

    2015-01-01

    To increase the efficiency and reliability of the thermodynamics analysis of the hydraulic system, the method based on pseudo-bond graph is introduced. According to the working mechanism of hydraulic components, they can be separated into two categories: capacitive components and resistive components. Then, the thermal-hydraulic pseudo-bond graphs of capacitive C element and resistance R element were developed, based on the conservation of mass and energy. Subsequently, the connection rule for the pseudo-bond graph elements and the method to construct the complete thermal-hydraulic system model were proposed. On the basis of heat transfer analysis of a typical hydraulic circuit containing a piston pump, the lumped parameter mathematical model of the system was given. The good agreement between the simulation results and experimental data demonstrates the validity of the modeling method.

  3. Structural, quantum chemical, vibrational and thermal studies of a hydrogen bonded zwitterionic co-crystal (nicotinic acid: pyrogallol)

    Science.gov (United States)

    Prabha, E. Arockia Jeya Yasmi; Kumar, S. Suresh; Athimoolam, S.; Sridhar, B.

    2017-02-01

    In the present work, a new co-crystal of nicotinic acid with pyrogallol (NICPY) has been grown in the zwitterionic form and the corresponding structural, vibrational, thermal, solubility and anti-cancer characteristics have been reported. The single crystal X-ray diffraction analysis confirms that the structural molecular packing of the crystal stabilized through N-H⋯O and O-H⋯O hydrogen bond. The stabilization energy of the hydrogen bond motifs were calculated in the solid state. Vibrational spectral studies such as Fourier transform-infrared (FT-IR) and FT-Raman were adopted to understand the zwitterionic co-crystalline nature of the compound, which has been compared with theoretically calculated vibrational frequencies. The thermal stability of the grown co-crystal was analyzed by TG/DTA study. The solubility of the NICPY co-crystal was investigated in water at different temperature and compared with that of the nicotinic acid, which is the parent compound of NICPY co-crystal. The grown crystals were treated with human cervical cancer cell line (HeLa) to analyze the cytotoxicity of NICPY crystals and compared with the parent compound, which shows that NICPY has moderate activity against human cervical cancer cell line.

  4. Study of chemical bonding in the interhalogen complexes based on density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Poleshchuk, O. Kh., E-mail: poleshch@tspu.edu.ru [National Research Tomsk Polytechnic University (Russian Federation); Fateev, A. V.; Yarkova, A. G. [Tomsk State Pedagogical University (Russian Federation); Ermakhanov, M. N.; Saidakhmetov, P. A. [M. Auezov South Kazakhstan State University (Kazakhstan)

    2016-12-15

    The density functional theory analysis was used for a number XYL complexes (XY is a dihalogen molecule and L is a Lewis base), formed between molecules I{sub 2}, ICl, IBr and pyridine. The calculated geometrical parameters, IR spectra and nuclear quadrupole interaction constants of iodine are consistent with the data of microwave spectroscopy and nuclear quadrupole resonance. The good correlation between the experimental and calculated binding energies of the inner electrons of iodine, chlorine and nitrogen atoms were found with the calculation using both Gaussian and Slater functions. The comparison of experimental and calculated changes in the electron density on the atoms upon complex formation suggested the choice of scheme for calculating the effective charge on the atoms, which allow us to interpret the experimental spectra. It is shown that the use of both calculated schemes allows us to predict the enthalpy of complex formation in close agreement with the experimental values. The energy analysis shows that in the complexes the electrostatic binding energy dominates that of covalent binding.

  5. 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.

  6. A Conversation (Re)Analysis of Fraternal Bonding in the Locker Room.

    Science.gov (United States)

    Jimerson, Jason B.

    2001-01-01

    Reexamines the 15 talk fragments in "Fraternal Bonding in the Locker Room: A Profeminist Analysis of Talk about Competition and Women" (Curry, 1991), which epitomizes how sociologists utilize talk. The author examines the utterances and finds that 9 fragments reveal some dissent in how listeners react to crass talk, arguing that sport…

  7. Reply to "A Conversation (Re)Analysis of Fraternal Bonding in the Locker Room.

    Science.gov (United States)

    Curry, Timothy Jon

    2001-01-01

    Responds to a critique of "Fraternal Bonding in the Locker Room: A Profeminist Analysis of Talk about Competition and Women," defending its pro-feminist perspective, describing research methodology and follow-up research with one of the athletes from the original study; revisiting three of the original talk fragments; and commenting on…

  8. Porcelain laminate veneer conditioning for orthodontic bonding: SEM-EDX analysis.

    Science.gov (United States)

    Aksakalli, Sertac; Ileri, Zehra; Yavuz, Tevfik; Malkoc, Meral Arslan; Ozturk, Nilgun

    2015-09-01

    The purpose of this in vitro study was to evaluate and compare the effects of different surface treatments and laser irradiation on the bond strength of brackets bonded to porcelain laminate veneer. Porcelain laminate veneer specimens were embedded in the centers of acrylic resin blocks. Thirty-nine teeth were used for shear bond strength testing and the remaining three (one tooth for each group) were used for evaluation of the debonded bracket interface. Specimens were randomly divided into three groups, each containing 13 specimens. The details of the groups are as follows: Group SB, sandblasting with alumina particles (50 μm); Group HFA, 9.6 % hydrofluoric acid etching; Group ER, erbium-doped yttrium-aluminum-garnet (Er: YAG) irradiation (from 1 mm distance, 2 W, 10 Hz for 10 s). After conditioning, the upper central brackets were bonded to the porcelain surfaces. Porcelain laminate veneers were examined under stereomicroscope for adhesive remnant index and surface damage after debonding. The highest shear bond strength values were obtained with Group HFA (10.8 ± 3.8 MPa) and Group ER (9.3 ± 1.5 MPa), whereas Group SB revealed the lowest values. Scanning electron microscopy energy-dispersive X-ray (SEM-EDX) analysis revealed that the silicon level in the porcelain decreased after debonding in all groups. The sandblasting method did not demonstrate any ideal bond strength values; however, the 9.6 % hydrofluoric acid etching and Er: YAG laser did. There were no significant differences among all groups in terms of laminate surface damages. The Er: YAG laser therefore can be selected for ideal bond strength and minimal damage to porcelain laminates.

  9. Evaluation of the flocculation performance of carboxymethyl chitosan-graft-polyacrylamide, a novel amphoteric chemically bonded composite flocculant.

    Science.gov (United States)

    Yang, Zhen; Yuan, Bo; Huang, Xin; Zhou, Junyu; Cai, Jun; Yang, Hu; Li, Aimin; Cheng, Rongshi

    2012-01-01

    In the present work, a novel amphoteric chemically bonded composite flocculant (carboxymethyl chitosan-graft-polyacrylamide, denoted as CMC-g-PAM) was successfully prepared and used to flocculate the kaolin suspension. The flocculation performance of CMC-g-PAM in acidic, neutral, and alkaline conditions was systematically evaluated by light scattering in combination with fractal theory, as well as by traditional turbidity and zeta potential measurements. Based on the experimental facts from in situ size and fractal dimension measurements, different flocculation mechanisms play key roles at various pH levels, resulting in substantially varied flocculation kinetic processes under three pH conditions. In acidic condition, patching was the main mechanism involved in the opposite zeta potential between CMC-g-PAM and the kaolin suspension. A flat configuration was favored when the polymeric flocculant was adsorbed onto the particle surface, leading to a slower initial floc growth rate but larger and denser flocs. Bridging was the dominant mechanism in neutral and alkaline conditions. A faster initial rate of bridging resulted in smaller and more open floc structures. A rearrangement process in neutral pH subsequently led to more compact flocs, whereas no restructuration of flocs occurred in alkaline conditions because of the electrostatic repulsion of the same negative charges on the flocculant and particles.

  10. Simple fabrication of hydrophilic nanochannels using the chemical bonding between activated ultrathin PDMS layer and cover glass by oxygen plasma.

    Science.gov (United States)

    Kim, So Hyun; Cui, Yidan; Lee, Min Jung; Nam, Seong-Won; Oh, Doori; Kang, Seong Ho; Kim, Youn Sang; Park, Sungsu

    2011-01-21

    This study describes a simple and low cost method for fabricating enclosed transparent hydrophilic nanochannels by coating low-viscosity PDMS (monoglycidyl ether-terminated polydimethylsiloxane) as an adhesion layer onto the surface of the nanotrenches that are molded with a urethane-based UV-curable polymer, Norland Optical Adhesive (NOA 63). In detail, the nanotrenches made of NOA 63 were replicated from a Si master mold and coated with 6 nm thick layer of PDMS. These nanotrenches underwent an oxygen plasma treatment and finally were bound to a cover glass by chemical bonding between silanol and hydroxyl groups. Hydrophobic recovery that is observed in the bulk PDMS was not observed in the thin film of PDMS on the mold and the PDMS-coated nanochannel maintained its surface hydrophilicity for at least one month. The potentials of the nanochannels for bioapplications were demonstrated by stretching λ-DNA (48,502 bp) in the channels. Therefore, this fabrication approach provides a practical solution for the simple fabrication of the nanochannels for bioapplications.

  11. Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Wei [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Jiang, Ning [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Schwarz, W. H. Eugen [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Physical and Theoretical Chemistry, University of Siegen, Siegen 57068 Germany; Yang, Ping [Theoretical Division, Los Alamos National Laboratory, Los Alamos New Mexico 87545 USA; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA; Li, Jun [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA

    2017-07-11

    The geometric and electronic ground-state structures of six MS4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS4 species are compared to analogous MO4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4, whereas low MOS=II appears in high- spin septet D2d species Fe(S2)2 and (slightly excited) metastable Fe(O2)2. The ground states of all other molecules have intermediate MOS values, containing S2-, S22-, S21- (and resp. O2--, O1-, O22-, O21-) ligands, bonded by ionic, covalent and correlative contributions.

  12. Effects of lithium doping on microstructure, electrical properties, and chemical bonds of sol-gel derived NKN thin films

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Chun-Cheng [Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Department of Mathematic and Physical Sciences, R.O.C. Air Force Academy, Kaohsiung 820, Taiwan (China); Chen, Chan-Ching; Weng, Chung-Ming [Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Chu, Sheng-Yuan, E-mail: chusy@mail.ncku.edu.tw [Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan (China); Hong, Cheng-Shong [Department of Electronic Engineering, National Kaohsiung Normal University, Kaohsiung 802, Taiwan (China); Tsai, Cheng-Che [Department of Digital Game and Animation Design, Tung-Fang Design University, Kaohsiung 829, Taiwan (China)

    2015-02-28

    Highly (100/110) oriented lead-free Li{sub x}(Na{sub 0.5}K{sub 0.5}){sub 1−x}NbO{sub 3} (LNKN, x = 0, 0.02, 0.04, and 0.06) thin films are fabricated on Pt/Ti/SiO{sub 2}/Si substrates via a sol-gel processing method. The lithium (Li) dopants modify the microstructure and chemical bonds of the LNKN films, and therefore improve their electrical properties. The optimal values of the remnant polarization (P{sub r} = 14.3 μC/cm{sup 2}), piezoelectric coefficient (d{sub 33} = 48.1 pm/V), and leakage current (<10{sup −5} A/cm{sup 2}) are obtained for a lithium addition of x = 0.04 (i.e., 4 at. %). The observation results suggest that the superior electrical properties are the result of an improved crystallization, a larger grain size, and a smoother surface morphology. It is shown that the ion transport mechanism is dominated by an Ohmic behavior under low electric fields and the Poole-Frenkel emission effect under high electric fields.

  13. The structure and chemical bonding in the N(2)-CuX and N(2)...XCu (X = F, Cl, Br) systems studied by means of the molecular orbital and Quantum Chemical Topology methods.

    Science.gov (United States)

    Kisowska, Karolina; Berski, Slawomir; Latajka, Zdzislaw

    2008-12-01

    Ab initio studies carried out at the MP2(full)/6-311+G(2df) and MP2(full)/aug-cc-pVTZ-PP computational levels reveals that dinitrogen (N(2)) and cuprous halides (CuX, X = F, Cl, Br) form three types of systems with the side-on and end-on coordination of N(2): N[triple bond]N-CuX (C(infinity v)), N(2)-CuX (C(2v)) stabilized by the donor-acceptor bonds and weak van der Waals complexes N(2)...XCu (C(2v)) with dominant dispersive forces. An electron density transfer between the N(2) and CuX depends on type of the N(2) coordination and a comparison of the NPA charges yields the [N[triple bond]N](delta+)-[CuX](delta-) and [N(2)](delta-)-[CuX](delta+) formula. According to the NBO analysis, the Cu-N coordinate bonds are governed by predominant LP(N2)-->sigma*(Cu-X) "2e-delocalization" in the most stable N[triple bond]N-CuX systems, meanwhile back donation LP(Cu)-->pi*(N-N) prevails in less stable N(2)-CuX molecules. A topological analysis of the electron density (AIM) presents single BCP between the Cu and N nuclei in the N[triple bond]N-CuX, two BCPs corresponding to two donor-acceptor Cu-N bonds in the N(2)-CuX and single BCP between electron density maximum of the N[triple bond]N bond and halogen nucleus in the van der Waals complexes N(2)...XCu. In all systems values of the Laplacian nabla(2)rho(r)(r(BCP)) are positive and they decrease following a trend of the complex stability i.e. N[triple bond]N-CuX (C(infinity v)) > N(2)-CuX (C(2v)) > N(2)...XCu (C(2v)). A topological analysis of the electron localization function (ELF) reveals strongly ionic bond in isolated CuF and a contribution of covalent character in the Cu-Cl and Cu-Br bonds. The donor-acceptor bonds Cu-N are characterized by bonding disynaptic basins V(Cu,N) with attractors localized at positions corresponding to slightly distorted lone pairs V(N) in isolated N(2). In the N[triple bond]N-CuX systems, there were no creation of any new bonding attractors in regions where classically the donor-acceptor bonds

  14. Structures and chemical bonding of B3O3 (-/0) and B3O3H(-/0): A combined photoelectron spectroscopy and first-principles theory study.

    Science.gov (United States)

    Zhao, Li-Juan; Tian, Wen-Juan; Ou, Ting; Xu, Hong-Guang; Feng, Gang; Xu, Xi-Ling; Zhai, Hua-Jin; Li, Si-Dian; Zheng, Wei-Jun

    2016-03-28

    We present a combined photoelectron spectroscopy and first-principles theory study on the structural and electronic properties and chemical bonding of B3O3 (-/0) and B3O3H(-/0) clusters. The concerted experimental and theoretical data show that the global-minimum structures of B3O3 and B3O3H neutrals are very different from those of their anionic counterparts. The B3O3 (-) anion is characterized to possess a V-shaped OB-B-BO chain with overall C2 v symmetry (1A), in which the central B atom interacts with two equivalent boronyl (B≡O) terminals via B-B single bonds as well as with one O atom via a B=O double bond. The B3O3H(-) anion has a Cs (2A) structure, containing an asymmetric OB-B-OBO zig-zag chain and a terminal H atom interacting with the central B atom. In contrast, the C2 v (1a) global minimum of B3O3 neutral contains a rhombic B2O2 ring with one B atom bonded to a BO terminal and that of neutral B3O3H (2a) is also of C2 v symmetry, which is readily constructed from C2 v (1a) by attaching a H atom to the opposite side of the BO group. The H atom in B3O3H(-/0) (2A and 2a) prefers to interact terminally with a B atom, rather than with O. Chemical bonding analyses reveal a three-center four-electron (3c-4e) π hyperbond in the B3O3H(-) (2A) cluster and a four-center four-electron (4c-4e) π bond (that is, the so-called o-bond) in B3O3 (1a) and B3O3H (2a) neutral clusters.

  15. Microtensile bond strength and micromorphologic analysis of surface-treated resin nanoceramics

    Science.gov (United States)

    Park, Joon-Ho

    2016-01-01

    PURPOSE The aim of this study was to evaluate the influence of different surface treatment methods on the microtensile bond strength of resin cement to resin nanoceramic (RNC). MATERIALS AND METHODS RNC onlays (Lava Ultimate) (n=30) were treated using air abrasion with and without a universal adhesive, or HF etching followed by a universal adhesive with and without a silane coupling agent, or tribological silica coating with and without a universal adhesive, and divided into 6 groups. Onlays were luted with resin cement to dentin surfaces. A microtensile bond strength test was performed and evaluated by one-way ANOVA and Tukey HSD test (α=.05). A nanoscratch test, field emission scanning electron microscopy, and energy dispersive X-ray spectroscopy were used for micromorphologic analysis (α=.05). The roughness and elemental proportion were evaluated by Kruskal–Wallis test and Mann–Whitney U test. RESULTS Tribological silica coating showed the highest roughness, followed by air abrasion and HF etching. After HF etching, the RNC surface presented a decrease in oxygen, silicon, and zirconium ratio with increasing carbon ratio. Air abrasion with universal adhesive showed the highest bond strength followed by tribological silica coating with universal adhesive. HF etching with universal adhesive showed the lowest bond strength. CONCLUSION An improved understanding of the effect of surface treatment of RNC could enhance the durability of resin bonding when used for indirect restorations. When using RNC for restoration, effective and systemic surface roughening methods and an appropriate adhesive are required. PMID:27555896

  16. Bond strength of universal adhesives: A systematic review and meta-analysis.

    Science.gov (United States)

    Rosa, Wellington Luiz de Oliveira da; Piva, Evandro; Silva, Adriana Fernandes da

    2015-07-01

    A systematic review was conducted to determine whether the etch-and-rinse or self-etching mode is the best protocol for dentin and enamel adhesion by universal adhesives. This report followed the PRISMA Statement. A total of 10 articles were included in the meta-analysis. Two reviewers performed a literature search up to October 2014 in eight databases: PubMed, Web of Science, Scopus, BBO, SciELO, LILACS, IBECS and The Cochrane Library. In vitro studies evaluating the bond strength of universal adhesives to dentin and/or enamel by the etch-and-rinse and self-etch strategies were eligible to be selected. Statistical analyses were conducted using RevMan 5.1 (The Cochrane Collaboration, Copenhagen, Denmark). A global comparison was performed with random-effects models at a significance level of padhesives (p≥0.05). However, for the ultra-mild All-Bond Universal adhesive, the etch-and-rinse strategy was significantly different than the self-etch mode in terms of dentin micro-tensile bond strength, as well as in the global analysis of enamel micro-tensile and micro-shear bond strength (p≤0.05). The enamel bond strength of universal adhesives is improved with prior phosphoric acid etching. However, this effect was not evident for dentin with the use of mild universal adhesives with the etch-and-rinse strategy. Selective enamel etching prior to the application of a mild universal adhesive is an advisable strategy for optimizing bonding. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Numerical Parametric Analysis of Bond Coat Thickness Effect on Residual Stresses in Zirconia-Based Thermal Barrier Coatings

    Science.gov (United States)

    Abbas, Musharaf; Hasham, Hasan Junaid; Baig, Yasir

    2016-02-01

    Numerical-based finite element investigation has been conducted to explain the effect of bond coat thickness on stress distribution in traditional and nanostructured yttria-stabilized zirconia (YSZ)-based thermal barrier coatings (TBC). Stress components have been determined to quantitatively analyze the mechanical response of both kinds of coatings under the thermal shock effect. It has been found that maximum radial tensile and compressive stresses that exist at thermally grown oxide (TGO)/bond coat interface and within TGO respectively decrease with an increase in bond coat thickness. Effect of bond coat thickness on axial tensile stresses is not significant. However, axial compressive stresses that exist at the edge of the specimen near bond coat/substrate interface decrease appreciably with the increase in bond coat thickness. Residual stress profile as a function of bond coat thickness is further explained for comparative analysis of both coatings to draw some useful conclusions helpful in failure studies of TBCs.

  18. An assessment of the prestress force on the bonded tendon by SI and impact signal analysis techniques

    Energy Technology Data Exchange (ETDEWEB)

    Jang, J.B., E-mail: jbjang@kepco.co.kr [Korea Electric Power Corporation Research Institute, 105, Munji-Ro, Yuseong-Gu, Daejeon 305-760 (Korea, Republic of); Hwang, K.M. [Korea Electric Power Corporation Research Institute, 105, Munji-Ro, Yuseong-Gu, Daejeon 305-760 (Korea, Republic of); Lee, H.P. [Korea Hydro and Nuclear Power Company, 1312-70, Yuseong-Daero, Yuseong-Gu, Daejeon 305-343 (Korea, Republic of); Kim, B.H. [Kyungnam University, 449, Wolyoung, Masan, Kyungnam 631-701 (Korea, Republic of)

    2013-02-15

    Highlights: ► We developed SI and the impact signal analysis technique to evaluate the prestress force of bonded tendons. ► We assessed the prestress force of bonded tendons in a real reactor containment building using them. ► Our developed techniques suggested highly reliable results for the prestress force of bonded tendons. ► Our developed techniques can simply and accurately evaluate the prestress force of bonded tendons. ► Our study can be applied to other infra-structures with bonded tendons such as bridges and buildings. -- Abstract: The bonded tendon has been adopted to the reactor containment building of some operating nuclear power plants in Korea and the assessment of the prestress force on the bonded tendon is very important for the evaluation of the structural integrity. The prestress force of the bonded tendon at real reactor containment building was evaluated using the SI technique and impact signal analysis technique which were developed to improve the existing indirect assessment technique. For these techniques, the strain of the reactor containment building and the stress wave velocity of the bonded tendon were measured. Both SI technique and impact signal analysis technique give the highly reliable results comparison with the existing theoretical approach. Therefore, it is confirmed that the developed techniques are very useful for the evaluation of the prestress force on the bonded tendon.

  19. Experiment and simulation analysis of roll-bonded Q235 steel plate

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, G.; Huang, Q.; Zhou, C.; Zhang, Z.; Ma, L.; Wang, X.

    2016-10-01

    Heavy-gauge Q235 steel plate was roll bonded, and the process was simulated using MARC software. Ultrasonic testing results revealed the presence of cracks and lamination defects in an 80-mm clad steel sheet, especially at the head and tail of the steel plate. There were non-uniform ferrite + pearlite microstructures and unbound areas at a bond interface. Through scanning electron microscopy analysis, long cracks and additional inclusions in the cracks were observed at the interface. A fracture analysis revealed non-uniform inclusions that pervaded the interface. Moreover, MARC simulations demonstrated that there was little equivalent strain at the centre of the slab during the first rolling pass. The equivalent centre increased to 0.5 by the fourth rolling pass. Prior to the final pass, the equivalent strain was not consistent across the thickness direction, preventing bonding interfaces from forming consistent deformation and decreasing the residual stress. The initial rolling reduction rate should not be very small (e.g. 5%) as it is averse to the coordination of rolling deformation. Such rolling processes are averse to the rolling bond. (Author)

  20. Density functional theory investigation of hydrogen bonding effects on the oxygen, nitrogen and hydrogen electric field gradient and chemical shielding tensors of anhydrous chitosan crystalline structure.

    Science.gov (United States)

    Esrafili, Mehdi D; Elmi, Fatemeh; Hadipour, Nasser L

    2007-02-08

    A systematic computational investigation was carried out to characterize the 17O, 14N and 2H electric field gradient, EFG, as well as 17O, 15N, 13C and 1H chemical shielding tensors in the anhydrous chitosan crystalline structure. To include the hydrogen-bonding effects in the calculations, the most probable interacting molecules with the target molecule in the crystalline phase were considered through a hexameric cluster. The computations were performed with the B3LYP method and 6-311++G(d,p) and 6-31++G(d,p) standard basis sets using the Gaussian 98 suite of programs. Calculated EFG and chemical shielding tensors were used to evaluate the 17O, 14N and 2H nuclear quadrupole resonance, NQR, and 17O, 15N, 13C and 1H nuclear magnetic resonance, NMR, parameters in the hexameric cluster, which are in good agreement with the available experimental data. The difference between the calculated NQR and NMR parameters of the monomer and hexamer cluster shows how much hydrogen bonding interactions affect the EFG and chemical shielding tensors of each nucleus. These results indicate that both O(3)-H(33)...O(5-3) and N-H(22)...O(6-4) hydrogen bonding have a major influence on NQR and NMR parameters. Also, the quantum chemical calculations indicate that the intra- and intermolecular hydrogen bonding interactions play an essential role in determining the relative orientation of EFG and chemical shielding principal components in the molecular frame axes.

  1. Analysis, synthesis and design of chemical processes

    Energy Technology Data Exchange (ETDEWEB)

    Turton, R. [West Virginia Univ., Morgantown, WV (United States); Bailie, R.C.; Whiting, W.B.

    1998-12-31

    The book illustrates key concepts through a running example from the real world: the manufacture of benzene; covers design, economic considerations, troubleshooting and health/environmental safety; and includes exclusive software for estimating chemical manufacturing equipment capital costs. This book will help chemical engineers optimize the efficiency of production processes, by providing both a philosophical framework and detailed information about chemical process design. Design is the focal point of the chemical engineering practice. This book helps engineers and senior-level students hone their design skills through process design rather than simply plant design. It introduces all the basics of process simulation. Learn how to size equipment, optimize flowsheets, evaluate the economics of projects, and plan the operation of processes. Learn how to use Process Flow Diagrams; choose the operating conditions for a process; and evaluate the performance of existing processes and equipment. Finally, understand how chemical process design impacts health, safety, the environment and the community.

  2. Experimental and finite element analysis of bond-slip in reinforced concrete

    Directory of Open Access Journals (Sweden)

    A. R. V. WOLENSKI

    Full Text Available Abstract The modeling of reinforced concrete structures has taken advantage of the increasing progress on Computational Mechanics, in such way that complex phenomena, such as cracking and crushing, creep, reinforcement yielding, steel-concrete bond loss, can be modeled in a reasonable realistic way, using the proper set of numerical and computational resources. Among several options, the ones based on the Finite Element Method (FEM allow complex analysis simulations of reinforced concrete structures, including the interaction of different nonlinear effects. This paper deals with the nonlinear finite element analysis of the bond-slip between reinforcing steel and concrete, taking into account an experimental study previously performed. The FEM analysis presented uses a combination of resources where the material behavior of concrete is described by the Microplane Constitutive Model, and an embedded reinforcement model is used to represent steel inside the concrete and take into account the effect of bond-slip. The FEM models were created using the INSANE (INteractive Structural ANalysis Environment computational system, open source software that has a set of FEM tools for nonlinear analysis of reinforced concrete structures. The correlations between numerical-experimentals results and several parameters validate the proposed combination of resources and identifies the significance of various effects on the response.

  3. Chemical bond properties and Mossbauer spectroscopy in (La1-xMx)2CuO4 (M=Ba, Sr)

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    By using the average band-gap model, the chemical bond properties of (La1-x Mx)2CuO4(M=Ba, Sr) were calculated . The calculated covalencies for Cu(O and La(O bond in the compounds are 0.3 and 0.03 respectively. M?ssbauer isomer shifts of 57Fe doped in La2CuO4 and 119Sn doped in La2CuO4 were calculated by using the chemical surrounding factor defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified in 57Fe and 119Sn doped La2CuO4.

  4. Curing lights for orthodontic bonding: a systematic review and meta-analysis.

    Science.gov (United States)

    Fleming, Padhraig S; Eliades, Theodore; Katsaros, Christos; Pandis, Nikolaos

    2013-04-01

    were included in both groups. Little statistical heterogeneity was observed in this analysis (I(2) = 4.8%; P = 0.379). There was no statistical difference in bond failure risk between the groups (OR, 0.92; 95% CI, 0.68-1.23; prediction intervals, 0.54, 1.56). Similarly, no statistical difference in bond failure risk was observed in the meta-analysis comparing halogen lights and LEDs (OR, 0.96; 95% CI, 0.64-1.44; prediction intervals, 0.07, 13.32). The pooled estimates from both comparisons were OR, 0.93; 95% CI, 0.74-1.17; and prediction intervals, 0.69, 1.17. There is no evidence to support the use of 1 light cure type over another based on risk of attachment failure. Copyright © 2013 American Association of Orthodontists. Published by Mosby, Inc. All rights reserved.

  5. Chemical Engineering Data Analysis Made Easy with DataFit

    Science.gov (United States)

    Brenner, James R.

    2006-01-01

    The outline for half of a one-credit-hour course in analysis of chemical engineering data is presented, along with a range of typical problems encountered later on in the chemical engineering curriculum that can be used to reinforce the data analysis skills learned in the course. This mini course allows students to be exposed to a variety of ChE…

  6. Strain analysis of a bonded, dissimilar, composite material T-joint using moiré interferometry

    Science.gov (United States)

    Gascoigne, H. E.; Abdallah, M. G.

    High-sensitivity moiré interferometry and finite-element analysis are used to analyze the state of deformation and stress in the region of contact between a plane orthotropic rectangular punch bonded to a foundation with dissimilar elastic properties which models a highly loaded region of a composite material rocket motor casing. Stress distributions are presented for the contact region and an estimate of the maximum shear stress in the foundation is given. The displacement components show good qualitative agreement between analysis and experiment. The lack of quantitative agreement between the experimental and the finite-element analysis is attributed to uncertainty of the material properties.

  7. 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.

  8. Comparison of bonding performance of self-etching and etch-and-rinse adhesives on human dentin using reliability analysis.

    Science.gov (United States)

    Bradna, Pavel; Vrbova, Radka; Dudek, Michal; Roubickova, Adela; Housova, Devana

    2008-12-01

    To estimate the in vitro reliability of typical self-etching and etch-and-rinse adhesives of various application protocols. The following adhesives were applied on flat dentin surfaces of extracted human teeth (n = 223): self-etching two-step adhesives: AdheSE (AH), Clearfil SE Bond (CL), OptiBond SE (OS); one-step adhesives: Adper Prompt L-Pop (ADP), Adper Prompt (AD), and Xeno III (XE); all-in-one adhesive: iBond (IB); etch-and-rinse three-step adhesives: OptiBond FL (OF), two-step Gluma Comfort Bond (G), Excite (E) and Prime & Bond NT (PB). Composite buildups were prepared using a microhybrid composite, Opticor New. Shear bond strength was determined after 24 h of storage at 37 degrees C in distilled water. The results were analyzed with a nested ANOVA (adhesive, type of adhesive) followed by the Fisher post-hoc tests of group homogeneity at alpha = 0.05. A two-parameter Weibull distribution was used to calculate the critical shear bond strength corresponding to 5% probability of failure as a measure of system reliability. ANOVA revealed a significant decrease (p AD=IB=XE>PB=ADP, but no significant difference (p > 0.48) between the etch-and-rinse and self-etching adhesives. The corresponding characteristic bond strength of Weibull distribution ranged between 24.1 and 12.1 MPa, Weibull modulus between 8.3 and 2.1, and the critical shear bond strength varied from 16.0 to 3.0 MPa. Pronounced differences in the critical shear bond strength suggest reliability variations in the adhesive systems tested, which originate from chemical composition rather than type of adhesive.

  9. 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.

  10. 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.

  11. Rod like attapulgite/poly(ethylene terephthalate nanocomposites with chemical bonding between the polymer chain and the filler

    Directory of Open Access Journals (Sweden)

    Q. Fu

    2012-08-01

    Full Text Available Poly(ethylene terephthalate (PET nanocomposites containing rod-like silicate attapulgite (AT were prepared via in situ polymerization. It is presented that PET chains identical to the matrix have been successfully grafted onto simple organically pre-modified AT nanorods (MAT surface during the in situ polymerization process. The covalent bonding at the interface was confirmed by Fourier transform infrared spectroscopy (FTIR and thermogravimetric analysis (TGA. The content of grafted PET polymer on the surface of MAT was about 26 wt%. This high grafting density greatly improved the dispersion of fillers, interfacial adhesion as well as the significant confinement of the segmental motion of PET, as compared to the nanocomposites of PET/pristine AT (PET/AT. Owing to the unique interfacial structure in PET/MAT composites, their thermal and mechanical properties have been greatly improved. Compared with neat PET, the elastic modulus and the yield strength of PET/MAT were significantly improved by about 39.5 and 36.8%, respectively, by incorporating only 2 wt % MAT. Our work provides a novel route to fabricate advanced PET nanocomposites using rod-like attapulgite as fillers, which has great potential for industrial applications.

  12. Electronic structure of alloxan and its dimers: QM/QD simulations and quantum chemical topology analysis.

    Science.gov (United States)

    Allehyani, Basmah H; Elroby, Shaaban A; Aziz, Saadalluh G; Hilal, Rifaat H

    2015-01-01

    This study aims to identify the origin of the extra stability of alloxan, a biologically active pyrimidine. To achieve this goal, detailed DFT computations and quantum dynamics simulations have been performed to establish the most stable conformation and the global minimum structure on the alloxan potential energy surface. The effects of the solvent, basis set, and DFT method have been examined to validate the theoretical model adopted throughout the work. Two non-covalent intermolecular dimers of alloxan, the H-bonded and dipolar dimers, have been investigated at the ωB97X-D and M06-2X levels of theory using the triple zeta 6-311++G** to establish their relative stability. Quantum chemical topology features and natural bond orbital analysis (NBO) have been performed to identify and characterize the forces that govern the structures and underlie the extra stability of alloxan.

  13. Synthesis, structure, spectral properties and DFT quantum chemical calculations of 4-aminoazobenzene dyes. Effect of intramolecular hydrogen bonding on photoisomerization

    Science.gov (United States)

    Georgiev, Anton; Bubev, Emil; Dimov, Deyan; Yancheva, Denitsa; Zhivkov, Ivaylo; Krajčovič, Jozef; Vala, Martin; Weiter, Martin; Machkova, Maria

    2017-03-01

    In this paper three different "push-pull" 4-aminoazobenzene dyes have been synthesized in order to characterize their photochromic behavior in different solvents. The molecular geometry was optimized by DFT/B3LYP functional combined with the standard 6-31 + G(d,p) basis set for trans (E) and cis (Z) isomers and the energy levels of HOMO and LUMO frontier orbitals were computed using IEFPCM solvation in CHCl3 and DMF. The calculated results were compared to the experimental optical band gap and HOMO values of cyclic voltammetry. The intramolecular six-membered hydrogen bond was formed in both isomers of the synthesized dyes. The thermodynamic parameters such as total electronic energy E (RB3LYP), enthalpy H298 (sum of electronic and thermal enthalpies), free Gibbs energy G298 (sum of electronic and thermal free Gibbs energies) and dipole moment μ were computed for trans (E) and cis (Z) isomers in order to estimate the ΔEtrans → cis, Δμtrans → cis, ΔHtrans → cis, ΔGtrans → cis and ΔStrans → cis values. The NBO analysis was performed in order to understand the intramolecular charge transfer and energy of resonance stabilization. The solvatochromic shift was evaluated by UV-VIS spectroscopy in CHCl3 (nonpolar), EtOH (polar protic) and DMF (polar aprotic) solvents to determine the electron withdrawing and donating properties of the substituents on electron transitions energy. Through the increasing solvent polarity a strong bathochromic shift is observed. The photoisomerization experiments have been performed in two solvents CHCl3 (nonpolar) and DMF (polar aprotic) by UV light irradiation with λ = 365 nm at equal concentrations and time of illuminations. The electronic spectra were computed by TD-DFT after geometry optimization using IEFPCM solvation in CHCl3 and DMF. The degree of photoisomerization was calculated for the three azo chromophores in both solvents. By using first derivative of the UV-VIS spectra it was possible to resolve the overlapped

  14. Bond-orientational analysis of hard-disk and hard-sphere structures.

    Science.gov (United States)

    Senthil Kumar, V; Kumaran, V

    2006-05-28

    We report the bond-orientational analysis results for the thermodynamic, random, and homogeneously sheared inelastic structures of hard-disks and hard-spheres. The thermodynamic structures show a sharp rise in the order across the freezing transition. The random structures show the absence of crystallization. The homogeneously sheared structures get ordered at a packing fraction higher than the thermodynamic freezing packing fraction, due to the suppression of crystal nucleation. On shear ordering, strings of close-packed hard-disks in two dimensions and close-packed layers of hard-spheres in three dimensions, oriented along the velocity direction, slide past each other. Such a flow creates a considerable amount of fourfold order in two dimensions and body-centered-tetragonal (bct) structure in three dimensions. These transitions are the flow analogs of the martensitic transformations occurring in metals due to the stresses induced by a rapid quench. In hard-disk structures, using the bond-orientational analysis we show the presence of fourfold order. In sheared inelastic hard-sphere structures, even though the global bond-orientational analysis shows that the system is highly ordered, a third-order rotational invariant analysis shows that only about 40% of the spheres have face-centered-cubic (fcc) order, even in the dense and near-elastic limits, clearly indicating the coexistence of multiple crystalline orders. When layers of close-packed spheres slide past each other, in addition to the bct structure, the hexagonal-close-packed (hcp) structure is formed due to the random stacking faults. Using the Honeycutt-Andersen pair analysis and an analysis based on the 14-faceted polyhedra having six quadrilateral and eight hexagonal faces, we show the presence of bct and hcp signatures in shear ordered inelastic hard-spheres. Thus, our analysis shows that the dense sheared inelastic hard-spheres have a mixture of fcc, bct, and hcp structures.

  15. 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.)

  16. Orbital entanglement in bond-formation processes

    CERN Document Server

    Boguslawski, Katharina; Barcza, Gergely; Legeza, Ors; Reiher, Markus

    2013-01-01

    The accurate calculation of the (differential) correlation energy is central to the quantum chemical description of bond-formation and bond-dissociation processes. In order to estimate the quality of single- and multi-reference approaches for this purpose, various diagnostic tools have been developed. In this work, we elaborate on our previous observation [J. Phys. Chem. Lett. 3, 3129 (2012)] that one- and two-orbital-based entanglement measures provide quantitative means for the assessment and classification of electron correlation effects among molecular orbitals. The dissociation behavior of some prototypical diatomic molecules features all types of correlation effects relevant for chemical bonding. We demonstrate that our entanglement analysis is convenient to dissect these electron correlation effects and to provide a conceptual understanding of bond-forming and bond-breaking processes from the point of view of quantum information theory.

  17. Analysis investigation for continuous and discrete athermal bondings on an eight-inch reflective mirror

    Science.gov (United States)

    Chan, Chia-Yen; You, Zhen-Ting; Chen, Yi-Cheng; Huang, Ting-Ming

    2016-10-01

    Effects of continuous and discrete bondings with an RTV glue (DOW CORNING® 6-1104) on an eight-inch reflective mirror have been carried out numerically. The finite element analysis and Zernike polynomial fitting are applied to the whole process. Under the integrated optomechanical analysis, the comparison of the optical aberrations, equivalent stresses and natural frequencies with various bondline thicknesses under the self-weight loading and temperature difference has also been investigated. The separated thermal and gravity effects on PV values with various bondline thicknesses for the discrete bonding are studied. It is found that the thermal effect has absolute influence than the gravity effect since the latter approaches zero for all bondline thicknesses. Besides, the simulation results have been verified by the analytical solution. It can be concluded that in the design of the bondline thickness, the bonding method and the temperature range should be considered simultaneously to reduce the temperature-induced stress and aberration and to increase the natural frequency.

  18. Micro-computed tomography and bond strength analysis of different root canal filling techniques

    Directory of Open Access Journals (Sweden)

    Juliane Nhata

    2014-01-01

    Full Text Available Introduction: The aim of this study was to evaluate the quality and bond strength of three root filling techniques (lateral compaction, continuous wave of condensation and Tagger′s Hybrid technique [THT] using micro-computed tomography (CT images and push-out tests, respectively. Materials and Methods: Thirty mandibular incisors were prepared using the same protocol and randomly divided into three groups (n = 10: Lateral condensation technique (LCT, continuous wave of condensation technique (CWCT, and THT. All specimens were filled with Gutta-percha (GP cones and AH Plus sealer. Five specimens of each group were randomly chosen for micro-CT analysis and all of them were sectioned into 1 mm slices and subjected to push-out tests. Results: Micro-CT analysis revealed less empty spaces when GP was heated within the root canals in CWCT and THT when compared to LCT. Push-out tests showed that LCT and THT had a significantly higher displacement resistance (P < 0.05 when compared to the CWCT. Bond strength was lower in apical and middle thirds than in the coronal thirds. Conclusions: It can be concluded that LCT and THT were associated with higher bond strengths to intraradicular dentine than CWCT. However, LCT was associated with more empty voids than the other techniques.

  19. In search of low cost biological analysis: Wax or acrylic glue bonded paper microfluidic devices

    KAUST Repository

    Kodzius, Rimantas

    2011-01-22

    In this body of work we have been developing and characterizing paper based microfluidic fabrication technologies to produce low cost biological analysis. Specifically we investigated the performance of paper microfluidics that had been bonded using wax or acrylic glue, and characterized the affect of these and other microfluidic materials on the polymerase chain reaction (PCR). We report a simple, low-cost and detachable microfluidic chip incorporating easily accessible paper, glass slides or other polymer films as the chip materials along with adhesive wax or cyanoacrylate-based resin as the recycling bonding material. We use a laser to cut through the paper or film to form patterns and then sandwich the paper and film between glass sheets or polymer membranes. The hot-melt adhesive wax or simple cyanoacrylate-based resin can realize bridge bonding between various materials, for example, paper, polymethylmethacrylate film, glass sheets, or metal plate. The wax bonding process is reversible and the wax is reusable through a melting and cooling process. With this process, a three-dimensional (3D) microfluidic chip is achievable by evacuating the channels of adhesive material in a hot-water. We applied the wax-paper based microfluidic chip to HeLa cell electroporation. Subsequently, a prototype of a 5-layer 3D chip was fabricated by multilayer wax bonding. To check the sealing ability and the durability of the chip, green fluorescence protein recombinant E. coli bacteria were cultured, with which the chemotaxis of E. coli was studied in order to determine the influence of antibiotic ciprofloxacin concentration on the E. coli migration. The chip bonded with cyanoacrylate-based resin was tested by measuring protein concentration and carrying out DNA capillary electrophoresis. To study the biocompatibility and applicability of our microfluidic chip fabrication technology, we tested the PCR compatibility of our chip materials along with various other common materials

  20. Comparative anti-inflammatory activities of curcumin and tetrahydrocurcumin based on the phenolic O-H bond dissociation enthalpy, ionization potential and quantum chemical descriptor.

    Science.gov (United States)

    Murakami, Yukio; Ishii, Hiroaki; Takada, Naoki; Tanaka, Shoji; Machino, Mamoru; Ito, Shigeru; Fujisawa, Seiichiro

    2008-01-01

    Curcumin and its reduced derivative tetrahydrocurcumin have been shown to exhibit chemopreventive activity. Cyclooxygenase-2 (COX-2) inhibition in lipopolysaccharide (LPS)- or Porphyromonas gingivalis fimbria-stimulated RAW 264.7 cells was investigated using Northern blot analysis. The fimbria-stimulated expression of the COX-2 gene was inhibited by curcumin but not by tetrahydrocurcumin. LPS-stimulated COX-2 gene expression was completely inhibited by curcumin, but an increase in the concentration of tetrahydrocurcumin did not cause complete inhibition of COX-2 expression. The inhibitory effect of curcumin on nuclear factor kappa B (NF-kappaB) activation in the cells was clearly observed, but that of tetrahydrocurcumin was incomplete even at a concentration of 20 microM. To explain the difference in effect between the two compounds, analysis of the frontier orbital was performed using ab initio 6-31G* wave function. The calculated chemical hardness (eta) for curcumin was clearly smaller, whereas its electronegativity (chi) and electrophilicity (omega) were clearly greater than the corresponding values for the curcumin-related compounds tetrahydrocurcumin, isoeugenol and eugenol. This suggested that the anti-inflammatory activities of curcumin may be related to eta-, chi- and/or omega-controlled enzymes. In addition, the bond dissociation enthalpy (BDE) of the phenolic OH was calculated using the density function theory (DFT)/B3LY. The total BDE values of curcumin and tetrahydrocurcumin were almost identical, but the BDE of one-electron oxidation and ionization potential (IP) for curcumin were lower than those for tetrahydrocurcumin, suggesting the highly pro-oxidative activity of curcumin. Curcumin has both oxidant and antioxidant properties. A causal link between the anti-inflammatory activities and molecular properties of phenolic antioxidants is suggested.

  1. Current trends of the development of chemical analysis

    Directory of Open Access Journals (Sweden)

    Rema Matakova

    2014-12-01

    Full Text Available This paper presents dynamics of the development of all stages of chemical analysis during last 15 years. The ways of the quality improvement of chemical analysis and its considerable advancement into the field of trace concentrations of substances are shown. Features of development of analytical methods, modern techniques for concentration and separation of substances, as well as chemomerrical processing of results are analyzed. Huge importance of computerization and automation of the analysis is shown.

  2. Hydrogen bonding in thiobenzamide synthon and its Cadmium complex: Crystal structure and Hirshfeld analysis

    Indian Academy of Sciences (India)

    INES RIGANE; SIWAR WALHA; ABDELHAMID BEN SALAH

    2016-09-01

    The thiobenzamid TBA and its Cd(II) complex, dichlorothiobenzamidecadmium(II) [Cd(TBA)Cl₂] complex has been synthesized and characterized by FT-IR, FT-Raman and UV–Vis spectroscopy. The crystal and molecular structure of TBA and [Cd(TBA)Cl₂] were determined by single crystal X-ray diffraction analysis. The molecular arrangement in the crystal structure of TBA can be described on the basis of supramolecular dimeric synthons built up by four independent TBA molecules stacked via N-H. . .S hydrogen bonds. The 3D Hirshfeld surfaces and the associated 2D fingerprint plots were investigated for intermolecular interactions. The N-H. . .S hydrogen bond percentages were estimated to be 23.1%, 22.9%, 30.6% and 27.3% of Hirshfeld surfaces area respectively for each TBA molecule. Synthons are associated through C–H. . . π interactions at percentage of 33.8%, 38.2%, 24.3% and 19.4% to result in 3D network. The dichlorothiobenzamide cadmium(II) complex bonded by sulfur atom of thiobenzamide shows a double chain of distorted octahedra around the cadmium atoms running along the a axis and the packing is stabilized by intra- and inter-chain hydrogen bonding interactions of the type N–H. . .Cl and aromatic π. . .π stacking interactions between ring centroids at 21.8% and 7.6% of the Hirshfeld surface area, respectively. The decomposition of the complex to cadmium sulfide has been investigated by thermogravimetric analysis (TGA).

  3. Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods.

    Science.gov (United States)

    Siskos, Michael G; Choudhary, M Iqbal; Gerothanassis, Ioannis P

    2017-03-07

    The exact knowledge of hydrogen atomic positions of O-H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i) density functional theory (DFT) calculations after a structure has been determined by X-ray from single crystals or from powders; (ii) ¹H-NMR chemical shifts as constraints in DFT calculations, and (iii) use of root-mean-square deviation between experimentally determined and DFT calculated ¹H-NMR chemical shifts considering the great sensitivity of ¹H-NMR shielding to hydrogen bonding properties.

  4. Chemical Diversity, Origin, and Analysis of Phycotoxins

    DEFF Research Database (Denmark)

    Rasmussen, Silas Anselm; Andersen, Aaron John Christian; Andersen, Nikolaj Gedsted;

    2016-01-01

    Microalgae, particularly those from the lineage Dinoflagellata, are very well-known for their ability to produce phycotoxins that may accumulate in the marine food chain and eventually cause poisoning in humans. This includes toxins accumulating in shellfish, such as saxitoxin, okadaic acid......, yessotoxins, azaspiracids, brevetoxins, and pinnatoxins. Other toxins, such as ciguatoxins and maitotoxins, accumulate in fish, where, as is the case for the latter compounds, they can be metabolized to even more toxic metabolites. On the other hand, much less is known about the chemical nature of compounds...... complex natural compounds known to mankind, with chemical structures that show no resemblance to what has been characterized from plants, fungi, or bacteria. In addition, it will summarize algal species known to be related to fish-killing blooms, but from which ichthyotoxins are yet to be characterized....

  5. Quantifying chemical reactions by using mixing analysis.

    Science.gov (United States)

    Jurado, Anna; Vázquez-Suñé, Enric; Carrera, Jesús; Tubau, Isabel; Pujades, Estanislao

    2015-01-01

    This work is motivated by a sound understanding of the chemical processes that affect the organic pollutants in an urban aquifer. We propose an approach to quantify such processes using mixing calculations. The methodology consists of the following steps: (1) identification of the recharge sources (end-members) and selection of the species (conservative and non-conservative) to be used, (2) identification of the chemical processes and (3) evaluation of mixing ratios including the chemical processes. This methodology has been applied in the Besòs River Delta (NE Barcelona, Spain), where the River Besòs is the main aquifer recharge source. A total number of 51 groundwater samples were collected from July 2007 to May 2010 during four field campaigns. Three river end-members were necessary to explain the temporal variability of the River Besòs: one river end-member is from the wet periods (W1) and two are from dry periods (D1 and D2). This methodology has proved to be useful not only to compute the mixing ratios but also to quantify processes such as calcite and magnesite dissolution, aerobic respiration and denitrification undergone at each observation point.

  6. Effect of different mechanical and chemical surface treatments on the repaired bond strength of an indirect composite resin.

    Science.gov (United States)

    Kimyai, Soodabeh; Oskoee, Siavash Savadi; Mohammadi, Narmin; Rikhtegaran, Sahand; Bahari, Mahmoud; Oskoee, Parnian Alizadeh; Vahedpour, Hafez

    2015-02-01

    This study compared the effects of two mechanical surface preparation techniques, air abrasion and Nd:YAG laser, with the use of two adhesive systems, self-etch and etch and rinse, on the repair bond strengths of an indirect composite resin. One hundred fifty cylindrical samples of an indirect composite resin were prepared and randomly divided into six groups (n = 25). In groups 1-3, the composite resin surfaces were respectively prepared as follows: no roughening, roughening by air abrasion, and roughening by Nd:YAG laser, followed by application of an etch-and-rinse adhesive. In groups 4-6, the preparation techniques were respectively the same as those in groups 1-3, followed by application of a self-etch adhesive. Subsequently, a direct composite resin was added and repair bond strengths were measured. Data were analyzed with two-way ANOVA and post hoc Tukey's test. Mean bond strength value was significant based on the preparation technique (P composite resin with air abrasion and Nd:YAG laser resulted in a significant increase in the repair bond strength, with air abrasion being more effective. There were no significant differences in bond strength between the two adhesives.

  7. The effect of antimicrobial agents on bond strength of orthodontic adhesives: a meta-analysis of in vitro studies.

    Science.gov (United States)

    Altmann, A S P; Collares, F M; Leitune, V C B; Samuel, S M W

    2016-02-01

    Antimicrobial orthodontic adhesives aim to reduce white spot lesions' incidence in orthodontic patients, but they should not jeopardizing its properties. Systematic review and meta-analysis were performed to answer the question whether the association of antimicrobial agents with orthodontic adhesives compromises its mechanical properties and whether there is a superior antimicrobial agent. PubMed and Scopus databases. In vitro studies comparing shear bond strength of conventional photo-activated orthodontic adhesives to antimicrobial photo-activated orthodontic adhesives were considered eligible. Search terms included the following: orthodontics, orthodontic, antimicrobial, antibacterial, bactericidal, adhesive, resin, resin composite, bonding agent, bonding system, and bond strength. The searches yielded 494 citations, which turned into 467 after duplicates were discarded. Titles and abstracts were read and 13 publications were selected for full-text reading. Twelve studies were included in the meta-analysis. The global analysis showed no statistically significant difference between control and experimental groups. In the subgroup analysis, only the chlorhexidine subgroup showed a statistically significant difference, where the control groups had higher bond strength than the experimental groups. Many studies on in vitro orthodontic bond strength fail to report test conditions that could affect their outcomes. The pooled in vitro data suggest that adding an antimicrobial agent to an orthodontic adhesive system does not influence bond strength to enamel. It is not possible to state which antimicrobial agent is better to be associated.

  8. Evaluation of Questions in General Chemistry Textbooks According to the Form of the Questions and the Question-Answer Relationship (QAR): The Case of Intra-and Intermolecular Chemical Bonding

    Science.gov (United States)

    Pappa, Eleni T.; Tsaparlis, Georgios

    2011-01-01

    One way of checking to what extent instructional textbooks achieve their aim is to evaluate the questions they contain. In this work, we analyze the questions that are included in the chapters on chemical bonding of ten general chemistry textbooks. We study separately the questions on intra- and on intermolecular bonding, with the former…

  9. Synthesis, solid-state structure, and bonding analysis of a homoleptic beryllium azide

    Energy Technology Data Exchange (ETDEWEB)

    Naglav, Dominik; Tobey, Briac; Lyhs, Benjamin; Roemer, Beate; Blaeser, Dieter; Woelper, Christoph; Jansen, Georg; Schulz, Stephan [Faculty of Chemistry and Center for Nanointegration Duisburg-Essen (Cenide), Duisburg-Essen Univ., Essen (Germany)

    2017-07-10

    [Ph{sub 4}P]{sub 2}[Be(N{sub 3}){sub 4}] (1) and [PNP]{sub 2}[Be(N{sub 3}){sub 4}] (2; PNP=Ph{sub 3}PNPPh{sub 3}) were synthesized by reacting Be(N{sub 3}){sub 2} with [Ph{sub 4}P]N{sub 3} and [PNP]N{sub 3}. Compound 1 represents the first structurally characterized homoleptic beryllium azide. The electronic structure and bonding situation in the tetraazidoberyllate dianion [Be(N{sub 3}){sub 4}]{sup 2-} were investigated by quantum-chemical calculations (NPA, ELF, LOL). (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Tribology analysis of chemical-mechanical polishing

    Energy Technology Data Exchange (ETDEWEB)

    Runnels, S.R.; Eyman, L.M. (Sematech, Austin, TX (United States))

    1994-06-01

    To better understand the variation of material removal rate on a wafer during chemical-mechanical polishing (CMP), knowledge of the stress distribution on the wafer surface is required. The difference in wafer-surface stress distributions could be considerable depending on whether or not the wafer hydroplanes during polishing. This study analyzes the fluid film between the wafer and pad and demonstrates that hydroplaning is possible for standard CMP processes. The importance of wafer curvature, slurry viscosity, and rotation speed on the thickness of the fluid film is also demonstrated.

  11. Electronic structure, chemical bonding and elastic properties of the first thorium-containing nitride perovskite TaThN{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Bannikov, V.V.; Shein, I.R.; Ivanovskii, A.L. [Institute of Solid State Chemistry of the Ural Division of the Russian Academy of Sciences, GSP-145, 620041 Ekaterinburg (Russian Federation)

    2007-05-15

    The full-potential linearized augmented plane wave method with the generalized gradient approximation for the exchange and correlation potential (LAPW-GGA) is used to understand the electronic and elastic properties of the first thorium-containing nitride perovskite TaThN{sub 3}. Total and partial density of states, charge distributions as well as the elastic constants, bulk modulus, compressibility, shear modulus, Young modulus and Poisson ratio are obtained for the first time and analyzed in comparison with cubic ThN. The chemical bonding in TaThN{sub 3} is a combination of ionic Th-N and of mixed covalent-ionic Ta-N bonds. The cubic TaThN{sub 3} is semiconducting with the direct gap at about 0.65 eV. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. FTIR, FT-Raman, UV-Visible spectra and quantum chemical calculations of allantoin molecule and its hydrogen bonded dimers.

    Science.gov (United States)

    Alam, Mohammad Jane; Ahmad, Shabbir

    2015-02-05

    FTIR, FT-Raman and electronic spectra of allantoin molecule are recorded and investigated using DFT and MP2 methods with 6-311++G(d,p) basis set. The molecular structure, anharmonic vibrational spectra, natural atomic charges, non-linear optical properties, etc. have been computed for the ground state of allantoin. The anharmonic vibrational frequencies are calculated using PT2 algorithm (Barone method) as well as VSCF and CC-VSCF methods. These methods yield results that are in remarkable agreement with the experiment. The coupling strengths between pairs of modes are also calculated using coupling integral based on 2MR-QFF approximation. The simulations on allantoin dimers have been also performed at B3LYP/6-311++G(d,p) level of theory to investigate the effect of the intermolecular interactions on the molecular structure and vibrational frequencies of the monomer. Vibrational assignments are made with the great accuracy using PED calculations and animated modes. The combination and overtone bands have been also identified in the FTIR spectrum with the help of anharmonic computations. The electronic spectra are simulated in gas and solution at TD-B3LYP/6-311++G(d,p) level of theory. The important global quantities such as electro-negativity, electronic chemical potential, electrophilicity index, chemical hardness and softness based on HOMO, LUMO energy eigenvalues are also computed. NBO analysis has been performed for monomer and dimers of allantoin at B3LYP/6-311++G(d,p) level of theory. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Natural Bond Orbital (NBO) Population Analysis, First Order Hyperpolarizabilities and Thermodynamic Properties of Cyclohexanone.

    Science.gov (United States)

    Gangadharan, Rubarani P; Krishnan, S Sampath

    2015-06-01

    The molecular structure of cyclohexanone was calculated by the B3LYP density functional model with 6-31G(d, p) and 6-311++G(d,p) basis set by Gaussian program. The results from natural bond orbital (NBO) analysis have been analyzed in terms of the hybridization of atoms and the electronic structure of the title molecule. The electron density based local reactivity descriptors such as Fukui functions were calculated. The dipole moment (μ) and polarizability (a), anisotropy polarizability (Δα) and first order hyperpolarizability (β(tot)) of the molecule have been reported. Thermodynamic properties of the title compound were calculated at different temperatures.

  14. Natural Bond Orbital (NBO) Population Analysis,First Order Hyperpolarizabilities and Thermodynamic Properties of Cyclohexanone

    Institute of Scientific and Technical Information of China (English)

    Rubarani P Gangadharan; S Sampat H Krishnan

    2015-01-01

    The molecular structure of cyclohexanone was calculated by the B3LYP density functional model with 6‐31G(d ,p) and 6‐311+ +G(d ,p) basis set by Gaussian program .The results from natural bond orbital (NBO) analysis have been analyzed in terms of the hybridization of atoms and the electronic structure of the ti‐tle molecule .The electron density based local reactivity descriptors such as Fukui functions were calculated . The dipole moment (μ) and polarizability (α) ,anisotropy polarizability (Δα) and first order hyperpolarizability (βtot ) of the molecule have been reported .Thermodynamic properties of the title compound were calculated at different temperatures .

  15. Reliability Analysis for Adhesive Bonded Composite Stepped Lap Joints Loaded in Fatigue

    DEFF Research Database (Denmark)

    Kimiaeifar, Amin; Sørensen, John Dalsgaard; Lund, Erik

    2012-01-01

    This paper describes a probabilistic approach to calculate the reliability of adhesive bonded composite stepped lap joints loaded in fatigue using three- dimensional finite element analysis (FEA). A method for progressive damage modelling is used to assess fatigue damage accumulation and residual...... strength under fully reversed cyclic loading based on stiffness/strength degradation. The FEA simulations are conducted using the commercial FEA code ANSYS 12.1. A design equation for fatigue failure of wind turbine blades is chosen based on recommendations given in the wind turbine standard IEC 61400...

  16. Vibrational analysis on the revised potential energy curve of the low-barrier hydrogen bond in photoactive yellow protein

    Directory of Open Access Journals (Sweden)

    Yusuke Kanematsu

    2016-01-01

    Full Text Available Photoactive yellow protein (PYP has a characteristic hydrogen bond (H bond between p-coumaric acid chromophore and Glu46, whose OH bond length has been observed to be 1.21 Å by the neutron diffraction technique [Proc. Natl. Acad. Sci. 106, 440–4]. Although it has been expected that such a drastic elongation of the OH bond could be caused by the quantum effect of the hydrogen nucleus, previous theoretical computations including the nuclear quantum effect have so far underestimated the bond length by more than 0.07 Å. To elucidate the origin of the difference, we performed a vibrational analysis of the H bond on potential energy curve with O…O distance of 2.47 Å on the equilibrium structure, and that with O…O distance of 2.56 Å on the experimental crystal structure. While the vibrationally averaged OH bond length for equilibrium structure was underestimated, the corresponding value for crystal structure was in reasonable agreement with the corresponding experimental values. The elongation of the O…O distance by the quantum mechanical or thermal fluctuation would be indispensable for the formation of a low-barrier hydrogen bond in PYP.

  17. High and low oxidation states and special bonding situations. An investigation of f-elements, xenon and fluorine by matrix-isolation spectroscopy and quantum-chemical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Vent-Schmidt, Thomas

    2015-11-30

    asymmetric H-An-H stretching frequencies. Unfortunately the An-Se stretching mode was not observed. The assignment is supported by experiments with deuterated H{sub 2}Se and by electronic structure calculations. The Kohn-Sham orbitals show a polarized triple bond for the An-Se bonds which is supported by a NBO analysis. However, we do note that the description of the bonding can be done in different ways and that it might depend on the applied method. The results obtained for the H{sub 2}AnSe molecules are comparable to the H{sub 2}AnS compounds, but a comparison with the H{sub 2}AnTe species would be interesting. The investigation of the lanthanides is focussed on fluorides with high oxidation states on the metal center. In a first project, the Pr/F{sub 2} system is investigated experimentally and theoretically, with the focus on the question if there might exists a Pr(V) fluoride. The electronic structure calculations predict the pentafluoride, PrF{sub 5}, to be stable under cryogenic conditions. However, there is only little experimental evidence for its formation. Besides the investigation of the pentafluoride, IR bands for the tetrafluoride are reported for the first time herein and the known matrix IR bands of PrF{sub 3} are extended by values for the neon matrix. In addition, there is evidence for the formation of the low valent PrF and PrF{sub 2} species. Using the experience obtained from the Pr/F{sub 2} system, experiments were extended to other lanthanides in order to find possible new LnF{sub 4} species. Besides the known tetrafluorides CeF{sub 4}, PrF{sub 4} and TbF{sub 4}, NdF{sub 4} and DyF{sub 4} have been synthesized and characterized for the fist time in neon and argon matrices. The results are confirmed by experiments in neat fluorine matrixes and by quantum-chemical calculations. These calculations show that the synthesized LnF{sub 4} compounds are in the +IV oxidation state with only little backbonding from F orbitals into empty 5d metal orbitals. The

  18. Nitrilotris(methylenephosphonato)potassium K[μ6-NH(CH2PO3)3H4]: Synthesis, structure, and the nature of the K-O chemical bond

    Science.gov (United States)

    Somov, N. V.; Chausov, F. F.; Zakirova, R. M.

    2016-07-01

    The crystal structure of nitrilotris(methylenephosphonato)potassium K[μ6-NH(CH2PO3)3H4]—a three-dimensional coordination polymer—was determined. The potassium atom is coordinated by seven oxygen atoms belonging to the six nearest ligand molecules, resulting in distorted monocapped octahedral coordination geometry. The complex contains the four-membered chelate ring K-O-P-O. The K-O chemical bond is predominantly ionic. Meanwhile, the bonds of the potassium atom with some oxygen atoms have a noticeable covalent component. In addition to coordination bonds, the molecules in the crystal packing are linked by hydrogen bonds.

  19. Annealing-induced changes in chemical bonding and surface characteristics of chemical solution deposited Pb0.95La0.05Zr0.54Ti0.46O3 thin films

    Science.gov (United States)

    Batra, Vaishali; Ramana, C. V.; Kotru, Sushma

    2016-08-01

    We report the effect of post deposition annealing temperature (Ta = 550 and 750 °C) on the surface morphology, chemical bonding and structural development of lanthanum doped lead zirconate titanate (Pb0.95La0.05Zr0.54Ti0.46O3; referred to PLZT) thin films prepared using chemical solution deposition method. Atomic force microscopy demonstrates formation of nanocrystallites in the film annealed at Ta = 750 °C. X-ray photoelectron spectroscopy (XPS) analyses indicate that the binding energies (BE) of the Pb 4f, Zr 3d, and Ti 2p doublet experience a positive energy shift at Ta = 750 °C, whereas the BE of O 1s and La 3d doublet show a negative shift with respect to the BE of the films annealed at Ta = 750 °C. Thermal induced crystallization and chemical modification is evident from XPS results. The Ar+ sputtering of the films reveals change in oxidation state and chemical bonding between the constituent atoms, with respect to Ta. Raman spectroscopy used to study phonon-light interactions show shift in longitudinal and transverse optical modes with the change in Ta, confirming the change in phase and crystallinity of these films. The results suggest annealing at Ta = 750 °C yield crystalline perovskite PLZT films, which is essential to obtain photovoltaic response from devices based on such films.

  20. Prevalence of Bimolecular Routes in the Activation of Diatomic Molecules with Strong Chemical Bonds (O2, NO, CO, N2) on Catalytic Surfaces.

    Science.gov (United States)

    Hibbitts, David; Iglesia, Enrique

    2015-05-19

    Dissociation of the strong bonds in O2, NO, CO, and N2 often involves large activation barriers on low-index planes of metal particles used as catalysts. These kinetic hurdles reflect the noble nature of some metals (O2 activation on Au), the high coverages of co-reactants (O2 activation during CO oxidation on Pt), or the strength of the chemical bonds (NO on Pt, CO and N2 on Ru). High barriers for direct dissociations from density functional theory (DFT) have led to a consensus that "defects", consisting of low-coordination exposed atoms, are required to cleave such bonds, as calculated by theory and experiments for model surfaces at low coverages. Such sites, however, bind intermediates strongly, rendering them unreactive at the high coverages prevalent during catalysis. Such site requirements are also at odds with turnover rates that often depend weakly on cluster size or are actually higher on larger clusters, even though defects, such as corners and edges, are most abundant on small clusters. This Account illustrates how these apparent inconsistencies are resolved through activations of strong bonds assisted by co-adsorbates on crowded low-index surfaces. Catalytic oxidations occur on Au clusters at low temperatures in spite of large activation barriers for O2 dissociation on Au(111) surfaces, leading to proposals that O2 activation requires low-coordination Au atoms or Au-support interfaces. When H2O is present, however, O2 dissociation proceeds with low barriers on Au(111) because chemisorbed peroxides (*OOH* and *HOOH*) form and weaken O-O bonds before cleavage, thus allowing activation on low-index planes. DFT-derived O2 dissociation barriers are much lower on bare Pt surfaces, but such surfaces are nearly saturated with CO* during CO oxidation. A dearth of vacant sites causes O2* to react with CO* to form *OOCO* intermediates that undergo O-O cleavage. NO-H2 reactions occur on Pt clusters saturated with NO* and H*; direct NO* dissociation requires vacant

  1. Analysis of blood spots for polyfluoroalkyl chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Kayoko; Wanigatunga, Amal A.; Needham, Larry L. [Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA (United States); Calafat, Antonia M., E-mail: acalafat@cdc.gov [Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA (United States)

    2009-12-10

    Polyfluoroalkyl chemicals (PFCs) have been detected in humans, in the environment, and in ecosystems around the world. The potential for developmental and reproductive toxicities of some PFCs is of concern especially to children's health. In the United States, a sample of a baby's blood, called a 'dried blood spot' (DBS), is obtained from a heel stick within 48 h of a child's birth. DBS could be useful for assessing prenatal exposure to PFCs. We developed a method based on online solid phase extraction coupled with high performance liquid chromatography-isotope dilution tandem mass spectrometry for measuring four PFCs in DBS, perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate, perfluorooctanoate (PFOA), and perfluorononanoate. The analytical limits of detection using one whole DBS ({approx}75 {mu}L of blood) were <0.5 ng mL{sup -1}. To validate the method, we analyzed 98 DBS collected in May 2007 in the United States. PFOS and PFOA were detected in all DBS at concentrations in the low ng mL{sup -1} range. These data suggest that DBS may be a suitable matrix for assessing perinatal exposure to PFCs, but additional information related to sampling and specimen storage is needed to demonstrate the utility of these measures for assessing exposure.

  2. Molecular determinants for ATP-binding in proteins: a data mining and quantum chemical analysis.

    Science.gov (United States)

    Mao, Lisong; Wang, Yanli; Liu, Yuemin; Hu, Xiche

    2004-02-20

    Adenosine 5'-triphosphate (ATP) plays an essential role in all forms of life. Molecular recognition of ATP in proteins is a subject of great importance for understanding enzymatic mechanism and for drug design. We have carried out a large-scale data mining of the Protein Data Bank (PDB) to analyze molecular determinants for recognition of the adenine moiety of ATP by proteins. Non-bonded intermolecular interactions (hydrogen bonding, pi-pi stacking interactions, and cation-pi interactions) between adenine base and surrounding residues in its binding pockets are systematically analyzed for 68 non-redundant, high-resolution crystal structures of adenylate-binding proteins. In addition to confirming the importance of the widely known hydrogen bonding, we found out that cation-pi interactions between adenine base and positively charged residues (Lys and Arg) and pi-pi stacking interactions between adenine base and surrounding aromatic residues (Phe, Tyr, Trp) are also crucial for adenine binding in proteins. On average, there exist 2.7 hydrogen bonding interactions, 1.0 pi-pi stacking interactions, and 0.8 cation-pi interactions in each adenylate-binding protein complex. Furthermore, a high-level quantum chemical analysis was performed to analyze contributions of each of the three forms of intermolecular interactions (i.e. hydrogen bonding, pi-pi stacking interactions, and cation-pi interactions) to the overall binding force of the adenine moiety of ATP in proteins. Intermolecular interaction energies for representative configurations of intermolecular complexes were analyzed using the supermolecular approach at the MP2/6-311 + G* level, which resulted in substantial interaction strengths for all the three forms of intermolecular interactions. This work represents a timely undertaking at a historical moment when a large number of X-ray crystallographic structures of proteins with bound ATP ligands have become available, and when high-level quantum chemical analysis of

  3. Bonding analysis of planar hypercoordinate atoms via the generalized BLW-LOL.

    Science.gov (United States)

    Bomble, Laetitia; Steinmann, Stephan N; Perez-Peralta, Nancy; Merino, Gabriel; Corminboeuf, Clemence

    2013-10-05

    The multicenter bonding pattern of the intriguing hexa-, hepta-, and octacoordinate boron wheel series (e.g., CB62-, CB7-, B82-, and SiB8 as well as the experimentally detected CB7- isomer) is revised using the block-localized wave function analyzed by the localized orbital locator (BLW-LOL). The more general implementation of BLW combined with the LOL scalar field is not restricted to the analysis of the out-of-plane π-system but can also provide an intuitive picture of the σ-radial delocalization and of the role of the central atom. The results confirm the presence of a π-ring current pattern similar to that of benzene. In addition, the LOLπ isosurfaces along with the maximum intensity in the ΔLOL profiles located above and below the ring suggest that the central atom plays a minor role in the π-delocalized bonding pattern. Finally, the analysis of the σ-framework in these boron wheels is in line with a moderated inner cyclic rather than disk-type delocalization.

  4. The Bond Strength of Composite Resin to Dental Casting Alloys Using an Electro-Chemical Tin Plating System.

    Science.gov (United States)

    1985-06-01

    limit and modulus of elasticity of acrylic resins may lead to excessive plastic deformation when placed under the stresses encounted in prosthetic...etching process has been recently introduced which is reported to be effective in bonding composite resin to both base metal and gold based alloys. (Veen et... dentures , porcelain inlays, metal ceramic restorations, and porcelain laminate veneers. (Tylman, 1970; Craig, 1980; Horn, 1983) The complete porcelain

  5. Socialization of didactic units for teaching-learning of chemical bond to students of basic course in high school

    National Research Council Canada - National Science Library

    Mercedes Cárdenas-Ojeda

    2016-01-01

    .... The test Covalent Bond and its structure was applied as a diagnostic tool to 42 students of Chemistry and Bachelor of Natural Science and Environmental Education of the Universidad Pedagógica y Tecnológica de Colombia, (UPTC) the perception of this topic becomes a field that allows to explain the natural phenomena and its accurate explanation allows, on one hand, to avoid the students adapt conceptual mistakes, and on the other, foster meaningful learning in them.

  6. Bond strength analysis of the bone cement- stem interface of hip arthroplasties

    Institute of Scientific and Technical Information of China (English)

    Lan-Feng Zhang; Shi-Rong Ge; Hong-Tao Liu; Kai-Jin Guo; Shu-Yang Han; Juan-Yan Qi

    2014-01-01

    Objective:To study and establish the preliminary linear and modified models for the interface shear mechanics performance between implant and bone cement and to explore its damage significance.Method:The loosening research between artificial hip joint prosthesis stem and bone cement interface performance can be evaluated by the push-in test.Based on the debonding performance test, the analytical expressions of the average load and displacement from the debonding failure and splitting failure process were deduced and determined.The correlations of the expressions of the average load-displacement and statistical experimental data were analyzed.Results:It demonstrated that the interface debonding failure mechanical model could be characterized as interface bond strength mechanical performance.Based on analysis of models and experimental data by the three statistical analysis methods, the results indicated the modified model could be better represented by the interfacial debonding strength properties. The bond stressτand relative slidings distribution along the embedment regional were coupling affected by both pressure arch effect and shear lag effect in bone cement.Two stress peaks of implant have been found at the distance from0.175La loading tip to0.325Lafree tip, which also verified the early loosening clinical reports for the proximal and latter region.As the bone cement arch effect, the bond stress peak tend to move to the free tip when the debonding failure would be changed into the splitting failure, which presents a preliminary study on the mechanism of early debonding failurefor the stem-cement interface.Conclusions:Functional models of the stem-bone cement interfacial debonding failure are developed to analyze the relevant mechanism.The different locational titanium alloy stress, and the interfacial bond stress and the relative slides are evaluated to acquire a guide of the different positions of interfacial damage.The coupling effect which is original from

  7. Impact of post-deposition annealing on interfacial chemical bonding states between AlGaN and ZrO{sub 2} grown by atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Gang; Arulkumaran, Subramaniam; Ng, Geok Ing; Li, Yang; Ang, Kian Siong [Novitas, Nanoelectronics Center of Excellence, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Wang, Hong, E-mail: ewanghong@ntu.edu.sg [Novitas, Nanoelectronics Center of Excellence, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); CINTRA CNRS/NTU/Thales, UMI 3288, 50 Nanyang Drive (Singapore); Ng, Serene Lay Geok; Ji, Rong [Data Storage Institute, Agency for Science Technology and Research (A-STAR), 5 Engineering Drive 1, 117608 (Singapore); Liu, Zhi Hong [Singapore-MIT Alliance for Research and Technology, 1 CREATE Way, Singapore 138602 (Singapore)

    2015-03-02

    The effect of post-deposition annealing on chemical bonding states at interface between Al{sub 0.5}Ga{sub 0.5}N and ZrO{sub 2} grown by atomic layer deposition (ALD) is studied by angle-resolved x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. It has been found that both of Al-O/Al 2p and Ga-O/Ga 3d area ratio decrease at annealing temperatures lower than 500 °C, which could be attributed to “clean up” effect of ALD-ZrO{sub 2} on AlGaN. Compared to Ga spectra, a much larger decrease in Al-O/Al 2p ratio at a smaller take-off angle θ is observed, which indicates higher effectiveness of the passivation of Al-O bond than Ga-O bond through “clean up” effect near the interface. However, degradation of ZrO{sub 2}/AlGaN interface quality due to re-oxidation at higher annealing temperature (>500 °C) is also found. The XPS spectra clearly reveal that Al atoms at ZrO{sub 2}/AlGaN interface are easier to get oxidized as compared with Ga atoms.

  8. A theoretical study of water clusters: the relation between hydrogen-bond topology and interaction energy from quantum-chemical computations for clusters with up to 22 molecules.

    Science.gov (United States)

    Lenz, Annika; Ojamäe, Lars

    2005-05-07

    Quantum-chemical calculations of a variety of water clusters with eight, ten and twelve molecules were performed, as well as for selected clusters with up to 22 water molecules. Geometry optimizations were carried out at the B3LYP/cc-pVDZ level and single-point energies were calculated at the B3LYP/aug-cc-pVDZ level for selected clusters. The electronic energies were studied with respect to the geometry of the oxygen arrangement and six different characteristics of the hydrogen-bond arrangement in the cluster. Especially the effect of the placement of the non-hydrogen bonding hydrogens on the interaction energy was studied. Models for the interaction energy with respect to different characteristics of the hydrogen-bond arrangement were derived through least-square fits. The results from the study of the clusters with eight, ten and twelve molecules are used to predict possible low-energy structures for various shapes of clusters with up to 22 molecules.

  9. The Different Sensitive Behaviors of a Hydrogen-Bond Acidic Polymer-Coated SAW Sensor for Chemical Warfare Agents and Their Simulants

    Directory of Open Access Journals (Sweden)

    Yin Long

    2015-07-01

    Full Text Available A linear hydrogen-bond acidic (HBA linear functionalized polymer (PLF, was deposited onto a bare surface acoustic wave (SAW device to fabricate a chemical sensor. Real-time responses of the sensor to a series of compounds including sarin (GB, dimethyl methylphosphonate (DMMP, mustard gas (HD, chloroethyl ethyl sulphide (2-CEES, 1,5-dichloropentane (DCP and some organic solvents were studied. The results show that the sensor is highly sensitive to GB and DMMP, and has low sensitivity to HD and DCP, as expected. However, the sensor possesses an unexpected high sensitivity toward 2-CEES. This good sensing performance can’t be solely or mainly attributed to the dipole-dipole interaction since the sensor is not sensitive to some high polarity solvents. We believe the lone pair electrons around the sulphur atom of 2-CEES provide an electron-rich site, which facilitates the formation of hydrogen bonding between PLF and 2-CEES. On the contrary, the electron cloud on the sulphur atom of the HD molecule is offset or depleted by its two neighbouring strong electron-withdrawing groups, hence, hydrogen bonding can hardly be formed.

  10. The Different Sensitive Behaviors of a Hydrogen-Bond Acidic Polymer-Coated SAW Sensor for Chemical Warfare Agents and Their Simulants.

    Science.gov (United States)

    Long, Yin; Wang, Yang; Du, Xiaosong; Cheng, Luhua; Wu, Penglin; Jiang, Yadong

    2015-07-28

    A linear hydrogen-bond acidic (HBA) linear functionalized polymer (PLF), was deposited onto a bare surface acoustic wave (SAW) device to fabricate a chemical sensor. Real-time responses of the sensor to a series of compounds including sarin (GB), dimethyl methylphosphonate (DMMP), mustard gas (HD), chloroethyl ethyl sulphide (2-CEES), 1,5-dichloropentane (DCP) and some organic solvents were studied. The results show that the sensor is highly sensitive to GB and DMMP, and has low sensitivity to HD and DCP, as expected. However, the sensor possesses an unexpected high sensitivity toward 2-CEES. This good sensing performance can't be solely or mainly attributed to the dipole-dipole interaction since the sensor is not sensitive to some high polarity solvents. We believe the lone pair electrons around the sulphur atom of 2-CEES provide an electron-rich site, which facilitates the formation of hydrogen bonding between PLF and 2-CEES. On the contrary, the electron cloud on the sulphur atom of the HD molecule is offset or depleted by its two neighbouring strong electron-withdrawing groups, hence, hydrogen bonding can hardly be formed.

  11. 水对液相氧化处理聚乙烯木塑复合材胶接性能的影响%Effect of water on bonding properties for liquidoid chemical oxidation treated wood/PE composites

    Institute of Scientific and Technical Information of China (English)

    滕晓磊; 邸明伟

    2011-01-01

    The surface of wood/polyethylene (PE) composites was treated by liquidoid chemical oxidation to improve its adhesion properties.The water-resistance of treated wood/PE composites bonding joint was studied and the failure mechanism at soaking in water for the bonding joint was investigated by using analysis of contact angle,scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) through effect of water on the surface properties of treated wood/PE composites in soaking experiments.The results showed that the untreated wood/PE composites were hard to be adhered due to the polyethylene component gathered on the surface of composites, and the bonding strength and water-resistance for wood/PE composites bonding joint were improved after liquidoid chemical oxidation treatment.Water showed a remarkable effect on the surface properties for oxidation treated wood/PE composites,the surface structure changed and the crack appeared on the surface due to the moisture absorption and expansion of the wood fiber within composites under soaking in water,which resulted in the failure of bonding joint for wood/PE composites.%采用液相氧化方法对木粉/聚乙烯木塑复合材料进行表面处理以改善其胶接性能研究了氧化处理后木塑复合材料胶接接头的耐水性,并利用接触角测试、SEM、FT-IR等分析手段,探讨了木塑复合材料胶接接头在水环境下的老化失效原因 结果表明,未处理的聚乙烯木塑复合材料难以胶接,经过液相氧化处理后,不但可以提高聚乙烯木塑复合材料的胶接强度,还可改善木塑复合材料胶接接头的耐水性 在水的作用下,液相氧化处理聚乙烯木塑复合材的表面结构会发生改变,复合材料中木质纤维的吸水膨胀也会导致材料表面出现裂纹,致使胶接接头失效.

  12. Three-dimensional Material and Geometrical Nonlinear Analysis of Adhesively Bonded Single Lap Joint

    Directory of Open Access Journals (Sweden)

    S. Narasimhan

    2003-04-01

    Full Text Available The paper presents 3-D viscoplastic analysis of adhesively bonded single lap joint considering material and geometric nonlinearity. Total Lagrangian formulation is used to develop a 3-D finite element for geometric nonlinear analysis. The overall geometry of the single lap joint, the loading, and the boundary conditions has been considered, both according to the ASTM testing standards and from those adopted in earlier investigations. The constitutive relations for the adhesive are developed using a pressure-dependant (modified von Mises yield function and Ramberg-Osgood idealisation for the experimental stress-strain curve. The adherends and adhesive layers are both modelled using 20-noded solid elements. However, observations have been made, in particular, on peel and shear stresses in the adhesive layer, which provide useful insight into the 3-D nature of the problem.

  13. Particle Motion Analysis Reveals Nanoscale Bond Characteristics and Enhances Dynamic Range for Biosensing.

    Science.gov (United States)

    Visser, Emiel W A; van IJzendoorn, Leo J; Prins, Menno W J

    2016-03-22

    Biofunctionalized colloidal particles are widely used as labels in bioanalytical assays, lab-on-chip devices, biophysical research, and in studies on live biological systems. With detection resolution going down to the level of single particles and single molecules, understanding the nature of the interaction of the particles with surfaces and substrates becomes of paramount importance. Here, we present a comprehensive study of motion patterns of colloidal particles maintained in close proximity to a substrate by short molecular tethers (40 nm). The motion of the particles (500-1000 nm) was optically tracked with a very high localization accuracy (below 3 nm). A surprisingly large variation in motion patterns was observed, which can be attributed to properties of the particle-molecule-substrate system, namely the bond number, the nature of the bond, particle protrusions, and substrate nonuniformities. Experimentally observed motion patterns were compared to numerical Monte Carlo simulations, revealing a close correspondence between the observed motion patterns and properties of the molecular system. Particles bound via single tethers show distinct disc-, ring-, and bell-shaped motion patterns, where the ring- and bell-shaped patterns are caused by protrusions on the particle in the direct vicinity of the molecular attachment point. Double and triple tethered particles exhibit stripe-shaped and triangular-shaped motion patterns, respectively. The developed motion pattern analysis allows for discrimination between particles bound by different bond types, which opens the possibility to improve the limit of detection and the dynamic range of bioanalytical assays, with a projected increase of dynamic range by nearly 2 orders of magnitude.

  14. Surface chemical composition analysis of heat-treated bamboo

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Fan-dan, E-mail: fandan_meng@163.com [MOE Key Laboratory of Wooden Material Science and Application, Beijing Forestry University, 35 Qinghua East Road, Haidian District, Beijing 100083 (China); Yu, Yang-lun, E-mail: yuyanglun@caf.ac.cn [Research Institute of Wood Industry, Chinese Academy of Forestry, No 1 Dongxiaofu, Haidian District, Beijing 100091 (China); Zhang, Ya-mei, E-mail: zhangyamei@caf.ac.cn [Research Institute of Wood Industry, Chinese Academy of Forestry, No 1 Dongxiaofu, Haidian District, Beijing 100091 (China); Yu, Wen-ji, E-mail: yuwenji@caf.ac.cn [Research Institute of Wood Industry, Chinese Academy of Forestry, No 1 Dongxiaofu, Haidian District, Beijing 100091 (China); Gao, Jian-min, E-mail: gaojm@bjfu.edu.cn [MOE Key Laboratory of Wooden Material Science and Application, Beijing Forestry University, 35 Qinghua East Road, Haidian District, Beijing 100083 (China)

    2016-05-15

    Highlights: • Investigate the detailed chemical components contents change of bamboo due to heating. • Chemical analysis of bamboo main components during heating. • Identify the connection between the oxygen to carbon atomic ratio changes and chemical degradation. - Abstract: In this study, the effect of heat treatment on the chemical composition of bamboo slivers was studied. The chemical properties of the samples were examined by chemical analysis. Results showed a decrease in the contents of holocellulose and α-cellulose, as well as an increase in the contents of lignin and extractives. Changes in the chemical structure of bamboo components were analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). FTIR spectroscopy results indicated that hemicellulose contents decrease, whereas lignin contents increase after heat treatment. Ester formation linked to lignin decreased the hygroscopicity of the bamboo samples and consequently improved their dimensional stability and durability. XPS spectroscopy results showed that hemicelluloses and celluloses are relatively more sensitive to the heating process than lignin. As a consequence, hemicellulose and cellulose contents decreased, whereas lignin contents increased during heat treatment. The results obtained in this study provide useful information for the future utilization of heat-treated bamboo.

  15. Theoretical Analysis of the Effect of C═C Double Bonds on the Low-Temperature Reactivity of Alkenylperoxy Radicals.

    Science.gov (United States)

    You, Xiaoqing; Chi, Yawei; He, Tanjin

    2016-08-04

    Biodiesel contains a large proportion of unsaturated fatty acid methyl esters. Its combustion characteristics, especially its ignition behavior at low temperatures, have been greatly affected by these C═C double bonds. In this work, we performed a theoretical analysis of the effect of C═C double bonds on the low-temperature reactivity of alkenylperoxy radicals, the key intermediates from the low-temperature combustion of biodiesel. To understand how double bonds affect the fate of peroxy radicals, we selected three representative peroxy radicals from heptane, heptene, and heptadiene having zero, one, and two double C═C bonds, respectively, for study. The potential energy surfaces were explored at the CBS-QB3 level, and the reaction rate constants were computed using canonical/variational transition state theories. We have found that the double bond is responsible for the very different bond dissociation energies of the various types of C-H bonds, which in turn affect significantly the reaction kinetics of alkenylperoxy radicals.

  16. Magnetovolume and chemical bonding effects of Ni atom in γ’-(Fe1-xNix)4N compounds

    Institute of Scientific and Technical Information of China (English)

    薛德胜; 李发伸

    1997-01-01

    By X-ray diffraction and high pressure Mossbauer spectroscopy, the structure and the hyperfine parameters of Ni substituted γ-Fe4N were investigated. The results of X-ray diffraction indicate that single phase γ’-(Fe1-xNix)4N compounds can be prepared in the composition range of 0≤x≤0.6, and with the increase of Ni content the lattice parameter is fit for the relationship a0(x) = 3.790 5-0.021 57x-0.031 67x2. By high pressure Mossbauer spectra, effects of magnetovolume and chemical bonding of Ni atom on hyperfine magnetic field and isomer shift of iron were distinguished for the first time, and their composition dependences for different lattice sites were studied simultaneously. It is found that the magnetovolume and chemical bonding have different influences on the properties of γ’-(Fe1-xNix)4N, and the latter one plays a key role in the property changes of γ-(Fe1-xNix)4N.

  17. The Analysis of Corporate Bond Valuation under an Infinite Dimensional Compound Poisson Framework

    Directory of Open Access Journals (Sweden)

    Sheng Fan

    2014-01-01

    Full Text Available This paper analyzes the firm bond valuation and credit spread with an endogenous model for the pure default and callable default corporate bond. Regarding the stochastic instantaneous forward rates and the firm value as an infinite dimensional Poisson process, we provide some analytical results for the embedded American options and firm bond valuations.

  18. Arrays in biological and chemical analysis

    DEFF Research Database (Denmark)

    Christensen, Claus Bo Vöge

    2002-01-01

    Recently a dramatic change has happened for biological and biochemical analysis. Originally developed as an academic massive parallel screening tool, industry has caught the idea as well of performing all kinds of assays in the new format of microarrays. From food manufacturers over water supply...... plants to the omnipresent pharmaceutical industry, the buzz-word is bioarrays, attracting scientific funding and investor capital. Although only few commercial products are currently out in the research laboratorium, hospital clinic or at the local doctor, there are high expectations for arrays screening...... predispositions and following therapy, monitoring the amount of bacteria in food stuff, measuring the small signs from cardiac arrest before it happens, analysing the toxin level in a water sample (preferentially on-line) or deciphering the identity of an infecting bug. (C) 2002 Elsevier Science B.V. All rights...

  19. Estimation of Hydrogen-Exchange Protection Factors from MD Simulation Based on Amide Hydrogen Bonding Analysis

    Science.gov (United States)

    Park, In-Hee; Venable, John D.; Steckler, Caitlin; Cellitti, Susan E.; Lesley, Scott A.; Spraggon, Glen; Brock, Ansgar

    2015-01-01

    Hydrogen exchange (HX) studies have provided critical insight into our understanding of protein folding, structure and dynamics. More recently, Hydrogen Exchange Mass Spectrometry (HX-MS) has become a widely applicable tool for HX studies. The interpretation of the wealth of data generated by HX-MS experiments as well as other HX methods would greatly benefit from the availability of exchange predictions derived from structures or models for comparison with experiment. Most reported computational HX modeling studies have employed solvent-accessible-surface-area based metrics in attempts to interpret HX data on the basis of structures or models. In this study, a computational HX-MS prediction method based on classification of the amide hydrogen bonding modes mimicking the local unfolding model is demonstrated. Analysis of the NH bonding configurations from Molecular Dynamics (MD) simulation snapshots is used to determine partitioning over bonded and non-bonded NH states and is directly mapped into a protection factor (PF) using a logistics growth function. Predicted PFs are then used for calculating deuteration values of peptides and compared with experimental data. Hydrogen exchange MS data for Fatty acid synthase thioesterase (FAS-TE) collected for a range of pHs and temperatures was used for detailed evaluation of the approach. High correlation between prediction and experiment for observable fragment peptides is observed in the FAS-TE and additional benchmarking systems that included various apo/holo proteins for which literature data were available. In addition, it is shown that HX modeling can improve experimental resolution through decomposition of in-exchange curves into rate classes, which correlate with prediction from MD. Successful rate class decompositions provide further evidence that the presented approach captures the underlying physical processes correctly at the single residue level. This assessment is further strengthened in a comparison of

  20. Exploring Conceptual Frameworks of Models of Atomic Structures and Periodic Variations, Chemical Bonding, and Molecular Shape and Polarity: A Comparison of Undergraduate General Chemistry Students with High and Low Levels of Content Knowledge

    Science.gov (United States)

    Wang, Chia-Yu; Barrow, Lloyd H.

    2013-01-01

    The purpose of the study was to explore students' conceptual frameworks of models of atomic structure and periodic variations, chemical bonding, and molecular shape and polarity, and how these conceptual frameworks influence their quality of explanations and ability to shift among chemical representations. This study employed a purposeful sampling…

  1. Quantum chemical analysis of binary and ternary ferromagnetic alloys; Quantenchemische Untersuchungen binaerer und ternaerer ferromagnetischer Legierungen

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, Yasemin Erika Charlotte

    2007-02-23

    In this work the electronic structures, densities of states, chemical bonding, magnetic exchange Parameters and Curie temperatures of binary and ternary ferromagnetic alloys are analyzed. The electronic structure of ferromagnetic MnAl has been calculated using density-functional techniques (TB-LMTO-ASA, FPLAPW) and quantum chemically analyzed by means of the crystal orbital Hamilton population analysis. The crystal structure of the ferromagnetic tetragonal MnAl may be understood to originate from the structure of nonmagnetic cubic MnAl with a CsCl motif through a two-step process. While the nonmagnetic cubic structure is stable against a structural deformation, antibonding Mn-Mn interactions at the Fermi level lead to spin polarization and the onset of magnetism, i.e., a symmetry reduction taking place solely in the electronic degrees of freedom, by that emptying antibonding Mn-Mn states. Residual antibonding Al--Al states can only be removed by a subsequent, energetically smaller structural deformation towards the tetragonal system. As a final result, homonuclear bonding is strengthened and heteronuclear bonding is weakened. Corresponding DFT calculations of the electronic structure as well as the calculation of the chemical bonding and the magnetic exchange interactions have been performed on the basis of LDA and GGA for a series of ferromagnetic full Heusler alloys of general formula Co2MnZ (Z=Ga,Si,Ge,Sn), Rh2MnZ (Z=Ge,Sn,Pb), Ni2MnZ (Z=Ga,In,Sn), Pd2MnZ (Z=Sn,Sb) and Cu2MnZ (Z=Al,In,Sn). The connection between the electronic spectra and the magnetic interactions have been studied. Correlations between the chemical bondings in Heusler alloys derived from COHP analysis and magnetic phenomena are obvious, and different mechanisms leading to spin polarization and ferromagnetism are derived. The band dependence of the exchange parameters, their dependence on volume and valence electron concentration have been thoroughly analyzed within the Green function technique

  2. Influence of dental restorative material properties on bond interface reliability: a finite element analysis

    Institute of Scientific and Technical Information of China (English)

    ZHAO Yan-tao; ZHANG Yu-mei; HOU Shu-xun; KONG Liang; LIN Jun; ZHAO Yi-min; HUO Na

    2013-01-01

    Background Varieties of restorative materials are widely used in dentistry.The aim of this study is to explore the influence of different dental restorative materials on bond interface reliability.Methods A two-dimensional finite element analysis method was adopted to simulate the shear-bond efficacy test.The influence of elastic modulus and Poisson's ratio were investigated separately.Several dental restorative materials including resins,metals,and ceramics were analyzed in this study.Results The deformation and peak equivalent stress level of the dentin-adhesive interface rose sharply following a decrease in the elasticity of restorative materials,especially those with a low elastic modulus range.The influence of the Poisson's coefficient was not significant.Ceramics and gold alloy were preferred to resin composite in restorations bearing extensive shear load during service.Conclusions Restorative materials with an elastic modulus similar to that of teeth are not always the best clinical choice.This research provides a helpful guide for the application of different restorative materials in clinical practice.

  3. FEM thermal and stress analysis of bonded GaN-on-diamond substrate

    Science.gov (United States)

    Zhai, Wenbo; Zhang, Jingwen; Chen, Xudong; Bu, Renan; Wang, Hongxing; Hou, Xun

    2017-09-01

    A three-dimensional thermal and stress analysis of bonded GaN on diamond substrate is investigated using finite element method. The transition layer thickness, thermal conductivity of transition layer, diamond substrate thickness and the area ratio of diamond and GaN are considered and treated appropriately in the numerical simulation. The maximum channel temperature of GaN is set as a constant value and its corresponding heat power densities under different conditions are calculated to evaluate the influences that the diamond substrate and transition layer have on GaN. The results indicate the existence of transition layer will result in a decrease in the heat power density and the thickness and area of diamond substrate have certain impact on the magnitude of channel temperature and stress distribution. Channel temperature reduces with increasing diamond thickness but with a decreasing trend. The stress is reduced by increasing diamond thickness and the area ratio of diamond and GaN. The study of mechanical and thermal properties of bonded GaN on diamond substrate is useful for optimal designs of efficient heat spreader for GaN HEMT.

  4. Why does electron sharing lead to covalent bonding? A variational analysis.

    Science.gov (United States)

    Ruedenberg, Klaus; Schmidt, Michael W

    2007-01-15

    Ground state energy differences between related systems can be elucidated by a comparative variational analysis of the energy functional, in which the concepts of variational kinetic pressure and variational electrostatic potential pull are found useful. This approach is applied to the formation of the bond in the hydrogen molecule ion. A highly accurate wavefunction is shown to be the superposition of two quasiatomic orbitals, each of which consists to 94% of the respective atomic 1s orbital, the remaining 6% deformation being 73% spherical and 27% nonspherical in character. The spherical deformation can be recovered to 99.9% by scaling the 1s orbital. These results quantify the conceptual metamorphosis of the free-atom wavefunction into the molecular wavefunction by orbital sharing, orbital contraction, and orbital polarization. Starting with the 1s orbital on one atom as the initial trial function, the value of the energy functional of the molecule at the equilibrium distance is stepwise lowered along several sequences of wavefunction modifications, whose energies monotonically decrease to the ground state energy of H2+. The contributions of sharing, contraction and polarization to the overall lowering of the energy functional and their kinetic and potential components exhibit a consistent pattern that can be related to the wavefunction changes on the basis of physical reasoning, including the virial theorem. It is found that orbital sharing lowers the variational kinetic energy pressure and that this is the essential cause of covalent bonding in this molecule.

  5. Extension on KOLAS accreditation for chemical analysis of radioactive material

    Energy Technology Data Exchange (ETDEWEB)

    Sohn, Se Chul; Kim, Y. B.; Kim, W. H. and others

    2001-12-01

    The research includes the establishment of analytical target for radioactive mateials and analytical procedures fo ran international accreditatin. The determinatin of confidence level of chemical analysis for the uraniu, radium-226, radon-222, and boron was carried out. The instructions for the analysis of radioactive materials were written in this report. As a result of the research, the KOLAS accreditation was extended to the analysis of uranium innatural water, radon-222 or boron in industrial water, and cesium-137 in agricultural products.

  6. Black tea: chemical analysis and stability.

    Science.gov (United States)

    Li, Shiming; Lo, Chih-Yu; Pan, Min-Hsiung; Lai, Ching-Shu; Ho, Chi-Tang

    2013-01-01

    Tea is the most popular flavored and functional drink worldwide. The nutritional value of tea is mostly from the tea polyphenols that are reported to possess a broad spectrum of biological activities, including anti-oxidant properties, reduction of various cancers, inhibition of inflammation, and protective effects against diabetes, hyperlipidemia and obesity. Tea polyphenols include catechins and gallic acid in green and white teas, and theaflavins and thearubigins as well as other catechin polymers in black and oolong teas. Accurate analysis of black tea polyphenols plays a significant role in the identification of black tea contents, quality control of commercial tea beverages and extracts, differentiation of various contents of theaflavins and catechins and correlations of black tea identity and quality with biological activity, and most importantly, the establishment of the relationship between quantitative tea polyphenol content and its efficacy in animal or human studies. Global research in tea polyphenols has generated much in vitro and in vivo data rationally correlating tea polyphenols with their preventive and therapeutic properties in human diseases such as cancer, and metabolic and cardiovascular diseases etc. Based on these scientific findings, numerous tea products have been developed including flavored tea drinks, tea-based functional drinks, tea extracts and concentrates, and dietary supplements and food ingredients, demonstrating the broad applications of tea and its extracts, particularly in the field of functional food.

  7. Microwave-assisted acid and base hydrolysis of intact proteins containing disulfide bonds for protein sequence analysis by mass spectrometry.

    Science.gov (United States)

    Reiz, Bela; Li, Liang

    2010-09-01

    Controlled hydrolysis of proteins to generate peptide ladders combined with mass spectrometric analysis of the resultant peptides can be used for protein sequencing. In this paper, two methods of improving the microwave-assisted protein hydrolysis process are described to enable rapid sequencing of proteins containing disulfide bonds and increase sequence coverage, respectively. It was demonstrated that proteins containing disulfide bonds could be sequenced by MS analysis by first performing hydrolysis for less than 2 min, followed by 1 h of reduction to release the peptides originally linked by disulfide bonds. It was shown that a strong base could be used as a catalyst for microwave-assisted protein hydrolysis, producing complementary sequence information to that generated by microwave-assisted acid hydrolysis. However, using either acid or base hydrolysis, amide bond breakages in small regions of the polypeptide chains of the model proteins (e.g., cytochrome c and lysozyme) were not detected. Dynamic light scattering measurement of the proteins solubilized in an acid or base indicated that protein-protein interaction or aggregation was not the cause of the failure to hydrolyze certain amide bonds. It was speculated that there were some unknown local structures that might play a role in preventing an acid or base from reacting with the peptide bonds therein.

  8. Appendix C. Collection of Samples for Chemical Agent Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Koester, C; Thompson, C; Doerr, T; Scripsick, R

    2005-09-23

    This chapter describes procedures for the collection and analysis of samples of various matrices for the purpose of determining the presence of chemical agents in a civilian setting. This appendix is intended to provide the reader with sufficient information to make informed decisions about the sampling and analysis process and to suggest analytical strategies that might be implemented by the scientists performing sampling and analysis. This appendix is not intended to be used as a standard operating procedure to provide detailed instructions as to how trained scientists should handle samples. Chemical agents can be classified by their physical and chemical properties. Table 1 lists the chemical agents considered by this report. In selecting sampling and analysis methods, we have considered procedures proposed by the Organization for Prohibition of Chemical Weapons (OPCW), the U. S. Environmental Protection Agency (EPA), and peer-reviewed scientific literature. EPA analytical methods are good resources describing issues of quality assurance with respect to chain-of-custody, sample handling, and quality control requirements.

  9. Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations.

    Science.gov (United States)

    Romańczyk, Piotr P; Rotko, Grzegorz; Kurek, Stefan S

    2016-08-10

    Formal potentials of the first reduction leading to dechlorination in dimethylformamide were obtained from convolution analysis of voltammetric data and confirmed by quantum chemical calculations for a series of polychlorinated benzenes: hexachlorobenzene (-2.02 V vs. Fc(+)/Fc), pentachloroanisole (-2.14 V), and 2,4-dichlorophenoxy- and 2,4,5-trichlorophenoxyacetic acids (-2.35 V and -2.34 V, respectively). The key parameters required to calculate the reduction potential, electron affinity and/or C-Cl bond dissociation energy, were computed at both DFT-D and CCSD(T)-F12 levels. Comparison of the obtained gas-phase energies and redox potentials with experiment enabled us to verify the relative energetics and the performance of various implicit solvent models. Good agreement with the experiment was achieved for redox potentials computed at the DFT-D level, but only for the stepwise mechanism owing to the error compensation. For the concerted electron transfer/C-Cl bond cleavage process, the application of a high level coupled cluster method is required. Quantum chemical calculations have also demonstrated the significant role of the π*ring and σ*C-Cl orbital mixing. It brings about the stabilisation of the non-planar, C2v-symmetric C6Cl6˙(-) radical anion, explains the experimentally observed low energy barrier and the transfer coefficient close to 0.5 for C6Cl5OCH3 in an electron transfer process followed by immediate C-Cl bond cleavage in solution, and an increase in the probability of dechlorination of di- and trichlorophenoxyacetic acids due to substantial population of the vibrational excited states corresponding to the out-of-plane C-Cl bending at ambient temperatures.

  10. 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.

  11. 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.

  12. A chemical approach to understanding oxide surfaces

    Science.gov (United States)

    Enterkin, James A.; Becerra-Toledo, Andres E.; Poeppelmeier, Kenneth R.; Marks, Laurence D.

    2012-02-01

    Chemical bonding has often been ignored in favor of physics based energetic considerations in attempts to understand the structure, stability, and reactivity of oxide surfaces. Herein, we analyze the chemical bonding in published structures of the SrTiO3, MgO, and NiO surfaces using bond valence sum (BVS) analysis. These simple chemical bonding theories compare favorably with far more complex quantum mechanical calculations in assessing surface structure stability. Further, the coordination and bonding of surface structures explains the observed stability in a readily comprehensible manner. Finally, we demonstrate how simple chemical bonding models accurately predict the adsorption of foreign species onto surfaces, and how such models can be used to predict changes in surface structures.

  13. A review of chemical gradient systems for cell analysis.

    Science.gov (United States)

    Somaweera, Himali; Ibraguimov, Akif; Pappas, Dimitri

    2016-02-11

    Microfluidic spatial and temporal gradient generators have played an important role in many biological assays such as in the analysis of wound healing, inflammation, and cancer metastasis. Chemical gradient systems can also be applied to other fields such as drug design, chemical synthesis, chemotaxis, etc. Microfluidic systems are particularly amenable to gradient formation, as the length scales used in chips enable fluid processes that cannot be conducted in bulk scale. In this review we discuss new microfluidic devices for gradient generation and applications of those systems in cell analysis.

  14. ANALYSIS OF SAMPLES FROM TANK 5F CHEMICAL CLEANING

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, M.; Fink, S.

    2011-03-07

    The Savannah River Site (SRS) is preparing Tank 5F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning. SRS personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. The conclusions from this work are: (1) With the exception of iron, the dissolution of sludge components from Tank 5F agreed with results from the actual waste demonstration performed in 2007. The fraction of iron removed from Tank 5F by chemical cleaning was significantly less than the fraction removed in the SRNL demonstrations. The likely cause of this difference is the high pH following the first oxalic acid strike. (2) Most of the sludge mass remaining in the tank is iron and nickel. (3) The remaining sludge contains approximately 26 kg of barium, 37 kg of chromium, and 37 kg of mercury. (4) Most of the radioactivity remaining in the residual material is beta emitters and {sup 90}Sr. (5) The chemical cleaning removed more than {approx} 90% of the uranium isotopes and {sup 137}Cs. (6) The chemical cleaning removed {approx} 70% of the neptunium, {approx} 83% of the {sup 90}Sr, and {approx} 21% of the {sup 60}Co. (7) The chemical cleaning removed less than 10% of the plutonium, americium, and curium isotopes. (8) The chemical cleaning removed more than 90% of the aluminium, calcium, and sodium from the tank. (9) The cleaning operations removed 61% of lithium, 88% of non-radioactive strontium, and 65% of zirconium. The {sup 90}Sr and non-radioactive strontium were

  15. Detailed investigation of the analysis conditions in the evaluation of bonded joints by cohesive zone models

    Science.gov (United States)

    Rocha, R. J. B.; Campilho, R. D. S. G.

    2017-05-01

    Cohesive Zone Models (CZM) are widely used for the strength prediction of adhesive joints. This work studies the influence of different conditions used in CZM simulations to model a thin adhesive layer in single-lap joints (SLJ) under a tensile loading, for an estimation of their influence on the strength prediction under diverse geometrical and material conditions. Adhesives ranging from brittle to highly ductile and overlap lengths (LO) between 12.5 and 50 mm were considered. Several damage initiation and growth criteria were tested. The analysis carried out in this work allowed to conclude that CZM is a powerful technique for strength prediction of bonded joints, provided that the modelling conditions are properly defined.

  16. Surface chemical composition analysis of heat-treated bamboo

    Science.gov (United States)

    Meng, Fan-dan; Yu, Yang-lun; Zhang, Ya-mei; Yu, Wen-ji; Gao, Jian-min

    2016-05-01

    In this study, the effect of heat treatment on the chemical composition of bamboo slivers was studied. The chemical properties of the samples were examined by chemical analysis. Results showed a decrease in the contents of holocellulose and α-cellulose, as well as an increase in the contents of lignin and extractives. Changes in the chemical structure of bamboo components were analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). FTIR spectroscopy results indicated that hemicellulose contents decrease, whereas lignin contents increase after heat treatment. Ester formation linked to lignin decreased the hygroscopicity of the bamboo samples and consequently improved their dimensional stability and durability. XPS spectroscopy results showed that hemicelluloses and celluloses are relatively more sensitive to the heating process than lignin. As a consequence, hemicellulose and cellulose contents decreased, whereas lignin contents increased during heat treatment. The results obtained in this study provide useful information for the future utilization of heat-treated bamboo.

  17. ADVANCED 3D LASER MICROSCOPY FOR MEASUREMENTS AND ANALYSIS OF VITRIFIED BONDED ABRASIVE TOOLS

    Directory of Open Access Journals (Sweden)

    WOJCIECH KAPLONEK

    2012-12-01

    Full Text Available In many applications, when a precise non-contact assessment of an abrasive tools’ surface is required, alternative measurement methods are often used. Their use offers numerous advantages (referential method as they introduce new qualities into routinely realized measurements. Over the past few years there has been a dynamic increase in the interest for using new types of classical confocal microscopy. These new types are often defined as 3D laser microscopy. This paper presents select aspects of one such method’s application – confocal laser scanning microscopy – for diagnostic analysis of abrasive tools. In addition this paper also looks at the basis for operation, the origins and the development of this measurement technique.The experimental part of this paper presents the select results of tests carried out on grinding wheel active surfaces with sintered microcrystalline corundum grains SG™ bound with glass-crystalline bond. The 3D laser measuring microscopes LEXT OLS3100 and LEXT OLS4000 by Olympus were used in the experiments. Analysis of the obtained measurement data was carried out in dedicated OLS 5.0.9 and OLS4100 2.1 programs, supported by specialist TalyMap Platinum 5.0 software. The realized experiments confirmed the possibility of using the offered measurement method. This concerns both the assessment of grinding wheel active surfaces and their defects, as well as the internal structures of the tools (grain-bond connections. The method presented is an interesting alternative to the typical methods used in the diagnostics of abrasive tools.

  18. [Effect of surface pretreatment with chemical etchants on bond strength between a silicone-based resilient liner and denture base resin].

    Science.gov (United States)

    Zhang, Ying; Zhang, Huai-qin; Ma, Jun-chi; Jin, Si-yuan

    2011-12-01

    To evaluate the effect of denture base resin surface pretreatment with chemical etchants on microleakage and bond strength between silicone-based resilient liner and denture base resin. The initial bending strength of denture base resin after surface pretreatment was also examined. Thirty-six polymethyl methacrylate (PMMA) denture base resin blocks (30 mm × 30 mm × 2 mm) were prepared and divided into three groups: group acetone, group methyl methy acrylate (MMA) and group control. Subsequently, a 2 mm silicone-based resilient liner was applied between every two blocks. After 5000 cycles in the thermal cycler (5 and 55°C), they were immersed in the (131) I solution for 24 hours and γ-ray counts were measured. Another 36 PMMA resin blocks (30 mm × 10 mm × 7.5 mm) were prepared. The blocks were divided into three groups and treated as mentioned above. A 3 mm silicone-based resilient liner was applied between every two blocks. After 5000 thermal cycles, tensile bond strength of the sample was measured in a universal testing machine. Another 18 PMMA resin blocks (65 mm × 10 mm × 3.3 mm) were prepared. They were divided into 3 groups and treated in the same way. After an adhesive was applied, the bending strength was measured with three-piont bending test. Two experimental groups showed lower microleakage (520.0 ± 562.2 and 493.5 ± 447.9) and higher tensile bond strength [(1.5 ± 0.4) and (1.4 ± 0.5) MPa] than the group control [microleakage: (1369.5 ± 590.2); tensile bond strength: (0.9 ± 0.2) MPa, P 0.05). There was no statistically significant difference in bending strength among the three groups (P > 0.05). Treating the denture base resin surface with acetone and MMA decreased the microleakage, increased the tensile bond strength between the two materials and did not make the initial bending strength of denture base resin decline.

  19. Toxic hazard and chemical analysis of leachates from furfurylated wood.

    Science.gov (United States)

    Pilgård, Annica; Treu, Andreas; van Zeeland, Albert N T; Gosselink, Richard J A; Westin, Mats

    2010-09-01

    The furfurylation process is an extensively investigated wood modification process. Furfuryl alcohol molecules penetrate into the wood cell wall and polymerize in situ. This results in a permanent swelling of the wood cell walls. It is unclear whether or not chemical bonds exist between the furfuryl alcohol polymer and the wood. In the present study, five different wood species were used, both hardwoods and softwoods. They were treated with three different furfurylation procedures and leached according to three different leaching methods. The present study shows that, in general, the leachates from furfurylated wood have low toxicity. It also shows that the choice of leaching method is decisive for the outcome of the toxicity results. Earlier studies have shown that leachates from wood treated with furfuryl alcohol prepolymers have higher toxicity to Vibrio fischeri than leachates from wood treated with furfuryl alcohol monomers. This is probably attributable to differences in leaching of chemical compounds. The present study shows that this difference in the toxicity most likely cannot be attributed to maleic acid, furan, furfural, furfuryl alcohol, or 2-furoic acid. However, the difference might be caused by the two substances 5-hydroxymethylfurfural and 2,5-furandimethanol. The present study found no difference in the amount of leached furfuryl alcohol between leachates from furfurylated softwood and furfurylated hardwood species. Earlier studies have indicated differences in grafting of furfuryl alcohol to lignin. However, nothing was found in the present study that could support this. The leachates of furfurylated wood still need to be

  20. Hydrogen bond driven chemical reactions: Beckmann rearrangement of cyclohexanone oxime into epsilon-caprolactam in supercritical water.

    Science.gov (United States)

    Boero, Mauro; Ikeshoji, Tamio; Liew, Chee Chin; Terakura, Kiyoyuki; Parrinello, Michele

    2004-05-26

    Recent experiments have shown that supercritical water (SCW) has the ability to accelerate and make selective synthetic organic reactions, thus replacing the common but environmentally harmful acid and basic catalysts. In an attempt to understand the intimate mechanism behind this observation, we analyze, via first-principles molecular dynamics, the Beckmann rearrangement of cyclohexanone oxime into epsilon-caprolactam in supercritical water, for which accurate experimental evidence has been reported. Differences in the wetting of the hydrophilic parts of the solute, enhanced by SCW, and the disrupted hydrogen bond network are shown to be crucial in triggering the reaction and in making it selective. Furthermore, the enhanced concentrations of H(+) in SCW play an important role in starting the reaction.

  1. New sol–gel refractory coatings on chemically-bonded sand cores for foundry applications to improve casting surface quality

    DEFF Research Database (Denmark)

    Nwaogu, Ugochukwu Chibuzoh; Poulsen, T.; Stage, R.K.

    2011-01-01

    Foundry refractory coatings protect bonded sand cores and moulds from producing defective castings during the casting process by providing a barrier between the core and the liquid metal. In this study, new sol–gel refractory coating on phenolic urethane cold box (PUCB) core was examined....... The coating density, viscosity, moisture content and wet and dry weight of the coating were evaluated on cores that had been coated at three different dip-coating times. The coating coverage, surface appearance and depth of penetration into the cores were examined with a Stereomicroscope. Gray iron castings...... were produced with sol-gel coated and uncoated cores and the results were related to the coating properties. The casting results were also compared with castings made with cores coated with commercial alcohol-based and water-based foundry coatings. The analyses show that castings produced with sol...

  2. Stereocontrolled Synthesis of β-Lactams within [2]Rotaxanes: Showcasing the Chemical Consequences of the Mechanical Bond.

    Science.gov (United States)

    Martinez-Cuezva, Alberto; Lopez-Leonardo, Carmen; Bautista, Delia; Alajarin, Mateo; Berna, Jose

    2016-07-20

    The intramolecular cyclization of N-benzylfumaramide [2]rotaxanes is described. The mechanical bond of these substrates activates this transformation to proceed in high yields and in a regio- and diastereoselective manner, giving interlocked 3,4-disubstituted trans-azetidin-2-ones. This activation effect markedly differs from the more common shielding protection of threaded functions by the macrocycle, in this case promoting an unusual and disfavored 4-exo-trig ring closure. Kinetic and synthetic studies allowed us to delineate an advantageous approach toward β-lactams based on a two-step, one-pot protocol: an intramolecular ring closure followed by a thermally induced dethreading step. The advantages of carrying out this cyclization in the confined space of a benzylic amide macrocycle are attributed to its anchimeric assistance.

  3. LSENS - GENERAL CHEMICAL KINETICS AND SENSITIVITY ANALYSIS CODE

    Science.gov (United States)

    Bittker, D. A.

    1994-01-01

    LSENS has been developed for solving complex, homogeneous, gas-phase, chemical kinetics problems. The motivation for the development of this program is the continuing interest in developing detailed chemical reaction mechanisms for complex reactions such as the combustion of fuels and pollutant formation and destruction. A reaction mechanism is the set of all elementary chemical reactions that are required to describe the process of interest. Mathematical descriptions of chemical kinetics problems constitute sets of coupled, nonlinear, first-order ordinary differential equations (ODEs). The number of ODEs can be very large because of the numerous chemical species involved in the reaction mechanism. Further complicating the situation are the many simultaneous reactions needed to describe the chemical kinetics of practical fuels. For example, the mechanism describing the oxidation of the simplest hydrocarbon fuel, methane, involves over 25 species participating in nearly 100 elementary reaction steps. Validating a chemical reaction mechanism requires repetitive solutions of the governing ODEs for a variety of reaction conditions. Analytical solutions to the systems of ODEs describing chemistry are not possible, except for the simplest cases, which are of little or no practical value. Consequently, there is a need for fast and reliable numerical solution techniques for chemical kinetics problems. In addition to solving the ODEs describing chemical kinetics, it is often necessary to know what effects variations in either initial condition values or chemical reaction mechanism parameters have on the solution. Such a need arises in the development of reaction mechanisms from experimental data. The rate coefficients are often not known with great precision and in general, the experimental data are not sufficiently detailed to accurately estimate the rate coefficient parameters. The development of a reaction mechanism is facilitated by a systematic sensitivity analysis

  4. Computational singular perturbation analysis of stochastic chemical systems with stiffness

    Science.gov (United States)

    Wang, Lijin; Han, Xiaoying; Cao, Yanzhao; Najm, Habib N.

    2017-04-01

    Computational singular perturbation (CSP) is a useful method for analysis, reduction, and time integration of stiff ordinary differential equation systems. It has found dominant utility, in particular, in chemical reaction systems with a large range of time scales at continuum and deterministic level. On the other hand, CSP is not directly applicable to chemical reaction systems at micro or meso-scale, where stochasticity plays an non-negligible role and thus has to be taken into account. In this work we develop a novel stochastic computational singular perturbation (SCSP) analysis and time integration framework, and associated algorithm, that can be used to not only construct accurately and efficiently the numerical solutions to stiff stochastic chemical reaction systems, but also analyze the dynamics of the reduced stochastic reaction systems. The algorithm is illustrated by an application to a benchmark stochastic differential equation model, and numerical experiments are carried out to demonstrate the effectiveness of the construction.

  5. Analysis of Plasma-Sprayed Thermal Barrier Coatings With Homogeneous and Heterogeneous Bond Coats Under Spatially Uniform Cyclic Thermal Loading

    Science.gov (United States)

    Arnold, Steven M.; Pindera, Marek-Jerzy; Aboudi, Jacob

    2003-01-01

    This report summarizes the results of a numerical investigation into the spallation mechanism in plasma-sprayed thermal barrier coatings observed under spatially-uniform cyclic thermal loading. The analysis focuses on the evolution of local stress and inelastic strain fields in the vicinity of the rough top/bond coat interface during thermal cycling, and how these fields are influenced by the presence of an oxide film and spatially uniform and graded distributions of alumina particles in the metallic bond coat aimed at reducing the top/bond coat thermal expansion mismatch. The impact of these factors on the potential growth of a local horizontal delamination at the rough interface's crest is included. The analysis is conducted using the Higher-Order Theory for Functionally Graded Materials with creep/relaxation constituent modeling capabilities. For two-phase bond coat microstructures, both the actual and homogenized properties are employed in the analysis. The results reveal the important contributions of both the normal and shear stress components to the delamination growth potential in the presence of an oxide film, and suggest mixed-mode crack propagation. The use of bond coats with uniform or graded microstructures is shown to increase the potential for delamination growth by increasing the magnitude of the crack-tip shear stress component.

  6. Spectangular - Spectral Disentangling For Detailed Chemical Analysis Of Binaries

    Science.gov (United States)

    Sablowski, Daniel

    2016-08-01

    Disentangling of spectra helps to improve the orbit parameters and allows detailed chemical analysis. Spectangular is a GUI program written in C++ for spectral disentangling of spectra of SB1 and SB2 systems. It is based on singular value decomposition in the wavelength space and is coupled to an orbital solution.The results are the component spectra and the orbital parameters.

  7. Chemical analysis of Ginkgo biloba leaves and extracts

    NARCIS (Netherlands)

    Beek, van T.A.

    2002-01-01

    The chemical analysis and quality control of Ginkgo leaves and extracts is reviewed. Important constituents present in the medicinally used leaves are the terpene trilactones, i.e., ginkgolides A, B, C, J and bilobalide, many flavonol glycosides, biflavones, proanthocyanidins, alkylphenols, simple p

  8. Chemical analysis of the Assale (Ethiopia) rock salt deposit | Binega ...

    African Journals Online (AJOL)

    Chemical analysis of the Assale (Ethiopia) rock salt deposit. ... Log in or Register to get access to full text downloads. ... in common and table salt set by the Ethiopian Quality and Standards Authority. However, during excavation together with the rock salt some soil, mud and other contaminants are found that require further ...

  9. An Effective Hamiltonian Molecular Orbital-Valence Bond (MOVB) Approach for Chemical Reactions Applied to the Nucleophilic Substitution Reaction of Hydrosulfide Ion and Chloromethane.

    Science.gov (United States)

    Song, Lingchun; Mo, Yirong; Gao, Jiali

    2009-01-01

    An effective Hamiltonian mixed molecular orbital and valence bond (EH-MOVB) method is described to obtain an accurate potential energy surface for chemical reactions. Building upon previous results on the construction of diabatic and adiabatic potential surfaces using ab initio MOVB theory, we introduce a diabatic-coupling scaling factor to uniformly scale the ab initio off-diagonal matrix element H(12) such that the computed energy of reaction from the EH-MOVB method is in agreement with the target value. The scaling factor is very close to unity, resulting in minimal alteration of the potential energy surface of the original MOVB model. Furthermore, the relative energy between the reactant and product diabatic states in the EH-MOVB method can be improved to match the experimental energy of reaction. A key ingredient in the EH-MOVB theory is that the off-diagonal matrix elements are functions of all degrees of freedom of the system and the overlap matrix is explicitly evaluated. The EH-MOVB method has been applied to the nucleophilic substitution reaction between hydrosulfide and chloromethane to illustrate the methodology and the results were matched to reproduce the results from ab initio valence bond self-consistent valence bond (VBSCF) calculations. The diabatic coupling (the off-diagonal matrix element in the generalized secular equation) has small variations along the minimum energy reaction path in the EH-MOVB model, whereas it shows a maximum value at the transition state and has nearly zero values in the regions of the ion-dipole complexes from VBSCF calculations. The difference in the diabatic coupling stabilization is attributed to the large overlap integral in the computationally efficient MOVB method.

  10. Analysis of bonded anisotropic wedges with interface crack under anti-plane shear loading

    Institute of Scientific and Technical Information of China (English)

    M.GHADIRI; A.R.SHAHANI

    2014-01-01

    The antiplane stress analysis of two anisotropic finite wedges with arbitrary radii and apex angles that are bonded together along a common edge is investigated. The wedge radial boundaries can be subjected to displacement-displacement boundary condi-tions, and the circular boundary of the wedge is free from any traction. The new finite complex transforms are employed to solve the problem. These finite complex transforms have complex analogies to both kinds of standard finite Mellin transforms. The traction free condition on the crack faces is expressed as a singular integral equation by using the exact analytical method. The explicit terms for the strength of singularity are extracted, showing the dependence of the order of the stress singularity on the wedge angle, material constants, and boundary conditions. A numerical method is used for solving the resul-tant singular integral equations. The displacement boundary condition may be a general term of the Taylor series expansion for the displacement prescribed on the radial edge of the wedge. Thus, the analysis of every kind of displacement boundary conditions can be obtained by the achieved results from the foregoing general displacement boundary condition. The obtained stress intensity factors (SIFs) at the crack tips are plotted and compared with those obtained by the finite element analysis (FEA).

  11. Experiment and simulation analysis of roll-bonded Q235 steel plate

    Directory of Open Access Journals (Sweden)

    Zhao, Guanghui

    2016-06-01

    Full Text Available Heavy-gauge Q235 steel plate was roll bonded, and the process was simulated using MARC software. Ultrasonic testing results revealed the presence of cracks and lamination defects in an 80-mm clad steel sheet, especially at the head and tail of the steel plate. There were non-uniform ferrite + pearlite microstructures and unbound areas at a bond interface. Through scanning electron microscopy analysis, long cracks and additional inclusions in the cracks were observed at the interface. A fracture analysis revealed non-uniform inclusions that pervaded the interface. Moreover, MARC simulations demonstrated that there was little equivalent strain at the centre of the slab during the first rolling pass. The equivalent centre increased to 0.5 by the fourth rolling pass. Prior to the final pass, the equivalent strain was not consistent across the thickness direction, preventing bonding interfaces from forming consistent deformation and decreasing the residual stress. The initial rolling reduction rate should not be very small (e.g. 5% as it is averse to the coordination of rolling deformation. Such rolling processes are averse to the rolling bond.Planchas de acero Q235 de espesor grueso se unieron mediante laminación y el proceso fue simulado numéricamente utilizando el programa de cálculo MARC. Los resultados obtenidos en ensayos mediante ultrasonidos revelaron la presencia de grietas y defectos en la laminación en una plancha de acero revestido de 80 mm, especialmente en el comienzo y final de la plancha. La microestructura consistía en ferrita+perlita y desunión en la interfase de unión. Mediante análisis por microscopía electrónica de barrido se observó que la interfase contenía grietas con inclusiones. Un análisis de la fractura reveló la presencia de inclusiones no uniformes en la interfase. Además, los datos de simulación utilizando el programa MARC demostraron que había poca tensión equivalente en el centro de la plancha

  12. Forensic analysis of bicomponent fibers using infrared chemical imaging.

    Science.gov (United States)

    Flynn, Katherine; O'Leary, Robyn; Roux, Claude; Reedy, Brian J

    2006-05-01

    The application of infrared chemical imaging to the analysis of bicomponent fibers was evaluated. Eleven nominally bicomponent fibers were examined either side-on or in cross-section. In six of the 11 samples, infrared chemical imaging was able to spatially resolve two spectroscopically distinct regions when the fibers were examined side-on. As well as yielding characteristic infrared spectra of each component, the technique also provided images that clearly illustrated the side-by-side configuration of these components in the fiber. In one case it was possible to prepare and image a cross-section of the fiber, but in general the preparation of fiber cross-sections proved very difficult. In five of the 11 samples, the infrared spectra could be used to identify the overall chemical composition of the fibers, according to a published classification scheme, but the fiber components could not be spatially resolved. Difficulties that are inherent to conventional "single-point" infrared spectroscopy, such as interference fringing and sloping baselines, particularly when analyzing acrylic type fibers, were also encountered in the infrared chemical image analysis of bicomponent fibers. A number of infrared sampling techniques were investigated to overcome these problems, and recommendations for the best sampling technique are given. Chemical imaging results were compared with those obtained using conventional fiber microscopy techniques.

  13. Modeling and analysis of the electromechanical behavior of surface-bonded piezoelectric actuators using finite element method

    CERN Document Server

    Yu, Huangchao

    2016-01-01

    Piezoelectric actuators have been widely used to form a self-monitoring smart system to do Structural health monitoring (SHM). One of the most fundamental issues in using actuators is to determine the actuation effects being transferred from the actuators to the host structure. This report summaries the state of the art of modeling techniques for piezoelectric actuators and provides a numerical analysis of the static and dynamic electromechanical behavior of piezoelectric actuators surface-bonded to an elastic medium under in-plane mechanical and electric loads using finite element method. Also case study is conducted to study the effect of material properties, bonding layer and loading frequency using static and harmonic analysis of ANSYS. Finally, stresses and displacements are determined, and singularity behavior at the tips of the actuator is proved. The results indicate that material properties, bonding layers and frequency have a significant influence on the stresses transferred to the host structure.

  14. Effect of Si-H bond on the gas-phase chemistry of trimethylsilane in the hot wire chemical vapor deposition process.

    Science.gov (United States)

    Shi, Y J; Li, X M; Toukabri, R; Tong, L

    2011-09-22

    The effect of the Si-H bond on the gas-phase reaction chemistry of trimethylsilane in the hot-wire chemical vapor deposition (HWCVD) process has been studied by examining its decomposition on a hot tungsten filament and the secondary gas-phase reactions in a reactor using a soft laser ionization source coupled with mass spectrometry. Trimethylsilane decomposes on the hot filament via Si-H and Si-CH(3) bond cleavages. A short-chain mechanism is found to dominate in the secondary reactions in the reactor. It has been shown that the hydrogen abstractions of both Si-H and C-H occur simultaneously, with the abstraction of Si-H being favored. Tetramethylsilane and hexamethyldisilane are the two major products formed from the radical recombination reactions in the termination steps. Three methyl-substituted disilacyclobutane molecules, i.e., 1,3-dimethyl-1,3-disilacyclobutane, 1,1,3-trimethyl-1,3-disilacyclobutane, and 1,1,3,3-tetramethyl-1,3-disilacyclobutane are also produced in reactor from the cycloaddition reactions of methyl-substituted silene species. Compared to tetramethylsilane and hexamethyldisilane, a common feature with trimethylsilane is that the short-chain mechanism still dominates. However, a more active involvement of the reactive silene intermediates has been found with trimethylsilane.

  15. Shear bond strength evaluation of chemically-cured and light-cured orthodontic adhesives after enamel deproteinization with 5.25% sodium hypochlorite

    Science.gov (United States)

    Salim, J. C.; Krisnawati; Purbiati, M.

    2017-08-01

    This study aimed to assess the effect of enamel deproteinization with 5.25% sodium hypochlorite (NaOCl) before etching on the shear bond strength (SBS) of Unite (UN; 3M Unitek) and Xihu-BIOM adhesive (XB). Fifty-two maxillary first premolars were divided into four groups: (1) UN and (2) XB according to manufacturer’s recommendation and (3) UN and (4) XB deproteinized with 5.25% NaOCl. Brackets were bonded, and a mechanical test was performed using a universal testing machine. The mean SBS value for groups A1, A2, B1, and B2 was 13.51 ± 2.552, 14.36 ± 2.902, 16.43 ± 2.615, and 13.05 ± 2.348 MPa, respectively. A statistically significant difference in SBSs was observed between chemically cured groups and between group B (p adhesive groups and between group A (p > 0.05). NaOCl enamel deproteinization before acid etching has a significant effect on the SBS of Unite adhesive, but not on that of the Xihu-BIOM adhesive. Furthermore, a significant difference in the SBS of Unite and Xihu-BIOM adhesives within the enamel deproteinization group was observed in this study.

  16. Comparison of the Shear Bond Strength of Light-cured and Chemically-cured Resin Adhesive%光固化和化学固化树脂粘接剂剪切强度的对比研究

    Institute of Scientific and Technical Information of China (English)

    张隆祺; 王野平

    2001-01-01

    Objective To compare the shear bond strength of light-cured and chemically-cured resin adhesive. Methods Twenty recently extracted human premolars were randomly divided into two groups of 10 each.: Group A, using the chemically-cured resin adhesive (Jing Jinenamel adhesive) and Group B, using the light-cured resin adhesive (Transbond XT,3M Unitek). The brackets were bonded to prepared enamel surfaces and the samples were placed in a water bath at 37℃ for 24 hours, then measured the shear bond strength and assessed the remaining adhesive after debonded. Results The shear bond strength and assessing the remaining adhesive after debonded both had no statistical significanct difference between two adhesives. Conclusion The light-cured and the chemically-cured resin adhesive both have strong bond strength, but the light-cured resin adhesive has the advantage to offer more sufficient time for positioning and bonding the brackets, so it is recommended for using.%-05)。结论光固化和化学固化树脂粘接剂均具有较强的粘接强度,但光固化树脂粘接剂能够为托槽的定位和粘接提供充足的时间,推荐使用。

  17. Effects of combination modes of favorable growth unit of Al(OH)3 crystals precipitating on Van der Waals and chemical bond force

    Institute of Scientific and Technical Information of China (English)

    WU Zheng-ping; CHEN Qi-yuan; YIN Zhou-lan; LI Jie

    2005-01-01

    The dipole moment, total energy, atomic charge, orbital population and orbital energy of four representative combination models of the favorable growth unit Al6 (OH)18 (H2O)6 of Al(OH)3 crystals precipitating are calculated by ab initio at RHF/STO-3G, RHF/3-21G, RHF/6-31G levels and DFT at RB3LYP/STO-3G, RB3LYP/3-21G, RB3LYP/6-31G levels with Dipole & Sphere solvent model. The effect of various combination models on Van der Waals force is analyzed using dipole moment and molecular radius, and that on chemical bond force is analyzed using total energy, orbital population and orbital energy.

  18. Probing the structures and chemical bonding of boron-boronyl clusters using photoelectron spectroscopy and computational chemistry: B4(BO)(n)- (n = 1-3).

    Science.gov (United States)

    Chen, Qiang; Zhai, Hua-Jin; Li, Si-Dian; Wang, Lai-Sheng

    2012-07-28

    The electronic and structural properties of a series of boron oxide clusters, B(5)O(-), B(6)O(2)(-), and B(7)O(3)(-), are studied using photoelectron spectroscopy and density functional calculations. Vibrationally resolved photoelectron spectra are obtained, yielding electron affinities of 3.45, 3.54, and 4.94 eV for the corresponding neutrals, B(5)O, B(6)O(2), and B(7)O(3), respectively. Structural optimizations show that these oxide clusters can be formulated as B(4)(BO)(n)(-) (n = 1-3), which involve boronyls coordinated to a planar rhombic B(4) cluster. Chemical bonding analyses indicate that the B(4)(BO)(n)(-) clusters are all aromatic species with two π electrons.

  19. Probing the structures and chemical bonding of boron-boronyl clusters using photoelectron spectroscopy and computational chemistry: B4(BO)n- (n = 1-3)

    Science.gov (United States)

    Chen, Qiang; Zhai, Hua-Jin; Li, Si-Dian; Wang, Lai-Sheng

    2012-07-01

    The electronic and structural properties of a series of boron oxide clusters, B5O-, B6O2-, and B7O3-, are studied using photoelectron spectroscopy and density functional calculations. Vibrationally resolved photoelectron spectra are obtained, yielding electron affinities of 3.45, 3.54, and 4.94 eV for the corresponding neutrals, B5O, B6O2, and B7O3, respectively. Structural optimizations show that these oxide clusters can be formulated as B4(BO)n- (n = 1-3), which involve boronyls coordinated to a planar rhombic B4 cluster. Chemical bonding analyses indicate that the B4(BO)n- clusters are all aromatic species with two π electrons.

  20. Improving the state of the art in FEM analysis of PCCVs with bonded and unbonded prestress tendons

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Christopher A., E-mail: cajone@sandia.gov [Sandia National Laboratories, PO Box 5800, MS 0744, Albuquerque, NM 87125-0744 (United States); Dameron, Robert, E-mail: rdameron@moffattnichol.com [Moffatt and Nichol, 1660 Hotel Cir N, San Diego, CA 92108 (United States); Sircar, Madhumita, E-mail: Madhumita.sircar@nrc.gov [U.S. Nuclear Regulatory Commission, Washington, DC 20555-0001 (United States)

    2015-12-15

    Highlights: • A novel method for FE modeling of bonded and unbonded tendons was developed. • Bonded and unbonded tendon models were compared for use in PCCVs. • For internal overpressurization, unbonded tendons perform slightly better. • Tendon slip and load redistribution are credited for the increased performance. - Abstract: In order to assess the structural performance of grouted prestressing systems in nuclear power containment vessels, a full containment vessel was modeled using the finite element program, ABAQUS. Both bonded (grouted) and unbonded (ungrouted) prestressing systems were modeled. Prior to simulation of grouting, both models were identical, with the prestressing stages modeled explicitly, and friction represented along the tendons. The results indicate higher peak stresses and strains in the bonded model since the tendon system is not permitted to slip and redistribute forces as the vessel deforms. Correspondingly, it is noted that the analysis predicts failure of the vessel at a lower internal pressure in the case of the bonded system. This work is an extension of a collaborative study of finite element analysis (FEA) of prestressed concrete containment vessels (PCCVs) sponsored by the United States Nuclear Regulatory Commission (USNRC) and the Atomic Energy Regulatory Board (AERB) of India. Particular emphasis was placed on advancing the state of the art in modeling tendons (Akin et al., 2013a; Heitman et al., 2014).

  1. Enhanced Electrochemical Performances of Bi2O3/rGO Nanocomposite via Chemical Bonding as Anode Materials for Lithium Ion Batteries.

    Science.gov (United States)

    Deng, Zhuo; Liu, Tingting; Chen, Tao; Jiang, Jiaxiang; Yang, Wanli; Guo, Jun; Zhao, Jianqing; Wang, Haibo; Gao, Lijun

    2017-04-12

    Bismuth oxide/reduced graphene oxide (termed Bi2O3@rGO) nanocomposite has been facilely prepared by a solvothermal method via introducing chemical bonding that has been demonstrated by Raman and X-ray photoelectron spectroscopy spectra. Tremendous single-crystal Bi2O3 nanoparticles with an average size of ∼5 nm are anchored and uniformly dispersed on rGO sheets. Such a nanostructure results in enhanced electrochemical reversibility and cycling stability of Bi2O3@rGO composite materials as anodes for lithium ion batteries in comparison with agglomerated bare Bi2O3 nanoparticles. The Bi2O3@rGO anode material can deliver a high initial capacity of ∼900 mAh/g at 0.1C and shows excellent rate capability of ∼270 mAh/g at 10C rates (1C = 600 mA/g). After 100 electrochemical cycles at 1C, the Bi2O3@rGO anode material retains a capacity of 347.3 mAh/g with corresponding capacity retention of 79%, which is significantly better than that of bare Bi2O3 material. The lithium ion diffusion coefficient during lithiation-delithiation of Bi2O3@rGO nanocomposite has been evaluated to be around ∼10(-15)-10(-16) cm(2)/S. This work demonstrates the effects of chemical bonding between Bi2O3 nanoparticles and rGO substrate on enhanced electrochemical performances of Bi2O3@rGO nanocomposite, which can be used as a promising anode alterative for superior lithium ion batteries.

  2. The effects of reasoning, use of models, sex type, and their interactions on posttest achievement in chemical bonding after constant instruction

    Science.gov (United States)

    Staver, John R.; Halsted, Douglas A.

    The purpose of the authors in this study was to determine the effects of reasoning, use of models during testing, and sex type on posttest achievement in chemical bonding under controlled instruction. Eighty-four high school students taking chemistry were randomly assigned within their classes to models and no models groups for the posttest. Reasoning capabilities were assessed by the Piagetian Logical Operations Test (PLOT) (Staver & Gabel, JRST, Vol. 16, No. 6, 1979), prior to instruction. All students then received the same instruction on chemical bonding which included teacher demonstrations of concepts with three-dimensional molecular models, interspersed teacher questions during the introduction and development of concepts, student manipulation of three-dimensional molecular models during laboratory experiments, and text reading assignments on concepts prior to their instruction in class. The posttest on molecular geometry and shape contained three sections requiring memory and application (Bloom, Taxonomy of educational objective, handbook I: Cognitive domain. New York: David McKay, 1956). Data were analyzed by regression (Nie et al., Statistical package for the social sciences, 2nd ed. New York: McGraw-Hill, 1975). Results indicate that reasoning accounted for a significant portion (p 0.05) portion of the variance on total scores or any section of posttest. The three-way interaction of reasoning, model usage, and sex type accounted for a significant portion (p < 0.05) of the variance in total scores, and in the memory and application sections of the posttest. Discussion focused on the results, conclusions, and implications for science teaching.

  3. Chemical analysis of plasma-assisted antimicrobial treatment on cotton

    Science.gov (United States)

    Kan, C. W.; Lam, Y. L.; Yuen, C. W. M.; Luximon, A.; Lau, K. W.; Chen, K. S.

    2013-06-01

    This paper explores the use of plasma treatment as a pretreatment process to assist the application of antimicrobial process on cotton fabric with good functional effect. In this paper, antimicrobial finishing agent, Microfresh Liquid Formulation 9200-200 (MF), and a binder (polyurethane dispersion, Microban Liquid Formulation R10800-0, MB) will be used for treating the cotton fabric for improving the antimicrobial property and pre-treatment of cotton fabric by plasma under atmospheric pressure will be employed to improve loading of chemical agents. The chemical analysis of the treated cotton fabric will be conducted by Fourier transform Infrared Spectroscopy.

  4. An Extended Algorithm of Flexibility Analysis in Chemical Engineering Processes

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    An extended algorithm of flexibility analysis with a local adjusting method for flexibility region of chemical processes, which is based on the active constraint strategy, is proposed, which fully exploits the flexibility region of the process system operation. The hyperrectangular flexibility region determined by the extended algorithm is larger than that calculated by the previous algorithms. The limitation of the proposed algorithm due to imperfect convexity and its corresponding verification measure are also discussed. Both numerical and actual chemical process examples are presented to demonstrate the effectiveness of the new algorithm.

  5. Near-field Optical Imagigng and Chemical Analysis

    Science.gov (United States)

    Andres, La Rosa

    1998-03-01

    Identification of molecular structures in complex mixtures represents a major challenge in chemical research today. Microfabricated devices or lab-on-a-chip that perform chemical analysis allows dynamic sampling of picoliter microenvironments and separation. The long-term goals of nanochemistry down to the femtoliter scale involve refinement of the detection limit to single-molecule. Our approach consists in designing a very sensitive near-field optical microscope (NSOM-SIAM) to explore the mesoscopic properties of organic compounds. The validity, sensitivity and unique spatial resolution of this system will be discussed for multiple analyte chemosensing.

  6. Computational analysis of the mechanism of chemical reactions in terms of reaction phases: hidden intermediates and hidden transition States.

    Science.gov (United States)

    Kraka, Elfi; Cremer, Dieter

    2010-05-18

    Computational approaches to understanding chemical reaction mechanisms generally begin by establishing the relative energies of the starting materials, transition state, and products, that is, the stationary points on the potential energy surface of the reaction complex. Examining the intervening species via the intrinsic reaction coordinate (IRC) offers further insight into the fate of the reactants by delineating, step-by-step, the energetics involved along the reaction path between the stationary states. For a detailed analysis of the mechanism and dynamics of a chemical reaction, the reaction path Hamiltonian (RPH) and the united reaction valley approach (URVA) are an efficient combination. The chemical conversion of the reaction complex is reflected by the changes in the reaction path direction t(s) and reaction path curvature k(s), both expressed as a function of the path length s. This information can be used to partition the reaction path, and by this the reaction mechanism, of a chemical reaction into reaction phases describing chemically relevant changes of the reaction complex: (i) a contact phase characterized by van der Waals interactions, (ii) a preparation phase, in which the reactants prepare for the chemical processes, (iii) one or more transition state phases, in which the chemical processes of bond cleavage and bond formation take place, (iv) a product adjustment phase, and (v) a separation phase. In this Account, we examine mechanistic analysis with URVA in detail, focusing on recent theoretical insights (with a variety of reaction types) from our laboratories. Through the utilization of the concept of localized adiabatic vibrational modes that are associated with the internal coordinates, q(n)(s), of the reaction complex, the chemical character of each reaction phase can be identified via the adiabatic curvature coupling coefficients, A(n,s)(s). These quantities reveal whether a local adiabatic vibrational mode supports (A(n,s) > 0) or resists

  7. Chemical bond approach to optical properties of some flash evaporated Se100-XSbX chalcogenide alloys

    Science.gov (United States)

    Muiva, C. M.; Sathiaraj, T. S.; Mwabora, J. M.

    2012-07-01

    Amorphous thin films of Se100 - XSbX (X = 1, 5, 10, 15 and 20) were synthesized by flash evaporation of the premelt quenched bulk samples. The optical properties were investigated from spectrophotometric measurements in the UV-VIS-NIR spectral region using Swanepoel's standard envelope method and related techniques. The optical band gap energy (Egopt) was evaluated from the Wemple-Didomenico (WDD) single oscillator model and Tauc's extrapolation method in the region where the absorption coefficient, α ≥ 104 cm-1. The observed values of Egopt and oscillator energy Eo were found to decrease monotonously with increasing Sb additive. The complex dielectric constant (ɛ), Urbach energy (Eu), optical conductivity (σ), plasma frequency (ωp) and lattice dielectric constant (ɛL) were deduced for each alloy composition. The complex refractive index (n) fitted well to Sellmeier function which can allow extrapolation of n outside the measured spectral range. The observed changes in optical parameters with Sb content were explained on the basis of increased defect states and changes in cohesive energy indicators (average heat of atomization (Hs), mean coordination number and average single bond energy (Hs/).

  8. Chemically fixed p-n heterojunctions for polymer electronics by means of covalent B-F bond formation

    Science.gov (United States)

    Hoven, Corey V.; Wang, Huiping; Elbing, Mark; Garner, Logan; Winkelhaus, Daniel; Bazan, Guillermo C.

    2010-03-01

    Widely used solid-state devices fabricated with inorganic semiconductors, including light-emitting diodes and solar cells, derive much of their function from the p-n junction. Such junctions lead to diode characteristics and are attained when p-doped and n-doped materials come into contact with each other. Achieving bilayer p-n junctions with semiconducting polymers has been hindered by difficulties in the deposition of thin films with independent p-doped and n-doped layers. Here we report on how to achieve permanently fixed organic p-n heterojunctions by using a cationic conjugated polyelectrolyte with fluoride counteranions and an underlayer composed of a neutral conjugated polymer bearing anion-trapping functional groups. Application of a bias leads to charge injection and fluoride migration into the neutral layer, where irreversible covalent bond formation takes place. After the initial charging and doping, one obtains devices with no delay in the turn on of light-emitting electrochemical behaviour and excellent current rectification. Such devices highlight how mobile ions in organic media can open opportunities to realize device structures in ways that do not have analogies in the world of silicon and promise new opportunities for integrating organic materials within technologies now dominated by inorganic semiconductors.

  9. Facile Synthesis of Layer Structured GeP3/C with Stable Chemical Bonding for Enhanced Lithium-Ion Storage

    Science.gov (United States)

    Qi, Wen; Zhao, Haihua; Wu, Ying; Zeng, Hong; Tao, Tao; Chen, Chao; Kuang, Chunjiang; Zhou, Shaoxiong; Huang, Yunhui

    2017-01-01

    Recently, metal phosphides have been investigated as potential anode materials because of higher specific capacity compared with those of carbonaceous materials. However, the rapid capacity fade upon cycling leads to poor durability and short cycle life, which cannot meet the need of lithium-ion batteries with high energy density. Herein, we report a layer-structured GeP3/C nanocomposite anode material with high performance prepared by a facial and large-scale ball milling method via in-situ mechanical reaction. The P-O-C bonds are formed in the composite, leading to close contact between GeP3 and carbon. As a result, the GeP3/C anode displays excellent lithium storage performance with a high reversible capacity up to 1109 mA h g−1 after 130 cycles at a current density of 0.1 A g−1. Even at high current densities of 2 and 5 A g−1, the reversible capacities are still as high as 590 and 425 mA h g−1, respectively. This suggests that the GeP3/C composite is promising to achieve high-energy lithium-ion batteries and the mechanical milling is an efficient method to fabricate such composite electrode materials especially for large-scale application. PMID:28240247

  10. Facile Synthesis of Layer Structured GeP3/C with Stable Chemical Bonding for Enhanced Lithium-Ion Storage

    Science.gov (United States)

    Qi, Wen; Zhao, Haihua; Wu, Ying; Zeng, Hong; Tao, Tao; Chen, Chao; Kuang, Chunjiang; Zhou, Shaoxiong; Huang, Yunhui

    2017-02-01

    Recently, metal phosphides have been investigated as potential anode materials because of higher specific capacity compared with those of carbonaceous materials. However, the rapid capacity fade upon cycling leads to poor durability and short cycle life, which cannot meet the need of lithium-ion batteries with high energy density. Herein, we report a layer-structured GeP3/C nanocomposite anode material with high performance prepared by a facial and large-scale ball milling method via in-situ mechanical reaction. The P-O-C bonds are formed in the composite, leading to close contact between GeP3 and carbon. As a result, the GeP3/C anode displays excellent lithium storage performance with a high reversible capacity up to 1109 mA h g-1 after 130 cycles at a current density of 0.1 A g-1. Even at high current densities of 2 and 5 A g-1, the reversible capacities are still as high as 590 and 425 mA h g-1, respectively. This suggests that the GeP3/C composite is promising to achieve high-energy lithium-ion batteries and the mechanical milling is an efficient method to fabricate such composite electrode materials especially for large-scale application.

  11. Chemical bonding between antimony and ionic liquid-derived nitrogen-doped carbon for sodium-ion battery anode

    Science.gov (United States)

    Xu, Xin; Si, Ling; Zhou, Xiaosi; Tu, Fengzhang; Zhu, Xiaoshu; Bao, Jianchun

    2017-05-01

    Antimony has received a great deal of attention as a promising anode material for sodium-ion batteries (SIBs) due to its high theoretical capacity of 660 mAh g-1. However, this application is significantly hampered by inherent large volume change and sluggish kinetics. To address these issues, an antimony-cyano-based ionic liquid-derived nitrogen-doped carbon (Sbsbnd CNC) hybrid is proposed and synthesized by ball-milling and subsequent pyrolysis treatment. As an anode material for SIBs, the as-synthesized Sbsbnd CNC hybrid delivers reversible capacities of 475 mAh g-1 at a current density of 100 mA g-1 and 203 mAh g-1 at 5000 mA g-1, and a 92.4% capacity retention based on the first-cycle capacity after 150 cycles at 100 mA g-1. Using ex situ X-ray photoelectron spectroscopy and elemental mapping techniques, we attribute the good structural integrity to the formation of Sbsbnd Nsbnd C bonds between Sb and the cyano-based ionic liquid-derived N-doped carbon matrix. Moreover, the presence of N-doped carbon network in the hybrid material serves as a robust protective cover and an electrical highway, buffering the substantial volume expansion of Sb nanoparticles and ensuring the fast electron transport for stable cycling operation.

  12. Mass spectrometric analysis of chemical warfare agents in support of a chemical terrorist event

    Energy Technology Data Exchange (ETDEWEB)

    Hancock, J.R.; D' Agostino, P.A.; Chenier, C.L. [Defence R and D Canada Suffield, Medicine Hat, AB (Canada)

    2003-07-01

    Chemical warfare (CW) agents are considered to be any chemicals which, through their chemical action on life processes can cause death, temporary incapacitation or permanent harm to humans or animals. In Canada, the probability of a CW terrorist attack is low despite the catastrophic consequences that would result from such an attack. The three levels of government would be responding to such an event. CW agent response training for all levels of government is offered at Defence R and D Canada-Suffield. Appropriate samples must be collected for analysis in a laboratory, as such an event would lead to a criminal investigation. Research into new methods for the identification of CW agents is being conducted by the analytical laboratory at Defence R and D Canada-Suffield. Gas chromatography and mass spectrometry (GC-MS) are being used extensively to separate and characterize CW agents in organic extracts. In the case of aqueous samples, another method might be more appropriate, since additional sample handling is required before GC-MS analysis can be performed. Minimal sample handling is required when using liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) for direct analysis of CW agents. The authors demonstrated the use of LC-ESI-MS for analyzing CW agents and their hydrolysis products in aqueous samples. For the analysis of nerve agents and phosphonic acids in soil, comparable or superior results to organic extraction and GC-MS were obtained for aqueous extractions followed by LC-ESI-MS. The combination of GC-MS and LC-ESI-MS for the analysis of mustard related compounds in soil extracts from a former mustard storage area showed that the two methods are complementary in this situation. 9 refs., 3 tabs., 5 figs.

  13. In-vitro orthodontic bond strength testing : A systematic review and meta-analysis

    NARCIS (Netherlands)

    Finnema, K.J.; Ozcan, M.; Post, W.J.; Ren, Y.J.; Dijkstra, P.U.

    2010-01-01

    INTRODUCTION: The aims of this study were to systematically review the available literature regarding in-vitro orthodontic shear bond strength testing and to analyze the influence of test conditions on bond strength. METHODS: Our data sources were Embase and Medline. Relevant studies were selected b

  14. Invention of stimulus-responsive peptide-bond-cleaving residue (Spr) and its application to chemical biology tools.

    Science.gov (United States)

    Shigenaga, Akira; Yamamoto, Jun; Kohiki, Taiki; Inokuma, Tsubasa; Otaka, Akira

    2017-07-01

    Elucidation of biological functions of peptides and proteins is essential for understanding peptide/protein-related biological events and developing drugs. Caged peptides and proteins that release a parent active peptide/protein by photo-irradiation have successfully been employed to elucidate the functions. Whereas the usual caged peptide/protein enables conversion of an inactive form to an active form (OFF-to-ON conversion) by photo-induced deprotection, photo-triggered main chain cleavage is reported to be applicable to ON-to-OFF conversion. These peptides and proteins are photo-responsive; however, if peptides and proteins could respond to other stimuli such as disease-related environment or enzymes, their range of application should be widened. To convert the photo-responsive peptide/protein into other stimulus-responsive peptide/protein, quite laborious de novo design and synthesis of the stimulus-responsive unit are required. In this context, we designed a stimulus-responsive peptide-bond-cleaving residue (Spr) in which the stimuli available for the main chain cleavage vary according to the choice of protecting groups on the residue. In this review, design and synthesis of Spr are introduced, and challenges to apply Spr to other fields to enable, for example, functional control, localization control, delivery of cargos, labeling of a protein of interest in living cells, and identification of target proteins of bioactive ligands are discussed. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd.

  15. Are neighborhood bonding and bridging social capital protective against depressive mood in old age? A multilevel analysis in Japan.

    Science.gov (United States)

    Murayama, Hiroshi; Nofuji, Yu; Matsuo, Eri; Nishi, Mariko; Taniguchi, Yu; Fujiwara, Yoshinori; Shinkai, Shoji

    2015-01-01

    While the importance of distinguishing between bonding and bridging social capital is now understood, evidence remains sparse on their contextual effects on health. We examined the associations of neighborhood bonding and bridging social capital with depressive mood among older Japanese. A questionnaire survey of all community residents aged 65 and older in the city of Yabu, Hyogo Prefecture, Japan was conducted in July and August 2012. Bonding and bridging social capital were assessed by evaluating individual homogeneous and heterogeneous social networks in relation to age, gender, and socioeconomic status. Individual responses in each neighborhood were aggregated to create an index of neighborhood-level bonding/bridging social capital. Odds ratios (ORs) and 95% confidence intervals (CIs) were calculated to evaluate the associations of such social capital with depressive mood using multilevel binomial logistic regression analysis. Of the 7271 questionnaires distributed, 6416 were analyzed (covering 152 administrative neighborhoods). Approximately 56.8% of respondents were women, and the mean age was 76.2 ± 7.1 years. Neighborhood-level bonding social capital was inversely associated with depressive mood (OR = 0.84, 95% CI = 0.75-0.94), but neighborhood-level bridging social capital was not. Gender-stratified analysis revealed that neighborhood-level bonding social capital was inversely associated with depressive mood in both genders (OR = 0.83, 95% CI = 0.72-0.96 for men; OR = 0.85, 95% CI = 0.72-0.99 for women), while neighborhood-level bridging social capital was positively associated with depressive mood in women (OR = 1.15, 95% CI = 1.00-1.34). There was also a significant interaction between individual- and neighborhood-level bonding social capital, indicating that people with a weaker homogeneous network and living in a neighborhood with weaker bonding social capital were more likely to have depressive mood. Our results suggest that neighborhood social

  16. Comparative spectroscopic analysis of urinary calculi inhibition by Larrea Tridentata infusion and NDGA chemical extract

    Science.gov (United States)

    Manciu, Felicia

    2012-10-01

    In the present comparative spectroscopic study we try to understand calcium oxalate kidney stone formation as well as its inhibition by using a traditional medicine approach with Larrea Tridentata (LT) herbal extracts and nordihydroguaiaretic acid (NDGA), which is a chemical extract of the LT bush. The samples were synthesized without and with LT or NDGA using a simplified single diffusion gel growth technique. While the use of infusion from LT decreases the sizes of calcium oxalate crystals and also changes their structure from monohydrate for pure crystals to dihydrate for crystals grown with different amounts of inhibitor, both Raman and infrared absorption spectroscopic techniques, which are the methods of analysis employed in this work, reveal that NDGA is not responsible for the change in the morphology of calcium oxalate crystals and does not contribute significantly to the inhibition process. The presence of NDGA slightly affects the structure of the crystals by modifying the strength of the C-C bonds as seen in the Raman data. Also, the current infrared absorption results demonstrate the presence of NDGA in the samples through a vibrational line that corresponds to the double bond between carbon atoms of the ester group of NDGA.

  17. The determinants of bond angle variability in protein/peptide backbones: A comprehensive statistical/quantum mechanics analysis.

    Science.gov (United States)

    Improta, Roberto; Vitagliano, Luigi; Esposito, Luciana

    2015-11-01

    The elucidation of the mutual influence between peptide bond geometry and local conformation has important implications for protein structure refinement, validation, and prediction. To gain insights into the structural determinants and the energetic contributions associated with protein/peptide backbone plasticity, we here report an extensive analysis of the variability of the peptide bond angles by combining statistical analyses of protein structures and quantum mechanics calculations on small model peptide systems. Our analyses demonstrate that all the backbone bond angles strongly depend on the peptide conformation and unveil the existence of regular trends as function of ψ and/or φ. The excellent agreement of the quantum mechanics calculations with the statistical surveys of protein structures validates the computational scheme here employed and demonstrates that the valence geometry of protein/peptide backbone is primarily dictated by local interactions. Notably, for the first time we show that the position of the H(α) hydrogen atom, which is an important parameter in NMR structural studies, is also dependent on the local conformation. Most of the trends observed may be satisfactorily explained by invoking steric repulsive interactions; in some specific cases the valence bond variability is also influenced by hydrogen-bond like interactions. Moreover, we can provide a reliable estimate of the energies involved in the interplay between geometry and conformations.

  18. Ternary arsenides based on platinum–indium and palladium–indium fragments of the Cu{sub 3}Au-type: Crystal structures and chemical bonding

    Energy Technology Data Exchange (ETDEWEB)

    Zakharova, Elena Yu.; Andreeva, Natalia A.; Kazakov, Sergey M. [Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1-3, GSP-1, 119991 Moscow (Russian Federation); Kuznetsov, Alexey N., E-mail: alexei@inorg.chem.msu.ru [Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1-3, GSP-1, 119991 Moscow (Russian Federation); N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, Leninskii pr. 31, 119991 Moscow (Russian Federation)

    2015-02-05

    Highlights: • Three metal-rich platinum–indium and palladium–indium arsenides were synthesized. • Their crystal structures were determined from powder XRD. • Electronic structures and bonding were studied using DFT/FP-LAPW calculations. • Multi-centered Pt–In or Pd–In bonding was revealed using ELF and ELI-D analysis. • Extra pairwise Pt–Pt interactions are observed only for Pt-based compounds. - Abstract: Three metal-rich palladium–indium and platinum–indium arsenides, Pd{sub 5}InAs, Pt{sub 5}InAs, and Pt{sub 8}In{sub 2}As, were synthesized using a high-temperature ampoule technique. Their crystal structures were determined from Rietveld analysis of powder diffraction data. All the compounds crystallize in tetragonal system with P4/mmm space group (Pd{sub 5}InAs: a = 3.9874(1) Å, c = 6.9848(2) Å, Z = 1, R{sub p} = 0.053; R{sub b} = 0.013; Pt{sub 5}InAs: a = 3.9981(2) Å, c = 7.0597(4) Å, Z = 1, R{sub p} = 0.058, R{sub b} = 0.016; Pt{sub 8}In{sub 2}As: a = 3.9872(3) Å, c = 11.1129(7) Å, Z = 1, R{sub p} = 0.047; R{sub b} = 0.014). The first two compounds belong to the Pd{sub 5}TlAs structure type, while the third one is isotypic with the recently discovered Pd{sub 8}In{sub 2}Se. Main structural units in all arsenides are indium-centered [TM{sub 12}In] cuboctahedra (TM = Pd, Pt) of the Cu{sub 3}Au type, single- and double-stacked along the c axis in TM{sub 5}InAs and Pt{sub 8}In{sub 2}As, respectively, alternating with [TM{sub 8}As] rectangular prisms. DFT electronic structure calculations predict all three compounds to be 3D metallic conductors and Pauli-like paramagnets. According to the bonding analysis based on the electron localization function and electron localizability indicator topologies, all compounds feature multi-centered interactions between transition metal and indium in their heterometallic fragments. Additionally, pairwise interactions between platinum atoms are also observed, indicating a somewhat more localized bonding

  19. Improvement of ground granulated blast furnace slag on stabilization/solidification of simulated mercury-doped wastes in chemically bonded phosphate ceramics.

    Science.gov (United States)

    Liu, Zhongzhe; Qian, Guangren; Zhou, Jizhi; Li, Chuanhua; Xu, Yunfeng; Qin, Zhe

    2008-08-30

    This paper investigated the effectiveness of (ground granulated blast furnace slag) GGBFS-added chemically bonded phosphate ceramic (CBPC) matrix on the stabilization/solidification (S/S) of mercury chloride and simulated mercury-bearing light bulbs (SMLB). The results showed that the maximal compressive strength was achieved when 15% and 10% ground GGBFS was added for HgCl(2)-doped and SMLB-doped CBPC matrices, respectively. The S/S performances of GGBFS-added matrices were significantly better than non-additive matrices. As pore size was reduced, the leaching concentration of Hg(2+) from GGBFS-added CBPC matrix could be reduced from 697 microg/L to about 3 microg/L when treating HgCl(2). Meanwhile, the main hydrating product of GGBFS-added matrices was still MgKPO(4).6H(2)O. The improvement of S/S effectiveness was mainly due to physical filling of fine GGBFS particles and microencapsulation of chemical cementing gel.

  20. Reaction dynamics. Extremely short-lived reaction resonances in Cl + HD (v = 1) → DCl + H due to chemical bond softening.

    Science.gov (United States)

    Yang, Tiangang; Chen, Jun; Huang, Long; Wang, Tao; Xiao, Chunlei; Sun, Zhigang; Dai, Dongxu; Yang, Xueming; Zhang, Dong H

    2015-01-02

    The Cl + H2 reaction is an important benchmark system in the study of chemical reaction dynamics that has always appeared to proceed via a direct abstraction mechanism, with no clear signature of reaction resonances. Here we report a high-resolution crossed-molecular beam study on the Cl + HD (v = 1, j = 0) → DCl + H reaction (where v is the vibrational quantum number and j is the rotational quantum number). Very few forward scattered products were observed. However, two distinctive peaks at collision energies of 2.4 and 4.3 kilocalories per mole for the DCl (v' = 1) product were detected in the backward scattering direction. Detailed quantum dynamics calculations on a highly accurate potential energy surface suggested that these features originate from two very short-lived dynamical resonances trapped in the peculiar H-DCl (v' = 2) vibrational adiabatic potential wells that result from chemical bond softening. We anticipate that dynamical resonances trapped in such wells exist in many reactions involving vibrationally excited molecules.

  1. Fracture mechanics analysis on Smart-Cut technology. Part 2: Effect of bonding flaws

    Institute of Scientific and Technical Information of China (English)

    Bin Gu; Hongyuan Liu; Yiu-Wing Mai; Xi Qiao Feng; Shou Wen Yu

    2009-01-01

    In Part 2 of the paper on the Smart-Cut process,the effects of bonding flaws characterized by the size and internal pressure before and after splitting are studied by using fracture mechanics models. It is found that the bonding flaws with large size are prone to cause severe deviation of defect growth, leading to a non-transferred area of thin layer when splitting. In a practical Smart-Cut process where the internal pressure of bonding flaws is very small,large interfacial defects always promote defect growth in the splitting process. Meanwhile, increasing the internal pressure of the bonding flaws decreases the defect growth and its deviation before splitting. The mechanism of relaxation of stiffener constraint is proposed to clarify the effect of bonding flaws. Moreover, the progress of the splitting process is analyzed when bonding flaws are present. After splitting,those bonding flaws with large size and high internal pressure are vulnerable for the blistering of the thin film during high-temperature annealing.

  2. 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.

  3. 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

  4. Quantum chemical computations, vibrational spectroscopic analysis and antimicrobial studies of 2,3-Pyrazinedicarboxylic acid.

    Science.gov (United States)

    Beaula, T Joselin; Packiavathi, A; Manimaran, D; Joe, I Hubert; Rastogi, V K; Jothy, V Bena

    2015-03-05

    Density Functional Theory (DFT) calculations at B3PW91 level with 6-311G (d) basis sets were carried out for 2,3-Pyrazinedicarboxylic acid (PDCA) to analyze in detail the equilibrium geometries and vibrational spectra. Calculations reveal that the optimized geometry closely resembles the experimental XRD data. Vibrational spectra were analyzed on the basis of potential energy distribution (PED) of each vibrational mode, which provides quantitative as well as qualitative interpretation of IR and Raman spectra. Information about size, shape, charge density distribution and site of chemical reactivity of the molecule were obtained by mapping electron density isosurface with the electrostatic potential surface (ESP). Based on optimized ground state geometries, NBO analysis was performed to study donor-acceptor (bond-antibond) interactions. TD-DFT analysis was also performed to calculate energies, oscillator strength of electronic singlet-singlet transitions and the absorption wavelengths. The (13)C and (1)H nuclear magnetic resonance (NMR) chemical shifts of the molecule in the ground state were calculated by gauge independent atomic orbital (GIAO) method and compared with the experimental values. PDCA was screened for its antimicrobial activity and found to exhibit antifungal and antibacterial effects. Molecular docking was also performed for the different receptors.

  5. Car-Parrinello Molecular Dynamics Simulations of Infrared Spectra of Crystalline Vitamin C with Analysis of Double Minimum Proton Potentials for Medium-Strong Hydrogen Bonds.

    Science.gov (United States)

    Brela, Mateusz Z; Wójcik, Marek J; Boczar, Marek; Witek, Łukasz; Yasuda, Mitsuru; Ozaki, Yukihiro

    2015-06-25

    We studied proton dynamics of a hydrogen bonds of the crystalline l-ascorbic acid. Our approach was based on the Car-Parrinello molecular dynamics. The focal point of our study was simulation of the infrared spectra of l-ascorbic acid associated with the O-H stretching modes that are very sensitive to the strength of hydrogen bonding. In the l-ascorbic acid there are four kinds of hydrogen bonds. We calculated their spectra by using anharmonic approximation and the time course of the dipole moment function as obtained from the Car-Parrinello simulation. The quantization of the nuclear motion of the protons was made to perform detailed analysis of strength and properties of hydrogen bonds. We presented double minimum proton potentials with small value of barriers for medium-strong hydrogen bonds. We have also shown the difference character of medium-strong hydrogen bonds compared to weaker hydrogen bonds in the l-ascorbic acid.

  6. Chemical and Microbiological Analysis of Sliced, Precooked, Canned Bacon

    Science.gov (United States)

    1979-09-01

    salt, protein , fat, ash, pressure and water activity) and microbiological tests (aerobic plate count, yeast and mold, and coagulase positive...SnOV80d SnCUIYY CLASIFICATION OF THIS PAGC(U&M Dm e M w*Q vas any reason to believe that the bacon was acceptable for its intended purpose The results...Laboratory. 70 - 71 7 CHEMICAL AND MICROBIOLOGICAL ANALYSIS OF SLICED, PRECOOKED, CANNED BACON INTRODUCTION Legris traces the history of canned bacon

  7. Development of microfluidic devices for chemical analysis and fluid handling

    OpenAIRE

    Egidi, Giovanni; de Rooij, Nicolas F

    2004-01-01

    Miniaturization of chemical analysis and synthesis systems improve throughput, performance and accessibility, and lead to significantly reduced costs. In this work are described several components that find place in the process of miniaturization. This work is developed in the frame of the project CREAM (Cartridges with molecularly imprinted Recognition Elements for Antibiotic residues Monitoring in Milk). Antibiotics are widely used to treat cows' diseases, and traces can be found in milk so...

  8. Bonding Energy and Growth Habit of Lithium Niobate Single Crystals

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    On the basis of crystallographic structure of lithium niobate (LN), the bonding energy was quantitatively calculated by the bond valence sum model, which was employed to investigate the crystal growth. A possible relationship between the crystal growth habit and chemical bonding energy of LN crystals are found. It is found that the higher the bond energy, the slower the growth rate, and the more important the plane. The analytical results indicate that (012) plane is the most influential face for the LN crystal growth, which consists well with the standard card (JCPDS Card: 20-0631) and our previous experimental observation. The current work shows that the chemical bond analysis of LN crystals allows us to predict its growth habit and thus to obtain the expected morphology during the spontaneous growth.

  9. Global-Local Finite Element Analysis of Bonded Single-Lap Joints

    Science.gov (United States)

    Kilic, Bahattin; Madenci, Erdogan; Ambur, Damodar R.

    2004-01-01

    Adhesively bonded lap joints involve dissimilar material junctions and sharp changes in geometry, possibly leading to premature failure. Although the finite element method is well suited to model the bonded lap joints, traditional finite elements are incapable of correctly resolving the stress state at junctions of dissimilar materials because of the unbounded nature of the stresses. In order to facilitate the use of bonded lap joints in future structures, this study presents a finite element technique utilizing a global (special) element coupled with traditional elements. The global element includes the singular behavior at the junction of dissimilar materials with or without traction-free surfaces.

  10. Molecular structure, vibrational spectroscopic studies and natural bond orbital analysis of 7-amino-4-trifluoromethyl coumarin

    Indian Academy of Sciences (India)

    M K Subramanian; P M Anbarasan; S Manimegalai

    2010-05-01

    Quantum mechanical calculations of energies, geometries and vibrational wave numbers of 7-amino-4-trifluoromethyl coumarin (7A4TFMC) were carried out using Hartree–Fock (HF) and density functional theory (DFT) using hybrid functional BLYP and B3LYP with 6-31G(d,p) as basis set. The optimized geometrical parameters obtained by HF and DFT calculations are in good agreement with the experimental X-ray data. The best method to reproduce the experimental wave numbers is B3LYP method with the 6-31G(d,p) basis set. The difference between the observed and scaled wave number values of most of the fundamentals is very small. A detailed interpretation of the infrared spectra of 7A4TFMC was also reported. The entropy of the title compound was also performed at HF using the hybrid functional BLYP and B3LYP with 6-31 G(d,p) as basis set levels of theory. Natural bond orbital (NBO) analysis of the title molecule is also carried out. The theoretical spectrogram for FTIR spectra of the title molecule has been constructed.

  11. Mesoscale thermal-mechanical analysis of shocked induced granular explosives and polymer-bonded explosives

    Science.gov (United States)

    Wang, Xinjie; Wu, Yanqing; Huang, Fenglei

    2015-06-01

    The thermal-mechanical response of HMX-based granular explosives (GXs) and polymer-bonded explosives (PBXs) with variable number of crystals from 10 to 100 under impact loading is investigated with finite element software ABAQUS. A series of three dimensional mesoscale calculations are carried out with the crystal plasticity constitutive model for HMX crystals that accounts for nonlinear elasticity and crystalline plasticity and the viscoelastic model for the polymer binder. To make the analysis comparable, the morphology and the size of HMX crystals are kept the same for both GXs and PBXs. In order to quantify the effect of polymer binder under different strain rate, the calculation models are impacted with initial boundary velocities from 10 to 100 m/s. The results shows that the average pressure of PBXs is approximately 50% higher than GXs and that the localized stress and temperature is highly increased with the polymer binder, which indicates the crystal anisotropy as well as the polymer binder plays an important role in influencing the stress and thermal response of HMX crystals. The thermal-mechanical response analyzed here is essential to predict the formation of hot spot and the ignition of explosives.

  12. 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).

  13. In vitro analysis of bond strength of self-etching adhesives applied on superficial and deep dentin.

    Science.gov (United States)

    Garcia, Eugenio J; Gomes, Osnara M M; Gomes, João C

    2009-01-01

    The purpose of this study was to evaluate the bond strength of three adhesive systems to superficial and deep dentine using the microtensile bond strength test (microTBS). The occlusal enamel of thirty human third molars was removed to expose a flat surface of superficial or deep dentin. For each type of surface, the test specimens were randomly divided into three groups which underwent the application of a conventional two-step adhesive system [Single Bond (SB)] as the control group (n=10), a two-bottle self-etching system [One Coat SE Bond (OCSE)] (n=10) and a one bottle one-step system [Clearfil S3 Bond (CFS3)] (n=10). Adhesives were applied, a 5-mm high "crown" as built-up with resin composite Z250 (3M) and the specimens with a cross-sectional area of 0.7 +/- 0.1 mm2 were tested in tension (0.5 mm/min). Four fractured sticks from each tooth were randomly selected and the dentin side was gently abraded with a 1200-grit SiC paper etched with 35% phosphoric acid for 15 s and air dried. SEM micrographs at 70X and 2400X magnification were taken using scanning electron microscopy (SEM) to calculate the area of tubular dentin (ATD) and tubular density (TD) with Image Pro Plus 5. Two-way ANOVA (dentin depth-adhesive) showed higher bond strength values for SB. However the values did not depend on dentin depth. Linear regression showed a significant relationship between bond strength and area of intertubular dentin for SB (p = 0.004), and a significant inverse relationship between tubular density and bond strength for CFS3 (p = 0.009). OCSE exhibited a tendency that was similar to SB and opposite to CFS3, but was not statistically significant. The conventional two-step adhesive had higher bond strength values. The use of digital image analysis facilitates the manipulation of data and contributes to the interpretation of the behavior of new adhesive systems.

  14. Electrochemical approaches for chemical and biological analysis on Mars

    Science.gov (United States)

    Kounaves, Samuel P.

    2003-01-01

    Obtaining in situ chemical data from planetary bodies such as Mars or Europa can present significant challenges. The one analytical technique that has many of the requisite characteristics to meet such a challenge is electroanalysis. Described here are three electroanalytical devices designed for in situ geochemical and biological analysis on Mars. The Mars Environmental Compatibility Assessment (MECA) was built and flight qualified for the now cancelled NASA Mars 2001 Lander. Part of MECA consisted of four "cells" containing arrays of electrochemical based sensors for measuring the ionic species in soil samples. A next-generation MECA, the Robotic Chemical Analysis Laboratory (RCAL), uses a carousel-type system to allow for greater customization of analytical procedures. A second instrument, proposed as part of the 2007 CryoScout mission, consists of a flow-through inorganic chemical analyzer (MICA). CryoScout is a torpedo-like device designed for subsurface investigation of the stratigraphic climate record embedded in Mars' north polar cap. As the CryoScout melts its way through the ice cap, MICA will collect and analyze the meltwater for a variety of inorganics and chemical parameters. By analyzing the chemistry locked in the layers of dust, salt, and ice, geologists will be able to determine the recent history of climate, water, and atmosphere on Mars and link it to the past. Finally, electroanalysis shows its abilities in the detection of possible microorganism on Mars or elsewhere in the solar system. To identify an unknown microorganism, one that may not even use Earth-type biochemistry, requires a detection scheme which makes minimal assumptions and looks for the most general features. Recent work has demonstrated that the use of an array of electrochemical sensors which monitors the changes in a solution via electrical conductivity, pH, and ion selective electrodes, can be used to detect minute chemical perturbations caused by the growth of bacteria and

  15. Electron energy-loss spectroscopy analysis of low-temperature plasma-enhanced chemically vapor deposited a-C:H films

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A.J.; Benson, D.K.; Tracy, C.E.; Kazmerski, L.L.; Wager, J.F.

    1989-05-01

    Electron energy-loss spectroscopy (EELS) has been applied to the analysis of a-C:H films grown on various substrates by a unique low-temperature (<100 /sup 0/C) plasma-enhanced chemical vapor deposition (PECVD) process using ethylene and hydrogen gases. EELS data are used to characterize the relative amounts of fourfold coordinated sp/sup 3/ carbon bonding to threefold coordinated sp/sup 2/ carbon bonding as well as the relative order/disorder due to substrate effects. Ellipsometric and transmission measurements provide optical constants for the PECVD a-C:H films.

  16. Hydrogen bonding-driven rheological modulation of chemically reduced graphene oxide/poly(vinyl alcohol) suspensions and its application in electrospinning

    Science.gov (United States)

    Tan, Yeqiang; Song, Yihu; Zheng, Qiang

    2012-10-01

    Rheology of graphene oxide (GO) and chemically reduced graphene oxide (RGO) nanosheets suspended in poly(vinyl alcohol) (PVA) solution were investigated by altering nanosheet loading and reduction time of RGO in a wide range. A small amount (0.5 wt%) of GO and RGO in the dilute regime of filler resulted in a threefold increase and a fourfold decrease in steady viscosity at 0.01 s-1, respectively; increasing GO and RGO loadings in the semi-dilute regime of filler caused steady viscosity to increase to different degrees. Meanwhile, the steady viscosity of the suspension decreased gradually by more than one order of magnitude with increasing reduction time of RGO. By characterizing the microstructure in suspensions, the style and relative density of H-bonding between PVA chains and nanosheets were confirmed to account for the suspension rheology. Modulation of viscosity in a wide range via simply control of the loading and reduction time of RGO was hydrogen bonding-driven, which was successfully applied to electrospinning to prepare nanocomposite nanofibers. The addition of 1 wt% GO and RGO with respect to the polymer mass significantly improved PVA fibrous uniformity and fineness, and the spinnable concentration range of PVA was greatly broadened from (8.5-11.3 wt%) to (5-18 wt%). Meanwhile, the thermal stability of the nanofibers was also enhanced by GO or RGO addition.Rheology of graphene oxide (GO) and chemically reduced graphene oxide (RGO) nanosheets suspended in poly(vinyl alcohol) (PVA) solution were investigated by altering nanosheet loading and reduction time of RGO in a wide range. A small amount (0.5 wt%) of GO and RGO in the dilute regime of filler resulted in a threefold increase and a fourfold decrease in steady viscosity at 0.01 s-1, respectively; increasing GO and RGO loadings in the semi-dilute regime of filler caused steady viscosity to increase to different degrees. Meanwhile, the steady viscosity of the suspension decreased gradually by more than

  17. Quantum chemical calculations, vibrational studies, HOMO-LUMO and NBO/NLMO analysis of 2-bromo-5-nitrothiazole.

    Science.gov (United States)

    Gobinath, E; Xavier, R John

    2013-03-01

    The complete vibrational assignment and analysis of the fundamental modes of 2-bromo-5-nitrothiazole (BNT) was carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The observed vibrational data were compared with the wavenumbers derived theoretically for the optimized geometry of the compound from the ab initio HF and DFT-B3LYP gradient calculations employing 6-311++G(d,p) basis set. Thermodynamic properties like entropy, heat capacity and zero point energy have been calculated for the molecule. HOMO-LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using Natural Bond Orbital (NBO) and Natural Localized Molecular Orbital (NLMO) analysis. Important non-linear properties such as electric dipole moment and first hyperpolarizability of BNT have been computed using B3LYP quantum chemical calculation.

  18. Flexural and bond strengths of relined denture polymers assessed by four-point bending tests and Weibull analysis.

    Science.gov (United States)

    Polyzois, Gregory L; Lagouvardos, Panagiotis E; Frangou, Maria J

    2012-06-01

    The aim of this study was to (1) investigate the flexural strengths of three denture resins i.e. heat, photopolymerised and microwaved and how it was affected by relining with auto- and visible light-polymerised hard reliners, (2) investigate the bond strengths between denture resins and hard reliners and (3) interpret the results of both tests by utilising Weibull analysis. Specimens (65 × 10 × 2.5 mm) from denture resins, relined and bonded combinations were tested using a four-point bending test in a universal testing machine and a crosshead speed of 5 mm/min. Ten specimens for each bulk resin and denture resin-reliner combination for a total of 150 were tested. Statistical analysis indicated significant differences between bulk materials (p < 0.001) and between reliners (p < 0.001) for flexural and bond strength tests. was concluded that (1) the four-point flexural strength was different between the denture base materials, (2) flexure strength between bulk and relined or between relined with autopolymerised and photopolymerised bases was different, (3) flexural strength among relined denture bases was different and (4) bond strengths among relined denture bases were different. © 2011 The Gerodontology Society and John Wiley & Sons A/S.

  19. 论债转股的风险%Analysis of the Risk of Bond Changing Stock

    Institute of Scientific and Technical Information of China (English)

    谭利

    2001-01-01

    分析债转股过程中存在的博弈风险、道德风险及退出风险,有益于正确认识债转股的功效。%Through analyzing the risk of game, risk of morals and risk of resignation in the process of bond changing stock, this paper hopes to help recognizing correctly the effect of bond changing stock.

  20. Joining of Silicon Carbide: Diffusion Bond Optimization and Characterization

    Science.gov (United States)

    Halbig, Michael C.; Singh, Mrityunjay

    2008-01-01

    Joining and integration methods are critically needed as enabling technologies for the full utilization of advanced ceramic components in aerospace and aeronautics applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. In the application, several SiC substrates with different hole patterns to form fuel and combustion air channels are bonded to form the injector. Diffusion bonding is a joining approach that offers uniform bonds with high temperature capability, chemical stability, and high strength. Diffusion bonding was investigated with the aid of titanium foils and coatings as the interlayer between SiC substrates to aid bonding. The influence of such variables as interlayer type, interlayer thickness, substrate finish, and processing time were investigated. Optical microscopy, scanning electron microscopy, and electron microprobe analysis were used to characterize the bonds and to identify the reaction formed phases.

  1. Calamistrin E, the First Annonaceous Acetogenin with Double Bond in Aliphatic Chain from Genus Uvaria

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Calamistrin E, the first Annonaceous acetogenin with C=C bond in the aliphatic chain from the genus Uvaria was isolated from U. calamistrata. Its structure including relative and absolute configurations was determined by chemical derivation and spectral analysis.

  2. Contribution of Chemical Bonding to the Force in Atomic Force Microscopy%原子力显微镜中化学成键对力的贡献

    Institute of Scientific and Technical Information of China (English)

    李娜; 陈曦; 薛其坤

    2014-01-01

    迄今非接触原子力显微镜已经成为一个非常强大的工具。它不仅能够得到表面的原子周期结构,还能给出分子内部的化学键信息。针尖和样品之间的相互作用是原子力显微镜的有效信号,主要包括三种,即范德瓦尔斯相互作用、静电相互作用和化学键相互作用。本文在生长于Si(111)-7×7的铅薄膜上测量了针尖和样品之间的化学键相互作用。通过获取该相互作用随偏压的变化,并且利用抛物线拟合有效局域接触势的位置,我们发现它是随着针尖和样品之间距离的增大而减小的。这种趋势来自于针尖和样品之间波函数的交叠。从而可以得到电子的衰减长度。我们还测量到了该衰减长度随着铅薄膜厚度的变化会发生振荡,这种振荡归因于平顶楔形铅岛内电子的量子尺寸效应。%Non-contact atomic force microscope (NC-AFM) has become a powerful tool. It can provide the atomic structure and chemical bonding information at the atomic scale. Three kinds of tip-sample interactions are often concerned: including van der Waals interaction, electrostatic interaction, and chemical bonding interaction. In this work, the chemical bonding interaction between the tip and a Pb film is clearly demonstrated by NC-AFM based on a Q-plus force sensor. The tip-sample interaction energy versus the bias voltage was obtained and fitted by a parabolic function to find the effective local contact potential difference, which decreased with increasing tip-sample distance. Such a trend is caused by the wave function overlap. Thus, the decay length of the electron wave function was estimated. Oscillation of the decay length with film thickness was also observed, which can be attributed to the thickness-dependent quantum wel states in the Pb islands.

  3. Atomic Structure and Valence: Level II, Unit 10, Lesson 1; Chemical Bonding: Lesson 2; The Table of Elements: Lesson 3; Electrolysis: Lesson 4. Advanced General Education Program. A High School Self-Study Program.

    Science.gov (United States)

    Manpower Administration (DOL), Washington, DC. Job Corps.

    This self-study program for high-school level contains lessons on: Atomic Structure and Valence, Chemical Bonding, The Table of Elements, and Electrolysis. Each of the lessons concludes with a Mastery Test to be completed by the student. (DB)

  4. Chemical Abundance Analysis of Moving Group W11450 (Latham 1)

    CERN Document Server

    O'Connell, Julia E; Frinchaboy, Peter M

    2016-01-01

    We present elemental abundances for all seven stars in Moving Group W11450 (Latham 1) to determine if they may be chemically related. These stars appear to be both spatially and kinematically related, but no spectroscopic abundance analysis exists in literature. Abundances for eight elements were derived via equivalent width analyses of high resolution (R $\\sim$60,000), high signal-to-noise ratio ($\\langle$SNR$\\rangle\\sim$100) spectra obtained with the Otto Struve 2.1m telescope and Sandiford Echelle Spectrograph at McDonald Observatory. The large star-to-star scatter in metallicity, -0.55 $\\leq$ [Fe/H] $\\leq$ 0.06 dex ($\\sigma$= 0.25), implies these stars were not produced from the same chemically homogeneous molecular cloud, and are therefore not part of a remnant or open cluster as previously proposed. Prior to this analysis, it was suggested that two stars in the group, W11449 & W11450, are possible wide binaries. The candidate wide binary pair show similar chemical abundance patterns with not only ir...

  5. Analysis of interfacial structure and bond strength of self-etch adhesive systems

    Science.gov (United States)

    Pinzon, Lilliam M; Watanabe, Larry G; Reis, Andre F; Powers, John M; Marshall, Sally J; Marshall, Grayson W

    2013-01-01

    Purpose To determine the bond strength, nanoleakage and interfacial morphology of four self-etch adhesives bonded to superficial dentin. Methods Micro-tensile (MT, n=15) and single plane shear (SP, n=8) bond tests were performed using human dentin polished through 320-grit SiC paper. Clearfil Protect Bond (PB), Clearfil S3 Bond (S3), Prompt L-Pop (PLP) and G-BOND (GB) were used according to manufacturers’ instructions. Composite was applied as cylinders with a thickness of 4 mm with a 1-mm diameter and stored in water at 37° C for 24 hours. Specimens were debonded with a testing machine at a cross-head speed of 1 mm/min. Means and standard deviations of bond strength were calculated. Data were analyzed using ANOVA. Fisher’s PLSD intervals were calculated at the 0.05 level of significance. Failure modes were determined at 100X. The hybrid layer was revealed by treatment with 5N HCl/5% NaOCl or fractured perpendicular to the interface and sputter coated with gold. Specimens were viewed at 1000X, 2500X, and 5000X in a field emission SEM at 15 kV. Teeth (n=2) sectioned into 0.9-mm thick slabs were immersed in ammoniacal silver nitrate solution for 24 hours, rinsed and immersed in photo-developing solution for 8h. Specimens were sectioned (90-nm thick) and observed under TEM. Results Means ranged from 25.0 to 73.1 MPa for MT and from 15.5 to 56.4 MPa for SP. MT values were greater than SP, but were highly correlated (R2 = 0.99, p= 0.003) and provided the same order for the systems studied. Fisher’s PLSD intervals (pbond strength techniques and adhesives results were 1.7 and 2.3 MPa, respectively. Failures sites were mixed. TEM showed that hybrid layers were ~0.5 µm for PB, GB and S3 and ~5 µm for PLP. SEM showed morphologic differences among adhesives. Silver nitrate deposits were observed within interfaces for all adhesive systems. Clinical significance Simplification of application procedures appears to induce loss of adhesion capabilities. In this in vitro

  6. Bonding analysis using localized relativistic orbitals: water, the ultrarelativistic case and the heavy homologues H2X (X = Te, Po, eka-Po).

    Science.gov (United States)

    Dubillard, S; Rota, J-B; Saue, T; Faegri, K

    2006-04-21

    We report the implementation of Pipek-Mezey [J. Chem. Phys. 90, 4916 (1989)] localization of molecular orbitals in the framework of a four-component relativistic molecular electronic structure theory. We have used an exponential parametrization of orbital rotations which allows the use of unconstrained optimization techniques. We demonstrate the strong basis set dependence of the Pipek-Mezey localization criterion and how it can be eliminated. We have employed localization in conjunction with projection analysis to study the bonding in the water molecule and its heavy homologues. We demonstrate that in localized orbitals the repulsion between hydrogens in the water molecule is dominated by electrostatic rather than exchange interactions and that freezing the oxygen 2s orbital blocks polarization of this orbital rather than hybridization. We also point out that the bond angle of the water molecule cannot be rationalized from the potential energy alone due to the force term of the molecular virial theorem that comes into play at nonequilibrium geometries and which turns out to be crucial in order to correctly reproduce the minimum of the total energy surface. In order to rapidly assess the possible relativistic effects we have carried out the geometry optimizations of the water molecule at various reduced speed of light with and without spin-orbit interaction. At intermediate speeds, the bond angle is reduced to around 90 degrees , as is known experimentally for H(2)S and heavier homologues, although our model of ultrarelativistic water by construction does not allow any contribution from d orbitals to bonding. At low speeds of light the water molecule becomes linear which is in apparent agreement with the valence shell electron pair repulsion (VSEPR) model since the oxygen 2s12 and 2p12 orbitals both become chemically inert. However, we show that linearity is brought about by the relativistic stabilization of the (n + 1)s orbital, the same mechanism that leads to an

  7. Proximate analysis, backwards stepwise regression between gross calorific value, ultimate and chemical analysis of wood.

    Science.gov (United States)

    Telmo, C; Lousada, J; Moreira, N

    2010-06-01

    The gross calorific value (GCV), proximate, ultimate and chemical analysis of debark wood in Portugal were studied, for future utilization in wood pellets industry and the results compared with CEN/TS 14961. The relationship between GCV, ultimate and chemical analysis were determined by multiple regression stepwise backward. The treatment between hardwoods-softwoods did not result in significant statistical differences for proximate, ultimate and chemical analysis. Significant statistical differences were found in carbon for National (hardwoods-softwoods) and (National-tropical) hardwoods in volatile matter, fixed carbon, carbon and oxygen and also for chemical analysis in National (hardwoods-softwoods) for F and (National-tropical) hardwoods for Br. GCV was highly positively related to C (0.79 * * *) and negatively to O (-0.71 * * *). The final independent variables of the model were (C, O, S, Zn, Ni, Br) with R(2)=0.86; F=27.68 * * *. The hydrogen did not contribute statistically to the energy content.

  8. Analysis of chemical composition of high viscous oils

    Directory of Open Access Journals (Sweden)

    Irina Germanovna Yashchenko

    2014-07-01

    Full Text Available The spatial distribution of viscous oils which are considered as an important reserve for oil-production in future were studied on base of information from global database on oil physical and chemical properties. Changes in chemical composition of viscous oils in different basins and continents were analyzed as well. It is shown, on average, viscous oils are sulfur-bearing, low paraffin, highly resinous oils with an average content of asphaltenes and low content of the fraction boiling at 200 C. Study results of viscous oils peculiarities of Canada, Russia and Venezuela are given. The analysis results can be used to determine the optimal layouts and conditions of oil transportation, to improve the search methods of geochemical exploration, and to solve other problems in the oil chemistry.

  9. Molecular double core-hole electron spectroscopy for chemical analysis

    CERN Document Server

    Tashiro, Motomichi; Fukuzawa, Hironobu; Ueda, Kiyoshi; Buth, Christian; Kryzhevoi, Nikolai V; Cederbaum, Lorenz S

    2010-01-01

    We explore the potential of double core hole electron spectroscopy for chemical analysis in terms of x-ray two-photon photoelectron spectroscopy (XTPPS). The creation of deep single and double core vacancies induces significant reorganization of valence electrons. The corresponding relaxation energies and the interatomic relaxation energies are evaluated by CASSCF calculations. We propose a method how to experimentally extract these quantities by the measurement of single and double core-hole ionization potentials (IPs and DIPs). The influence of the chemical environment on these DIPs is also discussed for states with two holes at the same atomic site and states with two holes at two different atomic sites. Electron density difference between the ground and double core-hole states clearly shows the relaxations accompanying the double core-hole ionization. The effect is also compared with the sensitivity of single core hole ionization potentials (IPs) arising in single core hole electron spectroscopy. We have ...

  10. Thermal-hydraulic modeling and analysis of spool valve with sloping U-shape notch by bond graph

    Institute of Scientific and Technical Information of China (English)

    娄磊; 吴万荣; 王兆强; 梁向京

    2015-01-01

    To increase the efficiency and reliability of the thermodynamics analysis of the spool valve, the precise function expression of the flow area for the sloping U-shape notch orifice versus the spool stroke and thermal-hydraulic bond graph based on the conservation of mass and energy were introduced. Subsequently, the connection rule for the bond graph elements and the method to construct the complete thermal-hydraulic system model were proposed. On the basis of heat transfer analysis of a typical hydraulic circuit containing the spool valve, the lumped parameter for mathematical model of the system was given. At last, the reliability of the mathematical model of the flow area and the thermal-hydraulic system for the sloping U-shape notch orifice on the spool were demonstrated by the test. The good agreement between the simulation results and experimental data demonstrates the validity of the modeling method.

  11. QUALITY ASSURANCE GUIDELINES FOR LABORATORIES PERFORMING FORENSIC ANALYSIS OF CHEMICAL TERRORISM

    Science.gov (United States)

    The Scientific Working Group on Forensic Analysis of Chemical Terrorism (SWGFACT) has developed the following quality assurance guidelines to provide laboratories engaged in forensic analysis of chemical evidence associated with terrorism a framework to implement a quality assura...

  12. QUALITY ASSURANCE GUIDELINES FOR LABORATORIES PERFORMING FORENSIC ANALYSIS OF CHEMICAL TERRORISM

    Science.gov (United States)

    The Scientific Working Group on Forensic Analysis of Chemical Terrorism (SWGFACT) has developed the following quality assurance guidelines to provide laboratories engaged in forensic analysis of chemical evidence associated with terrorism a framework to implement a quality assura...

  13. IMPACT OF PHYSICAL AND CHEMICAL MUD CONTAMINATION ON WELLBORE CEMENT- FORMATION SHEAR BOND STRENGTH Authors: Arome Oyibo1 and Mileva Radonjic1 * 1. Craft and Hawkins Department of Petroleum Engineering, 2131 Patrick F. Taylor Hall, Louisiana State University, Baton Rouge, LA 70803, aoyibo1@tigers.lsu.edu, mileva@lsu.edu

    Science.gov (United States)

    Oyibo, A. E.

    2013-12-01

    /not contaminated, scrapped and washed composite cores. Similarly, for the chemically contaminated samples we had 3 different sample designs: 0%, 5% and 10% mud contaminated composite cores. Shear test were performed on the composite cores to determine the shear bond strength and the results suggested that the detrimental impact of the contamination is higher when the cores are physically contaminated i.e. when we have mud cake present at the surface of the wellbore before a cement job is performed. Also, the results showed that shear bond strength is higher for sandstone formations as compared to shale formations. Material characterization analysis was carried out to determine the micro structural changes at the cement-formation interface. The results obtained from the SEM and micro CT images taken at the bond interface confirmed that chemical contamination caused substantial changes in the spatial distribution of minerals that impacted bond strength. Keywords: Cement-Formation bond strength, mud contamination, shale, sandstone and material characterization *Corresponding author

  14. Electronic structure and chemical bonding in La1-x Sr x MnO3 perovskite ceramics

    Science.gov (United States)

    Thenmozhi, N.; Sasikumar, S.; Sonai, S.; Saravanan, R.

    2017-04-01

    This study reports on the synthesis of La1-x Sr x MnO3 (x  =  0.3, 0.4 and 0.5) manganites by high temperature solid state reaction method using lanthanum oxide, strontium carbonate and manganese oxide as starting materials. The synthesized samples were characterized by XRD, UV-vis, SEM/EDS and VSM. Structural characterization shows that all the prepared samples have the perovskite rhombohedral structure. Influence of Sr doping on electron density distributions in the lattice structure of LaMnO3 were analyzed through maximum entropy method (MEM). Cell parameters are found to be decreasing with the addition of Sr content. The qualitative and quantitative analysis by MEM reveals that, incorporation of Sr into LaMnO3 lattice enhances the ionic nature between La and O ions and decreases the covalent nature between Mn and O ions. Optical band gap values are determined from the UV-visible absorption spectra. Particles with polygonal form are observed from the SEM micrographs. The elemental compositions of the synthesized samples are confirmed by EDS. The magnetic properties studied from the M-H plot taken at room temperature indicated that, the prepared samples are exhibited ferromagnetic behavior.

  15. Comparison of the effect of shear bond strength with silane and other three chemical presurface treatments of a glass fiber-reinforced post on adhesion with a resin-based luting agent: An in vitro study

    Science.gov (United States)

    Belwalkar, Vaibhavi Ramkrishna; Gade, Jaykumar; Mankar, Nikhil Purushottam

    2016-01-01

    Background: Loss of retention has been cited to be the most common cause of the failure of postretained restoration with irreversible consequences when materials with different compositions are in intimate contact at the post/adhesive interface. With this background, a study was conducted to improve the adhesion at the resin phase of fiber posts using silane and other chemical pretreatments. Materials and Methods: Hundred glass fiber-reinforced posts were tested with 4 different protocols (n = 25) using silane as a control (Group A) and other three experimental groups, namely, Group B-20% potassium permanganate, Group C-4% hydrofluoric acid, and Group D-10% hydrogen peroxide were pretreated on the postsurface followed by silanization. These specimens were bonded with dual-polymerizing resin-based luting agent, which were then loaded at the crosshead speed of 1 mm/min to record the shear bond strength at the post/adhesive interface. The data were analyzed using one-way ANOVA test for multiple group comparisons and the post hoc Bonferroni test for pairwise comparisons (P < 0.05). Results: Group B showed more influence on the shear bond strength when compared to other protocols, respectively (P < 0.001). Conclusion: Alone silanization as a surface treatment did not improve the bond strength. Combination of chemical presurface treatments followed by silanization significantly enhanced the bond strength at the post/adhesive interface. PMID:27307666

  16. Comparison of the effect of shear bond strength with silane and other three chemical presurface treatments of a glass fiber-reinforced post on adhesion with a resin-based luting agent: An in vitro study

    Directory of Open Access Journals (Sweden)

    Vaibhavi Ramkrishna Belwalkar

    2016-01-01

    Full Text Available Background: Loss of retention has been cited to be the most common cause of the failure of postretained restoration with irreversible consequences when materials with different compositions are in intimate contact at the post/adhesive interface. With this background, a study was conducted to improve the adhesion at the resin phase of fiber posts using silane and other chemical pretreatments. Materials and Methods: Hundred glass fiber-reinforced posts were tested with 4 different protocols (n = 25 using silane as a control (Group A and other three experimental groups, namely, Group B-20% potassium permanganate, Group C-4% hydrofluoric acid, and Group D-10% hydrogen peroxide were pretreated on the postsurface followed by silanization. These specimens were bonded with dual-polymerizing resin-based luting agent, which were then loaded at the crosshead speed of 1 mm/min to record the shear bond strength at the post/adhesive interface. The data were analyzed using one-way ANOVA test for multiple group comparisons and the post hoc Bonferroni test for pairwise comparisons (P < 0.05. Results: Group B showed more influence on the shear bond strength when compared to other protocols, respectively (P < 0.001. Conclusion: Alone silanization as a surface treatment did not improve the bond strength. Combination of chemical presurface treatments followed by silanization significantly enhanced the bond strength at the post/adhesive interface.

  17. Influence of carbon chemical bonding on the tribological behavior of sputtered nanocomposite TiBC/a-C coatings

    Energy Technology Data Exchange (ETDEWEB)

    Abad, M.D. [Instituto de Ciencia de Materiales de Sevilla (CSIC-Univ. Sevilla), Avda. Americo Vespucio 49, 41092-Sevilla (Spain); Sanchez-Lopez, J.C., E-mail: jcslopez@icmse.csic.e [Instituto de Ciencia de Materiales de Sevilla (CSIC-Univ. Sevilla), Avda. Americo Vespucio 49, 41092-Sevilla (Spain); Brizuela, M.; Garcia-Luis, A. [Fundacion Inasmet-Tecnalia, Mikeletegui Pasealekua 2, 20009 Donostia-San Sebastian (Spain); Shtansky, D.V. [State Tecnological University ' Moscow Institute of Steel and Alloys' , Leninsky pr. 4, 119049-Moscow (Russian Federation)

    2010-07-30

    The tribological performance of nanocomposite coatings containing Ti-B-C phases and amorphous carbon (a-C) are studied. The coatings are deposited by a sputtering process from a sintered TiB{sub 2}:TiC target and graphite, using pulsed direct current and radio frequency sources. By varying the sputtering power ratio, the amorphous carbon content of the coatings can be tuned, as observed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The crystalline component consists of very disordered crystals with a mixture of TiB{sub 2}/TiC or TiB{sub x}C{sub y} phases. A slight increase in crystalline order is detected with the incorporation of carbon in the coatings that is attributed to the formation of a ternary TiB{sub x}C{sub y} phase. An estimation of the carbon present in the form of carbide (TiB{sub x}C{sub y} or TiC) and amorphous (a-C) is performed using fitting analysis of the C 1s XPS peak. The film hardness (22 to 31 GPa) correlates with the fraction of the TiB{sub x}C{sub y} phase that exists in the coatings. The tribological properties were measured by a pin-on-disk tribometer in ambient conditions, using 6 mm tungsten carbide balls at 1 N. The friction coefficients and the wear rates show similar behavior, exhibiting an optimum when the fraction of C atoms in the amorphous phase is near 50%. This composition enables significant improvement of the friction coefficients and wear rates ({mu} {approx} 0.1; k < 1 x 10{sup -6} mm{sup 3}/Nm), while maintaining a good value of hardness (24.6 GPa). Establishing the correlation between the lubricant properties and the fraction of a-C is very useful for purposes of tailoring the protective character of these nanocomposite coatings to engineering applications.

  18. Effect of surface pretreatment on interfacial chemical bonding states of atomic layer deposited ZrO{sub 2} on AlGaN

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Gang; Arulkumaran, Subramaniam; Ng, Geok Ing; Li, Yang; Ang, Kian Siong [School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Wang, Hong, E-mail: ewanghong@ntu.edu.sg [School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798, Singapore and CINTRA CNRS/NTU/Thales, UMI 3288, 50 Nanyang Drive, Singapore 637553 (Singapore); Ng, Serene Lay Geok; Ji, Rong [Data Storage Institute, Agency for Science Technology and Research (A-STAR), 5 Engineering Drive 1, Singapore 117608 (Singapore); Liu, Zhi Hong [Singapore-MIT Alliance for Research and Technology, 1 CREATE Way, Singapore 138602 (Singapore)

    2015-09-15

    Atomic layer deposition (ALD) of ZrO{sub 2} on native oxide covered (untreated) and buffered oxide etchant (BOE) treated AlGaN surface was analyzed by utilizing x-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy. Evidenced by Ga–O and Al–O chemical bonds by XPS, parasitic oxidation during deposition is largely enhanced on BOE treated AlGaN surface. Due to the high reactivity of Al atoms, more prominent oxidation of Al atoms is observed, which leads to thicker interfacial layer formed on BOE treated surface. The results suggest that native oxide on AlGaN surface may serve as a protecting layer to inhibit the surface from further parasitic oxidation during ALD. The findings provide important process guidelines for the use of ALD ZrO{sub 2} and its pre-ALD surface treatments for high-k AlGaN/GaN metal–insulator–semiconductor high electron mobility transistors and other related device applications.

  19. Advanced Fabrication of Chemically Bonded Graphene/TiO2 Continuous Fibers with Enhanced Broadband Photocatalytic Properties and Involved Mechanisms Exploration

    Science.gov (United States)

    Zhang, Qingzhe; Bao, Nan; Wang, Xinqiang; Hu, Xinde; Miao, Xinhan; Chaker, Mohamed; Ma, Dongling

    2016-12-01

    In this article, a novel route for the synthesis of graphene/TiO2 continuous fibers (GTF) using force-spinning combined with water vapor annealing method is reported for the first time. The morphology, structure and optical properties of the composite were fully characterized. With a single step of heat treatment process using steam at ambient conditions, we were able to initiate a series of chemical reactions, such as reduction of graphene oxide (GO), crystallization of TiO2, formation of C-Ti bond, and introduction of oxygen vacancies into TiO2. The incorporation of graphene in TiO2 fibers facilitated bandgap narrowing and improved photo-induced charge separation in the photocatalyst. As a result of synergistic effects, TiO2 fibers-2 wt% graphene (2%GTF) showed the highest photocatalytic activities in the degradation of X-3B under UV irradiation, superior to the benchmark photocatalyst P25. Under visible light irradiation, the same catalyst was about 4 times more efficient compared to pure TiO2 fibers (PTF). A detailed study of involved active species (in particular, ·, h+ and ·OH) unraveled the mechanism regarding photocatalysis.

  20. 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%.